JPH02282259A - Damping-waterless photosensitive planographic printing plate - Google Patents

Abstract

PURPOSE:To obtain the damping-waterless photosensitive planographic printing plate which substantially obviates the flawing of the plate surface at the time of preservation of the plate or plate making by providing a layer which contains a prescribed high-polymer compd. and is removed at the time of development onto a silicone rubber layer. CONSTITUTION:This damping-waterless photosensitive planographic printing plate of the upper silicone rubber upper layer type is constituted by having the layer (protective layer) which contains the high-polymer compd. having polyorganosiloxane in the side chain and is removed at the time of the development on the silicone rubber layer of this printing plate. The stagnation of the gases generated at the time of exposing at the boundary between the protective layer and the photosensitive layer is obviated at all in this constitution and the good exposing is assured; in addition, this protective layer is well applied on the silicone rubber layer and dissolves in a developing soln. and, therefore, the flawing of the plate surface at the time of the preservation of the plate or the plate making is obviated.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a photosensitive lithographic printing plate that does not require dampening water, and in particular, a photosensitive lithographic printing plate that does not require dampening water and is less likely to cause scratches on the plate surface during plate storage. Regarding the printed version.

[Prior Art] The surface of a photosensitive lithographic printing plate with a silicone rubber layer that does not require dampening water is usually extremely smooth and has good adhesion.

The IC had the disadvantage that the surface of these plates could be scratched or damaged during storage or plate making.

In order to solve these problems, a method of coating a protective layer on top of the silicone rubber layer is considered.3゜However, due to the low critical interfacial tension of silicone rubber, it is difficult to apply the coating at the time of application using a normal coating solution for a protective layer. There was a problem in that the liquid was repelled and the coating was not satisfactory.

For this reason, conventional methods have been proposed in which a protective layer is coated on a silicone rubber layer using a concentrated solution of a high molecular weight polymer, as described in, for example, Japanese Unexamined Patent Publication No. 61-275115.

[Problems to be Solved by the Invention] However, since the above method uses a concentrated solution, it is difficult to control the film thickness from one to one roll, and it is difficult to form a protective layer (the smooth protective layer has extremely poor adhesion with silicone rubber). It has the disadvantage that it easily peels off from the silicone rubber.

Therefore, an object of the present invention is to eliminate the above-mentioned drawbacks, to provide a photosensitive lithographic printing method that does not require dampening water and has a protective layer well coated on the silicone rubber layer, and which is resistant to scratches on the plate surface during plate storage or plate making. The purpose is to provide the version.

[Means for Solving the Problem 1] In view of the above-mentioned problems, the present inventors have made extensive inquiries and found that the above-mentioned object of the present invention is to provide a silicone rubber layer-type photosensitive lithographic printing plate that does not require dampening water. What is achieved by providing a photosensitive lithographic printing plate that does not require dampening water and is characterized by having a layer which contains a polymer compound having a polyorganosiloxane in its side chain and which can be removed during visual imaging. This discovery led to the present invention.

The present invention will be explained in detail below.

The dampening water-free photosensitive lithographic printing plate of the present invention contains, on the silicone rubber layer of the dampening water-free photosensitive lithographic printing plate, a polymer compound from graph 1 having polyorganosiloxane in its side chain. It is characterized by coating a layer (hereinafter referred to as the "protective layer of the present invention").

The polymer compound (hereinafter not referred to as the "graft polymer of the present invention") having polyorganosiloxane in its side chain used in the protective layer of the present invention is prepared using the polyorganosiloxane macromonomer described below. Synthesized ones are preferred.

For example, the macromonomer of polyorganosiloxane having a polymerizable group at the terminal, which is used as a constituent component of the graft polymer of the present invention, has a polyorganosiloxane as a main component having a repeating unit as shown in the following general formula (1). There is.

General formula (1) R+ (Si-〇)n Here, R1 and R2 each represent a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, an alkenyl group, or a phenyl group, and n is 2 or more. represents an integer,
, R1 and R2 include, for example, a halogen atom, a cyan group, an amino group, and the like.

Although the molecular weight of the macromonomer is arbitrary, preferably the number average molecular weight is in the range of about 100 to 50,000, particularly preferably in the range of 500 to 10,000.

When used in radical polymerization, the terminal polymerizable functional group of the macromonomer of polyorganosiloxane includes, for example, a methacryloyl group, an acryloyl group, a crotonoyl group, an isocrotonoyl group, an oleoyl group, etc.
Preferred are methacryloyl group, acryloyl group, and crotonoyl group. In addition, when polymerizing with polyester or polyamide, a hydroxyl group, dihydroxyl group, carboxyl group, dicarboxyl group, etc. can be used as the terminal polymerizable functional group.

Examples of copolymerizable components of the main chain of the graft polymer of the present invention include monomers copolymerizable with the above macromonomer.

In particular, as monomers for radical polymerization constituting these main chains, the following compounds having unsaturated bonds are used.

(1) Monomers having hydroxyl groups: 2-hydroxyethyl (meth)acryle-1, 2-hydroxypropyl (meth)acrylate-1~, 2-hydroxypentyl (meth)acrylate, 4-hydroxyphenyl (meth)acryle -1~, (meth)acrylate-1~ such as 2-hydroxyphenyl (meth)acryle-1-
Monomers: N-medirol (meth)acrylamide,
N-hydroxyethyl (meth)acrylamide, N-(
Hydroxyphenyl)-(meth)acrylamide, N-
(Hydroxynaphthyl) = (meth)acrylamide monomers such as (meth)acrylamide; 0m-1p-hydroxystyrene monomers, etc. (meth)acrylic acid ester or amide monomers other than (2>(1)): Methyl (meth) ) acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate
Alkyl (meth)acrylates such as acrylate; N
-Phenyl (meth)acrylamide, 0-1m-1p-
Methoxyphenyl (meth)acrylamide, 0-1m-
(3) Monomers having a cyano group in the side chain: (meth)acrylonidonitrile, 2-pentenitrile, 2-methyl-3-butenenitrile, 2-cyanoethyl acrylate, etc. , 0-1■-1p-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) Styrene: α-methyl Styrene, methylstyrene, chloromethylstyrene, styrene, etc. (7) Vinyl ketones: methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, etc. (8) Monomers other than (1) to (7): ethylene , propylene, isobutylene, butadiene, olefins such as vinyl chloride, N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, etc., but any other monomer that can undergo radical copolymerization with these monomers may be used. .

Although specific monomers have been listed above as constitutional units of the main chain component, the present invention is not limited to only those listed above.

The proportion of the polyorganosiloxane polymer component in the graft polymer of the present invention is 1 to the total weight.
) is 001% to 80% by weight, preferably 0
．． It is 1% to 50% by weight. The graft polymer of the present invention is molecularized by the generally known gel permeation chroma 1 to graph method, with a weight average molecular weight of preferably 10,000 to 1,000,000, more preferably 50,000 to 60,000.
A range of 10,000 is used.

The proportion of the graft polymer of the present invention in the protective layer is preferably 1% to 100% by weight, more preferably 5% to 100% by weight.

When this graft polymer made of polyorganosiloquiline as a branched polymer is coated on the silicone rubber layer, the film thickness is preferably 0.3 μm to 150 μM, more preferably 0.03 μm to 150 μM, more preferably
．． It is 6 μm to 100 μm.

In addition to the polymers from Graph 1 having polyorganosiloquiline in the side chain described above, the following additives may be added to the protective layer of the present invention. That is, coating properties improvers such as alkyl ethers (e.g. ethyl cellulose, methyl cellulose), fluorine surfactants, nonionic surfactants (e.g. Pluronic L-641 manufactured by Asahi Denka Co., Ltd.); for example, butylphthalyl, polyethylene Glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, 1-ricresyl phosphate, tributyl phosphate, 1-lyoctyl phosphate, tetrahydrafurfuryl oleate, acrylic acid or methacrylic acid Plasticizers to impart flexibility and abrasion resistance to coating films such as oligomers; for example, polyacrylic acid, tartaric acid, phosphoric acid, phosphorous acid, organic acids (acrylic acid, methacrylic acid, citric acid, oxalic acid) , benzenesulfonic acid, naphthalenesulfonic acid, 4-methoxy-2hydroxybenzophenone-5-sulfonic acid, etc.).

The amount of these additives added varies depending on the purpose of use (depending on the purpose of use), but generally 0.01% to 3% by weight based on the total solid content.
0% by weight is preferred.

Coating solvents for coating the protective layer on the silicone rubber layer include cellosolves such as methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, and ethyl cellosolve acetate, and carbazoles such as methyl calpitol and ethyl calpitol. Examples include toluene, hexane, dimethylformamide, dimethyl sulfoxide, dioxane, acetone, methyl vinyl ketone, cyclohexanone, trichloroethylene and the like. As the coating method, various conventionally known methods can be used, such as spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating, and curtain coating. After application,
Allow the paint film to dry thoroughly.

Further, the concentration of the graft polymer of the present invention in the coating solution when coating the protective layer on the silicone rubber layer is preferably 1 to 30:! ffi%, more preferably 2 to 10
Weight%.

Furthermore, in the present invention, it is possible to emboss the protective layer. Examples of such embossing methods include methods such as passing the coated surface through an embossed roller immediately after coating the protective layer, which includes the graft polymer of the present invention. The layer-coated photosensitive lithographic printing plate that does not require dampening water is applicable to all silicone rubber upper layer type photosensitive lithographic printing plates that do not require dampening water.

Examples of silicone rubber 7H type photosensitive lithographic printing plates that do not require dampening water and can be applied to the present invention include:
As described in Japanese Patent Publication No. 150, a dampening water-free photosensitive lithographic printing plate having a substrate, a photopolymerizable adhesive layer provided on the substrate, and a silicone rubber layer provided on the photopolymerizable adhesive layer, JP-B No. 1983- No. 542195. As described in JP-A-60-229031, JP-A-62-175759Q, etc., a primer layer such as an epoxy resin is provided on the substrate 1, and a photosensitive layer (a photopolymerizable adhesive layer or a photosensitive layer) is placed on the primer layer. A photosensitive lithographic printing plate that does not require dampening water and coats a cross-linked photosensitive layer (such as a cross-linked photosensitive layer) and a silicone rubber layer on the photosensitive layer, JP-A-56-8
Examples include negative-type photosensitive lithographic printing plates that do not require washing water and use quinonediazide or the like as a photosensitive composition, as described in 004f3@, JP-A-60-78452, and the like. Further examples include, for example, a photosensitive lithographic printing plate that does not require dampening water and has a substrate, a photosensitive layer containing a diazo resin provided on the substrate, and a silicone rubber layer provided on the photosensitive layer.

In the case of a positive type, the photosensitive layer that can be used in the present invention includes the above-mentioned photopolymerizable adhesive layer or photocrosslinkable photosensitive layer, and 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 quinonediazide compound, a binder resin, etc. can be used.

Various conventionally known diazo resins can be used as the above-mentioned diazo resin, but diazo resins represented by condensates of aromatic diazonium salts and active carbonyl-containing compounds, especially formaldehyde, etc. I like the resin.

Preferred specific examples of the diazo resin include resins represented by the following general formula (2).

General formula (2) where R+2. Rj3 and R+q each represent a hydrogen atom, an alkyl group or an alkoxy group, preferably a hydrogen atom. R15 is a hydrogen atom, an argyl group J
:ta[:1 represents a phenyl group, lYmashi・( is a hydrogen atom. Represents organic carboxylic acids such as acids, organic phosphoric acids such as phosphoric acid, and sulfonic acids such as methanesulfonic acid.

Y represents N days, S, and ○. Furthermore, 7 is a sulfonic acid group, a sulfonic acid group (Na salt, K salt, etc.) group, a sulfine group, a sulfinate group (Na salt, K salt, etc.) group, an OH group, and an 0
Represents a phenyl group or naphthyl group substituted with at least one exchange group selected from 00H groups. The ratio of m/n=1/○ to 10, preferably 110 to 2 in terms of molar ratio.

The diazo resin represented by the above general formula (2) preferably has a molecular weight of about 500''-10,000.

The content of diazo resin in the photosensitive layer is preferably fl:1
~70tfi%, more preferably i,, t3-60 small m
Selected from a range of %.

Negative grooved water-free photosensitive lithographic printing plate J3 and Or1
- Quinonediazide compounds are used, and examples of the compounds include Φ condensation resins of phenols and aldehydes or ketones and the following general formula <3) Examples include 1-quinonediazide sulfonic acid or carboxylic acid esters which can be prepared by chemically condensing 1-nonodij' with sulfonic acid or carboxylic acid derivatives.

General formula (3) - Cloth price (4) (wherein, X is a group represented by -3O2Y or 1a-coyr, and Y represents a group that can be removed during condensation of a halogen atom, an alkali metal, etc.). ) As a specific example of the compound represented by the above - Clothing fee (3),
1,2-benzoquinonediazide (2)-4-sulfonyl chloride, 1,2-benzoquinonediazide (2>-/I
-carbonyl chloride, 1°2-benzoquinonediazide (2)-5-sulfole chloride, 1,2-benzoquinonediazide (2)5-)vluponyl chloride, and the like. Specific examples of the compound represented by -Fukudai (4) above include 1.2-nano1 to quinone diazide (2>-4-
Sulbonyl chloride, 1,2-naphthoquinone diazide (
2)-4-carbonyl chloride, 1,2-naphthoquinone diazide (2)-5-sulfonyl chloride carbonyl chloride, and the like.

Polycondensation resins of phenols and aldehydes or phenols include, for example, polycondensates of pyrogallol and acetone as described in Japanese Patent Publication No. 43-28403, and polycondensates of pyrogallol and acetone as described in Japanese Patent Publication No. 55-76346. As described, a polycondensate of a mixture of pyrogallol and resorcinol and acetone, as described in Japanese Patent Publication No. 45-9610, phenol formaldehyde cresol formaldehyde novolac resin, as described in Japanese Patent Publication No. 50-5083 Para-substituted phenol-formalin resins (e.g., baracresol-formalin resin, para-t-butylphenol-formalin resin, para-ethylphenol-formalin resin,
(parapropylphenol/formalin resin, paraisopropylphenol/formalin resin, para-n-butylphenol/polmarin resin, paraoctylphenol/formalin resin, etc.), as described in Japanese Patent Publication No. 62-60407, having 3 or more carbon atoms. A polycondensate of formaldehyde and a phenol mixture containing phenol substituted with 12 alkyl or phenyl groups and phenol or its methyl substituted product or a mixture thereof in a molar ratio of 1:9 to 9:1 (for example, a polycondensate of the para-substituted phenol and phenol) , a polycondensate of varacresol, metacresol, or orthocresol), and the like.

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 ortho-1-quinonediazide compounds, polyhydroxybenzophenone orthodef-1-quinonediazide sulfonic acid ester (for example, 1,2-naphthoquinonediazide<2)-5-sulfonic acid ester, 1,2-naph[~
Examples include quinone diazide (2>-4 sulfonic acid ester, etc.).

This polyhydroxybenzophenone is a compound formed by replacing two or more hydrogen atoms of benzophenone with hydroxyl groups, such as dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, octahydroxybenzophenone, or a derivative thereof (for example, Substituents of a halogen atom, an alkyl group, an aryl group, an aralkyl group, a carboxylic acid group, and the like can be mentioned. Preferably trihydroxybenzophenone or tetrahydroxybenzophenone, more preferably 23,4-1-dihydroxybenzophenone, 2,3.

4,4'-tetrahydroxybenzophenone is mentioned.

In addition, the esterification rate for hydroxyl groups is 30 to 100%.
is preferred.

As the orthoquinone diazide compound used in the present invention, each of the above compounds may be used alone, or two or more thereof may be used in combination.

Among these orthoquinone diazide compounds listed above, 1 of 2.3.4-t-lyhydroxybenzophenone
, 2-naphthoquinonediazide (2)-5-sulfonic acid ester or 1,2-naphthoquinonediazide (214-
Sulfonic acid ester, 1,2-naphthoquinone diazide of metacresol formaldehyde novolak resin (
21-5-sulfonic acid ester or 1,2-naphthoquinone diazide (2i4-sulfonic acid ester or
The proportion of the above-mentioned orthoquinonediazide compound in the photosensitive layer is preferably 5 to 60% by weight, and more preferably 20 to 50% by weight.
It is.

(1) Examples of binder resins used in the photosensitive layer include acrylic resins and novolac resins. As the copolymerization component of the acrylic resin, any copolymerizable monomer can be used. In particular, as the monomer for radical polymerization, the following compounds having an unsaturated bond are used.

(1) Heptamers having a hydroxyl group: 2-hydroxyethyl (meth)acrylate-1-, 2-hydroxypropyl (meth)acrylate, 2- and droxypentyl (meth)acrylate, 4-hydroxyphenyl (meth)acrylate , 2-hydroxyphenyl (
(meth)acrylates such as meth)acrylate; N-methylol(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, N-(hydroxyphenyl)-(meth)acrylamide, N-(hydroxy (meth)acrylamide monomers such as naphthyl)-(meth)acrylamide: 0m-1ρ-hydroxystyrene monomers, etc. <2) (meth)acrylic acid ester or amide monomers other than (1): Methyl (meth)acrylate , ethyl (meth)acrylate, propyl (meth)acrylate-1 to butyl (meth)acrylate-1, alkyl (meth)acrylates, N-phenyl (meth)acrylamide, 0-1m-1
p-Me[~xyphenyl(meth)acrylamide, 0-
(3) Monomers having a cyan group in the side chain: (meth)acryloni-1-21-lyl, 2-pentenitrile, 2-methyl-3-butenenitrile , 2-cyanoethyl acrylate, 0-1m-1p-cyanostyrene, etc. (4) Monomers having carboxylic acid in the side chain (meth)
Acrylic acid, itaconic acid and its anhydride, maleic acid and its anhydride, chlorohenic acid, etc., (5) Vinyl ethers: Propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether, etc., (6) Styrene: α-Methylstyrene, methylstyrene, chloro1]methylstyrene, styrene, etc. (a) Vinyl ketones: medyl vinyl ketone, cochyl vinyl ketone, probyl vinyl ether, etc. (8) Other than (1) to (7) Monomers: Examples include ethylene, propylene, isobutylene, butadiene, vinyl chloride, etc., N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, etc., and radical copolymerization with these heptamers. Any monomer that can be used may be used.

In the present invention, in addition to the above-mentioned materials, the photosensitive layer may also include dyes, pigments, coating properties improvers, plasticizers, sensitizers, stabilizers, etc. A curing agent 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 BO 1, Oil Blue #603, and Oil Pink #31.
2. Patent picoa blue, crystal violet,
Leuco Crystal Biol Fu 1~, Brilliant Green, Ethyl Violet 1~, Methyl Green, Erythrosin B, Pesic Tsuksin, Malachite Green,
Leucomalachi 1-green, W-cresol purple, cresol red, xylenol blue, rhodamine 81 auramine, 4-I)-diethylaminophenyl imino naphthoquinone, cyano-p-diethylaminophenyl ace 1-anilide, etc. Examples include rifhenylmethane-based, diphenylmethane-based, oxazine-based, xanthine-based, iminodef1-quinone-based, azomedine-based, and an[heraquinone-based dyes.

The dye is generally contained in the photosensitive layer in an amount of about 0.001 to about 10% by weight, preferably about 0.05 to 8% by weight.

Examples of the coating properties improver include alkyl ethers (e.g., ethyl cellulose, methyl cellulose), fluorine-based surfactants, nonionic surfactants (e.g., Pluronic L-64- (manufactured by Layaka Co., Ltd.)), and the like. .

Examples of plasticizers for imparting flexibility and abrasion resistance to coating films include butylphthalyl, polyethylene glycol,
Tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioquidyl phthalate, 1-ricresyl phosphate, 1-helibutyl phosphate, trioctyl phosphate, telyl-hydrafurufrif oleate, acrylic acid or methacrylic acid Examples include oligomers such as

The amount of these additives added varies depending on the purpose for which they are used, but is generally preferably from 0.01% to 30% by weight based on the total solid content.

The thickness of the photosensitive layer used in the present invention is usually 0.2 to 100.
μm, preferably 0.5 to 2 Ofim.

In the present invention, a silicone rubber layer is coated on the photosensitive layer. The silicone rubber used in the silicone rubber layer of the present invention is preferably linear or crosslinked polyorganosiloquiline to some extent.

The polyolganosiloxane usually has a molecular weight of 100,000 to several hundred thousand, and is liquid or waxy at room temperature, or moderately crosslinked into a curved shape.

The polyorganosiloquiline can be divided into condensed type and addition type depending on the method of crosslinking.

In the condensed type, crosslinking occurs during the condensation reaction, and water, alcohol, and a certain amount of mM are released by the reaction. Particularly useful condensation-type silicone rubbers include a mixture of a linear polyorganosiloxy compound having a hydroxyl group, an acetyl-oxy group, etc. at both ends or a part of the main chain, and a silicone crosslinking agent, or a silicone crosslinking agent in the hydroxyl group. In either case, adding a condensation catalyst is advantageous in terms of crosslinking speed.

The main chain of the polyorganosiloquiline has the following repeating units.

1+5i-0→- ■ In the formula, R1 and R2 are an alkyl group, an aryl group, an alkenyl group, each of which may have an exchange group, or a combination thereof, and include a methyl group, a phenyl group, a vinyl group, Lifluoropropyl group is preferred, and methyl group is particularly preferred.

The above-mentioned silicone crosslinking agent has a functional group represented by -01- ((in the formula, R and R' are alkyl groups), and is a so-called acetic acid removal type, a removal type, an alcohol removal type, a removal type, and a removal type. Examples include condensation type silicone crosslinking agents such as , 1 yen water type and the like.

Examples of such crosslinking agents include tetra-toxysilane, methyltrimethoxysilane, ethyl-1-lyacetoxysilane, phenyl-1-lyacetoxysilane, dimethyldiacetoxysilane, dimethyldiacetoxysilane, vinyltriacetoxysilane, methyltriacetoxysilane, Methoxysilane, dimethyldime-1-xysilane, vinyl-1-rimethoxysilane, methyltris(acetoneoxime)silane,
Methyl 1-li(N-methyl, N-acedelamino)silane, beer)~su(methylethylketoxime)silane, methyltri(methylethylketoxime)silane or I
Examples include oligomers thereof.

These crosslinking agents are all polyorganosiloxane 1
The amount is preferably in the range of 0.5 to 30 parts by weight per 00 parts by weight.

Examples of the condensation catalyst include organic carboxylic acids, titanate esters, acetylacetone metal complexes, chloroplatinic acid, naphthenic acid, and the like.

"A" membership refers to unsaturated groups in the main body, such as vinyl groups (-
It refers to something that is crosslinked by the addition of a water-based group in a crosslinking agent to CH═CH2>.

Specifically, vinyl group-containing organoborisiloxane, hydrogenated organopolysiloxane, and the like mixed with a platinum-based catalyst (for example, platinum chloride M) may be used.

The polyorganosiloxane has repeating units similar to those of the condensed type in the main chain.

In the silicone rubber layer of 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.

In the present invention, an adhesive layer made of acrylic resin or the like may be provided between the photosensitive layer and the silicone layer.
The layer can also contain various reactive crosslinking agents, silane coupling agents, etc., and the thickness of the adhesive layer is 0.1 m.
G/ (1 m2 to 5 m (1/du2 is preferred).

As the substrate used in the present invention, any substrate can be used as long as it has flexibility that can be used in a normal lithographic printing machine and can withstand the load applied during printing. Not restricted. Examples include papers such as coated paper, metal plates such as aluminum plates, and plastic films such as polyethylene terephthalate 1 to 1.

In particular, an aluminum plate or a composite material of aluminum foil and other materials is preferable, and from the viewpoint of printing durability, an aluminum plate is particularly preferable.

In addition, from the viewpoint of storage stability, the substrate, especially the aluminum plate or the aluminum foil and other composite side, can be surface-treated by a known method before use.

Such surface treatment includes, for example, a method of treating the surface of an aluminum plate with silicate (U.S. Pat. No. 2,714).
, 066), a method of treatment with organic acid salts (U.S. Patent No. 2
．． 714.066), treatment with phosphonic acids and their derivatives (U.S. Pat. No. 3.220832), treatment with potassium hexafluorozirconate (U.S. Pat. No. 2.946.683), anodizing There are methods such as a method of treating with an aqueous solution of an alkali metal silicate after anodization (US Pat. No. 3,181,461), and the like.

Furthermore, a primer layer may be provided on these substrates for the purpose of improving ink adhesion.

Examples of the resin used for the primer layer include acrylic resin, epoxy resin, polyester resin, and urethane resin. It is more preferable to use these resins after being cured by heat or light. For example, when an acrylic resin containing a hydroxyl group and/or a carboxyl group is cured by heat, a melamine resin, diisocyanates, etc. can be used as a crosslinking agent. Also,
When curing with light, diazo resin or the like can be used.

The thickness of the above primer layer is usually 1 to 200 mg/d2.
and preferably 3 to 100 mg/(1112).

In the present invention, the photosensitive lithographic printing plate prepared as described above is imagewise exposed, and then developed with a developer to dissolve the photosensitive layer and removed together with the silicone rubber layer thereon. A waterless plate is formed. At this time, the protective layer is dissolved in a developer and removed.

The light source used for the above exposure may be any general-purpose light source including ultraviolet rays of 180 nm or more and visible light, but carbon arc lamps, mercury lamps, xenon lamps, metal halide lamps, strobes, etc. are particularly preferred.

The developer used in the development process includes water, the following polar solvents, alkaline compounds such as amines, surfactants, and, if necessary, aliphatic hydrocarbons (hexano, heptane, etc.).
``Isopar E, l-1, G'' (trade name of aliphatic hydrocarbons manufactured by Esso Chemical) or gasoline, kerosene, etc.), aromatic hydrocarbons (1~ toluene, xylene, etc.) or halogenated hydrocarbons ( It is preferable to add 1 to 1 to 20% of the total amount of chlorine (such as 1 to 1).

Polar solvent alcohols (methanol, ethanol, water, etc.) 1-thyls (methyl cellosolve, ethyl cellosolve, butyl cellosolve, methylcarbyl, dilcarbyl, butylcarbyl, diol4non, etc.) Ketones (ace[... ethyl acetate, methyl ethyl ketone, etc.) esters (ethyl acetate, methyl cellosolve acetate,
Cellosolve acetate 1 ~, carpitol acetate - Development can be carried out by various known methods, such as using a developing pad containing a developer as described above, or pouring a developer onto the plate surface and then rubbing it with a developing brush. It can be done with

[Example] An aluminum plate that has been degreased and cleaned is oxidized with sulfuric acid, then treated with sodium silicate in a 1% aqueous sodium silicate solution at 85°C for 25 seconds, and then washed with water to form a substrate. Created.

Preparation of upper layer silicone type photosensitive lithographic printing plate sample that does not require dampening water A primer layer composition shown below was coated on the substrate prepared above using a whirler (50°C, 130ppm) and heated at 85°C.
Dry for 3 minutes and apply a primer layer.

Primer layer composition binder resin ioo part didiazo resin 20 parts methylcellosolve 2000 parts (binder resin is 2 parts
-Hydroxyethyl methacrylate-1, a copolymer of acrylonitrile, methyl methacrylate, and methacrylic acid with a composition ratio (mole percent of 1 or more) of 50:20:
23:7, and the weight average molecular weight is about 100,000. In addition, diazo resin is P of p-diazodiphenylamine.
It is a formaldehyde composite of F5 salt and has a weight average molecular weight of 1100. ) The weight of the primer layer is 16 m! ]/di'.

The primer layer coated on this substrate was heated once with a mercury lamp.
0 00 mJ/(y?) It was cured by exposure.

The photosensitive layer composition shown below was applied onto the above-mentioned brimer layer using a boiler (50°C, 1! iorl) + 1).
A photosensitive layer was formed by drying at 30° C. for 3 minutes.

Photosensitive layer composition binder resin 100 parts diazo resin 8 parts dye (BIKU 1 Helia Pure Blue) 1 part methyl cellosolve gooo part (binder resin is 2 parts
-Hydroxyethylmethacrylate-1-, acrylonitrile, methylmethacrylate-1-, and methacrylic acid copolymer composition (mole percent): 50:20:
23:7, and the weight average molecular weight is about 100,000. In addition, diazo resin is P of p-diazodiphenylamine.
It is a formaldehyde composite of F s m and a weight average molecular weight of 1100. ) The maximum film weight of the photosensitive layer was 31B/di2.

Next, the silicone rubber composition shown below was coated on the photosensitive layer using a whirler (150 ppm), and the silicone rubber composition shown below was coated at 50'C.
The silicone rubber was cured by drying for 16 hours to obtain an upper layer silicone type photosensitive lithographic printing plate sample that did not require dampening water.

Silicone rubber composition YF-3057
100 parts (manufactured by Shiba Silicone Co., Ltd.) Methyl] - Liacetoxysilane 10 parts Dibutyltin dilaurate 08 parts Hexane
2000 parts The weight of the silicone rubber layer of this sample when cured is 1 0
mg/ (I'll'.1 CH3 220 g (0.1 mol) of CH3 and 9.49 g (1 (0.1 mol) of pyridine)
A 10% diethyl ether solution of 12.06 (1 (0.05 mol)) of γmethacryloxypropyldimethylchlorosilane was gradually added dropwise over 1 hour at room temperature to a solution of 12.06 (12.06 mol) of γ-methacryloxypropyldimethylchlorosilane dissolved in 400 mol of diethyl ether.

The reaction proceeded immediately and white crystals of pyridine hydrochloride were precipitated. After the dropwise addition was completed, the mixture was further stirred at room temperature for 1 hour, and the crystals of pyridine hydrochloride were removed by filtration. Next, this filtrate was put into a separatory funnel, and 50011 g of water was added thereto, thoroughly shaken, and washed with water.

After washing with water, the liquid funnel was allowed to stand, the upper ether layer and the lower aqueous layer were separated, and anhydrous sulfate was added to the obtained ether layer, and the mixture was left overnight at room temperature to dehydrate.

Thereafter, anhydrous sulfuric acid was removed by filtration, and the resulting filtrate was distilled under reduced pressure to remove ether, yielding 225 g of polyorganosiloxane macromonomer.

Synthesis of polyorganosiloxane graft polymer for protective layer Table 1 shows the preparation of each monomer and the polyorganosiloxane macromonomer having a polymerizable group at the end. The terminal polymerizable functional group of the polyorganosiloxane macromonomer used is a methacryloyl group, and the polyorganosiloxane macromonomer is dimethylpolysiloxane having a number average molecular weight of about 5,000 as shown in the synthesis example. Monomers in the table are expressed in weight %.

Table 1 (AN in the table represents acrylonitrile, MMA represents methyl methacrylate, M△△ represents methacrylic acid, and M-1 represents polydimethylsiloxane macromonomer). 1 whose weight is 15 times the weight
Each component and azobisisobutyronitrile (A
5 mol % of IBN) L was dissolved therein, and the mixed solution was heated at 60° C. for 6 hours while stirring. After the reaction was completed, the reaction solution was dropped into water and reprecipitated, and the solid matter was filtered out, followed by vacuum drying at 60°C for 20 hours to obtain polymer compounds -1 and -2.

The above-mentioned polyorganosiloxane graft polymer for the protective layer was applied to a boiler (
It was coated at 50° C. and 10,100 rpm, and dried at 85° C. for 3 minutes to form protective layer-1 and protective layer-2. Also, polyorganosiloxane graft polymer polymer compound -
Protection 1ijl-3 was prepared by blending 1 with acrylic resin and applying it in the same manner as described above.Furthermore, as a sample for comparison, protection 1ijl-3 was prepared using only acrylic resin containing no polyorganosiloxane graft polymer. I applied the coating.

Protective layer-1 High molecular compound-1100 parts Toluene 2000 parts Protective layer-2 High molecular compound-2100 parts Toluene 2000 parts Protective layer-3 High molecular compound-150 parts Styrene, methyl methacrylate acrylic acid 2:2:1 copolymer 50 parts Methyl ethyl ketone 2000 parts Protective layer-4 (comparison) Styrene Methyl methacrylate acrylic acid 2:2:1 copolymer 100 parts Methymethylketone 2000 parts Protective layer 1-
The membrane weight of all three samples was about 40 mfl/11.1.

However, the protective layer 4 was repelled by the silicone rubber layer 2 and could not be coated.

The photosensitive lithographic printing plate sample provided with the protective layer 1 was mechanically embossed after coating. The average height difference between the unevenness caused by the embossing process is 0.4 to 1.
The area was 1 m wide, and there were about 2000 unevenness per 1 cm2.

The time required to bring this plate into close contact with a similar plate without embossing using a vacuum contact method was measured.

As a result, it took 28 seconds for the embossed version and 160 seconds for the non-embossed version, indicating that embossing is effective for vacuum adhesion.

Each of the photosensitive lithographic printing plate samples provided with protective layers 1 to 3 was coated with a sapphire nail with a diameter of 20 mm at the tip of a sapphire nail with a diameter of 0.5 mm using a surface property measuring device HEIDON14 (manufactured by Shinraikagakusha).
Scratches were made by applying a load of ~500 ().For comparison, a similar scratch was also made to a sample to which no protective layer was applied.

Apply positive film to these plates and apply 100mJ/C.
After 12 exposures, it was immersed in the following developer for 1 minute, and then washed with water to obtain a fixed image.

Developer composition Phenyl Cellsolve 15 parts by weight Jetanolamine 15 parts by weight Water
At the time of development at 70 parts by weight, all of the protective layers 1 to 3 were dissolved in the developer and removed. Using the thus obtained lithographic printing plate that does not require dampening water,
Aquares V on a Heidelberg GTO printing press with the dampening water supply system removed.

1- Mark 111 was made using Beni (manufactured by Toyo Ink Co., Ltd.) ink to evaluate the presence or absence of scratch marks on the printed matter. The results are shown in Table 2.

The contact printing method is as follows: A photographic film (500x700nu++) with a 20% halftone image source made with Konica L100E film and a sample 11M (800x
1003mm) and horizontal vacuum baking frame KD manufactured by Kamo Electric Laboratory.
Table 2 Roughly, the protective layer of the present invention is well coated on the silicone rubber layer and is soluble in the developer, so
You will no longer have to worry about peeling off the protective film, which was required in the past.

As is clear from Table 2, all of the samples provided with protective layers 1 to 3 of the present invention have significantly improved resistance to scratches compared to the samples provided with no protective layer.

In addition, since diazo resin is used in the photosensitive layer in this example, nitrogen gas is generated during exposure, but the generated gas does not remain at the interface between the protective layer and the photosensitive layer and there is no problem. I was able to do the exposure.

[Effect of the invention]

Claims (1)

[Claims] A photosensitive lithographic printing plate with a silicone rubber layer that does not require dampening water, which has a dampening water layer on the silicone rubber layer that contains a polymer compound having a polyorganosiloxane in its side chain and can be removed during development. Water-free photosensitive lithographic printing plate.