Preparing method for support body for lithographic printing

[Detailed Description of the Invention]

The present invention relates to the manufacturing method of the base material for lithographic printing plates, and after carrying out surface roughening especially of the aluminum plate (an aluminum alloy plate is also included.) mechanically, it is related with the manufacturing method of the base material for lithographic printing plates which consists of carrying out surface roughening electrochemically under conditions which give a specific sand-like pattern. It is the structure of Then and the sand-like pattern concerned at the aluminum plate by which the sand-like pattern which has puncturing was provided in the surface at Japanese Patent Application No. No. 35788 [ 53 to ]. 1 It Has Distribution of Puncturing of as [ whose Diameters of Puncturing equivalent to 5% of Cumulative Frequency Curves of the Diameter of Puncturing and 95% are 3Micro or More and 10±1Micro, Respectively ], 2 Oh [ Center Line Average / of Sand-like Pattern ] -- Base Material for Lithographic Printing Plates, wherein To Ra is Range Which is 0.6~1.0Micro The photosensitive lithographic printing plate which it Disclosed and was created using this base material (called a pre sensitized plate (Pre-Sensitized Plate)) it is called the PS version for short. the purport that the lithographic printing plate from which it is high, and also it was engraved after this, and sensitivity was obtained is excellent in print durability -- it is indicated. For manufacturing the aluminum plate which has the sand-like pattern structure within the limited limits like the above on the surface by the electrochemical surface roughening method, carrying out a deer, For the that [ to which terms and conditions, such as composition of Electrolytic bath, its temperature, current density, and electrolysis time, were restricted extremely ], and intermediary Cause reason, it became clear that difficulty with great making such an aluminum plate industrially followed. The base material for lithographic printing plates which carried out surface roughening mechanically first, carried out surface roughening of the aluminum plate electrochemically, and subsequently manufactured it as a result of this artificer's repeating research wholeheartedly in view of the above-mentioned fault, It found out giving the lithographic printing plate of the performance which shall not have puncturing distribution of the limited sand-like pattern like the above, and was extremely excellent also in When. That is, in the manufacturing method of the base material for lithographic printing plates which has a sand-like pattern which has puncturing on the surface which consists of carrying out surface roughening electrochemically after the present invention carries out surface roughening of the aluminum plate mechanically, The electrochemical surface roughening is performed using police box waveform current which the amount of electricity consists large of rather than the amount of electricity in chloride or a nitric acid electrolytic solution at the time of the negative pole at the time of the anode, It is a manufacturing method, wherein the diameter of puncturing equivalent to 5% of the cumulative frequency curves of the path of the puncturing and 95% has the distribution which is 3micro or less and 7micro or less, respectively. Hereinafter, order is explained for the present invention later on still in detail. Pure aluminum and an aluminum alloy plate are contained in the aluminum plate used in the present invention. Various things can be used as an aluminium alloy, for example, metal, such as Clock matter, copper, manganese, magnesium, chromium, zinc, a lead, bismuth, and nickel, and the alloy of aluminum are used. The example of a concrete aluminium alloy is shown in the following table. The unit of the number in front is weight %, and the remainder is aluminum.

[Table]

The impurities which are the grades which could be added to some iron and titanium, in addition were not put up, and which can be disregarded can also be included in these constituents. Although surface roughening of the above aluminum plates is carried out mechanically first, sanctification processing is performed before that if needed for the purpose of removing oil and fats, rust, garbage, etc. adhering on the surface of an aluminum plate. As this sanctification processing, the alkaline degreasing equalization study purification by solvent degreasing by Trichloren etc., for example, caustic alkali of sodium etc., is included as described, for example in the 186~210th pages of the surface-of-metal technical manual (Nikkan Kogyo Shimbun). Since Sumato occurs when alkaline degreasing like caustic alkali of sodium is carried out, in order to remove this, processing immersed in 10~30% of nitric acid is further performed. As a method of carrying out surface roughening of the surface of an aluminum plate mechanically, publicly known various methods can be used conventionally. For example, the method of a sandblast, ball grain, Wower grain, brush grain, etc. is included, and especially brush grain is preferred also among these. The further details of the brush grain method are described in JP,51-46003,B (or U.S. Pat. No. 3891516 specification) and JP,50-40047,B. the center line average of the base material for lithographic printing plates from which mechanical surface roughening is obtained by the method of the present invention -- oh, it is preferred to be given so that To Ra may be set to 0.4~1.0 micro. here -- the center line average of a sand-like pattern -- oh, it is indicated in JIS-B 0601-1970 as To Ra -- as -- oh -- from a To curve extracting the portion of measurement length l in the direction of that center line, and setting the Y-axis as the direction of the X-axis and length for the center line of this sampling portion -- oh, when a To curve is denoted by y=f(x), the value of Ra given by following () formula is expressed per micron. Ra=1/Lintegral^l_pf(x)d_x() If it opts for the additional processing performed the conditions of the electrochemical surface roughening performed behind, and if needed, a person skilled in the art can determine easily the grade of the mechanical surface roughening for making it become the range of such Ra. Although surface roughening of the aluminum plate by which surface roughening was carried out mechanically is subsequently carried out electrochemically, it is preferred to etch the surface of an aluminum plate chemically before that. This chemical etching processing has the operation which removes the abrasive soap which ate into the surface of the aluminum plate by which mechanical surface roughening was carried out, aluminum waste, etc., and can make the electrochemical surface roughening performed after that attain more uniformly and effectively. The details of this chemical etching method are described in the U.S. Pat. No. 3834998 specification. When it explains more concretely, they are solution which may dissolve aluminum, and the method of more specifically immersing to solution of acid or a base. As the above-mentioned acid, sulfuric acid, fault sulfuric acid, chloride, etc. are contained, for example, and sodium hydroxide, a potassium hydrate, the third phosphoric acid sodium, the second phosphoric acid sodium, the third phosphoric acid potassium, the second phosphoric acid potassium, sodium aluminate, sodium carbonate, etc. are contained as the above-mentioned base. Since it is [ the etching rate ] earlier to use solution of the latter base also especially among these, it is desirable. The quantity of etching is 0.5~30g/m.²It is suitably chosen from Range. Since Sumato generally generates the above-mentioned chemical etching on the surface of aluminum to a It was done case using solution of a base, it is preferred to perform what is called a desmut treatment processed in this case with the mixed acid containing two or more of phosphoric acid, nitric acid, sulfuric acid, chromic acid, or acid of these. Next, surface roughening of the aluminum plate processed as mentioned above is carried out electrochemically. This electrochemical surface roughening is performed using police box waveform current which the amount of electricity consists large of rather than the amount of electricity in chloride or a nitric acid electrolysis solution at the time of the negative pole at the time of the anode, It is carried out so that it may have distribution of as [ whose diameters of puncturing equivalent to 5% of the cumulative frequency curves of the path of the puncturing and 95% are 3micro or less and 7micro or less, respectively ]. The aluminum plate which has a sand-like pattern of such a range on the surface, In spite of being recognized as not suitable as a base material for lithographic printing plates as indicated by JP,59-26480,B, When it is the aluminum plate processed like the present invention combining mechanical surface roughening and electrochemical surface roughening, it is a very surprising thing to say that it excels as a base material for lithographic printing plates. And since it is comparatively easy to obtain the surface of the above sand-like patterns by the electrochemical surface roughening method, such the present invention brings about a manufacturing remarkable advantage. In the present invention, Electrolytic bath used for a method of electrochemical surface roughening is a base or nitric acid. It is appropriate for the concentration to be chosen out of about 0.5 to about 5% of the weight of a range in any case. And these Electrolytic bath can be made to contain a corrosion depressant (or stabilizer) further. For example, in base Electrolytic bath, they are zinc chloride, ammonium chloride, and sodium chloride, Chlorides, such as an aluminium chloride, trimethylamine, triethyl amine, Dimethylamine, Diethyl amine, methylamine, ethyl amine, carbamic acid, Amine, such as triethanol amine, Diethanol amine, and monoethanolamine Gia Min, such as ethylene diamine and hexamethylenediamine, formaldehyde, When acid, such as aldehyde, such as acetaldehyde and n-hexyl aldehyde, phosphoric acid, chromic acid, and nitric acid, is mentioned and it is nitric acid Electrolytic bath, Nitrates, such as zinc nitrate, ammonium nitrate, and sodium nitrate, the above monoamines, Gia Min and aldehyde, phosphoric acid, chromic acid, sulfosalicylic acid, etc. are mentioned. As for the amount of addition to the electrolysis solution of these corrosion depressants, it is preferred to be chosen out of about 0.05 % of the weight ~ about 3% of the weight of the range. Although exchange of a trapezoid wave and a rectangle wave besides the single phase of a sine wave and a three phase alternating current can also be used as police box waveform current used by the present invention, police box waveform current which the amount Qa of electricity consists large of rather than the amount Qc of electricity also in which waveform at the time of the negative pole at the time of the anode is used. Such an electrolysis surface roughening method is written in detail in the U.S. Pat. No. 4087341 specification. The conditions at the time of performing electrochemical surface roughening in the present invention, If it is within the limits which gives the sand-like pattern of as [ whose diameters of puncturing equivalent to 5% of the cumulative frequency curves of the diameter of puncturing of the sand-like pattern obtained by that cause like the above and 95% are 3micro or less and 7micro or less, respectively ], Generally the conditions which give such a sand-like pattern although what kind of conditions may be sufficient are about 50 v, more preferably 2~30 v in voltage from about 1 v, and current densities are about 10 A / dm.²100 A of From about / dm²More preferably they are 10~80 A / dm.²Come out, it is and the amounts of electricity are about 100 C / dm.²30000 C of From about / dm²More preferably they are 100~18000 C / dm.²It is chosen out of Range. As for the ratio of Qc/Qa, 0.3~0.8 is preferred. The temperature of Electrolytic bath is about 45degreeC from about 10degreeC, more preferably 15~45degreeC. For example using a scanning electron microscope, the above-mentioned cumulative frequency curve expands one piece of surface of the aluminum plate by which surface roughening was carried out electrochemically by 100~700 times, and takes a photograph of it, and it measures the diameter of puncturing and number in a unit area from this photograph, It can obtain by drawing the graph which made the horizontal axis the diameter (mu) of puncturing, and made the vertical axis cumulative frequency (%). Although the aluminum plate processed as mentioned above can be used as a base material for lithographic printing plates, it can also process anodization processing, conversion treatment, etc. further. Anodization processing may be performed immediately after washing the aluminum plate processed like the above, but chemical etching processing is more preferably performed to it before that. Such chemical etching processing can be performed like the case of the chemical etching processing which can be performed after the mechanical surface roughening explained previously. And it is the same as that of the case in previous chemical etching processing that it is also more desirable to perform a desmut treatment for chemical etching processing subsequently to the It was done case in solution of a base. Anodization processing can be performed by the method currently conventionally performed in this field. If the current of a direct current or exchange is specifically sent through aluminum in the solution which combined these two or more kinds or non-solution, such as sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid, and benzenesulfonic acid, an anodization tunic can be made to form in an aluminum support surface. Since it changes with the electrolysis solutions used variously, it must generally have been determined, but the concentration of an electrolysis solution of the processing conditions of anodization is generally 1~80-% of the weight and solution temperature 5~70degreeC, and the current density of 0.5~60 A / dm.²The range for voltage 1~100V, and electrolysis time 30-second~50 minutes is suitable. The method of anodizing as Electrolytic bath the phosphoric acid written in the method and U.S. Pat. No. 3511661 specification which are used also among these anodization processings by the invention written especially in the British patent No. 1,412,768 specification, and which are anodized by high-electric-current density in sulfuric acid is preferred. The anodized aluminum plate is alkaline metal silicate as further described in each specification of U.S. Pat. No. 2714066 and 3181461, For example, it can process by methods, such as immersion, in solution of silicic acid sodium, or the lower coating layer of the hydrophilic cellulose (for example, carboxymethyl cellulose etc.) containing water-soluble metal salt (for example, zinc acetate etc.) can also be provided as it writes in the U.S. Pat. No. 3860426 specification. The lithographic printing plate which could provide the photosensitive layer known conventionally as a photosensitive layer of the PS version on the base material for lithographic printing plates by the present invention, could obtain the photosensitive lithographic printing plate, and obtained this by carrying out platemaking processing has the outstanding performance. The following is contained as a constituent of the above-mentioned photosensitive layer. As the photosensitive layer negative operation type photosensitivity diazo compound consisting of diazo resin and a binder U.S. Pat.2063631issue And the condensation product of the diphenylamine p-diazonium salt and form aldehyde which are the reaction products of the diazonium salt currently indicated by each specification of 2667415, and the organic condensing agent containing a reactive-carbonyls machine like Al Dole or Acetal (What is called photosensitive diazo resin) is used suitably. Other useful condensation diazo compounds are indicated by each gazette of JP,49-48001,B, 49-45322, and 49-45323. These types of photosensitive diazo compound is usually obtained in the form of water-soluble mineral salt, therefore can be applied from solution. It is one piece or phenolic hydroxyl beyond it by the method indicated by JP,47-1167,B in these water-soluble diazo compounds, It can be made to be able to react to the aromatic series or aliphatic compound which has a sulfonic group or its both, and photosensitive diazo resin of insoluble in water nature can also be used for the real target which is the reaction product. As an example of the reaction thing which has phenolic hydroxyl, Then and these may have a substitution machine further with diphenolic acid like hydroxy benzophenone, 4, and 4-bis(4'-hydroxyphenyl)pentanoic acid, resorcinol, or diresorcinol. 2, 4-dihydroxy benzophenone, 2-hydroxy 4-methoxybenzophenone, 2, and 2'-dihydroxy 4, 4'-dimethoxy benzophenone or 2, 2', 4, and 4'-tetra-hydroxy benzophenone is contained in hydroxy benzophenone. As desirable sulfonic acid, soluble salts, for example, ammonium, such as aromatic sulphonic acid like sulfonic acid, such as benzene, toluene, xylene, naphthalene, phenol, naphthol, and benzophenone, or it, and alkali metal salt can be illustrated, for example. Generally the sulfonic group content compound may be replaced by low-grade Alkyl, a nitro group, a Halo machine, and/or another sulfonic group. As a desirable thing of such a compound, they are benzenesulfonic acid and toluenesulfonic acid, Naphthalenesulfonic acid, 2, 5-Dimethyl benzenesulfonic acid, sodium benzenesulfonate, Naphthalene 2-sulfonic acid, 1-naphthol 2(or 4)-sulfonic acid, 2, 4-dinitro 1-naphthol 7-sulfonic acid, 2-hydroxy 4-methoxybenzophenone 5-sulfonic acid, m-(p'-Anilino phenylazo) sodium benzenesulfonate, ant Sarin sulfonic acid, o-Toluidine- m-sulfonic acid, ethane sulfonic acid, etc. are raised. The sulfonic ester and salts of alcohol are also useful. Such a compound can usually be easily obtained as an anionic surface-active agent. As the example, ammonium or alkali metal salt, such as lauryl sulfate, alkyl aryl sulfate, p-Nonyl phenyl sulfate, 2-phenylethyl sulfate, and iso Octylphenoxide ethoxyethyl sulfate, are raised. Photosensitive diazo resin of insoluble in water nature isolates as precipitation substantially [ this etc. ] by mixing water-soluble photosensitive diazo resin, the above-mentioned aromatic series, or solution of an aliphatic compound in the quantity which becomes desirable almost an equivalent amount. The diazo resin written in the British patent No. 1312925 specification is also preferred. But suitable diazo resin is 2-methoxy 4-hydroxy 5-benzoyl benzenesulfonic acid salt of the condensation thing of p-Diazo diphenylamine and formaldehyde. It is appropriate for the content of diazo resin to be contained 5~50% of the weight in a photosensitive layer. If the quantity of diazo resin decreases, naturally photosensitivity will become large, but temporal stability falls. The quantity of the optimal diazo resin is about 8~20 % of the weight. On the other hand, although various high molecular compounds may be used as a binder, in the present invention, the thing containing bases, such as hydroxy , amino , carboxylic acid, amide, Sulfone amide, active methylene, a Thio record, and epoxy, is desirable. Sierra described in such a desirable binder at the U.S. Pat. No. 1350521 specification, Polymer which includes a hydroxyethyl acrylate unit or a hydroxyethyl methacrylate unit which is described in the British patent No. 1460978 and each thin document of U.S. Pat. No. 4123276 as main repeat units, Polyamide resin described in the U.S. Pat. No. 3751257 specification, For example, phenol resin and polyvinyl Vollmar resin which are described in the British patent No. 1074392 specification, Polyvinyl acetal resin like polyvinyl butyral resin, line polyurethane resin described in the U.S. Pat. No. 3660097 specification, Phthalate-ized resin of polyvinyl alcohol, the epoxy resin condensed from bisphenol A and epichlorohydrin, Cellulose derivatives containing an amino group like Polya Minos Tschirren or poly Aluminum amino (meta) acrylate, such as polymer, cellulose acetate, cellulose alkyl ether, and cellulose acetate phthalate, are included. Additive agents, such as PH indicator which is described in the British patent No. 1041463 specification, phosphoric acid described in the U.S. Pat. No. 3236646 specification, and dye, can be further added to the constituent consisting of diazo resin and a binder. The photosensitive layer, especially desirable o-quinone diazide compound consisting of o-quinone diazide compound are an o-naphthoquinonediazide compound, For example, U.S. Pat. No. 2766118, 2767092, 2772972, 2859112, 2907665, 3046110, 3046111, 3046115, 3046118, 3046119, 3046120, 3046121, Including each specification of 3046122, 3046123, 3061430, 3102809, 3106465, 3635709, and 3647443, it is describing in many publications and can use these conveniently. But they are [ among these ] o-Nasu Tokinonji Ad Disulfone acid ester of an aromatic series hydroxy compound, or o-naphthoquinonediazide carboxylate ester especially, And o-naphthoquinonediazide sulfonic acid amide of an aromatic series amino compound or o-naphthoquinonediazide carboxylic amide is preferred, What carried out the ester reaction of the o-naphthoquinonediazide sulfonic acid to the condensation thing of pyrogallol and acetone which are described especially in the U.S. Pat. No. 3635709 specification, It is o-naphthoquinonediazide sulfonic acid to the polyester which has a hydroxy group at the end described in the U.S. Pat. No. 4028111 specification, Or the thing to which the ester reaction of the o-naphthoquinonediazide carboxylic acid was carried out, What carried out the ester reaction of o-naphthoquinonediazide sulfonic acid or the o-naphthoquinonediazide carboxylic acid to the copolymer with the monomer of the homopolymer of p-hydroxystyrene which is described in the British patent No. 1494043 specification or this, and others which may copolymerize, What carried out the amide reaction of o-naphthoquinonediazide sulfonic acid or the o-naphthoquinonediazide carboxylic acid to the copolymer with the monomer of p-amino styrene which is described in United States patent 3759th and No. 711 specification, and others which may copolymerize is very excellent. Although it can be used alone, it is more desirable to have mixed with alkali solubility resin and to use these o-quinone diazide compounds. Novolac type phenol resin is contained in suitable alkali solubility resin, and phenol formaldehyde resin, o-cresol formaldehyde resins, m-cresol formaldehyde resins, etc. are contained in Included and a concrete target. It is the above phenol resin as described in the U.S. Pat. No. 4123279 specification, When the condensation thing of the phenol or cresol replaced with the Alkyl machine of carbon number 3~8 like t-butylphenol formaldehyde resins, and formaldehyde is used together, it is much more desirable. being based on the full weight of the constituent which constitutes a photosensitive layer by alkali solubility resin -- inside -- about -- 50~about 85 weight -- more desirable, you are made to contain 60~80% of the weight In the photosensitive composition consisting of o-quinone diazide compound, Additive agents, such as an ingredient which gives print-out performance which is further described in each specification of dye, plasticizer No. 1041463, for example, the British patent, 1039475, and U.S. Pat. No. 3969118 if needed, can be added. A Azide compound and binder (photosensitive layer which consists of high molecular compounds) No. 1235281, for example, the British patent, Each specification and JP,51-32331,A of 1495861, The constituent consisting of the Azide compound, the water solubility, or the alkali solubility high molecular compound described in the 51-36128 gazette etc., etc. The constituent consisting of polymer containing the azido group described in each gazette of JP,50-5102,A, 50-84302, 50-84303, and 53-12984 and the high molecular compound as a binder is contained. Other photosensitive resin layers For example, the polyester compound currently indicated by the JP,52-96696,A certificate, The British patent No. 1112277, 1313390, 1341004, The photo polymerization type photopolymer constituent described in each specification of polyvinyl cinnamate system resin of a statement, U.S. Pat. No. 4072528, and 4072527 is contained in each specification, such as 1377747. The quantity of the photosensitive layer provided on a base material is abbreviation 0.1~about 79-/m.²Preferably it is 0.5~49/m.²It is Range. A resin picture is formed by the processing which includes development by a usual state method after picture exposure of the PS version is carried out. For example, in the case of the PS version which has the above-mentioned photosensitive layer (1) which consists of diazo resin and a binder, after picture exposure, the photosensitive layer of an unexposed portion is removed by development and a lithographic printing plate is obtained. In the case of the PS version which has a photosensitive layer (2), by developing negatives with alkaline water solution, an exposure portion is removed and a lithographic printing plate is obtained after picture exposure. Hereinafter, based on an example, it explains still in detail. % shall show weight %. Example 1 and comparative example 1 The 0.24-mm-thick aluminum plate was often washed with water, after graining the surface using a nylon brush and the pumice T- water-suspended liquid of 400 meshes. After being immersed in sodium hydroxide solution for 20 seconds by 50 degreeC 10% and etching, it washed for 1 minute with running water (20degreeC). Next, in 20 degreeC, exchange of the sine wave of voltage 10V and duty cycle (it is a ratio of time at the time of the anode to exchange 1 cycle time) 0.6 is used using 1.5% of nitric acid solution at the time of the anode, and they are the amount of electricity of 900 C / dm.²In (Qc/Qa=0.8), electrochemical graining during 20 seconds is immersed for 30 seconds after I got it and into 20% phosphoric acid of 70 degreeC, and it is I got it about a desmut treatment. As a result of observing the aluminum plate obtained as a result with a scanning electron microscope, average surface coarseness Ra is 0.7micro, and the surface is Oh. Electrochemical graining was performed for the aluminum plate which is not grained mechanically on the other hand on the above-mentioned case and the conditions, the surface was expanded by 600 times with the scanning electron microscope, the diameter of puncturing of the sand-like pattern was measured, and the cumulative frequency curve was created. As a result, the diameters of puncturing equivalent to 5% of the curve and 95% are 2.5micro and 6.5micro, and intermediary There was, respectively. It is 3.0g/m by direct current of voltage 22V in 15% sulfuric acid solution (25degreeC) to these two aluminum plates.²Of anodized film was provided. On two sorts of base materials prepared as mentioned above, the sensitizing solution of the following composition was applied, and it dried and provided the photosensitive layer. The thickness of a photosensitive layer is the weight after dryness, and is 2.5g/m.²Was. Naphth quinone 1 of acetone pyrogallol resin, 2-diazido (2)-5-sulfonic ester (a synthetic method is based on the method of U.S. Pat. No. 3635709 specification example 1) 5g ---50530 (product [ made from the Sumitomo Giurais ] tertiary butylphenol formaldehyde resins) 0.5g Hitanol #3110(cresol formaldehyde resins by Hitachi Chemical Co., Ltd.)5g Methyl ethyl ketone 50g Cyclohexanone 40g Thus, the made photosensitive lithographic printing plate lets a transparent positive film pass in a vacuum printing frame, By 1 m of distance to the Fuji Photo Film PS light (what has a Toshiba metal halide lamp MU2000-2-OL type 3kW light source, and is sold from Fuji Photo Film Co., Ltd.), they are after I got it and SiO about exposure for 30 seconds.₂/Na₂Negatives were developed in 5.26% solution (PH=12.7) of the sodium silicate of O= 1.74, and gum influence was carried out in gum arabic solution of 14 *Be'. Although the lithographic printing plate which uses as a base material the aluminum plate which performed mechanical graining as a result of printing in the usual procedure using two sorts of lithographic printing plates engraved in this way gave the outstanding printed matter of 150,000 sheets, The lithographic printing plate which uses as a base material the aluminum plate which did not perform mechanical graining gave the printed matter in which the nonimage area became dirty. From the above result, the diameter of puncturing equivalent to 5% of cumulative frequency curves and 95%, When electrochemical graining which is set to 2.5micro and 6.5micro, respectively is used, Although the aluminum plate grained only by independent [ its ] is not the thing outstanding as a base material for lithographic printing plates, it turns out that the aluminum plate grained in combination with mechanical graining is excellent as a base material for lithographic printing plates. Example 2 It is I got it about graining by the wire brush made from stainless steel in a 0.2-mm-thick aluminum plate. Next, after being immersed for 60 seconds and etching by 80 degreeC into 8% of the third sodium phosphate solution, it washed for 1 minute with running water (20degreeC). It removed by immersing Sumato succeedingly adhering on the surface of the aluminum plate for 15 seconds into 30% nitric acid, and washing it at room temperature (25degreeC). Next, in 25 degreeC, exchange of the sine wave of the voltage of 22 v and duty cycle 0.7 is used using 2% of aqueous hydrochloric acid at the time of the anode, and they are the amount of electricity of 950 C / dm.²In (Qc/Qa=0.6), electrochemical graining is immersed for 30 seconds into after I got it, the 3% chromic acid of 80 degreeC, and 3.5% of phosphoric acid mixed water solution, and it is I got it about a desmut treatment. The average surface coarseness Ra is 0.65micro, and is Oh. The diameters of puncturing which are equivalent to 5% and 95% when distribution of the diameter of puncturing is measured like the case of Example 1 and a cumulative frequency curve is created, in order to check the conditions of the above-mentioned electrochemical graining are 2micro and 6micro, respectively, and are Oh. The quantity of an oxidization coat is 2.0g/m in 20% sulfuric acid (30degreeC) about this aluminum plate.²It anodized so that it might become. Next, 2% of 70 degreeC After being immersed for 30 seconds into JIS No. 3 Silicic acid sodium solution and carrying out flush dryness, p-toluenesulfonic acid salt of the 1:1 condensation thing of negative type p-Diazo diphenylamine and formaldehyde is made into a photosensitive layer, and the thickness after dryness is 1.8g/m.²It applies and is I got it about dryness so that it may become. Thus, it was able to print by the ability to have attached the printing plate obtained by developing negatives after exposing the obtained photosensitive lithographic printing plate to the Heidelberg KOR printing machine, and was able to obtain the outstanding printed matter of 100,000 sheets. Example 3 The surface of the 0.3-mm-thick aluminum plate was grained using a nylon brush and the pumice T- water-suspended liquid of 400 meshes. Next, after being immersed for 60 seconds and etching by 80 degreeC into 8% of the third sodium phosphate solution, it washed for 1 minute with running water (20degreeC). It removed by immersing Sumato succeedingly adhering on the surface of the aluminum plate for 15 seconds into 30% nitric acid, and washing it at room temperature (25degreeC). Next, in 20 degreeC, the plus side voltage of 13 v, the minus side voltage of 6 v, and the special wave-like exchange current of duty cycle 0.3 are used using 1.5% of nitric acid solution, and it is I got it about electrolysis graining for 20 seconds. The amounts of electricity in that case are 750 C / dm.²It is (Qc/Qa=0.95), the average surface coarseness is 0.8micro, and it is Oh. Next, it was immersed for 70 seconds into 20% sulfuric acid of 60 degreeC, the desmut treatment was performed, the surface was further anodized by phosphoric acid solution 20%, and the oxidization coat of about 1 micro of film thickness was provided. It was checked from the cumulative frequency curve of the diameter of puncturing which obtained the above-mentioned electrochemical graining like the case of Example 1 that they are the conditions as [ whose diameters of puncturing equivalent to 5% and 95% are 3micro and 5micro, respectively ]. The lithographic printing plate was able to be created like the case of Example 1 by the ability to have used as the base material the aluminum plate produced by making it above, and a I got it result and the outstanding printed matter of 150,000 sheets were able to be obtained for printing. Example 4 Brush graining of the surface of a 0.3-mm-thick aluminum plate was carried out by the same method as the case of Example 3. Next, it was immersed for 15 seconds into 20% sodium aluminate solution of 45 degreeC. As a result on the surface of the aluminum plate, the black insoluble solution residual substance was accepted. In order to remove this Sumato, it was immersed for 60 seconds at room temperature (25degreeC) into solution of the Death mat agent of the following composition. {peroxosulfuric acid potassium 2g acid potassium sulfate 6g water 100g} After often washing the surface, plus side voltage 13V, minus side voltage 6V, and the special wave-like exchange current of duty cycle 0.3 are used in 1.5% of nitric acid solution, and it is I got it about electrochemical graining during 20 seconds. The amounts of electricity in that case are 600 C / dm.²It is (Qc/Qa=0.95), the average surface coarseness is 0.7micro, and it is Oh. It is equivalent to it in Example 3, and the cumulative frequency curve of the diameter of puncturing by the above-mentioned electrochemical graining is Oh. Next, it was immersed for 60 seconds into 30% sulfuric acid of 50 degreeC, the desmut treatment was performed, the surface was further anodized by phosphoric acid solution 20%, and the oxidization coat of about 1 micro of film thickness was provided. It is about 1.8g/m about the sensitization thing of the following composition after providing a lower coating layer in the surface of this aluminum plate using the solution which melted 0.35 mol of carboxymethyl cellulose, and 0.35 mol of zinc acetate in water 1.²It applied and dried so that it might become. Photosensitive polyester 4.0g(1 mol %p-phenylene diethoxy acrylate, and 1 mol %1, condensation thing of 4-G beta-hydroxy cyclohexanone)2-benzoyl methylene 3-methyl beta-naphth thiazoline 0.32g benzoic acid 0.16g Hydroquinone 0.08g mono-chlorobenzene 100.0g paints (CI pigment Blue 15) After exposing the photosensitive lithographic printing plate produced by carrying out 0.8g in this way through a transparent negative original picture using a 3-kW metal halide lamp and developing negatives by the developing solution of the following composition, gum influence was carried out in 14 * Baume's gum arabic solution. 4-Butyro lactone ...... 500g triethanol amine ...... 50g Glycerol ...... 50g Methyl red-throated loon Etate ...... 5g Hydrogenation wood rosin ...... 0.5g wetting agent (Zonyl A of E. I. du Pont de Nemours & Co.) ...... 4.5g This lithographic printing plate gave the good printed matter of 200,000 sheets. Comparative example 2 After carrying out alkali etching by immersing a 0.2-mm-thick aluminum plate for 30 seconds into 6% sodium hydroxide solution of 80 degreeC, it is I got it about a flush. It removed by washing, after Sumato adhering to the aluminum surface is immersed for 15 seconds at room temperature (25degreeC) into 30% nitric acid. Next, in 25 degreeC, exchange of a sine wave with a voltage of 25 v is used using 2% of aqueous hydrochloric acid, and they are the amount of electricity of 2400 C / dm.²It is alike, it sets and is I got it about day Sumato processing like after [ I got it ] example 2 in electrochemical graining during 30 seconds. It became clear that average surface coarseness Ha of the aluminum plate obtained as a result was 0.8micro. This aluminum plate was anodized by the same method as the case of Example 2, and the after [ I got it ] negative type photosensitive layer was provided for silicate processing. Thus, after exposing like the case of Example 2 and developing negatives using the obtained photosensitive printing plate, it attached to the printing machine and I got it was obtained only for the printed matter of 60,000 sheets in printing. As a result of creating the cumulative frequency curve of the diameter of puncturing by the above-mentioned electrochemical graining, the diameters of puncturing equivalent to 5% and 95% of those are 4micro and 13micro, respectively, and are Oh. Comparative example 3 The 0.24-mm-thick aluminum plate was often washed with water, after graining the surface mechanically by the same method as Example 1, and after being immersed in 10%NaOH for 20 seconds and etching into it by 50 degreeC, it washed for 1 minute with running water. Next, in 20 degreeC, it is 25 A/dm using 2.5% of aqueous hydrochloric acid.²Sine wave exchange is used for 10 seconds by Of current density, and it is I got it about electrolysis surface roughening. Subsequently, 20% of 70 degreeCH₃PO₄It is immersed for 30 seconds in inside, and is I got it about a desmut treatment. Surface coarseness is 0.70micro and is Oh. Next, it is 15%H succeedingly about the surface processed in this way.₂SO₄A direct current of voltage 22V is used in inside, and it is 3g/m.²Of anodized film was provided. the usual state method after providing the photosensitive layer of Positive type shown in Example 1 in this surface -- therefore, after exposing and developing negatives, when it attached and printed to the printing machine, only the printed matter of 70,000 sheets was obtained. In order to measure distribution of the diameter of puncturing by the above-mentioned electrolysis surface roughening, electrolysis surface roughening was performed for the aluminum plate which is not grained mechanically on the same conditions as the above-mentioned case, the surface was expanded by 600 times with the scanning electron microscope, puncturing of the sand-like pattern was measured, and cumulative frequency was created. The diameters of puncturing which are equivalent to 5% and 95% as a result are 3micro and 15micro, respectively, and are Oh. Puncturing was unevenly formed in the surface.