JPH04113895A - Photosensitive lithographic printing plate without requirement for wetting water - Google Patents

Abstract

PURPOSE:To improve smoothness on the surface of an obtained primer layer by providing the primer layer consisting of a coating liquid containing at least, a polymer containing a hydroxyl and a nonionic surfactant. CONSTITUTION:A polymer containing a hydroxyl is such as ester or amide polyacrylate containing a hydroxyl. However, a polymer containing alcoholic hydroxyl is recommended from a viewpoint of dyeing and adhesion properties. The recommended monomer having an alcoholic hydroxyl is such as 2- hydroxyethyl(meth)acrylate. The blending ratio of the polymer containing a hydroxyl for the primer layer is 40 to 97wt.%. The blending ratio of diazo resin in the primer layer is preferably 3 to 80wt.%. A nonionic surfactant is essential as an applicability improver. The recommended nonionic surfactant is such as polyethylene glycol and polyoxyethylene alkylether, although a variety of known chemicals are used.

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 hydrophilic area which is a non-image area. 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 the dampening water and the ink, which can cause emulsification of the ink, or the ink may mix with the dampening water, causing poor ink density and background smudges, which can lead to major problems such as wasted paper. had.

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"). A waterless planographic plate having a structure in which a silicone layer is provided on a photosensitive layer on a body is disclosed, and a plate making method in which the photosensitive layer is further dissolved in a developer to remove the upper silicone rubber layer to form an image area. 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 photopeeling.

In the waterless plate as described above, a primer layer is provided between the support and the photosensitive layer.

The primer layer brings the support and photosensitive layer into close contact with each other, and especially in the case of a method in which the photosensitive layer is dissolved in a developer, the primer layer is exposed, resulting in poor ink receptivity and dyeability (image area and image area after development). Coloring of printed areas to distinguish non-printed areas) must be excellent.

An example of a primer layer that satisfies these conditions is a primer layer in which a layer made of a diazo resin and a hydroxyl group-containing polymer is photocured.

In addition to the above-mentioned components, the primer layer may also contain fillers such as titanium oxide and zinc oxide, yellow pigments to prevent rations, and silane camping agents to improve adhesion. be.

In order to coat the primer layer on the support, these are dispersed and melted in a suitable solvent and coated. Examples of the solvent used include methyl cellosolve, lactic acid alkyl ester, and cyclohexanone.

[Problem to be solved by the invention]

However, even with these coating property improvers, there are still problems in the dispersibility of titanium oxide and the like. In such cases, the surface of the primer layer obtained has lost smoothness due to agglomeration of the filler, and in severe cases, the photosensitive layer coated on the primer layer,
The particles become larger than the thickness of the silicone layer, causing the silicone layer to be missing and resulting in dotted stains on printed matter, causing inconvenience.

In view of the above problems, the present inventors conducted intensive research and found that the primer layer contains at least a hydroxyl group-containing polymer and a nonionic surfactant as a coating property improver, and more preferably, a lactic acid alkyl ester is used as a coating solvent. The present invention was achieved by discovering that this can be achieved by providing a primer layer coated with a liquid. In other words, the purpose of the present invention is to provide better dispersibility of fillers such as titanium oxide and zinc oxide than conventional coating properties improvers during production, and to provide excellent surface smoothness of the resulting primer layer without the need for dampening water. It is an object of the present invention to provide a photosensitive lithographic printing plate, and further to provide a photosensitive lithographic printing plate that improves the smoothness of the surface of the brimer layer, is less prone to scumming, and does not require dampening water. The object of the present invention is to provide a coating comprising at least a primer layer, a photosensitive layer, and a silicone rubber layer in this order from the substrate side on a substrate, the primer layer containing at least a hydroxyl group-containing polymer and a nonionic surfactant. This can be easily achieved using a photosensitive lithographic printing plate that does not require dampening water and is characterized in that a primer layer is provided by applying a liquid.

The present invention will be explained in more detail below.

In the present invention, the primer layer is cured before coating the photosensitive layer, but either heat curing or photo curing is possible.

Examples of thermosetting resins include epoxy resins and urethane resins disclosed in Japanese Patent Publication No. 61-54219.

As the photocurable type, a combination of a hydroxyl group-containing polymer and a diazo resin as shown in Japanese Patent Application No. 1-104287 is preferably used.

Examples of the hydroxyl group-containing polymer in the present invention include esters or amides of hydroxyl group-containing polyacrylic acid, polyvinyl alcohol derivatives, epoxy resins, novolac resins, gelatin, cellulose, etc.; is preferably used.

Examples of hexamers having an alcoholic hydroxyl group include 2-hydroxyethyl (meth)acrylate (hereinafter, both acrylic and methacrylic compounds are collectively referred to as (meth)acrylic, etc.) ), N-
Examples include (4-hydroxyethylphenyl)(meth)acrylamide, hydroxy-methyldiacetone (meth)acrylamide, and the like.

Monomers copolymerizable with the above-mentioned hydroxyl group-containing monomers include (1) aromatic hydroxyl group-containing monomers such as N(4-
hydroxyphenyl)(meth)acrylamide, 0-1
α, β of m-1p-hydroxystyrene, 0-1m-2p-hydroxyphenyl-(meth)acrylate, (2) (meth)acrylic acid, maleic anhydride, etc.
-Unsaturated carboxylic acid, (3) methyl (meth)acrylate, ethyl (ruta)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate , cyclohexyl (meth)acrylate,
(meth)octyl acrylate, (meth)acrylic acid-2
- (Substituted) alkyl (meth)acrylates such as chloroethyl, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate, N-dimethylaminoethyl (meth)acrylate, (4 ) (meth)acrylamide, N-methylol (meth)acrylamide, N-ethyl (meth)acrylamide, N-hexyl (meth)acrylamide, N-cyclohexyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N-phenyl (meth)acrylamide, N-nitrophenyl (meth)acrylamide,
(meth)acrylamides such as N-ethyl-N-phenyl (meth)acrylamide; (5) vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether; , (5) H,,Z) L, Vinyl esters such as 7cetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate, (7) Styrene, styrene such as α-methylstyrene, methylstyrene, chloromethylstyrene, etc. Class, (8)
Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl getone, (9) Olefins such as ethylene, propylene, isobutylene, butadiene, isoprene, 00) N-vinylpyrrolidone, N-vinylcarbazole, 4 -vinylpyridine, (meth)acrylonitrile, etc. Particularly preferred are the above groups (1) to (3).

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 GPC method is preferably 5,000 to 1,000,000 (in terms of styrene). If the value is lower than 5,000, it may be damaged by the coating solvent or developer of the photosensitive layer even after photocuring, and 1
If the value is larger than 000000, it is difficult to select a coating solvent.

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

Examples of the diazo resin used in the present invention include those described in Photographic Science and Engineering (Photo, Sci, Eng), Volume 17, Page 33 (1973L U.S. Patent No. 2,063,631,
Diazo compounds and active carbonyl compounds (e.g. formaldehyde, acetaldehyde, or henzaldehyde, etc.) in an acidic medium such as sulfuric acid, phosphoric acid, hydrochloric acid, etc. Diazo resin obtained by condensing diazo compounds and diphenyl ether derivatives whose manufacturing method is described in Japanese Patent Publication No. 49-4001 A diazo resin obtained by a condensation reaction between the above and the like can be used.

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, henzenesulfonic acid, toluenesulfonic acid, mesitylenesulfonic acid and anthraquinonesulfonic acid, 2-hydroxy-4-methoxyhensiphenone-5-sulfone. acid, hydroquinone sulfonic acid, 4-acetylhenzenesulfonic acid, dimethyl-5
=Aliphatic and aromatic sulfonic acids such as sulfoisophthalate, 2.2',4.4'-tetrahydroxybenzophenone, 1,2.3-)lihydroxybenzophenone, 2.2',4-)ri Hydroxyl group-containing aromatic compounds such as hydroxybenzophenone, halogenated Lewis acids such as hexafluorophosphoric acid and tetrafluoroboric acid, ClO4,
Examples include, but are not limited to, perhalogen acids such as IO4. The coupled product with β-naphthol was prepared using gel permeation chromatography ((1,
The weight average molecular weight measured by PC) is 200 to 10,000.
(Styrene equivalent) is preferably in the range of 500 to 500
A range of 0 is more preferable.

In the present invention, the proportion of the diazo resin in the primer layer is preferably 3 to 80% by weight, more preferably 5 to 60% by weight.

In the present invention, a nonionic surfactant is contained as an essential component as a coating property improver.

Although various known nonionic surfactants can be used, surfactants having at least one of the following structural units CII) and [I) can be particularly preferably used.

Structural unit [I[) -(-CI(2CH20+V-) Structural unit CLI CH3 -(-CH, CHO±" (In each formula, n represents an integer from 2 to 5000.) In particular, structural unit (n) and (I Compounds in which n is an integer within the range of 2 to 5,000 and have a boiling point of 240°C or higher are preferred, and more preferably, n is 2 to 5.
The compound is an integer within the range of 00 and has a boiling point of 280°C or higher, most preferably n is 3 to 100.
is a compound that is an integer within the range of .

Examples of such compounds include: ・Polyethylene glycol (HO+CHzCHzOtirH) ・Polyoxyethylene alkyl ether (RO(CH2
CH2O), lfl ・Polyoxyethylene polystyrylphenyl ether ・Polyoxyethylene-polyoxybrobylene glycol ・Polyoxyethylene-polyoxypropylene alkyl ether ・Polyoxyethylene alkylphenyl ether ・Ethylene oxide derivative of alkylphenol formalin condensate ・Polyoxyethylene polyhydric alcohol fatty acid partial esters include, for example, polyoxyethylene fatty acid ester (for example, RCOO (CH2CH2O), H), polyoxyethylene alkylamine, and polyoxyethylene phosphate ester.

Specific examples of the above-mentioned compounds include the following. That is, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether,
Polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene higher alcohol ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, poly Oxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitol tetraoleate, polyethylene glycol monolaurate, polyethylene glycol monostearate , polyethylene glycol monooleate, polyethylene glycol distearate, polyoxyethylene nonylphenyl ether formaldehyde condensate, oxyethylene oxypropylene brochloride copolymer, tetraethylene glycol, polyethylene glycol, and the like.

The proportion of the nonionic surfactant in the photogenic composition is preferably 0.05 to 20% by weight, more preferably 0.1 to 10% by weight based on the total composition. .

In the present invention, in addition to the above components, the primer layer is optionally filled with titanium oxide, etc., or colored with antihalation agents, dyes, pigments, etc., plasticizers, silane coupling agents, and sensitizers as adhesive properties. 10% by weight of fattening agent, etc.
It may be included as long as it does not exceed.

It is also possible to use in combination various conventionally known polymers, such as polyamide and polyurethane, which are usually used in primer layers.

Examples of dyes that can be included in the primer layer include Victoria Pure Blue BOH, Oil Blue #
6031, oil pink #312, patent pure blue, crystal violet, leuco crystal violet, brilliant green, ethyl violet,
Methyl green, erythrosin B1 basic tsuksin, malachite green, leucomalachite green, m
- Triphenylmethane type, diphenylmethane type, oxazine type, xanthine type, represented by resol purple, cresol red, xylenol blue, rhodamine B1 auramine, 4-p-diethylaminophenylimino naphthoquinone, cyano-p-diethylaminophenylacetanilide, etc. Examples include iminonaphthoquinone-based, azomethine-based, and anthraquinone-based dyes.

Inorganic fillers such as aluminum oxide, zinc oxide, titanium oxide, barium sulfate, and silica are used as fillers.

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. .

Further, as an adhesion improver, a known silane coupling agent such as γ-methacryloxypropyltrimethoxysilane can be added and used.

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, JJLpt7' thylphenol benzaldehyde resin, rosin-modified novolak, etc. Modified novolak resins such as resins, and 0-naphthoquinonediazide sulfonic acid esters (OHM esterification rate of 20 to 70 mol %) of these modified novolak resins can be added.

The primer composition is dispersed in a suitable organic solvent using a known dispersion method (SGI, homogenizer, etc.) and then filtered.

As the organic solvent, generally known ones such as cellosolve, lactic acid alkyl ester, cyclohexanone, or those containing these as main components can be used. More preferred among these are solvents containing lactic acid alkyl ester as a main component, and lactic acid alkyl ester is particularly preferred. The reason for this is that lactic acid alkyl ester has the best dispersibility, diazo has the highest solubility, and is also excellent in terms of safety. In addition, in the case of a solvent, the main component refers to the component with the largest amount among the constituent components of the solvent.

The primer layer of the present invention is formed by applying the dispersion onto a support, drying it, and then thermally or photocuring it. Heat curing is done at high temperatures of 100℃ to 300℃.
It is carried out within a range of 0 seconds to 30 minutes.

For photocuring, a known light source such as a mercury lamp, xenon lamp, or natural light is used, and the amount of exposure (
Usually, for example, 50 mJ/cj ~ 5 J/Cl1l
This can be done by exposing to light within a range of

Further, it is desirable that the above-mentioned curing be performed at least before the coating of the photosensitive layer is completed.

In the present invention, the thickness of the primer layer is lr! Ig/d
tm” to 200 ■/dm t,
More preferably, it is 3 .mu./da+2 to 100 .mu./dm".

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, O-
Examples include a commercially solubilized photosensitive layer containing a nitrobenzyl carbinol ester compound and the like, a photoinsolubilizable photosensitive layer containing a diazo compound, a compound having an addition polymerizable vinyl group, and the like.

The above-mentioned 0-quinonediazide compounds are compounds having at least one 0-quinonediazide group, preferably 0-benzoquinonediazide group or 0-naphthoquinonediazide group, and include known compounds of various structures, such as ``Light'' by Jay Kosar. Sensitivity Systems” (Published by Gitan, Willey & Sams, 1965) No. 3
Compounds described in detail on pages 39 to 353 are included. For example, various hydroxyl compounds and henzquinone-1,2-diazide sulfonic acid, naphthoquinone-1
, 2-diazide sulfonic acid and the like. Examples of the hydroxyl compound used include condensation resins of phenols such as phenol, cresol and pyrogallol, and carbonyl-based compounds such as formaldehyde, henzaldehyde and acetone, particularly resins obtained by condensation in the presence of an acidic catalyst. It will be done.

As a photosensitive layer containing a diazo compound, Japanese Patent Application No. 1-104
Diazo resin shown in 286 and having water M group (meth)
A photosensitive layer containing an acrylic ester or amide-containing polymer as an essential component is preferred.

The proportion of the diazo resin in the photosensitive layer is preferably 1 to 90% by weight, 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 more under normal pressure and having two or more polymerizable terminal ethylene groups, such as unsaturated carboxylic acids, unsaturated carboxylic acids, and fatty acids. esters with group polyhydroxy compounds, esters between unsaturated carbonic acids and aromatic polyhydroxy compounds, 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 with compounds, 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 in terms of adhesion to the primer layer.

Furthermore, 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 property improvers, etc. to improve the visible imageability of development and exposure. Visibility and coating properties can be improved.

Further, in the present invention, it is preferable that the photosensitive layer contains a hydroxyl group-containing polymer. As such a hydroxyl group-containing polymer, the same polymers as those used in the primer layer described above can be used.

The film thickness of the photosensitive layer is preferably 0.1 μ/dm” to 30 μ/dm2, and 0.5 mg/dm2 to I0111 g/dm.
d+w2 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 layer is preferably a linear or somewhat crosslinked organopolysiloxane. The organopolysiloxane usually has a molecular weight of 100,000 to several hundred thousand, and is suitably crosslinked in the form of a liquid, wax, or cake at room temperature. The organopolysiloxanes are classified into condensed type and addition type depending on the method of crosslinking.

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

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

-(S i -0) In the formula, R 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, a hydroxyl group, and a methyl group, a phenyl group, A vinyl group and a trifluoropropyl group are preferred, and a methyl group is particularly preferred.

As the silicone crosslinking agent, 10 COCHff.

(In the formula, R and R' are alkyl groups) Condensation type silicone crosslinking agents such as the so-called acetic acid-removed type, oxime-eliminated type, primary alcohol type, deamined type, and dehydrated type are listed. It will be done. Examples of such crosslinkers include tetraacetoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, phenyltriacetoxysilane, dimethyldiacetoxysilane, diethyldiacetoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane, dimethyl dimethoxysilane,
Examples include vinyltrimethoxysilane, methyltris(acetoneoxime)silane, methyltri(N-methyl, N-acetylamino)silane, vinyltri(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 cyphtyltin dilaurate, dibutyltin acetate, dibutyltin maleate, and the like.

The addition type refers to an unsaturated group in the main body, such as a vinyl group (-C
H=CHz), which is crosslinked by the addition of a hydrogen group in a crosslinking agent.

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

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

Present invention (D-thin) For the D-thin rubber layer, it is possible to use either or both of a condensation type silicone rubber and an addition type silicone rubber.

It is also possible to use condensed and addition type organopolysiloxanes having hydroxyl groups, unsaturated groups, etc. in one organopolysiloxane.

Among the commercial products available as the silicone rubber according to the present invention, a preferable example is "KS-705F" manufactured by Shin-Etsu.
”, “KE-41”, “KE-42”KE-44
”, Toshiba Silicone ■ “YE-5505” °, ° “YF
3057", east silicone■"'SH~781"
Condensation type silicone rubber such as “PRX-305” and “SH-237” and “KS-837” manufactured by Shin-Etsu ■, °
“KE-103°°,”KE106”°, “KE-1
300”, Toshiba Silicone■ “TSE-3032”
Examples include addition type silicone rubbers such as "RTU-B" and Toshi Silicone ■'5H-9555".

Further, for the purpose of improving the strength of silicone rubber, an inorganic filler such as silica, titanium oxide, or 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 nm 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 printing durability, printing stains, etc., so generally 31 g / dra" to 50*/da" is preferable, and 5■/d-! ~30 .mu./dIlz is preferred.

Further, in the waterless planographic plate of the present invention, a protective layer may be provided on the thin cone 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. 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 able to pass through 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, 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 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 aliphatic hydrocarbons (hexane, heptane, "Isopar E,"
H,G” (trade name of MW aliphatic hydrocarbons made by Esso) or gasoline, kerosene, etc.), aromatic hydrocarbons (toluene, xylene, etc.) or halogenated hydrocarbons (triclene, etc.). It was added accordingly.

h Blood bath soot Alcohols (methanol, ethanol, water, etc.) Ethers (methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl calpitol, ethyl carpitol, butyl carpitol, dioxane, etc.) Ketones (acetone, methyl ethyl ketone, etc.) Esters (ethyl acetate, methyl cellosolve acetate, cellosolve acetate, carpitol acetate, etc.) Development can be done, for example, by rubbing it with a developer pad containing a developer like the one above, or by pouring the developer onto the plate and then rubbing it with a developer brush. , can be carried out by various known methods.

[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 unless the gist thereof is exceeded.

(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 in this reaction solution
．． Og of paraformaldehyde 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 cooled with water for 500 min.
IIN was added dropwise to ethanol, and the resulting precipitate was filtered.

After washing with ethanol, remove this precipitate for 100 years! of pure water, and to this solution was added a cold concentrated aqueous solution containing 6.8 g of zinc chloride. The resulting precipitate was filtered, washed with ethanol, and dissolved in 150+ liters of pure water. To this liquid was added a cold concentrated aqueous solution in which 8 g of ammonium hexafluorophosphate was dissolved. The resulting precipitate was collected by filtration, washed with water, and then dried at 30° C. for a day and night to obtain diazo resin 1.

The styrene-equivalent weight average molecular weight (Mw
) was 1500, and the number average molecular weight was 500.

(Examples 1, 2, & Comparative Example 1) The following primer layer composition was coated at 40"C using a whirler on a chemical conversion treated aluminum substrate (manufactured by Mitsubishi Aluminum) with an ff of 0.24 mm, and then heated at 85°C. The dry film thickness of the primer layer formed by drying for 3 minutes was 60 .mu./dva".

The primer layer composition was dispersed using a high-pressure bulb homogenizer. Parts used below are parts by weight unless otherwise specified.

(Primer layer composition) (1) Diazo resin - 18 parts (4) Zinc oxide Sakai Chemical Co., Ltd. fine zinc white 60 parts (5) “K
ET-YELLOW 402” (Dainippon Ink Chemical (
Yellow pigment) 12 parts (6) Various nonionic surfactants (see Table 1) (7) Methyl lactate 9
After applying 00 parts and drying, apply 40 (1+) with a metal halide lamp.
J/cm, and dried at 120°C for 5 minutes.

Next, a photosensitive composition having the composition shown below was coated on the primer layer and dried at 80° C. for 2 minutes to form a photosensitive layer having a thickness of 0° and 3 μm.

(Photosensitive composition) (1) Diazo resin - 170 parts (3) "Victoria Pure Blue B OH" (dye manufactured by Odugaya Kagaku ■) 1 part (4) Methyl cellosolve 900 parts Then, the following silicone rubber was applied on the photosensitive layer. The composition was applied to a thickness of 2.0 g/m'' and dried at 90°C for 10 minutes.

(Silicone rubber layer composition) (2) The following reactive silane compound OCJi, Si (OMe) 3 (3) 0.8 parts of dibutyltin dilaurate (4) 900 parts of Isopar E (manufactured by Esso Chemical) Next, the above silicone rubber A single-sided matted polypropylene film having a thickness of 6 μm was laminated on the layer to obtain a waterless planographic plate.

After vacuum-adhering a positive film to the top surface of the above plate material, a metal halide lamp was used as a light source and a 400aJ
/cm" exposure.Next, after performing standard development by immersing it in developer-1 below for 1 minute, the unexposed portions of the silicone rubber layer were rubbed by rubbing the surface of the plate material with a pad impregnated with the developer. The photosensitive layer was removed to obtain a printing plate.

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.

(Developer-1) β-anilinoethanol 0.5 parts Propylene glycol 1. O part p -tert
-Butylbenzoic acid 1.0 part Potassium hydroxide
1.0 part polyoxyethylene lauryl ether 0.1 part potassium sulfite
2.0 parts potassium metasilicate 3.
0 parts water
91 parts (staining solution) “Tsurfit” (manufactured by Kuraray Sobren Chemical ■ Solvent) 20 parts Benzyl alcohol 5.0 parts “Victoria Pure Blue BOH” 1.0 part water
The results for 100 copies are shown in Table 1.
It can be seen that the flatness is excellent when the nonionic surfactant is contained in an amount of 8 parts or more.

*Sanyo Chemical Co., Ltd. "Nonipol °°: Polyethylene glycol phosphate ester type" Ioned: Polyethylene glycol fatty acid ester type Book ratio Glossiness...Measured using a Horiba gloss meter The higher the glossiness, the higher the glossiness. Good dispersibility and good dispersibility.Main stains...With "Heidel GTO" (manufactured by Heidel) with the dampening water supply device removed, "manufactured by Toyo Ink ■"
2.0 using “Aquares Five Sumi TFM Ink”
00 sheets were printed and the occurrence of scumming was observed.

〔Effect of the invention〕

As described above in detail, the present invention makes it possible to provide a photosensitive lithographic printing plate that has good smoothness and does not require dampening water and is therefore less prone to scumming in non-image areas.

Claims (1)

[Claims] (1) At least a primer layer on the substrate from the substrate side,
A dampening water-free photosensitive material comprising a photosensitive layer and a silicone rubber layer in this order, and the primer layer is provided by applying a coating liquid containing at least a hydroxyl group-containing polymer and a nonionic surfactant. lithographic printing plate