JPH04216554A - Photosensitive planographic printing plate without requiring damping water - Google Patents

Abstract

PURPOSE:To avoid stains during printing and to obtain excellent image reproducibility and printing resistance by constituting a primer layer of a continuous phase and a discontinuous phase. CONSTITUTION:The primer layer contains epoxy resin, photo-dimerizable photosetting resin, gelatin, diazo resin, and/or photo-polymerizable photosensitive compsn. as a continuous phase to which hollow resin particles such as microcapsules and hollow emulsion are added as a discontinuous phase. The epoxy resin is obtd. by the reaction of epichlorohydrin and polyphenol such as bisphenol A. The conditions applied are a thermosetting resin compsn. obtd. by mixing phenol resin, urea resin, etc., a thermosetting resin compsn. or normal temp. setting-type resin compsn. obtd. by mixing amine as a hardening agent, or an epoxy resin obtd. by precondensation of phenol and melamine.

Description

Detailed Description of the Invention [0001] [Industrial Application Field] The present invention relates to a photosensitive lithographic printing plate that does not require dampening water. The present invention relates to a photosensitive lithographic printing plate that does not require dampening water and has excellent printing durability. BACKGROUND OF THE INVENTION Conventionally, photosensitive lithographic printing plates that do not require dampening water (hereinafter referred to as "plate materials" as necessary) have been prepared by sequentially coating a photosensitive layer and an ink repellent layer on a support. It is known. By exposing and developing this plate material, a lithographic printing plate that does not require dampening water (hereinafter referred to as "printing plate" as necessary) can be obtained. Generally, in such plate materials, a primer layer is provided between the support and the photosensitive layer in order to improve the adhesion between them. Various materials can be used for the primer layer. For example, Japanese Patent Publication No. 61-54219 describes a photosensitive lithographic printing plate that uses a primer layer made of epoxy resin and does not require dampening water. It has been shown that this prevents damage to the original printing plate and that the resulting printing plate has high printing durability. However, although the primer layer used in this plate material has the advantage of preventing damage to the printing plate and has excellent printing durability, it is susceptible to scratches, such as brushes during development or printing. The resistance to scratches caused by plate cleaning cloths, etc., is not necessarily sufficient, and eventually the latter causes stains during printing, resulting in problems such as deterioration of image quality and reduced printing durability. [0005] Furthermore, JP-A-62-194255 discloses a primer layer having a thickness in the range of 6 to 100 μm, which improves the scratch resistance of the silicone rubber layer. It has been shown that However, although this plate material has improved scratch resistance in the silicone rubber layer, the surface of the silicone rubber layer is less likely to be scratched by impact, but scratches, such as brushes during development or plate cleaning cloths during printing, may occur. The resistance to scratches caused by the latter is not necessarily sufficient, and eventually the latter causes stains during printing, resulting in a decrease in printing durability. [0007] Therefore, as a result of various studies in view of the above-mentioned problems, the present inventors achieved the intended purpose by incorporating hollow resin particles such as microcapsules and hollow emulsions into the primer layer as a discontinuous phase. We have discovered that it is possible to do this, and have hereby accomplished the present invention. OBJECTS OF THE INVENTION Therefore, an object of the present invention is to provide a photosensitive lithographic printing plate that does not require dampening water and has excellent image reproducibility without staining during printing and has excellent printing durability. . [0009] The object of the present invention is to provide a photosensitive lithographic printing plate that does not require dampening water and has a primer layer, a photosensitive layer, and an ink repellent layer in this order on a substrate, in which the primer layer is a continuous phase and an ink repellent layer. This was achieved by a dampening solution-free photosensitive lithographic printing plate consisting of a continuous phase. The structure of the present invention will be explained below.
This will be explained more specifically. The continuous phase contained in the primer layer according to the present invention is a continuous and uniform resin phase, and the discontinuous phase is a phase of hollow resin particles such as hollow capsules and hollow emulsions. The primer layer of the photosensitive lithographic printing plate that does not require dampening water of the present invention contains (1) an epoxy resin, (2) as a continuous phase.
) containing a photodimerizable photocurable resin, (3) gelatin, (4) a diazo resin and/or a photopolymerizable photosensitive composition,
Furthermore, hollow resin particles such as microcapsules and hollow emulsions are added as a discontinuous phase. The primer layer used in the present invention is as follows. (1) Epoxy resin and resin composition containing the same A typical example of the epoxy resin used in the primer layer of the present invention is a reaction product of epicluhydrin and a polyhydric phenol such as bisphenol A. The epoxy resin may be mixed with other components to make it three-dimensional, or may be modified with other components. Examples of its usage are as follows. (2) A thermosetting resin composition containing an epoxy resin obtained by mixing one or more thermosetting resins such as phenolic resin, urea resin, and melanin resin. ■ Room-temperature or heat-curable resin compositions containing epoxy resins obtained by adding amines, polyamides, acid anhydrides, etc. as curing agents ■ Phenol, melamine, polyester, polyamide,
Epoxy resin obtained by precondensation with one or more of polysulfides, etc. ■ Epoxy resin ester obtained by esterification with fatty acids These epoxy resins can be used by appropriately mixing them. It is also possible to mix and use vinyl resins, acrylic resins, amino resins, alkyd resins, urethane resins, etc. within a range that allows compatibility. [0014] When hardening the hardening fat containing these epoxy resins, a hardening reaction accelerator such as p-toluenesulfonic acid, boron trifluoride monoethylamine, etc. can be appropriately added and used as required. (2) A cured layer consisting of a photodimerizable photocurable resin The photodimerizable photocurable resin contains the following groups 1 in the main chain or side chain of the polymer. [Group 1] [0016] Polyesters, polycarbonates,
These include polyamides, polyacrylic acid esters, polyvinyl alcohol derivatives, etc., and the molecular weight is not limited as long as it is soluble in the solvent, but generally 1.00
It is advantageous to select from the range from 0 to several tens of thousands. Particularly preferred such polymers include photosensitive polymers containing a photosensitive group in the polymer main chain, such as p-phenylene diacrylic, as described in U.S. Pat. No. 3,030,208 and U.S. Pat. Photosensitive polyester consisting of acid, diacrylic acid, and diol, [
[0017] US Pat. No. 2,956,878 and US Pat. No. 31
73787, for example, photosensitive polyesters derived from 2-propolydenmalonic acid compounds such as cinnamylidenemalonic acid and difunctional glycols, U.S. Pat. 26909
66, No. 2752373, and No. 2732301, such as photosensitive polymers such as cinnamate esters of hydroxyl group-containing polymers such as polyvinyl alcohol, starch, cellulose, and the like. This includes those that become insolubilized by the action of actinic rays. Pigments and dyes are added to the above polymer as colorants. For example, phthalocyanine blue (C.I.
74160), Carmine 6B (C.I.15850)
, Rhodamine B Lake (C.I. 45170) are preferred, but oil blue BO (C.I. 74350) is preferred.
) can be used with dyes such as It goes without saying that the amount added will vary depending on conditions such as the amount of coating, but it is 1 to 50% of the polymer.
A particularly preferred range is 2 to 15 weight percent. [0019] It is preferable that the above polymer contains a sensitizer. Such sensitizers include, for example, U.S. Pat.
No. 0286, No. 2670287, No. 2732301, No. 2835656, No. 2956878, No. 302
No. 3100, No. 3066117, No. 3141770, No. 3173787, No. 3357831, No. 340
No. 9593, No. 3418295, No. 3453110, No. 3475617, No. 3561969, No. 357
These include those described in No. 5929, No. 3582327, No. 3647470, No. 3721566, No. 3737319, etc. Specific examples of particularly useful sensitizers include 2-benzoylmethylene-1-methyl-β-naphthothiazoline, 5-nitroacenaphthene, β-chloroanthraquinone, 1,2-benzalanthraquinone, p , p'-tetraethyldiaminodiphenylketone, p,p'-dimethylaminobenzophenone, 4-nitro-2-chloroaniline, and the like. The proportion of the sensitizer to be used is preferably in the range of 0.5 to 1.5% by weight, and particularly preferably in the range of 2 to 8% by weight. (3) Gelatin used as a binder As the gelatin, so-called photographic gelatin obtained from cow bones and skin by acid treatment or alkali treatment is mainly used. In addition to this, it is generally shown below. Any gelatin, which is a natural polymeric compound condensed with various amino acids, can be used. [Group 2] The following hardening agents are used for hardening (ie crosslinking) gelatin. (A) Inorganic hardener chrome alum, aluminum alum, etc. (B)
Organic hardener (B-1) Aldehyde type hardener Formaldehyde, glyoxal, succinaldehyde, glutaldehyde, etc. [Chemical formula 1] [Chemical formula 2] [Chemical formula 2] [Chemical formula 4] [0028] The amino acids in gelatin that can be used in the hardening reaction differ depending on the type of hardening agent used. Furthermore, the amino acid composition varies depending on the gelatin used. From this, the optimal amount of hardener to be added varies depending on the type of gelatin used and the type of hardener, but gelatin 1
The hardener is preferably added in an amount of 1 to 200 mmol, preferably 5 to 100 mmol, per 00 parts by weight. (4) One containing a diazo resin and/or a photopolymerizable photosensitive composition The primer layer used in the present invention includes:
For example, polyester resin, vinyl chloride-vinyl acetate copolymer, acrylic resin, vinyl chloride resin, polyamide resin, polyvinyl butyral resin, epoxy resin, acrylate copolymer, vinyl acetate copolymer, phenoxy resin, polyurethane resin, polycarbonate. Examples include resin, polyacrylonitrile butadiene, polyvinyl acetate, and the like. [0030] As the anchor agent constituting the primer layer, for example, the above-mentioned silane coupling agent, silicone primer, etc. can be used, and organic titanates and the like are also effective. The photosensitive composition contained in the primer layer used in the present invention will be specifically explained. (1) Photosensitive composition containing diazo resin The diazo resin used in the present invention includes various types, but is preferably a diazo resin typified by a condensate of p-diazodiphenylamine and formaldehyde. It may be water-soluble or organic solvent-soluble, but
Preferably, Japanese Patent Publication No. 47-1167 and No. 57-438
Those that are water-insoluble and soluble in ordinary organic solvents, such as those described in Japanese Patent No. 90, etc., are used. Particularly preferred is a diazo resin represented by the following formula 1. [Formula 1] [In the formula, R1, R2 and R3 are
Represents a hydrogen atom, an alkyl group, or an alkoxy group, and R4
represents a hydrogen atom, an alkyl group or a phenyl group. X represents PF6 or BF4, and Y represents -NH-, -S- or -O-. [0034] Examples of the diazo monomer in the diazo resin used in the present invention include 4-diazodiphenylamine, 1-diazo-4-N,N-dimethylaminobenzene, 1-diazo-4-N,N-diethylaminobenzene, 1-Diazo-4-N-ethyl-N-hydroxyethylaminobenzene, 1-diazo-4-N-methyl-N-hydroxyethylaminobenzene, 1-diazo-2,5-
Diethoxy-4-benzoylaminobenzene, 1-diazo-4-N-benzylaminobenzene, 1
-Diazo-4-morpholinobenzene, 1-diazo-2,
5-dimethoxy-4-p-tolylmercaptobenzene,
1-Diazo-2-ethoxy-4-N,N-dimethylaminobenzene, p-diazodimethylaniline, 1-diazo-2,5-dibutoxy-4-morpholinobenzene, 1-
Diazo-2,5-diethoxy-4-morpholinobenzene, 1-diazo-2,5-dimethoxy-4-morpholinobenzene, 1-diazo-2,5-diethoxy-4-p-tolylmercapbenzene, 1-diazo -4-N-ethyl-
N-hydroxyethylaminobenzene, 1
-Diazo-3-ethoxy-4-N-methyl-N-benzylaminobenzene, 1-diazo-3-chloro-4-N,
N-diethylaminobenzene, 1-diazo-3-methyl-4-pyrrolidinobenzene, 1-diazo-2-chloro-
4-N,N-dimethylamino-5-methoxybenzene,
1-diazo-3-methoxy-4-pyrrolidinobenzene,
Examples include 3-methoxy-4-diazodiphenylamine, 3-ethoxy-4-diazodiphenylamine, 3-(n-propoxy)-4-diazodiphenylamine, and 3-(isopropoxy)-4-diazodiphenylamine. Examples of the aldehyde used as a condensing agent with the diazo monomer include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, and benzaldehyde. Furthermore, regarding anions, a water-soluble diazo resin can be obtained by using chlorine ions, tetrachlorozinc acid, etc., and boron tetrafluoride, hexafluorophosphoric acid, triisopropylnaphthalenesulfonic acid, etc. ,4,4'
- Obtaining an organic solvent-soluble diazo resin by using biphenyldisulfonic acid, 2,5-dimethylbenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 2-methoxy-4-hydroxy-5-benzoyl-benzenesulfonic acid, etc. I can do it. Particularly preferably, a diazo resin made of hexafluorophosphoric acid is used. Diazo resins include film-forming resins such as polyester resins, vinyl chloride monovinyl acetate copolymers, acrylic resins, vinyl chloride resins, polyamide resins, polyvinyl butyral resins, epoxy resins, acrylate copolymers, and vinyl acetate. It is used in combination with a copolymer, phenoxy resin, polyurethane resin, polycarbonate resin, polyacrylonitrile butadiene, polyvinyl acetate, etc., and it is particularly preferable to use it in combination with a polymeric compound having a hydroxyl group. Particularly preferred examples of the polymer compound include copolymers of monomers having aliphatic hydroxyl groups in side chains, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, and other copolymerizable monomers. . In addition to these, polyvinyl butyral resin, polyurethane resin, polyamide resin,
Epoxy resins, novolac resins, natural resins, etc. may be added. [0041] In addition, various polymeric compounds can be used as the binder used in combination with the diazonium salt, but preferably a monomer having an aromatic hydroxyl group as described in JP-A No. 54-98613. mer, such as N-(4-
hydroxyphenyl)acrylamide, N-(4-hydroxyphenyl)methacrylamide, o-, m-, or p-hydroxystyrene, o-, m-, or p-hydroxyphenyl methacrylate, etc. and other monomers Copolymers containing hydroxyethyl acrylate units or hydroxyethyl methacrylate units as the main repeating unit as described in US Pat. No. 4,123,276, natural copolymers such as shellac, rosin, etc. Resin, polyvinyl alcohol, U.S. Patent Nos. 3 and 7
51,257, linear polyurethane resins as described in U.S. Pat. No. 3,660,097, phthalated resins of polyvinyl alcohol, condensed from bisphenol A and epichlorohydrin. It contains celluloses such as epoxy resin, cellulose acetate, and cellulose acetate phthalate. Examples of the alkali-soluble resin include novolac resins, vinyl polymers having phenolic hydroxyl groups, and condensation resins of polyhydric phenols and aldehydes or ketones described in JP-A-55-57841. . Examples of the novolac resin include phenol-formaldehyde resin, cresol-formaldehyde resin, phenol-cresol-formaldehyde copolycondensation resin as described in JP-A-55-57841, and phenol-cresol-formaldehyde copolycondensation resin as described in JP-A-55-127553. p-substituted phenols and phenols as described or
Examples include copolymer resins of cresol and formaldehyde. In addition to the above-mentioned materials, these photosensitive compositions also contain pigments such as dyes and pigments, sensitizing agents, plasticizers, surfactants, organic acids, acid anhydrides, and exposure to light. A compound capable of generating an acid can be added. These binders are contained in an amount of 10 to 95% by weight in the solid content of the photosensitive composition.
, preferably 40 to 80% by weight. The diazo resin is contained in an amount of 5 to 80% by weight, preferably 15 to 60% by weight. These photosensitive compositions include other dyes,
Dyes such as pigments, fat sensitizing agents, plasticizers, surfactants, etc. can be added. (2) Photopolymerizable composition comprising an addition polymerizable unsaturated compound This composition preferably comprises (a) a monomer having at least two terminal vinyl groups, and (b) a photopolymerization initiator. as well as(
c) Consisting of a polymer compound as a binder. The vinyl monomer of component (a) is as follows:
Special Publication No. 35-5093, No. 35-14719, No. 4
It is described in each publication of No. 4-28727. For example, acrylic or methacrylic esters of polyols, such as diethylene glycol (meth)acrylate, triethylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, or methylene bis(meth)acrylamide. , bis(meth)acrylamides such as ethylene bis(meth)acrylamide,
Or an unsaturated monomer containing a urethane group, 004
7] For example, di-(2'-methacryloxyethyl)-2,
Diol mono(
Examples include reaction products of meth)acrylate and diisocyanate. As the photopolymerization initiator of component (b), the compound represented by the above formula 1 can be used, but other types can also be used. For example, the above-mentioned J. Examples include carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, photoreducible dyes, etc., as described in Chapter 5 of "Light Sensitive Systems" by Kosar. More specifically, it is disclosed in British Patent No. 1,459,563. As the photopolymerization initiator, the following can be used. Benzoin methyl ether, benzoin isopropyl ether, α,α-dimethoxy-
Benzoin derivatives such as α-phenylacetophenone, benzophenone, 2,4-dichlorobenzophenone, o-
Benzophenone derivatives such as methyl benzoylbenzoate, 4,4'-bis(dimethylamino)benzophenone, and 4,4'-bis(diethylamino)benzophenone; Thioxanthone derivatives such as 2-chlorothioxanthone and 2-isopropylthioxanthone; 2 - Anthraquinone derivatives such as chloranthraquinone and 2-methylanthraquinone, acridone derivatives such as N-methylacridone and N-butylacridone, α,α-diethoxyacetophenone, benzyl, fluorenone, xanthone, uranyl compounds, halogen compounds, etc. Furthermore, as the binder for component (c),
In addition to the binder resin used in item (1) above, various known polymers can be used. Details of specific binders are described in US Pat. No. 4,072,527. Components (a), (b), and (c) are 20 to 80% by weight of (a) in the solid content of the photopolymerizable composition;
b) is 0.1-20% by weight, (c) is 20-80% by weight
Preferably, it is contained. These photopolymerizable compositions can contain thermal polymerization inhibitors, plasticizers, dyes, pigments, and the like. [0052] A sensitizing agent added to the photosensitive composition,
The types of additives such as surfactants, sensitizers, stabilizers, thermal polymerization inhibitors, plasticizers, anchoring agents (silane coupling agents, silicone primers, organic titanates), pigments such as dyes and pigments, etc. The amount added varies depending on the situation, but in general, the amount added is 0.
01-20% by weight, preferably 0.05-10% by weight is suitable. The hollow resin particles used in the present invention are formed from the following resins. Polystyrene, poly(1
, 6-hexanediaminediyl terephthaloyl), polyvinyl acetate, polyethylene, polymethyl methacrylate, polyamide resin, polyvinyl acetate, polyester, polyacrylate, polyvinyl formal, gum arabic, benzyl cellulose, ethyl cellulose, acrylonitrile-styrene copolymer Coalescence, vinylidene chloride-acrylonitrile copolymer, hydroxymethyl cellulose phthalate, nitrocellulose, cellulose acetate, vinyl chloride-butyl acetate copolymer, [0054] Note that the primer layer containing the resins (1) and (2) above includes If necessary, pigments such as dyes and pigments, sensitizing agents, plasticizers, surfactants, organic acids, acid anhydrides, and compounds capable of generating acids upon exposure to light may be added. Next, the hollow resin particles contained in the primer layer used in the present invention will be specifically explained. [0055] Hollow resin particles are a general term for resins having small pores inside, and can be made from microcapsules containing a low boiling point solvent. This microcapsule is
It is produced by an in situ polymerization method in which suspension polymerization is performed in the presence of a swelling agent. To make microcapsules with good thermal expansion properties, consider the boiling point, structure, particle size, particle size distribution of the expanding agent, softening point of the initiator and membrane polymer, elongation when heated, strength, gas barrier properties, etc. There is a need. [0056] Microcapsules are manufactured by appropriately using known techniques. Examples of the photosensitive layer that can be used in the present invention include, in the case of a positive type, a photopolymerizable adhesive layer or a photocrosslinkable photosensitive layer, a photosensitive layer made of a diazo resin, a binder resin, and the like. In the case of a negative type, a photosensitive layer made of a quinone diazide compound and a binder resin, etc. can be used. Various conventionally known diazo resins can be used as the above-mentioned diazo resin, but include diazo resins typified by condensates of aromatic diazonium salts and, for example, active carbonyl-containing compounds, especially formaldehyde; Solvent-soluble diazo resins are preferred. A preferred specific example of the diazo resin is a resin represented by Formula 1 used in the primer layer. As the diazo resin represented by the above formula 1,
Preferably, those having a molecular weight of about 500 to 10,000 are mentioned. The content of the diazo resin in the photosensitive layer is preferably selected from the range of 1 to 70% by weight, more preferably from 3 to 60% by weight. An orthoquinonediazide compound is used in a negative-working photosensitive lithographic printing plate that does not require dampening water, and examples of such compounds include, for example, polycondensation resins of phenols and aldehydes or ketones and the following formula 2 or 3. Orthoquinonediazide sulfonic acid ester or carboxylic acid ester obtained by chemically condensing orthoquinonediazide sulfonic acid or carboxylic acid derivative represented by: [Formula 2] [Formula 3] [In the formula, X is -SO2 Y or -COY
In the group represented by, Y represents a group that can be removed during condensation of a halogen atom, an alkali metal, etc. ] Specific examples of the compound represented by the above formula 2 include 1,2-benzoquinonediazide (2)-4-sulfonyl chloride, 1,2-benzoquinonediazide (2)-4-carbonyl chloride, and 1,2-benzoquinonediazide (2)-4-carbonyl chloride.
Examples include benzoquinone diazide (2)-, 5-sulfonyl chloride, 1,2-benzoquinone diazide (2)-5-carbonyl chloride, and the like. Specific examples of the compound represented by the above formula 3 include 1,2-naphthoquinonediazide (2)-4-sulfonyl chloride, 1,2-naphthoquinonediazide (2)
-4-carbonyl chloride, 1,2-naphthoquinonediazide (2)-5-sulfonyl chloride, 1,2-naphthoquinonediazide (2)-5-carbonyl chloride, and the like. Examples of polycondensation resins of phenols and aldehydes or ketones include those disclosed in Japanese Patent Publication No. 43-28
403, a polycondensate of pyrogallol and acetone; as described in JP-A-55-76346, a polycondensate of a mixture of pyrogallol and resorcin and acetone; JP-A-45-9610; As stated in the publication, phenol, formaldehyde,
Novolac resin or meta-cresol formaldehyde novolac resin; As described in Japanese Patent Publication No. 50-5083, para-substituted phenol formalin resin (e.g. para-cresol formalin resin, para-t-butylphenol formalin resin, Paraethylphenol formalin resin, parapropylphenol formalin resin, paraisopropylphenol formalin resin, para n-butylphenol formalin resin, paraoctylphenol formalin resin, etc.), [0066] described in Japanese Patent Publication No. 62-60407 Polycondensation of formaldehyde with a phenol mixture containing a phenol substituted with an alkyl group or phenyl group having 3 to 12 carbon atoms and phenol or its methyl substituted product or a mixture thereof in a molar ratio of 1:9 to 9:1. (eg, polycondensates of the para-substituted phenol and phenol, para-cresol, metacresol, etc.). The esterification rate of the orthoquinone diazide group to the hydroxyl group of the polycondensation resin of phenols and aldehydes or ketones is preferably 15 to 100 mol%, more preferably 20 to 80 mol%. Furthermore, as an orthoquinonediazide compound, orthonaphthoquinonediazide sulfonic acid ester of polyhydroxybenzophenone (for example, 1,2-naphthoquinonediazide (2)-5-sulfonic acid ester, 1,2-naphthoquinonediazide (2)-4)
-sulfonic acid esters, etc.). This polyoxybenzophenone is a compound obtained by replacing two or more hydrogen atoms of benzophenone with hydroxyl groups, such as dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, octahydroxybenzophenone, or derivatives thereof. , (for example, a substituent for a halogen atom, an alkyl group, an aryl group, an aralkyl group, a carboxylic acid group), and the like. Preferred are trihydroxybenzophenone and tetrahydroxybenzophenone, more preferred are 2,3,4-trihydroxybenzophenone and 2,3,4,4'-tetrahydroxybenzophenone. Furthermore, the esterification rate for hydroxyl groups is 3
0 to 100% is preferred. In the present invention, each of the above compounds may be used alone as the orthoquinone diazide compound, or two or more thereof may be used in combination. Among these orthoquinonediazide compounds listed above,
1,2- of 2,3,4-trihydroxybenzophenone
Naphthoquinonediazide (2)-5-sulfonic acid ester or 1,2-naphthoquinonediazide (2)-4-sulfonic acid ester, metacresol formaldehyde,
1,2-naphthoquinonediazide (2) of novolak resin
-5-sulfonic acid ester, 1,2-naphthoquinonediazide (2)-4-sulfonic acid ester, or a mixture thereof is more preferably used. The proportion of the orthoquinonediazide compound in the photosensitive layer is preferably 50 to 60% by weight, more preferably 20 to 50% by weight. Further, examples of binder resins used in the photosensitive layer include acrylic resins and novolak resins. All copolymerizable monomers can be used as the copolymerizable constituents of the acrylic resin, and in particular, the following compounds having unsaturated bonds are used as monomers for radical polymerization. (1) Monomers having a hydroxyl group: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxypentyl (meth)acrylate, 4-hydroxyphenyl (meth)acrylate, 2-hydroxy (Meth)acrylate monomers such as phenyl (meth)acrylate; N-methylol (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N-(hydroxyphenyl)-(meth)acrylamide, N-(hydroxynaphthyl)- (meth)acrylamide monomers such as (meth)acrylamide; o-, m-, p-hydroxystyrene monomers, etc. (meth)acrylic acid ester or amide monomers other than (2) and (1) ; Alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate; N-phenyl (meth)acrylamide, o-, m-, p-methoxy Phenyl (meth)acrylamide, o-, m-, p-ethoxyphenyl (meth)acrylamide, etc. (3) Monomers having a cyano group in the side chain; (meth)acrylonitrile, 2-pentenitrile, 2
-Methyl-3-butenenitrile, 2-cyanoethyl acrylate, o-, m-, p-cyanostyrene, etc.; (4)
Monomers having carboxylic acid in the side chain; (meth)acrylic acid, itaconic acid and its anhydride, maleic acid and its anhydride, crotonic acid, etc.; (5) Vinyl ethers; propyl vinyl ether, butyl vinyl ether, Octyl vinyl ether, phenyl vinyl ether, etc., (6) Styrenes; α-methylstyrene, methylstyrene, chloromethylstyrene, styrene, etc.; (7) Vinyl ketones; Methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, etc. (
8) Monomers other than (1) to (7); Examples include olefins such as ethylene, propylene, isobutylene, butadiene, and vinyl chloride, N-vinylpyrrolidone, N-vinylcarbazole, and 4-vinylpyridine, but others Any monomer can be used as long as it can undergo radical copolymerization with these monomers. In the present invention, in addition to the above-mentioned materials, the photosensitive layer may further contain dyes, pigments, coating properties improvers, plasticizers,
A fat sensitizer, a stabilizer, etc. can be added. It is advantageous that the photosensitive layer of the positive type photosensitive lithographic printing plate that does not require dampening water further contains a known exposure-visible image imparting agent. Examples of the above dyes include Victoria Pure Blue BOH, Oil Blue #603, Oil Pink #312, Patent Pure Blue, Crystal Violet, Leuco Crystal Violet, Brilliant Green, Ethyl Violet, Methyl Green, Erythrosin B, and Basic Fuchsin. , Malachi Green,
Leucomalachite green, m-cresol purple,
Cresol red, xylenol blue, rhodamine B
, auramine, 4-p-diethylaminophenylimino naphthoquinone, cyano-p-diethylaminophenyl acetanilide, etc.; triphenylmethane, diphenylthane, oxazine, xanthene, iminonaphthoquinone, azomethine, or anthraquinone pigments; can be mentioned. The dye is usually contained in the photosensitive layer in an amount of about 0.01 to about 1
0% by weight, preferably about 0.05-8% by weight. Examples of the coating property improver include alkyl ethers (eg, ethyl cellulose, methyl cellulose), fluorine-based surfactants, nonionic surfactants (eg, Bluronic L64 (manufactured by Asahi Denka)), and the like. Plasticizers for imparting flexibility and abrasion resistance to the coating film include, for example, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate,
Dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrafurfuryl oleate,
Examples include oligomers of acrylic acid or methacrylic acid. [0080] The amount of these additives added varies depending on the purpose of use, but is generally 0.01% of the total solid content.
% to 30% by weight is preferred. The thickness of the photosensitive layer used in the present invention is usually 0.05 to 10 μm, preferably 0.05 μm to 10 μm, preferably 0.05 μm to 10 μm, preferably
．． It is 1 to 5 μm. In the present invention, preferably a silicone rubber layer is coated on the photosensitive layer as an ink repellent layer. The silicone rubber used in the present invention is preferably a cotton-like or somewhat crosslinked polyorganosiloxane. The polyorganosiloxane usually has a molecular weight of 1,000 to several hundred thousand, and is suitably crosslinked in the form of a liquid, wax, or cake at room temperature. The polyorganosiloxane is classified into condensed type and addition type depending on the method of crosslinking. [0082] In the condensed type, crosslinking is performed by a condensation reaction, and water, alcohol, organic acid, etc. are released by the reaction. Particularly useful condensation silicone rubbers include:
Examples include mixtures of linear polyorganosiloxanes having hydroxyl groups, acetoxy groups, etc. at both ends or part of the main chain, and silicone crosslinking agents, or those in which hydroxyl groups are reacted with silicone crosslinking agents, and in both cases, a condensation catalyst is added. This is more advantageous in terms of crosslinking speed. Particularly preferred are those obtained by condensation crosslinking of linear dimethylorganopolysiloxanes having hydroxyl groups at both ends. The main chain of the polyorganosiloxane has the following repeating units. [Formula 4] In the formula, R1 and R2 are an alkyl group, an aryl group, an alkenyl group, each of which may have a substituent, or a combination thereof, and include a methyl group, a phenyl group, a vinyl group, a tri- A fluoropropyl group is preferred, and a methyl group is particularly preferred. As the silicone crosslinking agent, -OCO
CH3, -ONR(R'), -ON=CR(R'),
-OR, -NR(R') or -OH (wherein R and R'
is an alkyl group. ) Condensation type silicone crosslinking agents such as so-called deacetic acid type, deoxime type, dealcoholized type, deaminated type, dehydrated type, and the like, which have a functional group represented by the following formulas, can be mentioned. Examples of such crosslinking agents include tetraacetoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, phenyltriacetoxysilane, dimethyldiacetoxysilane, diethylacetoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane. , dimethyldimethoxysilane, vinyltrimethoxysilane, methyltris(acetoneoxime)silane, methyltris(N-methyl-N-acetylamino)silane, vinyltris(methylethylketoxime)silane,
Examples include methyltri(methylethylketoxime)silane and oligomers thereof. The amount of each of these crosslinking agents is preferably in the range of 0.5 to 30 parts by weight per 100 parts by weight of the polyorganosiloxane. Examples of the condensation catalyst include organic carboxylic acids, titanate esters, acetylacetone metal complexes, chloroplatinic acid, naphthenic acid, and the like. The addition type refers to one in which a water-based group in a crosslinking agent is added to an unsaturated group in the main body, such as a vinyl group (-CH=CH2), resulting in crosslinking. Specifically, examples include vinyl group-containing organopolysiloxanes, hydrogenated organopolysiloxanes, and the like mixed with platinum-based catalysts (for example, chloroplatinic acid). The polyorganosiloxane has repeating units similar to those of the condensed type described above in the main chain. For the silicone rubber layer used in the present invention, either or both of condensation type and addition type silicone rubbers can be used. It is also possible to use condensed and addition type polyorganosiloxanes having hydroxyl groups, unsaturated groups, etc. in one polyorganosiloxane. The thickness of the silicone rubber layer used in the present invention is usually 0.5 to 10 μm, preferably 1 to 5 μm.
It is m. In the present invention, an adhesive layer made of acrylic resin or the like may be provided between the photosensitive layer and the silicone rubber layer, and the adhesive layer may contain various reactive crosslinking agents, silane coupling agents, etc. The thickness of the adhesive layer is preferably 0.01 μm to 0.5 μm. [0092] As the substrate used in the present invention, any substrate can be used as long as it has the flexibility to be set in a normal lithographic printing machine and can withstand the load applied during printing, including the layer structure. There are no particular restrictions. For example, paper such as coated paper, aluminum plate (JIS standard H
Examples include metal plates such as (-16, H-18, etc.), and plastic films such as polyethylene terephthalate. [0093] In particular, an aluminum plate or a composite material of aluminum foil and other materials is preferable, and an aluminum plate is particularly preferable from the viewpoint of printing durability. The thickness of the support is 50-400μ
m, preferably 100 to 300 μm. In addition, from the viewpoint of storage stability, the substrate, particularly an aluminum plate, or a composite material of aluminum foil and other materials, can be surface-treated by a known method before use. Such surface treatments include, for example, a method of treating the surface of an aluminum plate with a silicate (US Pat. No. 2,714,066), a method of treating the surface of an aluminum plate with an organic acid salt (US Pat. No. 2,714, No. 066), a method of treatment with phosphonic acids and their derivatives (U.S. Pat. No. 3,220,
No. 832), treatment with potassium hexafluorozirconate (U.S. Pat. No. 2,946,683), anodic oxidation, and treatment with an aqueous solution of alkali metal silicate after anodization (U.S. Pat. No. 3, 181,461) etc. In the present invention, a protective layer may be provided on the upper surface of the silicone rubber layer, if necessary. As the material for this protective layer, it is preferable to use a water-soluble film such as polyvinyl alcohol, a biodegradable film such as polyhydroxyalkanoate, or polyesteramide. The photosensitive lithographic printing plate that does not require dampening water of the present invention is produced, for example, as follows. [0096] The composition solution to form the primer layer is applied onto the support using a conventional coater such as a reverse roll coater, air knife coater, Meyer bar coater, etc., or a rotary coating device such as Whaler, and is dried and cross-linked and cured. let Next, a composition solution to form a photosensitive layer is applied and dried, or after being applied and dried, it is crosslinked and cured by light or heat. Next, a composition solution constituting the photosensitive layer is applied and dried. [0097] A silicone rubber solution is applied onto the photosensitive layer in a similar manner and heat-treated for several minutes, usually at a temperature of 100 to 120°C, to sufficiently cure the solution to form a silicone rubber layer. If necessary, a protective film can be provided on the silicone rubber layer using a laminator. Next, a method for producing a dampening water-free printing plate using the dampening water-free photosensitive lithographic printing plate of the present invention will be described. A positive film, which is the manuscript, is vacuum-adhered to the surface of the positive plate material and exposed. The light sources for this exposure include mercury lamps, carbon arc lamps, xenon lamps, and
Metal halide lamps, fluorescent lamps, etc. are used. Next, the positive film is peeled off and developed using a developer. As the developer, any known developer can be used for plate materials that do not require dampening water, but preferably an aqueous developer is used. The aqueous developer is a developer containing water as a main component, and is described in, for example, Japanese Patent Application Laid-Open No. 61-275759.
Preferably, a developer containing an organic solvent and a surfactant in an amount of 50% to 98% by weight can be mentioned, and more preferably an alkaline agent is included. [0100] Examples of the organic solvents contained in the water-based developer include aliphatic hydrocarbons (hexane, heptane, Isopar E, H, G (manufactured by Esso Chemical Co., Ltd., aliphatic hydrocarbon products). alcohols (methanol, ethanol, 1-butoxy-2-propanol, 3-methyl- 3-methoxybutanol, β-anilinoethanol, benzyl alcohol, etc.), 0101]
Ethers (methyl cellosolve, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, ethylene glycol dibutyl ether, propylene glycol, dipropylene glycol) butyl ether, tripropylene glycol methyl ether, polypropylene glycol methyl ether, etc.)
, Ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, 4-
methyl-1,3-dioxolan-2-one, etc.), esters (ethyl acetate, propyl acetate, hexyl acetate, methyl acetate, propyl acetate, diethyl succinate, dibutyl oxalate, diethyl maleate, benzyl benzoate, methyl cellosolve acetate) , cellosolve acetate, carbitol acetate, etc.). [0103] As the surfactant added to the developer used in the present invention, anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric ionic surfactants are used. The surfactants described in No. 206041 are used. These surfactants can be used alone or in combination of two or more. The appropriate amount of the surfactant used in the present invention is 0.01% to 60% by weight, preferably 0.1% to 10% by weight. Further, the surfactant used in the present invention is preferably used together with an alkaline agent, and the alkaline agent includes (1) sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, lithium hydroxide. (2) Mono-, di- or trimethylamine, mono- or di-isopropylamine, n-butylamine, mono-, di- or tri- Examples include organic amine compounds such as ethanolamine, mono-, di- or tri-isopropanolamine, ethyleneimine, ethylenediimine and the like. [0106] The amount of alkaline agent used is from 0.05% by weight.
20% by weight, preferably 0.2% to 10% by weight is suitable. It is also possible to dye the image area simultaneously with development by adding a dye such as crystal violet or astrazonelet to the developer. Development can be carried out, for example, by rubbing with a developing pad containing a developer as described above, or by pouring a developer onto the printing plate and then rubbing with a developing brush. By the above development, a printing plate is obtained in which the photosensitive layer and silicone rubber in the unexposed areas are removed, or a printing plate in which the silicone rubber layer is removed and the photosensitive layer is exposed, and the silicone rubber layer remains in the exposed areas. [0108] The photosensitive lithographic printing plate that does not require dampening water and is used in the present invention may be of the type in which only the silicone rubber layer in the image area is removed after development, but it is preferable that the silicone rubber layer in the image area be removed after development. A type in which the photosensitive layer is removed and the primer layer in the image area is exposed is preferable. [Examples] The present invention will be explained below using Examples.
The present invention is not limited to these. Example 1 [Synthesis of Hollow Capsule-1] A mixture of 22.6 g of 20.4% isobam, 54.5 g of water, and 30.8 g of gum arabic was heated to 60°C with stirring, and 20% By adding sulfuric acid p
H was adjusted to 4.0. Then, 8.3g of urea and 0
．． 8g of resorcinol was added and the solution was maintained at 60°C to create a continuous phase. [0110] This continuous phase was placed in a Waring blender, and 50 g of TMPTA and 12 g of Irgacu were added.
re 151 (2,2'-1 dimethoxy-2-phenylacetophenone) and 1 g of Quaniacure
ITX (isopropyl thioxanthone) and 1g
of Quaniacure EPD (ethyl-p-dimethylaminobenzoate) and 6 g of 50 g Copik
dibutyl succinate solution with em
The mixture was added while stirring at 90 V/sec. The blender speed was then reduced to 40V and 21.4 milliliters of 37% formaldehyde was added. Stirring was carried out at this speed for 2 hours at 60°C. The emulsion was then transferred to a metal beaker and a solution of 0.6 g ammonium sulfate in 12.2 g water was added. The emulsion was stirred for an additional hour at 60 DEG C. with an overhead mixer, and the pH was adjusted to 9.0 with a 10% solution of sodium hydroxide. Finally, 2.8 g of sodium bisulfite was dissolved in the mixture with stirring, and then dried to obtain hollow capsules-1 with an average particle size of 12 μm. Synthesis of Diazo Resin-1 14.5 g (50 mmol) of p-diazodiphenylamine sulfate was dissolved in 40.9 g of concentrated sulfuric acid under ice cooling. 1.35 to this reaction solution
g (45 mmol) of paraformaldehyde were added slowly so that the reaction temperature did not exceed 10°C. This reaction mixture was added dropwise to 500 ml of ethanol under ice cooling, and the resulting precipitate was filtered. After washing with ethanol, this precipitate was dissolved in 100 ml of pure water, and a cold concentrated aqueous solution containing 6.8 g of zinc chloride was added to this solution. The resulting precipitate was filtered, washed with ethanol, and dissolved in 150 ml of pure water. To this liquid was added a cold concentrated aqueous solution in which 8 g of ammonium hexafluorophosphate was dissolved. The resulting precipitate was collected by filtration, selected, and dried to obtain diazo resin-1. [0114] Manufacturing thickness of aluminum plate a: 0.24 mm
After immersing an aluminum plate in a 3% aqueous sodium hydroxide solution and washing with water, it was immersed in a 32% aqueous sulfuric acid solution at 30°C for 50 minutes.
Anodic oxidation was performed for 10 seconds under the condition of A/dm2, washed with water, and injected into a 2% sodium metasilicate aqueous solution at a temperature of 85°C for 30 minutes.
Immerse for 7 seconds, then soak in water (pH 8.5) at a temperature of 90°C for 2 seconds.
It was immersed for 5 seconds, washed with water, and dried to obtain aluminum plate a. [0115] A primer layer composition having the following composition was applied to an aluminum plate a, and after drying at 85°C for 3 minutes,
The entire surface was exposed at 1000 mj/cm2 using a KW ultra-high pressure mercury lamp. Further dry at 100℃ for 4 minutes to a thickness of 1.
A 5 μm primer layer was formed. [Primer layer composition] Hollow capsule-1

150 parts by weight diazo resin-1

10 parts by weight 2-hydroxyethyl methacrylate/methyl methacrylate (50/50
molar ratio) copolymer
100 parts by weight zinc oxide (white pigment)
20 parts by weight Kett Yellow 402 (yellow pigment)
10 parts by weight methyl lactate
80
0 parts by weight Next, a photosensitive composition having the composition shown below was coated on the primer layer and dried at 100°C for 2 minutes to give a thickness of 0.3
A photosensitive layer of μm was formed. [Photosensitive composition] (1) Diazo resin-1

50 parts by weight (2) Copolymer resin-1 of 2-hydroxyethyl methacrylate, N-(hydroxyphenyl)methacrylamide, and methacrylic acid in a molar ratio of 40/57/3
50 parts by weight (3
) Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.)
dye)

1 part by weight (4) Methyl cellosolve

Next, 900 parts by weight of the following silicone rubber composition was coated on the photosensitive layer so as to have a dry film thickness of 1.8 μm, and dried at 90° C. for 10 minutes. [Silicone rubber layer composition] (1) Dimethylpolysiloxane having hydroxyl groups at both ends (molecular weight 82,000)
100
Part by weight (2) Triacetoxymethylsilane
10 parts by weight (3) dibutyltin laurate
0.8
Weight part (4) Isopar E (manufactured by Esso Chemical)
900 parts by weight [0119] Next, a layer with a thickness of 5 μm was applied on the silicone rubber layer.
A photosensitive lithographic printing plate that does not require dampening water was obtained by laminating a polypropylene film of 100 m. After a positive film was vacuum-adhered to the upper surface of the above plate material, it was exposed to light using a metal halide lamp as a light source. [0120] Next, after immersing it in the following developer for 1 minute,
By rubbing the surface of the plate material with a pad impregnated with a developer, the unexposed silicone rubber layer and photosensitive layer are removed, resulting in a printing plate with good halftone dot reproduction of 2% to 98%. Ta. Further, the image area of the above printing plate could be vividly dyed by applying a dyeing solution having the composition shown below to cloth, rubbing the plate lightly, and then washing with water. [0121] This printing plate was also mounted on a Heidelberg GTO printing machine with the dampening water supply device removed, and black ink (
Manufactured by Toyo Ink, TOYO KING ULTRAT
200,000 clean prints were obtained. [Developer] β-anilinoethanol
0.5
Parts by weight of propylene glycol

1.0 parts by weight p-tert-butylbenzoic acid

1.0 parts by weight potassium hydroxide

1.0 parts by weight polyoxyethylene lauryl ether
0.1 part by weight potassium sulfite

2.0 parts by weight potassium metasilicate
3.0
Part by weight water

91 parts by weight [Dyeing solution] Solfit (manufactured by Clarei Soprene Chemical Co., Ltd., solvent)
10 parts by weight Rheodol TW-01
20 (manufactured by Kao Corporation, surfactant) 0.5
Part by weight benzyl alcohol

2.5 parts by weight Victoria Pure Blue BOH

0.5 parts by weight water

100 parts by weight 012
4 Comparative Example 1 A dampening water-free photosensitive lithographic printing plate was obtained in the same manner as in Example 1, except that Hollow Capsule-1 was not added to the primer layer composition of Example 1. When development and dyeing were carried out in the same manner as in Example 1, the halftone dot reproduction in the shadow area was poor and showed only 95% reproducibility. Also, Example 1
When printing in the same manner as above, stains appeared in the non-image area after 55,000 sheets. Example 2 [Synthesis of Hollow Capsule-2] An oil layer was formed consisting of 900 parts of acrylonitrile, 2100 parts of vinylidene chloride, 15 parts of divinylbenzene, 500 parts of isobutane and 15 parts of diisopropyl peroxydicarbonate. Next, 6300 parts of deionized water, 1390 parts of a colloidal silica dispersion with a solid content of 20%, 30 parts of a 2.5% potassium dichromate aqueous solution, and 10 parts of a condensate of diethanolamine and adipic acid were added.
% aqueous solution was adjusted to pH 4 with hydrochloric acid to form an aqueous phase. [0126] Subsequently, the above oil phase and water phase were heated at 10,000 rpm.
Mixed at m for 60 seconds and charged into a 15 liter pressurized polymerization reactor purged with nitrogen, 3.5 to 4.5 kg/cm2
The reaction was carried out at 50°C for 20 hours. The product thus obtained is a pale yellow liquid with a viscosity of 210 cps at room temperature.
Repeated filtration and water washing using a centrifuge to reduce water content to 31%
A cake-like product with an average particle size of 13 μm was obtained. [0127] This cake-like material was dispersed in an equivalent amount of deionized water, the pH was adjusted to 9.5 with caustic soda as a reagent, and the mixture was charged into a 1-liter pressurized reactor to remove the acrylonitrile remaining in the particles (microcapsules). Add monomethylamine equivalent to 1.5 equivalents and add 4.8 kg/cm with nitrogen gas.
A cake-like product was formed by performing a cyanoethylation reaction at 50° C. for 1 hour under pressure of 2, and the cake-like product thus obtained was dried to obtain powder hollow capsules-2. A dampening water-free photosensitive lithographic printing plate was obtained in the same manner as in Example 1, except that the primer layer composition of Example 1 was changed as follows. [Primer layer composition] Hollow capsule-2

250 parts by weight 2-hydroxyethyl methacrylate/methyl methacrylate (50/50 molar ratio) copolymer
100 parts by weight Pentaerythritol tetraacrylate 100
Part by weight DETX (initiator, manufactured by Nippon Kayaku Co., Ltd.)
5 parts by weight EPA (sensitizer, manufactured by Nippon Kayaku Co., Ltd.)
5 parts by weight zinc oxide (manufactured by Sakai Chemical Co., Ltd., white pigment)
30 parts by weight Kett Yellow 402 (manufactured by Dainippon Ink Co., Ltd., yellow pigment)
10 parts by weight methyl lactate

1000 parts by weight [0129] When development was carried out in the same manner as in Example 1, the silicone rubber layer and photosensitive layer in the unexposed areas were removed, and the dyeability was also good.
A printing plate in which halftone dots of % to 98% were well reproduced was obtained. Further, when printing was carried out in the same manner as in Example 1, 180,000 sheets of prints without stains were obtained. Comparative Example 2 A dampening water-free photosensitive lithographic printing plate was obtained in the same manner as in Example 2, except that Hollow Capsule-2 was not added to the primer layer composition of Example 2. When development and dyeing were carried out in the same manner as in Example 1, halftone dot reproduction in the shadow area was poor and showed only 90% reproducibility. Also, Example 1
When printing in the same manner as above, stains appeared in the non-image area after 70,000 sheets. Example 3 [Synthesis of Hollow Capsule-3] Into a 500 ml stainless steel beaker, 250 g of water, 2.5 g of Zo
nyl-A (manufactured by DuPont, surfactant), 1.0g
Newcol 707SF (Nippon Nyukazai Co., Ltd., surfactant) was weighed, and the pH was adjusted to 4.0 using a 20% aqueous sulfuric acid solution.
After adjusting to 0, the aqueous solution was heated at 7000 r. using a homogenizer. p. m. Add 52 g of trimethylolpropane triacrylate while stirring at
The process was continued for several hours to obtain an emulsion. [0132] Next, the temperature was set to 65°C, and the rotation speed of the homogenizer was set to 3000r. p. m. 8.3 g of urea in 10 g of water, 0.8 g of resorcinol in 10 g of water, 21.6 g of formalin (37%), and 0.6 g of ammonium sulfate in 10 g of water were added at 2 minute intervals. , heating and stirring was continued for 3 hours. Next, stop heating and add sodium bisulfite 2.
After adding 8 g and allowing the capsule preparation to cool to room temperature,
The microcapsules were washed with water and methyl cellosolve, filtered, and taken out to obtain hollow capsules-3 having an average particle size of 4 μm. The primer layer composition of Example 1 was changed as follows, and it was coated on an aluminum plate a, and heat treated at 200° C. for 20 minutes to form a primer layer with a thickness of 6 μm. A photosensitive lithographic printing plate requiring no dampening water was obtained in the same manner as in Example 1 except for the primer layer. [Primer layer composition] Hollow capsule-3

100 parts by weight Epicote 1007 (epoxy resin, manufactured by Shell Oil Co., Ltd.) 50 parts by weight Hytanol 4
010 (phenol resin, manufactured by Hitachi Chemical Co., Ltd.)
50 parts by weight ethyl cellosolve

360 parts by weight ethyl cellosolve acetate
360 parts by weight butyl cellosolve

180 parts by weight 0135
When developed in the same manner as in Example 1, the silicone rubber layer and the photosensitive layer in the unexposed areas were removed, and a printing plate with good dyeability and well-reproduced halftone dots was obtained. Furthermore, when printing was carried out in the same manner as in Example 1, 17 prints without stains were obtained.
5,000 pieces were obtained. Comparative Example 3 A dampening water-free photosensitive lithographic printing plate was obtained in the same manner as in Example 3, except that Hollow Capsule-3 was not added to the primer layer composition of Example 3. When development and dyeing were carried out in the same manner as in Example 1, the halftone dot reproduction in the shadow area was poor and showed only 95% reproducibility. Also, Example 1
When printing in the same manner as above, stains appeared in the non-image area after 40,000 sheets. Example 4 [Synthesis of Hollow Capsule-4] After adding an equal amount of water to 7.5 ml of an aqueous solution containing 0.4 M 1,6-hexanediamine and 0.45 M sodium carbonate, 15ml of a chloroform-cyclohexane mixture containing 5% (V/V) Span85 (1:4 by volume)
Or 1:3), add to 75 ml and stir for 5 minutes, then add a chloroform-cyclohexane mixed solution containing 5% (V/V) Span85 (1:4 or 1:3 by volume).
Add dissolved terephthaloyl dichloride. The reaction temperature is in the range of 0 to 4°C, and the stirring is in the range of about 200 to 600 rpm. Further, the molar ratio of diamine and terephthaloyl dichloride is 1:1. In addition, the terephthaloyl dichloride solution is added to 75 ml of the mixed solvent immediately before use.
It is desirable to add and dissolve 6g of powder before use. By centrifuging the reaction product and then drying it, the average particle size was reduced to 2.
A hollow capsule-4 having a diameter of μm was obtained. A lithographic printing plate material requiring no dampening water was obtained in the same manner as in Example 1 except that the primer layer composition of Example 1 was changed as follows. [Primer layer composition] Hollow capsule-4

15 parts by weight Photosensitive unsaturated polyester produced by 1:1 polycondensation of p-phenylene diacrylic acid ester and -1,4-dihydroxyethyloxycyclohexane
10 parts by weight 1-methyl-2-benzoylmethylene-
β-Naphthothiazoline

0.6 parts by weight KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd., silane coupling agent, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane)

0.5 parts by weight Methyl cellosolve acetate
150 parts by weight toluene

150 parts by weight Methyl cellosolve

150 parts by weight [0141] When developed in the same manner as in Example 1, the silicone rubber layer and photosensitive layer in the unexposed areas were removed, and a printing plate with good dyeability and well-reproduced halftone dots was obtained. Ta. Further, when printing was carried out in the same manner as in Example 1, 150,000 prints without stains were obtained. Comparative Example 4 A dampening water-free photosensitive lithographic printing plate was obtained in the same manner as in Example 4, except that Hollow Capsule-4 was not added to the primer layer composition of Example 4. When development and dyeing were carried out in the same manner as in Example 1, halftone dot reproduction in the shadow area was poor and showed only 90% reproducibility. Also, Example 1
When printing in the same manner as above, stains appeared in the non-image area after 20,000 sheets. Example 5 [Synthesis of hollow latex-5] Emulsion polymerization of seed polymer A 5 liter flask equipped with a stirrer, thermometer, nitrogen inlet and reflux condenser is used. Deionized water (2900 g) and 2.0 g of sodium dodecylbenzene sulfonate are heated to 79° C. with stirring under a nitrogen atmosphere in a flask. A monomer emulsion is prepared from 266 g of deionized water, 0.40 g of sodium dodecylbenzene sulfonate, 416 g of butyl acrylate, 374 g of methyl methacrylate, and 10.4 g of methacrylic acid. Add 50 g of the monomer emulsion to the flask followed by 3.0 g of ammonium persulfate dissolved in 10 ml of water. After 15 minutes, a gradual feed of the remaining monomer emulsion is started at 16 g/min. The temperature is increased to 85°C and maintained there throughout the monomer addition. 15 minutes after the monomer addition is complete, the reaction mixture is cooled. 1-Butyl hydroperoxide (
70%) Add sodium formaldehyde sulfoxylate dissolved in 1.0 ml and 20 liters of water. Add 28% aqueous ammonia at 25°C. The acrylic seed polymer dispersion is obtained by filtering the product through a 100-mesh screen. A. A 5 liter round bottom flask is equipped with a stirrer, thermometer, nitrogen inlet and reflux condenser. 25 g of water was added to 2115 g of deionized water heated to 84° C. in a flask under nitrogen atmosphere.
4.2 g of sodium persulfate dissolved in 1.5 g of the acrylic acid polymer dispersion (solids content: 19.2 g) were added.
5%, average particle diameter 0.095 microns). 235 g of deionized water, 0.5 g of sodium dodecylbenzene sulfonate, 49 g of methyl methacrylate
A monomer emulsion consisting of 0 g, 210 g methacrylic acid and 3.5 g ethylene glycol diacrylate is added to the kettle at 85° C. over a period of 3 hours. After the monomer feed is complete, the dispersion is held at 85° C. for 30 minutes, cooled to 25° C. and filtered to remove coagulum. The filtered dispersion has a pH of 2.3, a solids content of 22.4%, and an average particle diameter of 0.35 microns. A diluted sample of the dispersion is neutralized to pH 10 with ammonia. B. Water heated to 85°C in a stirred reaction kettle 8
0 parts, add 0.07 parts of sodium persulfate, and then add 4.0 parts of the polymer dispersion of Part A (1 part of solid polymer) above.
Add 5 parts. 18 parts of methyl methacrylate are added over a period of 1 hour while maintaining the temperature at 85°C. The temperature is maintained at 85° C. until more than 98% of the monomers have reacted. The composition dispersion consists of individually spherical granules having an average diameter of 1.0 microns, in which the polymethylmetalate is formed as a layer or sheath around the core obtained in Part A. It is something that exists. A sample of the two-stage polymer of Part B was prepared with an equivalent weight of (solid polymer 0.
18maq/g) After neutralizing with ammonium hydroxide,
By drying, hollow latex-5 having an average particle diameter of 1 μm is obtained. [0150] The primer layer composition of Example 1 was changed as follows, and it was coated on an aluminum plate a with a dry weight of 1
．． The primer layer was coated at a concentration of 0 g/m2, heated at 100°C for 2 minutes, and then stored at about 20°C for 4 days to form a primer layer. In addition, except for the primer layer, the same procedure as in Example 1 was carried out,
A lithographic printing plate material that does not require dampening water was obtained. [Primer layer composition] Hollow latex-5
1
25 parts by weight Photographic Gelatin 680 (Nitta Gelatin Co., Ltd.)
) 100 parts by weight CH2
=CHSO2 CH2 CH(OH)CH2 SO2
CH=CH2 0152
14.4 parts by weight N-(β-aminoethyl)-γ-aminopropyl trimethoxysilane

7 parts by weight pure water

4000 parts by weight Example 1
When developed in the same manner as above, the silicone rubber layer and photosensitive layer in the unexposed areas were removed, and a printing plate with good dyeability and well-reproduced halftone dots was obtained. Further, when printing was carried out in the same manner as in Example 1, the number of clean prints was 170.0.
00 pieces were obtained. Comparative Example 5 A dampening water-free photosensitive lithographic printing plate was obtained in the same manner as in Example 5, except that Hollow Latex-5 was not added to the primer layer composition of Example 5. When development and dyeing were carried out in the same manner as in Example 1, halftone dot reproduction in the shadow area was poor and showed only 90% reproducibility. Further, when printing was performed in the same manner as in Example 1, stains occurred in the non-image area after 15,000 sheets. [0155] Effects of the Invention The present invention provides a dampening solution which is free from stains during printing by configuring the primer layer into a continuous layer and a discontinuous layer, has excellent image reproducibility, and has excellent printing durability. An unnecessary photosensitive lithographic printing plate is obtained.

Claims (1)

[Claims] 1. A dampening water-free photosensitive lithographic printing plate having a primer layer, a photosensitive layer, and an ink repellent layer in this order on a substrate, wherein the primer layer is composed of a continuous layer and a discontinuous layer. Lithographic printing plate.