JPH04257857A - Coloring method of damping waterless photosensitive planographic form plate - Google Patents

Abstract

PURPOSE:To obtain a damping waterless photosensitive planographic form plate which does not make stain hands, clothes, equipments or the like with dying solution and obtains a bright image. CONSTITUTION:In the coloring method of damping waterless photosensitive planographic form plate by successively laminating a primer layer, photosensitive layer and ink-repelling layer on a substrate, at least one layer of the primer layer or photosensitive layer contains a dye coloring at pH>=7 and colored image is obtained by processing with alkaline processing agent after or simultaneously developing.

Description

Detailed Description of the Invention [0001] [Field of Industrial Application] The present invention relates to a method for coloring a photosensitive lithographic printing plate that does not require dampening water. To provide a photosensitive lithographic printing plate that does not require dampening water and does not require time for a subsequent dyeing process, does not stain hands or clothes with a dyeing solution, and does not stain an automatic developing machine during dyeing. BACKGROUND OF THE INVENTION Conventionally, photosensitive lithographic printing plates that do not require dampening water (hereinafter referred to as "plate material" as necessary) have been prepared by coating a photosensitive layer and an ink repellent layer on a support in this order. something is known. A printing plate can be obtained by exposing and developing this plate material. For such plate materials, it is necessary to examine the condition of the plate (developability, scratches, stains on the plate, etc.) during or after development, and therefore it must have excellent plate inspection properties. [0003] In order to improve this plate inspection property, conventionally, Japanese Patent Publications No. 61-53716 and Japanese Patent Publication No. 63-22304 have been proposed.
No. 63-280251, etc. disclose that a photosensitive lithographic printing plate that does not require dampening water is imagewise exposed, which is formed by sequentially laminating a primer layer, a photosensitive layer, and an ink repellent layer on a substrate, and then a developer solution is applied. The photosensitive layer in the unexposed area is eluted or swollen using a dye, and then the photosensitive layer in the unexposed area and the silicone rubber layer in contact with the photosensitive layer are removed to reveal a primer layer, and only this primer layer is dyed. dyeing with liquid is 000
4] However, in this method, the dyeing process takes time, and the dyeing solution needs to be replenished during the series of plate-making processes.
Storage and management methods (when the staining solution concentration changes, the staining image density also changes and is not constant) are complicated, and
During dyeing, when replenishing the dyeing solution or replacing the dyeing solution, there are problems such as staining hands and clothes with the dyeing solution, and staining the automatic processor with the dyeing solution. Furthermore, the dyeing process increases the number of processing steps, which increases the size of the automatic developing machine, which is not desirable in terms of equipment. Furthermore, there is a problem of pollution in the treatment of the dye solution after use. [0005] Therefore, the inventors of the present invention took into consideration the above-mentioned plate inspection properties and conducted various studies on methods that do not use a staining solution. It has been discovered that a visible image can be obtained by incorporating a dye, which is exposed to light, and then treated with an alkaline processing liquid after or simultaneously with development, and has thus achieved the present invention. OBJECTS OF THE INVENTION Therefore, an object of the present invention is to obtain a clear image and eliminate the need for a staining solution, so that the dyeing process does not take much time, the equipment does not become large, and the staining solution is not required. To provide a method for coloring a photosensitive lithographic printing plate which does not require dampening water and which does not stain hands or clothes or stains an automatic developing machine and therefore provides a good working environment. [0007] The object of the present invention is to provide a method for coloring a photosensitive lithographic printing plate that does not require dampening water and which comprises sequentially laminating a primer layer, a photosensitive layer, and an ink repellent layer on a substrate. Or, a dampening solution containing a dye that colors at a pH of 7 or more in at least one of the photosensitive layers, and which is characterized in that a colored image is obtained by processing with an alkaline processing solution after or simultaneously with development. This is achieved by a method of coloring unnecessary light-sensitive lithographic printing plates. The structure of the present invention will be explained in more detail below. In the present invention, the primer layer or the photosensitive layer has a pH
By containing a dye that colors the image when the color is 7 or more and treating it with an alkaline processing solution after or simultaneously with development, a colored image can be obtained, and the dyeing solution may stain hands and clothes or stain the automatic processing machine. Therefore, the working environment will be better. Furthermore, since no dyeing liquid is required, the dyeing process does not take much time and the apparatus does not become large. [0009] In the present invention, the primer layer or the photosensitive layer contains a dye that colors at a pH of 7 or more, and this dye includes, for example, bromothymol blue, phenol red, cresol red, m-cresol purple, and chlorophenol red. , p-nitrophenol, bromcresol purple, tropeolin OO, thymol blue, alizarin, and the like. Among these, dyes that change color to blue or red are preferred. Further, when the pH is 7 or lower, dyes that are colorless or exhibit a pale color such as yellow are preferred. It is particularly preferable when the developer used in the present invention is alkaline, since coloring can be achieved in one bath treatment. Further, it is preferable to add an organic solvent such as benzyl alcohol or a surfactant to the developer to facilitate penetration into the photosensitive layer and the primer layer. Examples of organic solvents include aliphatic hydrocarbons (hexane, heptane, Isopar E, H, G (manufactured by Esso Chemical Co., Ltd., product names of aliphatic hydrocarbons, gasoline, kerosene, etc.), aromatic hydrocarbons, etc. Hydrogen (toluene, xylene, etc.) or halogenated hydrocarbons (triclene, etc.)
, alcohols (methanol, ethanol, 1-butoxy-2-propanol, 3-methyl-3-methoxybutanol, β-anilinoethanol, benzyl alcohol, etc.), 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.). [0014] 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 specification No. 206041 are used. Examples of anionic surfactants include (1) higher alcohol sulfate esters (for example, sodium salt of lauryl alcohol sulfate, ammonium salt of octyl alcohol sulfate, ammonium salt of lauryl alcohol sulfate, sulfonic sodium alkyl sulfate, etc.); (2) Aliphatic alcohol phosphate ester salts (for example, sodium salt of cetyl alcohol phosphate ester, etc.) (3) Alkylaryl sulfonates (for example, dodecylbenzenesulfonic acid sodium salt, isopropylnaphthalene sulfonic acid sodium salt) , dinaphthalenesulfonic acid sodium salt, metanitrobenzenesulfonic acid sodium salt, etc.) (4) Alkylamidesulfonic acid salts, (C17H35
(CON(CH3)CH2CH2SO3Na, etc.) (5) Sulfonic acid salts of dibasic aliphatic esters (for example, sodium sulfosuccinate dioctyl ester, sodium sulfosuccinate dihexyl ester, etc.) (6) Formaldehyde condensates of alkylnaphthalene sulfonates , (for example, formaldehyde condensate of sodium dibutylnaphthalene sulfonate, etc.). Examples of nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, oxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, oxyethylene oxypropylene block polymer, etc. Can be mentioned. Examples of the cationic surfactant include alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamines, and the like. Examples of amphoteric surfactants include alkyl betaines, and among these, anionic surfactants are suitable. 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. In the photosensitive lithographic printing plate that does not require dampening water and is used in the present invention, when the photosensitive layer in the image area is removed by development, a dye that colors at a pH of 7 or more is added to the primer layer. Further, when only the silicone rubber layer in the image area is removed by development and the photosensitive layer is not removed, a dye that colors at a pH of 7 or higher is added to the photosensitive layer. The photosensitive layer used in the present invention can contain either a positive-working photosensitive composition or a negative-working photosensitive composition. A polymer compound containing an orthoquinonediazide group is mainly used, but a polymer compound containing an orthoquinonediazide group is a reaction product of a compound containing an orthoquinonediazide group and an alkali-soluble resin, or a reaction product of a compound containing an orthoquinonediazide group and an alkali-soluble resin. It is used to mean either or both of the cases where it is a mixture with a soluble resin. Typical examples will be explained below. Examples of polymeric compounds containing orthoquinonediazide groups include ester compounds of o-naphthoquinonediazide sulfonic acid and polycondensation resins of phenols and aldehydes or ketones. Examples of the above-mentioned phenols include monohydric phenols such as phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol, carvacrol, and thymol, and dihydric phenols such as catechol, resorcinol, and hydroquinone. Examples include trihydric phenols such as hydric phenols, pyrogallol, and phloroglucin. Examples of the aldehyde include formaldehyde, benzaldehyde, acetaldehyde, crotonaldehyde, and furfural. Preferred among these aldehydes are formaldehyde and benzaldehyde. [0024] Further, examples of the above-mentioned ketones include acetone and methyl ethyl ketone. Specific examples of the polycondensation resin include phenol formaldehyde resin, m-cresol formaldehyde resin, m-, o-
Examples include mixed cresol/formaldehyde resin, resorcinol/benzaldehyde resin, and pyrogallol/acetone resin. The condensation rate of o-naphthoquinonediazide sulfonic acid with respect to the OH group of the phenol of the o-naphthoquinonediazide compound (reaction rate with respect to one OH group) is:
15-80% is preferable, more preferably 20-45%
It is. Further, as the o-quinonediazide compound used in the present invention, compounds described in JP-A-58-43451 can also be used. Among the above o-quinonediazide compounds, 1
,2-benzoquinonediazide sulfonyl chloride or 1,2-naphthoquinonediazide sulfonyl chloride and pyrogallol acetone condensation resin or 2,3,4
Most preferred is an o-quinone diazide ester compound obtained by reacting -trihydroxybenzophenone. As the o-quinonediazide compound used in the present invention, each of the above compounds may be used alone, or two or more compounds may be used in combination. The o-quinonediazide-containing polymer compound used in the present invention preferably has a molecular weight of 1,500 or more, more preferably 2,000 or more, in view of coating properties. The o-quinonediazide compound described above is preferably used in combination with an alkali-soluble resin. Examples of alkali-soluble resins 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 novolac resins include phenol formaldehyde resin, cresol formaldehyde resin, and JP-A-55-578.
Phenol 00 as described in Publication No. 41
29] Cresol/formaldehyde copolycondensation resins, copolycondensation resins of p-substituted phenol and phenol or cresol and formaldehyde as described in JP-A-55-127553, and the like. In addition, the vinyl polymer having a phenolic hydroxyl group is a polymer having a unit having the phenolic hydroxyl group in its molecular structure, and a polymer containing at least one structural unit of the following formulas 1 to 5 is used. preferable. [Formula 1] [Formula 2] [Formula 2] [Formula 3] [Formula 4] [Formula 5] [Formula 1 and R2 are hydrogen atoms and alkyl atoms, respectively] or carboxyl group, preferably a hydrogen atom. R3 represents a hydrogen atom, a halogen atom, or an alkyl group, preferably a hydrogen atom or an alkyl group such as a methyl group or an ethyl group. R4 represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, preferably a hydrogen atom. A represents an alkylene group which may have a substituent connecting a nitrogen atom or an oxygen atom and an aromatic carbon atom, m represents an integer from 0 to 10, and B may have a substituent. Represents a phenylene group or a naphthylene group which may have a substituent. [0036] The polymer used in the photosensitive composition of the present invention preferably has a copolymer type structure, and a polymer that can be used in combination with the structural units represented by the above formulas 1 to 5, respectively. Examples of the mer unit include ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene, such as styrene, α-methylstyrene, p-methylstyrene, and p-methylstyrene.
- styrenes such as chlorostyrene, e.g. acrylic acid,
Acrylic acids such as methacrylic acid, unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid, and maleic anhydride, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, 2-chloroethyl acrylate, [
Esters of α-methylene aliphatic monocarboxylic acids such as phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, and ethyl ethacrylate; nitriles such as acrylonitrile and methacrylonitrile; for example, acrylamide; amides such as acrylanilide, p-chloroacrylamide, m-nitroacrylanilide, m-methoxyacrylanilide, e.g. vinyl acetate,
Vinyl propionate, vinyl benzoate, 0038
Vinyl esters such as vinyl butyrate, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isobuty vinyl ether, β-chloroethyl vinyl ether, vinyl chloride, vinylidene chloride, vinylidene cyanide, such as 1-methyl-1-methoxyethylene, 1,1-dimethoxyethylene, 1,2-
Ethylene derivatives such as dimethoxyethylene, 1,1-dimethoxycarbonylethylene, 1-methyl-1-nitroethylene, such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidene, N- There are N-vinyl monomers such as vinylpyrrolidone. These vinyl monomers exist in polymer compounds with a structure in which unsaturated double bonds are cleaved. Among the above-mentioned monomers, esters of aliphatic monocarboxylic acids and nitriles are preferred because they exhibit excellent performance for the purpose of the present invention. These alkali-soluble resins preferably have a molecular weight of 1,500 or more, more preferably 2,000 or more, in view of coating properties. In addition to the above-mentioned materials, these photosensitive compositions may also contain pigments such as dyes and pigments, sensitizers, plasticizers, surfactants, organic acids, acid anhydrides, and other additives that can be added by exposure to light. A compound capable of generating an acid, etc. can be added. There are various types of negative photosensitive materials used in the present invention, including:
Typical examples will be explained below. (1) Photosensitive composition p- containing diazo resin
The diazo resin represented by the condensate of diazodiphenylamine and formaldehyde may be water-soluble or water-insoluble, but preferably those described in Japanese Patent Publication No. 47-1167 and Japanese Patent Publication No. 57-43890, etc. Those which are water-insoluble and soluble in ordinary organic solvents are used. Particularly preferred is a diazo resin represented by the following formula 6. [Formula 6] [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 PF or BF4, Y represents -NH-, -S- or -
Indicates O-. ] The diazo resin is preferably used in combination with a film-forming resin, particularly a lipophilic polymer compound having a hydroxyl group. Examples of such lipophilic polymer compounds include those listed above, as well as monomers having an aliphatic hydroxyl group in the side chain, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, and other copolymerizable compounds. Examples include copolymers with monomers. In addition to these, polyvinyl butyral resin, polyurethane resin, polyamide resin, epoxy resin,
Novolak resin, natural resin, etc. may be added. Various polymer compounds can be used as the binder used in combination with the diazonium salt, but monomers having an aromatic hydroxyl group as described in JP-A No. 54-98613 are preferable. , such as N-(4-hydroxyphenyl)acrylamide, N-(4-hydroxyphenyl)methacrylamide, o-, m-, or p-
Copolymers of hydroxystyrene, o-, m-, or p-hydroxyphenyl methacrylate and other monomers, as described in US Pat. No. 4,123,276. Polymers containing hydroxyethyl acrylate units or hydroxyethyl methacrylate units as main repeating units, natural resins such as shellac and rosin, 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 present in an amount of 40 to 99% by weight in the solid content of the photosensitive composition.
, preferably 50 to 95% by weight. The diazo resin is contained in an amount of 1 to 60% by weight, preferably 3 to 30% by weight. Other dyes, pigments such as pigments, fat-sensitizing agents, plasticizers, surfactants, etc. can be added to these photosensitive compositions. (2) -CH=C in the main chain or side chain of the polymer
Photosensitive composition containing a polymer compound having an H-CO- group Examples of such a polymer compound include polyesters containing -CH=CH-CO- as a photosensitive group in the main chain or side chain of the polymer; Those mainly composed of photosensitive polymers such as polyamides and polycarbonates (for example, U.S. Patent No. 3
(2-properidene)malonic acids such as cinnamylidenemalonic acid; Products whose main component is photosensitive polyesters derived from compounds and difunctional glycols (
For example, U.S. Patent Nos. 2,956,878 and 3,1
73,787); Cinnamate esters of hydroxyl-containing polymers such as polyvinyl alcohol, starch, cellulose and the like (e.g. U.S. Patent No. 2,690,966;
Polymers such as those described in the specifications of the same No. 2,752,372, the same No. 2,732,301, etc. can be mentioned. These photosensitive compositions may contain other sensitizers, stabilizers, plasticizers, pigments, dyes, and the like. (3) 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, 005
4] For example, di-(2'-methacryloxyethyl)-2,
Diol mono(
Examples include reaction products of meth)acrylate and diisocyanate. As the photopolymerization initiator for component (b), the compound represented by the formula 6 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),
A variety of known polymers can be used. Details of specific binders can be found in U.S. Patent No. 4,072,527.
It is stated in the number. In addition, the binder used when used in combination with the above-mentioned diazonium salt can be used. These photopolymerizable compositions can contain thermal polymerization inhibitors, plasticizers, dyes, pigments, and the like. (4) Photosensitive composition containing an azide group As the photosensitive azide compound, an aromatic azide compound in which the azide group is bonded to an aromatic ring directly or via a carbonyl group or a sulfonyl group is preferably used. . For example, polyazidostyrene, polyvinyl-p-azidobenzoate, polyvinyl-p-
Azidobenzal, reaction product of azidoarylsulfonyl chloride and unsaturated hydrocarbon polymer described in Japanese Patent Publication No. 45-9613, and Japanese Patent Publication No. 43-2101
No. 7, No. 44-229, No. 44-22954, No. 4
Examples include polymers having sulfonyl azide and carbonyl azide, as described in each publication of No. 5-24915. [0061] A liposensitizing agent added to the photosensitive composition,
The amount of additives such as surfactants, sensitizers, stabilizers, thermal polymerization inhibitors, and plasticizers varies depending on their type, but in general, they are added in amounts relative to the photosensitive composition contained in the photosensitive coating solution. , 0.01 to 20% by weight, preferably 0.05 to 10% by weight. The silicone rubber used in the present invention is a linear organic polymer having a repeating unit represented by the following formula 7 and having a molecular weight of several thousand to hundreds of thousands and a hydroxyl group in the main chain or at the end of the main chain. Those containing siloxane as a main component are preferred. [Formula 7] Here, n is an integer of 2 or more, and R has 1 to 1 carbon atoms.
10 alkyl groups, halogenated alkyl groups, alkoxyl groups, vinyl groups, aryl groups, silanol groups (OH groups)
It is preferable that 60% or more of R is a methyl group. The silanol group (OH group) may be located either in the main chain or at the end of the main chain, but is preferably located at the end. Silane coupling agent used in the present invention (
or silicone crosslinking agent), those represented by the following formula 8 are preferred. Formula 8 Rn SiX4-n (where n is an integer of 1 to 3, R represents a monovalent group of alkyl, aryl, alkenyl or a combination thereof, and may have a functional group such as halogen, amine, hydroxy, alkoxy, aryloxy, thiol, etc. X is -OH, -OR2, -OAc, -O-N=C(R
2) Represents a substituent such as R3, -Cl, -Br, -I, etc. Here, R2 and R3 represent the same thing as R above, and R2 and R3 may be the same or different. Moreover, Ac represents an acetyl group. ) is a silane compound represented by That is, the silicone rubber useful in the present invention is obtained by a condensation reaction between such a silicone base polymer and a silicone crosslinking agent such as those listed above. Specific examples of the silane coupling agent used in the present invention include HN[(CH2)3Si(OM
e)3]2, vinyltriethoxylan, Cl(CH
2)3Si(OMe)3,CH3Si(OAc
)3, HS(CH2)3si(OMe)3, vinyltris(methylethylketoxime)silane, and the like. The silicone rubber described above is also available as a commercial product, such as YE-3085 manufactured by Toshiba Silicone Co., Ltd. Other useful silicone rubbers can be produced by reacting the above-mentioned base polymer with a silicone oil having a repeating unit represented by the following formula 9, or by reacting a silicone base polymer in which about 3% of R is a vinyl group. - It can also be obtained by addition reaction with a polymer or reaction between the silicone oils. [Formula 9] (wherein, R has the same meaning as R, which is a substituent of the polymer represented by Formula 7, m is an integer of 2 or more, and n is 0
or an integer greater than or equal to 1. ) In order to obtain silicone rubber by such a crosslinking reaction, the crosslinking reaction is carried out using a catalyst. This catalyst includes tin, zinc, cobalt,
Organic carboxylates of metals such as lead, calcium, manganese, etc., such as dibutyltin laurate, tin(II) octoate, cobalt naphthenate, etc., or chloroauric acid, etc. are used. Further, in order to improve the strength of the silicone rubber and obtain a silicone rubber that can withstand the frictional forces generated during printing operations, a filler may be added. Silicone rubber mixed with filler in advance is commercially available as silicone rubber stock or silicone rubber dispersion, and when it is preferable to obtain a silicone rubber film by coating as in the present invention, RTV or LTV silicone rubber can be used. Dice version is preferred. Examples of this include Syl off 23 manufactured by Toray Silicone;
There are silicone rubber disk versions for paper coating such as SRX-257 and SH237. In the present invention, it is preferable to use condensation and crosslinking type silicone rubber. The silicone rubber layer preferably contains a silane coupling agent having an amino group in order to further improve adhesiveness. Examples of preferable silane coupling agents include the following. (a) H2 NCH2 CH2 NH(C
H2)3 Si(OCH3)3 (b)H2 NCE2 CH2 NH(CH2)3
Si(OCH3 )2 (CH3) (C)H2 N(CH2)3 Si(OE)3 However, E
is an ethyl group. The silicone rubber layer used in the present invention may further contain a small amount of a photosensitizer. The silicone rubber layer used in the present invention is prepared by dissolving silicone rubber in a suitable solvent, applying it onto the photosensitive layer, and drying it. The support has a primer layer, and examples of the primer layer include polyester resin, vinyl chloride-vinyl acetate copolymer, acrylic resin, vinyl chloride resin, polyamide resin, polyvinyl butyral resin,
Examples include epoxy resins, acrylate copolymers, vinyl acetate copolymers, phenoxy resins, polyurethane resins, polycarbonate resins, polyacrylonitrile butadiene, and polyvinyl acetate. [0077] These primer layers may contain a compound that generates an acid upon exposure to light and a dye that changes color or fades when exposed to acid. Further, as the anchor agent constituting the primer layer, for example, the silane coupling agent, silicone primer, etc. described above can be used, and organic titanates and the like are also effective. [0078] 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, aluminum (for example, JIS standard H-16, H-1
8 etc.), metal plates such as zinc, copper, and steel, and chromium, zinc,
Metal plates plated or vapor-deposited with copper, nickel, aluminum, etc., paper treated to make them hydrophilic, plastic films such as polyethylene terephthalate, paper and plastic films coated with metals, glass plates, resin-coated paper (coated paper) , paper covered with metal foil such as aluminum, etc. [0079] 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. 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. Particularly in the case of an aluminum plate support,
It is preferable that surface treatments such as graining, anodizing, and, if necessary, sealing are performed. As a method for the above-mentioned graining treatment, a technique is adopted in which the surface of the aluminum plate or the like is degreased and then a brush polishing method, a ball polishing method, a chemical polishing method, an electrolytic etching method, or the like is applied. [0081] The above-mentioned anodic oxidation treatment is performed using an inorganic salt such as phosphoric acid, chromic acid, boric acid, or sulfuric acid, or an aqueous or non-aqueous solution of oxalic acid, sulfamic acid, etc. alone or in a mixture of two or more of these acids. This is done by passing an electric current through an aluminum plate or the like as an anode. [0082] Further, the pore sealing treatment is performed using a sodium silicate aqueous solution,
It is carried out by immersion in a hot aqueous solution of hot water and some inorganic or organic salts, or by a steam bath. In the present invention,
The amount of photosensitive coating liquid applied to the support varies depending on the application, but is generally 0.5 to 3.5 g/m2 as a solid content.
is appropriate. Other surface treatments include, for example, a method of treating the surface of an aluminum plate with a silicate (US Pat. No. 2,
714,066), treatment with organic acid salts (U.S. Pat. No. 2,714,066), treatment with phosphonic acids and their derivatives (U.S. Pat. No. 3,220,83),
No. 2), a method of treatment with potassium hexafluorozirconate (U.S. Pat. No. 2,946,683), a method of treatment with an aqueous solution of an alkali metal silicate after anodization (U.S. Pat. No. 3,181,461) etc. In order to obtain sufficient adhesion between the photosensitive layer and the support, a primer layer is provided on such a support, and a photosensitive layer is provided thereon. The thickness of each layer constituting the plate material of the present invention is as follows. That is, the support is 50 to 400
μm, preferably 100 to 300 μm, photosensitive layer 0.0
5 to 10 μm, preferably 0.1 to 1.0 μm, and the silicone rubber layer has a thickness of 0.5 to 100 μm, preferably 1
~4 μm. The primer layer has a thickness of 0.1 to 30 μm, preferably 0.3 μm.
~20 μm. 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 plate material of the present invention that does not require dampening water is manufactured, for example, as follows. [0086] The composition solution to form the primer layer is applied onto the support using a conventional coater such as a reverse roll coater, an air knife coater, a Meyer bar coater, or a rotary coater such as a Whaler, and is dried and crosslinked. let Next, a composition solution to form a photosensitive layer is applied and dried. [0087] 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 manufacturing a printing plate that does not require dampening water using the plate material that does not require dampening water of the present invention will be explained. A positive film, which is the manuscript, is vacuum-adhered to the surface of the positive plate material and exposed. As a light source for this exposure, a mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, etc., which generate abundant ultraviolet light, are used. Next, the positive film is peeled off and developed using a 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. [Examples] The present invention will be explained in detail below using Examples, but the present invention is not limited to these Examples in any way. Example 1 The following primer layer composition was applied to an aluminum plate with a thickness of 0.3 mm, and the mixture was heated at 200°C for 2 hours.
A 5μ thick primer layer was applied by heat treatment for 1 minute. [Primer layer composition] (1) Polyurethane resin (Samplan LQ-T1331
, manufactured by Sanyo Chemical Industries, Ltd.)
10
0 parts by weight (2) Blocked isocyanate (Takenate B
830, manufactured by Takeda Pharmaceutical Co., Ltd.)

20 parts by weight (3) Epoxy/phenol/urea resin (SJ9372, manufactured by Kansai Paint Co., Ltd.)

8 parts by weight (4) dimethylformamide
725 parts by weight Next, the following photosensitive composition was coated on the conoprimer layer and heat treated at 120° C. for 2 minutes to form a photosensitive layer with a thickness of 2.6 μm. (1) 100 parts by weight of naphthoquinone-1,2-diazide-5-sulfonic acid ester of phenol novolak resin with a degree of esterification of 44% (Sumilight Resin PR50235, manufactured by Sumitomo Duress) (2) 4,4'-diphenylmethane diisocyanate Nath
20 parts by weight (3) dibutyltin laurate

0.2 parts by weight (4) Bromothymol blue

0.5 parts by weight (5) Salicylic acid

0.5 parts by weight (6) Methyl cellosolve acetate
2000 parts by weight Next, a silicone rubber composition having the following composition was coated on this photosensitive layer, and 1
A silicone rubber layer having a thickness of 2.2 μm was provided by heat curing at 20° C. for 2 minutes. (1) Dimethylpolysiloxane with hydroxyl group at the end
(Molecular weight: approx. 80,000)
100 parts by weight (2) Ethyltriacetoxysilane
5 parts by weight (3) dibutyltin acetate
0.2 parts by weight (4) γ-aminopropyltriethoxysilane
3 parts by weight (5) Isopar E
1650 parts by weight [0094] A dot original was vacuum-adhered to the thus obtained photosensitive lithographic printing plate that did not require dampening water, and exposed for 30 seconds from a distance of 1 m using a 2KW metal halide lamp. Next, the exposed photosensitive lithographic printing plate, which did not require dampening water, was developed by rubbing it with a sponge for 3 minutes using a developer consisting of 90 parts of diethylene glycol monoethyl ether and 10 parts of water. Then, add 1 ethanolamine to monoethanolamine.
When immersed in an aqueous solution containing 0% by weight for 20 seconds, the image area was colored blue and a colored image with good halftone dots was obtained. Since this method does not use a dyeing solution, the worker's hands and clothes are not stained with the dyeing solution, resulting in a good working environment. Example 2 [Synthesis of diazo resin -1] 14.5 g (50 mmol) of p-diazodiphenylamine sulfate was mixed with 40.0 g of p-diazodiphenylamine sulfate under ice cooling.
Dissolved in 9g of concentrated sulfuric acid. Add 1.35g (4
5 mmol) of paraformaldehyde at a reaction temperature of 10
It was added gradually so as not to exceed ℃. 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. After filtering the resulting precipitate,
It was 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, washed with water, and then dried to obtain diazo resin-1. Production of aluminum plate a An aluminum plate with a thickness of 0.24 mm was immersed in a 3% aqueous sodium hydroxide solution and washed with water, and then anodized in a 32% aqueous sulfuric acid solution at a temperature of 30°C and a flow rate of 5 A/dm2 for 10 seconds. , washed with water, immersed in a 2% sodium metasilicate aqueous solution at a temperature of 85°C for 37 seconds, further immersed in water at a temperature of 90°C (pH 8.5) for 25 seconds, washed with water, and dried to obtain aluminum plate a. . A primer layer composition having the following composition was applied to aluminum plate a, and after drying at 85°C for 3 minutes, 3K
The entire surface was exposed to light at 1000 mJ/cm2 using a W ultra-high pressure mercury lamp. Further dry at 100℃ for 4 minutes to a thickness of 15mm.
A primer layer of μm was formed. [Primer layer composition] (1) Diazo resin-1

8 parts by weight (2) 2-hydroxyethyl methacrylate/methyl methacrylate molar ratio 34/6
4 copolymer resin-1
82 parts by weight (3) HPC LP (manufactured by Shin-Etsu Chemical Co., Ltd., hydroxypropyl cellulose)

20 parts by weight (4) Phenol red

1 part by weight (5) Methyl cellosolve

900 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 form a photosensitive layer having a thickness of 0.3 μm. [Photosensitive composition] (1) Diazo resin-1

50 parts by weight (2) 50 parts by weight of a copolymer resin with a molar ratio of 2-hydroxyethyl methacrylate/N-(4-hydroxyphenyl)methacrylamide/melacrylic acid 40/57/3 (3) Victoria Pure Blue BOH (Hodogaya Chemical) Manufactured by Co., Ltd.; Dye)

1 part by weight (4) Methyl cellosolve

900 parts by weight Next, 1.8 g (dry weight) of the following silicone rubber layer composition was placed on the photosensitive layer.
/m2 and dried at 90°C for 10 minutes to form a silicone rubber layer. [Silicone rubber composition] (1) Dimethylpolysiloxane having hydroxyl groups at both ends (molecular weight: 82,000)
100 parts by weight (2) Triacetoxymethylsilane
10 parts by weight (3) dibutyltin laurate
0.8 parts by weight (4) 900 parts by weight of Isobar E (manufactured by Exxon Chemical Co., Ltd.; solvent) [0102] Furthermore, a 5 μm thick one-sided matted polypropylene film was laminated on the silicone rubber layer, and moistened with water. A water-free photosensitive lithographic printing plate was obtained. After a positive film was vacuum-adhered to the upper surface of the plate material, exposure was performed using a metal halide lamp as a light source. [0103] Next, the exposed plate was developed and washed with water using the following developer diluted 6 times with water. As a result of development, an image was obtained in which the image area was colored red. . As is clear from this example, since no dyeing solution is used, the operator does not get his or her hands or clothes dirty, and even if many plates are processed, the density of the colored image remains constant, ensuring the same finish. Ta. Note that the water washing section was provided with a temperature control device (or temperature device) to maintain the liquid temperature at 30° C.±1° C. [Developer] (10 liters of developer) (1) Potassium silicate A
10 parts by weight (
2) Potassium hydroxide (50% by weight)
2.5 parts by weight (3) Gluconic acid (50% by weight aqueous solution)
0.5 part by weight [0105] Effect of the invention: The present invention provides the following advantages:
By containing a dye that colors when H is 7 or more, when processed with an alkaline processing solution after or at the same time as development, the resulting image will be clear and the dyeing process will be unnecessary. You can save the time it takes to
The apparatus does not need to be large-sized, and furthermore, there is no staining of hands or clothes by the dyeing solution, and furthermore, the automatic developing machine is not soiled, resulting in an excellent working environment.

Claims (1)

[Claims] 1. A method for coloring a photosensitive lithographic printing plate that does not require dampening water and is formed by sequentially laminating a primer layer, a photosensitive layer, and an ink repellent layer on a substrate, wherein at least one of the primer layer or the photosensitive layer has a pH value. 1. A method for coloring a photosensitive lithographic printing plate that does not require dampening water, which contains a dye that colors when the number is 7 or more, and obtains a colored image by treating with an alkaline processing liquid after or simultaneously with development.