Oil based ink for electrostatic ink jet

Description: TECHNICAL FIELD [Detailed description of the invention]

【0001】

[Technical field to which the invention belongs]

The present invention relates to an oil-based ink for electrostatic inkjet used for forming an image by an electrostatic (electrostatic attraction type or electrostatic suction type) inkjet recording method.

【0002】

[Conventional technology]

Inkjet recording is a recording method capable of high-speed printing with low noise, and is a recording method that is rapidly becoming widespread in recent years. Inkjet recording is a method of injecting highly fluid liquid ink from a fine nozzle and recording it on recording paper, and there are on-demand (voluntary injection) and continuous (continuous injection) methods. Further, a recording method called an electrostatic method (Sweet type, Hertx type) for the continuous type, a piezo piezoelectric method, a thermal inkjet method, and an electrostatic acceleration type for the on-demand type is known.

【0003】

Susumu Ichinose, Yuji Ohba, IEICE Transactions vol.J66-C (No.1), p47 (1983), Tadayoshi Ohno, Mamoru Mizuguchi, IEICE Journal vol. A method called electrostatic pressure type inkjet or slit jet described in 10, (No. 3), p157 (1981), etc. is known, and specific embodiments thereof are, for example, JP-A-56-170 and JP-A-56-. It is disclosed in No. 4467, No. 57-151374, etc. This is done by supplying ink from the ink tank to the slit-shaped ink chamber in which a large number of electrodes are arranged on the inner surface of the slit-shaped ink holding portion, and by selectively applying a high voltage to these electrodes to form a slit. Ink in the vicinity of the electrodes is ejected onto the recording papers facing each other for recording.

【0004】

Further, as another method that does not use a slit-shaped recording head, Japanese Patent Application Laid-Open No. 61-211048 states that the holes of a film-shaped ink support having a plurality of micropores are filled with ink and selected by a multi-needle electrode. A means of applying a voltage to move the ink in the holes to the recording paper is disclosed.

【0005】

The flying principle of these inks is that the high voltage applied to the arranged electrodes injects an electric charge into the ink in contact with the electrodes, and the ink in the vicinity of the electrodes is charged, so that an electrostatic force is generated and the ink is ejected. It is interpreted as being done. Therefore, the ink is not normally charged, and only when a voltage is applied, the ink in the vicinity of the electrodes is charged by energization to obtain an ejection force. The ink used in these methods is 10⁶From 10⁸Those having an electrical resistance of about ohm cm are used. Since water has low electrical resistance, generally, a colorant composed of a dye is dispersed in an oily solvent with a dispersion aid such as a surfactant to adjust the electrical resistance.

【0006】

Further, as the oil-based ink to be used, a method of controlling its viscosity and specific resistance (Japanese Patent Publication No. 52-13127) and a method of controlling the relative permittivity of the dispersion medium used in the ink and the specific resistance of the ink (Japanese Patent Laid-Open No. 53-29808). No.), a method of changing the type of dispersion medium of oil-based ink or containing a specific compound as an ink composition (Japanese Patent Laid-Open No. 3-79677, JP-A-3-64377, JP-A-4-202386, JP-A-7). -109431) etc. have been proposed. However, these prior art techniques include storage stability of oil-based inks, reproducibility of recorded images during repeated use, ink bleeding resistance on the transferred material, clogging resistance in nozzles and ink supply paths, and ink. Discharge stability and the like are not yet fully satisfactory, and further improvement in performance is desired.

【0007】

On the other hand, another electrostatic suction inkjet technique is disclosed in WO93 / 11866. In this method, an ink in which charged particles or particles exhibiting chargeability under an electric field are dispersed in an insulating liquid is supplied to an ink ejection device, and the tip of the ejection electrode for ejecting the ink under the application of an electric field is used. A series of forming an ink meniscus, electrophoresing and concentrating the particle concentration in the ink meniscus, forming an electric field between the counter electrode on which the recording medium is placed and the ejection electrode, and flying the aggregated particles. Has the process of.

【0008】

Unlike the conventional method, the features of this method, which does not require an ink nozzle structure, are that ink containing dispersed particles such as pigments can be ejected in the size of fine droplets of about several μm, and the droplets to be ejected are concentrated particles. In addition to being able to achieve a high density, the dot size of the image can be changed by changing the droplet size by controlling the ejection signal. Therefore, it is possible to draw an image based on a light-resistant and water-resistant pigment and to form a clear halftone dot gradation image with high resolution and high density.

【0009】

The oil-based ink used has an electrical resistance value of 10.⁹WO95 / 1404 and WO96 / 10058 disclose insoluble and chargeable particles and a charging agent in an insulating liquid of Ω · cm or more. Furthermore, the amount of charge of the charged particles or the average particle size of the particles is specified (Japanese Patent Laid-Open Nos. 9-193389 and 8-291267), or the thermal properties of the dry matter of the ink composition are specified (Japanese Patent Laid-Open No. 9-193389, 8-291267). Japanese Patent Application Laid-Open No. 9-137094) and the like have been proposed.

【0010】

[Problems to be Solved by the Invention]

However, when inkjet recording is performed using these oil-based inks, instability of ink ejection or insufficient concentration of pigment particles in the ink occurs, resulting in missing images, image blurring, or image density. It becomes insufficient (especially the solid image part). Alternatively, when ink that has been stored for a long time is used, the ejection conditions (applied voltage, etc.) fluctuate with the case of using fresh ink, and the concentration and ejection rate changes significantly, and the obtained image is in the ink storage state. If the ink changes or the ink is ejected for a long period of time, ink particles adhere to the ejected portion, causing problems such as ejection abnormality.

【0011】

On the other hand, with the recent development of office equipment and the progress of OA, in the field of light printing, lithographic printing original plates having an image receiving layer on a water-resistant support are made by various methods, that is, image formation is performed to produce a printing plate. The offset lithographic printing method for creating has become widespread, and as one of the plate-making methods, plate-making is also performed by the inkjet method. When a printing plate on which a clear image is formed is actually printed using conventional oil-based ink, the number of printed matter that can obtain a clear printed matter without missing an image portion is limited to about several hundreds at most. It was inadequate. That is, offset printing has a problem that the fixing strength of an image composed of ink particles is insufficient.

【0012】

Therefore, an object of the present invention is to provide an electrostatic inkjet oil-based ink having excellent ink ejection stability, clear image forming property, and image intensity. Another object of the present invention is to provide an oil-based ink for electrostatic inkjet that can form a printing plate that enables printing of a large number of printed matter of a clear image. Another object of the present invention is to provide an oil-based ink for electrostatic inkjet which is excellent in redispersibility and storage stability of dispersed particles, does not clog in the ink supply path, and stabilizes ink ejection.

【0013】

[Means for solving problems]

It was found that the above objectives were achieved by the following configurations. (1) Electrical resistance 10⁹In an oil-based electrostatic ink for inkjet in which at least charged resin particles are dispersed in a non-aqueous carrier liquid having a dielectric constant of Ω · cm or more and a dielectric constant of 3.5 or less, the dispersed resin particles are soluble in a non-aqueous solvent. One end of the main chain of a polymer consisting of at least one of the monofunctional monomer (A) that becomes insoluble by polymerization and a repeating unit having a substituent containing a fluorine atom and / or a silicon atom. The weight average molecular weight is 2 × 10 obtained by bonding the polymerizable double-bonding group represented by the following general formula (MI).⁴Polymerization and granulation of a solution containing at least one of the following monofunctional macromonomers (MM) and at least one of a dispersion stabilizing resin (P) containing at least a component represented by the following general formula (PI). An oil-based ink for electrostatic inkjet, which is a copolymer resin particle obtained by the above.

【0014】

[Chemical 5]

<img file="JP2000336291A_D0001.tif" />【0015】

In equation (MI), J¹Is -COO-, -OCO-,-(CH₂)_dCOO-,-(CH₂)_dOCO-, -O-, -SO₂-, -CONHCOO-, -CONHCONH-, -CON (K)¹)-, -SO₂N (K¹)-Or represents a phenylene group (where K¹Indicates a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, and d indicates an integer of 1 to 4). m¹And m²Can be the same or different from each other, each of which is a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 7 carbon atoms, and -COO-K.², Or via a hydrocarbon group-COO-K²Represents (here K²Indicates a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms).

【0016】

[Chemical 6]

<img file="JP2000336291A_D0002.tif" />【0017】

In general formula (PI), A¹Is -COO-, -OCO-,-(CH₂)_aCOO-,-(CH₂)_aOCO-, -O-, or [0018]

[Chemical 7]

<img file="JP2000336291A_D0003.tif" />【0019】

(Where E stands for mere binding, -O-, -OCO- or -COO-). a represents an integer from 1 to 12. L represents an alkyl group having 8 to 32 carbon atoms or an alkenyl group having 8 to 32 carbon atoms. p¹, P²May be the same or different, and m in equation (MI)¹, M²Represents the same content as.

【0020】

(2) A single amount of the dispersed resin particles containing the amino group represented by the following general formula (II) together with the monofunctional monomer (A) and the monofunctional macromonomer (MM). Copolymerization obtained by coexisting at least one type of monofunctional monomer (B) copolymerizable with the body (A) and having no direct bond between a polymerizable double-bonding group and an amino group and polymerizing and granulating. The oil-based electrostatic ink for electrostatic inkjet according to (1) above, which is a polymer resin particle.

【0021】

[Chemical 8]

<img file="JP2000336291A_D0004.tif" />【0022】

In general formula (II), R¹And R²Can be the same or different, each representing a hydrogen atom or a hydrocarbon group having 1-22 carbon atoms, or R¹And R²May combine to form a ring.

【0023】

(3) The dispersed resin particles, together with the monofunctional monomer (A), the monofunctional macromonomer (MM) and the monofunctional monomer (B), are -PO.₃H₂Group, -SO₃H group and -SO₂Obtained by polymerizing and granulating by coexisting at least one of a copolymerizable monofunctional monomer (C) with a monomer (A) containing at least one acidic group selected from H groups. The oil-based electrostatic ink for electrostatic inkjet according to (1) above, which is a copolymer resin particle.

【0024】

(4) The dispersion-stabilizing resin (P) has the same polymerizable double bond as represented by the general formula (MI) in one end of the polymer main chain or in the substituent of the polymer copolymer component. The oil-based electrostatic ink for electrostatic ink according to (1) above, which is formed by bonding groups.

【0025】

BEST MODE FOR CARRYING OUT THE INVENTION

The oil-based ink for electrostatic inkjet of the present invention will be described below. Electrical resistance used in the present invention 10⁹Non-aqueous carrier liquids having a dielectric constant of Ω · cm or more and a dielectric constant of 3.5 or less are preferably linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and halogen substitutions of these hydrocarbons. Examples include body, silicone liquids or silicone oils.

【0026】

For example, as hydrocarbon solvents, pentane, isopeptane, octane, isooctane, decane, isodecan, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, isoper E, isoper G, Isopar H, Isopar L (Isoper; Exxon's trade name), Shelsol 70, Shelsol 71 (Shelzol; Shell Oil's trade name), Amsco OMS, Amsco 460 Solvent (Amsco; Spirits' trade name), etc. There is.

【0027】

As a halogen-substituted hydrocarbon solvent, there is a fluorocarbon solvent, for example, C.₇F₁₆, C₈F₁₈Such as C_nF_{2n + 2}Perfluorocarbons represented by (Sumitomo 3M's "Fluorinert PF5080", "Florinert PF5070" (trade name), etc.), fluorocarbon-based inert liquids (Sumitomo 3M's "Fluorinert FC series" (trade name), etc.) ), Fluorocarbons ("Clitex GPL series" (trade name) manufactured by DuPont Japan Limited), Freons ("HCFC-141b" (trade name) manufactured by Daikin Industries, Ltd.), [F (CF)₂)₄CH₂CH₂I], [F (CF)₂)₆There are iodinated fluorocarbons such as I] ("I-1420", "I-1600" (trade name), etc. manufactured by Daikin Fine Chemical Research Institute).

【0028】

As the silicon solvent for silicone liquid and silicone oil, dialkylpolysiloxane (for example, hexamethyldisiloxane, tetramethyldisiloxane, octamethyltrisiloxane, hexamethyltrisiloxane, heptamethyltrisiloxane, decamethyltetrasiloxane, trifluoropropyl) Heptamethyltrisiloxane, diethyltetramethyldisiloxane, etc.), Cyclic dialkylpolysiloxane (eg, hexamethylcyclotrisiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetra (trifluoropropyl)) Tetramethylcyclotetrasiloxane, etc.), methylphenyl silicon oil (for example, KF56, KF58 (trade name manufactured by Shinetsu Silicon Co., Ltd.), etc.) and the like can be mentioned.

【0029】

In the present invention, these solvents are used alone or in combination. The upper limit of the electrical resistance of such a non-aqueous carrier liquid is 10.¹⁶It is preferably about Ω · cm, and the lower limit of the dielectric constant is about 1.80.

【0030】

The non-aqueous dispersion resin particles (hereinafter, also referred to as latex particles), which are the most important constituents of the oil-based ink of the present invention, are dispersion-stable containing a specific component (formula (PI)) in a non-aqueous solvent. In the presence of the resin (P), at least one of the monofunctional monomer (A) and the polymerizable double-bonding group represented by the general formula (MI) are bonded to one end of the polymer main chain. It is polymerized and granulated by polymerizing at least one of monofunctional macromonomers (MM).

【0031】

Here, as the non-aqueous solvent, basically any solvent can be used as long as it is mixed with the non-aqueous carrier liquid of the oil-based ink.

【0032】

That is, the solvent used in producing the dispersed resin particles may be any solvent that is mixed with the carrier liquid, and is preferably a linear or branched aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon. And these halogen-substituted products and the like. For example, octane, isooctane, decane, isodecan, decalin, nonane, dodecane, isododecane, isoper E, isoper G, isoper H, isoper L, chelsol 70, chelsol 71, amsco OMS, amsco 460 solvent, etc., alone or in combination. Use [0033]

Solvents that can be mixed and used with these organic solvents include alcohols (eg, ethyl alcohol, propyl alcohol, butyl alcohol, ethylene glycol monomethyl ether, fluoroalcohol, etc.) and ketones (eg, methyl ethyl ketone, acetophenone, cyclohexanone). Etc.), Carous acid esters (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, ethylene glycol monomethyl ether acetate, etc.), ethers (eg, dipropyl ether, ethylene glycol dimethyl ether, etc.) , Tetrahydrofuran, dioxane, etc.), halogenated hydrocarbons (eg, chloroform, dichloroethane, methyl chloroform, etc.) and the like.

【0034】

It is desirable that the organic solvent used by mixing these is distilled off under heating or reduced pressure after polymerization granulation, but even if it is brought into an oil-based ink as a latex particle dispersion, the resistance of the ink is 10.⁹There is no problem as long as the conditions of Ω · cm or more and the dielectric constant of 3.5 or less can be satisfied.

【0035】

Usually, it is preferable to use the same solvent as the carrier liquid at the stage of resin dispersion structure, and as described above, linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenation Hydrocarbons and the like can be mentioned.

【0036】

The monofunctional monomer (A) in the present invention may be any monofunctional monomer that is soluble in a non-aqueous solvent but insolubilized by polymerization. Specifically, for example, a monomer represented by the following general formula (I) can be mentioned.

【0037】

[Chemical 9]

<img file="JP2000336291A_D0005.tif" />【0038】

In general formula (I), V¹Is -COO-, -OCO-, -CH₂OCO-, -CH₂COO-, -O-, -CONHCOO-, -CONHOCO-, -SO₂-, -CON (Q¹)-, -SO₂N (Q¹)-Or phenylene group (Hereinafter, the phenylene group may be referred to as "-Ph-". The phenylene group includes 1,2-, 1,3- and 1,4-phenylene groups). Represents. Q here¹Is a hydrogen atom or an optionally substituted aliphatic group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-Hydroxyethyl group, benzyl group, chlorobenzyl group, methylbenzyl group, methoxybenzyl group, phenethyl group, 3-phenylpropyl group, dimethylbenzyl group, fluorobenzyl group, 2-methoxyethyl group, 3-methoxypropyl group, etc. ).

【0039】

T is a hydrogen atom or an aliphatic group that may be substituted with 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2,2-dichloroethyl group, 2,2). , 2-Trifluoroethyl group, 2-bromoethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 2,3-dihydroxypropyl group, 2-hydroxy-3-chloropropyl group, 2-cyanoethyl group, 3- Cyanopropyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-ethoxyethyl group, trimethoxysilylpropyl group, 3-bromopropyl group, 4-hydroxybutyl group, 2-flufuryl Ethyl group, 2-thienyl ethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2-carboxyamide ethyl group, 2-N-methylcarboxyamide ethyl group, cyclopentyl group, chlorocyclohexyl group , Dichlorohexyl group, etc.).

【0040】

a¹And a²May be the same or different from each other, preferably hydrogen atom, halogen atom (for example, chlorine atom, bromine atom, etc.), cyano group, alkyl group having 1 to 3 carbon atoms (for example, methyl group, ethyl group, propyl group, etc.) ), -COO-Q²Or-CH₂-COO-Q²[Q here²Represents a hydrogen atom or a hydrocarbon group having 10 or less carbon atoms which may be substituted (for example, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, etc.).

【0041】

Specific examples of the monofunctional monomer (A) include vinyl esters or allyl esters of aliphatic carboxylic acids having 1 to 6 carbon atoms (acetic acid, propionic acid, butyric acid, monochloroacetic acid, trifluoropropionic acid, etc.). Classes; Alkyl esters or amides having 1 to 4 carbon atoms of unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, and maleic acid (for example, methyl group and ethyl group as alkyl groups). , Propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 2-fluoroethyl group, trifluoroethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-nitroethyl group, 2-methoxyethyl group, 2 -Methyl sulfonyl ethyl group, 2-benzenesulfonyl ethyl group, 2-carboxyethyl group, 4-carboxybutyl group, 3-chloropropyl group, 2-hydroxy-3-chloropropyl group, 2-furfurylethyl group, 2- Thienylethyl group, 2-carboxyamide ethyl group, etc.); [0042]

Styrene derivatives (eg styrene, vinyl toluene, α-methylstyrene, vinylnaphthalene, chlorostyrene, dichlorostyrene, bromostyrene, vinylbenzenecarboxylic acid, chloromethylstyrene, hydroxymethylstyrene, methoxymethylstyrene, vinylbenzenecarboxyamide, vinyl Styrene sulfoamide, etc.); Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid; cyclic acid anhydrides of maleic acid, itaconic acid; acrylonitrile; methacrylonitrile; polymerizable double-bonding group Containing heterocyclic compounds (specifically, for example, compounds described in "Styrene Data Handbook-Basics-" edited by the Society of Styrene, pp. 175-184, Styrene (1986), for example, N-vinylpyridine, N-vinylimidazole, N-vinylpyrrolidone, vinylthiophene, vinyl tetrahydrofuran, vinyloxazoline, vinylthiazole, N-vinylmorpholine, etc.) and the like. Two or more types of monomer (A) may be used in combination.

【0043】

Next, a monofunctional macromonomer (MM) copolymerizable with the monomer (A) used in the present invention will be described. The monofunctional macromonomer (MM) is represented by the above general formula (MI) only at one end of the polymer main chain containing at least a repeating unit (m) having a substituent containing a fluorine atom and / or a silicon atom. The weight average molecular weight is 2 × 10 which is composed of the polymerizable double-bonding groups bonded together.⁴It is as follows.

【0044】

The substituent containing a fluorine atom and / or a silicon atom in the repeating unit preferably has the following aspects. Examples of the substituent containing a fluorine atom include the following monovalent or divalent organic residues. -C_n(F)_{2n + 1}(n is an integer from 1 to 22), -CFH₂, -CFHCl, -CFCl₂, -CF₂Cl,-(CF₂)_mCF₂H (m is 0 or an integer from 1 to 17), -CF₂-, -CFH-, -CFCl- [0045]

These fluorine atom-containing organic residues may be composed by combining them, in which case they may be directly bonded or may be combined via other linking groups. Specific examples of the linking group include divalent organic residues, and -O-, -S-, and -N (g).¹)-, -CO-, -SO-, -SO₂-, -COO-, -OCO-, -CONHCO-, -NHCONH-, -CON (g)¹)-, -SO₂N (g¹)-An organic residue composed of a divalent aliphatic group or a divalent aromatic group, or a combination of these divalent residues, which may be interposed with a linking group selected from the above. .. Where g¹Represents an alkyl group having 1 to 3 carbon atoms.

【0046】

As the substituent containing a silicon atom, those containing the following siloxane structure (or silyloxy structure) or silyl group are preferable.

【0047】

[Chemical 10]

<img file="JP2000336291A_D0006.tif" />【0048】

In the above structure, R¹¹And R¹²And R¹³, R¹⁴And R¹⁵May be the same or different from each other and represent an aliphatic group, an aromatic group or a heterocyclic group, respectively. R¹¹~ R¹⁵Are each preferably a linear or branched alkyl group having 1 to 18 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, heptyl group, octyl group, nonyl group) which may be substituted. , Decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, 2-fluoroethyl group, trifluoromethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group , 2-Methyl ethyl group, 3-Bromopropyl group, 2-Methylcarbonylethyl group, 2,3-Dimethoxypropyl group, Alkyl fluoride group {For example-(CH₂)_hC_iF_{2i + 1}Group (where h is an integer from 1 to 6 and i is an integer from 1 to 12) Group,-(CH₂)_h-(CF₂)_j-R¹⁶Group (where j is 0 or an integer from 1 to 12, R¹⁶The group is an alkyl group with 1 to 12 carbon atoms, -CF₂H, -CFH₂, -CF₃Represents), -CH (CF)₃)₂, -CF₂Cl, -CFCl₂, -CFClH, -CF (CF)₃) OC_iF_{2i + 1}, -OC_iF_{2i + 1}, -C (CF)₃)₂OC_iF_{2i + 1}etc}, [0049]

Substituent alkenyl groups having 4 to 18 carbon atoms (eg, 2-methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 1-pentenyl group, 1 -Hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, decenyl group, dodecenyl group, tridecenyl group, hexadecenyl group, octadecenyl group, linolell group, etc.), optionally substituted aralkyl with 7 to 12 carbon atoms Groups (eg, benzyl group, phenetyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, Dimethoxybenzyl group, etc.), optionally substituted alicyclic group having 5 to 8 carbon atoms (eg, cyclopentyl group, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, polyfluorohexyl group, methylcyclohexyl group) , Phenylcyclohexyl group, optionally substituted aromatic group with 6-12 carbon atoms (eg, phenyl group, naphthyl group, trill group, xsilyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, Methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, fluorophenyl group, chlorophenyl group, difluorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group , Acetamide phenyl group, propioamide phenyl group, trifluoromethylphenyl group, etc.), or a heterocyclic group (eg, a heterocyclic group containing at least one atom selected from a nitrogen atom, an oxygen atom, and a sulfur atom). Heterocycles include pyran ring, furan ring, thiophene ring, morpholine ring, pyrrole ring, thiazole ring, oxazole ring, pyridine ring, piperidine ring, pyrrolidone ring, benzothiazole ring, benzoxazole ring, quinoline ring, tetrahydrofuran ring, etc.) And so on.

【0050】

Especially preferably, R¹¹And R¹²Substituents of, and R¹³, R¹⁴And R¹⁵Two or more substituents are each composed of an alkyl group or an alkenyl group.

【0051】

A plurality of these fluorine atom-containing substituents and siloxane (or silyloxy) structure-containing substituents may be contained in the molecule of the repeating unit (m). Specific examples of the repeating unit (m) are shown below, but the scope of the present invention is not limited thereto.

【0052】

[Chemical 11]

<img file="JP2000336291A_D0007.tif" />【0053】

[Chemical 12]

<img file="JP2000336291A_D0008.tif" />【0054】

[Chemical 13]

<img file="JP2000336291A_D0009.tif" />【0055】

[Chemical 14]

<img file="JP2000336291A_D0010.tif" />【0056】

These repeating units are preferably at least 50% by weight or more, more preferably 60% by weight or more, still more preferably 80% by weight or more in the total polymer component of the macromonomer (MM).

【0057】

The macromonomer (MM) of the present invention is formed by bonding a polymerizable double bond group represented by the general formula (MI) to one end of the polymer main chain. In equation (MI), J¹Is -COO-, -OCO-,-(CH₂)_dCOO-,-(CH₂)_dOCO-, -O-, -SO₂-, -CONHCOO-, -CONHCONH-, -CON (K)¹)-, -SO₂N (K¹)-Or represents a phenylene group (where K¹Indicates a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, and d indicates an integer of 1 to 4). m¹And m²Can be the same or different from each other, each of which is a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 7 carbon atoms, and -COO-K.², Or via a hydrocarbon group-COO-K²Represents (here K²Indicates a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms.

【0058】

In general formula (MI) m¹, M², J¹Each of the hydrocarbon groups contained in is having the indicated carbon number (as an unsubstituted hydrocarbon group), but these hydrocarbon groups may be substituted. Examples of these hydrocarbon groups include hydrogen atoms, and preferred hydrocarbon groups include alkyl groups having 1 to 22 carbon atoms which may be substituted (for example, methyl group, ethyl group, propyl group, butyl group and heptyl group). , Hexyl group, octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosanyl group, docosanyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2 -Methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.), optionally substituted alkenyl group with 4-18 carbon atoms (eg 2-methyl-1-propenyl group, 2-butenyl group, etc.) 2-Pentenyl group, 3-Methyl-2-pentenyl group, 1-Pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, decenyl group, dodecenyl group, tridecenyl group, hexadecenyl group, Octadesenyl group, linolel group, etc.), optionally substituted aralkyl group having 7 to 12 carbon atoms (eg, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, Bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), optionally substituted alicyclic group having 5 to 8 carbon atoms (eg, cyclohexyl group, 2-cyclohexyl) Ethyl group, 2-cyclopentylethyl group, etc.) or optionally substituted aromatic group with 6-12 carbon atoms (eg, phenyl group, naphthyl group, trill group, xsilyl group, propylphenyl group, butylphenyl group, octylphenyl) Group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxyca

【0059】

J represented by the general formula (MI)¹If represents -Ph- (phenylene group), the benzene ring may have a substituent. Examples of the substituent include a halogen atom (for example, chlorine atom, bromine atom, etc.), an alkyl group (for example, methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.) and the like.

【0060】

The macromonomer (MM) of the present invention has a polymerizable double bond group represented by the general formula (MI) bonded to the repeating unit (m) component described above, and is represented by the following formula (MIa), for example. It binds to the end of the main chain of the polymer in a simple manner.

【0061】

[Chemical 15]

<img file="JP2000336291A_D0011.tif" />【0062】

In general formula (MIa), G⁰Except for, the contents are the same as each symbol in the formula (MI). G⁰Represents a bond that directly links to one end of the polymer backbone, or a binding group via any linking group.

【0063】

Bonding groups include carbon-carbon bonds (single or double bonds), carbon-heteroatom bonds (for example, oxygen atoms, sulfur atoms, nitrogen atoms, silicon atoms, etc.), and heteroatom-heteroatom bonds. It is composed of any combination of atomic groups. For example [0064]

[Chemical 16]

<img file="JP2000336291A_D0012.tif" />【0065】

z¹, Z²Indicates a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, a hydroxyl group, an alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.) and the like. z³, Z⁴Are hydrogen atoms, hydrocarbon groups with 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, benzyl group, phenethyl group, phenyl group, trill group, etc.) or -Oz⁵(z⁵Is z³(Showing the same content as the hydrocarbon group in)} and the like.

【0066】

The polymerizable double bond group represented by the general formula (MI) that is bonded to only one end of the polymer main chain as described above is specifically shown below. However, in the following specific example, A is -H, -CH₃Or-CH₂COOCH₃Represents, B is -H or -CH₃Represents. Also, n represents an integer of 2 to 10, m represents 2 or 3, t represents 1, 2 or 3, p represents an integer of 1 to 4, and q represents 1 or 2.

【0067】

[Chemical 17]

<img file="JP2000336291A_D0013.tif" />【0068】

[Chemical 18]

<img file="JP2000336291A_D0014.tif" />【0069】

[Chemical 19]

<img file="JP2000336291A_D0015.tif" />【0070】

[Chemical 20]

<img file="JP2000336291A_D0016.tif" />【0071】

The macromonomer (MM) of the present invention in which a polymerizable double-bonding group is bonded to only one end of the polymer main chain can be obtained by conventionally known radical polymerization (for example, iniferter method), anionic polymerization or cationic polymerization. Reactate a reagent containing various double-binding groups at the end of the living polymer, or "specific reactive groups" (eg-OH, -COOH, -SO) at the end of this living polymer.₃H, -NH₂, -SH, -PO₃H₂, -NCO, -NCS, [0072]

[Chemical 21]

<img file="JP2000336291A_D0017.tif" />【0073】

-COCl, -SO₂After reacting a reagent containing Cl, etc.), a method of introducing a polymerizable double-bonding group by a polymer reaction (method by an ionic polymerization method), or a method of containing the above-mentioned "specific reactive group" in the molecule. After radical polymerization using a polymerization initiator and / or a chain transfer agent, a polymer reaction is carried out using a "specific reactive group" bonded to only one end of the main chain of the polymer to carry out the polymerization. It can be easily produced by a synthetic method such as a method of introducing a heavy bonding group.

【0074】

Specifically, Takayuki Otsu, Polymer, 33 (No.3), 222 (1984), P. Dreyfuss &amp; RP Quirk, Encycl. Polym. Sci. Eng., 7, 551 (1987), Yoshiki Chujo, Yamashita. Yuya "Dyes and Chemicals", 30, 232 (1985), Akira Ueda, Susumu Nagai "Chemistry and Industry", 60, 57 (1986), PF Rempp &amp; E. Franta, Advances in Polymer Science, 58, 1 (1984) , Koichi Ito, "Polymer Processing", 35, 262 (1986), V. Percec, Applied Polymer Science, 285, 97 (1984), etc. The group can be introduced.

【0075】

Further, specifically, i) a mixture of at least one of the monomers corresponding to the repeating unit (m) and the chain transfer agent containing the above-mentioned "specific reactive group" in the molecule is used as a polymerization initiator (. For example, a method of polymerizing with an azobis-based compound, a peroxide, etc.), ii) a method of polymerizing using a polymerization initiator containing the above-mentioned "specific reactive group" in the molecule without using the above-mentioned chain transfer agent, Alternatively, iii) by using a compound containing the above-mentioned "specific reactive group" in the molecule for both the chain transfer agent and the polymerization initiator, etc., only one end of the polymer main chain has a "specific reactive group". A method of synthesizing a polymer to which "" is bonded and then introducing a polymerizable double bond by carrying out a polymer reaction using this "specific reactive group" can be mentioned.

【0076】

As the chain transfer agent to be used, for example, a mercapto compound containing a "specific reactive group" or a substituent capable of inducing the "specific reactive group" {for example, thioglycolic acid, thioalinic acid, thiosalicylic acid, 2 -Mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 1-Mercapto-2-propanol, 3-Mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol, etc.}, or the "specific reactive group" or the said. Alkyliodated compounds containing substituents that can be derived to "specific reactive groups" (eg, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.) Can be mentioned. Preferred are mercapto compounds.

【0077】

Examples of the polymerization initiator containing a substituent capable of inducing a "specific reactive group" or a "specific reactive group" include 4,4'-azobis (4-cyanovaleric acid), 4, 4'-azobis (4-cyanovaleric acid chloride), 2,2'-azobis (2-cyanopropanol), 2,2'-azobis (2-cyanopentanol), 2,2'-azobis [2- ( 5-Hydroxy-3,4,5,6-tetrahydropyrimidine-2-yl) propane], 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl) ] Propionamide}, 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propioamide}, 2,2'-azobis [2-methyl-N- (2-hydroxy) Ethyl) -propioamide], 2,2'-azobis (2-amidinopropane), benzyl N-methyl-N-hydroxyethyl dithiocarbamate, 2-carboxyethyl N, N-diethyldithiocarbamate, 3-hydroxypropyl N, N -Dimethyldithiocarbamate and the like can be mentioned.

【0078】

The amount of these chain transfer agents or polymerization initiators used is 0.1 to 15 parts by weight, preferably 0.5 to 8 parts by weight, based on 100 parts by weight of all the monomers. Within these amounts, the weight average molecular weight of macromonomer (MM) is 1 × 10.³~2×10⁴, Preferably 3x10³~1.5×10⁴It is adjusted within the range of.

【0079】

Next, the amino group-containing monomer (B) represented by the general formula (II), which is copolymerizable with the monofunctional monomer (A), will be described. The monofunctional monomer (B) is a monomer copolymerizable with the monomer (A) and not directly bonded to the polymerizable double bond group.

【0080】

In equation (II), R¹, R²May be the same or different, preferably a hydrogen atom or an alkyl group optionally substituted with 1-22 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl). Group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosanyl group, docosanyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group , 2-Methyl-1-propenyl group, 3-bromopropyl group, etc.), optionally substituted alkenyl group having 4 to 18 carbon atoms (eg, 2-methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-Methyl-2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, decenyl group, dodecenyl group, tridecenyl group, hexadecenyl group, octadecenyl group, linolell group etc), [0081]

A optionally substituted aralkyl group having 7 to 12 carbon atoms (eg, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, Ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), optionally substituted alicyclic group having 5 to 8 carbon atoms (for example, cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group) Etc.) or optionally substituted aromatic groups with 6-12 carbon atoms (eg, phenyl group, naphthyl group, trill group, xsilyl group, propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl) Group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl Group, propioamide phenyl group, dodecylamide phenyl group, etc.).

【0082】

Also, R¹, R²Represents an organic residue that binds to form a sensation with a nitrogen atom. This organic residue may further contain a hetero atom (eg, oxygen atom, nitrogen atom, sulfur atom, etc.). Examples of the cyclic group formed include a morpholino group, a piperidino group, a pyridinyl group, an imidazolyl group, a quinolinyl group and the like. A plurality of amino groups may be contained in the molecule of the monomer (B).

【0083】

Specific examples of the monomer (B) will be shown below, but the present invention is not limited thereto.

【0084】

[Chemical 22]

<img file="JP2000336291A_D0018.tif" />【0085】

Next, a monofunctional monomer (C) containing a specific acidic group, which is copolymerizable with the monomer (A) preferably used in the present invention, will be described. The monofunctional monomer (C) is -PO₃H₂Group, -SO₃H group and -SO₂It is a monomer copolymerizable with the monomer (A), which contains at least one acidic group selected from H groups. By coexisting the monomer (C), the effect of the present invention is more effectively exhibited.

【0086】

Specific examples of the monomer (C) are shown below. The scope of the present invention is not limited to these. However, Y⁰Is-PO₃H₂, -OPO₃H₂, -SO₃H or -SO₂Represents H. Y¹Is-PO₃H₂, -SO₃H or -SO₂Represents H.

【0087】

[Chemical 23]

<img file="JP2000336291A_D0019.tif" />【0088】

[Chemical 24]

<img file="JP2000336291A_D0020.tif" />【0089】

The monomer (A) and macromonomer (MM) used in the present invention, the monomer (B) if necessary, and the monomer (C) if necessary are copolymerized by a polymerization reaction. It becomes a resin that is insoluble in a non-aqueous solvent. The macromonomer (MM) is preferably used in an amount of 0.5 to 15% by weight, more preferably 2 to 10% by weight, based on the total amount of all the monomers. The amount of the monomer (B) is 1 to 20% by weight, preferably 2 to 15% by weight, based on the total amount of the total monomers. When the monomer (C) is used, the ratio of the monomer (B) / monomer (C) is preferably in the range of 0.2 to 2.5 molar ratio, more preferably 0.5 to 2.0 molar ratio.

【0090】

The resin insoluble in the non-aqueous solvent of the present invention preferably has a glass transition point of 0 to 80 ° C or a softening point of 40 to 100 ° C, and further has a glass transition point of 10 to 70 ° C or a softening point of 45 to 80. The ° C range is more preferred. Select a combination of monomer (A), macromonomer (MM), and if necessary, monomer (B) and monomer (C) so as to be a copolymer exhibiting these thermal properties. Can be done. Within the above-mentioned predetermined ranges, each of them exhibits particularly excellent effects on the distribution uniformity of the particle size of the dispersed resin particles, dispersion stability, charge stability, image fixability, and prevention of particle adhesion to the ejection electrode.

【0091】

In the present invention, the dispersion stabilizing resin (P) used to obtain a solvent-insoluble polymer produced by polymerizing a monomer in a non-aqueous solvent as a stable resin dispersion has the above general formula (PI). ) Is a polymer containing at least one repeating unit. The component represented by the general formula (PI) is a component that is soluble in the dispersion medium used for oil-based inks.

【0092】

In formula (PI), A¹Is preferably -COO-, -OCO-, CH₂COO-, CH₂Represents OCO- or -O-, more preferably -COO-, -OCO-, CH₂Represents COO-.

【0093】

L preferably represents an alkyl or alkenyl group which may be substituted with 8 to 32 carbon atoms. As the substituent, for example, a halogen atom (for example, a fluorine atom, a base atom, a bromine atom, etc.), -OD², -COO-D², -OCO-D²(Here, D²Represents an alkyl group having 6 to 22 carbon atoms, and examples thereof include a hexyl group, an octyl group, a decyl group, a dodecyl group, a hexadecyl group, and an octadecyl group). More preferably, L represents an alkyl or alkenyl group having 10 to 22 carbon atoms. For example, decyl group, dodecyl group, tridecylic group, tetradecyl group, hexadecyl group, octadecyl group, docosanyl group, eikosanyl group, decenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, Dodecenyl groups, etc.

【0094】

p¹And p²May be the same as or different from each other, preferably hydrogen atom, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, etc.), cyano group, alkyl group having 1 to 3 carbon atoms, -COO-. D³, Or -CH₂COO-D³(Here D³Represents an aliphatic group having 1 to 22 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a hexadecyl group and an octadecyl group. , Docosanyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, decenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group and the like, and these aliphatic groups are the same substituents as represented by L above. May have). More preferably p¹And p²Are hydrogen atoms, alkyl groups with 1 to 3 carbon atoms (eg, methyl group, ethyl group, propyl group, etc.), -COO-D, respectively.⁴Or-CH₂COO-D⁴(Here D⁴Represents an alkyl or alkenyl group having 1 to 12 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a pentenyl group, a hexenyl group, a heptenyl group, Examples thereof include an octenyl group and a decenyl group, and these alkyl groups and alkenyl groups may have the same substituents as represented by L above).

【0095】

The dispersion stabilizing resin (P) of the present invention preferably contains a monomer corresponding to the repeating unit represented by the above general formula (PI) and another monomer copolymerizable with the monomer. It is a copolymer containing a copolymer component obtained by copolymerization.

【0096】

The other monomer that can be copolymerized may be any as long as it contains a polymerizable double bond group, for example, an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, and itaconic acid; and has 6 or less carbon atoms. Examples thereof include ester derivatives or amide derivatives of unsaturated carboxylic acids; vinyl esters or allyl esters of carboxylic acids; styrenes; methacrylonitrile; acrylonitrile; heterocyclic compounds containing a polymerizable double bond group. More specifically, a compound having the same content as the insolubilizing monomer (A) described above can be mentioned.

【0097】

Among the polymer components in the dispersion stabilizing resin (P), the component of the repeating unit represented by the general formula (PI) is at least 50% by weight or more, preferably 60% by weight or more, and more preferably 70% by weight or more. is there. Further, in the dispersion stabilizing resin (P), other monomers that can be copolymerized with the copolymerization component represented by the general formula (PI) that is soluble in the dispersion medium used for the oil-based ink (for example, insoluble in the dispersion medium). The monomer (polymerization component corresponding to A) may be either random copolymerization or block copolymerization, preferably block copolymerization.

【0098】

Further, as a preferred embodiment of the dispersion stabilizing resin (P) of the present invention, a polymerizable double bond represented by the general formula (MI) is formed at one end of the polymer main chain or in the substituent of the polymer copolymer component. It is formed by bonding groups (sometimes referred to as dispersion stabilizing resin (PG)), and the polymerizable double-binding group is copolymerized with the monomer (A) constituting the dispersed resin particles. It may be a functional group of.

【0099】

Specifically, for example, as a dispersion stabilizing resin in which a polymerizable group is bonded to one end of the polymer main chain, the following general formula (Pa) is used, or a polymerizable group is bonded in a substituent of a copolymerization component of the polymer. The general formula (Pb) is exemplified as the dispersion stabilizing resin.

【0100】

[Chemical 25]

<img file="JP2000336291A_D0021.tif" />【0101】

In formula (Pa), m¹, M², J¹, L, G¹, A¹, P¹, P²Is synonymous with the cases of the above equations (MI), (MIa) and (PI). t¹, T²Is p¹, P²Is synonymous with. In the formula (Pb), two or more kinds of x component and y component may be contained in the resin (P). A³And A⁴Are each A in equation (PI)¹Represents the same content as. G²Is a bond A³And binding group A⁴It represents a carbon-carbon bond group (where the hetero atom is an oxygen atom, a sulfur atom, a silicon atom or a nitrogen atom) which may be via a hetero atom connecting the above G.¹Represents the same content as.

【0102】

In the y component in the general formula (Pb), the linking group: [-A⁴-G²-A³The linked main chain composed of-] is preferably composed of a total number of atoms of 8 or more. Here, the number of atoms in the linked main chain is, for example, A.⁴When represents -COO- and -CONH-, oxo group (= O group) and hydrogen atom are not included as the atomic number, and carbon atom, ether type oxygen atom and nitrogen atom constituting the connecting main chain are the atomic number. Included as. Therefore, -COO- and -CONH- are counted as 2 atoms.

【0103】

Specific examples of the repeating unit (y component) containing a polymerizable bonding group will be shown below, but the present invention is not limited thereto. In the following formula, each symbol represents the following contents.

【0104】

[Chemical 26]

<img file="JP2000336291A_D0022.tif" />【0105】

[Chemical 27]

<img file="JP2000336291A_D0023.tif" />【0106】

[Chemical 28]

<img file="JP2000336291A_D0024.tif" />【0107】

The dispersion stabilizing resin (P) of the present invention can be easily synthesized by a conventionally known synthesis method. That is, as a method of introducing a copolymerization component (y component) containing a polymerizable double bond group into the resin, a "specific reactive group" (for example, -OH, -COOH, -SO) is introduced in advance.₃H, -NH₂, -SH, PO₃H₂, -NCO, -NCS, -COCl, -SO₂A monomer containing Cl, an epoxy group, etc.) was subjected to a polymerization reaction together with a monomer corresponding to the x component in the general formula (Pb), and then a reactive reagent containing a polymerizable double bond group was reacted. Later, a method of introducing a polymerizable reactive group by a polymer reaction can be mentioned.

【0108】

Specifically, a polymerizable double bond group is introduced at one end of the main chain of the polymer according to the method described in the review illustrated by the macromonomer (MM) containing a polymerizable double bond group and the references cited therein. can do.

【0109】

As another method, bifunctional monomers having different copolymerizability in the radical polymerization reaction are polymerized together with the monomer corresponding to the x component, and the general formula is used without causing a gelation reaction. Examples thereof include the method described in JP-A-60-185962 for synthesizing the copolymer represented by (Pb).

【0110】

In the resin represented by the general formula (Pb), the abundance ratio of the x component / y component is 90/10 to 99 / l weight ratio, preferably 92/8 to 98/2 weight ratio. Within this range, during the polymerization granulation reaction, the dispersion stability and redispersion stability of the obtained particles are good without causing gelation of the reaction mixture or coarsening of the produced resin particles.

【0111】

Further, the dispersion stabilizing resin (PG) used in the present invention may contain other repeating units as copolymerization components in addition to the repeating units represented by the general formulas (Pa) and (Pb). The other copolymerization component may be any compound as long as it is composed of a monomer corresponding to each repeating unit of the general formulas (Pa) and (Pb) and a copolymerizable monomer. However, it is preferable to use it in a range not exceeding 20 parts by weight out of 100 parts by weight of the total polymer component at most. At 20 parts by weight or less, good dispersion stability of the dispersed resin particles can be obtained.

【0112】

The weight average molecular weight (Mw) of the dispersion stabilizing resin (P) of the present invention is 2 × 10.⁴~1×10⁶Is preferable, and more preferably 3 × 10.⁴~2×10⁵Is.

【0113】

In order to produce the dispersed resin particles used in the present invention, generally, the dispersion stabilizing resin (P), the monomer (A) and the macromonomer (MM) as described above, and if necessary, the monomer (B) are produced. ) And the monomer (C) may be thermally polymerized in a non-aqueous solvent in the presence of a polymerization initiator such as benzoyl peroxide, azobisisobutyronitrile, and butyl lithium. Specifically, a polymerization initiator is added to a mixed solution of a dispersion stabilizing resin (P), a monomer (A), a macromonomer (MM), a monomer (B) and a monomer (C). Method, Macromonomer (MM), monomer (A), monomer (B) and monomer (C) are added dropwise together with the polymerization initiator in a solution in which the dispersion stabilizing resin (P) is dissolved. Method, or in a solution in which the dispersion stabilizing resin (P) is dissolved, a mixture of half the amount of the monomer (A) and the monomer (B) and half the amount of the monomer (A), the monomer (C) ) And the mixture with the polymerization initiator are added dropwise at the same time, or in the above method, the macromonomer (MM) is placed in the same direction as the dispersion stabilizing resin (P). It can also be produced by using the method of.

【0114】

The total amount of the monomer (A), the macromonomer (MM), and if necessary, the monomer (B) and the monomer (C) is preferably about 10 to 100 parts by weight with respect to 100 parts by weight of the non-aqueous solvent. It is more preferably 10 to 80 parts by weight. The dispersion stabilizing resin (P) is preferably 3 to 25 parts by weight, more preferably 5 to 20 parts by weight, based on 100 parts by weight of all the monomers used above. The appropriate amount of polymerization initiator is 0.1 to 10% by weight for all monomers. The polymerization temperature is preferably about 40 to 180 ° C, more preferably 50 to 120 ° C. The reaction time is preferably 3 to 20 hours.

【0115】

When the above-mentioned polar solvents such as alcohols, ketones, ethers, and esters are used in combination with the non-aqueous solvent used in the reaction, or the final reaction product of the monomer (A) to be polymerized and granulated is If it remains, it is preferable to remove it by heating it above the boiling point of the solvent or monomer and distilling it off, or by distilling it under reduced pressure.

【0116】

The non-aqueous dispersion resin particles produced according to the present invention as described above exist as fine particles having a uniform particle size distribution. Its average particle size is preferably 0.15 to 5 μm and preferably 0.2 to 1.5 μm. This particle size can be determined by CAPA-500 (trade name manufactured by HORIBA, Ltd.).

【0117】

The average weight molecular weight (Mw) of the dispersed resin of the present invention is preferably 5 × 10.³~1×10⁶And more preferably 8x10³~5×10⁵Is. Further, the dispersed resin of the present invention preferably has a glass transition point of 15 ° C to 80 ° C or a softening point of 35 ° C to 120 ° C, more preferably a glass transition point of 20 ° C to 60 ° C, as its thermophysical properties. Alternatively, the softening point is 38 ° C to 90 ° C.

【0118】

The oil-based ink of the present invention is excellent in dispersion stability, redispersion stability, and storage stability of dispersed resin particles, has good quick fixability after image formation, and maintains sufficient strength even during printing for high printing. Show sex. That is, it shows extremely stable dispersibility, especially in a recording device, it has good dispersibility even if it is used repeatedly for a long time, and it is easy to redisperse, and it is completely recognized that it adheres to each part of the device and causes stains. I can't. Furthermore, when the ink image was formed and then fixed by rapid treatment such as heating, a strong film was easily formed on the surface of the lithographic printing plate precursor, and good fixability was exhibited. As a result, even in offset printing, it is possible to print a large number of sheets (high print resistance). The oil-based ink of the present invention that brings about the above effects is made possible by the insoluble latex provided by the present invention.

【0119】

More preferably, a dispersion stabilizing resin (P) composed of a block copolymer of a soluble component and an insoluble component represented by the general formula (PI) is used. In that case, a dispersion stabilizing resin is used on the insoluble resin particles. The block portion of the insoluble component of (P) is sufficiently adsorbed. Alternatively, a dispersion stabilizing resin (PG) containing a polymerizable double bond group is used, in which case the resin (PG) chemically bonds with the insoluble resin particles. As a result, it is considered that the so-called steric repulsion effect is brought about by improving the affinity of the soluble component of the dispersion stabilizing resin (P) sufficiently adsorbed or chemically bonded to the dispersed resin particles to the dispersion medium.

【0120】

The dispersed resin particles in the oil-based ink used in the present invention are positively charged by the coexistence of a charge modifier (CD). Immobilization of these particles can be achieved by appropriately using the technique of a wet electrostatic photographic developer. Specifically, "Recent Development and Practical Use of Electrophotodeveloping Systems and Toner Materials", pp. 139-148, "Basics and Applications of Xerographic Technology" edited by the Society of Xerography, pp. 497-505 (Corona, 1988). , Yuji Harasaki, "Electrographs" 16 (N0.2), p. 44 (1977), etc., using the voltage detection materials and other additives.

【0121】

For example, as metal salts, fatty acids having 6 to 24 carbon atoms (for example, 2-ethylhexic acid, 2-ethylcaproic acid, lauric acid, palmitic acid, ellagic acid, linoleic acid, ricinolic acid, oleic acid, stearic acid, enanthic acid , Nafthenic acid, ethylenediamine tetraacetic acid, etc.), resin acids, dialkylsuccinic acids, alkylphthalic acids, alkylsalicylic acids, and other metal salts (Na, K, Li, B, Al, Ti, Ca, Pb, Mn as metal of metal ions , Co, Zn, Mg, Cl, Ag, Cd, Zr, Cu, Fe, Ba, etc.). Specific examples are US Pat. Nos. 3,411,936, 3,900,412, Japanese Patent Publication No. 49-27707, Japanese Patent Application Laid-Open No. 51-37651, Japanese Patent Application Laid-Open No. 52-38937, No. 52-107837, No. 53. -It is described in No. 123138, etc.

【0122】

Examples of organic phosphoric acid or salts thereof include monos composed of alkyl groups having 3 to 18 carbon atoms, di or trialkylphosphoric acid, dialkyldithiophosphoric acid, etc. in British Patents 1, 411, 739, 1,276, 363 and the like. As organic sulfonic acids or salts thereof, long-chain aliphatic sulfonic acids, long-chain alkylbenzene sulfonic acids, dialkyl sulfosuccinic acids and the like or metal salts thereof are listed in Japanese Patent Application Laid-Open No. 47-37128, JP-A-53-123138 and 51-47437. No. 50-79640, No. 53-30340, etc.

【0123】

As amphoteric surfactants, phospholipids such as lecithin and seharin (for example, Japanese Patent Publication No. 51-47046) and β-alanines containing an alkyl group having 8 or more carbon atoms (Japanese Patent Laid-Open No. 50-17642, 49-17741). No.), etc., metal complexes of β-diketones (No. 49-27707, etc.), copolymers containing a maleic acid semi-amide component (for example, No. 6-19596, No. 6-19595, No. 6) -23865 etc.) etc.

【0124】

These charge regulators (CDs) can be used alone or in combination of two or more. It is preferable to use 0.001 to 1.0 parts by weight of the charge adjusting agent as described above with respect to 1000 parts by weight of the dispersion medium which is the carrier liquid.

【0125】

The oil-based ink of the present invention contains at least a macromonomer (MM), and further contains an amino group-containing basic monomer (monomer (B)), more preferably a basic monomer and a monomer containing a specific acidic group (a monomer (B)). It is formed by dispersing positively charged particles composed of dispersed resin particles containing a monomer (C)) and a charge adjusting agent (CD) as described above.

【0126】

When the oil-based ink of the present invention is used in the method of forming an image by the electrostatic inkjet recording method disclosed in WO93 / 11866, the ink dots to be printed are missing or the dots are printed even at high-speed printing speed and fine dot ejection. A high-definition image is formed without deformation of the shape, and the thickness of the printed dot image is sufficiently maintained at 1 μm or more. This means that the positively charged resin particles in the oil-based ink are rapidly electrophoresed in the ink meniscus formed on the surface of the ejection electrode by applying an electrostatic field to concentrate the particles, which accompanies the image signal. It is considered that this is because the ink is discharged completely in response to the application of the pulse voltage.

【0127】

In the above electrostatic inkjet recording method, if the electric field strength at the time of image formation is too low, good ejection properties may not be obtained, so about 1 × 10⁵V / cm or more is appropriate. On the other hand, if it is too high, dot splitting and satellites will occur and the image quality will tend to deteriorate, so about 1x10.⁸V / cm or less is preferable. More preferably 2x10⁵From 5x10⁷It is in the range of V / cm.

【0128】

Further, the oil-based ink used in this method preferably has a high ratio of the amount of charge of the dispersed particles (charge fraction of the particles) in the ink. When the charge fraction of the particles is low, the concentration of the particles is unlikely to occur, the required image quality thickness cannot be obtained, and therefore the printing durability as a printing plate is inferior. Specifically, the charge fraction of waves and particles is preferably about 10% or more, preferably 30% or more, and more preferably 40% or more. The charge fraction of the particles and the calculation method thereof will be described later.

【0129】

If the surface tension of the oil-based ink of the present invention is too low, the ink tends to spill out from the head and the stability tends to deteriorate. Therefore, the surface tension is in the range of about 15 dyn / cm to 30 dyn / cm. Further, if the viscosity of the oil-based ink is too low, the ink tends to spill out from the head and the stability tends to deteriorate. Therefore, about 0.4 cP or more is suitable. On the other hand, if it is too high, the discharge property is lowered, so that it is preferably about 15 cP or less. More preferably, it is in the range of 0.5 cP to 10 cP.

【0130】

Furthermore, the oil-based ink of the present invention has the same performance as a fresh product immediately after ink production even if inkjet recording is performed after long-term storage or storage at high temperature and high humidity (for example, 40 ° C / 80RH%). Is shown. It is considered that this is because the charge characteristics of the oil-based ink of the present invention, particularly the chargeability of the positively charged particles, are stably maintained.

【0131】

Various additives may be further added to the oil-based ink of the present invention if desired, and the upper limit of the total amount of these additives is regulated by the electrical resistance of the oil-based ink. That is, the electric low resistance of the ink with the dispersed particles removed is 10.⁹If it is lower than Ωcm, it becomes difficult to obtain a high-quality continuous gradation image, so it is necessary to control the amount of each additive added within this limit.

【0132】

It is preferable that the oil-based ink used in the present invention contains a coloring material as a coloring component together with the dispersed resin particles for inspecting a plate after plate making. As the coloring material, any pigment or dye conventionally used in an oil-based ink composition or a liquid developer for electrostatic photography can be used.

【0133】

As the pigment, regardless of whether it is an inorganic pigment or an organic pigment, those generally used in the technical field of printing can be used. Specifically, for example, carbon black, cadmium red, molybdenum red, chrome yellow, cadmium yellow, titanium yellow, chromium oxide, pyridian, cobalt green, ultramarine blue, prusian blue, cobalt blue, azo pigment, phthalocyanine pigment. , Kinacridone pigments, isoindolinone pigments, dioxazine pigments, slene pigments, perylene pigments, perinone pigments, thioindigo pigments, quinophthalone pigments, metal complex pigments, etc. Can be used without.

【0134】

Dyes include azo dyes, metal complex salt dyes, naphthol dyes, anthraquinone dyes, indigo dyes, carbonium dyes, quinoneimine dyes, xanthene dyes, cyanine dyes, quinoline dyes, nitro dyes, nitroso dyes, benzoquinone dyes, naphthoquinone dyes, phthalocyanine dyes, Oil-soluble dyes such as metallic phthalocyanine dyes are preferable.

【0135】

These pigments and dyes may be used alone or in combination as appropriate, but it is desirable that these pigments and dyes are contained in the range of 0.05 to 5% by weight with respect to the entire ink.

【0136】

In addition to the dispersed resin particles, these coloring materials may be dispersed in a non-aqueous solvent as dispersed particles, or may be contained in the dispersed resin particles. As one of the methods for containing the resin, as described in JP-A-57-48738 and the like, there is a method of dyeing the dispersed resin product with a preferable dye. Alternatively, as another method, as disclosed in Japanese Patent Application Laid-Open No. 53-54029, there is a method of chemically bonding the dispersed resin product and the dye, or also described in Tokushu Shosho 44-22955, etc. As described above, there is a method in which a dye-containing monomer is used in advance to obtain a dye-containing copolymer when produced by the polymerization granulation method.

【0137】

Next, a method of forming an image on a transfer material by an electrostatic inkjet method using the oil-based ink of the present invention will be described. Here, a method of forming an image (plate making) using a printing original plate as a transfer material to obtain a printing plate will be described as an example.

【0138】

The original plate for printing is roughly classified into an original plate having a hydrophilic surface that can be printed on a lithographic plate and an original plate having a hydrophobic surface, and any of them can be used. The former includes those in which the support itself has a hydrophilic surface and those in which the support has an image receiving layer having a hydrophilic surface on the support.

【0139】

The water-resistant support having a hydrophilic surface capable of lithographic printing may be any as long as it provides a hydrophilic surface suitable for lithographic printing, and the support conventionally provided for offset printing plates can be used as it is. Specifically, bimetal plates such as aluminum plate, zinc plate, copper-aluminum plate, copper-stainless steel plate, chrome-copper plate, chrome-copper-aluminum plate, chrome-lead-iron plate, chrome-copper-stainless steel plate, etc. A substrate having a hydrophilic surface such as a trimetal plate is used. Further, a laminate of these metal plates and a plastic sheet or paper is also used. Its thickness is preferably 0.1 to 3 mm, particularly preferably 0.1 to 1 mm.

【0140】

In the case of a support having an aluminum surface, the surface treatment such as sand sharpening treatment, immersion treatment in an aqueous solution of sodium silicate, potassium zirconium tungrate, phosphate or the like, or anodization treatment may be performed. preferable. In addition, as described in US Pat. No. 2,714,066, an aluminum plate that has been sanded and then immersed in an aqueous sodium silicate solution, and as described in Tokusho 47-5125, the aluminum plate is anodized. After that, those which have been immersed in an aqueous solution of alkali metal silicate are also preferably used.

【0141】

The anodic oxidation treatment is performed by, for example, electrolysis of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, or boric acid, an organic acid such as oxalic acid or sulfamic acid, or an aqueous solution or a non-aqueous solution of salts thereof alone or in combination of two or more. It is carried out by passing an electric current through an aluminum plate as an anode in the liquid. In addition, silicate electrodeposition as described in US Pat. No. 3,658,662 is also effective. The treatment with polyvinyl sulfonic acid described in West German Patent Publication No. 1,621,478 is also appropriate.

【0142】

According to the combination of the ink and the recording method of the present invention, even in the formation of an image on a metal surface, the ink bleeds and the image bleeds on the printed surface when the particles in the ink are printed in a sufficiently concentrated state. Does not occur.

【0143】

These hydrophilization treatments are performed not only to make the surface of the support hydrophilic, but also to improve the adhesion to the toner image provided on the support. Further, a surface layer may be provided on the surface of the support in order to adjust the adhesion between the support and the ink image.

【0144】

When a plastic sheet or paper is used as a support, since the parts other than the ink image portion must be hydrophilic, those provided with a hydrophilic surface layer (image receiving layer) are provided. Specifically, a known direct drawing type lithographic printing original plate or a plate material having a layer similar to the image receiving layer of the original plate can be used.

【0145】

For example, the image receiving layer is composed mainly of a water-soluble binder, an inorganic pigment, and a water resistant agent. As the binder, water-soluble such as PVA, modified PVA such as carboxy PVA, starch and its derivatives, CMC, hydroxyethyl cellulose, casein, gelatin, polyvinylpyrrolidone, vinyl acetate-crotonic acid copolymer, styrene-maleic acid copolymer and the like. Resin is used.

【0146】

As the water resistant agent, an initial condensate of aminoblast such as glioxal, melamine formaldehyde resin, ureaformaldehyde resin, modified polyamide resin such as methylolated polyamide resin, polyamide / polyamine / epichlorohydrin adduct, polyamide epichlorohydrin resin, modified polyamide polyimide resin. And so on. Examples of the inorganic pigment include kaolin, clay, calcium carbonate, silica, titanium oxide, zinc oxide, barium sulfate, alumina and the like, and silica is preferable among them.

【0147】

In addition, a cross-linking agent such as ammonium chloride or a silane coupling agent can be used in combination in the image receiving layer.

【0148】

On the other hand, in a printing original plate having an image receiving layer composed of a hydrophobic surface, after image formation, the non-image portion is desensitized by a desensitizing treatment (that is, converted into a hydrophilic surface repulsive to printing ink). To make a print version. As these plates, the image receiving layer is a printing original plate having an image receiving layer containing at least zinc oxide and a binder resin, and is hydrophobically formed by desensitizing treatment (treatment liquid, light irradiation, heat treatment, etc.). Original printing plate having an image receiving layer containing at least a binder resin that chemically reacts with the resin to convert it into a hydrophilic binder resin (for example, described in JP-A No. 1-226394, JP-B-7-94191, etc.), etc. Can be mentioned.

【0149】

A lithographic printing master plate having an image receiving layer containing at least zinc oxide and a binder resin will be described.

【0150】

The zinc oxide used is, for example, zinc oxide, zinc oxide, wet zinc oxide, or active zinc oxide, as described in "New Edition Pigment Handbook", p. 319, Seibundo Co., Ltd., (1968), edited by Japan Pigment Technology Association. It may be any of those commercially available as. That is, zinc oxide includes the French method (indirect method), the American method (direct method), and the wet method as dry methods depending on the starting material and the manufacturing method. For example, Shodo Chemical Co., Ltd. and Sakai Chemical Co., Ltd. Examples include those commercially available from companies such as Shiramizu Chemical Co., Ltd., Honjo Chemical Co., Ltd., Toho Zinc Co., Ltd., and Mitsui Mining &amp; Smelting Co., Ltd.

【0151】

If the amount of zinc oxide in the image receiving layer is small, the surface of the image receiving layer becomes insufficiently hydrophilic by the desensitizing treatment, and if it is too large, the required amount of binder resin cannot be secured, which is not preferable. The content of zinc oxide in the image receiving layer is preferably 10 to 25 wt%, more preferably 12 to 22 wt%.

【0152】

As described above, the binder resin provided for the image receiving layer is a hydrophobic resin that constitutes the image receiving layer together with zinc oxide, and the molecular weight of the resin is a weight average molecular weight Mw, preferably 10.³~10⁵, More preferably 5x10³~5×10⁵Is. The glass transition point of this resin is preferably 0 ° C to 120 ° C, more preferably 10 to 90 ° C.

【0153】

Specific examples thereof include styrene copolymers, methacrylate copolymers, acrylate copolymers, vinyl acetate copolymers, polyvinyl butyral, alkyd resins, epoxy resins, epoxy ester resins, polyester resins, polyurethane resins and the like. These resins may be used alone or in combination of two or more.

【0154】

The image receiving layer may contain other constituent components in addition to the above-mentioned components. Other components that may be contained include other inorganic pigments of zinc oxide, such as kaolin, clay, calcium carbonate, barium carbonate, calcium sulfate, barium sulfate, magnesium carbonate, for example. , Titanium oxide, silica, alumina and the like. When these other inorganic pigments are used in combination, they can be used in a range not exceeding 20 parts by weight with respect to zinc oxide.

【0155】

Furthermore, in order to improve the desensitization of the image receiving layer, JP-A-4-201387, No.4-223196, No.4-319491, No.5-58071, No.4-353495, No.5-119545 No. Resin particles such as acrylic acid resin particles containing a specific functional group described in each publication may be contained. These resin particles are usually spherical, and the average particle size thereof is preferably 0.1 to 2 μm. The content of the resin particles is preferably 20% by weight or less of the image receiving layer.

【0156】

By using these other inorganic pigments or resin particles, the non-image area is sufficiently desensitized (hydrophilic) by the desensitizing treatment, the background stain of the printed matter is suppressed, and the image area is the image receiving layer. It is possible to obtain sufficient print resistance without causing image loss even when the number of printed sheets is large.

【0157】

In addition, a cross-linking agent may be added to the image receiving layer in order to further improve the film strength.

【0158】

The binder resin is preferably lightly and / or thermoset after applying the image receiving layer composition. In order to perform thermosetting, for example, the drying conditions are made stricter than the drying conditions at the time of producing the conventional image receiving layer. For example, it is preferable that the drying conditions are high temperature and / or long time, or the coating solvent is dried and then further heat-treated. For example, process at 60 ° C to 150 ° C for 5 to 120 minutes. When used in combination with a reaction accelerator, treatment can be performed under milder conditions.

【0159】

Further, a specific functional group in the resin may be photocured, and as a method of curing by light irradiation, a step of irradiating with light with a chemically activated light beam may be included. The chemically activated rays may be visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, γ-rays, α-rays and the like, but are preferably ultraviolet rays, more preferably rays having a wavelength in the range of 310 nm to 500 nm. .. Generally, low-pressure, high-pressure or ultra-high-pressure mercury lamps, halogen lamps, and the like are used. The light irradiation process can usually be sufficiently performed by irradiating from a distance of 5 cm to 50 cm for 10 seconds to 10 minutes.

【0160】

The thickness of the image receiving layer is 1 m for the original plate.²It is preferable that the coating amount (after drying) of the image receiving layer composition per hit is about 3 to 30 g. Further, the image receiving layer usually has a porosity of about 3 to 50 vol%, preferably about 10 to 40 vol%.

【0161】

The image receiving layer is provided on the water resistant support. As the water resistant support, a water resistant paper, a plastic film, a paper laminated with a metal leaf, a plastic film, or the like can be used.

【0162】

The support preferably has a highly smooth surface. That is, the smoothness of the surface adjacent to the image receiving layer is preferably adjusted to 300 (seconds / 10cc) or more, preferably 900 to 3000 (seconds / 10cc) in Beck smoothness, and more preferably. It is preferably 1000 to 3000 (seconds / 10cc).

【0163】

By limiting the smoothness of the surface of the support adjacent to the image receiving layer to 300 (seconds / 10cc) or more in Beck smoothness, image reproducibility and printing durability can be further improved. Such an improvement effect can be obtained even if the surface smoothness of the image receiving layer itself is the same, and the adhesion between the image portion and the image receiving layer is improved by increasing the smoothness of the support surface. It is probable that it was done.

【0164】

The highly smooth surface of such a water-resistant support means a surface to which the image receiving layer is directly applied. For example, when an under layer or an overcoat layer described later is provided on the support, the undercoat layer is provided. The surface of the layer or overcoat layer. As a result, the image receiving layer whose surface condition has been adjusted as described above is sufficiently held without receiving the unevenness of the surface of the support, and the image quality can be further improved.

【0165】

As a method for setting the smoothness range, various conventionally known methods can be used. Specific examples thereof include a method of adjusting the Beck smoothness of the surface of the support by a method of melt-bonding the surface of the substrate with a resin, a method of strengthening a calendar with a highly smooth heat roller, and the like.

【0166】

As a method of melt-bonding the resin, it is preferable to coat the resin by an extrusion laminating method. By coating by this extrusion laminating method, a support adjusted to a desired smoothness can be produced. The extrusion laminating method is a method in which a resin is melted, made into a film, immediately pressed against a base paper, cooled, and laminated, and various devices are known. The thickness of the resin layer laminated in this way is 10 μm or more from the viewpoint of manufacturing stability. It is preferably 10 μm to 30 μm.

【0167】

Further, as described above, an under layer is provided between the support and the image receiving layer for the purpose of improving water resistance and interlayer adhesion, and a backcoat layer is provided on the support surface opposite to the image receiving layer for the purpose of preventing curling. (Back surface layer) can be provided, but the back coat layer preferably has a smoothness in the range of 150 to 700 (seconds / 10cc). As a result, when the printing plate is fed to the offset printing machine, the printing plate is accurately set in the printing machine without causing deviation or slippage.

【0168】

When adjusting the smoothness of the underlayer and the backcoat layer of such a support, for example, the calendar processing is performed once after the underlayer is formed, and the calendar processing is performed again after the backcoat layer is formed. The smoothness is controlled by performing the treatment step multiple times, or by combining the composition adjustment of the under layer and the back coat layer, for example, the ratio and particle size of the pigment, and the adjustment of the calendar processing conditions, which will be described later. It is desirable to do.

【0169】

As the substrate to be used for the original plate, for example, a substrate such as wood pulp paper, synthetic pulp paper, mixed paper of wood pulp and synthetic pulp, non-woven fabric, plastic film, cloth, metal sheet, and a composite sheet of these can be used as it is. it can. In addition, a hydrophobic resin, a water-dispersible or a water-soluble resin used for an under layer or a back coat layer described later on the above-mentioned substrate in order to obtain a specific smoothness and to adjust water resistance and other properties. Or a paint made of a pigment or the like may be impregnated.

【0170】

An underlayer and a backcoat layer were provided on the substrate in order to satisfy printability such as recording characteristics, water resistance, and durability required for a lithographic printing master plate, and to adjust the smoothness to a desired level as described above. It is preferable to use a support. Such an under layer and a back coat layer are formed by applying, drying, or laminating a coating liquid containing a resin, a pigment, or the like on a support. As the resin used here, various resins are appropriately selected and used. Specifically, examples of the hydrophobic resin include acrylic resin, vinyl chloride resin, styrene resin, urethane resin, vinylidene chloride resin, vinyl acetate resin and the like, and examples of the hydrophilic resin are polyvinyl chloride. Examples thereof include alcohol-based resins, cellol-based derivatives, starch and its derivatives, polyacrylamide-based resins, and maleic anhydride-based copolymers.

【0171】

Examples of the pigment include clay, kaolin, talc, diatomaceous earth, calcium carbonate, aluminum hydroxide, magnesium hydroxide, titanium oxide, mica and the like. In order to achieve the desired smoothness, these pigments are preferably used by appropriately selecting the particle size. For example, since a relatively high degree of smoothness is required in the under layer, those having a small particle size or large particles are required. A pigment having a particle size of 8 μm or less, preferably 0.5 to 5 μm after cutting the particles is preferably used. Further, since the backcoat layer is required to have a lower smoothness than the underlayer, a pigment having a large particle size, specifically, a pigment having a particle size of about 0.5 to 10 μm is preferably used. The pigment as described above is preferably used in a ratio of 80 to 150 parts by weight in the under layer and 80 to 200 parts by weight in the back coat layer with respect to 100 parts by weight of the resin. In addition, in order to obtain excellent water resistance, it is effective that the under layer and the back coat layer contain a water resistant agent such as a melamine-based resin or a polyamide epichlorohydrin-based resin. The above particle size can be measured by a scanning electron microscope (SEM) photograph. When the particles are not spherical, the diameter is obtained by converting the projected area into a circle.

【0172】

To make a lithographic original plate, generally, a solution containing an underlayer component is applied to one surface of a support and dried to form an underlayer, and if necessary, a backcoat layer component is applied to the other surface. After the solution containing the above is applied and dried to form the backcoat layer, the coating solution containing the image receiving layer component may be applied and dried to form the image receiving layer. The coating amount of the image receiving layer, the under layer, and the back coat layer is 1 to 30 g / m, respectively.², Especially 6 ~ 20g / m²Is appropriate. More preferably, the film thickness of the water resistant support provided with the under layer or the backcoat layer is in the range of 90 to 130 μm, preferably in the range of 100 to 120 μm.

【0173】

Next, a method for forming an image on the above-mentioned lithographic printing master plate (hereinafter, also referred to as master) will be described. As an apparatus system for carrying out such a method, for example, there is one shown in FIG. The device system shown in FIG. 1 includes an inkjet recording device 1 that uses oil-based ink.

【0174】

As shown in FIG. 1, first, the pattern information of the image (figure or sentence) to be formed on the master 2 is transmitted from an information source such as a computer 3 through a transmission means such as a bus 4, and oil-based ink is used. Supply to the inkjet recording device 1. The inkjet recording head 10 of the recording device 1 stores oil-based ink inside the recording device 1, and when the master 2 passes through the recording device 1, a minute droplet of ink is sprayed onto the master 2 according to the above information. As a result, the ink adheres to the master 2 in the pattern. In this way, the image is formed on the master 2 to obtain a plate-making master (plate-making printing original plate).

【0175】

2 and 3 show a configuration example of an inkjet recording device as in the device system of FIG. FIG. 2 is a diagram showing a part of the head of such an inkjet recording device, and FIG. 3 is a diagram for further detailing the structure.

【0176】

As shown in FIG. 2, the head 10 provided in the inkjet recording device includes a head body 14 made of an insulating material such as plastic or ceramic, and meniscus control plates 15 and 16. In the figure, reference numeral 17 denotes a discharge electrode that applies a voltage to perform discharge. Further, the head body will be described in detail with reference to FIG. 3 in which the regulation plates 15 and 16 are removed from the head.

【0177】

The head body 14 is provided with a plurality of ink grooves 3 for circulating ink perpendicular to the edge of the head body, and a discharge electrode 17 is provided inside the ink grooves 3. Two adjacent ink grooves form one cell, and ejection portions 20 and 20'are provided at the tip of the partition wall 19 at the center thereof. In the discharge portions 20 and 20', the partition wall is thinner and sharper than the other partition wall portions 19. The tip of the discharge portion may be slightly chamfered, such as 20'. Although only two cells are shown in the figure, the cells are separated by a partition wall 21, and the tip portion 22 thereof is chamfered so as to be retracted from the discharge portions 20 and 20'.

【0178】

Ink is flowed from the I direction through the ink groove to the head by an ink supply means (not shown), and the ink is supplied to the ejection portion. Further, excess ink is collected in the O direction by an ink collecting means (not shown), and as a result, fresh ink is always supplied to the ejection unit. In this state, by applying a voltage to the ejection electrode to the counter electrode (not shown), which is provided in a form opposed to the ejection portion and holds the master 2 on the surface thereof, ink is ejected from the ejection portion and onto the master 2. An image is formed.

【0179】

As described above, an image is formed on the original plate for lithographic printing by an inkjet method using an oil-based ink to obtain a plate making master. When the lithographic printing plate used is composed of a hydrophilic surface layer, it is used as it is for offset printing as a printing plate.

【0180】

On the other hand, in the case of a lithographic printing original plate accompanied by desensitization, a printing plate is produced by surface-treating with a desensitizing treatment liquid to desensitize a non-image portion. Zinc oxide desensitization has conventionally been carried out as this type of desensitization treatment solution, which includes a ferrocyan salt, a cyanide-containing treatment solution containing a ferricyan salt as a main component, an amminecobalt complex, phytic acid and its derivative, and a guanidine derivative. A cyanide-free treatment liquid containing the above-mentioned main component, a treatment liquid containing an inorganic acid or an organic acid as a main component that forms a chelate with zinc ions, a treatment liquid containing a water-soluble polymer, and the like are known.

【0181】

For example, examples of the cyanide-containing treatment liquid include those described in Tokusho 44-9045, 46-39403, Japanese Patent Application Laid-Open No. 52-76101, No. 57-107889, No. 54-117201, and the like. Examples of the phytic acid-based compound-containing treatment liquid include JP-A-53-83807, No. 53-83805, No. 53-102102, No. 53-109701, No. 53-127003, No. 54-2803, and No. 54. -The ones described in No. 44901 etc. can be mentioned.

【0182】

Examples of the treatment liquid containing a metal complex compound such as a cobalt complex include those described in JP-A-53-104301, No. 53-140103, No. 54-18304, and No. 43-28404. Examples of the inorganic or organic acid-containing treatment liquid include those described in Tokusho No. 39-13702, No. 40-10308, No. 43-28408, No. 40-26124, Japanese Patent Application Laid-Open No. 51-118501, and the like. ..

【0183】

Examples of the guanidine compound-containing treatment liquid include those described in JP-A-56-111695 and the like. Examples of the treatment liquid containing a water-soluble polymer include Japanese Patent Application Laid-Open No. 52-126302, No. 52-134501, No. 53-49506, No. 53-59502, No. 53-104302, No. 38-9665, and No. 38-9665. Examples thereof include those described in No. 39-22263, No. 40-763, No. 40-2202, and Japanese Patent Application Laid-Open No. 49-36402.

【0184】

In any of the above desensitization treatments, zinc oxide in the surface layer is ionized to zinc ions, and these ions cause a chelating reaction with a chelate-forming compound in the desensitization treatment liquid to produce a zinc chelated product. Is believed to form and deposit in the surface layer to make it hydrophilic.

【0185】

The desensitizing treatment is usually performed at room temperature (about 15 ° C to 35 ° C) for about 2 to 60 seconds. About 5,000 sheets can be printed off-set using dampening water using this printing plate.

【0186】

[Example]

Hereinafter, the present invention will be described in more detail with reference to production examples of macromonomers used in the present invention, production examples and examples of resin particles, but the present invention is not limited thereto.

【0187】

Production example of macromonomer (MM) 1: Macromonomer (MM-1) A mixed solution of 100 g of monomer (M-1) having the following structure, 2 g of 3-mercaptopropionic acid and 200 g of toluene was heated to a temperature of 70 ° C while stirring under a nitrogen stream. 1.0 g of 2,2'-azobis (isobutyronitrile) (abbreviation: AIBN) was added and reacted for 4 hours, 0.5 g of AIBN was further added for 3 hours, and 0.3 g of AIBN was further added for 3 hours. Next, 8 g of glycidyl methacrylate, 1.0 g of N, N-dimethyldodecylamine and 0.5 g of t-butylhydroquinone were added to this reaction solution, and the mixture was stirred at a temperature of 100 ° C. for 10 hours. After cooling, the reaction solution was redisposited in 2 liters of methanol to give 82 g of white powder. The weight average molecular weight (Mw) of the polymer is 1 × 10.⁴(The weight average molecular weight represents the polystyrene-equivalent value by the GPC method. The same applies hereinafter).

【0188】

[Chemical 29]

<img file="JP2000336291A_D0025.tif" />【0189】

Production example of macromonomer (MM) 2 ~ 13: Macromonomer (MM-2) ~ (MM-13) In Production Example 1 of macromonomer (MM), the reaction was carried out in the same manner as in Production Example 1 except that only the monomer (M-1) was replaced with each compound corresponding to -A below, and the macromonomer (MM- 2) ~ (MM-13) were synthesized. The weight average molecular weight of each of the obtained macromonomers is 9 × 10.³~1×10⁴Was in the range of.

【0190】

[table 1]

<img file="JP2000336291A_D0026.tif" />【0191】

[Table 2]

<img file="JP2000336291A_D0027.tif" />【0192】

Production example of macromonomer (MM) 14: Macromonomer (MM-14) A mixed solution of 100 g of monomer (M-2) having the following structure, 2 g of thioethanol and 20 g of toluene was heated to a temperature of 70 ° C while stirring under a nitrogen stream. 1.0 g of AIBN was added and the reaction was carried out for 4 hours. Further, 0.5 g of AIBN was added and the reaction was carried out for 3 hours, and then 0.3 g of AIBN was further added and the reaction was carried out for 3 hours. The reaction solution was cooled to room temperature, 8 g of 2-carboxyethyl acrylate was added, and a mixed solution of 12.7 g of dicyclohexylcarbodiimide (abbreviated as DCC) and 60 g of methylene chloride was added dropwise over 1 hour. 1.0 g of t-butyl hydroquinone was added, and the mixture was stirred as it was for 4 hours. The filtrate obtained by filtering the precipitated crystals was reprecipitated in 2 liters of methanol. The precipitated oil was decanted, dissolved in 150 ml of methylene chloride and reprecipitated in 1 liter of methanol. Oil is collected, dried under reduced pressure, yield 60 g, Mw 8 × 10³Was obtained.

【0193】

[Chemical 30]

<img file="JP2000336291A_D0028.tif" />【0194】

Production example of macromonomer (MM) 15 ~ 17: Macromonomer (MM-15) ~ (MM-17) In Production Example 14 of macromonomer (MM), the monomer (M-2) and unsaturated carboxylic acid (corresponding to 2-carboxyethyl methacrylate) are replaced with each other in the same manner as in Production Example 14, and the following table- Each macromonomer of B was produced. The yield was 60 to 70 g, and the weight average molecular weight of each macromonomer obtained was 7 × 10.³~9×10³Was in the range of.

【0195】

[Table 3]

<img file="JP2000336291A_D0029.tif" />【0196】

Production example of macromonomer (MM) 18: Macromonomer (MM-18) A mixed solution of 100 g of monomer (M-3) having the following structure, 150 g of tetrahydrofuran and 50 g of isopropyl alcohol was heated to a temperature of 75 ° C. under a nitrogen stream. 5.0 g of 4,4'-azobis (4-cyanovaleric acid) (abbreviation: ACV) was added and reacted for 5 hours, and 1.0 g of ACV was further added and reacted for 4 hours. After cooling, the reaction solution was reprecipitated in 1.5 liters of methanol, the oil was decanted and dried under reduced pressure. The yield was 85 g. A mixture of 50 g of this oil, 15 g of glycidyl methacrylate, 1.0 g of N, N-dimethyldodecylamine, 1.0 g of 2,2'-methylenebis (6-t-butyl-p-cresol) and 100 g of toluene was placed at a temperature of 100 ° C. Stirred for 15 hours. After cooling, the reaction was redisposited in 1 liter of petroleum ether to give 63 g of white powder. Weight average molecular weight is 7 × 10³Met.

【0197】

[Chemical 31]

<img file="JP2000336291A_D0030.tif" />【0198】

Production example of resin particles (L) 1: Resin particles (L-1) A mixture of 10 g of dispersion stabilizing resin (P-1) having the following structure, 97 g of vinyl acetate, 3 g of macromonomer (MM-19) having the following structure and 286 g of Isopar H was heated to a temperature of 75 ° C while stirring under a nitrogen stream. .. To this, 2 g of 2,2'-azobis (isovaleronitrile) (abbreviation: AIVN) was added, and the mixture was stirred for 3 hours. Next, 1.2 g of AIVN was added and stirred for 2 hours, then 0.8 g of 2,2'-azobisisobutyronitrile (abbreviation: AIBN) was added, and the mixture was heated to a temperature of 80 ° C and stirred for 3 hours. .. Then, the temperature was raised to 100 ° C., and the mixture was stirred under a reduced pressure of 200 mmHg for 2 hours to distill off unreacted monomers. After cooling, it was passed through a 200 mesh nylon cloth, and the obtained white dispersion was a latex having a polymerization rate of 93% and an average particle size of 0.40 μm. The particle size was measured with CAPA-500 (manufactured by HORIBA, Ltd.). Centrifuge a part of the white dispersion (rotation speed 1 x 10)⁴The precipitated resin particles were collected and dried over rpm (rotation time 1 hour), and the weight average molecular weight (Mw) and glass transition point (Tg) of the resin particles were measured. As a result, Mw was 9 × 10.⁴(Polystyrene conversion value by GPC. The same applies hereinafter), Tg was 39 ° C.

【0199】

[Chemical 32]

<img file="JP2000336291A_D0031.tif" />【0200】

Production Examples of Resin Particles (L) 2 ~ 15: Resin Particles (L-2) ~ (L-15) In Production Example 1 of resin particles (L), each particle was used in the same manner as in Production Example 1 except that 3 g of each macromonomer (MM) in Table-C below was used instead of 3 g of macromonomer (MM-19). Manufactured. The average particle size of each of the obtained particles was a latex in the range of 0.35 to 0.45 μm. Mw for resin particles is 8 × 10⁴~1×10⁵, Tg was in the range of 35-45 ° C.

【0201】

[Table 4]

<img file="JP2000336291A_D0032.tif" />【0202】

Production example of resin particles (L) 16: Resin particles (L-16) A mixture of 12 g of a dispersion stabilizing resin (P-2) having the following structure and 280 g of Isopar G was heated to a temperature of 70 ° C while stirring under a nitrogen stream. A mixture of 30 g of methyl methacrylate, 62 g of methyl acrylate, 2 g of macromonomer (MM-15), 6 g of acrylic acid and 1.5 g of AIVN was added dropwise to this in 1 hour, and the mixture was stirred as it was for 2 hours. Next, 1.0 g of AIVN was added and the mixture was heated to a temperature of 75 ° C and stirred for 3 hours. Further, 0.8 g of AIBN was added and the mixture was heated to a temperature of 80 ° C and stirred for 3 hours. Then, the temperature was raised to 100 ° C., and the mixture was stirred under a reduced pressure of 200 mmHg for 2 hours to distill off unreacted monomers. After cooling, it was passed through a 200 mesh nylon cloth, and the obtained white dispersion was a latex having a polymerization rate of 99% and an average particle size of 0.40 μm. Mw for resin particles is 2 × 10⁵, Tg was 42 ° C.

【0203】

[Chemical 33]

<img file="JP2000336291A_D0033.tif" />【0204】

Production Examples of Resin Particles 17 ~ 22: Resin Particles (L-17) ~ (L-22) In Production Example 16 of the resin particles, instead of 12 g of the dispersion stabilizing resin (P-2) and 2 g of the macromonomer (MM-15), 12 g of the dispersion stabilizing resin (P-3) having the following structure and the following Table-D Each dispersion was produced in the same manner as in Production Example 16 except that each macromonomer (MM) was used. The polymerization rate of each dispersion was 98 to 99%, and the average particle size of each particle was in the range of 0.38 to 0.45 μm.

【0205】

[Chemical 34]

<img file="JP2000336291A_D0034.tif" />【0206】

[Table 5]

<img file="JP2000336291A_D0035.tif" />【0207】

Production example of resin particles (L) 23: Resin particles (L-23) A mixture of 10 g of a dispersion stabilizing resin (P-4) having the following structure, 2 g of a macromonomer (MM-20) and 280 g of Isopar G was heated to a temperature of 70 ° C while stirring under a nitrogen stream. A mixture of 30 g of methyl methacrylate, 53 g of methyl acrylate, 7 g of 2- (N, N-dimethylamino) ethyl methacrylate and 1.5 g of AIVN was added dropwise thereto in 1 hour, and the mixture was stirred as it was for 2 hours. Next, 1.0 g of AIVN was added and the mixture was heated to a temperature of 75 ° C and stirred for 3 hours. Further, 0.8 g of AIBN was added and the mixture was heated to a temperature of 80 ° C and stirred for 3 hours. Then, the temperature was raised to 100 ° C., and the mixture was stirred under a reduced pressure of 200 mmHg for 2 hours to distill off unreacted monomers. After cooling, it was passed through a 200 mesh nylon cloth, and the obtained white dispersion was a latex having a polymerization rate of 99% and an average particle size of 0.40 μm. Mw for resin particles is 2 × 10⁵, Tg was 42 ° C.

【0208】

[Chemical 35]

<img file="JP2000336291A_D0036.tif" />【0209】

Production Examples of Resin Particles (L) 24 ~ 31: Resin Particles (L-24) ~ (L-31) In Production Example 23 of the resin particles (L), instead of 10 g of the dispersion stabilizing resin (P-4) and 7 g of 2- (N, N-dimethylamino) ethyl methacrylate, 15 g of the following dispersion stabilizing resin (P-5) Each particle was produced in the same manner as in Production Example 23 above, except that 7 g of the basic monomer (B) shown in Table-E below was used. The polymerization rate of each of the obtained dispersions was 99%, and the average particle size of each particle was in the range of 0.40 to 0.45 μm.

【0210】

[Chemical 36]

<img file="JP2000336291A_D0037.tif" />【0211】

[Table 6]

<img file="JP2000336291A_D0038.tif" />【0212】

Production example of resin particles (L) 32: Resin particles (L-32) A mixture of 10 g of a dispersion stabilizing resin (P-6) having the following structure and 280 g of Isopar G was heated to a temperature of 75 ° C while stirring under a nitrogen stream. To this, 15 g of methyl methacrylate, 26 g of methyl acrylate, 2 g of macromonomer (MM-21) having the following structure, 8 g of 4- (N, N-dimethylamino) ethyl methacrylate and AIBN, a mixture of 1.5 g, 15 g of methyl methacrylate, and methyl acrylate. A mixture of 28 g, 5 g of 2-phosphonoethyl methacrylate and 10 g of ethanol was added dropwise simultaneously for 1 hour, and the mixture was stirred as it was for 2 hours. Next, 1.0 g of AIBN was added and the mixture was stirred for 3 hours. Further, 0.8 g of AIBN was added and the mixture was heated to a temperature of 80 ° C. and stirred for 3 hours. Next, the temperature was raised to 100 ° C., and the mixture was stirred under a reduced pressure of 200 mmHg for 2 hours to distill off ethanol and unreacted monomers. After cooling, it was passed through a 200 mesh nylon cloth, and the obtained white dispersion was a latex having a polymerization rate of 99% and an average particle size of 0.45 μm. Mw for resin particles is 1 × 10⁵, Tg was 40 ° C.

【0213】

[Chemical 37]

<img file="JP2000336291A_D0039.tif" />【0214】

Production Examples of Resin Particles (L) 33 ~ 38: Resin Particles (L-33) ~ (L-38) In Production Example 32 of the resin particles (L), instead of 10 g of the dispersion stabilizing resin (P-6), 2 g of the macromonomer (MM-21) and 5 g of 2-phosphonoethyl methacrylate, the dispersion stabilizing resin having the following structure ( 0.034 mol (monomer (B) / monomer (C) =) of P-7) 8 g, the macromonomer (MM-19) 2 g, and each acidic group-containing monomer (C) in Table F below. Each particle was produced in the same manner as in Production Example 32 above, except that 1.5 molar ratio) was used. The average particle size of each of the obtained particles was a latex in the range of 0.40 to 0.50 μm. Mw for resin particles is 9 × 10⁴~2×10⁵, Tg was in each range of 40-48 ° C.

【0215】

[Chemical 38]

<img file="JP2000336291A_D0040.tif" />【0216】

[Table 7]

<img file="JP2000336291A_D0041.tif" />【0217】

Production Example of Resin Particles for Comparison 1: Resin Particles (LL-1) In Production Example 1 of the resin particles (L), a dispersion was produced in the same manner as in Production Example 1 except that the macromonomer (MM-19) was removed. The polymerization rate of the obtained white dispersion was 94%, and the latex had an average particle size of 0.36 μm. Mw for resin particles is 3 × 10⁵, Tg was 38 ° C.

【0218】

Production Example of Resin Particles for Comparison 1: Resin Particles (LL-2) In Production Example 23 of the resin particles (L), a dispersion was produced in the same manner as in Production Example 23 except that the macromonomer (MM-20) was removed. The polymerization rate of the obtained white dispersion was 99%, and the latex had an average particle size of 0.40 μm. Mw for resin particles is 2 × 10⁵, Tg was 41 ° C.

【0219】

Example 1 and Comparative Example A &lt;Preparation of original plate for lithographic printing&gt; The composition with the following contents was placed in a paint shaker (manufactured by Toyo Seiki Co., Ltd.) together with glass beads, dispersed for 60 minutes, and then the glass beads were filtered to obtain a dispersion. ..

【0220】

Gelatin 7g Alkoxysilane-modified polyvinyl alcohol R1130 4g (Made by Kuraray Co., Ltd.) Silica: Silysia 310 (manufactured by Fuji Silysia Chemical Ltd.) 8g Colloidal silica 20% solution: Snowtech CR503 38g (Manufactured by Nissan Chemical Industries, Ltd.) Fluorine alkyl ester FC430 (manufactured by 3M) 0.8g Dural compound CH₂= CHSO₂CH₂CONH (CH)₂)₃NHCOCH₂SO₂CH = CH₂ 0.24g Water 54g [0221]

Using the support of ELP-I type master (trade name manufactured by Fuji Photo Film Co., Ltd.) used as an electrophotographic flat plate printing original plate for light printing, the above composition is applied on it using a wire bar. , Dry at 100 ° C for 10 minutes, coating amount 8g / m²An image receiving layer was formed in the above, and an original plate for lithographic printing was obtained. The surface smoothness of the obtained image receiving layer was measured by using a Beck smoothness tester (manufactured by Kumagai Riko Co., Ltd.) under the condition of an air capacity of 10 cc, and the smoothness (sec / 10 cc) was measured to 250 (sec / 10 cc). It was sec / 10cc). The contact angle of the surface with water was 0 degrees. However, for the surface contact angle, 2 μl of distilled water is placed on the surface of the original plate, and the surface contact angle (degrees) after 30 seconds is measured using the surface contact meter CA-D (trade name, manufactured by Kyowa Interface Science Co., Ltd.). Was measured.

【0222】

&lt;Creation of oil-based ink (IK-1)&gt; 10 g of polydodecyl methacrylate, 10 g of alkaline blue and 30 g of isoper G were placed in a paint shaker (manufactured by Tokyo Seiki Co., Ltd.) together with glass beads, dispersed for 4 hours, and the glass beads were filtered. Separately, a fine blue dispersion was obtained. 50 g of the resin particles (L-1) produced in Production Example 1 of the resin particles (L) (as a solid content), 3 g of the alkali blue dispersion (as a solid content), and dodecene-semimaleic acid tetradecylamide. A blue oil-based ink was prepared by diluting 0.08 g of the polymer with Isopar E so as to have a total volume of 1 liter.

【0223】

(Comparative Example A) In Example 1, the same procedure as in Example 1 was carried out except that the oil-based ink (IKR-1) having the following contents was used instead of the oil-based ink (IK-1). &lt;Creation of comparative oil-based ink (IKR-1)&gt; In the preparation of oil-based ink (IK-1), 50 g (as solid content) of comparative resin particles (LL-1) was used instead of resin particles (L-1). Other than that used, it was prepared in the same manner as the ink (IK-1).

【0224】

The ejection stability, image reproducibility, running stability, etc. of these oil-based inks were investigated, and the results are shown in Table-G.

【0225】

[Table 8]

<img file="JP2000336291A_D0042.tif" />【0226】

Note 1) Dischargeability As a discharge experiment device, the measurement was performed with a device using an injection needle as shown in FIG. 4 for the discharge head. The injection needle is made of stainless steel and has an inner diameter of 360 μm, an outer diameter of 615 μm, a cutting angle of the tip of 19 degrees, and a radius of curvature of 13 μm. It was transmitted and collected. The ink flow rate at this time was 0.75 cc / min. This injection needle was placed 300 μm away from the surface of the plate material mounted on the counter electrode, and a pulse voltage of 800 V and 100 μSec width was superimposed and applied to a bias voltage of 700 V as a discharge voltage at a frequency of 2.5 kHz for printing. The discharge rate was calculated from the number of dots actually printed with respect to the number of applied pulses (%). Further, Samples I and II show changes in the time-lapse state after ink production, and I (fresh product: condition I) means that the ink obtained by blending all the composition components is naturally aged for one week (normal temperature). On the other hand, in II (aged product: condition II), sample I was stored under high temperature and high humidity (40 ° C, 85% RH) for 2 weeks and allowed to age forcibly. It is an ink.

【0227】

Note 2) Shape of print dots The following evaluations were performed using ink samples that had been forcibly aged. Film thickness A discharge experiment was performed in the above discharge property evaluation items. The film thickness of the printed dots of the sample was measured from a scanning electron microscope (SEM) photograph. The thicker the film thickness is printed, the more the particles in the ink are concentrated and ejected. ·shape Similarly, using the above sample, the presence or absence of dot bleeding, distortion, etc. was examined by observing photographs with an optical microscope and SEM.

【0228】

Note 3) Drawability (A) Using the original plate for lithographic printing created as described above, the graphtec servo, Protar DA8400, which can draw computer output, was modified, and the ink ejection head shown in Fig. 2 was attached to the Ben plotter section, and the size was 500 μm. Plates were made by printing on the original plate for lithographic printing installed on the counter electrodes at intervals using the oil-based ink (IK-1) having the above contents. At this time, printing was performed under the conditions of a bias voltage of 650 V, a discharge voltage of 700 V, and a pulse voltage having a width of 100 μSec at a frequency of 2.0 kHz. Subsequently, using a RICOH FUSER model 592 (manufactured by Ricoh Co., Ltd.), the surface temperature of the ink image surface was adjusted to 95 ° C and heated for 20 seconds to sufficiently fix the image portion. A copy image of the obtained plate-making product (that is, a printing plate) was visually observed with an optical microscope at a magnification of 200 times.

【0229】

Note 4) Running performance An ink injection test was conducted by putting ink (II) over time into the ejection experiment device used for ejection performance evaluation, and the continuous ejection time at which the ejection rate was maintained at 100% was measured. In addition, the state of adhesion of particles to the head portion of the discharge electrode when the turbulence of discharge was observed was observed.

【0230】

Note 5) Printing resistance The plate making plate obtained according to the method of Note 3) is used for the printing plate, and a solution obtained by diluting SLM-OD (manufactured by Mitsubishi Paper Mills Limited) 30 times with water is used as the dipping water, and Oliver 94 is used as the printing material. Printing was performed with black ink for offset printing using a mold (manufactured by Sakurai Seisakusho Co., Ltd.). The number of printed matter with a clear image that has no background stains and no omissions such as fine lines and characters is expressed as print durability.

【0231】

As shown in Table-G, Example 1 showed good results even in the aged sample in terms of ejection stability, shape of printed dots and drawability. On the other hand, Comparative Example A showed almost the same performance as that of Example 1 in the fresh product, but the aged sample did not eject due to the ejection abnormality, or the ejected dots also had problems such as thinning of the dot film thickness and bleeding. Arose. Further, when the running property of the ink was examined, Example 1 was printed without any problem for a long time, and no abnormality was found in the electrode portion. However, in Comparative Example A, it became difficult to discharge in a few hours, and when the head portion was observed, agglomerates of particles were attached. Further, when this plate making plate was printed, only Example 1 had a printing resistance of 3,000 sheets or more. In Comparative Example A, the image portion was missing from the printout and could not be put into practical use. However, the formed image portion had a print resistance of about 1,000 at most, and the image disappeared. From the above results, the ink of the present invention can form a good ejection property and a film thickness of dots, and a large number of printed matter having a clear image can be obtained even when printed as a printing plate. Furthermore, even if it is used for a long period of time, it does not adhere to the electrode portion and exhibits stable performance.

【0232】

Examples 2 to 15 In Example 1, instead of 50 g of the resin particles (L-1) in the oil-based ink (IK-1), 50 g of each resin particle (as a solid content) in Table-H below was used, and the oil-based ink (IK-) was used. Each oil-based ink was prepared in the same manner as in 1) and evaluated in the same manner as in Example 1.

【0233】

[Table 9]

<img file="JP2000336291A_D0043.tif" />【0234】

Each oil-based ink (IK-2) to (IK-15) showed the same performance as the oil-based ink (IK-1). Results equivalent to those of Example 1 were obtained in terms of ejection property, dot shape, drawing property, running property, and printing resistance.

【0235】

Example 16 &lt;Preparation of original plate for lithographic printing&gt; The composition having the following contents was placed in a paint shaker together with glass beads and dispersed for 80 minutes, and then the glass beads were filtered off to obtain a dispersion.

【0236】

Silica: Silysia 445 (manufactured by Fuji Silysia Chemical Ltd.) 40g Silica gel Silica 20% solution: Snowtech C 200g (Manufactured by Nissan Chemical Industries, Ltd.) Clay 50% dispersion liquid 40g -Polyvinyl alcohol: PVA-117, 10% solution 120g (Made by Kuraray Co., Ltd.) Melamine resin 2.0g Ammonium chloride 0.2g Water 50g [0237]

Using the support of ELP-2 type master (manufactured by Fuji Photo Film Co., Ltd., trade name) used as an electrophotographic flat plate printing original plate for light printing, the above composition is applied on it using a wire bar. Then heat at 110 ° C for 10 minutes, and apply 6g / m.²An image receiving layer was formed in the above, and an original plate for lithographic printing was obtained. The surface smoothness of the obtained image receiving layer was 300 (sec / 10cc) in Beck smoothness, and the contact angle of the surface with water was 0 degrees. This printing original plate was made in the same manner as in Example 1, and offset printing was performed as a printing plate. However, instead of the oil-based ink (IK-1) used in Example 1, the oil-based ink (IK-16) having the following contents was used.

【0238】

&lt;Preparation of oil-based ink (IK-16)&gt; A mixture of 100 g (as a solid content) of the resin particles (L-16) obtained in Production Example 16 of the resin particles (L) and Victoria Blue B, 5 g at a temperature of 100. The mixture was heated to ° C and heated and stirred for 3 hours. After cooling to room temperature, a 200 mesh nylon cloth was passed through the cloth to remove the remaining dye, whereby a blue resin dispersion having an average particle size of 0.45 μm was obtained. Dilute 60 g of the above blue resin dispersion (as solid content) and 0.20 g of zirconium naphthenate salt as a charge adjuster in a mixed solution of hexamethyldisiloxane / isopar G (3/2) weight ratio to make the total amount 1 liter. By doing so, a blue oil-based ink (IK-16) was created.

【0239】

The physical characteristics of the obtained ink were measured in the same manner as in Example 1. The ejection performance was 100% for both conditions I and II, and the shape of the printed dots was 1.8 μm spherical, which was good. The actual drawn image was also good, and the ink sample over time was the same, so there was no problem. When printed using this plate, 10,000 clear printed matter without image omission was obtained under both conditions I and II. Furthermore, the running performance also showed the same performance as in Example 1.

【0240】

Examples 17-22 In Example 16, 100 g (as solid content) of each particle in Table-I below was used instead of 100 g (as solid content) of the resin particles (L-16) in the oil-based ink (IK-16). , Each oil-based ink was prepared in the same manner as the oil-based ink (IK-16).

【0241】

[Table 10]

<img file="JP2000336291A_D0044.tif" />【0242】

When each performance was evaluated in the same manner as in Example 1 using each oil-based ink, each ink showed the same good performance as in Example 1.

【0243】

Example 23 and Comparative Example B &lt;Creation of oil-based ink (IK-23)&gt; 10 g of the dispersion stabilizing resin (P-2), 10 g of Microlith-Blue 4GT (manufactured by Ciba Geigy) and 80 g of Isopar G are placed in a paint shaker together with glass beads and dispersed for 3 hours to glass. The beads were filtered off to give a fine blue dispersion. 60 g of the resin particles (L-23) produced in Production Example 23 of the resin particles (L) (as a solid content), 3 g of the above blue dispersion (as a solid content), and a decene-semimaleic acid tetrasadecylamide copolymer. 0.08 g was diluted with Isopar G to 1 liter to prepare a blue oil-based ink (IK-23).

【0244】

&lt;Comparative Example B&gt; In Example 23, the same procedure as in Example 23 was carried out except that the oil-based ink (IKR-2) having the following contents was used instead of the oil-based ink (IK-23). &lt;Creation of comparative oil-based ink (IKR-2)&gt; In the preparation of oil-based ink (IK-23), 50 g (as solid content) of comparative resin particles (LL-2) was used instead of resin particles (L-23). Other than that used, it was prepared in the same manner as the ink (IK-23).

【0245】

Image reproducibility, running stability, etc. were investigated for these oil-based inks in the same manner as in Example 1, and the results are shown in Table-J.

【0246】

[Table 11]

<img file="JP2000336291A_D0045.tif" />【0247】

Note 6) Dischargeability (B) In the ejection property evaluation method (A) of Example 1, the measurement was performed in the same manner as in the ejection property (A) except that the pulse voltage of dot printing was increased from 2.5 kHz to a frequency of 5.0 kHz (that is, the printing speed). Measured by doubling). Note 7) Drawability (B) In the drawing method (A) of Example 1, the pulse voltage of dot printing was increased from 2.0 kHz to a frequency of 5.0 kHz and drawn and evaluated.

【0248】

As shown in Table-J, in Example 23, both the fresh product and the aged product showed good performance even when the ejection property and the drawing property were doubled in the printing speed. The printed dots were also spherical dots with a film thickness of 2 μm or more and no bleeding. On the other hand, Comparative Example B showed the same performance as that of Example 23 in the fresh product, but in the aged product, both the ejection property and the drawing property were significantly deteriorated, and the print dots also had a large variation in the film thickness and the shape was distorted. .. Further, the running performance and the printing resistance at the time of printing were good in Example 23 without any change even in the product over time. The running performance of the product over time in Comparative Example B was abnormal in about 1 hour, and a coarse substance, which was considered to be an agglomerate, adhered to the electrode portion at that time. The printing durability of Example 23 was as good as 10,000 or more, but in Comparative Example B, images were missing from the printing. From the above, the oil-based ink of the present invention exhibits excellent durability against running over time.

【0249】

Examples 24 to 38 In Example 23, plate making and printing were performed in the same manner as in Example 23, except that the oil-based ink shown in Table-K below was used instead of the oil-based ink (IK-23). As for the oil-based ink used, 50 g (as a solid content) of the resin particles shown in Table-K below is used instead of the resin particles (L-23) used in the oil-based ink (IK-23) in Example 23. It was created in the same way.

【0250】

[Table 12]

<img file="JP2000336291A_D0046.tif" />【0251】

When evaluated in the same manner as in Example 23, the performance was exactly the same as that in Example 23 and was good. Furthermore, when printed as printing plates, all plates showed a printing durability of 10,000 sheets or more. Further, as in Example 23, the aged ink also showed the same drawing performance and printing durability as the fresh product as in Example 23.

【0252】

Example 39 &lt;Creation of water resistant support&gt; Weighing 100 g / m as a substrate²Using high-quality paper, apply the underlayer paint with the following composition to one surface of the substrate using a wire bar, and dry coating amount 10 g / m.²An underlayer was provided. The smoothness of the surface of the under layer was 150 seconds / 10cc, and the smoothness was adjusted to 1500 (seconds / 10cc) by calendering.

【0253】

&lt;Paint for underlayer&gt; 10 parts by weight of silica gel SBR latex (50% by weight aqueous dispersion, Tg 25 ° C) 92 parts by weight Clay (45% by weight aqueous dispersion) 110 parts by weight Melamine (80% by weight aqueous solution) 5 parts by weight Water 191 parts by weight [0254]

Further, a backcoat layer paint having an unspecified composition is applied to the other surface of the substrate using a wire bar, and a dry coating amount of 12 g / m is applied.²After the backcoat layer was provided, calendar processing was performed by setting calendar conditions so that the smoothness of the backcoat layer was about 50 (seconds / 10cc).

【0255】

&lt;Paint for back coat layer&gt; 200 parts of kaolin (50% aqueous dispersion) 60 parts of polyvinyl alcohol aqueous solution (10%) 100 parts of SBR latex (solid content 49%, Tg 0 ° C) 5 parts of melamine resin initial condensate (Solid content 80%, Sumiretz resin SR-613) [0256]

&lt;Preparation of original plate for lithographic printing&gt; A mixture of zinc oxide 100 g, binder resin (B-1) 16 g with the following structure, binder resin (B-2) 2 g, benzoic acid 0.15 g and toluene 155 g is mixed with a wet disperser homogenizer ( Rotation speed 6 × 10 using Nippon Seiki Co., Ltd.³Dispersed at rpm for 8 minutes.

【0257】

[Chemical 39]

<img file="JP2000336291A_D0047.tif" />【0258】

This dispersion is applied on the above water resistant support using a wire bar in an amount of 10 g / m.²After coating and drying, an original plate for lithographic printing with a surface smoothness of 250 (seconds / 10cc) was prepared. The contact angle of the surface with water was 102 degrees.

【0259】

&lt;Creation of oil-based ink (IK-39)&gt; Dispersion stability resin (P-1) 10 g, black pigment: Microlith Black CT (manufactured by Ciba Geigy) 10 g and Isopar E, 113 g in a paint shaker with glass beads for 6 hours After dispersion, the glass beads were filtered off to obtain a black dispersion. Hexamethyldicyclo contains 40 g (as a solid content) of the resin particles (L-32) produced in Production Example 32 of the resin particles (L), 66 g of the black dispersion, and 0.03 g of an octadecyl vinyl ether / semi-maleic acid decylamide copolymer. Black oil-based ink (IK-39) was prepared by diluting with xan so that the total amount became 1 liter.

【0260】

When the plate was made in the same manner as in Example 1 except that the printing original plate and the oil-based ink (IK-39) were used, a plate-making product having a clear image without missing fine lines and characters was obtained. The thickness of the dots was 0.2 μm, and the circular ones without bleeding and distortion were good.

【0261】

Next, after plate making as described above, a desensitizing treatment liquid (ELP-E2: product name manufactured by Fuji Photo Film Co., Ltd.) is applied to a fully automatic printing machine (AM-2850, product name manufactured by AM Co., Ltd.). Put the solution of the desensitizing treatment liquid (ELP-E2) 4 times with distilled water as a dampening water in the etcher part of the printing press, put it in the dampening water saucer, and print using black ink for offset printing. Printing was performed through a plate-making material on the machine. As a result, more than 3,000 printed matter with clear images without background stains was obtained.

【0262】

[Effect of the invention]

By using the oil-based ink of the present invention, in the electrostatic inkjet recording method, an image excellent in ink ejection stability, clear image forming property and image strength can be formed, and a large number of printed matter of clear image can be printed. Can provide a printing plate that can be used. Further, according to the oil-based ink for electrostatic inkjet of the present invention, the dispersed particles are excellent in redispersibility and storage stability, the ink supply path is not clogged, and the ink ejection is stable.

[Simple explanation of drawings]

[Figure 1]

It is a schematic block diagram which shows an example of the apparatus system used in this invention.

[Figure 2]

It is a figure which shows a part of the head of the inkjet recording apparatus used in this invention.

[Fig. 3]

It is the figure which removed the meniscus regulation plate 15, 16 from the head shown in FIG.

[Fig. 4]

It is a figure which shows the discharge experimental apparatus used in an Example.

[Explanation of symbols]

1 Inkjet recording device 2 Master 3 computer 4 bus 10 Inkjet recording head 13 Inkjet recording head 14 Head body 15, 16 Meniscus regulation board 17 Discharge electrode 18 Ink groove 19, 21 bulkhead 20, 20'Discharge 22 Tip 31 Drum-shaped counter electrode 32 Recording medium 33 Power supply 34 Recording head 35 Liquid transfer pump 36 ink tank 37 Waste liquid tank