JPH0490550A - Dampening waterless photosensitive planographic printing plate - Google Patents

Abstract

PURPOSE:To obtain the printing plate with which a stress relaxant function is sufficiently exhibited and which is not attained during printing and has excellent plate wear by incorporating an azide compd. and cyclized rubber into a primer layer. CONSTITUTION:The printing plate which substantially prevents the flawing of an ink repulsion layer surface at the time of handling of the printing plate, printing and developing of the plate material, is, therefore, not stained during printing, and has the excellent plate wear is obtd. by incorporating the azide compd. and cyclized rubber into the primer layer. The stress relevant function refers to the function that the primer layer relieves the stress to prevent the flawing of the ink repulsion layer even if the impact (stress) is applied on the ink repulsion layer in the case of the primer layer having rubber elasticity. As the azide compd. to be incorporated into the primer layer, 2, 6-dichloro-nitro azide benzene, etc., are used. The cyclized rubber to be used in combination with the diazide compd. includes the rubber formed by partially cyclizing natural rubber or polyisoprene rubber by the effect of an acidic catalyst, the rubber formed by partially cyclizing 1, 4-polybutadiene with a catalyst combined with an org. aluminum compd. and org. halogen compd., etc.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a photosensitive lithographic printing plate that does not require dampening water, and more specifically to a dampening solution that does not smudge during printing and has excellent printing durability. This invention relates to a photosensitive lithographic printing plate that does not require water.

[Background of the Invention] Conventionally, photosensitive lithographic printing plates (hereinafter referred to as "plate materials" as necessary) that do not require dampening water have been known to have a photosensitive layer and an ink repellent layer coated on a support in this order. It is being By exposing and developing this plate material, a lithographic printing plate (hereinafter referred to as "printing plate" as necessary) that does not require dampening water can be obtained.

Generally, in such plate materials, a primer layer is provided between the support and the photosensitive layer in order to improve the adhesion between them.

Various materials are used for the primer layer, but
As an example, JP-A No. 60-229031 describes a photosensitive lithographic printing plate that does not require dampening water and uses a primer layer formed by photocuring a layer made of a photodimerizable photocurable resin. This indicates that the silicone rubber layer has excellent scratch resistance and abrasion resistance, and the resulting waterless plate has high printing durability.

Furthermore, this primer layer has the advantage of good scratch resistance, particularly the resistance to scratches on the surface of the silicone rubber layer due to impact.

However, the primer layer used in this waterless plate has the advantage of good scratch resistance, especially the resistance to scratches on the surface of the silicone rubber layer by i-blows, and has excellent stiffness resistance. However, because the stress relaxation function of this primer layer is insufficient, the resistance to scratches, such as those caused by brushes during development or plate cleaning cloth during printing, is not necessarily sufficient, and in the end, the scratches caused by the latter are the cause of the problem. Since stains occur during printing and the printing durability decreases, it is necessary to be very careful when handling them.

Therefore, in view of the above-mentioned problems, the present inventors conducted various studies from the viewpoint of stress relaxation function, and as a result, by using an azide compound and a cyclized rubber together in the primer layer,
It has been discovered that effects equivalent to or superior to those disclosed in the above-mentioned documents can be obtained, and the present invention has now been completed.

[Purpose of the Invention] Accordingly, an object of the present invention is to provide a photosensitive lithographic printing plate that fully exhibits a stress relaxation function, is free from stains during printing, has excellent stiffness resistance, and does not require dampening water. .

[Structure of the Invention] The object of the present invention is to provide a photosensitive lithographic printing plate that does not require dampening water and has a primer layer, a photosensitive layer, and an ink repellent layer in this order on a substrate, wherein the primer layer is made of an azide compound and a cyclized rubber. This was achieved with a photosensitive lithographic printing plate that does not require dampening water and is characterized by containing.

Below, the configuration of the present invention will be explained in more detail.

The present invention contains an azide compound and a cyclized rubber in the primer layer of a photosensitive lithographic printing plate that does not require water, so that the surface of the ink repellent layer is less likely to be scratched when handling the printing plate, printing, developing the plate material, etc. , so there are no smudges when printing,
A product with excellent printing durability can be obtained.

The stress relaxation function described in this specification means that when the primer layer has rubber elasticity, even if an impact (stress) is applied to the ink repellent layer, the primer layer relieves the stress and the ink repellent layer is not scratched. It means that it is difficult to attach.

If the photosensitive layer coating solvent is resistant, when the photosensitive layer is coated on the primer layer, the coating solvent for the photosensitive layer will not dissolve the primer layer, and mixing between the photosensitive layer and the primer layer will not occur, so stress will be reduced. Has a relaxing function.

The water-free photosensitive lithographic printing plate used in the present invention can also be used in a type in which only the silicone rubber layer in the image area is removed after development, but preferably the photosensitive layer in the image area is removed after development. A type that can be removed to expose the primer layer in the image area is preferable.

The method for producing the plate material used in the present invention requires that after photocuring a primer layer provided on a support, a photosensitive layer and an ink repellent layer are sequentially applied.

Examples of the primer layer used in the present invention include polyester resin, vinyl chloride-vinyl acetate copolymer, acrylic resin, vinyl chloride resin, polyamide resin, polyvinyl butyral resin, epoxy resin, acrylate copolymer, and vinyl acetate copolymer. Polymers, phenoxy resins, polyurethane, tan resins, polycarbonate resins, polyacrylonitrile butadiene, polyvinyl acetate and the like can be mentioned.

In addition, as the anchor agent constituting the primer layer,
For example, silane coupling agents, silicone primers, etc. can be used, and organic titanates and the like are also effective.

The thickness of the above primer layer is usually 0.1μ■~20μ
m, preferably 0.3 μm to 10 μm.

The azide compounds contained in the primer layer used in the present invention include (1) 2,6-dichloro-4-nitro-azidobenzene rl) azido diphenylamine (7) 4' nitrophenylazobenzene-azido 3'-dimethoxy- 4,4'-Diazidiphenyl 1-azidopyrene (4) 4' 1methoxy 4-azidodiphenyladiphenyln (5) 4,4'-Diazidiphenylamine (10) 4
．． 4'-Diazidophenylazonaphthalene 4'-Diazidodiphenylmethane p-phenylenebisazide p-azidobenzophenone 2゜6-di(4'-azidobenzal) -4-methylcyclohexane (13) 4.4'-diazidobenzophenone 3 In the present invention, the cyclized rubber used in combination with the diazide compound is natural rubber or boly(14)4,4'-diazidostilpentubrene rubber partially cyclized by the action of an acidic catalyst. Examples include those in which 4-polybutadiene is partially cyclized into -(15)4,4'-diazide chalcone using a catalyst containing a combination of an organoaluminum compound and an organohalogen compound.

In the present invention, Dial added to the primer layer The amount of azide compound and cyclized rubber added is 2゜ 6-G (4' (1-azidobenzal) For compounds, 0.1 Parts by weight ~ 3 0 parts by weight cyclohexane The amount is preferably 2 parts by weight to 20 parts by weight.

Further, the amount of cyclized rubber added to the primer layer used in the present invention is 70 parts by weight to 99 parts by weight, preferably 80 parts by weight to 95 parts by weight.

Examples of the photosensitive layer that can be used in the present invention include, in the case of a positive type, a photopolymerizable adhesive layer or a photocrosslinkable photosensitive layer, a photosensitive layer made of a diazo resin, a binder resin, and the like. In the case of a negative type, a photosensitive layer made of a quinonediazide compound, a binder resin, etc. can be used.

Various conventionally known diazo resins can be used as the above-mentioned diazo resin, but include diazo resins typified by condensates of aromatic diazonium salts and active carbonyl-containing compounds, especially formaldehyde, among which diazo resins soluble in organic solvents are used. Resins are preferred.

Preferred specific examples of the diazo resin include resins represented by the following formula [1].

- Formula [1] [In the formula, R12, R13R14 are each a hydrogen atom,
It represents an alkyl group or an alkoxy group, preferably a hydrogen atom. RI5 represents a hydrogen atom, an alkyl group or a phenyl group, preferably a hydrogen atom. X represents the counter anion of the diazo resin, specifically, PFa, B
F4. Represents organic carboxylic acids such as decanoic acid and benzoic acid, organic phosphoric acids such as phenylphosphoric acid, and sulfonic acids such as methanesulfonic acid. Y represents NH, S, 0. Furthermore, 2 is at least one or more selected from a sulfonic acid group, a sulfonate (Na salt, K salt, etc.) group, a sulfine group, a sulfinate group (Na salt, K salt, etc.), an OH group, and a COOH group. The ratio of Ill and n, which represents a phenyl group or a naphthyl group substituted with a substituent, is m/n in molar ratio.
-110 to 10, preferably I10 to 2. ] The diazo resin represented by the above-mentioned formula [II] preferably has a molecular weight of about 500 to 10,000.

The content of the diazo resin in the photosensitive layer is preferably from 1 to 0.
It is selected from the range of 3% to 60% by weight, more preferably 3% to 60% by weight.

Orthoquinonediazide compounds are used in negative-working photosensitive lithographic printing plates that do not require dampening water. Examples of such compounds include polycondensation resins of phenols and aldehydes or ketones and the following formula [II] or general formula III. Examples include orthoquinonediazide sulfonic acid esters or carboxylic acid esters obtained by chemically condensing orthoquinonediazide sulfonic acid or carboxylic acid derivatives represented by the following.

General formula [I summer] - Numerical formula [III] (wherein, X is a group represented by -5OzY or -coy, and Y
represents a group that can be removed during condensation of a halogen atom, alkali metal, etc. ) Specific examples of the compound represented by the above formula [11] include 1,2-benzoquinonediazide (2)-4-sulfonyl chloride, 1,2-benzoquinonediazide (2)-4
-carbonyl chloride, 1°2-benzoquinonediazide (2)-5-sulfonyl chloride, 1,2-benzoquinonediazide (2)-5-carbonyl chloride, and the like.

Specific examples of the compound represented by the above formula [Ill] include 1,2-naphthoquinonediazide (2) -4-sulfonyl chloride, 1,2-naphthoquinonediazide (2)
)-4-carbonyl chloride, 12-naphthoquinonediazide (2)-5-sulfonyl chloride, 1,2-naphthoquinonediazide (2)-5-carbonyl chloride, and the like.

Examples of polycondensation resins of phenols and aldehydes or ketones include polycondensates of pyrogallol and acetone as described in Japanese Patent Publication No. 43-28403, and polycondensates of pyrogallol and acetone as described in Japanese Patent Publication No. 55-76346. As described in Irugoto, a polycondensate of a mixture of pyrogallol and resorcin and acetone, as described in Japanese Patent Publication No. 45-9610, phenol formaldehyde novolak resin or metacresol formaldehyde novolac resin, Japanese Patent Publication No. 50-5083 Para-substituted phenol/formalin resins (e.g. para-cresol/formalin resin, para-t-butylphenol/formalin resin, para-ethylphenol/formalin resin, para-propylphenol/formalin resin, para-isopropylphenol/formalin resin) , para-n-butylphenol/formalin resin, para-octylphenol/formalin resin, etc.), Special Publication 1986
Phenol containing a phenol substituted with an alkyl group or a phenyl group having 3 to 12 carbon atoms and phenol or its methyl substituted product or a mixture thereof in a molar ratio of 1:9 to 9:1, as described in Publication No. -60407. Polycondensates of formaldehyde and formaldehyde mixtures (for example, polycondensates of the para-substituted phenol and phenol, vala-cresol, metacresol, etc.) can be mentioned.

The esterification rate of the orthoquinone diazide group to the hydroxyl group of the polycondensation resin of phenols and aldehydes or ketones is preferably 15 to 100 mol%, and 20 to 80 mol%.
Mol% is more preferred.

Furthermore, as an orthoquinonediazide compound, orthonaphthoquinone cyanosulfonic acid ester of polyhydroxybenzophenone (for example, 1,2-naphthoquinonediazide (
2)-5-sulfonic acid ester, 1,2-naphthoquinonediazide (2)-4-sulfonic acid ester, etc.).

This polyhydroxybenzophenone is a compound formed by replacing two or more hydrogen atoms of benzophenone with hydroxyl groups, such as dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, octahydroxybenzophenone, or a derivative thereof (for example, Examples include substituents for halogen atoms, alkyl groups, aryl groups, aralkyl groups, and carboxylic acid groups. Preferred are trihydroxybenzophenone or tetrahydroxybenzophenone, and more preferred are 2°3.4-1-lyhydroxybenzophenone and 23.4.4'-tetrahydroxybenzophenone.

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

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

Among these orthoquinone diazide compounds listed above, 1 of 2,3,4-)-dihydroxybenzophenone
．． 2-naphthoquinonediazide (2)-5-sulfonic acid ester or 1,2-naphthoquinonediazide (2)-4
- Sulfonic acid ester, 1,2-naphthoquinonediazide (2)-5-sulfonic acid ester or 1,2-naphthoquinonediazide (2)-4-sulfonic acid ester of metacresol formaldehyde novolak resin, or a mixture thereof. More preferably used.

The proportion of the above-mentioned orthoquinonediazide compound in the photosensitive layer is preferably 5 to 60% by weight, more preferably 20 to 60% by weight.
It is 50% by weight.

Further, examples of binder resins used in the photosensitive layer include acrylic resins and novolak resins. As a copolymerizable component of the acrylic resin, any monomer that can be copolymerized can be used. In particular, as a monomer for radical polymerization, the following compounds having an unsaturated bond can be used.

(1) Monomers having hydroxyl groups: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxypentyl (meth)acrylate, 4-hydroxyphenyl (meth)acrylate, 2-hydroxyphenyl ( (Meth)acrylate monomers such as meth)acrylate: N-methylol(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, N-(hydroxyphenyl)-(meth)acrylamide, N-(hydroxynaphthyl)-(meth) ) (meth)acrylamide monomers such as acrylamide; 0-1m-5p-hydroxystyrene monomers, etc. (2) (meth)acrylic acid ester or amide monomers other than (1): methyl (meth)acrylate, ethyl ( meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate
Alkyl (meth)acrylates such as acrylate; N
-phenyl (meth)acrylamide, 吋, m-1p-methoxyphenyl (meth)acrylamide, o-, m-,
p-nitoxyphenyl (meth)acrylamide, etc. (3) Monomers having a cyano group in the side chain; (meth)acrylonidonitrile, 2-pentenitrile, 2-methyl-3-butenenitrile, 2-cyanoethyl acrylate, o-, m-, p-cyanostyrene, etc. (4) Chimers having carboxylic acid in the side chain: (meth)
(5) Vinyl ethers: propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether, etc. (6) Styrenes.

α-methylstyrene, methylstyrene, chloromethylstyrene, styrene, etc. (7) Vinyl ketones: methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, etc. (8) Monomers other than (1) to (7): ethylene , propylene, isobutylene, butadiene, olefins such as vinyl chloride, N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, etc.; Good to have.

In the present invention, in addition to the above-mentioned materials, the photosensitive layer may also include dyes, pigments, coating properties improvers, plasticizers, sensitizers, stabilizers, etc. A curing agent etc. can be added. It is advantageous for the photosensitive layer of the positive type photosensitive lithographic printing plate that does not require dampening water to further contain a known exposure-visible image coloring agent.

Examples of the above dyes include Victoria Pure Blue BOH, Oil Blue #603. Oil pink #312
, patent pure blue, crystal violet, leuco crystal violet, brilliant green,
Ethyl violet, methyl green, erythrosin B
1 Heisic Tsuksin, malachite green, leucomalachite green, m-cresol purple, cresol red, xylenol blue Rhodamine B1 auramine, 4-p-diethylaminophenylimino naphthoquinone, cyano-p-diethylaminophenyl acetanilide, etc. Examples include phenylmethane-based, diphenylmethane-based, oxazine-based, xanthine-based, iminonaphthoquinone-based, azomethine-based, and anthraquinone-based dyes.

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

Examples of the coating property improver include alkyl ethers (eg, ethyl cellulose, methyl cellulose), fluorine-based surfactants, nonionic surfactants (eg, Pluronic L64 (manufactured by Asahi Denka)), and the like.

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. .

The amount of these additives added varies depending on the purpose of use, but is generally 0.01% to 30% by weight based on the total solid content.
Weight percent is preferred.

The thickness of the photosensitive layer used in the present invention is usually 0.2 to 100.
μm, preferably 0.5 to 20 μm.

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

The polyorganosiloxane 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 polyorganosiloxane is 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 mixtures of linear polyorganosiloxanes having hydroxyl groups, acetoxy groups, etc. at both ends or in a part of the main chain, and silicone crosslinking agents;
Examples include those in which hydroxyl groups are reacted with a silicone crosslinking agent, and in any case, adding a condensation catalyst is advantageous in terms of crosslinking speed.

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

(Si-0+ In the formula, R+ and R2 are an alkyl group, an aryl group, an alkenyl group, each of which may have a substituent, or a combination thereof, and preferably a methyl group, a phenyl group, a vinyl group, or a trifluoropropyl group. , particularly a methyl group.

The above-mentioned silicone crosslinking agents include the so-called acetic acid-removal type, oxime-removal type, alcohol-removal type, and deamine-removal type, which have a functional group represented by -〇H (in the formula, R and R' are alkyl groups). and dehydrated type silicone crosslinking agents. Examples of such crosslinkers include tetraacetoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, phenyltriacetoxysilane, dimethyldiacetoxysilane, diethyldiacetoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane, dimethyl Dimethoxysilane, vinyltrimethoxysilane, methyltris(acetoneoxime)silane, methyltri(N-methyl-N-
Examples include acetylamino)silane, vinyltri(methylethylketoxime)silane, methyltri(methylethylketoxime)silane, and oligolimers thereof.

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

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

The addition type refers to an unsaturated group in the main body, such as a vinyl group (-C
It refers to something that is crosslinked by adding a water-based group in a crosslinking agent to H=CH,).

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

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

In the silicone rubber layer of the present invention, either or both of condensation type and addition type silicone rubber can be used.

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

In the present invention, an adhesive layer made of acrylic resin or the like may be provided between the photosensitive layer and the silicone layer, and the adhesive layer may also contain various reactive crosslinking agents, silane coupling agents, etc. , and the thickness of the adhesive layer is 0.1 m.
g/dm' to 5 mg/dm2 is preferred.

As the substrate that can be 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 layer structure. Examples include papers such as coated paper, metal plates such as aluminum plates, and plastic films such as polyethylene terephthalate.

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

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

Such surface treatment includes, for example, a method of treating the surface of an aluminum plate with silicate (U.S. Pat. No. 2,714).
, 066), a method of treatment with organic acid salts (U.S. Patent No. 2
, 714,066), methods of treatment with phosphonic acids and their conductors (U.S. Pat. No. 3,220,832)
, a method of treatment with potassium hexafluorozirconate (
(U.S. Pat. No. 2,946,683), a method of anodizing, and a method of treating with an aqueous solution of an alkali metal silicate after anodizing (U.S. Pat. No. 3,181,461).

Such a support is provided with a primer layer and then a photosensitive layer in order to obtain sufficient adhesion between the photosensitive layer and the support.

The thickness of each layer constituting the plate material of the present invention is as follows. That is, the support has a thickness of 50 to 400 μm, preferably 100 μm.
~300μm Photosensitive layer: 0.05~10μm, preferably 0.1~1.0μm, silicone rubber layer: 0.5~10μm
It is 100 μm, preferably 1 to 4 μm. The primer layer has a thickness of 0.1 to 20 μm, preferably 0.3 to 10 μm.

In the present invention, a protective layer may be provided on the upper surface of the silicone rubber layer, if necessary.

The plate material of the present invention that does not require dampening water is manufactured, for example, as follows.

A composition solution to form a primer layer is applied onto a support using a conventional coater such as a reverse roll coater, an air knife coater, a Meyer bar coater, or a rotary coating device such as a Whaler, and is dried and crosslinked to cure. Next, a composition solution to form a photosensitive layer is applied and dried.

A silicone rubber solution is applied on the photosensitive layer in the same manner, and then heat-treated at a temperature of usually 100 to 20°C for several minutes.
Fully cure to form a silicone rubber layer. If necessary, a protective film can be provided on the silicone rubber layer using a laminator.

Next, a method for manufacturing a printing plate that does not require dampening water using the plate material that does not require dampening water of the present invention will be explained.

A positive film, which is the manuscript, is vacuum-adhered to the surface of the positive plate material and exposed. As a light source for this exposure, a mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, etc., which generate abundant ultraviolet rays, are used.

Next, the positive film is peeled off and developed using a developer. As the developer, any known developer can be used for plate materials that do not require dampening water, but preferably an aqueous developer is used.

The aqueous developer is a developer containing water as a main component, such as those described in Japanese Patent Laid-Open No. 61-275759, etc., which contain water in an amount of 30% by weight or more, preferably 50% by weight to 9% by weight.
Examples include a developer containing 8% by weight of 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" (manufactured by Esso Chemical Co., Ltd., product name of aliphatic hydrocarbons), gasoline, kerosene, etc.), aromatic hydrocarbons (toluene, xylene, etc.) ), or halogenated hydrocarbons (triclene, etc.), alcohols (methanol, ethanol, 1-butoxy-2-propatol, 3-methyl-3-methoxybutanol, β-anilinoethanol, benzyl alcohol, etc.) , ethers (methyl cellosolve, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, methyl calpitol, ethyl calpitol, butyl calpitol,
dioxane, diethylene glycol dimethyl ether,
Diethylene glycol diethyl ether, diethylene glycol dibutyl ether, ethylene glycol dibutyl ether, propylene glycol, dipropylene glycol butyl ether, tripropylene glycol methyl ether, polypropylene glycol methyl ether, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, 4- methyl-1,3-dioxolan-2-one, etc.), esters (
ethyl acetate, propyl acetate, hexyl acetate, methyl acetate, propyl acetate, diethyl succinate, dibutyl oxalate, diethyl maleate, benzyl benzoate, methyl cellosolve acetate, cellosolve acetate, carpitol acetate, etc.).

As the surfactant added to the developer of the present invention, anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric ionic surfactants are used, and specific examples include the following.

Examples of anionic surfactants include (1) higher alcohol sulfate esters (e.g. sodium salt of lauryl alcohol sulfate, ammonium salt of octyl alcohol sulfate, ammonium salt of lauryl alcohol sulfate, dibasic sodium alkyl sulfate, etc.) (2) ) Aliphatic alcohol phosphate ester salts (e.g.
(3) Alkylaryl sulfonates such as sodium dodecylbenzenesulfonate, isopropylnaphthalenesulfonate sodium salt, dinaphthalenesulfonate sodium salt, metanitrobenzenesulfonate sodium salt, etc.) 4) Alkylamide sulfonates (5) Sulfonates of dibasic aliphatic esters (e.g., sodium sulfosuccinate dioctyl ester, sodium sulfosuccinate dihexyl ester, etc.) (6) Formaldehyde condensates of alkylnaphthalenesulfonates (e.g., (formaldehyde condensate of sodium dibutylnaphthalene sulfonate, etc.).

Examples of nonionic surfactants include polyoxyerylene alkyl ether, polyocoxyethylene alkylphenol ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, oxyethylene oxypropylene block polymer, etc. .

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

Examples of amphoteric surfactants include alkyl betaines, but among these, anionic surfactants are commonly used.

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

The appropriate amount of the surfactant used in the present invention is 0.01% to 60% by weight, preferably 0.1% to 10% by weight.

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, (2) mono, di or trimethylamine, mono, di or triethylamine, mono or diisopropylamine, n-butylamine, mono, Examples include organic amine compounds such as di- or triethanolamine, mono-, di- or toso-isopropanolamine, ethyleneimine, and ethylenediimine.

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

It is also possible to dye the image area simultaneously with development by adding a dye such as crystal violet or astrazonelet to the developer.

Development can be carried out, for example, by rubbing a developing solution as described above with a developing vat, or by pouring the developing solution onto the printing plate and then rubbing it with a developing brush.

By the above development, a printing plate is obtained in which the photosensitive layer and silicone rubber in the unexposed areas are removed, or a printing plate in which the silicone rubber layer is removed and the photosensitive layer is exposed, and the silicone rubber layer remains in the exposed areas. .

Example-1 [Synthesis of Diazo Resin-1] 14.5 g (50 mmol) of p-diazodiphenylamine sulfate was dissolved in 40.9 g of concentrated sulfuric acid under ice cooling. To this reaction solution, 1.35 g (45 mmol) of rose formaldehyde was slowly added so that the reaction temperature did not exceed 10 tons.

This reaction mixture was added dropwise to 5001 ethanol under ice cooling, and the resulting precipitate was filtered. After washing with ethanol, this precipitate was dissolved in 100 ml of pure water, and 6.8
A concentrated aqueous solution containing g of zinc chloride was added.

The resulting precipitate was filtered, washed with ethanol, and dissolved in 150 mu of pure water. To this liquid was added a concentrated aqueous solution containing 8 g of ammonium hexafluorophosphate dissolved therein. The resulting precipitate was collected by filtration, washed with water, and then dried to obtain diazo resin-1.

[Synthesis of Azide Compound-1] 36 g of 4-azidobenzaldehyde and 40 g of 4-azidoacetophenone were dissolved in 400 mI2 of ethanol, and 40 al of 25% aqueous sodium hydroxide solution was added dropwise with stirring.

After stirring this solution at room temperature for 1 hour, the resulting yellow crystalline substance was collected by filtration, washed with alcohol, and dried. The yield was 64g.

[Synthesis of Cyclized Rubber-1] Catalytic amounts of tin chloride and acetic acid trichloride were added to a toluene solution of 1.4-polybutadiene, and the mixture was reacted at 40° C. for 60 minutes to obtain a cyclized rubber.

Production of Aluminum Plate A An aluminum plate with a thickness of 0.24 mm was immersed in a 3% aqueous sodium hydroxide solution, washed with water, and then anodized in a 32% aqueous sulfuric acid solution at a temperature of 30°C and a condition of 5 A/dm' for 10 seconds. , washed with water, immersed in a 2% sodium metasilicate aqueous solution at a temperature of 85°C for 37 seconds, and further heated to a temperature of 90°C.
The aluminum plate was immersed in water (pH 8.5) for 25 seconds, washed with water, and dried to obtain an aluminum plate a.

A primer layer composition having the following composition was applied to an aluminum plate a, and after drying at 85° C. for 3 minutes, front exposure was performed at 10,100 O/cm 2 using a 3 KW ultra-high pressure mercury lamp.

Further, it was dried at 100° C. for 4 minutes to form a primer layer with a thickness of 1 μm.

[Primer layer composition Coresite compound - 10.5 parts by weight Cyclized rubber - 110 parts by weight Methyl cellosolve acetate: Xylene (1.1)
100 parts by weight Next, a photosensitive composition having the composition shown below was coated on the primer layer, and 2 parts by weight was applied at 100°C.
It was dried for a minute to form a photosensitive layer with a thickness of 0.3 μm.

(Photosensitive composition) (1) Diazo resin - 150 parts (2) 2-hydroxyethyl methacrylate, N(4-
(hydroxyphenyl) methacrylamide and methacrylic acid in a molar ratio of 40157/3 copolymer resin - 150 parts (3) Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.
(4) Methyl cellosolve 900 parts The following silicone rubber composition was coated on the photosensitive layer at a dry weight of 1.8 g/m 2 and dried at 90° C. for 10 minutes.

(Silicone rubber layer composition) (1) Dimethylpolysiloxane having hydroxyl groups at both ends (molecular weight 82,000) 100 parts (2) Triacetoxymethylsilane 10 parts (3) Dibutyltin laurate 0.8 part (4) Isopar E (manufactured by Esso Chemical) 900 parts Next, a 5 μm thick polypropylene film was laminated on the silicone rubber layer to obtain a waterless planographic plate.

After a positive film was vacuum-adhered to the upper 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-1 for 1 minute, the surface of the plate material is rubbed with a pad impregnated with the developer.
The silicone rubber layer and photosensitive layer in the unexposed areas are removed, and
A printing plate was obtained in which halftone dots of % to 98% were well reproduced.

This waterless plate was also mounted on a Heidelberg GTO printing machine with the water supply device removed, and black ink (manufactured by Toyo Ink, TOYOKING ULTRA TU)
70,000 sheets of clean prints were obtained when printed with K Aquares G).

[Developer] β-anilinoethanol 0.5 parts Bepropylene glycol 1.0 parts p-ter
t-Butylbenzoic acid 1.0 part Potassium hydroxide 10 parts Polyoxyethylene lauryl ether 0.1 part Potassium sulfite
2.0 parts potassium metasilicate
3.0 parts water
91 parts Comparative Example-1 A lithographic printing plate material requiring no dampening water was obtained in the same manner as in Example-1, except that the primer layer composition of Example-1 was changed as follows.

(Primer layer composition) Photosensitive unsaturated polyester obtained by 1=1 polycondensation of p-phenylene diarylic acid ester and 1,4-dihydroxyethyloxycyclohexane 10 parts by weight 1-methyl-2-hendiylmethylene-β- Naphthothiazoline 0.6 parts by weight KB
M-603 (manufactured by Shin-Etsu Chemical Co., Ltd., silane coupling agent,
N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane) 0.5 parts by weight Methyl cellosolve acetate 150 parts by weight Toluene
150 parts by weight of methyl cellosolve 150 parts by weight This primer layer composition was coated and then cured by heating at 120° C. for 5 minutes.

Next, development was performed using the above developer.

When printing was performed in the same manner as in Example 1, stains occurred in the non-image area after 50,000 sheets.

Example-2 [Synthesis of azide compound-2 100mj! Dissolve 16.1 g of 4-azidobenzaldehyde and 5.5 g of cyclohexane in methanol,
While stirring, 5 mR of a 25% aqueous sodium chloride solution was added dropwise.

After stirring this solution at room temperature for 4 hours, the resulting yellow crystalline substance was collected by filtration, washed with alcohol, and dried. The yield was 8.8 g.

[Synthesis of Cyclized Rubber-1] Catalytic amounts of aluminum chloride and acetic acid trichloride were added to a toluene solution of 1,4-polybutadiene, and the mixture was reacted at 40° C. for 20 minutes to obtain a cyclized rubber.

A lithographic printing plate material requiring no dampening water was obtained in the same manner as in Example-1, except that the primer layer composition of Example-1 was changed as follows.

(Primer layer composition) Azide compound - 20.5 parts by weight Cyclized rubber - 210 parts by weight Toluene 100 parts by weight When developed in the same manner as in Example 1, the silicone rubber layer and photosensitive layer in the unexposed areas were removed. A printing plate in which halftone dots of 2% to 98% were well reproduced was obtained.

Further, when printing was carried out in the same manner as in Example 1, 75,000 sheets of prints without stains were obtained.

[Effects of the Invention] In the present invention, by containing an azide compound and a cyclized rubber in the primer layer, a printing plate with high stiffness resistance and an excellent printing plate without staining during printing can be obtained.

Claims (1)

[Claims] A dampening water-free photosensitive lithographic printing plate having a primer layer, a photosensitive layer, and an ink repellent layer in this order on a substrate, wherein the primer layer contains an azide compound and a cyclized rubber. photosensitive lithographic printing plate.