JP2000112128A - Photosensitive planographic printing plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photosensitive planographic printing plate having both of printing durability and color remaining property, good adhesion property with a mat, and to provide a positive photosensitice planographic printing plate showing good printing durability and color remaining property even when the plate is developed with a developer containing no silicate. SOLUTION: This printing plate is produced by forming an intermediate layer on an aluminum supporting body subjected to hydrophilicity imparting treatment, and by forming a photosensitive layer on the intermediate layer. The intermediate layer contains a polymer compd. having a structural component having acid groups and a structural component having onium groups. The photosensitive layer contains a polymer compd. consisting of the structural components of (a) polymerizable monomers expressed by the formula, (b) (meth) acrylonitrile, (c) (meth)acrylate and (d) other polymerizable monomers. In the formula, P and R are independently bivalent org. groups, Q and Z are independently aromatic or substd. aromatic groups, R8 is a hydrogen atom, alkyl group or halogen atom, p, q, r, z are independently 0 or 1, and n is an integer 1 to 3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive lithographic printing plate, and more particularly to a positive photosensitive lithographic printing plate.

[0002]

2. Description of the Related Art Conventionally, a positive type photosensitive lithographic printing plate widely used is a positive type lithographic printing plate comprising an o-quinonediazide compound on an aluminum support which has been subjected to surface roughening treatment, alkali etching or anodic oxidation treatment. It is provided with a photosensitive layer. It is known that an o-quinonediazide compound changes to a carboxylic acid upon exposure to ultraviolet light,
When developed with an aqueous alkali solution after image exposure, only the exposed portions of the photosensitive layer are dissolved and removed, exposing the support surface. Therefore, the unexposed portion (image portion) becomes an ink receiving portion because the lipophilic photosensitive layer remains, and the exposed portion (non-image portion) retains water because the hydrophilic support surface is exposed. Become a rebound part. However, the aluminum support surface has insufficient hydrophilicity, so that the ink repulsion force is insufficient, and there is a problem that ink adheres to non-image areas (hereinafter referred to as stain performance). Therefore, usually for the purpose of improving the stain performance,
It is necessary to make the non-image area hydrophilic. However, generally, when a positive photosensitive layer is provided on a support subjected to hydrophilization treatment, adhesion between the hydrophilic support surface and the lipophilic photosensitive layer is poor,
There is a problem that the number of sheets that can be printed normally decreases (hereinafter referred to as printing durability). Therefore, usually at the time of development, only a non-image portion is made hydrophilic by using a developer containing a silicate such as sodium silicate or potassium silicate. However, when a developer containing a silicate is used, a solid due to SiO ₂ is likely to precipitate, or a gel due to SiO ₂ is generated when performing a neutralization treatment when processing a waste developing solution. And so on.

Accordingly, there has been a demand for a technique in which even if a positive photosensitive layer is provided on a support whose surface has been subjected to hydrophilic treatment in advance, the support and the photosensitive layer have good adhesion and the printing durability does not deteriorate.

In order to solve the above problems, US Pat. No. 3,136,636 proposes to provide an intermediate layer of a water-soluble polymer such as polyacrylic acid and carboxymethylhydroxyethylcellulose. However, it was still unsatisfactory in terms of printing durability. In U.S. Pat. No. 4,483,913,
It has been proposed to provide an intermediate layer of a quaternary ammonium compound such as poly (dimethyldiallylammonium chloride), but the stain performance was insufficient and unsatisfactory.

[0005] Therefore, we have maintained the adhesion between the aluminum support having sufficient hydrophilicity and the photosensitive layer during printing, and in the non-image area, sufficiently washed the photosensitive layer and the intermediate layer with an alkali developing solution. As a method for dissolving and removing,
An intermediate layer containing a polymer described in JP-A-0-69092 was developed to realize both printing durability and stain resistance. As a result, the adhesive strength of the image area was improved, and in the non-image area, the photosensitive layer and the intermediate layer could be sufficiently removed with an alkali developing solution, so that the surface of the hydrophilic support was exposed and the stain performance was maintained. However, in this method, the residual color (the degree to which the dye added in the photosensitive layer remains on the non-image portion support after development) is not sufficient, and improvement thereof has been desired.

[0006]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a positive photosensitive lithographic printing plate which achieves both printing durability and residual color and has good matt adhesion.
It is a further object of the present invention to provide a positive photosensitive lithographic printing plate having good printing durability and residual color even when developed using a developer containing no silicate.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have achieved the above object by including a specific polymer in the intermediate layer and a specific polymer compound in the photosensitive layer. And arrived at the present invention. That is, the present invention has the following configuration. An intermediate layer containing a polymer compound having a component having an acid group and a polymer compound having a component having an onium group was provided on an aluminum support subjected to a hydrophilic treatment, and (a) the following general formula [I] (B) (meth) acrylonitrile, (c) a (meth) acrylic acid ester, and (d) a photosensitive layer containing a polymer compound comprising a polymerizable monomer. A photosensitive lithographic printing plate, characterized in that:

[0008]

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(Wherein P and R each independently represent a divalent organic group; Q and Z each independently represent an aromatic or substituted aromatic group; R ₈ represents a hydrogen atom, an alkyl group or Represents a halogen atom, p, q, r, and z each independently represent 0 or 1. n is an integer of 1 to 3.)

Conventionally, when a photosensitive layer is provided on an aluminum support which has been subjected to a hydrophilic treatment by a silicate treatment or the like, the adhesion is low and the printing durability is extremely low. And an intermediate layer containing a polymer compound obtained by polymerizing a component having an onium group and a polymer compound having an optionally substituted aromatic group having at least one hydroxyl group. By providing the layer, the adhesion between the support and the intermediate layer, the intermediate layer and the photosensitive layer is controlled by the intermolecular interaction due to the functional group of each polymer compound, and the polymer compound contained in the intermediate layer Both acid groups and hydroxyl groups in the polymer compound contained in the photosensitive layer are easily dissociated in an alkali developer, so that both polymer compounds can be dissolved and removed from the support surface. Estimates that have become factors that provide good printing durability and residual color property. Furthermore, surprisingly, in the present invention, the mat adhesion was also good. Although the cause is not clear, the improvement in the adhesion between the photosensitive layer and the mat layer due to the intermolecular interaction by the functional group of the polymer compound contained in the photosensitive layer is a factor that gives good mat adhesion. I guess it is.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. [1] Photosensitive composition (photosensitive layer) First, a polymer compound, a positive photosensitive compound, and other components which are the photosensitive composition used for forming the photosensitive layer of the photosensitive lithographic printing plate of the present invention will be described in detail. I do. (1) Polymer compound (a) Polymerizable monomer represented by the above general formula [I] In the polymer compound according to the present invention, P and R in the formula of the polymerizable monomer represented by the general formula (I) Each independently represents a divalent organic group. Q and Z each independently represent an aromatic or substituted aromatic group. R ₈ is a hydrogen atom,
Represents an alkyl group or a halogen atom. p, q, r, z
Each independently represents 0 or 1. n is an integer of 1 to 3. More preferably, P is -COO- or -CO
Represents NH-. Q represents a phenylene group or a substituted phenylene group, and the substituent is a hydroxyl group, a halogen atom, an alkyl group or an alkoxyl group. R represents a divalent organic group. Z represents a phenylene group, a substituted phenylene group, a naphthylene group or a substituted naphthylene group, and the substituent is a halogen atom, an alkyl group, an alkoxyl group, a phenyl group or an aralkyl group. p, q, r, and z each independently represent 0 or 1;
Will not be. n is an integer of 1 to 3.

[0012] The content of the polymerizable monomer represented by the general formula [I] in the polymer compound according to the present invention is preferably 5 to 90 mol%, more preferably 10 to 70 mol%, based on all repeating units. , More preferably in the range of 15 to 50 mol%. Hereinafter, specific examples of the polymerizable monomer represented by the general formula [I] are shown, but the present invention is not limited thereto.

[0013]

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[0014]

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[0015]

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(B) (Meth) acrylonitrile The content of acrylonitrile or methacrylonitrile, which is one of the repeating units in the polymer compound according to the present invention, is preferably from 5 to 90 with respect to all the repeating units.
Mol%, more preferably 10 to 70 mol%, more preferably 15 to 50 mol%.

(C) (Meth) acrylate The content of the acrylate or methacrylate which is one of the repeating units in the polymer compound according to the present invention is preferably 5 to 5 with respect to all the repeating units.
The range is 90 mol%, more preferably 10 to 70 mol%, and more preferably 15 to 50 mol%. Hereinafter, specific examples of the (meth) acrylic acid ester are shown, but the present invention is not limited thereto.

For example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, phenyl acrylate, benzyl acrylate, acrylate 2- (Substituted) acrylates such as chloroethyl, 4-hydroxybutyl acrylate, glycidyl acrylate, N-dimethylaminoethyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate , Cyclohexyl methacrylate, octyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-chloroethyl methacrylate, 4-hydroxybutyl methacrylate, glycidyl Methacrylate, (substituted) methacrylic acid esters such as N- dimethylaminoethyl methacrylate.

In the above (meth) acrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, phenyl acrylate, acrylic acid Benzyl, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, phenyl methacrylate,
Benzyl methacrylate is more preferred.

Particularly preferred are methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, and benzyl methacrylate.

(D) Other polymerizable monomers The content of the other polymerizable monomer, which is one of the repeating units in the polymer compound according to the present invention, is preferably 0 to 85 mol% with respect to all the repeating units. Preferably 0
７０70 mol%, more preferably 0-55 mol%. In the range of the content of each of the above components (a) to (d), the polymer compound has an excellent balance between hydrophilicity and hydrophobicity. In the unexposed portion, sufficient adhesion to the substrate is provided, so that good printing durability can be exhibited. Specific examples of other polymerizable monomers are shown below, but the present invention is not limited thereto.

(1) unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride and its half ester, itaconic acid, itaconic anhydride and its half ester, (2) N- (o-aminosulfonyl) Phenyl) acrylamide, N- (m-aminosulfonylphenyl) acrylamide, N- (p-aminosulfonylphenyl) acrylamide, N- [1- (3-aminosulfonyl) naphthyl] acrylamide, N- (2
Acrylamides such as -aminosulfonylethyl) acrylamide, N- (o-aminosulfonylphenyl)
Methacrylamide, N- (m-aminosulfonylphenyl) methacrylamide, N- (p-aminosulfonylphenyl) methacrylamide, N- [1- (3-aminosulfonyl) naphthyl] methacrylamide, N- (2-aminosulfonyl) Methacrylamides such as ethyl) methacrylamide, o-aminosulfonylphenyl acrylate, m-aminosulfonylphenyl acrylate, p-aminosulfonylphenyl acrylate, 1-
Unsaturated sulfonamides such as acrylates such as (3-aminosulfonylphenylnaphthyl) acrylate, o-aminosulfonylphenyl methacrylate,
unsaturated sulfonamides such as methacrylates such as m-aminosulfonylphenyl methacrylate, p-aminosulfonylphenyl methacrylate, 1- (3-aminosulfonylphenylnaphthyl) methacrylate;

(3) phenylsulfonylacrylamide which may have a substituent such as tosylacrylamide;
And phenylsulfonyl methacrylamide which may have a substituent such as tosyl methacrylamide. (4) Acrylic esters and methacrylic esters having an aliphatic hydroxyl group, for example, 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate,

(5) Acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N-hexylacrylamide, N
-Hexyl methacrylamide, N-cyclohexyl acrylamide, N-cyclohexyl methacrylamide, N
-Hydroxyethylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N
Acrylamides such as -phenylmethacrylamide, N-benzylacrylamide, N-benzylmethacrylamide, N-nitrophenylacrylamide, N-nitrophenylmethacrylamide, N-ethyl-N-phenylacrylamide and N-ethyl-N-phenylmethacrylamide Or methacrylamide, (6) ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether,
Vinyl ethers such as phenyl vinyl ether,

(7) vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate; (8) styrenes such as styrene, α-methyl styrene, methyl styrene and chloromethyl styrene; Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone; (10) olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene; (11) N-vinylpyrrolidone, N-vinylcarbazole; 4-vinylpyridine, and the like.

The polymer compound comprising the components (a) to (d) accounts for 80% by weight based on the total weight of the photosensitive composition.
Below, preferably 20 to 80% by weight, more preferably 4% by weight.
It is used in an amount of 0 to 70% by weight. This range is preferred from the viewpoint of developability and printing durability. Each of the components (a) to (d) may be used alone or in combination of two or more. Further, the polymer compound according to the present invention may be a mixture of two or more components having different components or different composition ratios or molecular weights. You may use it. Hereinafter, specific examples of the polymer compound used in the photosensitive layer according to the invention are shown, but the invention is not limited thereto.

[0027]

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[0028]

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[0029]

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Although the molecular weight of the polymer compound according to the present invention may be in a wide range, it is preferably from 500 to 2,000,000 in terms of standard polystyrene as measured by gel permeation chromatography (GPC). ,
000 to 1,500,000, more preferably 5,000 to 1,500,000.
Particularly preferred is 1,000,000. Further, the amount of unreacted monomer contained in the polymer compound may be wide, but is preferably 20% by weight or less, preferably 10% by weight or less.
More preferably, it is not more than wt%.

Next, a synthesis example of the polymer compound according to the present invention will be described. [Synthesis Example] Synthesis of Polymer Compound (A) N- (4-hydroxyphenyl) methacrylamide 2
6.6 g, acrylonitrile 10.6 g, methyl acrylate 10.8 g and benzyl acrylate 4.1 g were dissolved in a mixed solvent of 36.8 g of methyl ethyl ketone and 85.8 g of 1-methoxy-2-propanol. further,
1.2 g of dimethyl 2,2-azobis (isobutyrate) was added and dissolved. The solution is stirred under a nitrogen stream while stirring.
The solution was dropped into a 300 ml three-necked flask kept at 5 ° C. over 2 hours. After completion of the dropwise addition, stirring was continued for 4 hours while maintaining the temperature at 75 ° C. After completion of the reaction, the reaction solution was poured into 1 liter of water with stirring, and the precipitated solid was collected by filtration and dried. The yield was 48.3 g. The weight average molecular weight (Mw) of the obtained solid was 53,000 as a result of GPC measurement.

(2) Positive Photosensitive Compound The photosensitive compound of the photosensitive composition includes an o-quinonediazide compound, and a typical example thereof is an o-naphthoquinonediazide compound. The o-naphthoquinonediazide compound is preferably an ester of 1,2-diazonaphthoquinonesulfonic acid chloride and pyrogallol-acetone resin described in JP-B-43-28403.

Other suitable o-quinonediazide compounds include US Pat.
There are esters of 1,2-diazonaphthoquinone sulfonic acid chloride and phenol formaldehyde resin described in 188,210.

[0034] Other useful o-naphthoquinonediazide compounds include those reported and known in numerous patents. For example, JP-A-47-5303
No. 48-63802, No. 48-63803, No. 48-96575, No. 49-38701, No. 48-
13354, JP-B-37-18015, 41-1
No. 1222, No. 45-9610, No. 49-17481
JP-A-5-11444, JP-A-5-19477
JP-A-5-19478, JP-A-5-107755
No. 2,797,213 and No. 3,45.
No. 4,400, No. 3,544,323, No. 3,5
No. 73,917, No. 3,674,495, No. 3,
785,825, British Patent No. 1,227,602,
Nos. 1,251,345 and 1,267,005
No. 1,329,888, No. 1,330,93
No. 2, German Patent No. 854,890, and the like.

Further, as other o-quinonediazide compounds, o-naphthoquinonediazide compounds obtained by reacting a polyhydroxy compound having a molecular weight of 1,000 or less with 1,2-diazonaphthoquinonesulfonic acid chloride can be used. For example, JP-A-51-13940
No. 2, No. 58-150948, No. 58-203434
No., 59-165053, 60-12445
No. 60-134235, No. 60-16343
No. 61-118744, No. 62-10645,
No. 62-10646, No. 62-153950, No. 6
2-178562, 64-76047, U.S. Pat. Nos. 3,102,809 and 3,126,281,
No. 3,130,047, No. 3,148,983
No. 3,184,310, No. 3,188,21
No. 0, No. 4,639, 406, and the like, and those described in each gazette or specification.

When synthesizing these o-naphthoquinonediazide compounds, it is preferable to react 0.2-1.2 equivalents of 1,2-diazonaphthoquinonesulfonic acid chloride with respect to the hydroxyl groups of the polyhydroxy compound. More preferably, the reaction is performed in an amount of 0.3 to 1.0 equivalent. As the 1,2-diazonaphthoquinone sulfonic acid chloride, 1,2-diazonaphthoquinone-5-sulfonic acid chloride is preferable, but 1,2-diazonaphthoquinone-sulfonic acid chloride is preferred.
4-sulfonic acid chloride can also be used. The obtained o-naphthoquinonediazide compound is a mixture of various compounds having different positions and introduced amounts of 1,2-diazonaphthoquinonesulfonic acid ester groups. The proportion of the compound in the mixture (content of the completely esterified compound) is preferably 5 mol% or more, more preferably 20 to 99 mol%.

Further, as a photosensitive compound which acts positively without using an o-naphthoquinonediazide compound, for example, a polymer compound containing an o-nitrile carbinol ester group described in JP-B-52-2696 or pyridinium Group-containing compounds (for example, JP-A-4-365049) and diazonium group-containing compounds (for example, JP-A-5-2496).
No. 64, JP-A-6-83047, JP-A-6-3244
No. 95, JP-A-7-72621, etc.) can also be used in the present invention. Further, a compound capable of generating an acid by photolysis (JP-A-4-121748, JP-A-4-3650)
No. 43), a C—O—C group or a C— group dissociated by an acid.
A combination system with a compound having an O-Si group can also be used in the present invention. For example, a combination of a compound which generates an acid by photolysis and an acetal or an O, N-acetal compound (Japanese Patent Application Laid-Open No. 48-89003), a combination with an orthoester or amide acetal compound (Japanese Patent Application Laid-Open No. 51-120714) ), In combination with a polymer having an acetal or ketal group in the main chain
-133429, etc.), and a combination with an enol ether compound (JP-A-55-12995, JP-A-4-19).
748, JP-A-6-230574, etc.) and a combination with an N-acylimino carbon compound (JP-A-55-126).
236), a combination with a polymer having an orthoester group in the main chain (JP-A-56-17345, etc.),
Combination with a polymer having a silyl ester group (JP-A-60-10247, etc.) and combination with a silyl ether compound (JP-A-60-37549, JP-A-60-37549)
No. 0-112446, JP-A-63-236028, JP-A-63-236029, JP-A-63-276046
No. etc.). The amount of these positive-acting photosensitive compounds (including the above combination) occupying in the photosensitive composition of the present invention is suitably from 10 to 50% by weight, more preferably from 15 to 40% by weight. It is.

Although the o-quinonediazide compound alone can form the photosensitive layer, it is preferably used together with a resin soluble in alkaline water as a binder. Such resins soluble in alkaline water include novolak resins having this property, such as phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, and m- / p.
-Mixed cresol formaldehyde resin, phenol /
Cresol formaldehyde resin such as cresol (which may be any of m-, p-, o- or m- / p- / o-mixture) and the like. These alkaline soluble high molecular compounds preferably have a weight average molecular weight of 500 to 100,000. In addition, resol type phenol resins are also preferably used,
Phenol / cresol (m-, p-, o- or m- /
A mixed formaldehyde resin is preferable, and phenol resins described in JP-A-61-217034 are particularly preferable.

Further, a phenol-modified xylene resin, polyhydroxystyrene, polyhalogenated hydroxystyrene, an acrylic resin containing a phenolic hydroxyl group as disclosed in JP-A-51-34711, and JP-A-2-866. JP-A-7-28244, a vinyl resin or a urethane resin having a sulfonamide group described in
JP-A-7-36184, JP-A-7-36185
JP-A-7-248628, JP-A-7-26139
No. 4, JP-A-7-333839, etc., various alkali-soluble polymer compounds such as vinyl resins having a structural unit can be contained.

These alkali-soluble polymer compounds are
Those having a weight average molecular weight of 500 to 500,000 are preferred. Such an alkali-soluble polymer compound may be used alone or in combination of two or more kinds.
More preferably, it is used in an amount of 50 to 70% by weight. This range is preferred from the viewpoint of developability and printing durability.

Further, as described in US Pat. No. 4,123,279, a compound having an alkyl group having 3 to 8 carbon atoms as a substituent, such as a t-butylphenol formaldehyde resin and an octylphenol formaldehyde resin. It is preferable to use a condensate with phenol formaldehyde or an o-naphthoquinonediazidosulfonic acid ester of these condensates (for example, those described in JP-A-61-243446) in order to improve the oil sensitivity of an image.

(Development Accelerator) It is preferable to add cyclic acid anhydrides, phenols and organic acids to the photosensitive composition of the present invention in order to increase sensitivity and improve developability. As cyclic acid anhydrides, US Pat.
Phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride described in US Pat. No. 5,128;
3,6-Endoxy-Δ ⁴ -tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like can be used. Examples of phenols include bisphenol A, p-nitrophenol, p-ethoxyphenol, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 4-hydroxybenzophenone,
4,4 ', 4 "-trihydroxy-triphenylmethane, 4,4', 3", 4 "-tetrahydroxy-3,
5,3 ', 5'-tetramethyltriphenylmethane and the like can be mentioned.

Further, as the organic acids, JP-A-60-8
No. 8942, JP-A-2-96755 and the like, there are sulfonic acids, sulfinic acids, alkyl sulfates, phosphonic acids, phosphoric esters and carboxylic acids, and specifically, p-toluene sulfone Acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethyl sulfate, phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, diphenyl phosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid,
3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid, 1,4-cyclohexene-2,2-dicarboxylic acid,
Erucic acid, lauric acid, n-undecanoic acid, ascorbic acid and the like can be mentioned. The proportion of the above cyclic acid anhydrides, phenols and organic acids in the photosensitive composition is preferably 0.05 to 15% by weight, more preferably 0.1 to 5% by weight.

(Development Stabilizer) In the photosensitive composition of the present invention, JP-A-62-2517 is used in order to widen the stability of processing under development conditions (so-called development tolerance).
Non-ionic surfactants described in JP-A No. 40 and JP-A-4-68355, JP-A-59-1210
No. 44 and JP-A-4-13149 can be added. Specific examples of the nonionic surfactant include sorbitan tristearate, sorbitan monopalmitate, sorbitan triolate, monoglyceride stearate, polyoxyethylene sorbitan monooleate, and polyoxyethylene nonyl phenyl ether. Specific examples of the amphoteric surfactant include alkyldi (aminoethyl)
Glycine, alkyl polyaminoethyl glycine hydrochloride,
2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine and N-tetradecyl-
N, N-betaine type (for example, trade name Amogen K, manufactured by Daiichi Kogyo Co., Ltd.) and alkylimidazoline type (for example, trade name Levon 15, manufactured by Sanyo Chemical Co., Ltd.) and the like. The proportion of the nonionic surfactant and amphoteric surfactant in the photosensitive composition is preferably from 0.05 to 15% by weight, and more preferably from 0.1 to 5% by weight.

(Print-out Agent, Dye, Others) In the photosensitive composition of the present invention, a print-out agent for obtaining a visible image immediately after exposure, and a dye or other filler as an image coloring agent are added. be able to. As the dye that can be used in the present invention, a cation having a basic dye skeleton described in JP-A-5-313359 and a sulfonic acid group having only one exchange group and having 1 to 3 hydroxyl groups A basic dye comprising a salt with an organic anion having 10 or more carbon atoms can be used. The amount of addition is 0.2 to 5% by weight of the total photosensitive composition.

Compounds which generate a photo-decomposed product which changes color tone by interacting with a dye described in JP-A-5-313359, for example, JP-A-50-36209 (US Pat. No. 3,969,118) -Naphthoquinonediazide-4-sulfonic acid halogenide described in
No. 3-36223 (U.S. Pat. No. 4,160,671) discloses trihalomethyl-2-pyrone and trihalomethyltricidin, and JP-A-55-62444 (U.S. Pat.
38,801), various o-naphthoquinonediazide compounds described in JP-A-55-77742 (U.S. Pat.
279, 982).
An aryl 1,3,4-oxadiazole compound or the like can be added. These compounds can be used alone or as a mixture. 400n of these compounds
A compound having an absorption at m may be used as the yellow dye.

As a colorant for an image, the above-mentioned Japanese Patent Application Laid-Open No.
Other dyes besides the dyes described in JP 13359 can be used. Suitable dyes including salt-forming organic dyes include oil-soluble dyes and basic dyes.
Specifically, Oil Green BG, Oil Blue BO
S, Oil Blue # 603 (orientated by Orient Chemical Co., Ltd.), Victoria Pure Blue BOH, Victoria Pure Blue NAPS, Ethyl Violet 6H
NAPS (above, manufactured by Hodogaya Chemical Industry Co., Ltd.), rhodamine B (C145170B), malachite green (C1
42000), methylene blue (C152015) and the like.

In the photosensitive composition of the present invention,
The following yellow dyes can be added. General formula (I
A yellow dye represented by I], [III] or [IV] and having an absorbance at 417 nm of 70% or more of an absorbance at 436 nm

[0049]

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In the formula [II], R₁And R_TwoAre independently
A hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group or
Represents an alkenyl group. Also R₁And R_TwoForms a ring
Good. R_Three, R_Four, R_FiveAre each independently a hydrogen atom or carbon
Shows the alkyl groups of Formulas 1 to 10. G₁, G_TwoIs German
Alkoxycarbonyl group, aryloxy carbonyl
Group, acyl group, arylcarbonyl group, alkylthio
Group, arylthio group, alkylsulfonyl group, aryl
Represents a sulfonyl group or a fluoroalkylsulfonyl group
You. G₁And G_TwoMay form a ring. Further R₁,
R_Two, R_Three, R_Four, R _Five, G₁, G_TwoOne or more of one or more
Upper sulfonic acid group, carboxyl group, sulfonamide
Group, imido group, N-sulfonylamido group, phenolic
Hydroxyl group, sulfonimide group, or a metal salt thereof, inorganic or
Has an organic ammonium salt. Y is O, S, NR (R is
A hydrogen atom or an alkyl or aryl group), Se,
-C (CH_Three)_Two-, A divalent element selected from -CH = CH-
Indicates a gang, n₁Represents 0 or 1.

[0051]

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In the formula [III], R ₆ and R ₇ are each independently a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a heterocyclic group, a substituted heterocyclic group, an allyl group or a substituted allyl group. And both R ₆ and R ₇ may form a ring together with the carbon atom to which it is attached. n ₂ represents 0, 1 or 2. G ₃ and G ₄ are each independently a hydrogen atom, a cyano group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, an aryloxycarbonyl group, a substituted aryloxycarbonyl group, an acyl group, a substituted acyl group, an arylcarbonyl group, a substituted arylcarbonyl Represents an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, or a fluoroalkylsulfonyl group. However, G ₃ and G ₄ are not simultaneously hydrogen atoms. Further, G ₃ and G ₄ may form a ring composed of a nonmetallic atom together with the carbon atom to which they are bonded. Further, at least one of R ₆ , R ₇ , G ₃ and G ₄ has at least one sulfonic acid group, carboxyl group, sulfonamide group, imide group, N-sulfonylamide group, phenolic hydroxyl group, sulfonimide group. Or its metal salt, inorganic or organic ammonium salt.

[0053]

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In the formula (IV), R ₈ , R ₉ , R ₁₀ , R ₁₁ ,
R ₁₂ and R ₁₃ may be the same or different and may be a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkoxy group, a hydroxyl group, an acyl group, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl Group, nitro group, carboxyl group, chloro group and bromo group.

The photosensitive lithographic printing plate of the present invention can be obtained by dissolving the above-mentioned components of the photosensitive composition in a solvent capable of dissolving and coating the solution on a support. As the solvent used here, γ-butyrolactone, ethylene dichloride, cyclohexanone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate,
1-methoxy-2-propanol, 1-methoxy-2-
Propyl acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, dimethylacetamide, dimethylformamide, water, N-methylpyrrolidone, tetrahydrofurfuryl alcohol, acetone, diacetone alcohol, methanol, ethanol,
There are isopropanol, diethylene glycol dimethyl ether and the like, and these solvents are used alone or in combination. The concentration (solid content) in the above components is 2 to
50% by weight is suitable. 0.5 g / m as coating amount
^{A range of 2 to} 4.0 g / m ² is preferred. When the amount is less than 0.5 g / m ² , the printing durability deteriorates. When the amount is more than 4.0 g / m ² , the printing durability is improved, but the sensitivity is lowered.

In the photosensitive composition of the present invention, a surfactant for improving a coating method, for example, a surfactant described in
A fluorine-based surfactant as described in JP-A-170950 can be added. The preferred amount is
It is 0.01 to 1% by weight of the total photosensitive composition, and more preferably 0.05 to 0.5% by weight. With the lithographic printing plate obtained as described above, a printed matter faithful to the original picture film can be obtained, but the print blurring and the roughness of the printed matter are poor. As a method of improving the burning blur, there is a method of making the surface of the photosensitive amount provided as described above uneven. For example, as described in Japanese Patent Application Laid-Open No. 61-258255, there is a method in which particles of several μm are added to a photosensitive solution and the particles are coated. Is not improved at all.

However, for example, Japanese Patent Application Laid-Open No. 50-12580
No. 5, JP-B-57-6582, JP-B-61-28986
And Japanese Patent Application Laid-Open No. 62-62337, a method of forming a component having irregularities on the surface of a photosensitive amount can improve bokeh blur and improve the roughness of printed matter. Further, as described in JP-B-55-30619, when a light absorbing agent having absorption in the photosensitive wavelength region of the photosensitive material is contained in the mat layer, the burning blur and the roughness are further improved. In addition, an original film having a line number of 300 lines or more per inch and an original film obtained by FM screening, which is more easily burned out than an original film having a line number of 175 lines per inch and which easily gives a sense of roughness of a printed material, is used. Thus, a good printed matter can be obtained. As described above, the following minute patterns are desirably provided on the surface of the photosensitive layer of the photosensitive printing plate. That is, the height of the applied portion is preferably in the range of 1 to 40 μm, particularly 2 to 20 μm, and the size (width) is 10 to 10000 μm, especially 20
The range of -200 µm is preferred. The amount is 1 to 1000
Pieces / mm ² , preferably in the range of 5 to 500 pieces / mm ² .

Hereinafter, the polymer compound used for forming the intermediate layer of the present invention will be described in detail. [Intermediate Layer Composition] The polymer compound of the present invention is a polymer compound obtained by polymerizing a component having at least an acid group and a component having at least an onium group. Here, a preferable acid group is an acid group having an acid dissociation index (pKa) of 7 or less, more preferably -COOH,
_{-SO 3 H, -OSO 3 H,} -PO 3 H 2, -OPO 3 H
₂ , —CONHSO ₂ , —SO ₂ NHSO ₂ —,
Particularly preferred is -COOH. Preferred as onium groups are onium groups composed of atoms of Group V or Group VI of the periodic table, more preferred are onium groups composed of nitrogen, phosphorus and sulfur atoms, and particularly preferred are those of nitrogen. It is an onium group consisting of atoms. Among the polymer compounds of the present invention, preferably, a polymer characterized in that the main chain structure of the polymer compound is a vinyl-based polymer such as an acrylic resin, a methacrylic resin, or polystyrene, or a urethane resin, a polyester, or a polyamide. It is. More preferably,
The polymer is characterized in that the main chain structure of the polymer compound is a vinyl-based polymer such as an acrylic resin, a methacrylic resin, or polystyrene. Particularly preferably, the constituent having an acid group is a polymerizable compound represented by the following general formula (1) or (2), and the constituent having an onium group is represented by the following general formula (3), A polymer represented by the general formula (4) or (5).

[0059]

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In the formula, A represents a divalent linking group. B represents an aromatic group or a substituted aromatic group. D and E each independently represent a divalent linking group. G represents a trivalent linking group. X and X 'each independently represent an acid group having a pKa of 7 or less, or an alkali metal salt or ammonium salt thereof. R ₁ represents a hydrogen atom, an alkyl group or a halogen atom. a, b, d, and e each independently represent 0 or 1. t is an integer of 1 to 3. More preferably, among the components having an acid group, A is -COO- or -C
Represents ONH-, B represents a phenylene group or a substituted phenylene group, and the substituent is a hydroxyl group, a halogen atom or an alkyl group. Alkylene group or a molecular formula D and E are each independently represents C _n H _2n O, 2 divalent linking group represented by C _n H _2n S or C _n H _{2n + 1} N. G
The molecular formula represents _{C n H 2n-1, C} n H 2n-1 O, 3 -valent linking group represented by C _n H _2n-1 S or C _n H _2n N. However,
Here, n represents an integer of 1 to 12. X and X 'each independently represent a carboxylic acid, a sulfonic acid, a phosphonic acid, a sulfuric acid monoester or a phosphoric acid monoester. R ₁ represents a hydrogen atom or an alkyl group. a, b, d, and e each independently represent 0 or 1;
is not. Among the components having an acid group, particularly preferred is a compound represented by the general formula (1), wherein B represents a phenylene group or a substituted phenylene group, and the substituent is a hydroxyl group or an alkyl group having 1 to 3 carbon atoms. . D and E each independently represent an alkylene group having 1 to 2 carbon atoms or an alkylene group having 1 to 2 carbon atoms linked by an oxygen atom.
R ₁ represents a hydrogen atom or a methyl group. X represents a carboxylic acid group. a is 0 and b is 1.

Specific examples of the component having an acid group are shown below. However, the present invention is not limited to this specific example. (Specific examples of components having an acid group) acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, itaconic acid, maleic acid, maleic anhydride

[0062]

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[0063]

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[0064]

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Next, a polymer characterized in that the constituent component having an onium group is represented by the general formulas (3), (4) and (5) will be described.

[0066]

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In the formula, J represents a divalent linking group. K is aromatic
Represents an aromatic group or a substituted aromatic group. M are independent
Represents a divalent linking group. Y₁Represents an atom in Group V of the periodic table
Represents, Y_TwoRepresents an atom of Group VI of the periodic table. Z^-Is ani
Indicates ON. R_TwoIs a hydrogen atom, alkyl group or halogen
Represents an atom. R_Three, R_Four, R_Five, R₇Are independent of each other
A hydrogen atom or a substituent may be bonded in some cases.
Represents an alkyl group, an aromatic group, or an aralkyl group;₆Is
Represents an alkylidyne group or substituted alkylidyne,
_ThreeAnd R_FourOr R₆And R₇Each combine to form a ring
You may. j, k, and m each independently represent 0 or 1.
Represent. u represents an integer of 1 to 3. Structure having an onium group
More preferably, J is -COO- or-
CONH-, and K represents a phenylene group or a substituted phenylene group.
Represents a nylene group, the substituent of which is a hydroxyl group, a halogen atom, etc.
Or an alkyl group. M is an alkylene group or
Child expression is C_nH_2nO, C_nH_2nS or C_nH_{2n + 1}Table with N
Represents a divalent linking group. Here, n is 1 to 12
Represents an integer. Y₁Represents a nitrogen atom or a phosphorus atom,
Y_TwoRepresents a sulfur atom. Z^-Is a halogen ion, P
F₆ ^-, BF_Four ^-Or R₈SO_Three ^-Represents R_TwoIs a hydrogen atom
Or represents an alkyl group. R_Three, R_Four, R _Five, R₇Each
Independently form a hydrogen atom or, in some cases, a substituent.
An alkyl group having 1 to 10 carbon atoms, an aromatic group,
Represents an aralkyl group;₆Is an alkylene having 1 to 10 carbon atoms
Represents a gin group or a substituted alkylidine,_ThreeAnd R_FourAh
Or R₆And R₇May combine with each other to form a ring
No. j, k, and m each independently represent 0 or 1
However, j and k are not simultaneously 0. R₈Is a substituent
C1-C10 alkyl group, aromatic group, ara
Represents a alkyl group. Among the constituent components having an onium group,
K is preferably a phenylene group or a substituted phenylene
A hydroxyl group or a group having 1 to 3 carbon atoms.
Is an alkyl group. M is an alkylene group having 1 to 2 carbon atoms
Or an alkylene having 1 to 2 carbon atoms linked by an oxygen atom
Represents a group. Z^-Is chlorine ion or R₈SO_Three ^-Represents
R _TwoRepresents a hydrogen atom or a methyl group. j is 0
And k is 1.

Specific examples of the constituent having an onium group are shown below. However, the present invention is not limited to this specific example. (Specific examples of components having an onium group)

[0069]

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[0070]

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[0071]

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The polymer compound used here contains a component having an acid group in an amount of 20 mol% or more, preferably 40 mol% or more.
% Or more, and preferably contains 1% by mole or more, preferably 5% by mole or more of a component having an onium group.
When the component having an acid group is contained in an amount of 20 mol% or more, dissolution and removal during alkali development is further promoted. It is further improved. Further, the constituent component having an acid group may be used alone or in combination of two or more, and the constituent component having an onium group may be used alone or in a combination of two or more types. Further, as the polymer compound according to the present invention, two or more kinds of compounds having different constituent components or composition ratios or molecular weights may be used in combination. Next, typical examples of the polymer compound used in the present invention are shown below. The composition ratio of the polymer structure represents a mole percentage.

[0073]

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[0074]

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[0075]

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[0076]

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The polymer compound according to the present invention generally comprises
It can be produced using a radical chain polymerization method (“Textbook of Polymer Science” 3rd ed, (1984) FW
See Billmeyer, A Wiley-Interscience Publication).
Although the molecular weight of the polymer compound according to the present invention may be in a wide range, the weight average molecular weight (Mw) is preferably from 500 to 2,000,000 when measured using a light scattering method. More preferably, it is in the range of 2,000 to 600,000. Further, the amount of unreacted monomer contained in the polymer compound may be in a wide range.
wt% or less, more preferably 10 Wt% or less.

Next, a synthesis example of the polymer compound according to the present invention will be described. [Synthesis Example] Synthesis of copolymer (No. 1) of p-vinylbenzoic acid and vinylbenzyltrimethylammonium chloride p-vinylbenzoic acid [manufactured by Hokuko Chemical Co., Ltd.] 14
6.9 g (0.99 mol), vinyl benzyltrimethylammonium chloride 44.2 g (0.21 mol)
And 446 g of 2-methoxyethanol in a 1 L three-necked flask, and heated to 75 ° C. while stirring under a nitrogen stream.
Kept. Next, 2,76 g (12 mmol) of dimethyl 2,2-azobis (isobutyrate) was added, and stirring was continued. 2
After an hour, 2,2-azobis (isobutyric acid) dimethyl 2,7
An additional 6 g (12 mmol) was added. After another two hours,
2.76 g of dimethyl 2,2-azobis (isobutyrate) (1
2 mmol) was added. After stirring for 2 hours, the mixture was allowed to cool to room temperature. This reaction solution was poured into 12 L of ethyl acetate with stirring. The precipitated solid was collected by filtration and dried. The yield was 189.5 g. The obtained solid was measured for molecular weight by a light scattering method, and as a result, the weight average molecular weight (Mw) was 3.2.
It was 10,000. Other polymer compounds according to the present invention are synthesized in a similar manner.

Further, in addition to the above polymer, a compound represented by the following general formula (6) can be added to the intermediate layer in the photosensitive lithographic printing plate of the present invention. General formula (6)

[0080]

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(Wherein, R ₁ represents an arylene group having 6 to 14 carbon atoms, and m and n each independently represent an integer of 1 to 3.) The compound represented by the above general formula (6) Will be described. The carbon number of the arylene group represented by R ₁ is 6 to
14 is preferable, and 6 to 10 are more preferable. Specific examples of the arylene group represented by R ₁ include a phenylene group, a naphthyl group, an anthryl group, and a phenathril group. The arylene group represented by R ₁ has 1 to 1 carbon atoms.
10 alkyl groups, alkenyl groups having 2 to 10 carbon atoms, alkynyl groups having 2 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, carboxylic acid ester groups, alkoxy groups, phenoxy groups, sulfonic acid ester groups, phosphonic acid Ester group,
It may be substituted with a sulfonylamide group, a nitro group, a nitrile group, an amino group, a hydroxy group, a halogen atom, an ethylene oxide group, a propylene oxide group, a triethylammonium chloride group, or the like.

Specific examples of the compound represented by the general formula (6) include, for example, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, salicylic acid, 1-hydroxy-2-
Examples include naphthoic acid, 2-hydroxy-1-naphthoic acid, 2-hydroshiki 3-naphthoic acid, 2,4-dihydroxybenzoic acid, and 10-hydroxy-9-anthracene carboxylic acid. However, the present invention is not limited to the above specific examples, and the compound represented by the general formula (6)
They may be used alone or in combination of two or more.

The intermediate layer containing the polymer compound according to the present invention and the compound represented by the above general formula (6), which is optionally added, is formed on an aluminum support which has been subjected to a hydrophilic treatment described later. It is applied by the method described above.

This intermediate layer can be provided by the following method. A method in which a solution in which the polymer compound according to the present invention is dissolved in an organic solvent such as methanol, ethanol, and methyl ethyl ketone or a mixed solvent thereof or a mixed solvent of these organic solvents and water is coated on an aluminum plate, and dried and provided. The aluminum support is immersed in an organic solvent such as methanol, ethanol, methyl ethyl ketone, or a mixed solvent of these organic solvents and water, or a solution obtained by dissolving the polymer compound of the present invention in a mixed solvent thereof. Or cleaning with air, etc.
An application method of drying and providing an intermediate layer can be exemplified.

In the former method, the total of the above compounds is 0.0
A solution having a concentration of 05 to 10% by weight can be applied in various ways. For example, any method such as bar coater coating, spin coating, spray coating, and curtain coating may be used. In the latter method, the concentration of the solution is 0.005 to 20% by weight, preferably 0.01% to 10% by weight, and the immersion temperature is 0 ° C to 70 ° C, preferably 5 to 60 ° C. The time is 0.1 seconds to 5 minutes, preferably 0.5 seconds to 120 seconds.

The above solution may be a basic substance such as ammonia, triethylamine or potassium hydroxide, an inorganic acid such as hydrochloric acid, phosphoric acid, sulfuric acid or nitric acid, an organic sulfonic acid such as nitrobenzenesulfonic acid or naphthalenesulfonic acid, or phenylphosphonic acid. The pH is adjusted with various organic acidic substances such as organic phosphonic acids such as acids, benzoic acid, coumaric acid, and organic carboxylic acids such as malic acid, and organic chlorides such as naphthalene sulfonyl chloride and benzenesulfonyl chloride. More preferably, pH = 0 to 6
Can also be used. Further, in order to improve the tone reproducibility of the photosensitive lithographic printing plate, a substance absorbing ultraviolet light, visible light, infrared light or the like can be added.

After drying the compound constituting the intermediate layer of the present invention
Coating amount is 1 to 100 mg / m ^Two Is appropriate and good
Preferably 2 to 70 mg / m^Two It is. The above coating amount is 1mg / m^Two 
If it is less than this, a sufficient effect cannot be obtained. Also 100mg
/ m^Two The same applies to more than that.

Next, the positive photosensitive lithographic printing plate of the present invention will be described in detail in the order of [3] Support and [4] Development. In the present invention, the photosensitive lithographic printing plate may be a PS plate.

[3] Support The support used in the positive photosensitive lithographic printing plate of the present invention and the processing thereof will be described below. (Aluminum Plate) The aluminum plate used in the present invention is a plate-like body such as pure aluminum or an aluminum alloy containing aluminum as a main component and containing a small amount of a different atom. The hetero atoms include silicon, iron, manganese, copper, magnesium, chromium, zinc, bismuth, nickel, titanium and the like. The synthetic composition has a heteroatom content of 10% by weight or less. Aluminum that is suitable for the present invention is pure aluminum, but it is preferable that completely pure aluminum contains as little foreign atoms as possible because it is difficult to produce due to refining technology. Further, any aluminum alloy having a different atomic content of the above-described level can be said to be a material that can be used in the present invention. As described above, the composition of the aluminum plate used in the present invention is not particularly limited, and conventionally known and publicly available materials can be appropriately used. Preferred materials include JIS A 10
50, 1100, 1200, 3003, 310
3, the same 3005 materials are included. The thickness of the aluminum plate used in the present invention is about 0.1 mm to 0.6 mm. Prior to the surface roughening treatment of the aluminum plate, a degreasing treatment for removing a rolling oil on the surface, for example, a treatment with a surfactant or an alkaline aqueous solution is performed as necessary.

(Roughening and Anodizing) The surface of the aluminum plate is roughened mechanically, electrochemically dissolved and roughened, and chemically. There is a method of selectively dissolving the surface. As the mechanical method, a known method called a ball polishing method, a brush polishing method, a blast polishing method, a buff polishing method, or the like can be used. Further, as an electrochemical surface roughening method, there is a method of performing an alternating or direct current in a hydrochloric acid or nitric acid electrolyte. Further, as disclosed in JP-A-54-63902, a method in which both are combined can also be used.

The aluminum plate thus roughened is subjected to an alkali etching treatment and a neutralization treatment as required, and then subjected to an anodic oxidation treatment in order to increase the water retention and abrasion resistance of the surface. As the electrolyte used for the anodic oxidation treatment of the aluminum plate, any electrolyte that forms a porous oxide film can be used, and generally, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, or a mixed acid thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of the electrolyte.

The conditions of the anodizing treatment vary depending on the electrolyte to be used, and thus cannot be specified unconditionally. / Dm ² , voltage 1-100V, electrolysis time 10
It is suitable if it is in the range of seconds to 5 minutes. The amount of the anodized film is suitably 1.0 g / m ² or more, but more preferably in the range of 2.0 to 6.0 g / m ^2. When the anodic oxide film is less than 1.0 g / m ² , the printing durability is insufficient,
The non-image portion of the lithographic printing plate is easily scratched, and so-called "scratch stain" in which ink adheres to the scratched portion during printing is likely to occur. Although such anodizing treatment is performed on a surface used for printing of the support of the lithographic printing plate, the back around the electric lines of force, the anodized film 0.01 to 3 g / m ² on the back surface It is generally formed.

(Hydrophilization treatment) As the hydrophilization treatment used after the above-mentioned treatment, conventionally known hydrophilization treatments include:
A hydrophilization treatment is used. Examples of such a hydrophilic treatment include U.S. Pat. Nos. 2,714,066 and 3,181.
No. 461, No. 3,280,734, No. 3,902,7
No. 34 discloses an alkali metal silicate (for example, an aqueous solution of sodium silicate). In this method, the support is immersed or electrolytically treated in an aqueous solution of sodium silicate. Alternatively, Japanese Patent Publication No. 36-22
No. 063, potassium fluoride zirconate and U.S. Pat. Nos. 3,276,868 and 4,153.
For example, a method of treating with polyvinyl phosphonic acid as disclosed in No. 461, No. 4,689,272 is used. Among these, a particularly preferred hydrophilic treatment in the present invention is a silicate treatment. The silicate treatment will be described below.

(Silica treatment) The anodic oxide film of the aluminum plate treated as described above was treated with an alkali metal silicate of 0.1 to 30% by weight, preferably 0.5 to 10% by weight, Is immersed in an aqueous solution having a pH of 10 to 13 at, for example, 15 to 80 ° C. for 0.5 to 120 seconds. If the pH of the alkali metal silicate aqueous solution is lower than 10, the solution gels, and if it is higher than 13.0, the oxide film is dissolved. As the alkali metal silicate used in the present invention, sodium silicate, potassium silicate, lithium silicate and the like are used. Hydroxides used for increasing the pH of the aqueous alkali metal silicate solution include sodium hydroxide, potassium hydroxide, and lithium hydroxide. Incidentally, an alkaline earth metal salt or a Group IVB metal salt may be added to the above-mentioned treatment solution. Alkaline earth metal salts include nitrates such as calcium nitrate, strontium nitrate, magnesium nitrate, barium nitrate, sulfates, hydrochlorides, phosphates,
Water-soluble salts such as acetate, oxalate, and borate are exemplified. Group IVB metal salts include titanium tetrachloride, titanium trichloride, potassium titanium fluoride, titanium potassium oxalate, titanium sulfate, titanium tetraiodide, zirconium chloride, zirconium dioxide, zirconium oxychloride, zirconium tetrachloride and the like. Can be. Alkaline earth metal salts or Group IVB metal salts can be used alone or in combination of two or more. The preferred range of these metal salts is 0.01 to 10% by weight, and the more preferred range is 0.05 to 5.0% by weight. By silicate treatment,
Because the hydrophilicity on the aluminum plate surface is further improved,
At the time of printing, the ink hardly adheres to the non-image area, and the stain performance is improved.

(Backcoat) On the back surface of the support, a backcoat is provided if necessary. Examples of such a back coat include a coating comprising a metal oxide obtained by hydrolyzing and polycondensing an organic polymer compound described in JP-A-5-45885 and an organic or inorganic metal compound described in JP-A-6-35174. Layers are preferably used. Among these coating layers, Si (OCH ₃ ) ₄ , Si
(OC ₂ H ₅ ) ₄ , Si (OC ₃ H ₇ ) ₄ , Si (OC ₄ H ₉ )
Silicon alkoxy compounds such as ₄ are inexpensive and easily available,
A coating layer of a metal oxide provided therefrom is particularly preferable because of its excellent development resistance.

[3] Development Processing Next, the development processing of the photosensitive lithographic printing plate of the present invention will be described. (Exposure) The photosensitive lithographic printing plate of the present invention is developed after being subjected to image exposure. The light source of the active light beam used for the image exposure includes a carbon arc lamp, a mercury lamp, a metal halide lamp, a xenon lamp, a tungsten lamp, a chemical lamp and the like. Examples of the radiation include an electron beam, an X-ray, an ion beam, and a far-infrared ray. Also, g-line, i-line, D
Eep-UV light and high-density energy beam (laser beam) are also used. Examples of the laser beam include a helium-neon laser, an argon laser, a krypton laser, a helium-cadmium laser, a KrF excimer laser, a semiconductor laser, and a YAG laser.

(Developer) A preferable developer for the photosensitive lithographic printing plate of the present invention is an alkaline aqueous solution containing substantially no organic solvent. Specifically, sodium silicate, potassium silicate, NaOH, KOH, LiOH,
Aqueous solutions such as sodium phosphate, dibasic sodium phosphate, tribasic ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium carbonate, sodium bicarbonate, potassium carbonate, aqueous ammonia and the like are suitable.
More preferably, the developer contains (a) at least one kind of saccharide selected from non-reducing sugars and (b) at least one kind of base and has a pH in the range of 9.0 to 13.5. Hereinafter, the developer will be described in detail. In the present specification, unless otherwise specified, the developing solution means a developing solution (a developing solution in a narrow sense) and a developing replenisher.

(Non-Reducing Sugar and Base) The developer comprises at least one compound selected from non-reducing sugars and at least one base, and the pH of the solution is 9.
It is characterized by being in the range of 0 to 13.5. Such non-reducing sugars have no free aldehyde or ketone groups,
It is a saccharide that does not show reducing properties, and is classified as a trehalose-type oligosaccharide in which reducing groups are bonded to each other, a glycoside in which a reducing group of a saccharide is bonded to a non-saccharide, and a sugar alcohol obtained by hydrogenating and reducing a saccharide. It is preferably used. Trehalose-type oligosaccharides include saccharose and trehalose, and examples of glycosides include alkyl glycosides, phenol glycosides, and mustard oil glycosides. Examples of sugar alcohols include D, L-arabit, ribit, xylit, D, L
-Sorbit, D, L-mannit, D, L-idit, D, L-tallit, zuricit and allozurcit. Further, maltitol obtained by hydrogenation of disaccharide and reductant (reduced starch syrup) obtained by hydrogenation of oligosaccharide are preferably used. Among these, non-reducing sugars which are particularly preferred are sugar alcohols and saccharose, and D-sorbitol, saccharose and reduced starch syrup are particularly preferred because they have a buffering action in an appropriate pH range and are inexpensive. These non-reducing sugars can be used alone or in combination of two or more kinds, and their ratio in the developing solution is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight. Below this range, a sufficient buffering effect cannot be obtained, and at concentrations higher than this range, it is difficult to achieve high concentration and the problem of increased cost arises. still,
When a reducing sugar is used in combination with a base, there is a problem that the color changes to brown over time, the pH gradually decreases, and the developability decreases.

As the base to be combined with the non-reducing sugar, conventionally known alkaline agents can be used. For example, sodium hydroxide, potassium, lithium, trisodium phosphate, potassium, ammonium, disodium phosphate, potassium, ammonium, sodium carbonate, potassium, ammonium, sodium hydrogencarbonate, potassium, ammonium And inorganic alkali agents such as sodium borate, potassium and ammonium. Also, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, Organic alkali agents such as ethyleneimine, ethylenediamine and pyridine are also used. These alkali agents are used alone or in combination of two or more. Among these, sodium hydroxide and potassium hydroxide are preferred. The reason is that by adjusting these amounts to non-reducing sugars, pH
This is because adjustment becomes possible. Trisodium phosphate, potassium phosphate, sodium carbonate, potassium phosphate, etc. are also preferable because they have a buffering action by themselves. These alkaline agents are added so that the pH of the developing solution is in the range of 9.0 to 13.5, and the amount of addition is determined depending on the desired pH, the type and the amount of non-reducing sugar, but the more preferable pH is The range is from 10.0 to 13.2.

Further, an alkaline buffer consisting of a weak acid other than saccharides and a strong base can be used in combination with the developer. As a weak acid used as such a buffer, pKa is 10.0 to 1
3.2 are preferred. Such weak acids include Pe
IONISATION CONSTANTS OF ORGANI published by rgamon Press
C ACIDS IN AQUEOUS SOLUTION and the like, for example, 2,2,3,3-tetrafluoropropanol-1 (pKa 12.74), trifluoroethanol (12.37), Alcohols such as 12.24), pyridine-2-
Aldehydes such as aldehyde (12.68) and pyridine-4-aldehyde (12.05), salicylic acid (13.0), 3-hydroxy-2-naphthoic acid (12.84) and catechol (12.84) 12.6), gallic acid (12.4), sulfosalicylic acid (11.7),
3,4-dihydroxysulfonic acid (12.2 above), 3,
4-dihydroxybenzoic acid (11.94), 1,2,2
4-trihydroxybenzene (11.82), hydroquinone (11.56), pyrogallol (11.3)
4), o-cresol (10.33), resorcinol (11.27), p-cresol (10.2)
7) compounds having a phenolic hydroxyl group such as m-cresol (10.09);

2-butanone oxime (12.45);
Acetoxime (12.42), 1,2-cycloheptanedione dioxime (12.3), 2-hydroxybenzaldehyde oxime (12.10), dimethylglyoxime (11.9), ethanediamide dioxime (11.37) and acetophenone oxime (11.37).
Oximes such as 35) and adenosine (12.5
6), inosine (12.5) and guanine (12.
3), cytosine (12.2), hypoxanthine (1)
2.1), nucleic acid-related substances such as xanthine (11.9), and diethylaminomethylphosphonic acid (12.
32), 1-amino-3,3,3-trifluorobenzoic acid (12.29), isopropylidene diphosphonic acid (12.10), 1,1-ethylidene diphosphonic acid (11.54) , 1,1-ethylidene diphosphonic acid 1
-Hydroxy (11.52), benzimidazole (12.86), thiobenzamide (12.8),
Weak acids such as picoline thioamide (12.55) and barbituric acid (12.5).

Preferred among these weak acids are sulfosalicylic acid and salicylic acid. As the base to be combined with these weak acids, sodium hydroxide, ammonium hydroxide, potassium hydroxide and lithium hydroxide are preferably used.
These alkali agents are used alone or in combination of two or more. The above-mentioned various alkaline agents are used by adjusting the pH within a preferred range depending on the concentration and combination.

(Surfactant) To the developer, various surfactants and organic solvents can be added as necessary for the purpose of promoting the developability, dispersing the development residue, and increasing the ink affinity of the printing plate image area. Preferred surfactants include anionic,
Cationic, nonionic and amphoteric surfactants are included. Preferred examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polystyryl phenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid partial esters, and sorbitan. Fatty acid partial esters, pentaerythritol fatty acid partial esters, propylene glycol monofatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyethylene glycol fatty acid esters, poly Glycerin fatty acid partial esters, polyoxyethylenated castor oil, polyoxyethylene glycerin fatty acid partial esters, fatty acids Ethanol amides, N, N
Non-ionic surfactants such as -bis-2-hydroxyalkylamines, polyoxyethylene alkylamines, triethanolamine fatty acid esters, and trialkylamine oxides;

Fatty acid salts, abietic acid salts, hydroxyalkanesulfonic acid salts, alkanesulfonic acid salts,
Dialkyl sulfosuccinates, linear alkylbenzene sulfonates, branched alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkylphenoxy polyoxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-methyl- N-oleyltaurine sodium salt, N-alkylsulfosuccinic acid monoamide disodium salt, petroleum sulfonates, sulfated tallow oil, sulfates of fatty acid alkyl esters, alkyl sulfates, polyoxyethylene alkyl ether sulfates, Fatty acid monoglyceride sulfates, polyoxyethylene alkyl phenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, Alkyl phosphate salts, polyoxyethylene alkyl ether phosphate salts, polyoxyethylene alkyl phenyl ether phosphate salts, partially saponified styrene / maleic anhydride copolymers, partially olefin / maleic anhydride copolymers Anionic surfactants such as saponified products and naphthalene sulfonate formalin condensates; quaternary ammonium salts such as alkylamine salts and tetrabutylammonium bromide; cationic interfaces such as polyoxyethylene alkylamine salts and polyethylene polyamine derivatives. Activators, amphoteric surfactants such as carboxybetaines, aminocarboxylic acids, sulfobetaines, aminosulfates, and imidazolines. Among the surfactants mentioned above, the term "polyoxyethylene" can be read as a polyoxyalkylene such as polyoxymethylene, polyoxypropylene, or polyoxybutylene, and these surfactants are also included.

Further preferred surfactants are fluorine-based surfactants containing a perfluoroalkyl group in the molecule. Such fluorosurfactants include perfluoroalkyl carboxylate, perfluoroalkyl sulfonate, anionic type such as perfluoroalkyl phosphate, amphoteric type such as perfluoroalkyl betaine,
Cationic and perfluoroalkylamine oxides such as perfluoroalkyltrimethylammonium salts, perfluoroalkylethylene oxide adducts, oligomers containing perfluoroalkyl groups and hydrophilic groups,
Non-ionic types such as oligomers containing perfluoroalkyl groups and lipophilic groups, oligomers containing perfluoroalkyl groups, hydrophilic groups and lipophilic groups, and urethanes containing perfluoroalkyl groups and lipophilic groups are included. The above surfactants can be used alone or in combination of two or more, and are added to the developer in an amount of 0.001 to 10% by weight, more preferably 0.01 to 5% by weight.

(Development Stabilizer) Various development stabilizers are used in the developer. Preferred examples thereof include polyethylene glycol adducts of sugar alcohols described in JP-A-6-282079, tetraalkylammonium salts such as tetrabutylammonium hydroxide, phosphonium salts such as tetrabutylphosphonium bromide, and iodonium such as diphenyliodonium chloride. Salts are mentioned as preferred examples. Further, anionic surfactants or amphoteric surfactants described in JP-A-50-51324, water-soluble cationic polymers described in JP-A-55-95946,
There is a water-soluble amphoteric polymer electrolyte described in 142,528. Further, an organic boron compound to which an alkylene glycol is added described in JP-A-59-84241, a polyoxyethylene / polyoxypropylene block polymerization type water-soluble surfactant described in JP-A-60-111246, Polyoxyethylene / polyoxypropylene-substituted alkylenediamine compounds described in JP-A-60-129750, polyethylene glycol having a weight average molecular weight of 300 or more described in JP-A-61-215554, and cations described in JP-A-63-175858 Fluorinated surfactant having a functional group, JP-A-2-39157
And a water-soluble polyalkylene compound obtained by adding 4 moles or more of ethylene oxide to the acid or alcohol described in the publication.

(Organic Solvent) The developer of the present invention does not substantially contain an organic solvent, but an organic solvent is added if necessary. As such an organic solvent, those having a solubility in water of about 10% by weight or less are suitable, and preferably selected from those having a solubility of 5% by weight or less. For example, 1-phenylethanol, 2-phenylethanol, 3-phenyl-1-propanol, 4-phenyl-1-butanol,
4-phenyl-2-butanol, 2-phenyl-1-butanol, 2-phenoxyethanol, 2-benzyloxyethanol, o-methoxybenzyl alcohol, m
-Methoxybenzyl alcohol, p-methoxybenzyl alcohol, benzyl alcohol, cyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol and 4-methylcyclohexanol, N
-Phenylethanolamine and N-phenyldiethanolamine. "Substantially free of an organic solvent" in the developer of the present invention means that the content of the organic solvent is 5% by weight or less based on the total weight of the used solution. The amount used is closely related to the amount used of the surfactant, and it is preferable to increase the amount of the surfactant as the amount of the organic solvent increases. This is because when the amount of the surfactant is small and the amount of the organic solvent is large, the organic solvent is not completely dissolved, and therefore, it is impossible to expect good developing property.

(Reducing Agent) A reducing agent can be further added to the developer. This is to prevent stains on the printing plate, and is particularly effective when developing a negative photosensitive lithographic printing plate containing a photosensitive diazonium salt compound. Preferred organic reducing agents include phenolic compounds such as thiosalicylic acid, hydroquinone, methol, methoxyquinone, resorcinol and 2-methylresorcinol, phenylenediamine,
Amine compounds such as phenylhydrazine;
More preferred inorganic reducing agents include sulfurous acid, bisulfite, phosphorous acid, hydrogen phosphite, dihydrophosphite,
Examples thereof include sodium salts, potassium salts, and ammonium salts of inorganic acids such as thiosulfuric acid and dithionous acid. Among these reducing agents, sulfites are particularly excellent in the stain prevention effect. These reducing agents are preferably contained in a range of 0.05 to 5% by weight with respect to the developing solution at the time of use.

(Organic carboxylic acid) An organic carboxylic acid can be further added to the developer. Preferred organic carboxylic acids are aliphatic and aromatic carboxylic acids having 6 to 20 carbon atoms. Specific examples of the aliphatic carboxylic acid include caproic acid, enantiic acid, caprylic acid, lauric acid, myristic acid, palmitic acid and stearic acid, and particularly preferred are alkanoic acids having 8 to 12 carbon atoms. . Further, unsaturated fatty acids having a double bond in the carbon chain or branched fatty acids may be used. The aromatic carboxylic acid is a compound in which a carboxyl group is substituted on a benzene ring, a naphthalene ring, an anthracene ring, or the like. Specifically, o-chlorobenzoic acid, p-chlorobenzoic acid, o-hydroxybenzoic acid, p- Hydroxybenzoic acid, o-aminobenzoic acid, p-aminobenzoic acid, 2,4
-Dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, gallic acid, 1-hydroxy-2-naphthoic acid, 3 -Hydroxy-2-naphthoic acid, 2-hydroxy-1-naphthoic acid,
There are 1-naphthoic acid and 2-naphthoic acid, and hydroxynaphthoic acid is particularly effective. The above aliphatic and aromatic carboxylic acids are preferably used as a sodium salt, a potassium salt or an ammonium salt in order to enhance water solubility. The content of the organic carboxylic acid in the developer used in the present invention is not particularly limited, but if the content is less than 0.1% by weight, the effect is not sufficient, and if it exceeds 10% by weight, the effect is further improved. Not only can it not be measured, but it can hinder dissolution when another additive is used in combination. Therefore, the preferable addition amount is 0.1 to 10% by weight, more preferably 0.5 to 4% by weight, based on the developer used.

(Others) The developer may further contain a preservative, a coloring agent, a thickener, an antifoaming agent, a water softener and the like, if necessary. Examples of the water softener include polyphosphoric acid and its sodium salt, potassium salt and ammonium salt, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid, 1,2-diaminocyclohexanetetraacetic acid. Aminopolycarboxylic acids such as acetic acid and 1,3-diamino-2-propanoltetraacetic acid and their sodium, potassium and ammonium salts;
Aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), triethylenetetraminehexa (methylenephosphonic acid), hydroxyethylethylenediaminetri (methylenephosphonic acid) and 1-
Hydroxyethane-1,1-diphosphonic acid and its sodium, potassium and ammonium salts can be mentioned.

The optimum value of such a water softener varies depending on the chelating power, the hardness of the hard water used and the amount of hard water. 01 to 5% by weight, more preferably 0.01 to 5% by weight
It is in the range of 0.5% by weight. If the added amount is less than this range, the intended purpose is not sufficiently achieved, and if the added amount is larger than this range, an adverse effect on an image portion such as color omission appears. The remaining component of the developer is water. It is advantageous from the viewpoint of transportation that the developing solution is a concentrated solution having a smaller water content than at the time of use and is diluted with water at the time of use. In this case, the concentration is suitably such that the components do not separate or precipitate.

As the developer for the photosensitive lithographic printing plate of the present invention, the developer described in JP-A-6-282079 can also be used. This is because an alkali metal silicate having a molar ratio of SiO ₂ / M ₂ O (M represents an alkali metal) of 0.5 to 2.0, and a sugar alcohol having 4 or more hydroxyl groups are added with 5 mol or more of ethylene oxide. Developer containing a water-soluble ethylene oxide addition compound obtained by the above method. Sugar alcohol is a polyhydric alcohol corresponding to one obtained by reducing an aldehyde group and a ketone group of a sugar to form primary and secondary alcohol groups, respectively. Specific examples of sugar alcohols include D, L-trait, erythritol, D, L-arabit, ribit, xylit, D, L-sorbit, D, L-mannit, D, L-idit, D, L −
Talit, dursit, allozursit and the like, and also di-, tri-, tetra-, penta- and hexaglycerin obtained by condensing a sugar alcohol. The water-soluble ethylene oxide adduct is obtained by adding 5 mol or more of ethylene oxide to 1 mol of the sugar alcohol. Further, propylene oxide may be block-copolymerized with the ethylene oxide-added compound, if necessary, as long as the solubility is acceptable. These ethylene oxide addition compounds may be used alone or in combination of two or more. The addition amount of these water-soluble ethylene oxide addition compounds is 0.001 to the developing solution (used solution).
To 5% by weight, more preferably 0.001 to
2% by weight. The above-mentioned various surfactants and organic solvents can be further added to this developer, if necessary, for the purpose of promoting the developability, dispersing the developing residue and increasing the ink affinity of the printing plate image area.

(Development and Post-processing) A PS plate developed with a developer having such a composition may be washed with water, a rinsing solution containing a surfactant or the like, a finisher or a protective gum mainly composed of gum arabic or a starch derivative. The liquid is post-treated.
In the post-processing of the PS plate of the present invention, these processings can be used in various combinations. In recent years, in the plate making / printing industry, automatic developing machines for PS plates have been widely used in order to rationalize and standardize plate making operations. This automatic developing machine generally comprises a developing section and a post-processing section, and comprises a device for transporting a PS plate, each processing solution tank and a spray device, and pumps the exposed PS plate horizontally while pumping it. Each processing liquid is sprayed from a spray nozzle to perform development and post-processing. Recently, a PS plate is immersed and conveyed in a processing solution tank filled with a processing solution by a guide roll or the like to carry out development processing, or a fixed amount of small amount of washing water is supplied to the plate surface after development for washing. There is also known a method of reusing the waste water as dilution water of the undiluted developer solution. In such automatic processing, processing can be performed while replenishing each processing solution with a replenisher in accordance with the processing amount, operating time, and the like. Further, a so-called disposable processing method in which processing is performed with a substantially unused processing liquid can also be applied. The lithographic printing plate obtained by such a process is set on an offset printing machine and used for printing a large number of sheets.

[0114]

Embodiments of the present invention will be described below in detail. All percentages in the following examples are% by weight unless otherwise specified. (Examples 1 to 6, Comparative Examples 1 to 4) JI having a thickness of 0.24 mm
The surface of the SA1050 aluminum plate was grained using a nylon brush and an aqueous suspension of pumicestone of 400 mesh, and then thoroughly washed with water. After immersing in a 10% aqueous sodium hydroxide solution at 70 ° C. for 60 seconds for etching,
After washing with running water, it was neutralized and washed with a 20% aqueous nitric acid solution and washed with water. This was converted to 260 coulombs / dm ² with a 1% nitric acid aqueous solution using a sinusoidal alternating current under the condition of VA = 12.7V.
The electrolytic surface roughening treatment was performed using the quantity of electricity at the time of anode. When the surface roughness was measured, it was 0.55 μm (Ra display). Then immersed in a 30% aqueous sulfuric acid solution,
After desmutting at 2 ° C. for 2 minutes, the current density was 14 A / dm ² in a 20% aqueous sulfuric acid solution, and the amount of anodized film was 2.5 g / m ^2.
Substantially anodized and washed with water to form a substrate [A].

The substrate [A] was treated with a 0.15% by weight aqueous solution of sodium silicate at 22 ° C. for 10 seconds, and washed with water to prepare a substrate [B]. Further, the substrate [A] was treated with a 2.5% by weight aqueous solution of sodium silicate at 30 ° C. for 10 seconds, and washed with water to prepare a substrate [C]. Further, the substrate [A] was treated with a 2.5% by weight aqueous solution of sodium silicate at 50 ° C. for 5 seconds, and washed with water to prepare a substrate [D]. In addition, as a method for hydrophilization other than sodium silicate, the substrate [A] was treated with 1% saponin.
The substrate [E] was treated with an aqueous solution at 40 ° C. for 30 seconds, washed with water, and
Similarly, the substrate [A] is treated with a 1% aqueous solution of glucopon at 70 ° C. for 30 minutes.
Substrate [F] was prepared by treating for 2 seconds and washing with water. The intermediate layer-containing polymer compound (a) of the present invention shown in Table 1 on the surfaces of the substrates [B] to [F] thus treated, and, if necessary, the general formula shown in Table 1 The following coating solution prepared by mixing an additive (b) consisting of the compound represented by (6) was applied, and dried at 100 ° C. for 10 seconds.

Intermediate layer-containing polymer compound of the present invention (a) (shown as dry coating amount in Table 1) Additive shown in Table 1 (b) (shown as dry coating amount in Table 1) 100 g of methanol 100 g of water 0g

Next, a photosensitive layer was provided by applying a photosensitive solution [A] onto the substrate. The coated amount of the photosensitive layer after drying was 1.2 g / m ² . Further, in order to shorten the vacuum contact time during exposure, a photosensitive lithographic printing plate was prepared by forming a mat layer by the method described in JP-B-61-28986.

[Photosensitive solution A] Esterified product of 1,2-diazonaphthoquinone-5-sulfonyl chloride and pyrogallol-acetone resin (as described in Example 1 of US Pat. No. 3,635,709) 0.8 g cresol-formaldehyde novolak resin (meta-para ratio: 6: 4, weight average molecular weight 8000) 1.2 g phenol-formaldehyde novolak resin (weight average molecular weight 10,000) 0.3 g Photosensitive layer-containing polymer compound of the present invention ( C), see Table 1 0.7 g

Naphthoquinone-1,2-diazide-4-sulfonic acid chloride 0.1 g Tetrahydroxyphthalic anhydride 0.2 g Pyrogallol 0.05 g Benzoic acid 0.02 g 4- [pN, N-bis (ethoxycarbonylmethyl ) Aminophenyl] -2,6-bis (trichloromethyl) -s-triazine (hereinafter abbreviated as triazine A) 0.1 g Victoria Pure Blue BOH (the counter anion manufactured by Hodogaya Chemical Co., Ltd. was changed to 1-naphthalenesulfonic acid) 0.1 g Dye of structural formula (A) 0.01 g F-177 (fluorinated surfactant manufactured by Dainippon Ink and Chemicals, Inc.) 0.2 g Methyl ethyl ketone 30 g 1-methoxy-2-propanol 15 g

[0120]

Embedded image

The photosensitive lithographic printing plate thus prepared was
m with a 3 kW metal halide lamp for 1 minute from a distance of 30 m, using a developing solution shown below and a PS processor 900VR manufactured by Fuji Photo Film Co., Ltd. for 30 minutes.
Developing at 12 ° C. for 12 seconds. Developer A: D-sorbitol 5.1 parts by weight Sodium hydroxide 1.1 parts by weight Triethanolamine / ethylene oxide adduct (30 mol) 0.03 parts by weight Water 93.8 parts by weight Developer B: [SiO ₂ ] / [Na ₂ O] molar ratio 1.2 SiO ₂ 1.4 wt% aqueous solution of sodium silicate 100 parts by weight Ethylenediamine / ethylene oxide adduct (30 mol) 0.03 parts by weight

After the development processing as described above, the following evaluation was performed. (1) Printing durability When printing was performed using a printing machine Sprint manufactured by Komori Printing Machine Co., Ltd., it was evaluated how many sheets can be printed normally. The greater the number of printed sheets, the better the printing durability. (2) Remaining Color The residual color of the non-image portion was visually evaluated as follows, as a difference between the density of the non-image portion and the density of the substrate before coating. ◎: There is no color difference between the non-image area and the substrate before application. ○: There is almost no color difference between the non-image area and the substrate before application. △: The non-image area is more than the substrate before application. Looks slightly darker, ×: the non-image part looks clearly darker than the substrate before coating, 2 × ... the non-image part looks much darker than the substrate before coating,

(3) Mat Adhesion The mat layer formed on the surface of the photosensitive layer was evaluated for peeling as follows. …: No peeling of the mat layer was observed at all; Δ: slight peeling of the mat layer was observed; ×: peeling of the mat layer was clearly observed.

Table 1 shows the results. From the results shown in Table 1, the polymer having the acid group-containing component and the onium group-containing component of the present invention was used for the intermediate layer on the aluminum support subjected to the hydrophilic treatment. In addition, the photosensitive lithographic printing plate of the present invention has extremely high printing durability, residual color, and matt adhesion by incorporating a polymer compound comprising the components (a) to (d) of the present invention. It turns out that it is excellent.

[0125]

[Table 1]

[0126]

As described above, according to the present invention, it is possible to provide a photosensitive lithographic printing plate having good color retention and matt adhesion while maintaining printing durability. Further, according to the present invention, even when development is performed using a developing solution containing no silicate, that is, even when the non-image area is not subjected to a hydrophilic treatment by the developing solution, the stainability and the residual color are good. Has extremely high practicality.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Mitsuhiro Imaizumi 4,000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture Inside Fujisha Shin Film Co., Ltd. F-term (reference) in Film Co., Ltd.

Claims (1)

[Claims] 1. An intermediate layer containing a polymer compound having a component having an acid group and a polymer having a component having an onium group is provided on an aluminum support subjected to a hydrophilization treatment. A polymerizable monomer represented by the general formula [I], (b) (meth) acrylonitrile, (c) (meth)
A photosensitive lithographic printing plate comprising a photosensitive layer containing a polymer compound comprising an acrylate and (d) other polymerizable monomers. Embedded image (In the formula, P and R each independently represent a divalent organic group. Q and Z each independently represent an aromatic or substituted aromatic group. R ₈ represents a hydrogen atom, an alkyl group or a halogen atom. P, q, r and z are each independently 0
Or represents 1. n is an integer of 1 to 3. )