JPH0493840A - Dampening waterless photosensitive planographic printing plate - Google Patents

Abstract

PURPOSE:To obtain the printing plate having an excellent color proof property by incorporating a high-polymer compd. contg. a quaternary nitrogen atom or quaternary phosphorus atom into a primer layer. CONSTITUTION:This printing plate is provided with the primer layer, a photosensitive layer and an ink repulsion layer in this order on a substrate. This dampening waterless planographic printing plate contains the high-polymer compd. having the quaternary nitrogen atom or quaternary phosphorus atom in its primer layer. While the dampening waterless planographic printing plate of the type that only the silicone rubber layer of image parts are removed after development is used, the type that the photosensitive layer of the image parts is removed after the development and the primer layer of the image parts is exposed is more preferable. A so-called cationic high-polymer electrolyte is usable as the high-polymer compd. having the quaternary nitrogen atom or quaternary phosphorus atom to be incorporated into the primer layer. The printing plate having the good color proof property is obtd. in this way.

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 relates to a photosensitive planographic printing plate that does not require dampening water and has good plate inspection properties. Concerning lithographic printing plates.

[Background of the Invention] Conventionally, photosensitive lithographic printing plates that do not require dampening water (hereinafter referred to as "plate materials" as necessary) have been prepared by coating a support with a photosensitive layer and an ink-repellent layer in that order. Are known. By exposing and developing this plate material, a lithographic printing plate that does not require dampening water (hereinafter referred to as "printing plate" as necessary) 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.

For such plate materials, it is necessary to check the state of the plate during or after development, and therefore it must have excellent plate inspection properties.

Conventionally, the primer layer has been dyed in order to improve plate inspection properties, and various materials have been used for the primer layer.
Publication No. 133153 describes a method for dyeing the hardened gelatin in the brimer layer in a photosensitive lithographic printing plate that does not require dampening water, but this method has good dyeability because gelatin is dyed. However, since the staining spreads not only to the image area but also to the non-image area around the image area,
There is a problem that a clear stained image cannot be obtained and therefore plate inspection performance is poor.

Therefore, as a result of various studies with the above-mentioned plate inspection properties in mind, the inventors of the present invention have developed a staining solution by incorporating a polymer compound having a quaternary nitrogen atom or a quaternary phosphorus atom in the primer layer. It has been discovered that the dye can be prevented from diffusing into non-image areas, and clear stained images with good stainability can be obtained, and the present invention has thus been completed.

[Object of the Invention] Therefore, an object of the present invention is to provide a photosensitive lithographic printing plate that has good plate inspection properties 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. This is achieved by a photosensitive lithographic printing plate that does not require dampening water and is characterized by containing a polymer compound having a quaternary phosphorus atom.

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

In the present invention, by containing a polymer compound having a quaternary nitrogen atom or a quaternary phosphorus atom in the primer layer of a photosensitive lithographic printing plate that does not require water, it can be dyed well and has good plate inspection properties (quantity). It has the excellent effect of making it possible to make it look like it is being used.

The photosensitive lithographic printing plate that does not require water to be used in the present invention may also be used for a type in which only the silicone comb layer in the image area is removed after development, or preferably, after development, the photosensitive layer in the image area is removed. It is best to use a type that exposes the primer layer in the image area without removing it.

As the polymer compound having a quaternary nitrogen atom or a quaternary phosphorus atom contained in the primer layer, M, F
, 1(oover; J, Macromole, Sci-
So-called cationic polymer electrolytes, such as those described in Chem A-4, 1327 (1970), can be used.

This quaternary nitrogen atom or quaternary phosphorus atom may be present in the polymer compound or in a side chain. A typical example of a compound containing a quaternary nitrogen atom in the main chain is the general formula [1
] There are some containing an ionene type monomer unit represented by the formula [I].

General formula [II+] [where xlil is an anion; On the other hand, examples of monomer units containing a quaternary phosphorus atom in the main chain include those containing 1,000 units of loxyalkyl ammonium, and those having the general formula [II] \R [where x lit is an anion, R is an alkyl group]. ,
An example of a compound represented by the general formula [rV] and containing a quaternary phosphorus atom in the side chain is the general formula [IV] [where xo anion, R, R': alkyl group] There is something expressed as

[In the formula, xlil, anion, R: an alkyl group, n: a positive number] Vinylbenzylammo represented by the general formula [II+] and the following blanks General formula [V] C113 +C1h-C) y, "\ 11R [In the formula . It is preferred to form a copolymer with.Such copolymer units include alkyl acids, methacrylic acids and their esters, styrene, alkylenes, ethers, vinyl acetate, acrylonitrile, and the like.

Particularly useful in the present invention are U.S. Pat.
Compounds described in JP-A No. 9,690, JP-A-55-22766, and similar compounds thereof can be mentioned. However, the content of quaternary nitrogen atom-containing monomer units in these copolymers does not necessarily have to be within the range disclosed in these patent specifications and publications, but rather may be lower than the content described therein. On the contrary, it gives a favorable result.

The amount of the polymer compound having a quaternary nitrogen atom or a quaternary phosphorus atom is 0.1% to 30% by weight, preferably 0.5% to 2% by weight based on the total amount of the primer layer.
It is 0% by weight.

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. Examples include polymers, phenoxy resins, polyurethane resins, polycarbonate resins, polyacrylonitrile butadiene, polyvinyl acetate, and the like.

Preferred examples include acrylic resin, polyester resin, and urethane resin. These resins are preferably used in the form of being cured by heat or light.

For example, when an acrylic resin containing a hydroxyl group and/or a carboxyl group is cured by heat, a melamine resin, diisocyanates, etc. can be used as a crosslinking agent. In addition, when photocuring, diazo resin or the like can be used.

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 primer layer is usually 0.1 to 20 μm, preferably 0.3 to 10 μm.

An example of the dyeing solution used in the present invention is one obtained by dissolving or dispersing basic dyes, acid dyes, and disperse dyes that have the property of dyeing in a particularly polar organic solvent such as water or alcohols. do. Among these, a staining solution using an acid dye is preferred.

Carboxylic acids, amines,
It is also effective to add surfactants and other dyeing aids.

It can be used in the present invention. Examples of the photosensitive layer include, in the case of a positive type, a photopolymerizable adhesive layer, 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 quinone diazide 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 general formula [I].

General Formula [1] [In the formula, R12, 13, and R14 each represent a hydrogen atom, an alkyl group, or an alkoxy group, and are preferably a hydrogen atom. R+5 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, PF6
．． BF, organic carboxylic acids such as decanoic acid and benzoic acid,
Represents organic phosphoric acids such as phenylphosphoric acid and sulfonic acids such as methanesulfonic acid. Y represents NH, S, and O. Furthermore, 2 has a sulfonic acid group, a sulfonate (Na salt,
K salt, etc.) group, sulfine group, sulfinate salt (Na salt,
represents a phenyl group or a naphthyl group substituted with at least one substituent selected from K salt, etc.) group, OH group, and C○OH group. The ratio of m and n is m/n in molar ratio.
-110 to 10, preferably 110 to 2. ] Preferably, the diazo resin represented by the above general formula [I] has a molecular weight of about 500 to about 500 to ooo.

The content of diazo resin in the photosensitive layer is preferably 1 to 70
It is selected from a range of 3% to 60% by weight, more preferably 3% to 60% by weight.

In a negative-working photosensitive lithographic printing plate that does not require dampening water, an orthoquinone cyacyto compound is used, for example, a polycondensation resin of phenols and aldehydes or ketones and the following general formula [11] or General formula [I
Examples include orthoquinonediazide sulfonic acid esters or carboxylic acid esters obtained by chemically condensing orthoquinonediazide sulfonic acid or carbonic acid salt conductors represented by the following formula.

General formula [Ill General formula [Illco (wherein, X is a group represented by -3O2Y 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 general formula [11] include 1,2-benzoquinone diazide 1-(2)-4-sulfonyl chloride, 1,2-benzoquinone diazide (2)-
Examples thereof include 4-carbonyl chloride, 1°2-benzoquinonediazide (2)-5-sulfonyl chloride, and 1,2-benzoquinonediazide (2)-5-carbonyl chloride.

Specific examples of the compound represented by the above general formula [Ill] include 1,2-naphthoquinone siacit(2)-4-sulfonyl chloride, 1,2-naphthoquinonediazide(2)
)-4-carbonyl chloride, 1,2-naphthoquinone cyasito (2)-5-sulfonyl chloride, 1,2-naphthoquinone diazide (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 mixture of pyrogallol and resorcinol and acetone, a phenol/formaldehyde/novolac resin, or a meta-cresol/formaldehyde/novolac resin, as described in Japanese Patent Publication No. 45-9610, or a meta-cresol/formaldehyde/novolac resin, as described in Japanese Patent Publication No. 1983-5083. Para-substituted phenol/formalin resins (for example, para-cresol/formalin resin, para-t-butylphenol/formalin resin, para-ethylphenol/formalin resin, para-propylphenol/polmarin resin, para-isopropylphenol/formalin resin) listed in the Formalin resin, roselobylphenol formalin resin, paraoctylphenol formalin resin, etc.), Special Publication 1986
Phenol containing a phenol substituted with an alkyl group or 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. Examples include polycondensed metals of a mixture of the above and formaldehyde (for example, polycondensates of the para-substituted phenol and phenol, para-cresol, metacresol, etc.).

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

Furthermore, as an orthoquinone cyacyto compound, orthonaphthoquinonediazide sulfonic acid ester of polyhydroxybenzophenone (for example, 1,2-naphthoquinone siacite (
2)-5-sulfonic acid ester, 1,2-naphthoquinonediazide (2)-4-sulfonic acid ester, etc.).

This polyhydroxybenzophenone is a compound obtained by replacing two or more hydrogen atoms of benzophenone with hydroxyl groups, such as dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, octahydroxyhensiphenone, or a derivative thereof. , (for example, substituents for halogen atoms, alkyl groups, aryl groups, aralkyl groups, and carboxylic acid groups). Preferred are trihydroxyhensiphenone or tetrahydroxybenzophenone, and more preferred are 2°3.4-1-dihydroxybenzophenone 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, 1,3,4-trihydroxybenzophenone
2-naphthoquinonediazide (2)-5-sulfonic acid ester or 1,2-naphthoquinonediazide (2)-4-
Sulfonic acid ester, 1,2-naphthoquinone diazide of metacresol formaldehyde novolac resin (
2)-5-sulfonic acid ester, 1,2-naphthoquinone cyacyto(2)-4-sulfonic acid ester, or a mixture thereof is 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 copolymerization component of acrylic resin, there are several copolymerizable components.
All can be used, especially submers for radical polymerization.
As the compound, the following compounds having an unsaturated bond are used.

(1) Chemicals having a hydroxyl group: 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)acrylamide monomers such as meth)acrylamide; o-lm-, p-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, 0-1m-p-methoxyphenyl (meth)acrylamide, 0-1m-5
p-ethoxyphenyl (meth)acrylamide, etc. (3) Monomers having a cyan group on the side 61; (meth)acrylonidonitrile, 2-pentenitrile, 2-methyl-3-butenenitrile, 2-cyanoethyl acrylate, 0 -5m-p-cyanostyrene, etc. (4) Chimers having carbonic acid in the side chain: (meth)
Acrylic acid, itaconic acid and its anhydride, maleic acid and its anhydride, crotonic acid, etc. (5) Vinyl ethers: propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether, etc. (6) Styrene: α-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, imbutylene , butadiene, olefins such as vinyl chloride, N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine, etc., but any other monomer that can undergo radical copolymerization with these polymers may be used.

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

Examples of the above dyes include Hyctoria Viewer Blue BOH, Oil Blue #603, and Oil Pink #312.
．． Patent pure blue, crystal violet, leuco crystal violet, brilliant green,
Ethyl violet, methyl green, erythrosin B
, Pesic 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 triphenylmethane-based, diphenylmethane-based, oxazine-based, xanthine-based, iminonaphthoquinone-based, azomethine-based, or anthraquinone-based dyes.

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

Examples of 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,
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 05 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 a thread-like polyorganosiloxane or a polyorganosiloxane crosslinked to some extent.

The polyorganosiloxane 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 polyorcasiloxane 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 polyorcasiloxanes 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 a silicone crosslinking agent is reacted with a hydroxyl group, and in either 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, R1 and R2 are an alkyl group, an aryl group, an alkenyl group, or a combination thereof, each of which may have a substituent, and may be a methyl group, a phenyl group, a vinyl group, a trifluoropropyl group, or a combination thereof. Preferably, methyl group is particularly preferable.

The above-mentioned silicone crosslinking agents include so-called acetic acid-removal type, oxime-removal type, alcohol-removal type, deamine-removal type, which have a functional group represented by -OH (in the formula, R and R' are alkyl groups); Examples include condensation type silicone crosslinking agents such as dehydrated type. 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 carbonic acids, titanate esters, acetylacetone metal complexes, chloroplatinic acid, naphthenic acid, and the like.

The addition type refers to unsaturated groups in the main body, such as vinyl groups (CH
=CH7) by adding a water-based group in a crosslinking agent to crosslink it.

Specifically, examples include vinyl group-containing organopolysiloxanes, hydrogenated organopolysiloxanes, and the like mixed with platinum-based catalysts (eg, 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/dm2 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), a method of treatment with phosphonic acids and their rust 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 brimer layer, followed by 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.
-300 μm, photosensitive layer 0.05-10 μm, preferably 0.1-1,0 μm, silicone rubber layer 0.5-1
00 μm, preferably 1 to 4 μm. The brimer 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 brimer layer is applied onto a support using a conventional coater such as a reverse roll coater, an air knife coater, a Meyer 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 for several minutes at a temperature of usually IOO to 120°C.
Fully cure to form a silicone comb 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" (trade name of aliphatic hydrocarbons manufactured by Esso Chemical Co., Ltd.), 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,
ethylene glycol dibutyl 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 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, sulfonic sodium alkyl sulfate, etc.) (2) Fat Group alcohol phosphate ester salts (for example,
(3) Alkylaryl sulfonate salts, such as sodium dodecylbenzenesulfonate, inflovirnaphthalenesulfonate sodium salt, dinaphthalenesulfonate sodium salt, sodium metanitrohenzenesulfonate (4) Alkylamide sulfonates (C+71+3sCON-CH2CH2SO3Na, etc.)
H3 (5) Sulfonic acid salts of dibasic aliphatic esters (e.g., sodium sulfosuccinate dioctyl ester, sodium sulfosuccinate dihexyl ester, etc.) (6) Formaldehyde condensates of alkylnaphthalene sulfonates (e.g., dibutylnaphthalene sulfonic acid) Examples include formaldehyde condensates of sodium, 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. It will be done.

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

Examples of amphoteric surfactants include alkyl betaines, and among these, anionic surfactants are suitable.

These surfactants can be used alone or in combination with 2 fil! You can use a combination of the above.

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

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, mono-, di-isopropylamine, mono-, di- Alternatively, organic amine compounds such as triethanolamine, mono-, di-, or triisopropanolamine, ethyleneimine, and ethylenediimine can be mentioned.

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

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 is carried out using, for example, a developing bag containing a developing solution such as the one described above.
This can be done by rubbing with a brush or by pouring developer onto the plate and then rubbing 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. .

Below are blank spaces Example-1 Synthesis of diazo resin-1 p-diazodiphenylamine sulfate 14.5g (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 mN ethanol under water 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 cold concentrated aqueous solution of 1 g of zinc chloride was added.

The resulting precipitate was filtered, washed with ethanol, and dissolved in 150 ml 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 to obtain diazo resin-1.

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.
of water (p++8.5) for 25 seconds, washed with water, and dried to obtain aluminum plate a.

A primer layer composition having the following composition was applied to an aluminum plate a and dried at 85° C. for 3 minutes to form a primer layer with a thickness of 3.0 μm.

Primer layer composition diazo resin-1108 2-hydroxyethyl methacrylate/methyl methacrylate (50,750 molar ratio) 100
g Zinc oxide (white pigment) 20g Get Yellow 402 (yellow pigment) 10g poly(styrene-co-N,N,N-trimethyl-N-vinylhensyl ammonium chloride) (9:1) 8g Next, apply the following on the above brimer layer. Applying a photosensitive composition of the composition,
It was dried at 100° C. for 2 minutes to form a photosensitive layer with a thickness of 0.3 μm.

(Photosensitive composition) (1) Diazo resin - 150 parts (2) 2- and droxyethyl 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 developer-1 below for 1 minute, the surface of the plate material is rubbed with a pad impregnated with the developer.
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.

Furthermore, 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 results of the staining density and sharpness obtained are shown in Table-1.

(Developer) β-anilinoethanol 0.5 parts Bepropylene glycol 1.0 parts p-ter
t-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 (dyeing agent) Tulfit (manufactured by Kuraray Sobren Chemical Co., Ltd., solvent) 10 parts Resitor TW-0120 (manufactured by Kao Corporation, surfactant) 0
．． 5 parts Hensyl Alcohol 25 parts Victoria Pure Blue B OH 0.5 parts Water
100 parts Comparative Example-1 The brimer layer composition of Example-1 except that poly(styrene-N,N,N-1-methyl-N-vinylbenzylammonium chloride) (9+1) was removed.
A lithographic printing plate material requiring no dampening water was obtained in the same manner as in Example-1.

Next, after development using the developer described above, dyeing was performed. The results of the staining density and sharpness obtained are shown in Table-1.

The obtained results showed that the sharpness was good, but the staining density was insufficient.

Comparative Example 2 A lithographic printing plate material that did not require dampening water was obtained in the same manner as in Example 1, except that the primer layer of Example 1 was changed as follows.

(Brimer layer composition) Photographic gelatin 680 (manufactured by Nitta Gelatin Co., Ltd.) 100 parts by weight glyoxal solution (40μ aqueous solution, manufactured by Wako Pure Chemical Industries, Ltd.) 35 parts by weight Pure water 4000 parts by weight The above brimer layer composition was applied, It was heated at 120° C. for 5 minutes to dry and harden.

Next, the film was developed using the developer described above, and then dyed.

The obtained results were that although it was possible to dye vividly, non-image areas were also stained and the sharpness of the stained image was extremely poor.

The results are shown in Table-1.

Table 1 *Reflection density (white light), the larger the value, the greater the staining density.

** Width (μm) of seepage of the stained area to the non-image area; the larger the value, the less sharp the seepage is.

Example 2 A lithographic printing plate material that does not require dampening water was obtained in the same manner as in Example 1, except that the brimer layer composition of Example 1 was changed as follows.

A lithographic printing plate material 4 that does not require dampening water was obtained in the same manner as in Example-1, except that the primer layer of Example-1 was changed as follows.

(Brimer layer composition) 2-hydroxyethyl methacrylate/medyl methacrylate-1 (50,750 molar ratio) 100
℃Kebe Pentaerythritol Tetraacrylate 100 Melon Part DETX (Initiator, manufactured by Nikki Kayaku Co., Ltd.) 5 Melon Part EPA
(Multi-cutting, manufactured by Kuchiki Kayaku Co., Ltd.) 5ffi parts by weight Zinc oxide (manufactured by Sakai Chemical Co., Ltd., white pigment) 30 parts by weight Get Yellow 402 (manufactured by Inu Nippon Ink Co., Ltd., yellow pigment)
10 parts by weight Methyl lactate 10
00!1llfc part quaternary nitrogen atom-containing polymer
20 Ji! When developed in the same manner as in Quantitative Example 1, the silicone rubber layer and photosensitive layer in the unexposed areas were removed, and a printing plate with good dyeability and well-reproduced halftone dots was obtained.

Example 3 A lithographic printing plate material that does not require dampening water was obtained in the same manner as in Example 1, except that the photosensitive composition of Example 1 was changed as follows.

(Photosensitive composition) (1) 50 parts (2-1 ) 41 adduct of glycidyl methacrylate and metaxylene diamine 25 parts (2-2)
) Limethylolbrobantriethoxytriacrylate 10 parts (2-3) Tetramethylolmethanetetraacrylate 5 parts (2
-4) I-limethylolbroban triacrylate 10 parts (3) 2,4-diethylthioxanthone 7 parts (4) p-dimethylaminobenzoic acid isoamyl ester 3 parts (
5) Victoria Pure Blue BOH 0.2 parts (6) Methyl cellosolve 500 parts When developed in the same manner as in Example-1, the silicone rubber layer and photosensitive layer in the unexposed areas were removed, the dyeability was good, and halftone dots were formed. A printing plate with good reproduction 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] The present invention contains a polymer compound having a quaternary nitrogen atom or a quaternary phosphorus atom in the brimer layer, so it has good dyeing properties and is a printing plate with excellent optometry properties. was gotten.

Claims (1)

[Claims] In 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,
A photosensitive lithographic printing plate that does not require dampening water, wherein the primer layer contains a polymer compound having a quaternary nitrogen atom or a quaternary phosphorus atom.