JPH03280051A - Dampening-waterless photosensitive planographic printing plate - Google Patents

Abstract

PURPOSE:To obtain good visible image developability by forming a primer layer as a layer which is coated with a compsn. contg. a specific compd. and photopolymn. initiator and is then photocured. CONSTITUTION:The primer layer is the layer formed by coating the surface of a substrate with the compsn. contg. the compd. having at least the two constitutional units expressed by formula I and having no arom. group and the photopolymn. initiator, then curing the compsn. by light. In the formula, R denotes a hydrogen atom or -(CH2)nCH3 group, where n denotes 0 to 8 integer. The compd. is incorporated preferably at 20 to 95wt.% into the primer layer. The photopolymn. initiator is incorporated preferably at 1 to 10wt.% into the primer layer. The good visible image developability is obtd. 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, has a primer layer, a photosensitive layer, and a silicone rubber layer on a substrate, and has good development properties. This invention relates to a photosensitive lithographic printing plate that does not require dampening water and provides visible image quality.

[Prior art] Conventionally, in lithographic printing, it was necessary to perform printing by making use of the lipophilicity of the image area and the hydrophilicity of the non-image area, and by maintaining a delicate balance between water and ink, which required considerable skill. Needed.

In other words, in the conventional Ingiri method, which requires dampening water, an image-shaped lipophilic area is created 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 hydrophilic area which is a non-image area. During printing, water is first transferred to the non-image areas, and then ink is transferred. The ink does not adhere to the non-image area II where water is present, but only to the image area. However, with this method, it is difficult to control the delicate balance between dampening water and ink, which can cause emulsification of the ink, or the ink may mix with the dampening water, causing poor ink density and background stains, which is a major cause of paper waste. It had major problems such as:

Furthermore, the transfer of dampening water to the printing material causes a change in the dimensions of the printing material, which also 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, and in particular, lithographic printing plates that do not require dampening water and are made by coating a primer layer, a photosensitive layer, and a silicone rubber layer in this order on a substrate. The method of removing the silicone rubber layer in the image area and the underlying photosensitive layer by development makes it possible to develop the photosensitive layer with the aqueous developer by making it swellable or soluble in the aqueous developer. Compared to the conventional method of removing only the silicone rubber layer, this method has been adopted in recent years because it does not require the use of a developer containing an organic solvent as its main component and is advantageous in terms of working environment and safety.

Such photosensitive lithographic printing plates that do not require dampening water are disclosed in, for example, Japanese Patent Application Laid-open Nos. 61-275759, 63-280250, and 6
3-280251 etc.

[Problems to be Solved by the Invention] On the other hand, in planographic printing, plate inspection is usually performed after plate making and before printing to check tone reproducibility, fog, etc. Such plate inspection is usually carried out by staining the photosensitive layer or primer layer exposed by development with a staining solution.

However, in the photosensitive lithographic printing plate that does not require dampening water and is used in the method of removing the photosensitive layer as described above, the dyeability of the primer layer is insufficient, so that the developed visible image properties are insufficient.

For the purpose of improving the dyeing properties as mentioned above, JP-A-63-1
33153 and JP-A-1-172834 describe a method of using gelatin for the primer layer, but there are problems such as it takes time to harden the film and the pot life of the primer layer coating solution is extremely short. It was insufficient.

Accordingly, an object of the present invention is to provide a photosensitive lithographic printing plate that does not require dampening water and can obtain good developed visible image properties of a normal image.

Another object of the present invention is to provide a photosensitive lithographic printing plate that does not require dampening water and has a primer layer that exhibits good dyeability after development.

Furthermore, another object of the present invention is to provide a photosensitive lithographic printing plate that has a fast hardening speed and a long pot life of the primer HI coating solution that does not require dampening water.

[Means for Solving the Problems] In view of the above-mentioned problems, the present inventors have made extensive studies and found that the above-mentioned object of the present invention is to provide at least a primer layer on a substrate.
Dampening system I! having a photosensitive layer and a silicone rubber layer in this order! In the photosensitive lithographic printing plate, the primer layer comprises:
Applying a composition containing a small amount of (a) a compound having at least two structural units represented by the following general formula [I] and having no aromatic group, and (b) a photopolymerization initiator. The inventors have discovered that this can be achieved by providing a photosensitive lithographic printing plate that does not require dampening water and is characterized by a layer formed by photocuring after photocuring.

General Formula [1] (In the formula, R represents a hydrogen atom or a -(CH2)TICH3 group. However, n represents an integer of O to 8.) The present invention will be explained in more detail below.

The primer layer used in the photosensitive lithographic printing plate that does not require dampening water of the present invention is a compound having at least two structural units represented by the general formula [I] and having no aromatic group (hereinafter referred to as "the present invention"). This layer is formed by coating a composition containing a photopolymerization initiator and a photopolymerization initiator on a substrate, and then curing the composition with light.

Specifically, the compounds of the present invention include the following.

(However, R1 represents a hydrogen atom or Cn)-12n+1 group, and n is an integer of 1 to 9.

) (3) CH.

Hs (however, 2 is Cn represents an H2n group, n is 2~ It is an integer of 8.

) (5) ArcH2-CH, -〇+-CH, -CH, -A (n is an integer of 0 to 30, preferably O to 10) (n is an integer of O to 30, preferably O to 10) ( 7) A-fCH, CH2CH2CH2-○←CH, CH, C
H2CH, -A (n is an integer of O to 30, preferably O to 10) (8) A-(-R, -0SRIA (However, R3 represents CmH2ml, and the layer is an integer of 2 to 8. . n is an integer of O to 30, preferably O to 10.) (However, R4 represents a hydrogen atom or a CnH2n+1 group, and n is an integer of O to 30.) (11) CH2CH2A 1 (12) (14) OO A -C-+CH, 廿C-A (15) (16) HrBr A-CH, -C-CH, -A CH2 However, A is R1 -O-CH2-CH-CH, -0- C-CCH.

○H represents.

In the above specific examples, R1 in compounds (1) and <2) is preferably a hydrogen atom, a methyl group or an ethyl group. Also, compounds (9) and (10
R4 in ) is preferably a hydrogen atom.

The above compound of the present invention is preferably contained in the primer layer at 20%
It is contained in an amount of up to 95% by weight, more preferably in an amount of 30 to 70% by weight.

Moreover, the following can be cited as typical examples of photopolymerization initiators that can be used in the present invention.

(1) Benzophenone derivatives, such as benzophenone, Michler's ketone, xanthone, ammelone, etc. (2) Benzoin derivatives, such as benzoin, benzoin ethyl ether, etc. (3) Quinones, such as p-benzoquinone, β-naphthoquinone, β-methylanthraquinone (4) Sulfur compounds, such as dibenzyl disulfide,
-butyl disulfide, etc. (5) Azo or diazo compounds, such as 2-azo-bis-isobutyronitrile, 1-azo-bis-1-cyclohexanecarbonitrile, azobenzylethylaniline, Congo red, etc. (6) Halogen compounds, For example, carbon tetrabromide, silver bromide,
α-Chloromethylnaphthalene, trihalomethyl-s-
Triazine compounds, etc. (7) Peroxides, such as benzoyl peroxide, etc. (8)
In the present invention, the photopolymerization initiator such as uranyl salt, such as uranyl nitrate, is preferably present in the primer layer.
Contains ~10% by weight.

In the present invention, in addition to the above-mentioned essential components, the primer layer may include fillers such as titanium oxide or antihalation agents, coloring agents such as dyes and pigments, coating improvers, plasticizers, stabilizers, and oil sensitizers. It may also contain a curing agent, an additive that improves the adhesion between the support and the primer layer, and the like. It is also possible to use various conventionally known polymers, such as polyamide and polyurethane, which are usually used in primer layers.

Examples of antihalation agents include yellow pigments, yellow dyes, and UV absorbers, and these are preferably contained in the primer layer in an amount of 2 to 20% by weight.

Further, various known pigments are used as white pigments, and these are contained in the primer layer in an amount of 5 to 30111%.

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

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 adhesion of images, various additives having hydrophobic groups, such as p-octylphenol/formalin novolac resin, pt-butylphenol/formalin novolak resin, pt-butylphenol/benzaldehyde resin, are also used. Modified novolak resins such as rosin-modified novolak resins can be added and used.

As additives that improve the adhesion between the support and the primer layer, silane coupling agents, Arise titanate, etc. are preferably used, and these can be added, for example, from 1 to 1 in the primer layer.
Contains 20% by weight.

Examples of polymers used in the primer layer include polyester resins, vinyl chloride-vinyl acetate copolymers, acrylic resins, vinyl chloride resins, polyamide resins, polyvinyl butyral resins, epoxy resins, acrylate copolymers, and vinyl acetate copolymers. Examples include polymers, phenoxy resins, polyurethane resins, polycarbonate resins, polyacrylonitrile butadiene, and polyvinyl acetate.

Among these, preferred are polymers having alcoholic OH groups, such as copolymer resins of (meth)acrylic acid esters, such as 2-hydroxyethyl methacrylate. These polymers are preferably contained in the primer layer in an amount of 20 to 60% by weight.

The primer layer used in the present invention is photocured in order to improve the solvent resistance to the coating solvent of the photosensitive layer and the solvent of the developer.

A known crosslinking agent can be added to the primer layer used in the present invention as a component that accelerates curing. As such a crosslinking agent, for example, a polyvalent isocyanate compound, a diazo resin, a polyvalent epoxy compound, etc. are used.

Examples of the polyvalent incyanate compound include diphenylmethane-4,4'-diisocyanate, hexamethylene diincyanate, and Coronate E.

H.L. EH (manufactured by Nippon Polyurethane Kogyo Co., Ltd., a polyvalent isocyanate compound), and the like.

As the diazo resin, 4-diazodiphenylamine, sodium hexafluoride M salt-formaldehyde resin 3-methoxy-
Examples include mesitylene sulfonate salt of a condensate of diphenylamine-4-diazonium salt and 4,4'-bis-methoxymethyl-diphenyl ether.

Examples of the polyvalent epoxy compound include bisphenol epoxy resin, bisphenol F diglycidyl ether, novolac glycidyl ether, hexahydrophthalic acid glycidyl ether, triglycidyl isocyanurate, and the like.

Furthermore, the primer layer of the present invention contains two compounds other than the compound of the present invention.
It is preferable to add a compound having more than one polymerizable ethylenically unsaturated double bond.

Examples of such compounds include trimethylolpropane triacrylate-1-, tetramethylolmethane triacrylate, allyl acrylate, and 1°4-butanediol dimethacrylate. % by weight.

A composition containing the compound of the present invention and a photopolymerization initiator as described above is dissolved in a suitable organic solvent and coated on a support.
After drying, the primer layer of the present invention is formed by exposing and curing.

The above primer layer can be cured using a mercury lamp, xenon lamp,
Using a known light source such as natural light, the exposure amount is sufficient to cure the primer layer (usually, for example, 50 IJ/Ci' to 5 J/Ci').
This can be done by exposing to light within a range of Cf.

Further, it is desirable that the above-mentioned exposure be carried out at least before coating the photosensitive layer.

In the present invention, the thickness of the primer layer is 11Ω/df ~
It is preferably 200mg/df, more preferably 31fll/dv'' to 100S Q/d1'
It is.

In the present invention, a photosensitive layer is provided on the primer layer, but any photosensitive layer that can be used in the present invention can be used as long as its solubility in a developer changes before and after exposure. be.

Specifically, for example, 0-quinonediazide compound, 0-
Examples include a photo-insolubilizable photosensitive layer containing a nitrobenzyl carbinol ester compound and the like, a diazo compound, a photo-insolubilizable photosensitive layer containing a compound having an addition-polymerizable vinyl group, a photopolymerization initiator, and the like.

The above-mentioned O-quinonediazide compounds are compounds having at least one O-quinonediazide group, preferably an 0-benzoquinonediazide group or an O-naphtho-quinonediazide group, and include known compounds of various structures, such as G.I. Author: “Light Sensitive Systems” (
(John Wiley & Sams, Inc., 1965), pages 339 to 353.

For example, various hydroxyl compounds and benzoquinone-1
, 2-diazide sulfonic acid, naphthoquinone-1,2-diazide sulfonic acid, and the like. The hydroxyl compounds used include condensation resins of phenols such as phenol, cresol and pyrogallol and carbonyl group-containing compounds such as formaldehyde, benzaldehyde and acetone, particularly resins obtained by condensation in the presence of an acidic catalyst. Can be mentioned.

As the photosensitive layer containing a diazo compound, a photosensitive layer containing the following diazo resin is preferably used.

That is, as a diazo resin, for example, Photographic Science and Engineering (Pho
℃o, Sc+, Ena, ) Volume 17, Page 33 (
1973), the specifications of U.S. Patent No. 2.063.631, U.S. Patent No. 2,679.498, U.S. Pat. A diazo resin obtained by condensing a diazo compound with an active carbonyl compound (for example, formaldehyde, acetaldehyde, or benzaldehyde, etc.) in an acidic medium 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.

The counter anion of the diazo resin used in the present invention is
forming a stable salt with the diazo resin and containing the resin
Contains anions that are soluble in solvents.

These include organic carboxylic acids such as decanoic acid and benzoic acid;
Contains organic phosphoric acids such as phenyl phosphoric acid and sulnic acid,
Typical examples include methanesulfonic acid, chloroethanesulfonic acid, dodecanesulfonic acid, benzenesulfonic acid, toluenesulfone, mesitylenesulfonic acid and anthraquinonesulfonic acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, hydroquinone Aliphatic and aromatic sulfonic acids such as sulfonated 4-acetylbenzenesulfonic acid and dimethyl-5-sulfoisophthalate, 2.2', 4.4'-tetrahydroxybenzophenone, 1.2.3-trihydroxybenzophenone,
2. Hydroxyl group-containing aromatic compounds such as 2', 4-1-lyhydroxybenzophenone, halogenated Lewis acids such as hexafluorophosphoric acid and tetrafluoroboric acid, Cl1O+
, IO+ and other perhalogen acids, but are not limited thereto. The coupled product with β-naphthol was prepared using gel permeation chromatography (GP).
The weight average molecular weight measured in C) is 200 to 10,000
(in terms of styrene) is preferably in the range of 5 (t.

The range of 5,000 to 5,000 is more preferable. The proportion of such diazo resin in the photosensitive layer is 1 to 901! The amount is preferably 3% to 60% by weight, and more preferably 3 to 60% by weight.

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,
Esters of unsaturated carboxylic acids and aliphatic polyhydroxy compounds, esters of unsaturated carboxylic acids and aromatic polyhydroxy compounds, unsaturated carboxylic acids and polycarboxylic acids, and the aforementioned aliphatic polyhydroxy compounds, aromatic polyhydroxy Examples include esters obtained by an esterification reaction with a polyhydric hydroxy compound, and are specifically described in JP-A-59-71048 and the like.

In the present invention, all of the above-mentioned photosensitive layers can be used, but a photosensitive layer containing a diazo resin is preferred from the viewpoint of adhesion to the primer layer.

In addition to the above-mentioned materials, the photosensitive layer of the present invention may further contain dyes, pigments, known exposure-visible image agents, coating properties improvers, etc., to improve the visible imageability of the developable image and the exposure-visibility improvement agent. Visibility and coating properties can be improved.

The thickness of the photosensitive layer is 0, lll1g/df to 3omg/d1
2 is preferable, 0.5 mg/dot to 10 mQ/
d1' is more preferred.

In the present invention, a silicone rubber layer is further provided on the photosensitive layer, and the silicone rubber used in the silicone rubber layer is preferably linear or crosslinked organopolysiloxane. cough organoborishi 0
Xane has molecules ranging from 1 to 100,000 molecules,
At room temperature, it is suitably cross-linked in the form of a liquid, wax, or rice cake. The organopolysiloxanes are classified into integrated type and addition type depending on the crosslinking method.

In the integrated type, crosslinking is performed by a condensation reaction, and water, alcohol, organic acid, etc. are released by the reaction. Particularly useful integrated silicone rubbers include a mixture of a linear organopolysiloxane having one water group at both ends or a portion of the main chain and a silicone crosslinking agent, or one in which the hydroxyl groups are reacted with a silicone crosslinking agent. In both cases, adding a condensation catalyst is advantageous in terms of crosslinking speed.

The organopolysiloxane has the following repeating units in its main chain.

1 -(-3i-O+- 2 In the formula, R1 and R2 are alkyl, aryl, alkenyl, or a combination thereof, each of which may have a substituent such as a cyano group, a halogen atom, or a hydroxyl group, and a methyl group or a phenyl group. , a vinyl group, and a trifluorobyl group are preferred, and a methyl group is particularly preferred.

The silicone crosslinking agent is or -C)H (wherein R and R' are alkyl groups)
Examples include condensation type silicone crosslinking agents having a functional group represented by the following, so-called deacetic acid type, deoxime type, dealcoholized type, deamined type, and dehydrated type. Examples of such crosslinkers include tetraacetoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, phenyltriacetoxysilane, dimethyldiacetoxysilane, diethyldiacetoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane, dimethyl Dimethoxysilane, vinyltrimethoxysilane, methyltris (
acetone oxime) silane, methyltri(N-methyl,
Examples include N-acetylamino)silane, methyltri(methylethylketoxime)silane, methyltri(methylethylketoxime)silane, and oligomers thereof.

All of these crosslinking agents are organopolysiloxane 10
The amount is preferably in the range of 0.5 to 30 parts by weight relative to 0 parts by weight.

Examples of the condensation catalyst include organic carboxylic acids, titanate esters, naphthenic acids, and the like.

The addition type refers to one in which a hydroxyl group in a crosslinking agent is added to an unsaturated group in the main body, such as a vinyl group (-0H-CH2), resulting in crosslinking.

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

The organopolysiloxane 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 a condensed parentheses addition type organopolysiloxane having hydroxyl groups, unsaturated groups, etc. in one organopolysiloxane.

Among the commercially available silicone rubbers according to the present invention, preferred examples include KS705F and K manufactured by Shin-Etsu.
E-41, 42, 44, Toshiba Silnocone (manufactured) Y
E 5505. YF 3057, East Silicone (
SH-781, PRX-305, 8H-237, etc.)
37. KE-103, KE-106, KE-13001
Toshiba Silicone (manufactured) TSE-3032, RTU-8,
Examples include additive silicone rubber such as SH-9555 manufactured by Toshi Silicone Co., Ltd.

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 rvD or less.

In the present invention, the m 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 printing durability, printing stains, etc., so it is generally 3 WIQ. /df to 50 mg/dm' is preferred, and 5 Eg/di' to 30 J)/dv' is even more preferred.

In the present invention, an adhesive layer made of, for example, epoxy resin may be provided between the photosensitive layer and the silicone rubber layer, and the adhesive layer may contain various reactive crosslinking agents, silane coupling agents, etc. The thickness of the adhesive layer is 0.
1 mg/df to 5 mo/df is preferred.

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 a polypropylene film etc. described in Japanese Patent Publication No. 61-614, and the method of laminating a polypropylene film etc. A method of applying a high molecular weight polymer described in 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 printing durability, an aluminum plate is particularly preferable.

Particularly in the present invention, it is particularly preferable that the surface of the aluminum plate or aluminum foil is anodized and further treated with silicate. At that time, the silicic acid treatment, for example,
It is carried out by immersion in a sodium silicate aqueous solution with a concentration of 0.1 to 10% at a temperature of 30 to 95°C for 1 second to 2 minutes, and preferably then immersed in water at 40 to 95°C for 10 seconds to 2 minutes. It is processed. The thickness of the substrate is preferably 0.1 to 0.3111I.

In the present invention, the photosensitive lithographic printing plate prepared as described above is imagewise exposed, developed with a developer to dissolve the photosensitive layer, and removed together with the silicone rubber layer thereon, resulting in the primer layer forming an image area. Exposure and waterless lithography is formed.

In this case, it is preferable to dye the image area with an aqueous solution of a cationic dye such as crystal violet or Victoria blue BOH, or an aqueous solution containing an organic solvent during or after development.

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

The aqueous developer to which the dampening water-free photosensitive lithographic printing plate of the present invention is applied is a developer containing water as a main component, such as those described in JP-A-61-275759. 30% or more by weight of water, preferably 50% to 9% by weight
8% by weight, an organic solvent and a surfactant, and more preferably an alkali agent.

Organic solvents contained in water-based developers include:
For example, aliphatic hydrocarbons (hexane, heptane, "Isopar E, H, G" (trade name of aliphatic hydrocarbons manufactured by Esso Chemical Co., Ltd.), gasoline, kerosene, etc.), aromatic hydrocarbons (toluene, Xylene, etc.) or halogenated hydrocarbons (triclene, etc.) to which the following polar solvents are added are suitable.

Also, alcohols (methanol, ethanol, 1-butoxy-2-propanol, 3-methyl-3-methoxybutanol, benzyl alcohol, etc.), ethers (methyl cellosolve, ethyl cellosolve, butyl cellosolve,
Phenyl cellosolve, methylcarpitol, ethylcarpitol, butylcarpitol, 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,
diisobutylketone, 4-methyl-1,3-dioxolan-2-one, etc.), esters (ethyl acetate, propyl acetate, hexyl acetate, methyl butyrate, propyl butyrate, diethyl succinate, dibutyl oxalate, diethyl maleate, benzoic acid) benzyl, methyl cellosolve acetate, cellosolve acetate, carpitol acetate, etc.).

Examples of the surfactant contained in the developer of the present invention include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric ionic surfactants, and specific examples include the following.

Examples of anionic surfactants include (1) higher alcohol@acid esters (e.g. sodium salt of lauryl alcohol sulfate, ammonium salt of octyl alcohol sulfate, ammonium salt of lauryl alcohol sulfate, disodium alkyl sulfate, etc.), (2) Fatty alcohol phosphate ester salts (e.g.
(3) Alkylaryl sulfonates (e.g., sodium dodecylbenzenesulfonate, isopropylnaphthalenesulfonate sodium salt, dinaphthalenesulfonate sodium salt, metanitrobenzenesulfonate sodium salt, etc.) ), (4) alkylamide sulfonates,
(C+7H3sCON-CH2CH2SO3Na etc.)C
H3 (5) Sulfonic acid salts of dibasic aliphatic esters (e.g., dioctyl sodium sulfosuccinate, dihexyl sodium sulfosuccinate, etc.), (6) Formaldehyde condensates of alkylnaphthalene sulfonates (e.g., sodium dibutylnaphthalene sulfonate) formaldehyde condensates, etc.).

Examples of nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, oxyethylene oxybrobylene block polymer, etc. Can be mentioned.

Examples of the cationic surfactant include alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamines, and the like.

Examples of the zwitterionic surfactants include alkyl betaines and the like. Among these, anionic surfactants are suitable in the present invention.

These surfactants can be used alone or in combination of two or more.

The amount of surfactant used in the present invention is 0.013
Suitable amounts are from 1% to 60% by weight, preferably from 0.1% to 10% by weight.

Further, the surfactant used in the present invention is preferably used together with an alkaline agent, and the alkaline agents include (1) sodium silicate, potassium silicate, potassium hydroxide, sodium hydroxide, lithium hydroxide, or inorganic alkaline agents such as trisodium or ammonium phosphate, sodium metasilicate, sodium carbonate, ammonia, potassium metasilicate, (2) mono-, di- or trimethylamine, mono-, di- or triethylamine, mono- or diisopropylamine, n- Examples include organic amine compounds such as butylamine, mono-, di- or triethanolamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine, and the like.

Among them, sodium silicate, potassium silicate, lithium silicate, potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium metasilicate, potassium metasilicate, which can have a pH of 12 g or more when made into an aqueous solution.
Lithium metasilicate and the like are preferred.

The amount of alkaline agent used is 0.05% to 20% by weight,
Preferably, 0.2ii% to 10% by weight is appropriate.

Development can be carried out by various known methods, such as rubbing with a developing pad containing a developer as described above, or pouring a developer onto the printing plate and then rubbing with a developing 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 Examples.

Example 1 (Synthesis of diazo resin-1) p-diazodiphenylamine sulfate 14.547 (50
mmol) was dissolved in 40.9 g of concentrated sulfuric acid under water cooling.

1.35 g (45 mmol) of paraformaldehyde was slowly added to this reaction solution so that the reaction temperature did not exceed 10°C.

This reaction mixture was added dropwise to 500 d of ethanol under water cooling, and the resulting precipitate was filtered. After washing with ethanol, this precipitate was dissolved in 1001ρ pure water, and 6.81μ
A cold concentrated aqueous solution of zinc chloride in No. 11 was added. The resulting precipitate was filtered, washed with ethanol, and
It was dissolved in 0nQ 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 0.241 m was immersed in a 3% aqueous sodium hydroxide solution to degrease it, washed with water, and then immersed in a 32% aqueous sulfuric acid solution at a temperature of 30°C under the conditions of 5 A/df for 10
Anodized for 2 seconds, washed with water, immersed in a 2% sodium metasilicate aqueous solution for 37 seconds at a temperature of 85°C, and further heated to a temperature of 9.
It was immersed in water (1) H8, 5) at 0° C. for 25 seconds, washed with water, and dried to obtain an aluminum plate r.

A primer layer composition having the composition shown below was applied to an aluminum plate a, and after drying at 85° C. for 3 minutes, the entire surface was exposed to light of 1000 fflJ/Cf using a 3KW ultra-high pressure mercury lamp. It was further dried at 100° C. for 4 minutes to form a primer layer with a thickness of 0.8 μm.

(Primer layer composition) Aroma: Risu M-8060 Oligoester acrylate (manufactured by Toagosei ■ (polyfunctional monomer)) 30 parts Bunacol [I A-314 (manufactured by Nagase Kasei ■ (trifunctional monomer)) Kayamer P
M-2 (manufactured by Nippon Kayaku ■ (bifunctional monomer)) CH.

Rheodol TW○ 120 Polyoxyethylene sorbitan monooleate (Kao Kyoku Il! (surfactant)) 5 parts Kayacure D
ETX 2.4-Diethylthioxanthone (manufactured by Nippon Kayaku V7I (photopolymerization initiator)) 3 parts Kayacure EPA p-dimethylaminobenzoic acid ethyl ester (manufactured by Nippon Kayaku ■ (photopolymerization accelerator)) 3 parts Next, the above 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) Diazo resin - 150 parts Copolymer resin of 2-, droxyethyl methacrylate, N-(4-hydroxyphenyl) methacrylamide, methacrylic acid in a molar ratio of 45/45/10 - 150 parts Victoria Pure Blue BOH (dye manufactured by Hodugaya Kagaku ■) 1 part methyl cellosolve 900 parts Next, the following silicone rubber composition was added to the photosensitive layer at a dry weight of 1.81 parts.
11/f and dried at 90°C for 10 minutes.

(Silicone rubber layer composition) Dimethylpolysiloxane having hydroxyl groups at both ends (molecular weight 52,000) 100
1 part triacetoxymethylsilane 10 parts dibutyltin laurate 0.8 parts Isopar E
(manufactured by Esso Chemical) 900 parts Next, a single-sided matted polypropylene film having a thickness of 5 μm was laminated on the silicone rubber layer to obtain a photosensitive lithographic printing plate that did not require dampening water.

After a positive film was vacuum-sealed on the top surface of the above plate material, it was exposed to light using a metal halide lamp as a light source.

Next, after immersing it in the following developer solution-1 for 1 minute, the surface of the plate material is rubbed with a pad impregnated with the developer solution.
The silicone rubber layer and the photosensitive layer in the unexposed areas were removed, and a printing plate with well reproduced halftone dots was obtained.

Further, the image area of the above printing plate could be vividly dyed by applying a dyeing liquid having the composition shown below to a cloth, lightly rubbing the plate, and then washing with water.

The above printing plate was attached to a Heidelberg GTO printing machine, and 25,000 prints with good halftone dot reproducibility were obtained.

(Developer-1) Phenyl cellosolve 5.0 parts Jetanolamine 1.5 parts Bionin A
-44B 1.0 part (manufactured by n-butylnaphthalene sulfone MNa Takemoto Oil ■) Water
97.5 parts (staining solution) Tsurfit (manufactured by Kuraray Sobren Chemical ■, solvent) 20 parts Residor T W-0120 (manufactured by Kao ■, surfactant) 0.5 parts Benzyl alcohol 5.0 parts Victoria Pure Blue B OH1 , (1 part water
100 parts Comparative Example-1 A dampening water-free photosensitive lithographic printing plate material was obtained in the same manner as in Example-1 except that the primer layer composition of Example-1 was changed as follows.

(Comparative primer layer composition-1) Lipoxy 3p-1509 (manufactured by Showa Kobunshi Co., Ltd.).

Bisphenol A-based epoxy acrylate) 100 parts Trimethylolpropane triethoxy triacrylate 80 parts 2,4-diethylthioxanthone 1 part p-dimethylaminobenzoic acid ethyl ester 1 part Propylene glycol monomethyl ether 600 parts Then, exposed in the same manner as in Example 1 I then developed it.

Although development was possible, the stainability of the image area was insufficient and the visible image quality after development was insufficient.

Comparative Example-2 The primer layer composition of Example 1 was changed as follows,
A dampening water-free photosensitive lithographic printing plate material was obtained in the same manner as in Example 1, except that heat curing was performed at 120° C. for 5 minutes instead of exposure.

(Comparative Primer Layer Composition-2) Epikote 1001 (Bisphenol A-based epoxy resin manufactured by Shell Chemical Co., Ltd., epoxy current 450-500) 100 parts Methyltetrahydrophthalanhydride M36 parts 2.4.6-! −Squirrel (
dimethylaminomethyl)phenol
12 parts methyl cellosolve acetate
120 parts toluene 1
20 parts methyl ethyl ketone 120 parts Next, exposure and development were carried out in the same manner as in Example 1.

Development was possible, but the image area could not be dyed.

Example 2 A dampening water-free photosensitive lithographic printing plate material was obtained in the same manner as in Example 1 except that the primer layer composition was changed as follows.

(Primer layer composition) Aroma: Risu M -806030 parts Compound of the present invention CH2CH, -A 0 External c, N,,0 H 70 parts Kayamer PM-23 parts Rheodol TWo 120 388
Kayakure DETX 5 parts Kayakure EPA 3 parts Next, exposure and development were carried out in the same manner as in Example 1. Both development and dyeability were good.

Example 3 A dampening water-free photosensitive lithographic printing plate material was obtained in the same manner as in Example 1 except that the primer layer composition was changed as follows.

(Primer layer composition) Aroma: Risu M-806040 parts Bunacol DA-811 60 parts Kayamer PM-23 parts Rheodol TWO 1201 parts Kayacure DETX 5 parts Kayacure EPA 3 parts Next, it was exposed and developed in the same manner as in Example 1. I did it. 1! Both the image and stainability were good.

[Effects of the Invention] As described in detail above, the photosensitive lithographic printing plate that does not require dampening water of the present invention can provide good developed visible image properties.

Claims (1)

[Scope of Claims] A dampening water-free photosensitive lithographic printing plate having at least a primer layer, a photosensitive layer and a silicone rubber layer in this order on a substrate, wherein the primer layer has at least (a) the following general formula [I]. The layer is formed by applying a composition containing a compound having at least two of the structural units expressed and having no aromatic group, and (b) a photopolymerization initiator, and then photocuring the composition. A photosensitive lithographic printing plate that does not require dampening water. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R is a hydrogen atom or -(CH_2)_nCH_3
represents a group. However, n represents an integer from 0 to 8. )