Lithographic printing plate precursor and plate making method

CROSS-REFERENCE TO RELATED APPLICATIONS

0001This application claims the benefit of Japanese Patent Application <patcit id="pcit0001" dnum="JP2007165392A"><text>JP 2007-165392, filed June 22, 2007</text></patcit>, Japanese Patent Application <patcit id="pcit0002" dnum="JP2007240743A"><text>JP 2007-240743, filed September 18, 2007</text></patcit>, and Japanese Patent Application <patcit id="pcit0003" dnum="JP2008066744A"><text>JP 2008-066744, filed March 14, 2008</text></patcit>, the entire contents of which are hereby incorporated by reference, the same as if set forth at length.

FIELD OF THE INVENTION

0002The present invention relates to a lithographic printing plate precursor. More particularly, it relates to a lithographic printing plate precursor capable of undergoing image recording with laser and capable of being subjected to on-machine development or gum development.

BACKGROUND OF THE INVENTION

0003In general, a lithographic printing plate is composed of an oleophilic image area accepting ink and a hydrophilic non-image area accepting dampening water in the process of printing. Lithographic printing is a printing method utilizing the nature of water and oily ink to repel with each other and comprising rendering the oleophilic image area of the lithographic printing plate to an ink-receptive area and the hydrophilic non-image area thereof to a dampening water-receptive area (ink-unreceptive area), thereby making a difference in adherence of the ink on the surface of the lithographic printing plate, depositing the ink only to the image area, and then transferring the ink to a printing material, for example, paper.

0004In order to produce the lithographic printing plate, a lithographic printing plate precursor (PS plate) comprising a hydrophilic support having provided thereon an oleophilic photosensitive resin layer (image-recording layer) has heretofore been broadly used. Ordinarily, the lithographic printing plate is obtained by conducting plate making according to a method of exposing the lithographic printing plate precursor through an original, for example, a lith film, and then while leaving the image-recording layer corresponding to the image area, removing the unnecessary image-recording layer corresponding to the non-image area by dissolving with an alkaline developer or a developer containing an organic solvent thereby revealing the hydrophilic surface of support.

0005In the hitherto known plate making process of lithographic printing plate precursor, after exposure, the step of removing the unnecessary image-recording layer by dissolving, for example, with a developer is required. However, it is one of the subjects to save or simplify such an additional wet treatment described above. Particularly, since disposal of liquid wastes discharged accompanying the wet treatment has become a great concern throughout the field of industry in view of the consideration for global environment in recent years, the demand for the solution of the above-described subject has been increased more and more.

0006As one of simple plate making methods in response to the above-described requirement, a method referred to as on-machine development has been proposed wherein a lithographic printing plate precursor having an image-recording layer capable of being removed in the unnecessary areas during a conventional printing process is used and after exposure, the unnecessary area of the image-recording layer is removed on a printing machine to prepare a lithographic printing plate.

0007Specific methods of the on-machine development include, for example, a method of using a lithographic printing plate precursor having an image-recording layer that can be dissolved or dispersed in dampening water, an ink solvent or an emulsion of dampening water and ink, a method of mechanically removing an image-recording layer by contact with rollers or a blanket cylinder of a printing machine, and a method of lowering cohesion of an image-recording layer or adhesion between an image-recording layer and a support upon penetration of dampening water, ink solvent or the like and then mechanically removing the image-recording layer by contact with rollers or a blanket cylinder of a printing machine.

0008Also, as another example of simple plate making methods, a method referred to as gum development has been proposed wherein removal of the unnecessary area of the image-recording layer in the development processing step is carried out using a gum solution for finishing treatment which is conventionally performed after an alkali development in place of a conventional highly alkaline developer.

0009In the invention, unless otherwise indicated particularly, the term "development processing step" means a step of using an apparatus (ordinarily, an automatic developing machine) other than a printing machine and removing an unexposed area in an image-recording layer of a lithographic printing plate precursor upon contact with liquid (ordinarily, an alkaline developer) thereby revealing a hydrophilic surface of support. The term "on-machine development" means a method or a step of removing an unexposed area in an image-recording layer of a lithographic printing plate precursor upon contact with liquid (ordinarily, printing ink and/or dampening water) by using a printing machine thereby revealing a hydrophilic surface of support.

0010Of the processings including the "development processing step", the development using a gum solution as the developer is particularly referred to as "gum development".

0011On the other hand, digitalized technique of electronically processing, accumulating and outputting image information using a computer has been popularized in recent years, and various new image-outputting systems responding to the digitalized technique have been put into practical use. Correspondingly, attention has been drawn to a computer-to-plate technique of carrying digitalized image information on highly converging radiation, for example, a laser beam and conducting scanning exposure of a lithographic printing plate precursor with the radiation thereby directly preparing a lithographic printing plate without using a lith film. Thus, it is one of the important technical subjects to obtain a lithographic printing plate precursor adaptable to the technique described above.

0012In the simplification of plate making operation and the realization of dry system or non-processing system as described above, since the image-recording layer after the exposure is not fixed with the development processing, it is still sensitive to light and likely to be fogged before printing. Therefore, an image-recording layer capable of being handled in a bright room or under a yellow lump and a light source are necessary. As such a laser light source, a semiconductor laser emitting an infrared ray having a wavelength of 760 to 1,200 and a solid laser, for example, YAG laser, are extremely useful because these lasers having a large output and a small size are inexpensively available. Also, an UV laser can be used.

0013As the lithographic printing plate precursor of on-machine development type capable of conducting image-recording with an infrared laser, for example, lithographic printing plate precursors having provided on a hydrophilic support, an image-forming layer (image-recording layer) in which hydrophobic thermoplastic polymer particles are dispersed in a hydrophilic binder are described in Japanese Patent <patcit id="pcit0004" dnum="JP2938397B"><text>2,938,397</text></patcit> (corresponding to <patcit id="pcit0005" dnum="EP0770494A2"><text>EP0770494A2</text></patcit>). It is described in Japanese Patent <patcit id="pcit0006" dnum="JP2938397B"><text>2,938,397</text></patcit> (corresponding to <patcit id="pcit0007" dnum="EP0770494A2"><text>EP0770494A2</text></patcit>) that the lithographic printing plate precursor is exposed to an infrared laser to agglomerate the hydrophobic thermoplastic polymer particles by heat thereby forming an image, and mounted on a plate cylinder of a printing machine to be able to carry out on-machine development by supplying dampening water and/or ink.

0014Although the method of forming image by the agglomeration of fine particles only upon thermal fusion shows good on-machine development property, it has a problem in that the image strength is extremely weak and printing durability is insufficient.

0015Further, lithographic printing plate precursors having provided on a hydrophilic support, microcapsules containing a polymerizable compound encapsulated therein are described in <patcit id="pcit0008" dnum="JP2001277740A"><text>JP-A-2001-277740</text></patcit> (the term "JP-A" as used herein means an "unexamined published Japanese patent application") and <patcit id="pcit0009" dnum="JP2001277742A"><text>JP-A-2001-277742</text></patcit>.

0016Moreover, lithographic printing plate precursors having provided on a support, a photosensitive layer containing an infrared absorbing agent, a radical polymerization initiator and a polymerizable compound are described in <patcit id="pcit0010" dnum="JP2002287334A"><text>JP-A-2002-287334</text></patcit> (corresponding to <patcit id="pcit0011" dnum="US20020177074A1"><text>US2002/0177074A1</text></patcit>).

0017The methods using the polymerization reaction as described above have a feature that since the chemical bond density in the image area is high, the image strength is relatively good in comparison with the image area formed by the thermal fusion of fine polymer particles. However, it is necessary to provide an intermediate layer between the support and the image-recording layer in order to satisfy the printing durability, on-machine development property and stain resistance at the time of printing (staining property).

0018It is ordinarily known that a water-soluble resin imparted with a hydrophilicity is used in the intermediate layer of such a purpose and lithographic printing plate precursors of on-machine development type provided with an intermediate layer composed of a polymer having an adsorbing group to substrate, a polymerizable group and a hydrophilic group are described in <patcit id="pcit0012" dnum="JP2005125749A"><text>JP-A-2005-125749</text></patcit> (corresponding to <patcit id="pcit0013" dnum="US20050074692A1"><text>US2005/0074692A1</text></patcit>).

0019However, with respect to the lithographic printing plate precursor of on-machine development type and lithographic printing plate precursor of gum development type, even when such an intermediate layer is provided, the staining property of the non-image area is still insufficient, in particular, a round spot-like stain (hereinafter also referred to as a spot stain) of several mµ to several thousands mµ may occur in some cases and therefore, a further improvement has been requested.

SUMMARY OF THE INVENTION

0020The present invention has been made in consideration of the conventional technology described above and an object of the invention is to provide a lithographic printing plate precursor which is capable of being undergoing image recording with an infrared laser, is excellent in the on-machine development property or gum development property and printing durability and is improved in the staining property, particularly, the spot stain, and a plate making method using the lithographic printing plate precursor.

0021The present invention includes the following items. <ol id="ol0001" compact="compact" ol-style=""><li>(1) A lithographic printing plate precursor comprising: an aluminum support; an intermediate layer; and an image-recording layer, in this order, wherein a compound having an amino group and a functional group capable of interacting with the aluminum support in its molecule is incorporated into the intermediate layer or the image-recording layer.</li><li>(2) A lithographic printing plate precursor comprising: an aluminum support; an intermediate layer; and an image-recording layer, in this order, wherein a compound having an amino group and a functional group capable of interacting with the aluminum support in its molecule is incorporated into the intermediate layer.</li><li>(3) The lithographic printing plate precursor as described in (1) or (2) above, wherein the functional group capable of interacting with the aluminum support is a trialkoxysilyl group, an onium group or an acid group selected from a phenolic hydroxy group, a carboxyl group, -SO₃H, -OSO₃H, -PO₃H₂, -OPO₃H₂, -CONHSO₂-, - SO₂NHSO₂- and -COCH₂CO- and metal salts thereof.</li><li>(4) The lithographic printing plate precursor as described in any one of (1) to (3) above, wherein the compound having an amino group and a functional group capable of interacting with the aluminum support in its molecule is a compound represented by formula (1) shown below: <chemistry id="chem0001" num="0001"><img file="EP2006091A2_D0001.tif" /></chemistry> In formula (1), R represents a hydrogen atom or a group selected from an alkyl group, an alkenyl group, an alkynyl group, an aryl group and a heterocyclic group, each of which may have a substituent, and X^- represents an anion.</li><li>(5) The lithographic printing plate precursor as described in any one of (1) to (3) above, wherein the compound having an amino group and a functional group capable of interacting with the aluminum support in its molecule is a compound represented by formula (2) shown below: <img file="EP2006091A2_D0002.tif" /> In formula (2), W represents n-valent organic connecting group, n represents an integer of 2 or more, and X^- represents an anion.</li><li>(6) The lithographic printing plate precursor as described in any one of (1) to (3) above, wherein the compound having an amino group and a functional group capable of interacting with the aluminum support in its molecule is a compound represented by formula (3) shown below: <chemistry id="chem0002" num="0002"><img file="EP2006091A2_D0003.tif" /></chemistry> In formula (3), W represents divalent organic connecting group, R_i represents an organic residue, n represents an integer of 2 or 3, and m represents a number satisfying a formula, n x m = 2.</li><li>(7) The lithographic printing plate precursor as described in any one of (1) to (6) above, wherein the intermediate layer contains a polymer having an adsorbing group to substrate, a polymerizable group and a hydrophilic group.</li><li>(8) The lithographic printing plate precursor as described in any one of (1) to (7) above, wherein the image-recording layer contains (A) an infrared absorbing agent, (B) a polymerization initiator and (C) a polymerizable compound.</li><li>(9) The lithographic printing plate precursor as described in any one of (1) to (8) above, wherein the image-recording layer further contains (D) a binder polymer.</li><li>(10) The lithographic printing plate precursor as described in any one of (1) to (9) above, wherein the image-recording layer further contains (E) a microcapsule or microgel.</li><li>(11) The lithographic printing plate precursor as described in any one of (1) to (10) above, wherein the image-recording layer is an image-recording layer capable of forming an image by removing after imagewise exposure, an unexposed area of the image-recording layer by supplying printing ink and dampening water (fountain solution) on a printing machine or by development after imagewise exposure, with a gum solution.</li><li>(12) A plate making method of a lithographic printing plate precursor comprising a step of exposing imagewise the lithographic printing plate precursor as described in (11) above and a step of removing an unexposed area of the lithographic printing plate precursor by supplying printing ink and dampening water on a printing machine to initiate printing without carrying out any development processing of the exposed lithographic printing plate precursor.</li><li>(13) A plate making method of a lithographic printing plate precursor comprising a step of exposing imagewise the lithographic printing plate precursor as described in (11) above and a step of removing an unexposed area of the lithographic printing plate precursor by developing the exposed lithographic printing plate precursor with a gum solution.</li></ol>

0022According to the present invention, a lithographic printing plate precursor which is capable of undergoing image recording with an infrared laser, is excellent in the on-machine development property or gum development property and printing durability and is improved in the staining property, particularly, the spot stain, and a plate making method using the lithographic printing plate precursor can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS

0023<figref idref="f0001">Fig. 1</figref> is an illustration for showing a composition of an automatic development apparatus for the lithographic printing plate precursor according to the invention.

[Description of reference numerals and signs]

0024<ul id="ul0001" list-style="none" compact="compact"><li>1: Rotating brush roller</li><li>2: Backing roller</li><li>3: Transport roller</li><li>4: Transport guide plate</li><li>5: Spray pipe</li><li>6: Pipe line</li><li>7: Filter</li><li>8: Plate supply table</li><li>9: Plate discharge table</li><li>100: Developer tank</li><li>101: Circulating pump</li><li>102: Plate</li></ul>

DETAILED DESCRIPTION OF THE INVENTION

[Lithographic printing plate precursor]

0025The lithographic printing plate precursor according to the invention comprises: an aluminum support; an intermediate layer; and an image-recording layer provided in this order, wherein a compound having an amino group and a functional group capable of interacting with the aluminum support in its molecule is incorporated into the intermediate layer or the image-recording layer..

0026Also, in the lithographic printing plate precursor according to the invention, the intermediate layer preferably includes a polymer having an adsorbing group to substrate, a polymerizable group and a hydrophilic group. Further, in the lithographic printing plate precursor according to the invention, the image-recording layer preferably contains (A) an infrared absorbing agent, (B) a polymerization initiator and (C) a polymerizable compound. Moreover, the lithographic printing plate precursor according to the invention preferably has a protective layer on the image-recording layer.

0027The lithographic printing plate precursor according to the invention will be described in more detail below.

<Compound having amino group and functional group capable of interacting with aluminum support in its molecule>

0028The compound (hereinafter, also referred to as a "specific compound") having an amino group and a functional group capable of interacting with an aluminum support in its molecule according to the invention is incorporated into an intermediate layer or image-recording layer. It is particularly preferably incorporated into the intermediate layer. The specific compound according to the invention may have a plurality of amino groups and functional groups capable of interacting with an aluminum support respectively in its molecule.

0029The term "aluminum support" as used herein means an aluminum support subjected to an anodizing treatment and/or hydrophilizing treatment as described hereinafter. The term "functional group capable of interacting with an aluminum support" means a functional group capable of making interaction, for example, a covalent bond, an ionic bond, a hydrogen bond, polar interaction or van der Walls interaction with metal, a metal oxide, a hydroxy group or the like present on the aluminum support.

0030The amino group in the specific compound according to the invention is preferably a secondary amino group or a tertiary amino group, more preferably a tertiary amino group. Specific examples of the functional group capable of interacting with an aluminum support includes a trialkoxysilyl group, an onium group or an acid group selected from a phenolic hydroxy group, a carboxyl group, -SO₃H, -OSO₃H, -PO₃H₂, -OPO₃H₂, -CONHSO₂-, - SO₂NHSO₂- and -COCH₂COand metal salts thereof. Among them, a trialkoxysilyl group, an onium group, -PO₃H₂ or a metal salt thereof or -OPO₃H₂ or a metal salt thereof is more preferable.

0031The trialkoxysilyl group is preferably a trialkoxysilyl group having from 1 to 18 carbon atoms, particularly preferably a trimethoxysilyl group or a triethoxysilyl group. The onium group is preferably an ammonium group or a phosphonium group, most preferably an ammonium group. A counter anion for the onium group preferably includes, for example, a halide ion (for example, a chloride ion or a bromide ion), a sulfonate ion (for example, a methanesulfonate ion or a p-toluenesulfonate ion), a carboxylate ion (for example, an acetate ion or a propionate ion), a hydroxide ion, a monoalkylsulfate ion (for example, a monomethylsulfate ion or a monoethylsulfate ion), PF₆^- and BF₄^-. Among them, PF6^-, BF₄^-, a sulfonate ion or a carboxylate ion is particularly preferable.

0032Preferable examples of the ammonium group and phosphonium group are set forth below. <chemistry id="chem0003" num="0003"><img file="EP2006091A2_D0004.tif" /></chemistry><chemistry id="chem0004" num="0004"><img file="EP2006091A2_D0005.tif" /></chemistry><chemistry id="chem0005" num="0005"><img file="EP2006091A2_D0006.tif" /></chemistry>

0033Of the specific compounds according to the invention, a compound represented by formula (1) shown below is particularly preferable. <chemistry id="chem0006" num="0006"><img file="EP2006091A2_D0007.tif" /></chemistry>

0034In formula (1), R represents a hydrogen atom or a group selected from an alkyl group, an alkenyl group, an alkynyl group, an aryl group and a heterocyclic group, each of which may have a substituent, and X^- represents an anion.

0035The substituent includes, for example, an amino group, an acyl group, a carboxyl group, a hydroxy group, a substituted hydroxy group, a thiol group, a substituted thiol group, a silyl group, a nitro group, a cyano group, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a sulfo group, a substituted sulfonyl group, a sulfonato group, a substituted sulfinyl group, a phosphono group, a substituted phosphono group, a phosphonato group and a substituted phosphonato group, and when it is possible to introduce a substituent, the substituent may further be introduced.

0036The alkyl group represented by R is preferably includes a straight-chain, branched or cyclic alkyl group having from 1 to 20 carbon atoms. Of the alkyl groups, a straight-chain alkyl group having from 1 to 12 carbon atoms, a branched alkyl group having from 3 to 12 carbon atoms and a cyclic alkyl group having from 5 to 10 carbon atoms are more preferred. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a hexadecyl group, an octadecyl group, an eicosyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1-methylbutyl group, an isohexyl group, a 2-ethylhexyl group, a 2-methylhexyl group, a cyclohexyl group, a cyclopentyl group and a 2-norbornyl group.

0037When the alkyl group represented by R has a substituent (that is, in case of a substituted alkyl group), a preferable range of carbon atoms included in the alkyl moiety of the substituted alkyl group is same as that of the alkyl group described above.

0038Specific preferable examples of the substituted alkyl group represented by R include a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, a trifluoromethyl group, a methoxymethyl group, a methoxycarbonylmethyl group, an isopropoxymethyl group, a butoxymethyl group, a sec-butoxybutyl group, a methoxyethoxyethyl group, an allyloxymethyl group, a phenoxymethyl group, an acetyloxymethyl group, a methylthiomethyl group, a tolylthiomethyl group, a pyridylmethyl group, a tetramethylpiperidinylmethyl group, an N-acetyltetramethylpiperidinylmethyl group, a trimethylsilylmethyl group, a methoxyethyl group, an ethylaminoethyl group, a diethylaminopropyl group, a morpholinopropyl group, an acetyloxymethyl group, a benzoyloxymethyl group, an N-cyclohexylcarbamoyloxyethyl group, an N-phenylcarbamoyloxyethyl group, an acetylaminoethyl group, an N-methylbenzoylaminopropyl group, a 2-oxoethyl group, a 2-oxopropyl group, a carboxypropyl group, a methoxycarbonylethyl group, an allyloxycarbonylbutyl group, a chlorophenoxycarbonylmethyl group, a carbamoylmethyl group, an N-methylcarbamoylethyl group, an N,N-dipropylcarbamoylmethyl group, an N-(methoxyphenyl)carbamoylethyl group, an N-methyl-N-(sulfophenyl)carbarnoylmethyl, a sulfobutyl group, a sulfonatobutyl group, a sulfamoylbutyl group, an N-ethylsulfamoylmethyl group, an N,N-dipropylsulfamoylpropyl group, an N-tolylsulfamoylpropyl group, an N-methyl-N-(phosphonophenyl)sulfamoyloctyl group, a phosphonobutyl group, a phosphonatohexyl group, a diethylphosphonobutyl group, a diphenylphosphonopropyl group, a methylphosphonobutyl group, a methylphosphonatobutyl group, a tolylphosphonohexyl group, a tolylphosphonatohexyl, a phosphonoxypropyl group, a phosphonatoxybutyl group, a benzyl group, a phenethyl group, an α-methylbenzyl group, a 1-methyl-1-phenylethyl group and a p-methylbenzyl group.

0039Examples of the substituent capable of being introduced into the alkyl group represented by R include a monovalent substituent constituting from a non-metallic atom illustrated below in addition to the substituents described in the substituted alkyl group. Preferable examples of the substituent for the alkyl group including the substituents described above include a halogen atom (e.g., -F, -Br, -Cl or -I), a hydroxy group, an alkoxy group, an aryloxy group, a mercapto group, an alkylthio group, an arylthio group, an alkyldithio group, an aryldithio group, an amino group, an N-alkylamino group, an N,N-dialkylamino group, an N-arylamino group, an N,N-diarylamino group, an N-alkyl-N-arylamino group, an acyloxy group, a carbamoyloxy group, an N-alkylcarbamoyloxy group, an N-arylcarbamoyloxy group, an N,N-dialkylcarbamoyloxy group, an N,N-diarylcarbamoyloxy group, an N-alkyl-N-arylcarbamoyloxy group, an alkylsulfoxy group, an arylsulfoxy group, an acylthio group, an acylamino group, an N-alkylacylamino group, an N-arylacylamino group, a ureido group, an N'-alkyluxeido group, an N',N'-dialkylureido group, N'-arylureido group, an N',N'-diarylureido group, an N'-alkyl-N'-arylureido group, an N-alkylureido group, N-arylureido group, an N'-alkyl-N-alkylureido group, an N'-alkyl-N-arylureido group, an N',N'-dialkyl-N-alkylureido group, an N',N'-dialkyl-N-arylureido group, an N'-aryl-N-alkylurcido group, an N'-aryl-N-arylureido group, an N',N'-diaryl-N-alkylureido group, an N',N'-diaryl-N-arylureido group, an N'-alkyl-N'-aryl-N-alkylureido group, an N'-alkyl-N'-aryl-N-arylureido group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an N-alkyl-N-alkoxycarbonylamino group, an N-alkyl-N-aryloxycarbonylamino group, an N-aryl-N-alkoxycarbonylamino group, an N-aryl-N-aryloxycarbonylamino group, a formyl group, an acyl group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an N-alkylcarbamoyl group, an N,N-dialkylcarbamoyl group, an N-arylcarbamoyl group, an N,N-diarylcarbamoyl group, an N-alkyl-N-arylcarbamoyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfo group (-SO₃H) and a conjugate base group thereof (hereinafter, referred to as a sulfonato group), an alkoxysulfonyl group, an aryloxysulfonyl group, a sulfinamoyl group, an N-alkylsulfinamoyl group, an N,N-dialkylsulfinamoyl group, an N-arylsulfinamoyl group, an N,N-diarylsulfinamoyl group, an N-alkyl-N-arylsulfinamoyl group, a sulfamoyl group, an N-alkylsulfamoyl group, an N,N-dialkylsulfamoyl group, an N-arylsulfamoyl group, an N,N-diarylsulfamoyl group, an N-alkyl-N-arylsulfamoyl group, a phosphono group (-PO₃H₂) and a conjugate base group thereof (hereinafter, referred to as a phosphonato group), a dialkylphosphono group (-PO₃(alkyl)₂) wherein "alkyl" means an alkyl group, hereinafter the same, a diarylphosphono group (-PO₃(aryl)₂) wherein "aryl" means an aryl group, hereinafter the same, an alkylarylphosphono group (-PO₃(alkyl)(aryl)), a monoalkylphosphono group (-PO₃H(alkyl)) and a conjugate base group thereof (hereinafter, referred to as an alkylphosphonato group), a monoarylphosphono group (-PO₃H(aryl)) and a conjugate base group thereof (hereinafter, referred to as an arylphosphonato group), a phosphonoxy group (-OPO₃H₂) and a conjugate base group thereof (hereinafter, referred to as a phosphonatoxy group), a dialkylphosphonoxy group (-OPO₃(alkyl)₂), a diarylphosphonoxy group (-OPO₃(aryl)₂), an alkylarylphosphonoxy group (-OPO₃(alkyl)(aryl)), a monoalkylphosphonoxy group (-OPO₃H(alkyl)) and a conjugate base group thereof (hereinafter, referred to as an alkylphosphonatoxy group), a monoarylphosphonoxy group (-OPO₃H(aryl)) and a conjugate base group thereof (hereinafter, referred to as an arylphosphonatoxy group), a cyano group, a nitro group, an aryl group, an alkenyl group, an alkynyl group, a heterocyclic group and a silyl group.

0040Specific examples of the alkyl moiety in the substituent capable of being introduced into the alkyl group represented by R are same as those described in the case where R represents the substituted alkyl group. Also, the range of preferable number of carbon atoms is same as that of the alkyl group described above.

0041Also, specific examples of the aryl moiety in the substituent capable of being introduced into the alkyl group represented by R include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a chlorophenyl group, a bromophenyl group, a chloromethylphenyl group, a hydroxyphenyl group, a methoxyphenyl group, an ethoxyphenyl group, a phenoxyphenyl group, an acetoxyphenyl group, a benzoyloxyphenyl group, a methylthiophenyl group, a phenylthiophenyl group, a methylaminophenyl group, a dimethylaminophenyl group, an acetylaminophenyl group, a carboxyphenyl group, a methoxycarbonylphenyl group, an ethoxycarbonylphenyl group, a phenoxycarbonylphenyl group, an N-phenylcarbamoylphenyl group, a cyanophenyl group, a sulfophenyl group, a sufonatophenyl group, a phosphonophenyl group and a phosphonatophenyl group.

0042The alkenyl group represented R includes an alkenyl group having from 2 to 20 carbon atoms. Of the alkenyl groups, an alkenyl group having from 2 to 10 carbon atoms is preferable, and alkenyl group having from 2 to 8 carbon atoms is more referable. The alkenyl group may have a substituent. Examples of the substituent capable of being introduced include a halogen atom, an alkyl group, a substituted alkyl group, an aryl group and a substituted aryl group, and preferably a halogen atom and a straight-chain, branched or cyclic alkyl group having from 1 to 10 carbon atoms. Specific examples of the alkenyl group include a vinyl group, an allyl group, a 2-methylallyl group, a 1-propenyl group, a 1-butenyl group, a 2-butenyl group, a cinnamyl group, a 1-pentenyl group, a 1-hexenyl group, a 1-octenyl group, a 1-methyl-1-propenyl group, a 2-methyl-1-propenyl group, a 2-methyl-1-propenylmethyl group, a 2-methyl-1-butenyl group, a 2-phenyl-1-ehtenyl group and a 2-chloro-1-ethenyl group.

0043The alkynyl group represented by R includes an alkynyl group having from 2 to 20 carbon atoms. Of the alkynyl groups, an alkynyl group having from 2 to 10 carbon atoms is preferable, and alkynyl group having from 2 to 8 carbon atoms is more referable. Specific examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a phenylethynyl group and a trimethylsilylethynyl group.

0044The aryl group represented by R includes a benzene ring group, a condensed ring group of two to three benzene rings and a condensed ring group of a benzene ring and a 5-membered unsaturated ring. Specific examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group and a fluorenyl group. Among them, a phenyl group and a naphthyl group are preferable.

0045Also, the aryl group represented by R may have a substituent on the carbon atom forming the ring. Such a substituent includes a monovalent substituent constituting from a non-metallic atom. Preferable examples of the substituent capable of being introduced include the above-described alkyl group and substituted alkyl group and those described for the substituents of the substituted alkyl group.

0046The heterocyclic group represented by R is preferably a 3-membered to 8-membered heterocyclic group, more preferably a 3-membered to 6-membered heterocyclic group containing a nitrogen atom, an oxygen atom or a sulfur atom, still more preferably a 5-membered to 6-membered heterocyclic group containing a nitrogen atom, an oxygen atom or a sulfur atom. Specific examples of the heterocyclic group include a pyrrole ring group, a furan ring group, a thiophene ring group, a benzopyrrole ring group, a benzofuran ring group, a benzothiophene ring group, a pyrazole ring group, an isoxazole ring group, an isothiazole ring group, an indazole ring, a benzisoxazole ring group, a benzisothiazole ring group, an imidazole group, an oxazole ring group, a thiazole ring group, a benzimidazole group, a benzoxazole ring group, a benzothiazole ring group, a pyridine ring group, a quinoline ring group, an isoquinoline ring group, a pyridazine ring group, a pyrimidine ring group, a pyrazine ring group, a phthalazine ring group, a quinazoline ring group, a quinoxaline ring group, an aciridine ring group, a phenanthrydine ring group, a carbazole ring group, a purine ring group, a pyrane ring group, a piperidine ring group, a piperazine ring group, a morpholine ring group, an indole ring group, an indolizine ring group, a chromene ring group, a cinnnoline ring group, an acridine ring group, a phenothiazine ring group, a tetrazole ring group and a triazine ring group.

0047Also, the heterocyclic group represented by R may have a substituent on the carbon atom forming the ring. Such a substituent includes a monovalent substituent constituting from a non-metallic atom. Preferable examples of the substituent capable of being introduced include the above-described alkyl group and substituted alkyl group and those described for the substituents of the substituted alkyl group.

0048Preferable embodiments for R are described below.

0049R is preferably a hydrogen atom or an alkyl group having from 1 to 20 carbon atoms which may have a substituent, more preferably a hydrogen atom or an alkyl group having from 1 to 5 carbon atoms which may have a substituent, still more preferably a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms which may have a substituent.

0050X^- represents an appropriate anion and is preferably an acid anion. Specific examples of the anion include a halogen atom anion, BF4^-, BCl₄^-, ZnCl₄^-, SbCl₆^-, FeCl₄^-, GaCl₄^-, GaBr₄^-, AlI₄^-, AlCl₄^-, SbF₆^-, CF₃SO₃^-, PF₆^-, BPh₄^-, a benzenesulfonate anion, a p-toluenesulfonate anion, a condensed polynuclear sulfonic acid anion, for example, a naphthalene-1-sulfonate anion or an anthracene-1-sulfonate anion, an anthraquinonesulfonate anion, a sulfuric acid N-cyclohexylamide anion, a sulfuric acid N-phenylamide anion and a dye anion containing a sulfo group (anion containing a sulfo group and a chromophoric atomic group), but the invention should not be construed as being limited thereto.

0051The compound represented by formula (1) also includes a compound which contains in its molecule two or more of the cation skeleton portions formed by connecting two or more of the cation skeleton portions through R in formula (1), and such a compound is also preferably used.

0052As the compound which contains two or more of the cation skeleton portions in its molecule, a compound represented by formula (2) shown below is particularly preferable. <chemistry id="chem0007" num="0007"><img file="EP2006091A2_D0008.tif" /></chemistry>

0053In formula (2), W represents n-valent organic connecting group, n represents an integer of 2 or more, and X^- represents an anion.

0054In formula (2), X^- has the same meaning as X^- in formula (1). The n-valent organic connecting group represented by W is a multi-valent organic group and preferably a multi-valent organic group constituting from 1 to 60 carbon atoms, from 0 to 10 nitrogen atoms, from 0 to 50 oxygen atoms, from 1 to 100 hydrogen atoms and from 0 to 20 sulfur atoms. Specific examples thereof include organic connecting groups constituting individually or in combination from structures (connecting group unit structures) shown below.

(Connecting group unit structure)

0055<chemistry id="chem0008" num="0008"><img file="EP2006091A2_D0009.tif" /></chemistry><chemistry id="chem0009" num="0009"><img file="EP2006091A2_D0010.tif" /></chemistry><chemistry id="chem0010" num="0010"><img file="EP2006091A2_D0011.tif" /></chemistry><chemistry id="chem0011" num="0011"><img file="EP2006091A2_D0012.tif" /></chemistry> multi-valent naphthalene, multi-valent anthracene

0056The organic connecting group represented by W may have a substituent. The substituent capable of being introduced includes, for example, a halogen atom, a hydroxy group, a carboxyl group, a sulfonato group, a nitro group, a cyano group, an amido group, an amino group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a substituted oxy group, a substituted sulfonyl group, a substituted carbonyl group, a substituted sulfinyl group, a sulfo group, a phosphono group, a phosphonato group, a silyl group and a heterocyclic group.

0057As the compound which contains two or more of the cation skeleton portions in its molecule, a compound represented by formula (3) shown below is also particularly preferable. <img file="EP2006091A2_D0013.tif" />

0058In formula (3), W represents divalent organic connecting group, R₁ represents an organic residue, n represents an integer of 2 or 3, and m represents a number satisfying n x m = 2.

0059The organic residue represented by R₁ includes residues of aliphatic hydrocarbons, aromatic hydrocarbons and heterocyclic compounds each having 20 or less carbon atoms. Among them, aromatic hydrocarbon residues are preferable, divalent and trivalent residues of benzene and naphthalene are particularly preferable. Particularly preferable specific examples of the anion containing the residue include a 1,5-naphthalenedisulfonate anion, a 2,6-naphthalenedisulfonate anion, a 2,7-naphthalenedisulfonate anion, a 2-naphthol-6,8-disulfonate anion, a 1,3,6-naphthalenetrisulfonate anion and a 1,3-benzenesulfonate anion. W has the same meaning as W in formula (2) wherein W represents a divalent organic connecting group.

0060Moreover, the compound represented by formula (1) includes a compound in which the cation skeleton portion is introduced into a polymer side chain through R, and such a compound is also preferably used.

0061As the compound in which the cation skeleton portion is introduced into a polymer side chain, a compound represented by formula (4) shown below is particularly preferable. <chemistry id="chem0012" num="0012"><img file="EP2006091A2_D0014.tif" /></chemistry>

0062In formula (4), L represents a single bond or a divalent organic connecting group, m represents an integer of 1 or more, X- represents an anion, and P represents a polymer main chain.

0063The polymer main chain represented by P is not particularly restricted and preferably includes, for example, a poly(methacrylate) chain, a polystyrene chain, a polyvinyl chin, a polyurethane chain and a polyacetal chain. Among them, from the standpoint of the printing durability and the like when the polymer compound is applied to an image-recording layer of lithographic printing plate precursor, a poly(methacrylate) chain and a polystyrene chain and the like are particularly preferable.

0064The divalent organic connecting group represented by L is preferably a divalent organic group constituting from 1 to 60 carbon atoms, from 0 to 10 nitrogen atoms, from 0 to 50 oxygen atoms, from 1 to 100 hydrogen atoms and from 0 to 20 sulfur atoms. Specific examples thereof include organic connecting groups constituting individually or in combination from the connecting group unit structures described above.

0065The organic connecting group represented by L may have a substituent. The substituent capable of being introduced includes, for example, a halogen atom, a hydroxy group, a carboxyl group, a sulfonato group, a nitro group, a cyano group, an amido group, an amino group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a substituted oxy group, a substituted sulfonyl group, a substituted carbonyl group, a substituted sulfinyl group, a sulfo group, a phosphono group, a phosphonato group, a silyl group and a heterocyclic group.

0066m represents an integer of 1 or more and is preferably from 1 to 6, more preferably from 1 to 3.

0067X^- in formula (4) has the same meaning as X^- in formula (1), and the preferable examples thereof are also same as those described above.

0068Specific examples of the compounds represented by formulae (1) to (4) are set forth below, but the invention should not be construed as being limited thereto. <chemistry id="chem0013" num="0013"><img file="EP2006091A2_D0015.tif" /></chemistry><chemistry id="chem0014" num="0014"><img file="EP2006091A2_D0016.tif" /></chemistry><chemistry id="chem0015" num="0015"><img file="EP2006091A2_D0017.tif" /></chemistry><chemistry id="chem0016" num="0016"><img file="EP2006091A2_D0018.tif" /></chemistry><chemistry id="chem0017" num="0017"><img file="EP2006091A2_D0019.tif" /></chemistry><chemistry id="chem0018" num="0018"><img file="EP2006091A2_D0020.tif" /></chemistry><chemistry id="chem0019" num="0019"><img file="EP2006091A2_D0021.tif" /></chemistry><chemistry id="chem0020" num="0020"><img file="EP2006091A2_D0022.tif" /></chemistry><chemistry id="chem0021" num="0021"><img file="EP2006091A2_D0023.tif" /></chemistry><chemistry id="chem0022" num="0022"><img file="EP2006091A2_D0024.tif" /></chemistry><chemistry id="chem0023" num="0023"><img file="EP2006091A2_D0025.tif" /></chemistry><chemistry id="chem0024" num="0024"><img file="EP2006091A2_D0026.tif" /></chemistry><chemistry id="chem0025" num="0025"><img file="EP2006091A2_D0027.tif" /></chemistry><chemistry id="chem0026" num="0026"><img file="EP2006091A2_D0028.tif" /></chemistry><chemistry id="chem0027" num="0027"><img file="EP2006091A2_D0029.tif" /></chemistry><chemistry id="chem0028" num="0028"><img file="EP2006091A2_D0030.tif" /></chemistry>

0069The content of the specific compound in the intermediate layer is preferably from 10 to 90% by weight, more preferably from 20 to 80% by weight, most preferably from 25 to 75% by weight, based on the solid content of the intermediate layer. The content of the specific compound in the image-recording layer is preferably from 0.1 to 90% by weight, more preferably from 0.2 to 80% by weight, most preferably from 0.3 to 70% by weight, based on the solid content of the image-recording layer. In the range described above, good effect of improving the staining property is obtained.

(Intermediate layer)

0070In the intermediate layer provided between the image-recording layer and the support in the lithographic printing plate precursor according to the invention, heretofore known compounds for intermediate layer can be used in addition to the specific compound described above. As such a compound for intermediate layer, for example, a silane coupling agent having an addition-polymerizable ethylenic double bond reactive group described in <patcit id="pcit0014" dnum="JP10282679A"><text>JP-A-10-282679</text></patcit> and a phosphorus compound having an ethylenic double bond reactive group described in <patcit id="pcit0015" dnum="JP2304441A"><text>JP-A-2-304441</text></patcit> are preferably exemplified.

0071As a most preferable compound, a polymer for intermediate layer obtained by copolymerization of a monomer having an adsorbing group, a monomer having a hydrophilic group and a monomer having a crosslinkable group is exemplified.

0072The coating amount (solid content) of the intermediate layer is preferably from 0.1 to 100 mg/m², more preferably from 1 to 50 mg/m², in view of achievement of good compatibility between the printing durability and the stain resistance.

0073By the intermediate layer according to the invention, the staining property, particularly, the spot stain is improved and thus, the on-machine development property or gum development property, printing durability and the staining property can be fulfilled. The intermediate layer makes removal of the image-recording layer from the support in the unexposed area easy so that the on-machine development property or gum development property can be improved. Further, it is advantageous that in the case of infrared laser exposure, since the intermediate layer acts as a heat insulating layer, heat generated upon the exposure does not diffuse into the support and is efficiently utilized so that increase in sensitivity can be achieved. Moreover, since the intermediate layer remains at the time of printing and it is hydrophilic, the staining property is also achieved.

0074Furthermore, since the remaining layer due to dark polymerization reaction particularly occurred at the interface of the support with the lapse of time is restrained, the spot-like stain can be prevented.

<Polymer for intermediate layer having adsorbing group to substrate, polymerizable group and hydrophilic group>

0075The essential component in the polymer for intermediate layer is an adsorbing group to a hydrophilic surface of the support. Whether the adsorptivity to the hydrophilic surface of the support is present or not can be judged, for example, by the following method.

0076Specifically, a test compound is dissolved in a solvent in which the test compound is easily soluble to prepare a coating solution, and the coating solution is coated and dried on a support so as to have the coating amount after drying of 30 mg/m². After thoroughly washing the support coated with the test compound using the solvent in which the test compound is easily soluble, the residual amount of the test compound that has not been removed by the washing is measured to calculate the adsorption amount to the support. For measuring the residual amount, the amount of the residual test compound may be directly determined, or it may be calculated from the amount of the test compound dissolved in the washing solution. The determination for the compound can be performed, for example, by fluorescent X-ray measurement, reflection spectral absorbance measurement or liquid chromatography measurement. The compound having the adsorptivity to support means a compound that remains by 1 mglm² or more even after conducting the washing treatment described above.

0077The adsorbing group to the hydrophilic surface of the support is a functional group capable of forming a chemical bond (for example, an ionic bond, a hydrogen bond, a coordinate bond or a bond with intermolecular force) with a substance (for example, metal or a metal oxide) or a functional group (for example, a hydroxy group) present on the surface of the support. The adsorbing group is preferably an acid group or a cationic group.

0078The acid group preferably has an acid dissociation constant (pKa) of 7 or less. Examples of the acid group include a phenolic hydroxy group, a carboxyl group, -SO₃H, -OSO₃H, -PO₃H2, -OPO₃H₂, -CONHSO₂-, -SO₂NHSO₂- and -COCH₂COCH₃. Among them, -OPO₃H₂ and -PO₃H₂ are particularly preferred. The acid group may be the form of a metal salt.

0079The cationic group is preferably an onium group. Examples of the onium group include an ammonium group, a phosphonium group, an arsonium group, a stibonium group, an oxonium group, a sulfonium group, a selenonium group, a stannonium group and iodonium group. Among them, the ammonium group, phosphonium group and sulfonium group are preferred, the ammonium group and phosphonium group are more preferred, and the ammonium group is most preferred.

0080Particularly preferable examples of the monomer having the adsorbing group include a compound represented by the following formula (U1) or (U2): <chemistry id="chem0029" num="0029"><img file="EP2006091A2_D0031.tif" /></chemistry>

0081In formulae (U1) and (U2), R¹, R² and R³ each independently represents a hydrogen atom, halogen atom or an alkyl group having from 1 to 6 carbon atoms. R¹, R² and R³ each independently represents preferably a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms, most preferably a hydrogen atom or a methyl group. It is particularly preferred that R² and R³ each represents a hydrogen atom. Z represents a functional group adsorbing to the hydrophilic surface of support.

0082In the formulae above, X represents an oxygen atom (-O-) or amino group (-NH-). Preferably, X represents an oxygen atom. L represents a divalent connecting group. It is preferred that L represents a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkinylene group or a substituted alkinylene group), a divalent aromatic group (for example, an arylene group or a substituted arylene group), a divalent heterocyclic group or a combination of each of the groups described above with an oxygen atom (-O-), a sulfur atom (-S-), an imino group (-NH-), a substituted imino group (-NR-, wherein R represents an aliphatic group, an aromatic group or a heterocyclic group) or a carbonyl group (-CO-).

0083The aliphatic group may form a cyclic structure or a branched structure. The number of carbon atoms of the aliphatic group is preferably from 1 to 20, more preferably from 1 to 15, most preferably from 1 to 10. It is preferred that the aliphatic group is a saturated aliphatic group rather than an unsaturated aliphatic group. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an aromatic group and a heterocyclic group.

0084The number of carbon atoms of the aromatic group is preferably from 6 to 20, more preferably from 6 to 15, most preferably from 6 to 10. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an aliphatic group, an aromatic group and a heterocyclic group.

0085It is preferred that the heterocyclic group has a 5-membered or 6-membered ring as the heterocyclic ring. Other heterocyclic ring, an aliphatic ring or an aromatic ring may be condensed to the heterocyclic ring. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an oxo group (=O), a thio group (=S), an imino group (=NH), a substituted imino group (=N-R, where R represents an aliphatic group, an aromatic group or a heterocyclic group), an aliphatic group, an aromatic group and a heterocyclic group.

0086It is preferred in the formulae above that L represents a divalent connecting group containing a plurality of polyoxyalkylene structures. It is more preferred that the polyoxyalkylene structure is a polyoxyethylene structure. Specifically, it is preferred that L contains -(OCH₂CH₂)_n- (n is an integer of 2 or more).

0087In formula (U2), Y represents a carbon atom or a nitrogen atom. In the case where Y is a nitrogen atom and L is connected to Y to form a pyridinium group, Z is not mandatory and may be a hydrogen atom, because the pyridinium group itself exhibits the adsorptivity.

0088Representative examples of the compound represented by formula (U1) or (U2) are set forth below. <img file="EP2006091A2_D0032.tif" />

0089The hydrophilic group included in the polymer for intermediate layer for use in the invention preferably includes, for example, a hydroxy group, a carboxyl group, a carboxylate group, a hydroxyethyl group, a polyoxyethyl group, a hydroxypropyl group, a polyoxypropyl group, an amino group, an aminoethyl group, an aminopropyl group, an ammonium group, an amido group, a carboxymethyl group, a sulfo group or a phosphoric acid group. Among them, a monomer having a sulfo group exhibiting a highly hydrophilic property is preferable. Specific examples of the monomer having a sulfo group include sodium salts and amine salts of methallyloxybenzenesulfonic acid, allyloxybenzenesulfonic acid, allylsulfonic acid, vinylsulfonic acid, p-styrenesulfonic acid, methallylsulfonic acid, acrylamide-tert-butylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid and (3-acryloyloxypropyl)butylsulfonic acid. Among them, sodium salt of 2-acrylamido-2-methylpropanesulfonic acid is preferable in view of the hydrophilic property and handling property in the synthesis thereof.

0090It is preferred that the polymer for intermediate layer according to the invention has a crosslinkable group. The crosslinkable group acts to improve the adhesion to the image area. In order to impart the crosslinking property to the polymer for intermediate layer, introduction of a crosslinkable functional group, for example, an ethylenically unsaturated bond into the side chain of the polymer or introduction by formation of a salt structure between a polar substituent of the polymer and a compound containing a substituent having a counter charge to the polar substituent of the polymer and an ethylenically unsaturated bond is used.

0091Examples of the polymer having an ethylenically unsaturated bond in the side chain thereof include a polymer of an ester or amide of acrylic acid or methacrylic acid, which is a polymer wherein the ester or amide residue (R in -COOR or -CONHR) has an ethylenically unsaturated bond.

0092Examples of the residue (R described above) having an ethylenically unsaturated bond include -(CH₂)_nCR¹=CR²R³, -(CH₂O)_nCH₂CR¹=CR²R³, -(CH₂CH₂O)_nCH₂CR¹=CR²R³, -(CH₂)_nNH-CO-O-CH₂CR¹=CR²R³, -(CH₂)_n-O-CO-CR¹=CR²R³ and -(CH₂CH₂O)₂-X (wherein R¹ to R³ each represents a hydrogen atom, a halogen atom or an alkyl group having from 1 to 20 carbon atoms, an aryl group, alkoxy group or aryloxy group, or R¹ and R² or R¹ and R³ may be combined with each other to form a ring. n represents an integer of I to 10. X represents a dicyclopentadienyl residue).

0093Specific examples of the ester residue include -CH₂CH=CH₂ (described in <patcit id="pcit0016" dnum="JP7021633B"><text>JP-B-7-21633</text></patcit> (the term "JP-B" as used herein means an "examined Japanese patent publication")), -CH₂CH₂O-CH₂CH=CH₂, -CH₂C(CH₃)=CH₂, -CH₂CH=CH-C₆H₅, -CH₂CH₂OCOCH=CH-C₆H₅, -CH₂CH₂-NHCOO-CH₂CH=CH₂ and -CH₂CH₂O-X (wherein X represents a dicyclopentadienyl residue).

0094Specific examples of the amide residue include -CH₂CH=CH₂, -CH₂CH₂-Y (wherein Y represents a cyclohexene residue) and -CH₂CH₂-OCO-CH=CH₂.

0095As a monomer having a crosslinkable group for the polymer for intermediate layer, an ester or amide of acrylic acid or methacrylic acid having the above-described crosslinkable group is preferred.

0096The content of the crosslinkable group in the polymer for intermediate layer (content of the radical polymerizable unsaturated double bond determined by iodine titration) is preferably from 0.1 to 10.0 mmol, more preferably from 1.0 to 7.0 mmol, most preferably from 2.0 to 5.5 mmol, based on 1 g of the polymer. In the range described above, good compatibility between the sensitivity and staining property and good preservation stability can be achieved.

0097The weight average molecular weight of the polymer for intermediate layer is preferably 5,000 or more, more preferably from 10,000 to 300,000. The number average molecular weight of the polymer is preferably 1,000 or more, more preferably from 2,000 to 250,000. The polydispersity (weight average molecular weight/number average molecular weight) thereof is preferably from 1.1 to 10.

0098The polymer for intermediate layer may be any of a random polymer, a block polymer, a graft polymer and the like, and is preferably a random polymer.

0099The polymers for intermediate layer may be used individually or in a mixture of two or more thereof. Also, the specific compound may be used individually or in a mixture of two or more thereof. A coating solution for intermediate layer is obtained by dissolving the polymer for intermediate layer in an organic solvent (for example, methanol, ethanol, acetone or methyl ethyl ketone) and/or water. The coating solution for intermediate layer may contain an infrared absorbing agent.

0100In order to coat the coating solution for intermediate layer on the support, various known methods can be used. Examples of the method include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating and roll coating.

0101Two or more kinds of the polymers for intermediate layer may be incorporated into the intermediate layer. The amount of the polymer for intermediate layer added to the intermediate layer is preferably from 10 to 90% by weight, more preferably from 20 to 80% by weight, most preferably from 25 to 75% by weight, based on the solid content of the intermediate layer.

(Image-recording layer)

0102The image-forming element and component of the image-recording layer according to the invention will be described in detail below.

0103The image-forming element preferably used is any one of (1) an image-forming element utilizing polymerization and (2) an image-forming element utilizing thermal fusion or thermal reaction of a hydrophobilizing precursor. As to the image-forming element (1) utilizing polymerization, an element which contains (A) an infrared absorbing agent, (B) a polymerization initiator and (C) a polymerizable compound and is capable of undergoing image-recording with an infrared laser is preferable. With respect to the image-forming element (2) utilizing thermal fusion or thermal reaction of a hydrophobilizing precursor, an element which contains (A) an infrared absorbing agent and (D) a hydrophobilizing precursor and is capable of undergoing image-recording with an infrared laser is preferable. Further, the image-forming element (1) may additionally contain the hydrophobilizing precursor (D).

0104The image-recording layer according to the invention may contain other components, if desired, in addition to the element described above.

0105The constituting components of the image-recording layer and formation of the image-recording layer will be described below.

<(A) Infrared absorbing agent>

0106In the case wherein the lithographic printing plate precursor according to the invention is subjected to the image formation using as a light source, a laser emitting an infrared ray of 760 to 1,200 nm, it is ordinarily essential to use an infrared absorbing agent. The infrared absorbing agent has a function of converting the infrared ray absorbed to heat and a function of being excited by the infrared ray to perform electron transfer/energy transfer to a polymerization initiator (radical generator) described hereinafter. The infrared absorbing agent for use in the invention includes a dye and pigment each having an absorption maximum in a wavelength range of 760 to 1,200 nm.

0107As the dye, commercially available dyes and known dyes described in literatures, for example, <nplcit id="ncit0001" npl-type="b"><text>Senryo Binran (Dye Handbook) compiled by The Society of Synthetic Organic Chemistry, Japan (1970</text></nplcit>) can be used. Specifically, the dyes includes azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts and metal thiolate complexes.

0108Examples of preferable dye include cyanine dyes described, for example, in <patcit id="pcit0017" dnum="JP58125246A"><text>JP-A-58-125246</text></patcit>, <patcit id="pcit0018" dnum="JP59084356A"><text>JP-A-59-84356</text></patcit> and <patcit id="pcit0019" dnum="JP60078787A"><text>JP-A-60-78787</text></patcit>, methine dyes described, for example, in <patcit id="pcit0020" dnum="JP58173696A"><text>JP-A-58-173696</text></patcit>, <patcit id="pcit0021" dnum="JP58181690A"><text>JP-A-58-181690</text></patcit> and <patcit id="pcit0022" dnum="JP58194595A"><text>JP-A-58-194595</text></patcit>, naphthoquinone dyes described, for example, in <patcit id="pcit0023" dnum="JP58112793A"><text>JP-A-58-112793</text></patcit>, <patcit id="pcit0024" dnum="JP58224793A"><text>JP-A-58-224793</text></patcit>, <patcit id="pcit0025" dnum="JP59048187A"><text>JP-A-59-48187</text></patcit>, <patcit id="pcit0026" dnum="JP59073996A"><text>JP-A-59-73996</text></patcit>, <patcit id="pcit0027" dnum="JP60052940A"><text>JP-A-60-52940</text></patcit> and <patcit id="pcit0028" dnum="JP60063744A"><text>JP-A-60-63744</text></patcit>, squarylium dyes described, for example, in <patcit id="pcit0029" dnum="JP58112792A"><text>JP-A-58-112792</text></patcit>, and cyanine dyes described, for example, in British Patent <patcit id="pcit0030" dnum="GB434875A"><text>434,875</text></patcit>.

0109Also, near infrared absorbing sensitizers described in <patcit id="pcit0031" dnum="US5156938A"><text>U.S. Patent 5,156,938</text></patcit> are preferably used. Further, substituted arylbenzo(thio)pyrylium salts described in <patcit id="pcit0032" dnum="US3881924A"><text>U.S. Patent 3,881,924</text></patcit>, trimethinethiapyrylium salts described in <patcit id="pcit0033" dnum="JP57142645A"><text>JP-A-57-142645</text></patcit> (corresponding to <patcit id="pcit0034" dnum="US4327169A"><text>U.S. Patent 4,327,169</text></patcit>), pyrylium compounds described in <patcit id="pcit0035" dnum="JP58181051A"><text>JP-A-58-181051</text></patcit>, <patcit id="pcit0036" dnum="JP58220143A"><text>JP-A-58-220143</text></patcit>, <patcit id="pcit0037" dnum="JP59041363A"><text>JP-A-59-41363</text></patcit>, <patcit id="pcit0038" dnum="JP59084248A"><text>JP-A-59-84248</text></patcit>, <patcit id="pcit0039" dnum="JP59084249A"><text>JP-A-59-84249</text></patcit>, <patcit id="pcit0040" dnum="JP59146063A"><text>JP-A-59-146063</text></patcit> and <patcit id="pcit0041" dnum="JP59146061A"><text>JP-A-59-146061</text></patcit>, cyanine dyes described in <patcit id="pcit0042" dnum="JP59216146A"><text>JP-A-59-216146</text></patcit>, pentamethinethiopyrylium salts described in <patcit id="pcit0043" dnum="US4283475A"><text>U.S. Patent 4,283,475</text></patcit>, and pyrylium compounds described in <patcit id="pcit0044" dnum="JP5013514B"><text>JP-B-5-13514</text></patcit> and <patcit id="pcit0045" dnum="JP5019702B"><text>JP-B-5-19702</text></patcit> are also preferably used. Other preferable examples of the dye include near infrared absorbing dyes represented by formulae (I) and (II) in <patcit id="pcit0046" dnum="US4756993A"><text>U.S. Patent 4,756,993</text></patcit>.

0110Other preferable examples of the infrared absorbing dye according to the invention include specific indolenine cyanine dyes described in <patcit id="pcit0047" dnum="JP2002278057A"><text>JP-A-2002-278057</text></patcit> as illustrated below. <chemistry id="chem0030" num="0030"><img file="EP2006091A2_D0033.tif" /></chemistry><chemistry id="chem0031" num="0031"><img file="EP2006091A2_D0034.tif" /></chemistry><chemistry id="chem0032" num="0032"><img file="EP2006091A2_D0035.tif" /></chemistry>

0111Of the dyes, cyanine dyes, squarylium dyes, pyrylium dyes, nickel thiolate complexes and indolenine cyanine dyes are preferred. Further, cyanine dyes and indolenine cyanine dyes are more preferred. As a particularly preferable example of the dye, a cyanine dye represented by formula (i) shown below is exemplified. <chemistry id="chem0033" num="0033"><img file="EP2006091A2_D0036.tif" /></chemistry>

0112In formula (i), X¹ represents a hydrogen atom, a halogen atom, -NPh₂, X²-L¹ or a group represented by the structural formula shown below. X² represents an oxygen atom, a nitrogen atom or a sulfur atom, L¹ represents a hydrocarbon group having from 1 to 12 carbon atoms, an aromatic ring containing a hetero atom or a hydrocarbon group having from 1 to 12 carbon atoms and containing a hetero atom. The hetero atom used herein indicates a nitrogen atom, a sulfur atom, an oxygen atom, a halogen atom or a selenium atom. R^a represents a substituent selected from a hydrogen atom, an alkyl group, an aryl group, a substituted or unsubstituted amino group and a halogen atom, and Xa^- has the same meaning as Za" defined hereinafter. <img file="EP2006091A2_D0037.tif" />

0113R¹ and R² each independently represents a hydrocarbon group having from 1 to 12 carbon atoms. In view of the preservation stability of a coating solution for image-recording layer, it is preferred that R¹ and R² each represents a hydrocarbon group having two or more carbon atoms, and it is particularly preferred that R¹ and R² are combined with each other to form a 5-membered or 6-membered ring.

0114Ar¹ and Ar², which may be the same or different, each represents an aromatic hydrocarbon group which may have a substituent. Preferable examples of the aromatic hydrocarbon group include a benzene ring and a naphthalene ring. Also, preferable examples of the substituent include a hydrocarbon group having 12 or less carbon atoms, a halogen atom and an alkoxy group having 12 or less carbon atoms, and a hydrocarbon group having 12 or less carbon atoms and an alkoxy group having 12 or less carbon atoms are most preferable. Y¹ and Y², which may be the same or different, each represents a sulfur atom or a dialkylmethylene group having 12 or less carbon atoms. R³ and R⁴, which may be the same or different, each represents a hydrocarbon group having 20 or less carbon atoms, which may have a substituent. Preferable examples of the substituent include an alkoxy group having 12 or less carbon atoms, a carboxyl group and a sulfo group, and an alkoxy group having 12 or less carbon atoms is most preferable. R⁵, R⁶, R⁷ and R⁸, which may be the same or different, each represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. In view of the availability of raw materials, a hydrogen atom is preferred. Za" represents a counter anion. However, Za" is not necessary when the cyanine dye represented by formula (i) has an anionic substituent in the structure thereof and neutralization of charge is not needed. Preferable examples of the counter ion for Za^- include a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion and a sulfonate ion, and particularly preferable examples thereof include a perchlorate ion, a hexafluorophosphate ion and an arylsulfonate ion in view of the preservation stability of a coating solution for image-recording layer.

0115Specific examples of the cyanine dye represented by formula (i), which can be preferably used in the invention, include those described in paragraph Nos. [0017] to [0019] of <patcit id="pcit0048" dnum="JP2001133969A"><text>JP-A-2001-133969</text></patcit>.

0116Further, other particularly preferable examples include specific indolenine cyanine dyes described in <patcit id="pcit0049" dnum="JP2002278057A"><text>JP-A-2002-278057</text></patcit> described above.

0117Examples of the pigment for use in the invention include commercially available pigments and pigments described in <nplcit id="ncit0002" npl-type="b"><text>Colour Index (C.I.), Saishin Ganryo Binran (Handbook of the Newest Pigments) compiled by Pigment Technology Society of Japan (1977</text></nplcit>), <nplcit id="ncit0003" npl-type="b"><text>Saishin Ganryo Oyou Gijutsu (Newest Application on Technologies for Pigments), CMC Publishing Co., Ltd. (1986</text></nplcit>) and <nplcit id="ncit0004" npl-type="b"><text>Insatsu Ink Gijutsu (Printing Ink Technology), CMC Publishing Co., Ltd. (1984</text></nplcit>).

0118Examples of the pigment include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments and polymer-bonded dyes. Specific examples of usable pigment include insoluble azo pigments, azo lake pigments, condensed azo pigments, chelated azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perynone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, dying lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments and carbon black. Of the pigments, carbon black is preferred.

0119The pigment may be used without undergoing surface treatment or may be used after the surface treatment. For the surface treatment, a method of coating a resin or wax on the surface, a method of attaching a surfactant and a method of bonding a reactive substance (for example, a silane coupling agent, an epoxy compound or polyisocyanate) to the pigment surface. The surface treatment methods are described in <nplcit id="ncit0005" npl-type="b"><text>Kinzoku Sekken no Seishitsu to Oyo (Properties and Applications of Metal Soap), Saiwai Shobo</text></nplcit>,<nplcit id="ncit0006" npl-type="b"><text> Insatsu Ink Gijutsu (Printing Ink Technology), CMC Publishing Co., Ltd. (1984</text></nplcit>), and <nplcit id="ncit0007" npl-type="b"><text>Saishin Ganryo Oyo Gijutsu (Newest Application on Technologies for Pigments), CMC Publishing Co., Ltd. (1986</text></nplcit>).

0120The pigment has a particle size of preferably from 0.01 to 10 µm, more preferably from 0.05 to 1 µm, particularly preferably from 0.1 to 1 µm. In the range described above, good stability of the pigment dispersion in the coating solution for image-recording layer and good uniformity of the image-recording layer can be obtained.

0121For dispersing the pigment, a known dispersion technique for use in the production of ink or toner may be used. Examples of the dispersing machine include an ultrasonic dispersing machine, a sand mill, an attritor, a pearl mill, a super-mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three roll mill and a pressure kneader. The dispersing machines are described in detail in <nplcit id="ncit0008" npl-type="b"><text>Saishin Ganryo Oyo Gijutsu (Newest Application on Technologies for Pigments), CMC Publishing Co., Ltd. (1986</text></nplcit>).

0122The infrared absorbing agent may be added together with other components to the same image-recording layer or may be added to a different image-recording layer separately provided. With respect to the amount of the infrared absorbing agent added, in the case of preparing a negative-working lithographic printing plate precursor, the amount is so controlled that absorbance of the image-recording layer at the maximum absorption wavelength in the wavelength region of 760 to 1,200 nm measured by reflection measurement is in a range of 0.3 to 1.2, preferably in a range of 0.4 to 1.1. In the range described above, the polymerization reaction proceeds uniformly in the thickness direction of the image-recording layer and good film strength of the image area and good adhesion property of the image area to the support are achieved.

0123The absorbance of the image-recording layer can be controlled depending on the amount of the infrared absorbing agent added to the image-recording layer and the thickness of the image-recording layer. The measurement of the absorbance can be carried out in a conventional manner. The method for measurement includes, for example, a method of forming an image-recording layer having a thickness determined appropriately in the range necessary for the lithographic printing plate precursor on a reflective support, for example, an aluminum plate, and measuring reflection density of the image-recording layer by an optical densitometer or a spectrophotometer according to a reflection method using an integrating sphere.

<(B) Polymerization initiator>

0124The polymerization initiator for use in the invention is a compound that generates a radical with light energy, heat energy or both energies to initiate or accelerate polymerization of a compound having a polymerizable unsaturated group. The polymerization initiator for use in the invention includes, for example, known thermal polymerization initiators, compounds containing a bond having small bond dissociation energy and photopolymerization initiators. The compound generating a radical preferably used in the invention is a compound that generates a radical with heat energy to initiate or accelerate polymerization of a compound having a polymerizable unsaturated group. The thermal radical generator according to the invention is appropriately selected from known polymerization initiators and compounds containing a bond having small bond dissociation energy. The polymerization initiators can be used individually or in combination of two or more thereof.

0125The polymerization initiators include, for example, organic halides, carbonyl compounds, organic peroxides, azo compounds, azido compounds, metallocene compounds, hexaarylbiimidazole compounds, organic borate compounds, disulfone compounds, oxime ester compounds and onium salt compounds.

0126The organic halides described above specifically include, for example, compounds described in <nplcit id="ncit0009" npl-type="s"><text>Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969</text></nplcit>), <patcit id="pcit0050" dnum="US3905815A"><text>U.S. Patent 3,905,815</text></patcit>, <patcit id="pcit0051" dnum="JP46004605B"><text>JP-B-46-4605</text></patcit>, <patcit id="pcit0052" dnum="JP48035281A"><text>JP-A-48-35281</text></patcit>, <patcit id="pcit0053" dnum="JP55032070A"><text>JP-A-55-32070</text></patcit><patcit id="pcit0054" dnum="JP60239736A"><text>JP-A-60-239736</text></patcit>, <patcit id="pcit0055" dnum="JP61169835A"><text>JP-A-61-169835</text></patcit>, <patcit id="pcit0056" dnum="JP61169837A"><text>JP-A-61-169837</text></patcit>, <patcit id="pcit0057" dnum="JP62058241A"><text>JP-A-62-58241</text></patcit>, <patcit id="pcit0058" dnum="JP62212401A"><text>JP-A-62-212401</text></patcit>, <patcit id="pcit0059" dnum="JP63070243A"><text>JP-A-63-70243</text></patcit>, <patcit id="pcit0060" dnum="JP63298339A"><text>JP-A-63-298339</text></patcit> and <nplcit id="ncit0010" npl-type="s"><text>M. P. Hutt, Journal of Heterocyclic Chemistry, 1, No. 3 (1970</text></nplcit>). Particularly, oxazole compounds and s-triazine compounds each substituted with a trihalomethyl group are preferably exemplified.

0127More preferably, s-triazine derivatives and oxadiazole derivatives each of which has at least one of mono-, di- and tri-halogen substituted methyl groups connected are exemplified. Specific examples thereof include 2,4,6-tris(monochloromethyl)-s-triazine, 2,4,6-tris(dichloromethyl)-s-triazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-n-propyl-4,6-bis(trichloromethyl)-s-triaxine, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s-triaxine, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-bromophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-fluorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-trifluoromethylphenyl)-4,6-bis(trichloromethyl)-s-triaxine, 2-(2,6-dichlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2,6-difluorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2,6-dibromophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2(4-biphenylyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-chloro-4-biphenylyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-cyanophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-acetylphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-ethoxycarbonylphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-phenoxycarbonylphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methylsulfonylphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-dimethylsulfoniumphenyl)-4,6-bis(trichloromethyl)-s-triazine tetrafluoroborate, 2-(2,4-difluorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-dietoxyphosphorylphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[4-(4-hydroxyphenylcarbonylamino)phenyl]-4,6-bis(trichloromethyl)-s-triaxine, 2-[4-(p-methoxyphenyl)-1,3-butadienyl]-4,6-bis(trichloromethyl)-s-triazine, 2-styryl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-isopropyloxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-phenylthio-4,6-bis(trichloromethyl)-s-triazine, 2-benzylthio-4,6-bis(trichloromethyl)-s-triazine, 2,4,6-tris(dibromomethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, 2-methoxy-4,6-bis(tribromomethyl)-s-triazine, 2-(o-metboxystyryl)-5-trichloromethyl-1,3,4-oxadiazole, 2-(3,4-epoxystyryl)-5-trichloromethyl-1,3,4-oxadiazole, 2-[1-phenyl-2-(4-methoxyphenyl)vinyl]-5-trichloromethyl-1,3,4-oxadiazole, 2-(p-hydroxystyryl)-5 -trichloromethyl-1,3,4-oxadiazole, 2-(3,4-dihydroxystyryl)-5-trichloromethyl-1,3,4-oxadiazole and 2-(p-tert-butoxystyryl)-5-trichloromethyl-1,3,4-oxadiazole.

0128The carbonyl compounds described above include, for example, benzophenone derivatives, e.g., benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone or 2-carboxybenzophenone, acetophenone derivatives, e.g., 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenylketone, α-hydroxy-2-methylphenylpropane, 1-hydroxy-1-methylethyl-(p-isopropylphenyl)ketone, 1-hydroxy-1-(p-dodecylphenyl)ketone, 2-methyl-(4'-(methylthio)phenyl)-2-morpholino-1-propane or 1,1,1,-trichloromethyl-(p-butylphenyl)ketone, thioxantone derivatives, e.g., thioxantone, 2-ethylthioxantone, 2-isopropylthioxantone, 2-chlorothioxantone, 2,4-dimetylthioxantone, 2,4-dietylthioxantone or 2,4-diisopropylthioxantone, and benzoic acid ester derivatives, e.g., ethyl p-dimethylaminobenzoate or ethyl p-diethylaminobenzoate.

0129The azo compounds described above include, for example, azo compounds described in <patcit id="pcit0061" dnum="JP8108621A"><text>JP-A-8-108621</text></patcit>.

0130The organic peroxides described above include, for example, trimethylcyclohexanone peroxide, acetylacetone peroxide, 1,1 -bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1 -bis(tert-butylperoxy)cyclohexane, 2,2-bis(tert-butylperoxy)butane, tert-butylhydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-oxanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropylperoxy dicarbonate, di-2-ethylhexylperoxy dicarbonate, di-2-ethoxyethylperoxy dicarbonate, dimethoxyisopropylperoxy dicarbonate, di(3-methyl-3-methoxybutyl)peroxy dicarbonate, tert-butylperoxy acetate, tert-butylperoxy pivalate, tert-butylperoxy neodecanoate, tert-butylperoxy octanoate, tert-butylperoxy laurate, tersyl carbonate, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-hexylperoxycarbonyl)benxophenone, 3,3',4,4'-tetra(p-isopropylcumylperoxycarbonyl)benzophenone, carbonyl di(tert-butylperoxydihydrogen diphthalate) and carbonyl di(tert-hexylperoxydihydrogen diphthalate).

0131The metallocene compounds described above include, for example, various titanocene compounds described in <patcit id="pcit0062" dnum="JP59152396A"><text>JP-A-59-152396</text></patcit>, <patcit id="pcit0063" dnum="JP61151197A"><text>JP-A-61-151197</text></patcit>, <patcit id="pcit0064" dnum="JP63041484A"><text>JP-A-63-41484</text></patcit>, <patcit id="pcit0065" dnum="JP2000249A"><text>JP-A-2-249</text></patcit>, <patcit id="pcit0066" dnum="JP2004705A"><text>JP-A-2-4705</text></patcit> and <patcit id="pcit0067" dnum="JP5083588A"><text>JP-A-5-83588</text></patcit>, for example, dicyclopentadienyl-Ti-bisphenyl, dicyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, dicyclopentadienyl-Ti-bis-2,4-difluorophen-1-yl, dicyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl, dicyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl or dicyclopentadienyl-Ti-bis-2,6-difluoro-3-(pyrol-1-yl)phen-1-yl, and iron-arene complexes described in <patcit id="pcit0068" dnum="JP1304453A"><text>JP-A-1-304453</text></patcit> and <patcit id="pcit0069" dnum="JP1152109A"><text>JP-A-1-152109</text></patcit>.

0132The hexaarylbiimidazole compounds described above include, for example, various compounds described in <patcit id="pcit0070" dnum="JP6029285B"><text>JP-B-6-29285</text></patcit> and <patcit id="pcit0071" dnum="US3479185A"><text>U.S. Patents 3,479,185</text></patcit>, <patcit id="pcit0072" dnum="US4311783A"><text>4,311,783</text></patcit> and <patcit id="pcit0073" dnum="US4622286A"><text>4,622,286</text></patcit>; specifically, for example, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-bromophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o,p-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetrakis(m-methoxyphenyl)biimidazole, 2,2'-bis(o,o'-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-nitrophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenylbiimidazole or 2,2'-bis(o-trifluoromethylphenyl)-4,4'5,5'-tetraphenylbiimidazole.

0133The organic borate compounds described above include, for example, organic borates described in <patcit id="pcit0074" dnum="JP62143044A"><text>JP-A-62-143044</text></patcit>, <patcit id="pcit0075" dnum="JP62150242A"><text>JP-A-62-150242</text></patcit>, <patcit id="pcit0076" dnum="JP9188685A"><text>JP-A-9-188685</text></patcit>, <patcit id="pcit0077" dnum="JP9188686A"><text>JP-A-9-188686</text></patcit>, <patcit id="pcit0078" dnum="JP9188710A"><text>JP-A-9-188710</text></patcit>, <patcit id="pcit0079" dnum="JP2000131837A"><text>JP-A-2000-131837</text></patcit>, <patcit id="pcit0080" dnum="JP2002107916A"><text>JP-A-2002-107916</text></patcit>, Japanese Patent <patcit id="pcit0081" dnum="JP2764769B"><text>2,764,769</text></patcit>, <patcit id="pcit0082" dnum="JP2002116539A"><text>JP-A-2002-116539</text></patcit> and <nplcit id="ncit0011" npl-type="s"><text>Martin Kunz, Rad Tech '98, Proceeding, April 19-22 (1998</text></nplcit>), Chicago, organic boron sulfonium complexes or organic boron oxosulfonium complexes described in <patcit id="pcit0083" dnum="JP6157623A"><text>JP-A-6-157623</text></patcit>, <patcit id="pcit0084" dnum="JP6175564A"><text>JP-A-6-175564</text></patcit> and <patcit id="pcit0085" dnum="JP6175561A"><text>JP-A-6-175561</text></patcit>, organic boron iodonium complexes described in <patcit id="pcit0086" dnum="JP6175554A"><text>JP-A-6-175554</text></patcit> and <patcit id="pcit0087" dnum="JP6175553A"><text>JP-A-6-175553</text></patcit>, organic boron phosphonium complexes described in <patcit id="pcit0088" dnum="JP9188710A"><text>JP-A-9-188710</text></patcit>, and organic boron transition metal coordination complexes described in <patcit id="pcit0089" dnum="JP6348011A"><text>JP-A-6-348011</text></patcit>, <patcit id="pcit0090" dnum="JP7128785A"><text>JP-A-7-128785</text></patcit>, <patcit id="pcit0091" dnum="JP7140589A"><text>JP-A-7-140589</text></patcit>, <patcit id="pcit0092" dnum="JP7306527A"><text>JP-A-7-306527</text></patcit> and <patcit id="pcit0093" dnum="JP7292014A"><text>JP-A-7-292014</text></patcit>.

0134The disulfone compounds described above include, for example, compounds described in <patcit id="pcit0094" dnum="JP61166544A"><text>JP-A-61-166544</text></patcit> and <patcit id="pcit0095" dnum="JP2002328465A"><text>JP-A-2002-328465</text></patcit>.

0135The oxime ester compounds described above include, for example, compounds described in <nplcit id="ncit0012" npl-type="s"><text>J. C. S. Perkin II, 1653-1660 (1979</text></nplcit>), <nplcit id="ncit0013" npl-type="s"><text>J. C. S. Perkin II, 156-162 (1979</text></nplcit>), <nplcit id="ncit0014" npl-type="s"><text>Journal of Photopolymer Science and Technology, 202-232 (1995</text></nplcit>) and <patcit id="pcit0096" dnum="JP2000066385A"><text>JP-A-2000-66385</text></patcit>, and compounds described in <patcit id="pcit0097" dnum="JP2000080068A"><text>JP-A-2000-80068</text></patcit>. Specific examples thereof include compounds represented by the following structural formulae: <chemistry id="chem0034" num="0034"><img file="EP2006091A2_D0038.tif" /></chemistry>

0136The onium salt compounds described above include, for example, diazonium salts described in <nplcit id="ncit0015" npl-type="s"><text>S. I. Schlesinger, Photogr. Sci. Eng., 18, 387 (1974</text></nplcit>) and <nplcit id="ncit0016" npl-type="s"><text>T. S. Bal et al., Polymer, 21, 423 (1980</text></nplcit>), ammonium salts described in <patcit id="pcit0098" dnum="US4069055A"><text>U.S. Patent 4,069,055</text></patcit> and <patcit id="pcit0099" dnum="JP4365049A"><text>JP-A-4-365049</text></patcit>, phosphonium salts described in <patcit id="pcit0100" dnum="US4069055A"><text>U.S. Patents 4,069,055</text></patcit> and <patcit id="pcit0101" dnum="US4069056A"><text>4,069,056</text></patcit>, iodonium salts described in European Patent <patcit id="pcit0102" dnum="EP104143A"><text>104,143</text></patcit>, <patcit id="pcit0103" dnum="US339049A"><text>U.S. Patents 339,049</text></patcit> and <patcit id="pcit0104" dnum="US410201A"><text>410,201</text></patcit>, <patcit id="pcit0105" dnum="JP2150848A"><text>JP-A-2-150848</text></patcit> and <patcit id="pcit0106" dnum="JP2296514A"><text>JP-A-2-296514</text></patcit>, sulfonium salts described in European Patents <patcit id="pcit0107" dnum="EP370693A"><text>370,693</text></patcit>, <patcit id="pcit0108" dnum="EP390214A"><text>390,214</text></patcit>, <patcit id="pcit0109" dnum="EP233567A"><text>233,567</text></patcit>, <patcit id="pcit0110" dnum="EP297443A"><text>297,443</text></patcit> and <patcit id="pcit0111" dnum="EP297442A"><text>297,442</text></patcit>, <patcit id="pcit0112" dnum="US4933377A"><text>U.S. Patents 4,933,377</text></patcit>, <patcit id="pcit0113" dnum="US161811A"><text>161,811</text></patcit>,<patcit id="pcit0114" dnum="US410201A"><text> 410,201</text></patcit>,<patcit id="pcit0115" dnum="US339049A"><text> 339,049</text></patcit>, <patcit id="pcit0116" dnum="US4760013A"><text>4,760,013</text></patcit>, <patcit id="pcit0117" dnum="US4734444A"><text>4,734,444</text></patcit> and <patcit id="pcit0118" dnum="US2833827A"><text>2,833,827</text></patcit> and German Patents <patcit id="pcit0119" dnum="DE2904626"><text>2,904,626</text></patcit>,<patcit id="pcit0120" dnum="DE3604580"><text> 3,604,580 </text></patcit>and <patcit id="pcit0121" dnum="DE3604581"><text>3,604,581</text></patcit>, selenonium salts described in <nplcit id="ncit0017" npl-type="s"><text>J.V. Crivello et al., Macromolecules, 10 (6), 1307 (1977</text></nplcit>) and <nplcit id="ncit0018" npl-type="s"><text>J.V. Crivello et al., J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979</text></nplcit>), and arsonium salts described in <nplcit id="ncit0019" npl-type="s"><text>C.S. Wen et al., Teh, Proc. Conf. Rad. Curing ASIA, p. 478, Tokyo, Oct. (1988</text></nplcit>).

0137Particularly, in view of reactivity and stability, the oxime ester compounds and diazonium salts, iodonium salts and sulfonium salts described above are preferably exemplified. In the invention, the onium salt functions not as an acid generator but as an ionic radical polymerization initiator.

0138The onium salts preferably used in the invention include onium salts represented by the following formulae (RI-I) to (RI-III): <chemistry id="chem0035" num="0035"><img file="EP2006091A2_D0039.tif" /></chemistry><chemistry id="chem0036" num="0036"><img file="EP2006091A2_D0040.tif" /></chemistry><chemistry id="chem0037" num="0037"><img file="EP2006091A2_D0041.tif" /></chemistry>

0139In formula (RI-I), Ar¹¹ represents an aryl group having 20 or less carbon atoms, which may have 1 to 6 substituents. Preferable example of the substituent includes an alkyl group having from 1 to 12 carbon atoms, an alkenyl group having from 1 to 12 carbon atoms, an alkynyl group having from 1 to 12 carbon atoms, an aryl group having from 1 to 12 carbon atoms, an alkoxy group having from 1 to 12 carbon atoms, an aryloxy group having from 1 to 12 carbon atoms, a halogen atom, an alkylamino group having from 1 to 12 carbon atoms, a dialkylimino group having from 1 to 12 carbon atoms, an alkylamido group or arylamido group having from 1 to 12 carbon atoms, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, an thioalkyl group having from 1 to 12 carbon atoms and an thioaryl group having from 1 to 12 carbon atoms. Z^11- represents a monovalent anion and specifically includes a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thosulfonate ion and a sulfate ion. From the standpoint of stability and visibility of print-out image, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion or a sulfinate ion is preferable.

0140In the formula (RI-II), Ar²¹ and Ar²² each independently represents an aryl group having 20 or less carbon atoms, which may have 1 to 6 substituents. Preferable example of the substituent includes an alkyl group having from 1 to 12 carbon atoms, an alkenyl group having from 1 to 12 carbon atoms, an alkynyl group having from 1 to 12 carbon atoms, an aryl group having from 1 to 12 carbon atoms, an alkoxy group having from 1 to 12 carbon atoms, an aryloxy group having from 1 to 12 carbon atoms, a halogen atom, an alkylamino group having from 1 to 12 carbon atoms, a dialkylimino group having from 1 to 12 carbon atoms, an alkylamido group or arylamido group having from 1 to 12 carbon atoms, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, an thioalkyl group having from 1 to 12 carbon atoms and an thioaryl group having from 1 to 12 carbon atoms. Z^21- represents a monovalent anion and specifically includes a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thosulfonate ion, a sulfate ion and a carboxylate ion. From the standpoint of stability and visibility of print-out image, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion or a carboxylate ion is preferable.

0141In the formula (RI-III), R³¹, R³² and R³³ each independently represents an aryl group having 20 or less carbon atoms, which may have 1 to 6 substituents, an alkyl group, an alkenyl group or an alkynyl group and is preferably an aryl group from the standpoint of reactivity and stability. Preferable example of the substituent includes an alkyl group having from 1 to 12 carbon atoms, an alkenyl group having from 1 to 12 carbon atoms, an alkynyl group having from 1 to 12 carbon atoms, an aryl group having from 1 to 12 carbon atoms, an alkoxy group having from 1 to 12 carbon atoms, an aryloxy group having from 1 to 12 carbon atoms, a halogen atom, an alkylamino group having from 1 to 12 carbon atoms, a dialkylimino group having from 1 to 12 carbon atoms, an alkylamido group or arylamido group having from 1 to 12 carbon atoms, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, an thioalkyl group having from 1 to 12 carbon atoms and an thioaryl group having from 1 to 12 carbon atoms. Z^31- represents a monovalent anion and specifically includes a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thosulfonate ion, a sulfate ion and a carboxylate ion. From the standpoint of stability and visibility of print-out image, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion or a carboxylate ion is preferable. Carboxylate ions described in <patcit id="pcit0122" dnum="JP2001343742A"><text>JP-A-2001-343742</text></patcit> are more preferable, and carboxylate ions described in <patcit id="pcit0123" dnum="JP2002148790A"><text>JP-A-2002-148790</text></patcit> are particularly preferable.

0142Specific examples of the onium salt compound preferably used as the polymerization initiator in the invention are set forth below, but the invention should not be construed as being limited thereto. <chemistry id="chem0038" num="0038"><img file="EP2006091A2_D0042.tif" /></chemistry>          PF₆^-     (N-2) <chemistry id="chem0039" num="0039"><img file="EP2006091A2_D0043.tif" /></chemistry>          ClO₄^-     (N-4)          PF₈^-     (N-5) <chemistry id="chem0040" num="0040"><img file="EP2006091A2_D0044.tif" /></chemistry>          BF₄^-     (N-7) <chemistry id="chem0041" num="0041"><img file="EP2006091A2_D0045.tif" /></chemistry>          ClO₄^-     (N-9) <chemistry id="chem0042" num="0042"><img file="EP2006091A2_D0046.tif" /></chemistry><chemistry id="chem0043" num="0043"><img file="EP2006091A2_D0047.tif" /></chemistry>          PF₆^-     (N-12) <chemistry id="chem0044" num="0044"><img file="EP2006091A2_D0048.tif" /></chemistry>          ClO₄^-     (N-14) <chemistry id="chem0045" num="0045"><img file="EP2006091A2_D0049.tif" /></chemistry>          PF₈^-     (N-16) <chemistry id="chem0046" num="0046"><img file="EP2006091A2_D0050.tif" /></chemistry><chemistry id="chem0047" num="0047"><img file="EP2006091A2_D0051.tif" /></chemistry>          PF₆^-     (I-2) <chemistry id="chem0048" num="0048"><img file="EP2006091A2_D0052.tif" /></chemistry>          PF₆^-     (I-3) <chemistry id="chem0049" num="0049"><img file="EP2006091A2_D0053.tif" /></chemistry>          ClO₄^-     (I-5) <chemistry id="chem0050" num="0050"><img file="EP2006091A2_D0054.tif" /></chemistry><chemistry id="chem0051" num="0051"><img file="EP2006091A2_D0055.tif" /></chemistry>          CF₃SO₃     (I-8) <chemistry id="chem0052" num="0052"><img file="EP2006091A2_D0056.tif" /></chemistry><chemistry id="chem0053" num="0053"><img file="EP2006091A2_D0057.tif" /></chemistry><chemistry id="chem0054" num="0054"><img file="EP2006091A2_D0058.tif" /></chemistry><chemistry id="chem0055" num="0055"><img file="EP2006091A2_D0059.tif" /></chemistry><chemistry id="chem0056" num="0056"><img file="EP2006091A2_D0060.tif" /></chemistry>          BF₄^-     (I-13) <chemistry id="chem0057" num="0057"><img file="EP2006091A2_D0061.tif" /></chemistry><chemistry id="chem0058" num="0058"><img file="EP2006091A2_D0062.tif" /></chemistry><chemistry id="chem0059" num="0059"><img file="EP2006091A2_D0063.tif" /></chemistry>          ClO₄^-     (I-17)          PF₆^-     (I-18)          C₄F₉O₃^-     (I-19) <chemistry id="chem0060" num="0060"><img file="EP2006091A2_D0064.tif" /></chemistry>          CF₃COO^-     (I-21)          CF₃SO₃^-     (I-22) <chemistry id="chem0061" num="0061"><img file="EP2006091A2_D0065.tif" /></chemistry><chemistry id="chem0062" num="0062"><img file="EP2006091A2_D0066.tif" /></chemistry><chemistry id="chem0063" num="0063"><img file="EP2006091A2_D0067.tif" /></chemistry><chemistry id="chem0064" num="0064"><img file="EP2006091A2_D0068.tif" /></chemistry><chemistry id="chem0065" num="0065"><img file="EP2006091A2_D0069.tif" /></chemistry><chemistry id="chem0066" num="0066"><img file="EP2006091A2_D0070.tif" /></chemistry>          PF₆^-     (I-28)          ClO₄^-     (I-29) <chemistry id="chem0067" num="0067"><img file="EP2006091A2_D0071.tif" /></chemistry>          PF₆^-     (I-31)          C₄F₉SO₃^-     (I-32) <chemistry id="chem0068" num="0068"><img file="EP2006091A2_D0072.tif" /></chemistry><chemistry id="chem0069" num="0069"><img file="EP2006091A2_D0073.tif" /></chemistry>          BF₄^-     (I-34) <chemistry id="chem0070" num="0070"><img file="EP2006091A2_D0074.tif" /></chemistry>          PF_e^-     (I-36) <chemistry id="chem0071" num="0071"><img file="EP2006091A2_D0075.tif" /></chemistry>          PF₆^-     (I-37)          C₄F₉SO₃^-     (I-38) <chemistry id="chem0072" num="0072"><img file="EP2006091A2_D0076.tif" /></chemistry><chemistry id="chem0073" num="0073"><img file="EP2006091A2_D0077.tif" /></chemistry><chemistry id="chem0074" num="0074"><img file="EP2006091A2_D0078.tif" /></chemistry>          PF₆^-     (S-2)          ClO₄^-     (S-3) <chemistry id="chem0075" num="0075"><img file="EP2006091A2_D0079.tif" /></chemistry><chemistry id="chem0076" num="0076"><img file="EP2006091A2_D0080.tif" /></chemistry>          CF₃SO₃^-     (S-6) <chemistry id="chem0077" num="0077"><img file="EP2006091A2_D0081.tif" /></chemistry><chemistry id="chem0078" num="0078"><img file="EP2006091A2_D0082.tif" /></chemistry><chemistry id="chem0079" num="0079"><img file="EP2006091A2_D0083.tif" /></chemistry><chemistry id="chem0080" num="0080"><img file="EP2006091A2_D0084.tif" /></chemistry><chemistry id="chem0081" num="0081"><img file="EP2006091A2_D0085.tif" /></chemistry><chemistry id="chem0082" num="0082"><img file="EP2006091A2_D0086.tif" /></chemistry><chemistry id="chem0083" num="0083"><img file="EP2006091A2_D0087.tif" /></chemistry><chemistry id="chem0084" num="0084"><img file="EP2006091A2_D0088.tif" /></chemistry><chemistry id="chem0085" num="0085"><img file="EP2006091A2_D0089.tif" /></chemistry><chemistry id="chem0086" num="0086"><img file="EP2006091A2_D0090.tif" /></chemistry><chemistry id="chem0087" num="0087"><img file="EP2006091A2_D0091.tif" /></chemistry>          BF₄^-     (S-16) <chemistry id="chem0088" num="0088"><img file="EP2006091A2_D0092.tif" /></chemistry><chemistry id="chem0089" num="0089"><img file="EP2006091A2_D0093.tif" /></chemistry>

0143Also, as the polymerization initiator according to the invention, a polymerization initiator having an azinium structure represented by formula (RI-IV) shown below may be used. In formula (RI-IV), R¹, R², R³, R⁴, R⁵ and R⁶ each independently represents a hydrogen atom, a halogen atom or a monovalent substituent, and X^- represents an anion. <chemistry id="chem0090" num="0090"><img file="EP2006091A2_D0094.tif" /></chemistry>

0144The monovalent substituent described above includes, for example, a halogen atom, an amino group, a substituted amino group, substituted carbonyl group, a hydroxy group, a substituted oxy group, a thiol group, a thioether group, a silyl group, a nitro group, a cyano group, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a sulfo group, a substituted sulfonyl group, a sulfonato group, a substituted sulfinyl group, a phosphono group, a substituted phosphono group, a phosphonato group and a substituted phosphonato group, and when it is possible to introduce a substituent, the substituent may further be introduced.

0145The compound represented by formula (RI-IV) also includes a compound (multimer type) which contains in its molecule two or more of the skeletons (cation portions) of the specific structure in the compound represented by formula (RI-IV) connected through R¹, and such a compound is also preferably used.

0146Moreover, the compound represented by formula (RI-IV) may be a compound (polymer type) in which the skeletons are introduced into a polymer side chain through any one of R¹ to R⁶ and such an embodiment is also preferable.

0147Specific examples [Compounds AZ-1 to AZ-34] of the compound represented by formula (RI-IV) are set forth below, but the invention should not be construed as being limited thereto. <tables id="tabl0001" num="0001"><table frame="none"><tgroup cols="3" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="14mm" /><colspec colnum="2" colname="col2" colwidth="99mm" /><colspec colnum="3" colname="col3" colwidth="13mm" /><thead><row><entry align="right" valign="middle" /><entry align="center" valign="middle" /><entry valign="middle">IogP</entry></row></thead><tbody><row valign="middle"><entry align="center">AZ-1</entry><entry align="center"><chemistry id="chem0091" num="0091"><img file="EP2006091A2_D0095.tif" /></chemistry></entry><entry align="center">0.916</entry></row><row valign="middle"><entry align="center">AZ-2</entry><entry align="center"><chemistry id="chem0092" num="0092"><img file="EP2006091A2_D0096.tif" /></chemistry></entry><entry align="center">0.835</entry></row><row valign="middle"><entry align="center">AZ-3</entry><entry align="center"><chemistry id="chem0093" num="0093"><img file="EP2006091A2_D0097.tif" /></chemistry></entry><entry align="center">0.659</entry></row><row valign="middle"><entry align="center">AZ-4</entry><entry align="center"><chemistry id="chem0094" num="0094"><img file="EP2006091A2_D0098.tif" /></chemistry></entry><entry align="center">1.415</entry></row><row valign="middle"><entry align="center">AZ-5</entry><entry align="center"><chemistry id="chem0095" num="0095"><img file="EP2006091A2_D0099.tif" /></chemistry></entry><entry align="center">2.503</entry></row><row valign="middle"><entry align="center">AZ-6</entry><entry align="center"><chemistry id="chem0096" num="0096"><img file="EP2006091A2_D0100.tif" /></chemistry></entry><entry align="center">3.566</entry></row><row valign="middle"><entry align="center">AZ-7</entry><entry align="center"><chemistry id="chem0097" num="0097"><img file="EP2006091A2_D0101.tif" /></chemistry></entry><entry align="center">5.545</entry></row><row valign="middle"><entry align="center">AZ-8</entry><entry align="center"><chemistry id="chem0098" num="0098"><img file="EP2006091A2_D0102.tif" /></chemistry></entry><entry align="center">3.333</entry></row><row valign="middle"><entry align="center">AZ-9</entry><entry align="center"><chemistry id="chem0099" num="0099"><img file="EP2006091A2_D0103.tif" /></chemistry></entry><entry align="center">6.377</entry></row><row valign="middle"><entry align="center">AZ-10</entry><entry align="center"><chemistry id="chem0100" num="0100"><img file="EP2006091A2_D0104.tif" /></chemistry></entry><entry align="center">4.279</entry></row><row valign="middle"><entry align="center">AZ-11</entry><entry align="center"><chemistry id="chem0101" num="0101"><img file="EP2006091A2_D0105.tif" /></chemistry></entry><entry align="center">0.878</entry></row><row valign="middle"><entry align="center">AZ-12</entry><entry align="center"><chemistry id="chem0102" num="0102"><img file="EP2006091A2_D0106.tif" /></chemistry></entry><entry align="center">5.915</entry></row><row valign="middle"><entry align="center">AZ-13</entry><entry align="center"><chemistry id="chem0103" num="0103"><img file="EP2006091A2_D0107.tif" /></chemistry></entry><entry align="center">4.752</entry></row><row valign="middle"><entry align="center">AZ-14</entry><entry align="center"><chemistry id="chem0104" num="0104"><img file="EP2006091A2_D0108.tif" /></chemistry></entry><entry align="center">4.901</entry></row><row valign="middle"><entry align="center">AZ-15</entry><entry align="center"><chemistry id="chem0105" num="0105"><img file="EP2006091A2_D0109.tif" /></chemistry></entry><entry align="center">6.377</entry></row><row valign="middle"><entry align="center">AZ-16</entry><entry align="center"><chemistry id="chem0106" num="0106"><img file="EP2006091A2_D0110.tif" /></chemistry></entry><entry align="center">6.377</entry></row><row valign="middle"><entry align="center">AZ-17</entry><entry align="center"><chemistry id="chem0107" num="0107"><img file="EP2006091A2_D0111.tif" /></chemistry></entry><entry align="center">6.377</entry></row><row valign="middle"><entry align="center">AZ-18</entry><entry align="center"><chemistry id="chem0108" num="0108"><img file="EP2006091A2_D0112.tif" /></chemistry></entry><entry align="center">6.377</entry></row><row valign="middle"><entry align="center">AZ-19</entry><entry align="center"><chemistry id="chem0109" num="0109"><img file="EP2006091A2_D0113.tif" /></chemistry></entry><entry align="center">6.377</entry></row><row valign="middle"><entry align="center">AZ-20</entry><entry align="center"><chemistry id="chem0110" num="0110"><img file="EP2006091A2_D0114.tif" /></chemistry></entry><entry align="center">6.223</entry></row><row valign="middle"><entry align="center">AZ-21</entry><entry align="center"><chemistry id="chem0111" num="0111"><img file="EP2006091A2_D0115.tif" 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0148The polymerization initiator is not limited to those described above. In particular, the triazine type initiators, organic halogen compounds, oxime ester compounds, diazonium salts, iodonium salts and sulfonium salts are more preferable from the standpoint of reactivity and stability. Of the polymerization initiators, onium salt compounds including as a counter ion, an inorganic anion, for example, PF₆^- or BF₄^- are preferable in combination with the infrared absorbing agent from the standpoint of improvement in the visibility of print-out image. Further, in view of excellence in the color-forming property, a diaryl iodonium is preferable as the onium.

0149The polymerization initiator can be added preferably in an amount from 0.1 to 50% by weight, more preferably from 0.5 to 30% by weight, particularly preferably from 0.8 to 20% by weight, based on the total solid content of the image-recording layer. In the range described above, good sensitivity and good stain resistance in the non-image area at the time of printing are obtained. The polymerization initiators may be used individually or in combination of two or more thereof. Further, the polymerization initiator may be added together with other components to the same layer or may be added to a different layer separately provided.

<(C) Polymerizable compound>

0150The polymerizable compound for use in the invention is an addition-polymerizable compound having at least one ethylenically unsaturated double bond, and it is selected from compounds having at least one, preferably two or more, terminal ethylenically unsaturated double bonds. Such compounds are widely known in the field of art and they can be used in the invention without any particular limitation. The compound has a chemical form, for example, a monomer, a prepolymer, specifically, a dimer, a trimer or an oligomer, or a copolymer thereof, or a mixture thereof. Examples of the monomer and copolymer thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid or maleic acid) and esters or amides thereof. Preferably, esters of an unsaturated carboxylic acid with an aliphatic polyhydric alcohol compound and amides of an unsaturated carboxylic acid with an aliphatic polyvalent amine compound are used. An addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent, for example, a hydroxy group, an amino group or a mercapto group, with a monofunctional or polyfunctional isocyanate or epoxy, or a dehydration condensation reaction product of the unsaturated carboxylic acid ester or amide with a monofunctional or polyfunctional carboxylic acid is also preferably used. Furthermore, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent, for example, an isocyanato group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, or a substitution reaction product of an unsaturated carboxylic acid ester or amide having a releasable substituent, for example, a halogen atom or a tosyloxy group with a monofunctional or polyfunctional alcohol, amine or thiol is also preferably used. In addition, compounds in which the unsaturated carboxylic acid described above is replaced by an unsaturated phosphonic acid, styrene, vinyl ether or the like can also be used.

0151Specific examples of the monomer, which is an ester of an aliphatic polyhydric alcohol compound with an unsaturated carboxylic acid, include acrylic acid esters, for example, ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri(acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri(acryloyloxyethyl) isocyanurate, polyester acrylate oligomer or isocyanuric acid EO modified triacrylate; methacrylic acid esters, for example, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis[p-(3-methacryloxy-2-hydroxypropoxy)phenyl]dimethylmethane or bis[p-(methacryloxyethoxy)phenyl]dimethylmethane; itaconic acid esters, for example, ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate or sorbitol tetraitaconate; crotonic acid esters, for example, ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate or sorbitol tetradicrotonate; isocrotonic acid esters, for example, ethylene glycol diisocrotonate, pentaerythritol diisocrotonate or sorbitol tetraisocrotonate; and maleic acid esters, for example, ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate and sorbitol tetramaleate.

0152Other examples of the ester, which can be preferably used, include aliphatic alcohol esters described in <patcit id="pcit0124" dnum="JP51047334B"><text>JP-B-51-47334</text></patcit> and <patcit id="pcit0125" dnum="JP57196231A"><text>JP-A-57-196231</text></patcit>, esters having an aromatic skeleton described in <patcit id="pcit0126" dnum="JP59005240A"><text>JP-A-59-5240</text></patcit>, <patcit id="pcit0127" dnum="JP59005241A"><text>JP-A-59-5241</text></patcit> and <patcit id="pcit0128" dnum="JP2226149A"><text>JP-A-2-226149</text></patcit>, and esters containing an amino group described in <patcit id="pcit0129" dnum="JP1165613A"><text>JP-A-1-165613</text></patcit>.

0153The above-described ester monomers can also be used as a mixture.

0154Specific examples of the monomer, which is an amide of an aliphatic polyvalent amine compound with an unsaturated carboxylic acid, include methylene bisacrylamide, methylene bismethacrylamide, 1,6-hexamethylene bisacrylamide, 1,6-hexamethylene bismethacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide and xylylene bismethacrylamide. Other preferable examples of the amide monomer include amides having a cyclohexylene structure described in <patcit id="pcit0130" dnum="JP54021726B"><text>JP-B-54-21726</text></patcit>.

0155Urethane type addition polymerizable compounds produced using an addition reaction between an isocyanate and a hydroxy group are also preferably used, and specific examples thereof include vinylurethane compounds having two or more polymerizable vinyl groups per molecule obtained by adding a vinyl monomer containing a hydroxy group represented by formula (ii) shown below to a polyisocyanate compound having two or more isocyanate groups per molecule, described in <patcit id="pcit0131" dnum="JP48041708B"><text>JP-B-48-41708</text></patcit>.          CH₂=C(R ⁴)COOCH₂CH(R⁵)OH     (ii) wherein R⁴ and R⁵ each independently represents H or CH₃.

0156Also, urethane acrylates described in <patcit id="pcit0132" dnum="JP51037193A"><text>JP-A-51-37193</text></patcit>, <patcit id="pcit0133" dnum="JP2032293B"><text>JP-B-2-32293</text></patcit> and <patcit id="pcit0134" dnum="JP2016765B"><text>JP-B-2-16765</text></patcit>, and urethane compounds having an ethylene oxide skeleton described in <patcit id="pcit0135" dnum="JP58049860B"><text>JP-B-58-49860</text></patcit>, <patcit id="pcit0136" dnum="JP56017654B"><text>JP-B-56-17654</text></patcit>, <patcit id="pcit0137" dnum="JP62039417B"><text>JP-B-62-39417</text></patcit> and <patcit id="pcit0138" dnum="JP62039418B"><text>JP-B-62-39418</text></patcit> are preferably used. Furthermore, a photopolymerizable composition having remarkably excellent photosensitive speed can be obtained by using an addition polymerizable compound having an amino structure or a sulfide structure in its molecule, described in <patcit id="pcit0139" dnum="JP63277653A"><text>JP-A-63-277653</text></patcit>, <patcit id="pcit0140" dnum="JP63260909A"><text>JP-A-63-260909</text></patcit> and <patcit id="pcit0141" dnum="JP1105238A"><text>JP-A-1-105238</text></patcit>.

0157Other examples include polyfunctional acrylates and methacrylates, for example, polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with acrylic acid or methacrylic acid, described in <patcit id="pcit0142" dnum="JP48064183A"><text>JP-A-48-64183</text></patcit>, <patcit id="pcit0143" dnum="JP49043191B"><text>JP-B-49-43191</text></patcit> and <patcit id="pcit0144" dnum="JP52030490B"><text>JP-B-52-30490</text></patcit>. Specific unsaturated compounds described in <patcit id="pcit0145" dnum="JP46043946B"><text>JP-B-46-43946</text></patcit>, <patcit id="pcit0146" dnum="JP1040337B"><text>JP-B-1-40337</text></patcit> and <patcit id="pcit0147" dnum="JP1040336B"><text>JP-B-1-40336</text></patcit>, and vinylphosphonic acid type compounds described in <patcit id="pcit0148" dnum="JP2025493A"><text>JP-A-2-25493</text></patcit> can also be exemplified. In some cases, structure containing a perfluoroalkyl group described in <patcit id="pcit0149" dnum="JP61022048A"><text>JP-A-61-22048</text></patcit> can be preferably used. Moreover, photocurable monomers or oligomers described in <nplcit id="ncit0020" npl-type="s"><text>Nippon Secchaku Kyokaishi (Journal of Japan Adhesion Society), Vol. 20, No. 7, pages 300 to 308 (1984</text></nplcit>) can also be used.

0158Details of the method of using the addition polymerizable compound, for example, selection of the structure, individual or combination use, or an amount added, can be appropriately arranged depending on the characteristic design of the final lithographic printing plate precursor. For instance, the compound is selected from the following standpoints.

0159In view of the sensitivity, a structure having a large content of unsaturated groups per molecule is preferred and in many cases, a bifunctional or more functional compound is preferred. In order to increase the strength of image area, that is, cured layer, a trifunctional or more functional compound is preferred. A combination use of compounds different in the functional number or in the kind of polymerizable group (for example, an acrylic acid ester, a methacrylic acid ester, a styrene compound or a vinyl ether compound) is an effective method for controlling both the sensitivity and the strength.

0160The selection and use method of the polymerizable compound are also important factors for the compatibility and dispersibility with other components (for example, a binder polymer, a polymerization initiator or a coloring agent) in the image-recording layer. For instance, the compatibility may be improved in some cases by using the compound of low purity or using two or more kinds of the compounds in combination. A specific structure may be selected for the purpose of improving an adhesion property to a support or a protective layer described hereinafter.

0161The addition polymerizable compound is preferably used in an amount from 5 to 80% by weight, more preferably from 25 to 75% by weight, based on the nonvolatile component of the image-recording layer. The addition polymerizable compounds may be used individually or in combination of two or more thereof. In the method of using the addition polymerizable compound, the structure, blend and amount added can be appropriately selected by taking account of the extent of polymerization inhibition due to oxygen, resolution, fogging property, change in refractive index, surface tackiness and the like. Further, depending on the case, a layer construction, for example, an undercoat layer or an overcoat layer, and a coating method, may also be considered.

<Hydrophobilizing precursor>

0162The hydrophobilizing precursor for use in the invention is a fine particle capable of converting the image-recording layer to be hydrophobic when heat is applied. The fine particle is preferably at least one fine particle selected from hydrophobic thermoplastic polymer fine particles and thermo-reactive polymer fine particles.

0163As the hydrophobic thermoplastic polymer fine particles for use in the image-recording layer, hydrophobic thermoplastic polymer fine particles described, for example, in <nplcit id="ncit0021" npl-type="s"><text>Research Disclosure, No. 33303, January (1992</text></nplcit>), <patcit id="pcit0150" dnum="JP9123387A"><text>JP-A-9-123387</text></patcit>, <patcit id="pcit0151" dnum="JP9131850A"><text>JP-A-9-131850</text></patcit>, <patcit id="pcit0152" dnum="JP9171249A"><text>JP-A-9-171249</text></patcit>, <patcit id="pcit0153" dnum="JP9171250A"><text>JP-A-9-171250</text></patcit> and European Patent <patcit id="pcit0154" dnum="EP931647A"><text>931,647</text></patcit> are preferably exemplified. Specific examples of the polymer constituting the polymer fine particle include a homopolymer or copolymer of a monomer, for example, ethylene, styrene, vinyl chloride, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinylidene chloride, acrylonitrile or vinyl carbazole, and a mixture thereof. Of the polymers, polystyrene and polymethyl methacrylate are more preferable.

0164The average particle size of the hydrophobic thermoplastic polymer fine particle for use in the invention is preferably from 0.01 to 2.0 µm. Synthesis methods of the hydrophobic thermoplastic polymer fine particle include a method of dissolving the above compound in a water-insoluble organic solvent, mixing and emulsifying the solution with an aqueous solution containing a dispersant, and applying heat to the emulsion thereby solidifying the emulsion to a fine particle state while volatizing the organic solvent (a dissolution dispersion method), in addition to an emulsion polymerization method and a suspension polymerization method.

0165As the thermo-reactive polymer fine particle for use in the invention, a thermosetting polymer fine particle and a polymer fine particle having a thermo-reactive group are exemplified.

0166As the thermosetting polymer, a resin having a phenolic skeleton, a urea resin (for example, a resin obtained by resinification of urea or a urea derivative, for example, methoxymethylated urea, with an aldehyde, for example, formaldehyde), a melamine resin (for example, a resin obtained by resinification of melamine or a melamine derivative with an aldehyde, for example, formaldehyde), an alkyd resin, an unsaturated polyester resin, a polyurethane resin and an epoxy resin are exemplified. Of the resins, a resin having a phenolic skeleton, a melamine resin, a urea resin and an epoxy resin are especially preferable.

0167Preferable examples of the resin having a phenolic skeleton include a phenolic resin obtained by resinification of phenol or cresol with an aldehyde, for example, formaldehyde, a hydroxystyrene resin and a polymer or copolymer of methacrylamide, acrylamide, methacrylate or acrylate having a phenolic skeleton, for example, N-(p-hydroxyphenyl)methacrylamide or p-hydroxyphenyl methacrylate.

0168The average particle size of the thermosetting polymer fine particle for use in the invention is preferably from 0.01 to 2.0 µm. While the thermosetting polymer fine particle can be easily obtained by a dissolution dispersion method, a thermosetting polymer may be made fine particle when the thermosetting polymer is synthesized. However, the invention should not be construed as being limited to these methods.

0169As the thermo-reactive group of the polymer fine particle having a thermo-reactive group for use in the invention, a functional group performing any reaction can be used as long as a chemical bond is formed. For instance, an ethylenically unsaturated group (for example, an acryloyl group, a methacryloyl group, a vinyl group or an allyl group), a cationic polymerizable group (for example, a vinyl group or a vinyloxy group) performing a radical polymerization reaction, an isocyanate group performing an addition reaction or a blocked form thereof, an epoxy group, a vinyloxy group and a functional group having an active hydrogen atom (for example, an amino group, a hydroxy group or a carboxyl group) of the reaction partner, a carboxyl group performing a condensation reaction and a hydroxyl group or an amino group of the reaction partner, and an acid anhydride performing a ring opening addition reaction and an amino group or a hydroxyl group of the reaction partner are preferably exemplified.

0170The introduction of the functional group into polymer fine particle may be conducted at the polymerization or by utilizing a polymer reaction after the polymerization.

0171When the functional group is introduced at the polymerization, it is preferred that the monomer having the functional group is subjected to emulsion polymerization or suspension polymerization. Specific examples of the monomer having the functional group include allyl methacrylate, allyl acrylate, vinyl methacrylate, vinyl acrylate, 2-(vinyloxy)ethyl methacrylate, p-vinyloxystyrene, p-[2-(vinyloxy)ethyl]styrene, glycidyl methacrylate, glycidyl acrylate, 2-isocyanatoethyl methacrylate or a blocked isocyanato thereof, for example, with an alcohol, 2-isocyanatoethyl acrylate or a blocked isocyanato thereof, for example, with an alcohol, 2-aminoethyl methacrylate, 2-aminoethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, acrylic acid, methacrylic acid, maleic anhydride, a difunctional acrylate and a difunctional methacrylate, but the invention should not be construed as being limited to thereto.

0172In the invention, a copolymer of the monomer having the functional group and a monomer having no thermo-reactive group copolymerizable with the monomer can also be used. Examples of the copolymerizable monomer having no thermo-reactive group include styrene, an alkyl acrylate, an alkyl methacrylate, acrylonitrile and vinyl acetate, but the copolymerizable monomer having no thermo-reactive group should not be construed as being limited thereto.

0173As the polymer reaction used in the case where the thermo-reactive group is introduced after the polymerization, polymer reactions described, for example, in <patcit id="pcit0155" dnum="WO9634316A"><text>WO 96/34316</text></patcit> can be exemplified.

0174Of the polymer fine particles having a thermo-reactive group, polymer fine particles which are coalesced with each other by heat are preferable, and those having a hydrophilic surface and dispersible in water are particularly preferable. It is preferred that the contact angle (water droplet in air) of a film prepared by coating only the polymer fine particle and drying the particle at temperature lower than the solidification temperature is lower than the contact angle (water droplet in air) of a film prepared by coating only the polymer fine particle and drying at temperature higher than the solidification temperature. For making the surface of polymer fine particle hydrophilic, it is effective to let a hydrophilic .polymer or oligomer, for example, polyvinyl alcohol or polyethylene glycol, or a hydrophilic low molecular weight compound adsorb on the surface of the polymer fine particle. However, the method for hydrophilizing the surface of polymer fine particle should not be construed as being limited thereto.

0175The solidification temperature of the polymer fine particle having a thermo-reactive group is preferably 70°C or higher, more preferably 100°C or higher in consideration of the time-lapse stability. The average particle size of the polymer fine particle is preferably from 0.01 to 2.0 µm, more preferably from 0.05 to 2.0 µm, particularly preferably from 0.1 to 1.0 µm. In the range described above, good resolution and good time-lapse stability can be achieved.

<(D) Binder polymer>

0176In the image-recording layer according to the invention, a binder polymer can be used for the purpose of improving a film strength of the image-recording layer. The binder polymer which can be used in the invention can be selected from those heretofore known without restriction, and polymers having a film-forming property are preferable. Examples of the binder polymer include acrylic resins, polyvinyl acetal resins, polyurethane resins, polyurea resins, polyimide resins, polyamide resins, epoxy resins, methacrylic resins, polystyrene resins, novolac type phenolic resins, polyester resins, synthesis rubbers and natural rubbers.

0177The binder polymer may have a crosslinkable property in order to improve the film strength of the image area. In order to impart the crosslinkable property to the binder polymer, a crosslinkable functional group, for example, an ethylenically unsaturated bond is introduced into a main chain or side chain of the polymer. The crosslinkable functional group may be introduced by copolymerization.

0178Examples of the polymer having an ethylenically unsaturated bond in the main chain thereof include poly-1,4-butadiene and poly-1,4-isoprene.

0179Examples of the polymer having an ethylenically unsaturated bond in the side chain thereof include a polymer of an ester or amide of acrylic acid or methacrylic acid, which is a polymer wherein the ester or amide residue (R in -COOR or -CONHR) has an ethylenically unsaturated bond.

0180Examples of the residue (R described above) having an ethylenically unsaturated bond include -(CH₂)_nCR¹=CR²R³, -(CH₂O)_nCH₂CR¹=CR²R³, -(CH₂CH₂O)_nCH₂CR¹=CR²R³, -(CH₂)_nNH-CO-O-CH₂CR¹=CR²R³, -(CH₂)_n-O-CO-CR¹=CR²R³ and -(CH₂CH₂O)₂-X (wherein R¹ to R³ each represents a hydrogen atom, a halogen atom or an alkyl group having from 1 to 20 carbon atoms, an aryl group, alkoxy group or aryloxy group, or R¹ and R² or R¹ and R³ may be combined with each other to form a ring. n represents an integer of 1 to 10. X represents a dicyclopentadienyl residue).

0181Specific examples of the ester residue include -CH₂CH=CH₂ (described in <patcit id="pcit0156" dnum="JP7021633B"><text>JP-B-7-21633</text></patcit>), -CH₂CH₂O-CH₂CH=CH₂, -CH₂C(CH₃)=CH₂, -CH₂CH=CH-C₆H₅, -CH₂CH₂OCOCH=CH-C₆H₅, -CH₂CH₂-NHCOO-CH₂CH=CH₂ and -CH₂CH₂O-X (wherein X represents a dicyclopentadienyl residue).

0182Specific examples of the amide residue include -CH₂CH=CH₂, -CH₂CH₂-Y (wherein Y represents a cyclohexene residue) and -CH₂CH₂-OCO-CH=CH₂.

0183The binder polymer having crosslinkable property is cured, for example, by addition of a free radical (a polymerization initiating radical or a growing radical of a polymerizable compound during polymerization) to the crosslinkable functional group of the polymer and undergoing addition polymerization between the polymers directly or through a polymerization chain of the polymerizable compound to form crosslinkage between the polymer molecules. Alternately, it is cured by generation of a polymer radical upon extraction of an atom (for example, a hydrogen atom on a carbon atom adjacent to the functional crosslinkable group) in the polymer by a free radial and connecting the polymer radicals with each other to form cross-linkage between the polymer molecules.

0184The content of the crosslinkable group in the binder polymer (content of the radical polymerizable unsaturated double bond determined by iodine titration) is preferably from 0.1 to 10.0 mmol, more preferably from 1.0 to 7.0 mmol, most preferably from 2.0 to 5.5 mmol, based on 1 g of the binder polymer. In the range described above, good sensitivity and good preservation stability can be obtained.

0185From the standpoint of improvement in the on-machine development property or gum development property in the unexposed area of the image-recording layer, it is preferred that the binder polymer has high solubility or high dispersibility in ink and/or dampening water. In order to increase the solubility or dispersibility in the ink, the binder polymer is preferably oleophilic and in order to increase the solubility or dispersibility in the dampening water, the binder polymer is preferably hydrophilic. Therefore, it is effective in the invention that an oleophilic binder polymer and a hydrophilic binder polymer are used in combination.

0186The hydrophilic binder polymer preferably includes, for example, a polymer having a hydrophilic group, for example, a hydroxy group, a carboxyl group, a carboxylate group, a hydroxyethyl group, a polyoxyethyl group, a hydroxypropyl group, a polyoxypropyl group, an amino group, an aminoethyl group, an aminopropyl group, an ammonium group, an amido group, a carboxymethyl group, a sulfo group or a phosphoric acid group.

0187Specific examples the hydrophilic binder polymer include gum arabic, casein, gelatin, a starch derivative, carboxy methyl cellulose and a sodium salt thereof, cellulose acetate, sodium alginate, a vinyl acetate-maleic acid copolymer, a styrene-maleic acid copolymer, polyacrylic acid and a salt thereof, polymethacrylic acid and a salt thereof, a homopolymer or copolymer of hydroxyethyl methacrylate, a homopolymer or copolymer of hydroxyethyl acrylate, a homopolymer or copolymer of hydroxypropyl methacrylate, a homopolymer or copolymer of hydroxypropyl acrylate, a homopolymer or copolymer of hydroxybutyl methacrylate, a homopolymer or copolymer of hydroxybutyl acrylate, a polyethylene glycol, a hydroxypropylene polymer, polyvinyl alcohol, a hydrolyzed polyvinyl acetate having a hydrolysis degree of 60% by mole or more, preferably 80% by mole or more, polyvinyl formal, polyvinyl butyral, polyvinyl pyrrolidone, a homopolymer or copolymer of acrylamide, a homopolymer or polymer of methacrylamide, a homopolymer or copolymer of N-methylolacrylamide, polyvinyl pyrrolidone, an alcohol-soluble nylon, a polyether of 2,2-bis-(4-hydroxyphenyl)propane and epichlorohydrin.

0188The weight average molecular weight of the binder polymer is preferably 5,000 or more, more preferably from 10,000 to 300,000. The number average molecular weight of the binder polymer is preferably 1,000 or more, more preferably from 2,000 to 250,000. The polydispersity (weight average molecular weight/number average molecular weight) thereof is preferably from 1.1 to 10.

0189The binder polymer is available by purchasing a commercial product or synthesizing according to a known method.

0190The content of the binder polymer is ordinarily from 5 to 90% by weight, preferably from 5 to 80% by weight, more preferably from 10 to 70% by weight, based on the total solid content of the image-recording layer. In the range described above, good strength of the image area and good image-forming property can be obtained.

0191It is preferred that the polymerizable compound (C) and the binder polymer are used in a weight ratio of 0.5/1 to 4/1.

<(E) Microcapsule and/or microgel>

0192In the invention, several embodiments can be employed in order to incorporate the above-described constituting components of the image-recording layer (A) to (C) and other constituting components into the image-recording layer. One embodiment is an image-recording layer of molecular dispersion type prepared by dissolving the constituting components in an appropriate solvent to coat as described, for example, in <patcit id="pcit0157" dnum="JP2002287334A"><text>JP-A-2002-287334</text></patcit>. Another embodiment is an image-recording layer of microcapsule type prepared by encapsulating all or part of the constituting components into microcapsules to incorporate into the image-recording layer as described, for example, in <patcit id="pcit0158" dnum="JP2001277740A"><text>JP-A-2001-277740</text></patcit> and <patcit id="pcit0159" dnum="JP2001277742A"><text>JP-A-2001-277742</text></patcit>. In the image-recording layer of microcapsule type, the constituting components may be present outside the microcapsules. It is a more preferable embodiment of the image-recording layer of microcapsule type that hydrophobic constituting components are encapsulated in microcapsules and hydrophilic components are present outside the microcapsules.

0193A still another embodiment is an image-recording layer containing a crosslinked resin particle, that is, a microgel. The microgel can contain a part of the constituting components (A) to (C) inside and/or on the surface thereof. Particularly, an embodiment of a reactive microgel containing the polymerizable compound (C) on the surface thereof is preferable in view of the image-forming sensitivity and printing durability.

0194In order to achieve more preferable on-machine development property, the image-recording layer is preferably the image-recording layer of microcapsule type or microgel type.

0195As a method of microencapsulation or microgelation of the constituting components of the image-recording layer, known methods can be used.

0196Methods of producing the microcapsule include, for example, a method of utilizing coacervation described in <patcit id="pcit0160" dnum="US2800457A"><text>U.S. Patents 2,800,457</text></patcit> and <patcit id="pcit0161" dnum="US2800458A"><text>2,800,458</text></patcit>, a method of using interfacial polymerization described in <patcit id="pcit0162" dnum="US3287154A"><text>U.S. Patent 3,287,154</text></patcit>, <patcit id="pcit0163" dnum="JP3819574B"><text>JP-B-38-19574</text></patcit> and <patcit id="pcit0164" dnum="JP42446B"><text>JP-B-42-446</text></patcit>, a method of using deposition of polymer described in <patcit id="pcit0165" dnum="US3418250A"><text>U.S. Patents 3,418,250</text></patcit> and <patcit id="pcit0166" dnum="US3660304A"><text>3,660,304</text></patcit>, a method of using an isocyanate polyol wall material described in <patcit id="pcit0167" dnum="US3796669A"><text>U.S. Patent 3,796,669</text></patcit>, a method of using an isocyanate wall material described in <patcit id="pcit0168" dnum="US3914511A"><text>U.S. Patent 3,914,511</text></patcit>, a method of using a urea-formaldehyde-type or urea-formaldehyde-resorcinol-type wall-forming material described in <patcit id="pcit0169" dnum="US4001140A"><text>U.S. Patens 4,001,140</text></patcit>, <patcit id="pcit0170" dnum="US4087376A"><text>4,087,376</text></patcit> and 4,089,802, a method of using a wall material, for example, a melamine-formaldehyde resin or hydroxycellulose described in <patcit id="pcit0171" dnum="US4025445A"><text>U.S. Patent 4,025,445</text></patcit>, an in-situ method by monomer polymerization described in <patcit id="pcit0172" dnum="JP369163B"><text>JP-B-36-9163</text></patcit> and <patcit id="pcit0173" dnum="JP51009079B"><text>JP-B-51-9079</text></patcit>, a spray drying method described in British Patent <patcit id="pcit0174" dnum="GB930422A"><text>930,422</text></patcit> and <patcit id="pcit0175" dnum="US3111407A"><text>U.S. Patent 3,111,407</text></patcit>, and an electrolytic dispersion cooling method described in British Patents <patcit id="pcit0176" dnum="GB952807A"><text>952,807</text></patcit> and <patcit id="pcit0177" dnum="GB967074A"><text>967,074</text></patcit>, but the invention should not be construed as being limited thereto.

0197A preferable microcapsule wall used in the invention has three-dimensional crosslinking and has a solvent-swellable property. From this point of view, a preferable wall material of the microcapsule includes polyurea, polyurethane, polyester, polycarbonate, polyamide and a mixture thereof, and polyurea and polyurethane are particularly preferred. Further, a compound having a crosslinkable functional group, for example, an ethylenically unsaturated bond, capable of being introduced into the binder polymer described hereinbefore may be introduced into the microcapsule wall.

0198On the other hand, methods of preparing the microgel include, for example, a method of utilizing granulation by interfacial polymerization described in <patcit id="pcit0178" dnum="JP3819574B"><text>JP-B-38-19574</text></patcit> and <patcit id="pcit0179" dnum="JP42446B"><text>JP-B-42-446</text></patcit> and a method of utilizing granulation by dispersion polymerization in a non-aqueous system described in <patcit id="pcit0180" dnum="JP5061214A"><text>JP-A-5-61214</text></patcit>, but the invention should not be construed as being limited thereto.

0199To the method utilizing interfacial polymerization, known production methods of microcapsule can be applied.

0200The microgel preferably used in the invention is granulated by interfacial polymerization and has three-dimensional crosslinking. From this point of view, a preferable material to be used includes polyurea, polyurethane, polyester, polycarbonate, polyamide and a mixture thereof, and polyurea and polyurethane are particularly preferred.

0201The average particle size of the microcapsule or microgel is preferably from 0.01 to 3.0 µm, more preferably from 0.05 to 2.0 µm, particularly preferably from 0.10 to 1.0 µm. In the range described above, good resolution and good time-lapse stability can be achieved.

<Other components of image-recording layer>

0202The image-recording layer according to the invention may further contain various additives, if desired. Such additives will be described blow.

<1> Surfactant

0203In the image-recording layer according to the invention, a surfactant can be used in order to promote the on-machine development property or gum development property and to improve the state of coated surface. The surfactant used includes, for example, a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant and a fluorine-based surfactant. The surfactants may be used individually or in combination of two or more thereof.

0204The nonionic surfactant used in the invention is not particular restricted, and those hitherto known can be used. Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid partial esters, sorbitan fatty acid partial esters, pentaerythritol fatty acid partial esters, propylene glycol monofatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyethylene glycol fatty acid esters, polyglycerol fatty acid partial esters, polyoxyethylenated castor oils, polyoxyethylene glycerol fatty acid partial esters, fatty acid diethanolamides, N,N-bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, trialkylamine oxides, polyethylene glycols, and copolymers of polyethylene glycol and polypropylene glycol.

0205The anionic surfactant used in the invention is not particularly restricted and those hitherto known can be used. Examples of the anionic surfactant include fatty acid salts, abietic acid salts, hydroxyalkanesulfonic acid salts, alkanesulfonic acid salts, dialkylsulfosuccinic ester salts, straight-chain alkylbenzenesulfonic acid salts, branched alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic acid salts, alkylphenoxypolyoxyethylene propylsulfonic acid salts, polyoxyethylene alkylsulfophenyl ether salts, N-methyl-N-oleyltaurine sodium salt, N-alkylsulfosuccinic monoamide disodium salts, petroleum sulfonic acid salts, sulfated beef tallow oil, sulfate ester slats of fatty acid alkyl ester, alkyl sulfate ester salts, polyoxyethylene alkyl ether sulfate ester salts, fatty acid monoglyceride sulfate ester salts, polyoxyethylene alkyl phenyl ether sulfate ester salts, polyoxyethylene styrylphenyl ether sulfate ester salts, alkyl phosphate ester salts, polyoxyethylene alkyl ether phosphate ester salts, polyoxyethylene alkyl phenyl ether phosphate ester salts, partial saponification products of styrene/maleic anhydride copolymer, partial saponification products of olefin/maleic anhydride copolymer and naphthalene sulfonate formalin condensates.

0206The cationic surfactant used in the invention is not particularly restricted and those hitherto known can be used. Examples of the cationic surfactant include alkylamine salts, quaternary ammonium salts, polyoxyethylene alkyl amine salts and polyethylene polyamine derivatives.

0207The amphoteric surfactant used in the invention is not particularly restricted and those hitherto known can be used. Examples of the amphoteric surfactant include carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfuric esters, and imidazolines.

0208In the surfactants described above, the term "polyoxyethylene" can be replaced with "polyoxyalkylene", for example, polyoxymethylene, polyoxypropylene or polyoxybutylene, and such surfactants can also be used in the invention.

0209Further, a preferable surfactant includes a fluorine-based surfactant containing a perfluoroalkyl group in its molecule. Examples of the fluorine-based surfactant include an anionic type, for example, perfluoroalkyl carboxylates, perfluoroalkyl sulfonates or perfluoroalkyl phosphates; an amphoteric type, for example, perfluoroalkyl betaines; a cationic type, for example, perfluoroalkyl trimethyl ammonium salts; and a nonionic type, for example, perfluoroalkyl amine oxides, perfluoroalkyl ethylene oxide adducts, oligomers having a perfluoroalkyl group and a hydrophilic group, oligomers having a perfluoroalkyl group and an oleophilic group, oligomers having a perfluoroalkyl group, a hydrophilic group and an oleophilic group or urethanes having a perfluoroalkyl group and an oleophilic group. Further, fluorine-based surfactants described in <patcit id="pcit0181" dnum="JP62170950A"><text>JP-A-62-170950</text></patcit>, <patcit id="pcit0182" dnum="JP62226143A"><text>JP-A-62-226143</text></patcit> and <patcit id="pcit0183" dnum="JP60168144A"><text>JP-A-60-168144</text></patcit> are also preferably exemplified.

0210The surfactants can be used individually or in combination of two or more thereof.

0211The content of the surfactant is preferably from 0.001 to 10% by weight, more preferably from 0.01 to 5% by weight, based on the total solid content of the image-recording layer.

<2> Coloring agent

0212In the image-recording layer according to the invention, a dye having a large absorption in the visible region can be used as a coloring agent of the image formed. Specifically, the dye includes Oil yellow #101, Oil yellow #103, Oil pink #312, Oil green BG, Oil blue BOS, Oil blue #603, Oil black BY Oil black BS, Oil black T-505 (produced by Orient Chemical Industries, Ltd.), Victoria pure blue, Crystal violet (CI42555), Methyl violet (CI42535), Ethyl violet, Rhodamine B (CI45170B), Malachite green (CI42000), Methylene blue (CI52015) and dyes described in <patcit id="pcit0184" dnum="JP62293247A"><text>JP-A-62-293247</text></patcit>. Further, a pigment, for example, a phthalocyanine pigment, an azo pigment, carbon black or titanium oxide can also preferably be used.

0213It is preferred to add the coloring agent since distinction between the image area and the non-image area is easily conducted after the formation of image. The amount of the coloring agent added is preferably from 0.01 to 10% by weight based on the total solid content of the image-recording layer.

<3> Print-out agent

0214To the image-recording layer according to the invention, a compound undergoing discoloration with an acid or radical can be added in order to form a print-out image. As a compound used for such a purpose, various dyes, for example, of diphenylmethane type, triphenylmethane type, thiazine type, oxazine type, xanthene type, anthraquinone type, iminoquinone type, azo type and azomethine type are effectively used.

0215Specific examples thereof include dyes, for example, Brilliant green, Ethyl violet, Methyl green, Crystal violet, basic Fuchsine, Methyl violet 2B, Quinaldine red, Rose Bengal, Methanyl yellow, Thimol sulfophthalein, Xylenol blue, Methyl orange, Paramethyl red, Congo red, Benzo purpurin 4B, α-Naphthyl red, Nile blue 2B, Nile blue A, Methyl violet, Malachite green, Parafuchsine, Victoria pure blue BOH (produced by Hodogaya Chemical Co., Ltd.), Oil blue #603 (produced by Orient Chemical Industries, Ltd.), Oil pink #312 (produced by Orient Chemical Industries, Ltd.), Oil red 5B (produced by Orient Chemical Industries, Ltd.), Oil scarlet #308 (produced by Orient Chemical Industries, Ltd.), Oil red OG (produced by Orient Chemical Industries, Ltd.), Oil red RR (produced by Orient Chemical Industries, Ltd.), Oil green #502 (produced by Orient Chemical Industries, Ltd.), Spiron Red BEH special (produced by Hodogaya Chemical Co., Ltd.), m-Cresol purple, Cresol red, Rhodamine B, Rhodamine 6G, Sulfo rhodamine B, Auramine, 4-p-diethylaminophenyliminonaphthoquione, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2-carboxystearylamino-4-p-N,N-bis(hydroxyethyl)aminophenyliminonaphthoquin one, 1-phenyl-3-methyl-4-p-diethylaminopbenylimino-5-pyrazolon or 1-β-naphtyl-4-p-diethylaminophenylimino-5-pyrazolon, and a leuco dye, for example, p, p', p"-hexamethyltriaminotriphenylmethane (leuco crystal violet) or Pergascript Blue SRB (produced by Ciba Geigy Ltd.).

0216In addition to those described above, a leuco dye known as a material for heat-sensitive paper or pressure-sensitive paper is also preferably used. Specific examples thereof include crystal violet lactone, malachite green lactone, benzoyl leuco methylene blue, 2-(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)aminofluoran, 2-anilino-3-methyl-6-(n-ethyl-p-tolidino)fluoran, 3,6-dimethoxyfluoran, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluoran, 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilinofluoran, 3-(N-N-diethylamino)-6-methyl-7-anilinofluoran, 3-(N,N-diethylamino)-6-methyl-7-xylidinofluoran, 3-(N,N-diethylamino)-6-methyl-7-chlorofluoran, 3-(N,N-diethylamino)-6-methoxy-7-aminofluoran, 3-(N,N-diethylamino)-7-(4-chloroanilino)fluoran, 3-(N,N-diethylamino)-7-chlorofluoran, 3-(N,N-diethylamino)-7-benzylaminofluoran, 3-(N,N-diethylamino)-7,8-benzofluoran, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluoran, 3-(N,N-dibutylamino)-6-methyl-7-xylidinofluoran, 3-pipelidino-6-methyl-7-anilinofluoran, 3-pyrolidino-6-methyl-7-anilinofluoran, 3,3-bis(1-ethyl-2-methylindol-3-yl)phthalide, 3,3-bis(1-n-butyl-2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-phthalide and 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide.

0217The amount of the dye undergoing discoloration with an acid or radical is preferably from 0.01 to 10% by weight based on the solid content of the image-recording layer.

<4> Polymerization inhibitor

0218It is preferred to add a small amount of a thermal polymerization inhibitor to the image-recording layer according to the invention in order to inhibit undesirable thermal polymerization of the polymerizable compound (C) during the production or preservation of the image-recording layer.

0219The thermal polymerization inhibitor preferably includes, for example, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butyl catechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol) and N-nitroso-N-phenylhydroxylamine aluminum salt. The amount of the thermal polymerization inhibitor added is preferably from about 0.01 to about 5% by weight based on the total solid content of the image-recording layer.

<5> Higher fatty acid derivative

0220To the image-recording layer according to the invention, a higher fatty acid derivative, for example, behenic acid or behenic acid amide may be added to localize on the surface of the image-recording layer during a drying step after coating in order to avoid polymerization inhibition due to oxygen. The amount of the higher fatty acid derivative added is preferably from about 0.1 to about 10% by weight based on the total solid content of the image-recording layer.

<6> Plasticizer

0221The image-recording layer according to the invention may contain a plasticizer in order to improve the on-machine development property. The plasticizer preferably includes, for example, a phthalic acid ester, e.g., dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, octyl capryl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate or diallyl phthalate; a glycol ester, e.g., dimethylglycol phthalate, ethylphthalylethyl glycolate, methylphthalylethyl glycolate, butylphthalylbutyl glycolate or triethylene glycol dicaprylate ester; a phosphoric acid ester, e.g., tricresyl phosphate or triphenyl phosphate; an aliphatic dibasic acid ester, e.g., diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sebacate, dioctyl azelate or dibutyl maleate; polyglycidyl methacrylate, triethyl citrate, glycerin triacetyl ester and butyl laurate.

0222The amount of the plasticizer is preferably about 30% by weight or less based on the total solid content of the image-recording layer.

<7> Fine inorganic particle

0223The image-recording layer according to the invention may contain fine inorganic particle in order to increase the strength of cured film and to improve the on-machine development property.

0224The fine inorganic particle preferably includes, for example, silica, alumina, magnesium oxide, titanium oxide, magnesium carbonate, calcium alginate and a mixture thereof. The fine inorganic particle can be used, for example, for strengthening the film or enhancing interface adhesion property due to surface roughening.

0225The fine inorganic particle preferably has an average particle size from 5 nm to 10 µm, more preferably from 0.5 to 3µm. In the range described above, it is stably dispersed in the image-recording layer, sufficiently maintains the film strength of the image-recording layer and can form the non-imaging area excellent in hydrophilicity and prevented from the occurrence of stain at the time of printing.

0226The fine inorganic particle described above is easily available as a commercial product, for example, colloidal silica dispersion.

0227The amount of the fine inorganic particle added is preferably 40% by weight or less, more preferably 30% by weight or less, based on the total solid content of the image-recording layer.

<8> Hydrophilic low molecular weight compound

0228The image-recording layer according to the invention may contain a hydrophilic low molecular weight compound in order to improve the on-machine development property or gum development property. The hydrophilic low molecular weight compound includes a water-soluble organic compound, for example, a glycol compound, e.g., ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol or tripropylene glycol, or an ether or ester derivative thereof, a polyhydroxy compound, e.g., glycerine or pentaerythritol, an organic amine compound, e.g., triethanol amine, diethanol amine or monoethanol amine, or a salt thereof, an organic sulfonic acid compound, e.g., an alkyl sulfonic acid, toluene sulfonic acid or benzene sulfonic acid, or a salt thereof, an organic sulfamic acid compound, e.g., an alkyl sulfamic acid, or a salt thereof, an organic sulfuric acid compound, e.g., an alkyl sulfuric acid or an alkyl ether sulfuric acid, or a salt thereof, an organic phosphonic acid compound, e.g., phenyl phosphonic acid, or a salt thereof, an organic carboxylic acid, e.g., tartaric acid, oxalic acid, citric acid, malic acid, lactic acid, gluconic acid or an amino acid, or a salt thereof.

0229Of the compounds, sodium salt or lithium salt of an organic sulfonic acid, organic sulfamic acid or organic sulfuric acid is preferably used.

0230Specific examples of the salt of organic sulfonic acid include sodium n-butylsulfonate, sodium isobutylsulfonate, sodium sec-butylsulfonate, sodium tert-butylsulfonate, sodium n-pentylsulfonate, sodium 1-ethylpropylsulfonate, sodium n-hexylsulfonate, sodium 1,2-dimethylpropylsulfonate, sodium 2-ethylbutylsulfonate, sodium cyclohexylsulfonate, sodium n-heptylsulfonate, sodium n-octylsulfonate, sodium tert-octylsulfonate, sodium n-nonylsulfonate, sodium allylsulfonate, sodium 2-methylallylsulfonate, sodium benzenesulfonate, sodium p-toluenesulfonate, sodium p-hydroxybenzenesulfonate, sodium p-styrenesulfonate, sodium isophthalic acid dimethyl-5-sulfonate, disodium 1,3-benzenedisulfonate, trisodium 1,3,6-benzenetrisulfonate, sodium p-chlorobenzenesulfonate, sodium 3,4-dichlorobenzenesulfonate, sodium 1-naphtylsulfonate, sodium 2-naphtylsulfonate, sodium 4-hydroxynaphtylsulfonate, disodium 1,5-naphtyldisulfonate, disodium 2,6-naphtyldisulfonate, trisodium 1,3,6-naphtyltrisulfonate and lithium salts of these compounds wherein the sodium is exchanged with lithium.

0231Specific examples of the salt of organic sulfamic acid include sodium n-butylsulfamate, sodium isobutylsulfamate, sodium tert-butylsulfamate, sodium n-pentylsulfamate, sodium 1-ethylpropylsulfamate, sodium n-hexylsulfamate, sodium 1,2-dimethylpropylsulfamate, sodium 2-ethylbutylsulfamate, sodium cyclohexylsulfamate and lithium salts of these compounds wherein the sodium is exchanged with lithium.

0232The hydrophilic low molecular weight compound has the hydrophobic part of a small structure and almost no surface active function so that it can be clearly distinguished from the surfactant described hereinbefore in which a long-chain alkylsulfonate or a long-chain alkylbenzenesulfonate is preferably used.

0233As the salt of organic sulfuric acid, a compound represented by formula (iii) shown below is particularly preferably used. <chemistry id="chem0125" num="0125"><img file="EP2006091A2_D0129.tif" /></chemistry>

0234In formula (iii), R represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, m represents an integer of 1 to 4, and X represents sodium, potassium or lithium.

0235R in formula (iii) preferably represents a substituted or unsubstituted, straight-chain, branched or cyclic alkyl group having from 1 to 12 carbon atoms, a substituted or unsubstituted alkenyl group having from 1 to 12 carbon atoms, a substituted or unsubstituted alkynyl group having from 1 to 12 carbon atoms or a substituted or unsubstituted aryl group having 20 or less carbon atoms. Examples of the substituent include a straight-chain, branched or cyclic alkyl group having from 1 to 12 carbon atoms, an alkenyl group having from 1 to 12 carbon atoms, an alkynyl group having from 1 to 12 carbon atoms, a halogen atom and an aryl group having 20 or less carbon atoms.

0236Preferable examples of the compound represented by formula (iii) include sodium oxyethylene 2-ethylhexyl ether sulfate, sodium dioxyethylene 2-ethylhexyl ether sulfate, potassium dioxyethylene 2-ethylhexyl ether sulfate, lithium dioxyethylene 2-ethylhexyl ether sulfate, sodium trioxyethylene 2-ethylhexyl ether sulfate, sodium tetraoxyethylene 2-ethylhexyl ether sulfate, sodium dioxyethylene hexyl ether sulfate, sodium dioxyethylene octyl ether sulfate and sodium dioxyethylene lauryl ether sulfate. Most preferable examples thereof include sodium dioxyethylene 2-ethylhexyl ether sulfate, potassium dioxyethylene 2-ethylhexyl ether sulfate and lithium dioxyethylene 2-ethylhexyl ether sulfate.

0237The amount of the hydrophilic low molecular weight compound added to the image-recording layer is preferably from 0.5 to 20% by weight, more preferably from 1 to 10% by weight, still more preferably from 2 to 8% by weight, based on the total solid content of the image-recording layer. In the range described above, good on-machine development property or gum development property and good printing durability are achieved.

0238The hydrophilic low molecular weight compounds may be used individually or as a mixture of two or more thereof.

<11> Oil-sensitizing agent

0239In the lithographic printing plate precursor according to the invention, a phosphonium compound may be added to the image-recording layer and/or protective layer in order to improve the ink-receptive property. As preferable examples of the phosphonium compound, compounds represented by formula (iv) shown below as described in <patcit id="pcit0185" dnum="JP2006297907A"><text>JP-A-2006-297907</text></patcit> and compounds represented by formula (v) shown below as described in <patcit id="pcit0186" dnum="JP2007050660A"><text>JP-A-2007-50660</text></patcit> are exemplified. <chemistry id="chem0126" num="0126"><img file="EP2006091A2_D0130.tif" /></chemistry>

0240In formula (iv), R₁ to R₄ each independently represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkylthio group, an arylthio group or a heterocyclic group, which of which may have a substituent, or a hydrogen atom, or at least two of R₁ to R₄ may be combined with each other to form a ring, and X^- represents a counter anion.

0241In formula (v), Ar₁ to Ar₆ each independently represents an aryl group or a heterocyclic group, L represents a divalent connecting group, X^n- represents a n-valent counter anion, n represents an integer of 1 to 3, and m represents a number satisfying n x m = 2. In the formula, the aryl group preferably includes, for example, a phenyl group, a naphthyl group, a tolyl group, a xylyl group, a fluorophenyl group, a chlorophenyl group, a bromophenyl group, a methoxyphenyl group, an ethoxyphenyl group, a dimethoxyphenyl group, a methoxycarbonylphenyl group and a dimethylaminophenyl group. The heterocyclic group preferably includes, for example, a pyridyl group, a quinolyl group, a pyrimidinyl group, a thienyl group and a furyl group. L represents a divalent connecting group and a number of carbon atoms included in the connecting group is preferably from 6 to 15, more preferably from 6 to 12. X^n- represents a n-valent counter anion and preferable examples of the counter anion include a halogen anion, for example, Cl^-, Br^- or I^-, a sulfonate anion, a carboxylate anion, a sulfate ester anion, PF₆^-, BF₄^- and a perchlorate anion. Among them, a halogen anion, for example, Cl^-, Br^- or I^-, a sulfonate anion and a carboxylate anion are particularly preferable.

0242Specific examples of the phosphonium compound represented by formula (iv) or (v) are set forth below. <chemistry id="chem0127" num="0127"><img file="EP2006091A2_D0131.tif" /></chemistry><chemistry id="chem0128" num="0128"><img file="EP2006091A2_D0132.tif" /></chemistry><chemistry id="chem0129" num="0129"><img file="EP2006091A2_D0133.tif" /></chemistry><chemistry id="chem0130" num="0130"><img file="EP2006091A2_D0134.tif" /></chemistry><chemistry id="chem0131" num="0131"><img file="EP2006091A2_D0135.tif" /></chemistry>

0243The amount of the phosphonium compound added to the image-recording layer or protective layer is preferably from 0.01 to 20% by weight, more preferably from 0.05 to 10% by weight, most preferably from 0.1 to 5% by weight, based on the solid content of each of the layer. In the range described above, good ink-receptive property is obtained.

<Formation of image-recording layer>

0244The image-recording layer according to the invention is formed by dispersing or dissolving each of the necessary constituting components described above in a solvent to prepare a coating solution and coating the solution. The solvent used include, for example, ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methxyethyl acetate, 1-metboxy-2-propyl acetate, dimethoxyethane, methyl lactate, ethyl lactate, N,N-dimethylacetoamide, N,N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, γ-butyrolactone, toluene and water, but the invention should not be construed as being limited thereto. The solvents may be used individually or as a mixture. The solid content concentration of the coating solution is preferably from 1 to 50% by weight. The image-recording layer according to the invention may also be formed by preparing plural coating solutions by dispersing or dissolving the same or different components described above into the same or different solvents and conducting repeatedly the coating and drying plural times.

0245The coating amount of the image-recording layer (solid content) formed on a support after drying may be varied according to the intended purpose but is preferably from 0.3 to 3.0 g/m². In the range described above, good sensitivity and good film property of the image-recording layer can be achieved.

0246Various methods can be used for the coating. Examples of the coating method include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating and roll coating.

(Protective layer)

0247In the lithographic printing plate precursor according to the invention, it is preferable to provide a protective layer (overcoat layer) on the image-recording layer. The protective layer has a function for preventing, for example, occurrence of scratch in the image-recording layer or ablation caused by exposure with a high illuminance laser beam, in addition to the function for restraining an inhibition reaction against the image formation by means of oxygen blocking. Components for the protective layer will be described below.

0248Ordinarily, the exposure process of a lithographic printing plate precursor is performed in the air. The image-forming reaction occurred upon the exposure process in the image-recording layer may be inhibited by a low molecular weight compound, for example, oxygen or a basic substance present in the air. The protective layer prevents the low molecular weight compound, for example, oxygen or a basic substance from penetrating into the image-recording layer and as a result, the inhibition of image-forming reaction at the exposure process in the air can be avoided. Accordingly, the property required of the protective layer is to reduce permeability of the low molecular compound, for example, oxygen. Further, the protective layer preferably has good transparency to light used for the exposure, is excellent in an adhesion property to the image-recording layer, and can be easily removed during the on-machine development processing step after the exposure. With respect to the protective layer having such properties, there are described, for example, in <patcit id="pcit0187" dnum="US3458311A"><text>U.S. Patent 3,458,311</text></patcit> and <patcit id="pcit0188" dnum="JP55049729B"><text>JP-B-55-49729</text></patcit>.

0249As a material for use in the protective layer, any water-soluble polymer and water-insoluble polymer can be appropriately selected to use. Specifically, a water-soluble polymer, for example, polyvinyl alcohol, a modified polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl imidazole, polyacrylic acid, polyacrylamide, a partially saponified product of polyvinyl acetate, an ethylene-vinyl alcohol copolymer, a water-soluble cellulose derivative, gelatin, a starch derivative or gum arabic, and a polymer, for example, polyvinylidene chloride, poly(meth)acrylonitrile, polysulfone, polyvinyl chloride, polyethylene, polycarbonate, polystyrene, polyamide or cellophane are exemplified. The polymers may be used in combination of two or more thereof, if desired.

0250As a relatively useful material for use in the protective layer, a water-soluble polymer compound excellent in crystallinity is exemplified. Specifically, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl imidazole, a water-soluble acrylic resin, for example, polyacrylic acid, gelatin or gum arabic is preferably used. Above all, polyvinyl alcohol, polyvinyl pyrrolidone and polyvinyl imidazole are more preferably used from the standpoint of capability of coating with water as a solvent and easiness of removal with dampening water at the printing. Among them, polyvinyl alcohol (PVA) provides most preferable results on the fundamental properties, for example, oxygen blocking property or removability with development.

0251The polyvinyl alcohol for use in the protective layer may be partially substituted with ester, ether or acetal as long as it contains a substantial amount of unsubstituted vinyl alcohol units necessary for maintaining water solubility. Also, the polyvinyl alcohol may partially contain other copolymerization components. For instance, polyvinyl alcohols of various polymerization degrees having at random a various kind of hydrophilic modified cites, for example, an anion-modified cite modified with an anion, e.g., a carboxyl group or a sulfo group, a cation-modified cite modified with a cation, e.g., an amino group or an ammonium group, a silanol-modified cite or a thiol-modified cite, and polyvinyl alcohols of various polymerization degrees having at the terminal of the polymer chain a various kind of modified cites, for example, the above-described anion-modified cite, cation modified cite, silanol-modified cite or thiol-modified cite, an alkoxy-modified cite, a sulfide-modified cite, an ester modified cite of vinyl alcohol with a various kind of organic acids, an ester modified cite of the above-described anion-modified cite with an alcohol or an epoxy-modified cite are also preferably used.

0252Preferable examples of the polyvinyl alcohol include those having a hydrolysis degree of 71 to 100% by mole and a polymerization degree of 300 to 2,400. Specific examples of the polyvinyl alcohol include PVA-105, PVA-110, PVA-117, PVA-117H, PVA-120, PVA-124, PVA-124H, PVA-CS, PVA-CST, PVA-HC, PVA-203, PVA-204, PVA-205, PVA-210, PVA-217, PVA-220, PVA-224, PVA-217EE, PVA-217E, PVA-220E, PVA-224E, PVA-405, PVA-420, PVA-613 and L-8 produced by Kuraray Co., Ltd. Specific examples of the modified polyvinyl alcohol include that having an anion-modified cite, for example, KL-318, KL-118, KM-618, KM-118 or SK-5102, that having a cation-modified cite, for example, C-318, C-118 or CM-318, that having a terminal thiol-modified cite, for example, M-205 or M-115, that having a terminal sulfide-modified cite, for example, MP-103, MP-203, MP-102 or MP-202, that having an ester-modified cite with a higher fatty acid at the terminal, for example, HL-12E or HL-1203 and that having a reactive silane-modified cite, for example, R-1130, R-2105 or R-2130.

0253It is also preferable that the protective layer contains an inorganic stratiform compound. The stratiform compound is a particle having a thin tabular shape and includes, for instance, mica, for example, natural mica represented by the following formula: A (B, C)_2-5 D₄ O₁₀ (OH, F, O)₂, (wherein A represents any one of Li, K, Na, Ca, Mg and an organic cation, B and C each represents any one of Fe (II), Fe(III), Mn, Al, Mg and V, and D represents Si or Al) or synthetic mica, talc represented by the following formula: 3MgO·4SiO·H₂O, teniolite, montmorillonite, saponite, hectolite and zirconium phosphate.

0254Examples of the natural mica include muscovite, paragonite, phlogopite, biotite and lepidolite. Examples of the synthetic mica include non-swellable mica, for example, fluorphlogopite KMg₃(AlSi₃O₁₀)F₂ or potassium tetrasilic mica KMg_2.5(Si₄O₁₀)F₂, and swellable mica, for example, Na tetrasilic mica NaMg_2.5(Si₄O₁₀)F₂, Na or Li teniolite (Na, Li)Mg₂Li(Si₄O₁₀)F₂, or montmorillonite based Na or Li hectolite (Na, Li)_1/8Mg_2/5Li_1/8(Si₄O₁₀)F₂. Synthetic smectite is also useful.

0255Of the stratiform compounds, fluorine-based swellable mica, which is a synthetic stratiform compound, is particularly useful in the invention. Specifically, the swellable synthetic mica and an swellable clay mineral, for example, montmorillonite, saponite, hectolite or bentonite have a stratiform structure comprising a unit crystal lattice layer having thickness of approximately 10 to 15 angstroms, and metallic atom substitution in the lattices thereof is remarkably large in comparison with other clay minerals. As a result, the lattice layer results in lack of positive charge and to compensate it, a cation, for example, Li⁺, Na⁺, Ca²⁺, Mg²⁺ or an organic cation, e.g., an amine salt, a quaternary ammonium salt, a phosphonium salt or a sulfonium salt is adsorbed between the lattice layers. The stratiform compound swells upon contact with water. When share is applied under such condition, the stratiform crystal lattices are easily cleaved to form a stable sol in water. The bentnite and swellable synthetic mica have strongly such tendency.

0256With respect to the shape of the stratiform compound, the thinner the thickness or the larger the plain size as long as smoothness of coated surface and transmission of actinic radiation are not damaged, the better from the standpoint of control of diffusion. Therefore, an aspect ratio of the stratiform compound is ordinarily 20 or more, preferably 100 or more, particularly preferably 200 or more. The aspect ratio is a ratio of thickness to major axis of particle and can be determined, for example, from a projection drawing of particle by a microphotography. The larger the aspect ratio, the greater the effect obtained.

0257As for the particle diameter of the stratiform compound, an average diameter is ordinarily from 0.3 to 20 µm, preferably from 0.5 to 10 µm, particularly preferably from 1 to 5 µm. When the particle diameter is less than 0.3 µm, the inhibition of permeation of oxygen or moisture is insufficient and the effect of the stratiform compound can not be satisfactorily achieved. On the other hand, when it is larger than 20 µm, the dispersion stability of the particle in the coating solution is insufficient to cause a problem in that stable coating can not be performed. An average thickness of the particle is ordinarily 0.1 µm or less, preferably 0.05 µm or less, particularly preferably 0.01 µm or less. For example, with respect to the swellable synthetic mica that is the representative compound of the inorganic stratiform compounds, the thickness is approximately from 1 to 50 nm and the plain size is approximately from 1 to 20 µm.

0258When such an inorganic stratiform compound particle having a large aspect ratio is incorporated into the protective layer, strength of the coated layer increases and penetration of oxygen or moisture can be effectively inhibited so that the protective layer can be prevented from deterioration due to deformation, and even when the lithographic printing plate precursor is preserved for a long period of time under a high humidity condition, it is prevented from decrease in the image-forming property thereof due to the change of humidity and exhibits excellent preservation stability.

0259An example of common dispersing method for using the stratiform compound in the protective layer is described below. Specifically, from 5 to 10 parts by weight of a swellable stratiform compound which is exemplified as a preferable stratiform compound is added to 100 parts by weight of water to adapt the compound to water and to be swollen, followed by dispersing using a dispersing machine. The dispersing machine used include, for example, a variety of mills conducting dispersion by directly applying mechanical power, a high-speed agitation type dispersing machine providing a large shear force and a dispersion machine providing ultrasonic energy of high intensity. Specific examples thereof include a ball mill, a sand grinder mill, a visco mill, a colloid mill, a homogenizer, a dissolver, a polytron, a homomixer, a homoblender, a keddy mill, a jet agitor, a capillary type emulsifying device, a liquid siren, an electromagnetic strain type ultrasonic generator and an emulsifying device having Polman whistle. A dispersion containing from 5 to 10% by weight of the inorganic stratiform compound thus prepared is highly viscous or gelled and exhibits extremely good preservation stability. In the formation of a coating solution for protective layer using the dispersion, it is preferred that the dispersion is diluted with water, sufficiently stirred and then mixed with a binder solution.

0260The content of the inorganic stratiform compound in the protective layer is ordinarily from 5/1 to 1/100 in terms of a weight ratio of the inorganic stratiform compound to an amount of a binder used in the protective layer. When a plural kind of the inorganic stratiform compounds is used together, it is preferred that the total amount of the inorganic stratiform compounds is in the range of weight ratio described above.

0261The inorganic stratiform compound can be added to the image-recording layer in addition to the protective layer. The addition of inorganic stratiform compound to the image-recording layer is useful for improvements in the printing durability, polymerization efficiency (sensitivity) and time-lapse stability.

0262The amount of the inorganic stratiform compound added to the image-recording layer is preferably from 0.1 to 50% by weight, more preferably from 0.3 to 30% by weight, most preferably from 1 to 10% by weight, based on the solid content of the image-recording layer.

0263As other additive for the protective layer, glycerol, dipropylene glycol or the like can be added in an amount corresponding to several % by weight of the water-soluble or water-insoluble polymer to impart flexibility. Further, an anionic surfactant, for example, sodium alkyl sulfate or sodium alkyl sulfonate; an amphoteric surfactant, for example, alkylamino carboxylic acid salt or alkylamino dicarboxylic acid salt; or a non-ionic surfactant, for example, polyoxyethylene alkyl phenyl ether can be added. The amount of the surfactant added is from 0.1 to 100% by weight of the water-soluble or water-insoluble polymer.

0264Further, for the purpose of improving the adhesion property to the image-recording layer, for example, it is described in <patcit id="pcit0189" dnum="JP49070702A"><text>JP-A-49-70702</text></patcit> and BP-A-1,303,578 that sufficient adhesion can be obtained by mixing from 20 to 60% by weight of an acrylic emulsion, a water-insoluble vinyl pyrrolidone-vinyl acetate copolymer or the like in a hydrophilic polymer mainly comprising polyvinyl alcohol and coating the mixture on the image-recording layer. In the invention, any of such known techniques can be used.

0265Moreover, other functions can also be provided to the protective layer. For instance, by adding a coloring agent (for example, a water-soluble dye), which is excellent in permeability for infrared ray used for the exposure and capable of efficiently absorbing light at other wavelengths, a safe light adaptability can be improved without causing decrease in the sensitivity.

0266The formation of protective layer is performed by coating a coating solution for protective layer prepared by dispersing or dissolving the components of protective layer in a solvent on the image-recording layer, followed by drying. The coating solvent may be appropriately selected in view of the binder used, and when a water-soluble polymer is used, distilled water or purified water is preferably used as the solvent.

0267To the coating solution for protective layer can be added known additives, for example, an anionic surfactant, a nonionic surfactant, a cationic surfactant or a fluorine-based surfactant for improving coating property or a water-soluble plasticizer for improving physical property of the coated layer. Examples of the water-soluble plasticizer include propionamide, cyclohexanediol, glycerin or sorbitol. Also, a water-soluble (meth)acrylic polymer can be added. Further, to the coating solution for protective layer may be added known additives for increasing an adhesion property to the image-recording layer or for improving time-lapse stability of the coating solution.

0268A coating method of the protective layer is not particularly limited, and known methods, for example, methods described in <patcit id="pcit0190" dnum="US3458311A"><text>U.S. Patent 3,458,311</text></patcit> and <patcit id="pcit0191" dnum="JP55049729B"><text>JP-B-55-49729</text></patcit> can be utilized. Specific examples of the coating method for the protective layer include a blade coating method, an air knife coating method, a gravure coating method, a roll coating method, a spray coating method, a dip coating method and a bar coating method.

0269The coating amount of the protective layer is preferably in a range from 0.01 to 10 g/m², more preferably in a range from 0.02 to 3 g/m², most preferably in a range from 0.02 to 1 g/m², in terms of the coating amount after drying.

(Support)

0270The support for use in the lithographic printing plate precursor according to the invention is an aluminum plate.

0271The aluminum plate includes a pure aluminum plate, an alloy plate comprising aluminum as a main component and containing a trace amount of hetero elements and a thin film of aluminum or aluminum alloy laminated with plastic. The hetero element contained in the aluminum alloy includes, for example, silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel and titanium. The content of the hetero element in the aluminum alloy is preferably 10% by weight or less. Although a pure aluminum plate is preferred in the invention, since completely pure aluminum is difficult to be produced in view of the refining technique, the aluminum plate may slightly contain the hetero element. The composition is not specified for the aluminum plate and those materials conventionally known and used can be appropriately utilized.

0272The thickness of the support is preferably from 0.1 to 0.6 mm, more preferably from 0.15 to 0.4 mm.

0273In advance of the use of aluminum plate, a surface treatment, for example, roughening treatment or anodizing treatment is preferably performed. The surface treatment facilitates improvement in the hydrophilic property and ensure for adhesion property between the image-recording layer and the support. Prior to the roughening treatment of the aluminum plate, a degreasing treatment, for example, with a surfactant, an organic solvent or an aqueous alkaline solution is conducted for removing rolling oil on the surface thereof, if desired.

0274The roughening treatment of the surface of the aluminum plate is conducted by various methods and includes, for example, mechanical roughening treatment, electrochemical roughening treatment (roughening treatment of electrochemically dissolving the surface) and chemical roughening treatment (roughening treatment of chemically dissolving the surface selectively).

0275As the method of the mechanical roughening treatment, a known method, for example, ball graining, brush graining, blast graining or buff graining can be used. Also, a transfer method can be employed wherein using a roll having concavo-convex shape the concavo-convex shape is transferred to the surface of aluminum plate during a rolling step of the aluminum plate.

0276The electrochemical roughening treatment method includes, for example, a method of conducting by passing alternating current or direct current in an electrolytic solution containing an acid, for example, hydrochloric acid or nitric acid. Also, a method of using a mixed acid described in <patcit id="pcit0192" dnum="JP54063902A"><text>JP-A-54-63902</text></patcit> can be exemplified.

0277The aluminum plate subjected to the roughening treatment is subjected, if desired, to an alkali etching treatment using an aqueous solution, for example, of potassium hydroxide or sodium hydroxide and further subjected to a neutralizing treatment, and then subjected to an anodizing treatment for improving the abrasion resistance, if desired.

0278As the electrolyte used for the anodizing treatment of the aluminum plate, various electrolytes capable of forming porous oxide film can be used. Ordinarily, sulfuric acid, hydrochloric acid, oxalic acid, chromic acid or a mixed acid thereof is used. The concentration of the electrolyte can be appropriately determined depending on the kind of the electrolyte.

0279Since the conditions for the anodizing treatment are varied depending on the electrolyte used, they cannot be defined commonly. However, it is ordinarily preferred that electrolyte concentration in the solution is from 1 to 80% by weight, liquid temperature is from 5 to 70°C, current density is from 5 to 60 A/dm², voltage is from 1 to 100 V, and electrolysis time is from 10 seconds to 5 minutes. The amount of the anodized film formed is preferably from 1.0 to 5.0 g/m², more preferably from 1.5 to 4.0 glm². In the range described above, good printing durability and good scratch resistance in the non-image area of lithographic printing plate can be achieved.

0280The aluminum plate subjected to the surface treatment and having the anodized film is used as it is as the support in the invention. However, in order to more improve the adhesion property to a layer provided thereon, hydrophilicity, stain resistance, heat insulating property or the like, other treatment, for example, an enlarging treatment of micropores or a sealing treatment of micropores of the anodized film described in <patcit id="pcit0193" dnum="JP2001253181A"><text>JP-A-2001-253181</text></patcit> and <patcit id="pcit0194" dnum="JP2001322365A"><text>JP-A-2001-322365</text></patcit>, or a surface hydrophilizing treatment by immersing in an aqueous solution containing a hydrophilic compound may be appropriately conducted. Needless to say, the enlarging treatment and sealing treatment are not limited to those described in the above-described patents and any conventionally known method may be employed. For instance, as the sealing treatment, as well as a sealing treatment with steam, a sealing treatment with fluorozirconic acid alone, a sealing treatment with sodium fluoride or a sealing treatment with steam having added thereto lithium chloride may be employed.

0281The sealing treatment for use in the invention is not particularly limited and conventionally known methods can be employed. Among them, a sealing treatment with an aqueous solution containing an inorganic fluorine compound, a sealing treatment with water vapor and a sealing treatment with hot water are preferred. The sealing treatments will be described in more detail below, respectively.

<1> Sealing treatment with aqueous solution containing inorganic fluorine compound

0282As the inorganic fluorine compound used in the sealing treatment with an aqueous solution containing an inorganic fluorine compound, a metal fluoride is preferably exemplified.

0283Specific examples thereof include sodium fluoride, potassium fluoride, calcium fluoride, magnesium fluoride, sodium fluorozirconate, potassium fluorozirconate, sodium fluorotitanate, potassium fluorotitanate, ammonium fluorozirconate, ammonium fluorotitanate, potassium fluorotitanate, fluorozirconic acid, fluorotitanic acid, hexafluorosilicic acid, nickel fluoride, iron fluoride, fluorophosphoric acid and ammonium fluorophosphate. Among them, sodium fluorozirconate, sodium fluorotitanate, fluorozirconic acid and fluorotitanic acid are preferred.

0284The concentration of the inorganic fluorine compound in the aqueous solution is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, in view of performing satisfactory sealing of micropores of the anodized film, and it is preferably 1% by weight or less, more preferably 0.5% by weight or less, in view of the staining property.

0285The aqueous solution containing an inorganic fluorine compound preferably further contains a phosphate compound. When the phosphate compound is contained, the hydrophilicity on the anodized film surface is increased and thus, the on-machine development property and staining property can be improved.

0286Preferable examples of the phosphate compound include phosphates of metal, for example, an alkali metal or an alkaline earth metal.

0287Specific examples of the phosphate compound include zinc phosphate, aluminum phosphate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, monoammonium phosphate, monopotassium phosphate, monosodium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, calcium phosphate, sodium ammonium hydrogen phosphate, magnesium hydrogen phosphate, magnesium phosphate, ferrous phosphate, ferric phosphate, sodium dihydrogen phosphate, sodium phosphate, disodium hydrogen phosphate, lead phosphate, diammonium phosphate, calcium dihydrogen phosphate, lithium phosphate, phosphotungstic acid, ammonium phosphotungstate, sodium phosphotungstate, ammonium phosphomolybdate, sodium phosphomolybdate, sodium phosphite, sodium tripolyphosphate and sodium pyrophosphate. Among them, sodium dihydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate and dipotassium hydrogen phosphate are preferred.

0288The combination of the inorganic fluorine compound and the phosphate compound is not particularly limited, but it is preferred that the aqueous solution contains at least sodium fluorozirconate as the inorganic fluorine compound and at least sodium dihydrogen phosphate as the phosphate compound.

0289The concentration of the phosphate compound in the aqueous solution is preferably 0.01% by weight or more, more preferably 0.1 % by weight or more, in view of improvement in the on-machine development property and staining property, and it is preferably 20% by weight or less, more preferably 5% by weight or less, in view of solubility.

0290The ratio of respective compounds in the aqueous solution is not particularly limited, and the weight ratio between the inorganic fluorine compound and the phosphate compound is preferably from 1/200 to 10/1, more preferably from 1/30 to 2/1.

0291The temperature of the aqueous solution is preferably 20°C or more, more preferably 40°C or more, and it is preferably 100°C or less, more preferably 80°C or less.

0292The pH of the aqueous solution is preferably 1 or more, more preferably 2 or more, and it is preferably 11 or less, more preferably 5 or less.

0293A method of the sealing treatment with the aqueous solution containing an inorganic fluorine compound is not particularly limited and examples thereof include a dipping method and a spray method. One of the treatments may be used alone once or multiple times, or two or more thereof may be used in combination.

0294In particular, the dipping method is preferred. In the case of performing the treatment using the dipping method, the treating time is preferably one second or more, more preferably 3 seconds or more, and it is preferably 100 seconds or less, more preferably 20 seconds or less.

<2> Sealing treatment with water vapor

0295Examples of the sealing treatment with water vapor include a method of continuously or discontinuously bringing water vapor under applied pressure or normal pressure into contact with the anodized film.

0296The temperature of the water vapor is preferably 80°C or more, more preferably 95°C or more, and it is preferably 105°C or less.

0297The pressure of the water vapor is preferably in a range from (atmospheric pressure - 50 mmAg) to (atmospheric pressure + 300 mmAg) (from 1.008×10⁵ to 1.043x 10⁵ Pa).

0298The time period for which water vapor is contacted is preferably one second or more, more preferably 3 seconds or more, and it is preferably 100 seconds or less, more preferably 20 seconds or less.

<3> Sealing treatment with hot water

0299Examples of the sealing treatment with hot water include a method of dipping the aluminum plate having formed thereon the anodized film in hot water.

0300The hot water may contain an inorganic salt (for example, a phosphate) or an organic salt.

0301The temperature of the hot water is preferably 80°C or more, more preferably 95°C or more, and it is preferably 100°C or less.

0302The time period for which the aluminum plate is dipped in hot water is preferably one second or more, more preferably 3 seconds or more, and it is preferably 100 seconds or less, more preferably 20 seconds or less.

0303Preferable hydrophilizing treatment according to the invention includes an alkali metal silicate method described in <patcit id="pcit0195" dnum="US2714066A"><text>U.S. Patents 2,714,066</text></patcit>, <patcit id="pcit0196" dnum="US3181461A"><text>3,181,461</text></patcit>, <patcit id="pcit0197" dnum="US3280734A"><text>3,280,734 </text></patcit>and <patcit id="pcit0198" dnum="US3902734A"><text>3,902,734</text></patcit>. In the method, the support is subjected to immersion treatment or electrolytic treatment in an aqueous solution containing, for example, sodium silicate. In addition, the hydrophilizing treatment includes, for example, a method of treating with potassium fluorozirconate described in <patcit id="pcit0199" dnum="JP3622063B"><text>JP-B-36-22063</text></patcit> and a method of treating with polyvinyl phosphonic acid described in <patcit id="pcit0200" dnum="US3276868A"><text>U.S. Patents 3,276,868</text></patcit>, <patcit id="pcit0201" dnum="US4153461A"><text>4,153,461</text></patcit>, and <patcit id="pcit0202" dnum="US4689272A"><text>4,689,272</text></patcit>.

0304The support preferably has a center line average roughness of 0.10 to 1.2 µm. In the range described above, good adhesion property to the image-recording layer, good printing durability and good stain resistance can be achieved.

(Backcoat layer)

0305After applying the surface treatment to the support or forming the intermediate layer described hereinbrfore on the support, a backcoat layer can be provided on the back surface of the support, if desired.

0306The backcoat layer preferably includes, for example, a coating layer comprising an organic polymer compound described in <patcit id="pcit0203" dnum="JP5045885A"><text>JP-A-5-45885</text></patcit> and a coating layer comprising a metal oxide obtained by hydrolysis and polycondensation of an organic metal compound or an inorganic metal compound described in <patcit id="pcit0204" dnum="JP6034174A"><text>JP-A-6-34174</text></patcit>. Among them, use of an alkoxy compound of silicon, for example, Si(OCH₃)₄, Si(OC₂H₅)₄, Si(OC₃H₇)₄ or Si(OC₄H₉)₄ is preferred since the starting material is inexpensive and easily available.

[Plate making method]

0307The plate making method of the lithographic printing plate precursor according to the invention includes two embodiments. The first embodiment is on-machine development and the second embodiment is gum development.

(On-machine development method)

0308The on-machine development method includes a step in which the lithographic printing plate precursor is imagewise exposed and a printing step in which printing ink and dampening water are supplied to the exposed lithographic printing plate precursor without undergoing any development processing to perform printing, and it is characterized in that the unexposed area of the lithographic printing plate precursor is removed in the course of the printing step. The imagewise exposure may be performed after the lithographic printing plate precursor is mounted on a printing machine or after the imagewise exposure the exposed lithographic printing plate precursor is mounted on a printing machine. Then, the printing operation is initiated using the printing machine with supplying printing ink and dampening water and at an early stage of the printing the on-machine development, specifically, the image recording layer in the unexposed area is removed and the hydrophilic surface of support is revealed therewith to form the dampening water-receptive area so that the printing can be carried out.

0309The on-machine development method is described in more detail below.

0310As the light source used for the image exposure in the invention, a laser is preferable. The laser for use in the invention is not particularly restricted and includes, for example, a solid laser or semiconductor laser emitting an infrared ray having a wavelength of 760 to 1,200 nm.

0311With respect to the infrared ray laser, the output is preferably 100 mW or more, the exposure time per pixel is preferably within 20 microseconds, and the irradiation energy is preferably from 10 to 300 mJ/cm². With respect to the laser exposure, in order to shorten the exposure time, it is preferred to use a multibeam laser device.

0312The exposed lithographic printing plate precursor is mounted on a plate cylinder of a printing machine. In case of using a printing machine equipped with a laser exposure apparatus, the lithographic printing plate precursor is mounted on a plate cylinder of the printing machine and then subjected to the imagewise exposure.

0313After the imagewise exposure of the lithographic printing plate precursor by a laser, when dampening water and printing ink are supplied to perform printing without undergoing a development processing step, for example, a wet development processing step, in the exposed area of the image-recording layer, the image-recording layer cured by the exposure forms the printing ink receptive area having the oleophilic surface. On the other hand, in the unexposed area, the uncured image-recording layer is removed by dissolution or dispersion with the dampening water and/or printing ink supplied to reveal the hydrophilic surface in the area. As a result, the dampening water adheres on the revealed hydrophilic surface and the printing ink adheres to the exposed area of the image-recording layer, whereby printing is initiated.

0314While either the dampening water or printing ink may be supplied at first on the surface of lithographic printing plate precursor, it is preferred to supply the printing ink at first in view of preventing the dampening water from contamination with the component of the image-recording layer removed. For the dampening water and printing ink, dampening water and printing ink for conventional lithographic printing are used respectively.

0315Thus, the lithographic printing plate precursor is subjected to the on-machine development on an offset printing machine and used as it is for printing a large number of sheets.

(Gum development method)

0316After the imagewise exposure, the exposed lithographic printing plate precursor may be subjected to removal (development) of the image-recording layer in the unexposed area using a gum solution. After that, the resulting lithographic printing plate is used for printing. The term "gum solution" as used in the invention means an aqueous solution containing a hydrophilic resin. The incorporation of hydrophilic resin makes it possible to protect the hydrophilic support revealed by the removal of the image-recording layer in the unexposed area and to protect the image area.

0317In the gum solution, gum arabic which has a strong oil-desensitizing function is ordinarily used and an aqueous solution containing from about 15 to about 20% by weight of gum arabic is often used as the gum solution. Various water-soluble resins are used as the oil-desensitizing agent other than the gum arabic. For instance, dextrin, sterabic, stractan, alginic acid salt, polyacrylic acid salt, hydroxyethyl cellulose, polyvinyl pyrrolidone, polyacrylamide, methyl cellulose, hydroxypropyl cellulose, hydroxymethyl cellulose, carboxyalkyl cellulose salt and water-soluble polysaccharide extracted from soybean curd refuse are preferable, and pullulan, a derivative thereof and polyvinyl alcohol are also preferable.

0318Further, as a modified starch derivative, roast starch, for example, British gum, an enzymatically modified starch, for example, enzyme dextrin or Shardinger dextrin, oxidized starch, for example, solubilized starch, alphalized starch, for example, modified alphalized starch or unmodified alphalized starch, esterified starch, for example, starch phosphate, starch of fatty acid, starch sulfate, starch nitrate, starch xanthate or starch carbamate, etherified starch, for example, carboxyalkyl starch, hydroxyalkyl starch, sulfoalkyl starch, cyanoethyl starch, allyl starch, benzyl starch, carbamylethyl starch or dialkylamino starch, cross-linked starch, for example, methylol cross-linked starch, hydroxyalkyl cross-linked starch, phosphoric acid cross-linked starch or dicarboxylic acid cross-linked starch, or starch graft copolymer, for example, starch-polyacrylamide copolymer, starch-polyacrylic acid copolymer, starch-polyvinyl acetate copolymer, starch-polyacrylonitrile copolymer, cationic starch-polyacrylate copolymer, cationic starch-polyvinyl copolymer, starch-polystyrene-maleic acid copolymer, starch-polyethylene oxide copolymer or starch-polypropylene copolymer is preferably used.

0319Also, as a natural polymer compound, starch, for example, sweet potato starch, potato starch, tapioca starch, wheat starch or corn starch, a polymer obtained from seaweed, for example, carrageenan, laminaran, seaweed mannan, funori, Irish moss, agar or sodium alginate, plant mucilage, for example, of tororoaoi, mannan, quince seed, pectin, tragacanth gum, karaya gum, xanthine gum, guar bean gum, locust bean gum, carob gum or benzoin gum, bacteria mucilage, for example, of homopolysaccharide, e.g., dextran, glucan or levan or of heteropolysaccharide, e.g., succinoglucan or xanthan gum, or protein, for example, glue, gelatin, casein or collagen is preferably used.

0320Two or more of the water-soluble resins may be used in combination. The water-soluble resin may be preferably contained in a range of 1 to 50% by weight, more preferably in a range of 3 to 30% by weight in the gum solution.

0321The gum solution for use in the invention may contain, for example, a pH adjusting agent, a surfactant, an antiseptic agent, an antimold, an oleophilic substance, a wetting agent, a chelating agent or a defoaming agent, in addition to the oil-desensitizing agent described above.

0322The gum solution is advantageously used in a pH range of 3 to 12 and thus, a pH adjusting agent is ordinarily added to the gum solution. In order to adjust the pH of gum solution to a neutral or acidic condition, a mineral acid, an organic acid, an inorganic salt or the like is ordinarily added thereto. The amount thereof is from 0.01 to 2 % by weight. Examples of the mineral acid include nitric acid, sulfuric acid, phosphoric acid and metaphosphoric acid. Examples of the organic acid include acetic acid, oxalic acid, malonic acid, p-toluenesulfonic acid, levulinic acid, phytic acid, an organic phosphonic acid and an amino acid, for example, glycine, α-alanine, β-alanine. Examples of the inorganic salt include magnesium nitrate, sodium dihydrogen phosphate, disodium hydrogen phosphate, nickel sulfate, sodium hexametaphosphate or sodium tripolyphosphate. The mineral acid, organic acid, inorganic salt or the like may be used individually or in combination of two or more thereof.

0323Examples of the surfactant for use in the gum solution according to the invention include an anionic surfactant, a cationic surfactant, an amphoteric surfactant and a nonionic surfactant. As the anionic surfactant, a fatty acid salt, an abietic acid salt, a hydroxyalkanesulfonic acid salt, an alkanesulfonic acid salt, an α-olefinsulfonic acid salt, a dialkylsulfosuccinic acid salt, an alkyldiphenyl ether disulfonaic acid salt, a straight-chain alkylbenzenesulfonic acid salt, a branched alkylbenzenesulfonic acid salt, an alkylnaphthalenesulfonic acid salt, an alkylphenoxypolyoxyethylenepropylsulfonic acid salt, a polyoxyethylene alkyl sulfophenyl ether salt, N-methyl-N-oleyltaurin sodium salt, an N-alkylsulfosuccinic monoamide disodium salt, a petroleum sulfonic acid salt, sulfated caster oil, sulfated beef-tallow oil, a sulfuric eater salt of fatty acid alkyl ester, an alkylsulfuric acid ester salt, a polyoxyethylene alkyl ether sulfuric acid ester salt, a fatty acid monoglyceride sulfuric acid ester salt, a polyoxyethylene alkyl phenyl ether sulfuric acid ester salt, a polyoxyethylene styryl phenyl ether sulfuric acid ester salt, an alkylphosphoric acid ester salt, a polyoxyethylene alkyl ether phosphoric acid ester salt, a polyoxyethylene alkyl phenyl ether phosphoric acid ester salt, a partially saponified styrene/maleic anhydride copolymer, a partially saponified olefin/maleic anhydride copolymer and a formaldehyde condensate of naphthalenesulfonic acid salt are exemplified. Among them, a dialkylsulfosuccinic acid salt, alkylsulfuric acid ester salt, alkylnaphthalenesulfonic acid salt and α-olefinsulfonic acid salt are particularly preferably used.

0324As the cationic surfactant, an alkylamine salt and a quaternary ammonium salt are used.

0325As the amphoteric surfactant, an alkylcarboxy betaine, an alkylimidazoline and an alkylaminocarboxylic acid are used.

0326As the nonionic surfactant, a polyoxyethylene alkyl ether, a polyoxyethylene alkyl phenyl ether, a polyoxyethylene polystyryl phenyl ether, a polyoxyethylene polyoxypropylene alkyl ether, a glycerin fatty acid partial ester, a sorbitan fatty acid partial ester, a pentaerythritol fatty acid partial ester, a propylene glycol monofatty acid ester, a sucrose fatty acid partial ester, a polyoxyethylenesorbitan fatty acid partial esters, polyoxyethylenesorbitol fatty acid partial ester, a polyethylene glycol fatty acid ester, a polyglycerin fatty acid partial ester, a polyoxyethylenized castor oil, a polyoxyethyleneglycerin fatty acid partial ester, a fatty acid diethanolamide, an N,N-bis-2-hydroxyalkylamine, a polyoxyethylene alkylamine, a triethanolamine fatty acid ester, a trialkylamine oxide, polypropylene glycol having molecular weight of 200 to 5,000, trimethylol propane, a polyoxyethylene or polyoxypropylene adduct of glycerine or sorbitol and acetylene glycol are exemplified. Further, a nonionic fluorine-based or silicon-based surfactant is also used.

0327Two or more of the surfactants may be used in combination. The amount of the surfactant used is not particularly restricted and is preferably from 0.01 to 20% by weight, more preferably from 0.05 to 10% by weight, based on the total weight of the gum solution.

0328As the antiseptic agent, known antiseptic agents used in the fields, for example, of fiber, wood processing, food, medicine, cosmetic and agriculture can be employed. Known antiseptic agents, for example, a quaternary ammonium salt, a monovalent phenol derivative, a divalent phenol derivative, a polyvalent phenol derivative, an imidazole derivative, a pyrazolopyrimidine derivative, a monovalent naphthol, a carbonate, a sulfone derivative, an organic tin compound, a cyclopentane derivative, a phenyl derivative, a phenol ether derivative, a phenol ester derivative, a hydroxylamine derivative, a nitrile derivative, a naphthaline, a pyrrole derivative, a quinoline derivative, a benzothiazole derivative, a secondary amine, a 1,3,5-triazine derivative, a thiadiazole derivative, an anilide derivative, a pyrrole derivative, a halogen derivative, a dihydric alcohol derivative, a dithiol, a cyanic acid derivative, a thiocarbamide derivative, a diamine derivative, an isothiazole derivative, a monohydric alcohol, a saturated aldehyde, an unsaturated monocarboxylic acid, a saturated ether, an unsaturated ether, a lactone, an amino acid derivative, hydantoin, a cyanuric acid derivative, a guanidine derivative, a pyridine derivative, a saturated monocarboxylic acid, a benzenecarboxylic acid derivative, a hydroxycarboxylic acid derivative, biphenyl, a hydroxamic acid derivative, an aromatic alcohol, a halogenophenol derivative, a benzenecarboxylic acid derivative, a mercaptocarboxylic acid derivative, a quaternary ammonium salt derivative, a triphenylmethane derivative, hinokitiol, a furan derivative, a benzofuran derivative, an acridine derivative, an isoquinoline derivative, an arsine derivative, a thiocarbamic acid derivative, a phosphoric acid ester, a halogenobenzene derivative, a quinone derivative, a benzenesulfonic acid derivative, a monoamine derivative, an organic phosphoric acid ester, a piperazine derivative, a phenazine derivative, a pyrimidine derivative, a thiophanate derivative, an imidazoline derivative, an isoxazole derivative or an ammonium salt derivative can be used. Particularly preferable examples of the antiseptic agent include salt of pyridinethiol-1-oxide, salicylic acid and a salt thereof, 1,3,5-trishydroxyethylhexahydro-S-triazine, 1,3,5-trishydroxymethylhexahydro-S-triazine, 1,2-benzisothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one and 2-bromo-2-nitro-1,3-propanediol. The amount of the antiseptic agent preferably added is determined so as for the antiseptic agent to work in a stable and effective manner against a bacterium, mold, yeast or the like, and it is preferably from 0.01 to 4% by weight based on the gum solution at the use while it may be varied depending on the kind of bacterium, mold, yeast or the like. It is also preferred to use two or more kinds of antiseptic agents in order to effectively work against various kinds of molds and bacteria.

0329Into the gum solution, the oleophilic substance may be incorporated. Preferable examples of the oleophilic substance include an organic carboxylic acid having from 5 to 25 carbon atoms, for example, oleic acid, lauric acid, valeric acid, nonylic acid, capric acid, myristic acid or palmitic acid and castor oil. The oleophilic substances may be used individually or in combination of two or more thereof. The content of the oleophilic substance in the gum solution is preferably in a range from 0.005 to 10% by weight, more preferably from 0.05 to 5% by weight, based on the total weight of the gum solution.

0330Further, to the gum solution may be added as the wetting agent, glycerin, ethylene glycol, propylene glycol, triethylene glycol, butylenes glycol, hexylene glycol, diethylene glycol, dipropylene glycol, glycerin, trimethylol propane or diglycerin, if desired. The wetting agents may be used individually or in combination of two or more thereof. The wetting agent is preferably used in an amount of 0.1 to 5% by weight.

0331Moreover, the chelating compound may be added to the gum solution. The gum solution is ordinarily marketed as a concentrated solution and is diluted by addition of tap water, well water or the like to use. Calcium ion or the like included in the tap water or well water used for the dilution adversely affects printing and may be apt to cause stain on the printed material. In such a case, the problem can be solved by adding the chelating compound. Preferable examples of the chelating compound include ethylenediaminetetraacetic acid, potassium salt thereof, sodium salt thereof, diethylenetriaminepentaacetic acid, potassium salt thereof, sodium salt thereof, triethylenetetraminehexaacetic acid, potassium salt thereof, sodium salt thereof, hydroxyethylethylenediaminetriacetic acid, potassium salt thereof, sodium salt thereof, nitrilotriacetic acid or sodium salt thereof, and an organic phosphonic acid or a phosphonoalkane tricarboxylic acid, e.g., 1-hydroxyethane-1,1-diphosphonic acid, potassium salt thereof, sodium salt thereof, aminotri(methylenephosphonic acid), potassium salt thereof or sodium salt thereof. An organic amine salt is also effectively used in place of the sodium salt or potassium salt of the above-described chelating compound. The chelating compound which is stably present in the gum solution and does not disturb printing is preferably used. The amount of the chelating compound added is suitably from 0.001 to 1.0% by weight of the gum solution at the use.

0332Furthermore, to the gum solution may be added the defoaming agent. Particularly, a silicon defoaming agent is preferably used. Any silicone defoaming agent of emulsion dispersion type and solubilization type can be used. The amount of the defoaming agent added is optimally in a range of 0.001 to 1.0% by weight of the gum solution at the use.

0333The reminder of the gum solution is water. It is advantageous in view of transportation that the gum solution is stored in the form of a concentrated solution in which the content of water is reduced in comparison with the time of use and the concentrated solution is diluted with water at the use. In such a case, the concentration degree is suitably in a level that each component of the gum solution does not cause separation or deposition. The gum solution may also be prepared as an emulsion dispersion type. In the gum solution of emulsion dispersion type, an organic solvent is used as the oil phase thereof. Also, the gum solution may be in the form of solubilization type (emulsification type) by the aid of the surfactant described above.

0334The organic solvent preferably has solubility in water of 5% by weight or less at 20°C and a boiling point of 160°C or more. The organic solvent includes a plasticizer having a solidification point of 15°C or less and a boiling point of 300°C or more under 1 atmospheric pressure, for instance, a phthalic acid diester, for example, dibutyl phthalate, diheptyl phthalate, di-n-octyl phthalate, di-(2-ethylhexyl) phthalate, dinonyl phthalate, didecyl phthalate, dilauryl phthalate or butyl benzyl phthalate, an aliphatic dibasic acid ester, for example, dioctyl adipate, butyl glycol adipate, dioctyl azelate, dibutyl sebacate, di-(2-ethylhexyl) sebacate or dioctyl sebacate, an epoxidized triglyceride, for example, epoxidized soybean oil, a phosphate, for example, tricresyl phosphate, trioctyl phosphate or trischloroethyl phosphate and a benzoates, for example, benzyl benzoate.

0335Also, as an alcohol type organic solvent, 2-octanol, 2-ethylhexanol, nonanol, n-decanol, undecanol, n-dodecanol, trimethylnonyl alcohol, tetradecanol and benzyl alcohol are exemplified. As a glycol type organic solvent, ethylene glycol isoamyl ether, ethylene glycol monophenyl ether, ethylene glycol benzyl ether, ethylene glycol hexyl ether and octylene glycol are exemplified.

0336In selecting the compound, particularly, odor is taken account of. The amount of the organic solvent used is preferably from 0.1 to 5% by weight, more preferably from 0.5 to 3% by weight, based on the gum solution. The organic solvents may be used individually or in combination of two or more thereof.

0337The gum solution is produced by preparing an aqueous phase while controlling at temperature of 40°C ± 5°C with stirring at a high speed, gradually adding dropwise an oil phase prepared to the aqueous phase, thoroughly stirring and emulsifying and dispersing by passing through a homogenizer of pressure type.

0338In the plate making method according to the invention, a water washing process or a continuous oil-desensitizing process of the non-image area with a gum solution may be appropriately performed after the removing process of the image-recording layer in the non-image area using the gum solution described above.

0339The gum development processing according to the invention can be preferably carried out by an automatic processor equipped with a supplying means for the gum solution and a rubbing member. As the automatic processor, there is illustrated an automatic processor in which a lithographic printing plate precursor after image recording is subjected to a rubbing treatment while it is transporting described, for example, in <patcit id="pcit0205" dnum="JP2006235227A"><text>JP-A-2006-235227</text></patcit>. Particularly, an automatic processor using a rotating brush roll as the rubbing member is preferred.

0340The rotating brush roller which can be preferably used in the invention can be appropriately selected by taking account, for example, of scratch resistance of the image area and nerve strength of a support of the lithographic printing plate precursor.

0341As for the rotating brush roller, a known rotating brush roller produced by implanting a brush material in a plastic or metal roller can be used. For example, a rotating brush roller described in <patcit id="pcit0206" dnum="JP58159533A"><text>JP-A-58-159533</text></patcit> and <patcit id="pcit0207" dnum="JP3100554A"><text>JP-A-3-100554</text></patcit>, or a brush roller described in <patcit id="pcit0208" dnum="JPUMB62167253B"><text>JP-UM-B-62-167253</text></patcit> (the term "JP-UM-B" as used herein means an "examined Japanese utility model publication"), in which a metal or plastic groove-type member having implanted therein in rows a brush material is closely radially wound around a plastic or metal roller acting as a core, can be used.

0342As the brush material, a plastic fiber (for example, a polyester-based synthetic fiber, e.g., polyethylene terephthalate or polybutylene terephthalate; a polyamide-based synthetic fiber, e.g., nylon 6.6 or nylon 6.10; a polyacrylic synthetic fiber, e.g., polyacrylonitrile or polyalkyl (meth)acrylate; and a polyolefin-based synthetic fiber, e.g., polypropylene or polystyrene) can be used. For instance, a brush material having a fiber bristle diameter of 20 to 400 µm and a bristle length of 5 to 30 mm can be preferably used.

0343The outer diameter of the rotating brush roller is preferably from 30 to 200 mm, and the peripheral velocity at the tip of the brush rubbing the plate surface is preferably from 0,1 to 5 m/sec.

0344The rotary direction of the rotating brush roller for use in the invention may be the same direction or the opposite direction with respect to the transporting direction of the lithographic printing plate precursor according to the invention, but when two or more rotating brush rollers are used in an automatic processor as shown in <figref idref="f0001">Fig. 1</figref>, it is preferred that at least one rotating brush roller rotates in the same direction and at least one rotating brush roller rotates in the opposite direction with respect to the transporting direction. By such arrangement, the image-recording layer in the non-image area can be more steadily removed. Further, a technique of rocking the rotating brush roller in the rotation axis direction of the brush roller is also effective.

0345The gum solution in the gum development and water for washing in the post process can be independently used at an appropriate temperature, and is preferably used at temperature of 10 to 50°C.

0346In the gum development method according to the invention, it is possible to provide a drying process at an appropriate position after the gum development. The drying process is ordinarily carried out by blowing dry wind of appropriate temperature after removing most of the processing solution by a roller nip.

EXAMPLES

0347The present invention will be described in more detail with reference to the following examples, but the invention should not be construed as being limited thereto.

<Synthesis method of Specific compound (A-1)>

0348To a solution of 50 g of 1,4-diazabicyclo[2,2,2]octane (produced by Tokyo Chemical Industry Co., Ltd.) in 150 ml of acetonitrile was dropwise added at 0°C a solution of 83.1 g of methyl p-toluenesulfonate (produced by Tokyo Chemical Industry Co., Ltd.) in 30 ml of acetonitrile. After the completion of the dropwise addition, the mixture was stirred at room temperature for one hour and the crystals thus-deposited were collected by filtration. The crystals were washed with 200 ml of acetonitrile and dried to obtain 130 g (yield: 98%) of Specific compound (A-1) according to the invention. The structure identification of the compound was carried out by ¹H-NMR (solvent: DMSO). ¹H-NMR (400 MHz, DMSO-d6): δ 7.52 (d, J=7.0 Hz, 2H), 7.13 (d, J=7.0 Hz, 2H), 3.24 (t, J=7.0 Hz, 6H), 2.99 (t, J=7.0 Hz, 6H), 2.94 (s, 3H), 2.29 (s, 3H).

<Synthesis method of Specific compound (A-2)>

0349To a solution of 50 g of 1,4-diazabicyclo[2,2,2]octane (produced by Tokyo Chemical Industry Co., Ltd.) in 160 ml of acetonitrile was dropwise added at 0°C a solution of 89.3 g of ethyl p-toluenesulfonate (produced by Tokyo Chemical Industry Co., Ltd.) in 30 ml of acetonitrile. After the completion of the dropwise addition, the mixture was stirred at 0°C for 7 hours and then at room temperature for one hour to obtain 135 g (yield: 97%) of Specific compound (A-2) according to the invention. The structure identification of the compound was carried out by ¹H-NMR (solvent: DMSO). ¹H-NMR (400 MHz, DMSO-d6): δ 7.52 (d, J=7.0 Hz, 2H), 7.13 (d, J=7.0 Hz, 2H), 3.24 (t, J=7.0 Hz, 6H), 3.19 (q, J=7.0 Hz, 2H), 2.99 (t, J=7.0 Hz, 6H), 2.29 (s, 3H), 1.18 (t, J=7.0 Hz, 3H).

1. Preparation of Lithographic printing plate precursors (1) to (19)

(1) Preparation of support (No. 1)

0350An aluminum plate (material: JIS A 1050) having a thickness of 0.3 mm was subjected to a degreasing treatment at 50°C for 30 seconds using a 10% by weight aqueous sodium aluminate solution in order to remove rolling oil on the surface thereof and then grained the surface thereof using three nylon brushes embedded with bundles of nylon bristle having a diameter of 0.3 mm and an aqueous suspension (specific gravity: 1.1 g/cm³) of pumice having a median size of 25 µm, followed by thorough washing with water. The plate was subjected to etching by immersing in a 25% by weight aqueous sodium hydroxide solution of 45°C for 9 seconds, washed with water, then immersed in a 20% by weight aqueous nitric acid solution at 60°C for 20 seconds, and washed with water. The etching amount of the grained surface was about 3 g/m².

0351Then, using an alternating current of 60 Hz, an electrochemical roughening treatment was continuously carried out on the plate. The electrolytic solution used was a 1% by weight aqueous nitric acid solution (containing 0.5% by weight of aluminum ion) and the temperature of electrolytic solution was 50°C. The electrochemical roughening treatment was conducted using an alternating current source, which provides a rectangular alternating current having a trapezoidal waveform such that the time TP necessary for the current value to reach the peak from zero was 0.8 msec and the duty ratio was 1:1, and using a carbon electrode as a counter electrode. A ferrite was used as an auxiliary anode. The current density was 30 A/dm² in terms of the peak value of the electric current, and 5% of the electric current flowing from the electric source was divided to the auxiliary anode. The quantity of electricity in the nitric acid electrolysis was 175 C/dm² in terms of the quantity of electricity when the aluminum plate functioned as an anode. The plate was then washed with water by spraying.

0352The plate was further subjected to an electrochemical roughening treatment in the same manner as in the nitric acid electrolysis above using as an electrolytic solution, a 0.5% by weight aqueous hydrochloric acid solution (containing 0.5% by weight of aluminum ion) having temperature of 50°C and under the condition that the quantity of electricity was 50 C/dm² in terms of the quantity of electricity when the aluminum plate functioned as an anode. The plate was then washed with water by spraying. The plate was subjected to an anodizing treatment using as an electrolytic solution, a 15% by weight aqueous sulfuric acid solution (containing 0.5% by weight of aluminum ion) at a current density of 15 A/dm² to form a direct current anodized film of 2.5 g/m², washed with water and dried, thereby preparing Support (1).

0353In order to ensure the hydrophilicity of the non-image area, Support (1) was subjected to silicate treatment using an aqueous 1.5% by weight sodium silicate No. 3 solution at 70°C for 12 seconds. The amount of Si was measured by fluorescent X ray and the adhesion amount of the Si was 6 mg/m². Subsequently, the plate was washed with water to obtain Support (2). The center line average roughness (Ra) of Support (2) was measured using a stylus having a diameter of 2 µm and found to be 0.51 µm.

(2) Formation of intermediate layer

0354Coating solution (1) for intermediate layer shown below was coated on Support (2) so as to have a dry coating amount of 8 mg/m² to form an intermediate layer. <tables id="tabl0002" num="0002"><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="69mm" /><colspec colnum="2" colname="col2" colwidth="27mm" /><thead><row><entry namest="col1" nameend="col2" align="left" valign="top">Coating solution (1) for intermediate layer</entry></row></thead><tbody><row><entry>Polymer (1) for intermediate layer shown below</entry><entry>0.017 g</entry></row><row><entry>Methanol</entry><entry>9.00 g</entry></row><row><entry>Distilled water</entry><entry>1.00 g</entry></row><row><entry>Specific compound shown in Table 1</entry><entry>0.017 g</entry></row></tbody></tgroup></table></tables>

Polymer (1) for intermediate layer:

0355<chemistry id="chem0132" num="0132"><img file="EP2006091A2_D0136.tif" /></chemistry>

(3) Formation of image-recording layer

0356Coating solution (1) for image-recording layer having the composition shown below was coated on the above-described support provided with the intermediate layer shown in Table 1 by a bar and dried in an oven at 100°C for 60 seconds to form an image-recording layer having a dry coating amount of 1.0 g/m².

0357Coating solution (1) for image-recording layer was prepared by mixing Photosensitive solution (1) shown below with Microgel solution (1) shown below just before the coating, followed by stirring. <tables id="tabl0003" num="0003"><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="107mm" /><colspec colnum="2" colname="col2" colwidth="16mm" /><thead><row><entry namest="col1" nameend="col2" align="left" valign="top">Photosensitive solution (1)</entry></row></thead><tbody><row><entry>Binder polymer (1) shown below</entry><entry>0.162 g</entry></row><row><entry>Infrared absorbing agent (1) shown below</entry><entry>0.030 g</entry></row><row><entry>Polymerization initiator (1) shown below</entry><entry>0.162 g</entry></row><row><entry>Polymerizable compound (Aronics M-215, produced by Toagosei Co., Ltd.)</entry><entry>0.385 g</entry></row><row><entry>Pionine A-20 (produced by Takemoto Oil and Fat Co., Ltd.)</entry><entry>0.055 g</entry></row><row><entry>Oil-sensitizing agent (1) shown below</entry><entry>0.044 g</entry></row><row><entry>Fluorine-based surfactant (1) shown below</entry><entry>0.008 g</entry></row><row><entry>Methyl ethyl ketone</entry><entry>1.091 g</entry></row><row><entry>1-Methoxy-2-propanol</entry><entry>8.609 g</entry></row></tbody></tgroup></table></tables><tables id="tabl0004" num="0004"><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="58mm" /><colspec colnum="2" colname="col2" colwidth="16mm" /><thead><row><entry namest="col1" nameend="col2" align="left" valign="top">Microgel solution (1)</entry></row></thead><tbody><row><entry>Microgel (1) prepared as shown below</entry><entry>2.640 g</entry></row><row><entry>Distilled water</entry><entry>2.425 g</entry></row></tbody></tgroup></table></tables>

Infrared absorbing agent (1):

0358<chemistry id="chem0133" num="0133"><img file="EP2006091A2_D0137.tif" /></chemistry>

Binder polymer (1):

0359<chemistry id="chem0134" num="0134"><img file="EP2006091A2_D0138.tif" /></chemistry> Weight average molecular weight: 80,000

Polymerization initiator (1):

0360<chemistry id="chem0135" num="0135"><img file="EP2006091A2_D0139.tif" /></chemistry>

Oil-sensitizing agent (1):

0361<chemistry id="chem0136" num="0136"><img file="EP2006091A2_D0140.tif" /></chemistry>

Fluorine-based surfactant (1):

0362<chemistry id="chem0137" num="0137"><img file="EP2006091A2_D0141.tif" /></chemistry>

(Preparation of Microgel (1))

0363An oil phase component was prepared by dissolving 10 g of adduct of trimethylol propane and xylene diisocyanate (Takenate D-110N, produced by Mitsui Takeda Chemical Co., Ltd.), 3.15 g of pentaerythritol triacrylate (SR444, produced by Nippon Kayaku Co., Ltd.) and 0.1 g of Pionine A-41C (produced by Takemoto Oil and Fat Co., Ltd.) in 17 g of ethyl acetate. As an aqueous phase component, 40 g of a 4% by weight aqueous solution of PVA-205 was prepared. The oil phase component and the aqueous phase component were mixed and emulsified using a homogenizer at 12,000 rpm for 10 minutes. The resulting emulsion was added to 25 g of distilled water and stirred at room temperature for 30 minutes and then at 50°C for 3 hours. The microgel liquid thus-obtained was diluted using distilled water so as to have the solid concentration of 15% by weight to prepare Microgel (1). The average particle size of the particle in Microgel (1) was 0.2 µm.

(4) Formation of protective layer

0364Coating solution (1) for protective layer having the composition shown below was coated on the image-recording layer described above by a bar and dried in an oven at 120°C for 60 seconds to form a protective layer having a dry coating amount of 0.15 g/m², thereby preparing Lithographic printing plate precursors (1) to (19), respectively.

<Coating solution (1) for protective layer>

0365<tables id="tabl0005" num="0005"><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="153mm" /><colspec colnum="2" colname="col2" colwidth="13mm" /><tbody><row><entry>Dispersion of inorganic stratiform compound (I) prepared as shown below</entry><entry>1.5 g</entry></row><row><entry /><entry /></row><row><entry>Aqueous 6% by weight solution of polyvinyl alcohol (CKS 50, sulfonic acid-modified, saponification degree: 99% by mole or more, polymerization degree: 300, produced by Nippon Synthetic Chemical Industry Co., Ltd.)</entry><entry>0.55 g</entry></row><row><entry /><entry /></row><row><entry>Aqueous 6% by weight solution of polyvinyl alcohol (PVA-405, saponification degree: 81.5 % by mole, polymerization degree: 500, produced by Kuraray Co., Ltd.)</entry><entry>0.03 g</entry></row><row><entry /><entry /></row><row><entry>Aqueous 1% by weight solution of surfactant (Emalex 710, produced by Nihon Emulsion Co., Ltd.</entry><entry>8.60 g</entry></row><row><entry /><entry /></row><row><entry>Ion-exchanged water</entry><entry>6.0 g</entry></row></tbody></tgroup></table></tables>

(Preparation of Dispersion of inorganic stratiform compound (1))

0366To 193.6 g of ion-exchanged water was added 6.4 g of synthetic mica (Somasif ME-100, produced by CO-OP Chemical Co., Ltd.) and the mixture was dispersed using a homogenizer until an average particle size (according to a laser scattering method) became 3 µm to prepare Dispersion of inorganic stratiform compound (1). The aspect ratio of the inorganic particle thus-dispersed was 100 or more.

2. Preparation of Lithographic printing plate precursor (23)

0367Lithographic printing plate precursor (23) for comparison was prepared in the same manner as in the preparation of Lithographic printing plate precursor (1) except for changing Coating solution (1) for intermediate layer to Coating solution (23) for intermediate layer not containing the specific compound according to the invention as shown below. <tables id="tabl0006" num="0006"><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="70mm" /><colspec colnum="2" colname="col2" colwidth="27mm" /><thead><row><entry namest="col1" nameend="col2" align="left" valign="top">Coating solution (23) for intermediate layer</entry></row></thead><tbody><row><entry>Polymer (1) for intermediate layer shown below</entry><entry>0.017 g</entry></row><row><entry>Methanol</entry><entry>9.00 g</entry></row><row><entry>Distilled water</entry><entry>1.00 g</entry></row></tbody></tgroup></table></tables>

2. Preparation of Lithographic printing plate precursor (24)

0368Lithographic printing plate precursor (24) for comparison was prepared in the same manner as in the preparation of Lithographic printing plate precursor (1) except for not providing the intermediate layer described in the preparation of Lithographic printing plate precursor (1).

2. Preparation of Lithographic printing plate precursor (20)

0369Lithographic printing plate precursor (20) was prepared in the same manner as in the preparation of Lithographic printing plate precursor (1) except that Coating solution (23) for intermediate layer used in the preparation of Lithographic printing plate precursor (23) was coated on Support (2) and that the coating solution prepared by further adding 0.017 g of Specific compound (A-1) to Coating solution (1) for image-recording layer was used.

5. Preparation of Lithographic printing plate precursor (21)

(1) Formation of image-recording layer

0370The image-recording layer was formed in the same manner as in the preparation of Lithographic printing plate precursor (1) except for using Coating solution (21) for image-recording layer shown below in place of Coating solution (1) for image-recording layer. <tables id="tabl0007" num="0007"><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="138mm" /><colspec colnum="2" colname="col2" colwidth="22mm" /><thead><row><entry namest="col1" nameend="col2" align="left" valign="top">Coating solution (21) for image-recording layer</entry></row></thead><tbody><row><entry>Aqueous dispersion of polymer fine particle (hydrophobilizing precursor) prepared as shown below</entry><entry>33.0 g</entry></row><row><entry>Infrared absorbing agent (3) shown below</entry><entry>1.0 g</entry></row><row><entry>Pentaerythritol tetraacrylate</entry><entry>0.5 g</entry></row><row><entry>Disodium 1,5-naphthalenedisulfonate</entry><entry>0.1 g</entry></row><row><entry>Methanol</entry><entry>16.0 g</entry></row></tbody></tgroup></table></tables>

Infrared absorbing agent (3):

0371<chemistry id="chem0138" num="0138"><img file="EP2006091A2_D0142.tif" /></chemistry>

(Preparation of Aqueous dispersion of polymer fine particle (hydrophobilizing precursor))

0372A stirrer, a thermometer, a dropping funnel, a nitrogen inlet tube and a reflux condenser were attached to a 1,000 ml four-neck flask and while carrying out deoxygenation by introduction of nitrogen gas, 350 ml of distilled water was charged thereto and heated until the internal temperature reached 80°C. To the flask was added 1.5 g of sodium dodecylsufate as a dispersing agent, then was added 0.45 g of ammonium persulfate as an initiator, and thereafter was dropwise added a mixture of 45.0 g of glycidyl methacrylate and 45.0 g of styrene through the dropping funnel over a period of about one hour. After the completion of the dropwise addition, the mixture was continued to react as it was for 5 hours, followed by removing the unreacted monomers by steam distillation. The mixture was cooled, adjusted the pH to 6 with aqueous ammonia and finally added pure water thereto so as to have the nonvolatile content of 15% by weight to obtain an aqueous dispersion of polymer fine particle (hydrophobilizing precursor). The particle size distribution of the polymer fine particle had the maximum value at the particle size of 60 nm.

0373The particle size distribution was determined by taking an electron microphotograph of the polymer fine particle, measuring particle sizes of 5,000 fine particles in total on the photograph, and dividing a range from the largest value of the particle size measured to 0 on a logarithmic scale into 50 parts to obtain occurrence frequency of each particle size by plotting. With respect to the aspherical particle, a particle size of a spherical particle having a particle area equivalent to the particle area of the aspherical particle on the photograph was defined as the particle size.

(2) Formation of protective layer

0374Coating solution (2) for protective layer shown below was coated on the image-recording layer thus-prepared by a bar and dried in an oven at 60°C for 120 seconds to form a protective layer having a dry coating amount of 0.3 g/m², thereby preparing Lithographic printing plate precursor (21). <tables id="tabl0008" num="0008"><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="98mm" /><colspec colnum="2" colname="col2" colwidth="22mm" /><thead><row><entry namest="col1" nameend="col2" align="left" valign="top">Coating solution (2) for protective layer</entry></row></thead><tbody><row><entry>Carboxymethyl cellulose (weight average molecular weight: 20,000)</entry><entry>5.0 g</entry></row><row><entry>Water</entry><entry>50.0 g</entry></row></tbody></tgroup></table></tables>

6. Preparation of Lithographic printing plate precursor (22)

(1) Preparation of Support (No. 2)

0375In order to ensure the hydrophilicity of the non-image area, Support (1) described above was subjected to immersion in a treatment bath containing an aqueous 1% by weight polyvinyl sulfonic acid solution having temperature of 50°C for 10 seconds to prepare Support (3). The center line average roughness (Ra) of Support (3) was measured using a stylus having a diameter of 2 µm and found to be 0.51 µm.

0376Coating solution (1) for intermediate layer containing Specific compound (A-1) was coated on Support (3) so as to have a dry coating amount of 8 mg/m² to prepare Support B.

0377Lithographic printing plate precursor (22) was prepared in the same manner as in the preparation of Lithographic printing plate precursor (1) except for using Support (3) in place of Support (2).

7. Evaluation (1) of lithographic printing plate precursor: On-machine development

EXAMPLES 1 TO 22 AND COMPARATIVE EXAMPLES 1 TO 2

0378Each of Lithographic printing plate precursors (1) to (24) thus-obtained was exposed by Luxel Platesetter T-6000III equipped with an infrared semiconductor laser, produced by Fuji Film Co., Ltd. under the conditions of a rotational number of outer surface drum of 1,000 rpm, a laser output of 70% and a resolution of 2,400 dpi. The exposed image contained a solid image and a 50% halftone dot chart of a 20 µm-dot FM screen.

0379The exposed lithographic printing plate precursor was mounted without conducting development processing on a plate cylinder of a printing machine (Lithrone 26, produced by Komori Corp.). Using dampening water (Ecolity-2 (produced by Fuji Film Co., Ltd.)/tap water = 2/98 (volume ratio)) and Values-G (N) Black Ink (produced by Dainippon Ink &amp; Chemicals, Inc.), the dampening water and ink were supplied according to the standard automatic printing start method of Lithrone 26 to conduct on-machine development and printing on 100 sheets of Tokubishi art paper (76.5 kg) was conducted at a printing speed of 10,000 sheets per hour.

(A) On-machine development property

0380A number of the printing papers required until the on-machine development of the unexposed area of the image-recording layer on the printing machine was completed to reach a state where the ink was not transferred to the printing paper in the non-image area was measured to evaluate the on-machine development property. The results obtained are shown in Table 1 below.

(B) Printing durability

0381After the printing for evaluation of the on-machine development property, the printing was continued. As the increase in a number of printing papers, the image-recording layer was gradually abraded to cause decrease in the ink density on the printing paper. A number of printing papers wherein a value obtained by measuring a halftone dot area rate of a 50% halftone dot of FM screen on the printing paper using a Gretag densitometer decreased by 5% from the value measured on the 100^th paper of the printing was determined to evaluate the printing durability. The results obtained are shown in Table 1 below.

(C) Staining property

0382Each of the lithographic printing plate precursors thus-obtained was allowed to stand in a constant temperature and humidity chamber set at temperature of 60°C and relative humidity of 75% for 2 days. Then, the lithographic printing plate precursor was subjected to the exposure and printing in the same manner as described above and the number of spot-like stains occurred in the non-image area was visually counted using a loupe with 5-fold magnification. The results obtained are shown in Table I below. <tables id="tabl0009" num="0009"><table frame="all"><title><u style="single">TABLE 1</u></title><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="39mm" /><colspec colnum="2" colname="col2" colwidth="33mm" /><colspec colnum="3" colname="col3" colwidth="39mm" /><colspec colnum="4" colname="col4" colwidth="41mm" /><colspec colnum="5" colname="col5" colwidth="29mm" /><colspec colnum="6" colname="col6" colwidth="30mm" /><thead><row><entry valign="top" /><entry valign="top">Lithographic Printing Plate Precursor</entry><entry valign="top">Specific Compound Used</entry><entry valign="top">On-machine Development Property (sheets)</entry><entry valign="top">Printing Durability (x 10³ sheets)</entry><entry valign="top">Staining Property (number/100 cm²)</entry></row></thead><tbody><row><entry>Example 1</entry><entry>(1)</entry><entry>A-1</entry><entry>21</entry><entry>50</entry><entry>Less than 5</entry></row><row><entry>Example 2</entry><entry>(2)</entry><entry>A-2</entry><entry>22</entry><entry>50</entry><entry>Less than 5</entry></row><row><entry>Example 3</entry><entry>(3)</entry><entry>A-3</entry><entry>19</entry><entry>50</entry><entry>13</entry></row><row><entry>Example 4</entry><entry>(4)</entry><entry>A-4</entry><entry>20</entry><entry>50</entry><entry>20</entry></row><row><entry>Example 5</entry><entry>(5)</entry><entry>A-5</entry><entry>18</entry><entry>50</entry><entry>20</entry></row><row><entry>Example 6</entry><entry>(6)</entry><entry>A-9</entry><entry>18</entry><entry>50</entry><entry>20</entry></row><row><entry>Example 7</entry><entry>(7)</entry><entry>A-12</entry><entry>20</entry><entry>50</entry><entry>Less than 5</entry></row><row><entry>Example 8</entry><entry>(8)</entry><entry>A-15</entry><entry>21</entry><entry>50</entry><entry>Less than 5</entry></row><row><entry>Example 9</entry><entry>(9)</entry><entry>A-21</entry><entry>21</entry><entry>50</entry><entry>20</entry></row><row><entry>Example 10</entry><entry>(10)</entry><entry>A-25</entry><entry>22</entry><entry>50</entry><entry>20</entry></row><row><entry>Example 11</entry><entry>(11)</entry><entry>A-26</entry><entry>20</entry><entry>50</entry><entry>20</entry></row><row><entry>Example 12</entry><entry>(12)</entry><entry>A-29</entry><entry>22</entry><entry>50</entry><entry>30</entry></row><row><entry>Example 13</entry><entry>(13)</entry><entry>A-32</entry><entry>21</entry><entry>50</entry><entry>20</entry></row><row><entry>Example 14</entry><entry>(14)</entry><entry>A-33</entry><entry>20</entry><entry>50</entry><entry>30</entry></row><row><entry>Example 15</entry><entry>(15)</entry><entry>A-40</entry><entry>21</entry><entry>50</entry><entry>30</entry></row><row><entry>Example 16</entry><entry>(16)</entry><entry>A-56</entry><entry>21</entry><entry>50</entry><entry>10</entry></row><row><entry>Example 17</entry><entry>(17)</entry><entry>A-62</entry><entry>21</entry><entry>50</entry><entry>10</entry></row><row><entry>Example 18</entry><entry>(18)</entry><entry>A-63</entry><entry>18</entry><entry>50</entry><entry>10</entry></row><row><entry>Example 19</entry><entry>(19)</entry><entry>A-65</entry><entry>18</entry><entry>50</entry><entry>10</entry></row><row><entry>Example 20</entry><entry>(20)</entry><entry>A-1</entry><entry>21</entry><entry>50</entry><entry>10</entry></row><row><entry>Example 21</entry><entry>(21)</entry><entry>A-1</entry><entry>22</entry><entry>50</entry><entry>30</entry></row><row><entry>Example 22</entry><entry>(22)</entry><entry>A-1</entry><entry>24</entry><entry>50</entry><entry>30</entry></row><row><entry>Comparative Example 1</entry><entry>(23)</entry><entry>-</entry><entry>30</entry><entry>50</entry><entry>80</entry></row><row><entry>Comparative Example 2</entry><entry>(24)</entry><entry>-</entry><entry>100 or more</entry><entry>60</entry><entry>300</entry></row></tbody></tgroup></table></tables>

0383As is apparent from the results shown in Table 1, the lithographic printing plate precursor excellent in the on-machine development property and printing durability and improved in the staining property can be provided according to the invention.

8. Evaluation (2) of lithographic printing plate precursor: Gum development (1)

EXAMPLES 23 TO 44 AND COMPARATIVE EXAMPLES 3 TO 4

0384Each of Lithographic printing plate precursors (1) to (24) was exposed and subjected to gum development and printing evaluation as shown below. (A) Reproducibility of fine line (Developing property)

0385Using Trendsetter 3244VX, produced by Creo Co., equipped with an infrared semiconductor laser, each of the lithographic printing plate precursors was imagewise exposed under the conditions of an output of 6.4 W, a rotational number of outer surface drum of 150 rpm and resolution of 2,400 dpi. The exposed image contained a solid image and a fine line image.

0386The exposed lithographic printing plate precursor was subjected to development and oil-desensitizing treatment in one step using an automatic development apparatus having a structure shown in <figref idref="f0001">Fig. 1</figref>. Gum solution 1 having the composition shown below was used. <tables id="tabl0010" num="0010"><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78mm" /><colspec colnum="2" colname="col2" colwidth="15mm" /><thead><row><entry namest="col1" nameend="col2" align="left" valign="top"><Gum solution 1></entry></row></thead><tbody><row><entry>Gum arabic</entry><entry>1.6 %</entry></row><row><entry>Enzyme-modified potato starch</entry><entry>8.8 %</entry></row><row><entry>Phosphorylated waxy corn starch</entry><entry>0.80 %</entry></row><row><entry>Sodium salt of dioctylsulfosuccinic acid ester</entry><entry>0.10 %</entry></row><row><entry>Citric acid</entry><entry>0.14 %</entry></row><row><entry>α-alanine</entry><entry>0.11 %</entry></row><row><entry>Tetrasodium salt of EDTA</entry><entry>0.10 %</entry></row><row><entry>Disodium salt of dodecyldiphenyl ether disulfonic acid</entry><entry>0.18 %</entry></row><row><entry>Ethylene glycol</entry><entry>0.72 %</entry></row><row><entry>Benzyl alcohol</entry><entry>0.87 %</entry></row><row><entry>Sodium tetrahydroacetate</entry><entry>0.04 %</entry></row><row><entry>Emulsion type silicone defoaming agent</entry><entry>0.01 %</entry></row><row><entry>Water to make</entry><entry>100 %</entry></row></tbody></tgroup></table></tables> pH: 5.0

0387The lithographic printing plate obtained was mounted on a plate cylinder of printing machine (Speedmaster 52, produced by Heidelberg Co.). Using dampening water (IF102 (etching solution, produced by Fuji Film Co., Ltd.)/water = 3/97 (volume ratio)) and Trans-G (N) Black Ink (produced by Dainippon Ink &amp; Chemicals, Inc.), the dampening water and ink were supplied and printing of 100 sheets was conducted at a printing speed of 6,000 sheets per hour.

0388In order to evaluate whether the removal of the unexposed area of the image-recording layer was carried out in accordance with the desired image by the development processing described above, the following method was used. Specifically, of the exposed fine lines (test chart including white fine lines (fine linear unexposed portions in the image area) the width of which was varied from 10 to 50 µm every 2 µm), the limit of the width of fine line capable of being reproduced on a printing paper was determined according to the visual observation of the width of white fine line reproduced on the printing paper. It is indicated that as the value becomes small, finer line can be well developed and more preferable result is obtained. The results obtained are shown in Table 2 below.

(B) Printing durability

0389After the printing for evaluation of the reproducibility of fine line, the printing was continued and the printing durability was evaluated in the same manner as in the lithographic printing plate obtained by the on-machine development described above. The results obtained are shown in Table 2 below. (C) Staining property

0390Each of the lithographic printing plate precursors was allowed to stand in a constant temperature and humidity chamber set at temperature of 60°C and relative humidity of 75% for 2 days in the same as in Example 1. Then, the lithographic printing plate precursor was subjected to the exposure, plate making by the gum development and printing in the same manner as in the evaluation of the reproducibility of fine line described above and the number of spot-like stains occurred in the non-image area was visually counted using a loupe with 5-fold magnification. The results obtained are shown in Table 2 below. <tables id="tabl0011" num="0011"><table frame="all"><title><u style="single">TABLE 2</u></title><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="23mm" /><colspec colnum="2" colname="col2" colwidth="33mm" /><colspec colnum="3" colname="col3" colwidth="39mm" /><colspec colnum="4" colname="col4" colwidth="27mm" /><colspec colnum="5" colname="col5" colwidth="21mm" /><colspec colnum="6" colname="col6" colwidth="23mm" /><thead><row><entry valign="top" /><entry valign="top">Lithographic Printing Plate Precursor</entry><entry valign="top">Specific Compound Used</entry><entry valign="top">Gum Development Property (Reproducibility of fine line) (µm)</entry><entry valign="top">Printing Durability (x 10³ sheets)</entry><entry valign="top">Staining Property (number/100 cm²)</entry></row></thead><tbody><row><entry>Example 23</entry><entry>(1)</entry><entry>A-1</entry><entry>16</entry><entry>45</entry><entry>Less than 5</entry></row><row><entry>Example 24</entry><entry>(2)</entry><entry>A-2</entry><entry>20</entry><entry>45</entry><entry>Less than 5</entry></row><row><entry>Example 25</entry><entry>(3)</entry><entry>A-3</entry><entry>16</entry><entry>45</entry><entry>10</entry></row><row><entry>Example 26</entry><entry>(4)</entry><entry>A-4</entry><entry>16</entry><entry>45</entry><entry>15</entry></row><row><entry>Example 27</entry><entry>(5)</entry><entry>A-5</entry><entry>16</entry><entry>45</entry><entry>15</entry></row><row><entry>Example 28</entry><entry>(6)</entry><entry>A-9</entry><entry>20</entry><entry>45</entry><entry>15</entry></row><row><entry>Example 29</entry><entry>(7)</entry><entry>A-12</entry><entry>16</entry><entry>45</entry><entry>Less than 5</entry></row><row><entry>Example 30</entry><entry>(8)</entry><entry>A-15</entry><entry>20</entry><entry>45</entry><entry>Less than 5</entry></row><row><entry>Example 31</entry><entry>(9)</entry><entry>A-21</entry><entry>20</entry><entry>45</entry><entry>15</entry></row><row><entry>Example 32</entry><entry>(10)</entry><entry>A-25</entry><entry>20</entry><entry>45</entry><entry>15</entry></row><row><entry>Example 33</entry><entry>(11)</entry><entry>A-26</entry><entry>20</entry><entry>45</entry><entry>15</entry></row><row><entry>Example 34</entry><entry>(12)</entry><entry>A-29</entry><entry>20</entry><entry>45</entry><entry>20</entry></row><row><entry>Example 35</entry><entry>(13)</entry><entry>A-32</entry><entry>20</entry><entry>45</entry><entry>15</entry></row><row><entry>Example 36</entry><entry>(14)</entry><entry>A-33</entry><entry>16</entry><entry>45</entry><entry>20</entry></row><row><entry>Example 37</entry><entry>(15)</entry><entry>A-40</entry><entry>20</entry><entry>45</entry><entry>20</entry></row><row><entry>Example 38</entry><entry>(16)</entry><entry>A-56</entry><entry>16</entry><entry>45</entry><entry>Less than 5</entry></row><row><entry>Example 39</entry><entry>(17)</entry><entry>A-62</entry><entry>20</entry><entry>45</entry><entry>Less than 5</entry></row><row><entry>Example 40</entry><entry>(18)</entry><entry>A-63</entry><entry>16</entry><entry>45</entry><entry>Less than 5</entry></row><row><entry>Example 41</entry><entry>(19)</entry><entry>A-65</entry><entry>16</entry><entry>45</entry><entry>Less than 5</entry></row><row><entry>Example 42</entry><entry>(20)</entry><entry>A-1</entry><entry>16</entry><entry>45</entry><entry>Less than 5</entry></row><row><entry>Example 43</entry><entry>(21)</entry><entry>A-1</entry><entry>20</entry><entry>45</entry><entry>20</entry></row><row><entry>Example 44</entry><entry>(22)</entry><entry>A-1</entry><entry>20</entry><entry>45</entry><entry>20</entry></row><row><entry>Comparative Example 3</entry><entry>(23)</entry><entry>-</entry><entry>40</entry><entry>45</entry><entry>50</entry></row><row><entry>Comparative Example 4</entry><entry>(24)</entry><entry>-</entry><entry>50</entry><entry>60</entry><entry>200</entry></row></tbody></tgroup></table></tables>

9. Evaluation (3) of lithographic printing plate precursor: Gum development (2)

EXAMPLES 45 TO 66 AND COMPARATIVE EXAMPLES 5 TO 6

0391The processing solution used in the developing unit was changed from Gum solution 1 to week alkaline Gum solution 2 having pH of 9.7 prepared by adding sodium hydroxide to Gum solution 1. Each of Lithographic printing plate precursors (1) to (24) was subjected to the plate making and the evaluations of reproducibility of fine line (developing property), printing durability and staining property in the same manner as in Examples 23 to 44. The results obtained are shown in Table 3 below. <tables id="tabl0012" num="0012"><table frame="all"><title><u style="single">TABLE 3</u></title><tgroup cols="6"><colspec colnum="1" colname="col1" colwidth="23mm" /><colspec colnum="2" colname="col2" colwidth="33mm" /><colspec colnum="3" colname="col3" colwidth="39mm" /><colspec colnum="4" colname="col4" colwidth="27mm" /><colspec colnum="5" colname="col5" colwidth="21mm" /><colspec colnum="6" colname="col6" colwidth="23mm" /><thead><row><entry valign="top" /><entry valign="top">Lithographic Printing Plate Precursor</entry><entry valign="top">Specific Compound Used</entry><entry valign="top">Gum Development Property (Reproducibility of fine line) (µm)</entry><entry valign="top">Printing Durability (x 10³ sheets)</entry><entry valign="top">Staining Property (number/100 cm²)</entry></row></thead><tbody><row><entry>Example 45</entry><entry>(1)</entry><entry>A-1</entry><entry>16</entry><entry>45</entry><entry>Less than 5</entry></row><row><entry>Example 46</entry><entry>(2)</entry><entry>A-2</entry><entry>18</entry><entry>45</entry><entry>Less than 5</entry></row><row><entry>Example 47</entry><entry>(3)</entry><entry>A-3</entry><entry>14</entry><entry>45</entry><entry>10</entry></row><row><entry>Example 48</entry><entry>(4)</entry><entry>A-4</entry><entry>14</entry><entry>45</entry><entry>10</entry></row><row><entry>Example 49</entry><entry>(5)</entry><entry>A-5</entry><entry>14</entry><entry>45</entry><entry>10</entry></row><row><entry>Example 50</entry><entry>(6)</entry><entry>A-9</entry><entry>18</entry><entry>45</entry><entry>10</entry></row><row><entry>Example 51</entry><entry>(7)</entry><entry>A-12</entry><entry>14</entry><entry>45</entry><entry>Less than 5</entry></row><row><entry>Example 52</entry><entry>(8)</entry><entry>A-15</entry><entry>18</entry><entry>45</entry><entry>Less than 5</entry></row><row><entry>Example 53</entry><entry>(9)</entry><entry>A-21</entry><entry>18</entry><entry>45</entry><entry>10</entry></row><row><entry>Example 54</entry><entry>(10)</entry><entry>A-25</entry><entry>18</entry><entry>45</entry><entry>10</entry></row><row><entry>Example 55</entry><entry>(11)</entry><entry>A-26</entry><entry>18</entry><entry>45</entry><entry>10</entry></row><row><entry>Example 56</entry><entry>(12)</entry><entry>A-29</entry><entry>18</entry><entry>45</entry><entry>15</entry></row><row><entry>Example 57</entry><entry>(13)</entry><entry>A-32</entry><entry>18</entry><entry>45</entry><entry>10</entry></row><row><entry>Example 58</entry><entry>(14)</entry><entry>A-33</entry><entry>16</entry><entry>45</entry><entry>10</entry></row><row><entry>Example 59</entry><entry>(15)</entry><entry>A-40</entry><entry>18</entry><entry>45</entry><entry>10</entry></row><row><entry>Example 60</entry><entry>(16)</entry><entry>A-56</entry><entry>16</entry><entry>45</entry><entry>Less than 5</entry></row><row><entry>Example 61</entry><entry>(17)</entry><entry>A-62</entry><entry>20</entry><entry>45</entry><entry>Less than 5</entry></row><row><entry>Example 62</entry><entry>(18)</entry><entry>A-63</entry><entry>16</entry><entry>45</entry><entry>Less than 5</entry></row><row><entry>Example 63</entry><entry>(19)</entry><entry>A-65</entry><entry>14</entry><entry>45</entry><entry>Less than 5</entry></row><row><entry>Example 64</entry><entry>(20)</entry><entry>A-1</entry><entry>14</entry><entry>45</entry><entry>Less than 5</entry></row><row><entry>Example 65</entry><entry>(21)</entry><entry>A-1</entry><entry>16</entry><entry>45</entry><entry>10</entry></row><row><entry>Example 66</entry><entry>(22)</entry><entry>A-1</entry><entry>16</entry><entry>45</entry><entry>10</entry></row><row><entry>Comparative Example 5</entry><entry>(23)</entry><entry>-</entry><entry>36</entry><entry>45</entry><entry>30</entry></row><row><entry>Comparative Example 6</entry><entry>(24)</entry><entry>-</entry><entry>50</entry><entry>60</entry><entry>100</entry></row></tbody></tgroup></table></tables>

0392As is apparent from the results shown in Table 3, the lithographic printing plate precursor exhibiting good gum development property (reproducibility of fine line) and printing durability and improved in the staining property can be provided according to the invention.

0393Although the invention has been described above in relation to preferred embodiments and modifications thereof, it will be understood by those skilled in the art that other variations and modifications can be effected in these preferred embodiments without departing from the scope and spirit of the invention.