JPH03274555A - Photosensitive lithographic printing plate that does not require dampening water - Google Patents

Abstract

PURPOSE:To improve the adhesiveness between a photosensitive layer and a silicone layer, scratching strength, plate wear, and ink repulsiveness by incorporating a hydroxyl group-contg. polymer and a diazo resin into photosensitive layer and incorporating silicone rubber which executes crosslinking by the addition reaction of an SiH group and a -CH=CH- group into the silicone rubber layer. CONSTITUTION:The photosensitive layer contains at least the diazo resin and the silicone rubber contains the addition type silicone rubber which executes the crosslinking by the addition reaction of the SiH group and the -CH=CH- group. A diazo resin, etc., by bringing a diazo compd. and a diphenyl ether deriv. into condensation reaction are usable as the diazo resin. The ester of amide of alcoholic hydroxy group-contg. poly(meth)acrylic acid is preferably used as the hydroxyl group-contg. polymer. In addition, the addition type silicone rubber is incorporated as an essential component into the silicone rubber layer. The addition type refers to the type in which the hydrogen (-H) in a crosslinking agent is added and crosslinked to the unsatd. group in the body, for example, vinyl group (-CH=CH2). The improvement in the adhesiveness between the photosensitive layer and the silicone layer, the scratching strength, the plate wear and the ink repulsiveness is made in this way.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a photosensitive lithographic printing plate that does not require dampening water, and more specifically, a primer layer, a photosensitive layer, and a silicone rubber layer are formed on a substrate in this order. This invention relates to a photosensitive lithographic printing plate that does not require dampening water and is coated.

[Conventional technology]

Conventionally, in lithographic printing, it has been necessary to perform printing by making use of the lipophilicity of the imaged areas and the hydrophilicity of the non-imaged areas, with a delicate balance of water and ink, and this requires considerable skill.

In other words, in the conventional printing method that requires dampening water, an image-like lipophilic portion is formed by passing an image film through a plate material coated with a lipophilic photosensitive layer on a hydrophilic support, and then developing it. A printing plate is prepared by providing a parent wood portion which is a non-printing portion. During printing, water is first transferred to the non-image areas, and then ink is transferred. Ink does not adhere to non-print areas where water is present, but only to print areas. However, this method
It is difficult to control the delicate balance between dampening water and ink, which can cause emulsification of the ink, and the ink can mix with the dampening water, causing poor ink density and scumming, which can be a major cause of wasted paper. Was.

Furthermore, the transfer of dampening water to the printing material causes a change in the dimensions of the printing material, which has the disadvantage that the sharpness of the image is impaired, especially when printing in multiple colors.

For this reason, attempts have been made to develop lithographic printing plates that do not require dampening water (hereinafter referred to as "waterless lithographic plates"). Disclosed is a waterless lithographic plate having a structure in which a silicone layer is provided on a photosensitive layer on a support, and the upper silicone rubber layer is removed by dissolving the photosensitive layer in a developer to form an image area. A method is disclosed. Also,
Special Publication No. 54-26923 and No. 56-23150
The patent publication has a structure similar to the above in that a silicone rubber layer is provided on a photosensitive layer on a support, but the photosensitive layer does not dissolve in a developer and the photosensitive layer and silicone rubber layer are separated by image exposure. A method is disclosed in which the silicone rubber layer is selectively swelled and removed by causing photoadhesion or photo-III.

Furthermore, Japanese Patent Publication No. 61-54219, Japanese Patent Publication No. 60-22
No. 9031 and No. 62-194255 disclose waterless planographic plates having a structure in which a photosensitive layer and a silicone layer are provided on a primer layer on a support.

[Problem to be solved by the invention]

Most conventionally known silicone rubber layers are condensed silicone, so it is necessary to add a large amount of silane coupling agent for crosslinking, and because terminal silanol remains, ink repulsion is poor. The problem was that it was insufficient. Furthermore, since condensation type silicone is affected by both temperature and humidity during curing, there is also the problem that it is easily affected by the atmosphere during curing.

On the other hand, the addition type is disclosed in JP-A-61-73156, JP-A-62-157037, and JP-A-63-25776.
Although it is described in Publication No. 0, etc., the adhesion between the photosensitive layer and the silicone layer is insufficient, which is a drawback of the addition type, and there are problems in scratch strength and stiffness resistance.

As a result of intensive studies, the present inventors have determined that the photosensitive layer containing a hydroxyl group-containing polymer and a diazo resin and the silicone rubber layer are crosslinked by an addition reaction between SiH groups and -CH=CH- groups. The present inventors have discovered that this problem can be solved by containing silicone rubber.

[Means for Solving the Problems] That is, an object of the present invention is to provide a novel photosensitive lithographic printing plate that eliminates the above-mentioned disadvantages of the addition type and has excellent ink repulsion and does not require dampening water. , the object of the present invention is to
A substrate has at least a primer layer, a photosensitive layer, and a silicone rubber layer in this order from the substrate side, the photosensitive layer has at least a diazo resin, and the silicone rubber layer;
This is achieved by a photosensitive lithographic printing plate that does not require dampening water and is characterized by containing a silicone rubber that performs crosslinking through an addition reaction between an S i H group and a -CH=CH- group.

The present invention will be explained in more detail below.

The photosensitive layer used in the present invention contains a diazo resin and a hydroxyl group-containing polymer as essential components.

Examples of the above-mentioned diazo resin include photographic resin.
Science and Engineering (Photo
o, Sci, Eng, ) Volume 17, Page 33 (
1973), U.S. Patent No. 2.063.631, U.S. Pat.
．． 679,498, No. 3,050.502, JP-A-59-78340, etc., diazo compounds and active carbonyl compounds (
A diazo resin obtained by condensing formaldehyde, acetaldehyde, henzaldehyde, etc.) in an acidic catalyst such as sulfuric acid, phosphoric acid, or hydrochloric acid.
A diazo resin obtained by condensing a diazo compound and a diphenyl ether derivative, the manufacturing method of which is described in Publication No. 4001, can be used, and a condensate of P-diazodiphenyl amine and formalin is particularly preferred.

The counter anion of the diazo resin used in the present invention is
It contains an anion that forms a stable salt with the diazo resin and makes the resin soluble in organic solvents.

These include organic carboxylic acids such as decanoic acid and benzoic acid;
Contains organic phosphoric acids and sulfonic acids such as phenyl phosphoric acid,
Typical examples include methanesulfonic acid, chloroethanesulfonic acid, dodecanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, mesitylenesulfonic acid and anthraquinonesulfonic acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, hydroquinone Sulfonic acid, 4-acetylbenzenesulfonic acid, dimethyl-5
= Aliphatic and aromatic sulfonic acids such as sulfoisophthalate, 2.2', 4.4'-tetrahydroxybenzophenone, 1,2.3-)lihydroxybenzophenone,
2.2',4-) Hydroxyl group-containing aromatic compounds such as lyhydroxybenzophenone, halogenated Lewis acids such as hexafluorophosphoric acid and tetrafluoroboric acid, Cl0a, I
Examples include perhalogen acids such as Oa. Of these, A
Logenated Lewis acids are preferred from the viewpoint of visible images upon exposure, and hexafluorophosphoric acid is particularly preferred. The weight average molecular weight of the coupled product with β-naphthol measured by gel permeation chromatography (GPC) is 200 to 1.
The range is preferably 0,000 (in terms of styrene), and 500
A range of 5,000 to 5,000 is more preferable.

In the present invention, the proportion of the diazo resin in the photosensitive layer is usually 1 to 90% by weight, preferably 3 to 60% by weight.

Further, as the hydroxyl group-containing polymer in the present invention, an alcoholic hydroxyl group-containing poly(meth)acrylic acid ester or amide is preferably used.

Examples of the hexamer having an alcoholic hydroxyl group include 2-hydroxyethyl acrylate, 2hydroxyethyl methacrylate, N-(4-hydroxyethylphenyl) methacrylamide, and hydroxy-methyl diacetone (meth)acrylamide. Among these, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are particularly preferred.

Monomers copolymerizable with the above-mentioned hydroxyl group-containing monomers include (11) monomers having an aromatic hydroxyl group, such as N-(4
-Hydroxyphenyl)acrylamide, N-(4-hydroxyphenyl)methacrylamide, 0-1m-1p
-Hydroxystyrene, 0-1m, p-hydroxyphenyl-acrylate or -methacrylate, (2) α,β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic anhydride, (3) Methyl acrylate, acrylic acid (Substituted) alkyl such as ethyl, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-chloroethyl acrylate, 2-hydroxyethyl acrylate, glycidyl acrylate, N-dimethylaminoethyl acrylate, etc. acrylate, (4) methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, cyclohexyl methacrylate,
2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, glycidyl methacrylate, N
- (Substituted) alkyl methacrylates such as dimethylaminoethyl methacrylate (5) Acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethyl acrylamide, N-hexylmethacrylamide, N-cyclohexyl acrylamide, N- −
Acrylamides or methacrylamides such as hydroxyethyl acrylamide, N-phenylacrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenylacrylamide, (6) ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, Vinyl ethers such as butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether, etc. (7) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate, etc. (8) Styrene, α-methylstyrene, methylstyrene, chloro Styrenes such as methylstyrene, (9) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl ketone, α [Olefins such as ethylene, propylene, isobutylene, butadiene, isoprene, α11) N- Vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile■ Monomer CH, =CH containing an unsaturated group in the side chain shown in the following - Tsuzuriyo (1) [In the formula, R is Represents a hydrogen atom or a methyl group, R1゜Rt
, Rs, Ra and R2 are each a hydrogen atom, a halogen atom, a carboxy group, a sulfo group, a nitro group, a cyano group, an acid group, an amino group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylamino group, an aryl group. Amino, alkylsulfonyl, and arylsulfo groups are the selected groups, and Z is 10-, -3-, -NH
-, -NR.

(Rh is an alkyl group) -0CHtCH20- or 0CH
zCH(OH)-], etc. Of these +
Monomers 1) to (4) and (2) are preferable as monomers for copolymerization, and monomers (1) to (4) are particularly preferable.

The amount of hydroxyl group-containing monomer in the hydroxyl group-containing polymer is not particularly limited, but is preferably 5 to 100% by weight.
, particularly preferably from 20 to 100% by weight.

The weight average molecular weight of the hydroxyl group-containing polymer of the present invention measured by gel permeation chromatography (GPC method) is preferably 5,000 to 1,000,000 (in terms of styrene); if it is lower than 5,000, it may be damaged by the developer after photocuring. If the value is larger than 1,000,000, it is difficult to select a coating solvent.

The proportion of the hydroxyl group-containing polymer in the photosensitive layer is usually 10 to 99% by weight, preferably 40 to 97% by weight.

The weight ratio of diazo resin and hydroxyl group-containing polymer is 1/9
The range of 9 to 90/10 is preferable.

If the diazo resin is less than 1/99, it may not be sufficiently crosslinked even after photocuring and may be damaged by the coating solvent or developer. On the other hand, if the diazo resin is more than 90/10, the polymer ratio will inevitably be lowered. becomes smaller and the hydroxyl group content becomes lower, so the adhesion with the silicone layer tends to decrease.

Furthermore, the photosensitive layer of the present invention may also contain a photoinsolubilizable photosensitive substance such as a compound having an addition polymerizable vinyl group.

Examples of compounds having an addition polymerizable vinyl group include compounds having a boiling point of 100°C or higher under normal pressure and having two or more polymerizable terminal ethylene groups, such as unsaturated carboxylic acids, unsaturated carboxylic acids, and aliphatic polyhydroxy esters with compounds, esters between unsaturated carboxylic acids and aromatic polyhydroxy compounds, esters between unsaturated carboxylic acids and polyhydric carboxylic acids, and polyhydric hydroxy compounds such as the aforementioned aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds. Examples include esters obtained by esterification reactions, which are specifically described in JP-A-59-71048 and the like.

In addition to the above-mentioned materials, the photosensitive layer of the present invention may also contain dyes, pigments, or exposure-visible agents, if necessary.
By adding a coating property improver or the like, it is possible to improve the developed visible image properties, the exposed visible image properties, and the coating properties.

As the above dye, for example, Victoria Pure Flu B
OH, oil blue #603, oil pink #312,
Patent Pure Blue, Crystal Hiolesotho, Leuco Crystal Bioleft, Brilliant Green, Ethyl Violet, Methyl Green, Erythrosin B,
Representative examples include pacic tuxin, malachite green, leucomalachite green, m-cresol purple, cresol red, xylenol blue, rhodamine B1 auramine, 4-p-diethylaminophenylimino naphthoquinone, cyano-p-diethylaminophenylacetanilide, etc. Examples include triphenylmethane-based, diphenylmethane-based, oxazine-based, xanthine-based, iminolinaphthoquinone-based, azomethine-based, and anthraquinone-based dyes.

The above dye is usually contained in the photosensitive layer in an amount of about 0.01 to about 10% by weight.
, preferably about 0.05 to 8% by weight.

Examples of coating properties improvers include alkyl ethers (e.g., ethyl cellulose, methyl cellulose), fluorine-based surfactants, and nonionic surfactants (e.g., "Pluronifuku L-64" (manufactured by Asahi Denka)), "FC- 430”
(manufactured by 3M), etc.

In addition, as for the exposure visible image side, for example, JP-A-54-74
Examples thereof include oxadiazole compounds described in JP-A No. 728 and triazine compounds described in JP-A-53-36223.

In the present invention, the film thickness of the photosensitive layer is 0.1■/d n (~
30■/d r/ is preferable, 0.5■/d resistance to 10■
/d resistance is more preferable.

The silicone rubber layer used in the present invention contains as an essential component an addition-type silicone rubber that performs crosslinking by an addition reaction between a >S tH group and -CH=CH-.

The addition type refers to an unsaturated group in the main body, such as a vinyl group (-C
Hydrogen (-H) in a crosslinking agent is added to a crosslinking agent (-H-CHz) to form a crosslink.

Specifically, examples include vinyl group-containing organopolysiloxanes, hydrogenated organopolysiloxanes, and the like mixed with platinum-based catalysts (for example, chloroplatinic acid).

Addition-type silicone rubber lacks adhesive properties, but surprisingly, by coating the silicone layer on the photosensitive layer (the photosensitive layer consisting of at least a hydroxyl group-containing polymer and a diazo resin), scratch strength and rigidity resistance can be improved. Good adhesion can also be obtained.

It is necessary to contain at least two or more MiS i H groups in one molecule of organopolysiloxane unit, and it is also necessary to contain at least two or more 10H═CH- groups in one molecule of organopolysiloxane unit.

Preferably, (a) -CH= CH- group-containing organopolysiloxane 100 parts by weight (b)
; S i H group-containing organopolysiloxane 1 to 100
A composition containing at least 0 parts by weight (0.00001 to 1 part by weight of C1 addition catalyst) is cured.

Components forming silicone rubber (al, (-C of bl)
The H═CH- group and the Mi-SiH group may be present either at the end or in the middle of the coorganopolysiloxane. Also, the ingredients (at,
In (b), 60% or more of the organic groups are preferably methyl groups from the viewpoint of ink repellency. The weight average molecular weight of both (a) and (b) is preferably from 1,000 to several hundreds of thousands.

The addition catalyst for component (C) is arbitrarily selected from known ones, but platinum-based compounds are particularly preferred, and chloroplatinic acid is particularly preferred.

In combination with this photosensitive layer, the ratio of (a)/(bl) is preferably 3 to 30.

In addition to these compositions, it is more preferable to add a known adhesion imparting agent such as alkenyltrialkoxysilane to improve adhesion.

Furthermore, an organopolysiloxane containing water groups may be added.

Furthermore, for the purpose of improving the strength of silicone rubber, inorganic fillers such as silica, titanium oxide, and aluminum oxide may be added, and silica is particularly preferably used.

From the viewpoint of dispersibility or dispersion stability, such fillers preferably have an average particle diameter of 500 μm or less.

In the present invention, the thickness of the silicone rubber layer is preferably as thin as possible from the point of view of image quality and developability, but on the other hand, a certain degree of thickness is required from the point of view of rigidity resistance, printing stains, etc.; therefore, it is generally 3 rz / d rd ~50 @ / d n(
is preferable, and 5 .mu./dtri to 30 .mu./dm is more preferable.

In the present invention, an adhesive layer made of epoxy resin or the like may be provided between the photosensitive layer and the silicone layer, and the adhesive layer may contain various reactive crosslinking agents, silane coupling agents, etc. Also, the thickness of the adhesive layer is 0.1■/d
n(~5■/drr? is preferable.

In the present invention, surprisingly, the above-mentioned characteristics of the silicone rubber layer are particularly remarkable when the photosensitive layer contains at least a hydroxyl group-containing polymer and a diazo resin.
Although the detailed mechanism is unknown, it is presumed that the affinity of the silane compound of the present invention with the isocyanurate group and the presence of a large number of reactive silane compounds in one molecule are involved.

In the present invention, a primer layer can also be provided between the photosensitive layer and the substrate.

As the primer layer, any of a variety of known primer layers can be applied, but for example, the primer layer described in Japanese Patent Publication No. 61-54219, such as one made of epoxy resin, polyurethane resin, etc., heated and cured using an appropriate curing agent. Alternatively, the primer layer described in JP-A No. 60-229031, which is obtained by photo-curing a layer made of a photodimer-type curable resin, etc., can be used. Furthermore, a primer layer obtained by photocuring a layer mainly composed of a diazo resin and a hydroxyl group-containing polymer is also preferably used. Such a diazo resin is the same as the diazo resin contained in the photosensitive layer, and is usually 1 to 90% by weight, preferably 3% by weight, in the primer layer.
Contains ~60% by weight.

As the hydroxyl group-containing polymer, the same hydroxyl group-containing polymers contained in the photosensitive layer, polyvinyl alcohol derivatives, epoxy resins, novolac resins, gelatin, cellulose, etc. are used. Such hydroxyl group-containing polymers are contained in the primer layer in an amount ranging from 10 to 99% by weight, preferably from 40 to 97% by weight.

In the present invention, in addition to the above-mentioned essential components, the primer layer may contain fillers such as titanium oxide and zinc oxide, or antihalation agents, colorants such as dyes and pigments, coating properties improvers, plasticizers, and stabilizers. , a fattening agent, etc. may be included in an amount not exceeding 10% by weight.

As the above-mentioned dye and coatability improving agent, the same ones as those contained in the above-mentioned photosensitive layer are used.

Examples of plasticizers for imparting flexibility and abrasion resistance to coating films include butylphthalyl, polyethylene glycol,
Examples include tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrafurfuryl oleate, oligomers of acrylic acid or methacrylic acid, etc. .

In addition, in order to improve the printing ink receptivity of images, various additives having hydrophobic groups, such as p-octylphenol/formalin novolak resin, pt-butylphenol/formalin novolak resin, pt-butylphenol/benzaldehyde resin, Modified novolak resins such as rosin-modified novolak resins, and 0-naphthoquinonediazide sulfonic acid esters (esterification rate of OH groups of 20 to 70 mol %) of these modified novolac resins can be added.

The above-mentioned photocurable diazo resin or a composition containing the same and a hydroxyl group-containing polymer are dissolved in an appropriate organic solvent together with other additives added as necessary, and then applied onto a support and dried. After that, it is exposed to light to completely decompose the diazo resin and harden it, thereby forming a primer layer.

The thickness of the primer layer is 1■/d% to 200■/drrr
is preferable, more preferably 3■/drrr
~100■/dn? It is.

Further, in the waterless planographic plate of the present invention, a protective layer may be provided on the silicone rubber layer, and methods for providing the protective layer include the method of laminating polypropylene film etc. described in Japanese Patent Publication No. 61-614, and the method of laminating a polypropylene film etc. described in Japanese Patent Publication No. 61-614, A method of applying a high molecular weight polymer described in Japanese Patent No. 61-27545 is known.

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, and there are no particular restrictions on the substrate including the layer structure. . Examples include papers such as coated paper, metal plates such as aluminum plates, and plastic films such as polyethylene terephthalate.

The substrate used in the present invention is preferably an aluminum plate or a composite material of aluminum foil and other materials, and from the viewpoint of rigidity, an aluminum plate is particularly preferable.

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, so that the substrate or primer layer is removed. It is exposed as an image area and a waterless lithographic plate is formed.

In this case, it is preferable to dye the image area with a cationic dye such as crystal violet or Victoria blue BOH during or after development.

As the light source used for exposure, any general-purpose light source including ultraviolet rays of 180 nm or more and visible light may be used, 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 (hexane, heptane, etc.).
'Isopar E, H, G' (trade name of aliphatic hydrocarbons manufactured by FSO Chemical Co., Ltd.) or gasoline, kerosene, etc.), aromatic hydrocarbons (toluene, xylene, etc.), or halogenated hydrocarbons (triclene, etc.). It was added.

Extremely rare alcohols (methanol, ethanol, benzyl alcohol, etc.) Ethers (methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl carpitol, ethyl carpitol, butyl carpitol, dioxane, phenyl cellosolve, etc.) Ketones (acetone, Methyl ethyl ketone, etc.) Esters (1-ethyl acid, methyl cellosolve acetate, cellosolve acetate, carpitol acetate, etc.) Development can be done, for example, by rubbing with a developing pad containing a developer as described above, or by pouring a developer onto the plate and then developing. This can be done by various known methods such as rubbing with a brush.

(Examples) The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to the following Examples.

(Synthesis of Diazo Resin-1) 14.5 g of p-diazodiphenylamine sulfate was dissolved in 40.9 g of concentrated sulfuric acid under water cooling. 1.0 in this reaction solution
g of rose formaldehyde was slowly added dropwise so that the reaction temperature did not exceed 10°C.

Thereafter, stirring was continued for 2 hours under water cooling. This reaction mixture was added dropwise to 500 ml of ethanol under water cooling, and the resulting precipitate was filtered. After washing with ethanol, this precipitate was
To this solution was added a cold concentrated aqueous solution in which 6.8 g of zinc chloride was dissolved. The resulting precipitate was filtered, washed with ethanol, and dissolved in 150% 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 at 30°C for a day and night to obtain a diazo resin.
I got 1.

The styrene equivalent weight average molecular weight (MW) of the diazo resin measured by GPC method is 1500, and the number average molecular weight is 500.
Met.

[Synthesis of Polymer 1] 150 g of 2-hydroxyethyl methacrylate.

Acrylonitrile 60g, methyl methacrylate 79.
5g, methacrylic acid 10.5g (the molar ratio of each is 3
7:35:24:4) distilled dioxane 700
g (toquel monomer concentration = 4.6 mol/l)
) 15 g (2 mol %) of hensyl peroxide was gradually added, and a polymerization reaction was carried out under reflux in a nitrogen stream for 8 hours. After the reaction was completed, 0.5 g of hydroquinone was added, and the solvent was distilled off under reduced pressure. When the viscosity increased, it was poured onto a stainless steel plate and vacuum dried to obtain 270 g of plate-shaped resin (Polymer 1). The GPC measurement values of the polymer are shown below.

Mw: 4.80xl O', dispersion ratio: 2.2 [Synthesis of Polymer 2 Synthesis of Polymer 1 except that hydroxy-methyl diacetone (meth)acrylamide was used instead of 2-hydroxyethyl methacrylate in Copolymer 1 Polymer 2 was obtained in the same manner as above.

GPC measurements of Polymer 2 are shown below.

Mw:4.5
-Hydroxyphenyl)-methacrylamide (42g) and methacrylic acid (1g) were dissolved in distilled acetone (100%) and distilled methanol (100%) (total monomer concentration 2.5...
o1/1) and 0.8 g of azobisisobutyronitrile were added, and a polymerization reaction was carried out under reflux in a nitrogen stream for 5 hours. After the reaction was completed, the mixture was poured into water and separated to obtain a white resin (Polymer 3). GPC measurement values for the obtained polymer are shown below.

MW: 4.2 x 10', dispersion ratio: 3.6 [Synthesis of Polymer 4 Polymer 4 was obtained in the same manner as the synthesis of Polymer 1 except that ethyl methacrylate was used in place of 2-hydroxyethyl methacrylate in Copolymer 1.

Mw: 5.2X10', dispersion ratio: 3.0
Anodic oxidation treatment was performed for 2 minutes at 1.5 A/di at a temperature of 1.5 A/di, followed by washing with water. Further, the substrate was treated with sodium silicate in a 1% by weight aqueous sodium silicate solution at 85° C. for 25 seconds, and then washed with water to obtain Substrate-1.

A primer layer composition having the following composition was applied to this substrate-1 at 55°C using a polymer coater, and dried at 85°C for 3 minutes to provide a primer layer. Dry film thickness is 10■/do
(Met.

Primer Set polymer - 1100 parts (alcoholic hydroxyl group-containing polymer) Diazo resin - 120 parts (p-diazodiphenylamine formaldehyde resin) Methyl cellosolve 2400 parts Next, the board coated with the above composition was heated for 10 minutes using a 3KW ultra-high pressure mercury lamp.
The entire surface was exposed at 100 O/cd.

The following photosensitive composition was applied to the aluminum plate coated with the primer layer at a dry weight of 3 cm/dn? to become 55
A photosensitive layer was provided by coating the polymer at ℃ and drying it.

A-Kumi Charcoal Polymer 3 100 parts (polymer containing alcoholic hydroxyl groups and phenolic hydroxyl groups) Diazo resin - 1100 parts (p-diazodiphenylamine formaldehyde resin) Victoria Blue BOHI part Orange IV (C6H5NHC6H, N=N Cb
H= SO3Na ) 3-part methyl cellosolve
2000 parts ethyl cellosolve
1000 parts Next, 55 parts of the following silicone rubber composition was added to the photosensitive layer to give a dry weight of 20 μ/dr/.
The polymer was applied at 100°C and dried for 5 minutes to form a silicone rubber layer.

Silicone rubber α,ω-Divinylpolydimethylsiloxane (number average molecular weight: approx. 12,000) 100 parts Methylhydrodiene polysiloxane (number average molecular weight: approx. 3,000) 3 parts chloroplatinic acid 0.1 part hexane
A polypropylene film having a thickness of 6 μm was laminated on the surface of the silicone rubber layer obtained in an amount of 1400 parts to obtain a waterless planographic plate-1.

After overlaying a positive film on this printing plate and exposing it to 400mJ/cd using a 3KW ultra-high pressure mercury lamp, the laminated film was peeled off, immersed in a developer having the composition shown below for 1 minute, and rubbed with a development vat to separate the unexposed areas of the photosensitive layer and silicone rubber. was removed. Since the photosensitive layer was colored with a dye and the primer layer was not colored, it was possible to visually determine the end point of development at which the photosensitive layer was completely removed and the primer layer was exposed.

Phenyl Cellosolve 10 parts Jetanolamine 4 parts Pionine A-
44B (manufactured by Takemoto Yushi) 6 parts water
A bright purple positive image was obtained by applying 80 parts of a dyeing solution of the following composition to a cloth, lightly rubbing the plate, and washing with water.

Higashisegaoka Crystal Violet 0.5 parts benzyl alcohol 2 parts water
6 Heidel GTO with the dampening water supply device removed from the 150 copies thus obtained plate.
(manufactured by Heidel), “Aquares Five Sumi TPM”
When printing using Ink 4 (manufactured by Toyo Ink Manufacturing), 30,000 good prints with no background smudge were produced.
I was able to get more than one.

A diameter of 0.2 m was applied to the non-printing area of the printing plate using a continuous weight scratch strength test Type-HEIDON-18 manufactured by Shinan Kagaku Co., Ltd.
After making scratches at a load of 20 using a sapphire needle, printing was carried out in the same manner as above, but no scratch-like scumming occurred.

(Comparative Example-1) A waterless lithographic plate-2 was obtained in the same manner as in Example-1 except that the composition of the silicone rubber layer was changed as follows.

Silicone Rubber "YF-3057" manufactured by Toshiba Silicone 100 parts 'TSL-8180'' manufactured by Toshiba Silicone lO part Di-n-butyltin dilaurate 0.8 part Hexane
After exposing, developing and dyeing 1,400 copies in the same manner as in Example-1, in order to compare the ink repulsion properties, using a Heidel GTO (manufactured by Heidel) with the dampening water supply device removed, "Aquares" manufactured by Toyo Ink ■ was used. Printing was carried out using Five Beni TPM" ink while changing the plate surface temperature.

As is clear from Table 1, the addition type is superior to the condensation type in terms of paint repulsion.

(Example-1) A dry film thickness of 30 mm/drr on a smooth aluminum plate degreased in a conventional manner. The following primer layer composition was coated and cured by heating at 150° C. for 10 minutes to form a primer layer.

Primer Acid “Epicote 1001” (Shell Chemical Co., Ltd.) 50 parts of phenol/novolac resin with a molecular weight of 2000 100 parts Methyl cellosolve 1000 parts On the aluminum plate coated with the above primer layer, the following photosensitive composition was applied to a dry film thickness. 5■/drr? A photosensitive layer was formed by coating and drying.

Allied friend 1 Seishoko polymer - 1100 parts (alcoholic hydroxyl group-containing polymer) Diazo resin = 1 150 parts (p-diazophenylamine formaldehyde resin) Victoria Blue BOH 2 parts Methyl cellosolve 2000 parts Next, on the above photosensitive layer, apply the following silicone. Rubber composition by dry weight 1
It was coated at a rate of 5 cm/drrr and dried at 100°C*5' to form a silicone rubber layer.

Silicone rubber α,ω-Divinylpolydimethylsiloxane (average molecular weight 300.000) 90 parts Methylhydrodiene polysiloxane (average molecular weight 2500) 3 parts “KF”
410" (manufactured by Shin-Etsu Chemical: α-methylstyrene-modified dimethylsiloxane) 0.5 parts Olefin-chloroplatinic acid 2 parts Hexane
1600 copies A polypropylene film was laminated in the same manner as in Example 1 to obtain a waterless lithographic plate 3.

A printing plate was obtained by exposing, developing and dyeing in the same manner.

The thus obtained plate was printed using "Heidel GTO" (manufactured by Heidel) with the dampening water supply device removed, using Toyo Ink's "Aquares Five Beni TPM" ink, and the coverage was also good. We were able to obtain over 20,000 good quality prints with no scumming.

In addition, after making scratches on the printing plate in the non-printing area using a sapphire needle with a diameter of 0.2 fi using a continuous load type scratch strength tester "Type-HEIDEN-18' manufactured by Shinto Scientific Co., Ltd. under a load of 20 g. Although printing was carried out in the same manner as above, scratch-like scumming did not occur.

(Example 3) A printing plate was obtained in the same manner as in Example 1 except that Polymer 3 in the photosensitive layer composition was replaced with Polymer 2. When printing was carried out in the same manner as in Example 1, more than 20,000 good prints without background smudge could be obtained.

(Comparative Example-2) Polymer 3 of the photosensitive layer composition of Example-1 was replaced with Polymer 4.
I tried to obtain a plate in the same way except for changing to [hydroxyl group-free polymer], but when I peeled off the protective layer after exposure, the silicone layer peeled off, and the adhesion between the silicone layer and the photosensitive layer was poor. It turns out that it is.

Claims (1)

[Claims] A substrate has at least a primer layer, a photosensitive layer, and a silicone rubber layer in this order from the substrate side, the photosensitive layer has at least a hydroxyl group-containing polymer and a diazo resin, and the silicone rubber layer has a ▲ mathematical formula, chemical formula, table, etc. A photosensitive lithographic printing plate that does not require dampening water and is characterized by containing a silicone rubber that performs crosslinking through an addition reaction between a ▼ group and a -CH=CH- group.