JPH04122932A - Processing method for dampening-waterless photosensitive planographic printing plate - Google Patents

Abstract

PURPOSE:To eliminate the need for a stage using a dyeing liquid so as to improve workability and to miniaturize an automatic developing machine by incorporating a quinone diazide compd. into a primer layer and processing the above printing plate with a processing liquid contg. a basic compd. CONSTITUTION:The compsn. of the primer layer contg. the quinone diazide compd. is applied on a degreased smooth aluminum sheet and is cured by heating. The photosensitive compsn. is then applied on the primer layer and is dried to form a photosensitive layer. A silicone rubber compsn. is applied on the photosensitive layer and is dried to form a silicone rubber layer. Further, a polypropylene film is laminated on the silicone rubber layer to obtain the waterless photosensitive planographic printing plate. A positive film is brought into tight contact under a vacuum with the surface of the silicone rubber layer of this printing plate and is exposed. The film is developed by a developer contg. the basic compd. to remove the silicone rubber layer of the exposed parts. The photosensitive layer is thereafter subjected to rinsing, by which the layer is colored to a reddish brown color.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for processing photosensitive lithographic printing plates that does not require dampening water, and more specifically, improves printing properties and improves chemical resistance during printing. The present invention relates to a method for processing a photosensitive lithographic printing plate that does not require dampening water, has excellent properties, has improved workability, and can further downsize an automatic processor.

[Background of the Invention] Conventionally, a photosensitive lithographic printing plate that does not require dampening water (hereinafter referred to as "plate material 114J" if necessary) is one in which a photosensitive layer and an ink repellent layer are coated on a support in this 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.

It is necessary to control the state of the plate (developability, scratches, stains on the plate, etc.) during or after development of such plate materials, and therefore it must have excellent plate inspection properties.

In order to improve this plate inspection property, conventionally, JP-A-54-1
As described in Japanese Patent Laid-open No. 03103 and Japanese Patent Application Laid-open No. 57-198465, after development, the image area is dyed with an aqueous dye solution.

However, after developing the plate material, if it is treated with a staining solution containing dye in order to visualize the image area, hands and clothes will become dirty when replenishing the dyeing solution or replacing the dyeing solution, and the dyeing process will be difficult. Doing so increases the number of processing steps and therefore increases the size of the automatic processor, which is not desirable in terms of equipment.

Therefore, the present inventors have conducted various studies on methods that do not use a staining solution while considering the above-mentioned plate inspection properties, and have found that after photodegrading a part of the quinonediazide compound contained in the primer layer, and then developing or It was discovered that a printing plate with excellent printing properties, in which only the image area develops color, can be obtained by processing with a processing liquid containing a basic substance at the same time as development, and has now accomplished the present invention.

[Object of the Invention] Therefore, the first object of the present invention is to provide photosensitive lithographic printing that does not require a dampening solution and has good workability in that it does not require a dyeing solution and therefore does not stain hands or clothes with the dyeing solution. The purpose is to provide a method for processing editions.

A second object of the present invention is to provide a method for processing a photosensitive lithographic printing plate that does not require dyeing and therefore does not require dampening water and can downsize an automatic processor.

A third object of the present invention is to provide a photosensitive lithographic printing plate that does not require dampening water and has improved printing characteristics such as fine line reproducibility, shadow and highlight reproducibility, and improved chemical resistance during printing. The purpose is to provide a processing method.

[Structure of the Invention] The above aspects of the present invention are as follows: 1) A photosensitive lithographic printing plate that does not require dampening water and has a primer layer containing a quinonediazide compound, a photosensitive layer, and a silicone rubber layer in this order on a support is imagewise exposed. , and then treating the photosensitive lithographic printing plate with an aqueous processing solution containing a basic substance after or simultaneously with development to develop color in an image-wise manner. .

2) Achieved by a method for processing a photosensitive lithographic printing plate that does not require dampening water, characterized in that the aqueous processing solution containing a basic substance according to claim 1 contains 50% by weight or more of water and an organic solvent. be done.

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

In the present invention, a part of the quinone diazide compound contained in the primer layer of a photosensitive lithographic printing plate that does not require water is photolyzed, and then, after or simultaneously with development, the image area is treated with a processing solution containing a basic substance. By coloring only the image area, it is possible to obtain an image in which only the image area is colored. Therefore, it is possible to obtain an image with excellent plate inspection properties without using a staining solution. Therefore, it has excellent printing characteristics, improves workability, and can be automated. This has the excellent effect of making the developing machine smaller.

The quinonediazide compound contained in the primer layer used in the present invention is either a reaction product of a compound containing a quinonediazide group and an alkali-soluble resin, or a mixture of a compound containing a quinonediazide group and an alkali-soluble resin. Or used to mean both.

Typical examples will be explained below.

As a polymer compound containing an orthoquinone cyacyto group,
Examples include ester compounds of 0-naphthoquinone cyasitosulfonic acid and polycondensation resins of phenols and aldehydes or ketones.

Examples of the phenols include phenol, 0
-cresol, m-cresol, p-cresol, 3.
Examples include m-phenols such as 5-xylenol, carvacrol, and thymol, dihydric phenols such as catechol, resorcinol, and hydroquinone, and trihydric phenols such as pyrogallol and phloroglucin.

Examples of the aldehyde include formaldehyde, henzaldehyde, acetaldehyde, crotonaldehyde,
Examples include furfural.

Preferred among these aldehydes are formaldehyde and henzaldehyde.

Furthermore, examples of the above-mentioned ketones include acetone, methyl ethyl ketone, and the like.

Specific examples of the polycondensation resin include phenol/formaldehyde resin, m-cresol/formaldehyde resin, m-10-mixed cresol/formaldehyde resin, resorcinol/henzaldehyde resin, pyrogallol/acetone resin, and the like.

The condensation rate of 0-naphthoquinone cyacytosulfonic acid per 1 group of phenols in the 0-naphthoquinonediazide compound (reaction rate per 1 group) is 15 to 8.
It is preferably 0%, more preferably 20-45%.

Further, as the O-quinonediazide compound used in the present invention, compounds described in JP-A-58-43451 can also be used.

Among the above 0-quinonediazide compounds, 1,2-henzoquinone diazitosulfonyl chloride or 1,2-naphthoquinone cyaditosulfonyl chloride and pyrogallol acetone condensation resin or 2,3,4-1-lihydroxyhenzophenone are used. O-quinonediazide ester compounds obtained by the reaction are most preferred.

As the 0-quinonediaside compound used in the present invention, each of the above compounds may be used alone, or two or more kinds of compounds may be used in combination.
- The polymer compound containing quinonediazide preferably has a molecular weight of 1500 or more in consideration of coating properties,
More preferably, those having a molecular weight of 2000 or more are preferred.

Primer Jm containing the above 0-quinonediaside compound
is preferably used in combination with various resins.

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 phenolic resins such as polymers, phenoxy resins, polyurethane resins, polycarbonate resins, polyacrylonitrile butadiene, and polyvinyl acetate.

Preferred examples include epoxy resins, acrylic resins, polyester resins, urethane resins, etc., but it is preferable to use phenolic resins in combination. It is preferable to use these resins in a light-cured form.

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 1 μm.

This primer layer should not be alkali-soluble, but
For color development, a polymer with phenolic hydroxyl groups is used.
It is preferable that the content is from % to 50% by weight.

In the quinonediazide compound contained in the primer layer of the photosensitive lithographic printing plate that does not require dampening water and used in the present invention, 30 mol% to 70 mol% of the quinonediazide units of the quinonediazide compound photodecompose during proper image exposure. , preferably 40 mol % to 60 mol % of the quinonediazide units are photodecomposed. In order to adjust this, an ultraviolet absorber or a yellow dye can be added to the primer layer.

When the photodecomposition of quinonediazide units is 30 mol % or less, image reproducibility is poor and color density is low.

Furthermore, if the photodecomposition is 70 mol% or more, sufficient color density cannot be obtained in the image area.

The basic substance added to the treatment liquid used in the present invention means a base used in the ordinary chemical field, and may be either an inorganic or an organic base.

As the organic base, ammonia, hydrazine, hydroxyamine, and an organic base having 1 to 30 carbon atoms are preferred. Specific examples of these include ammonia (ammonium hydroxide), methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, propylamine, butylamine,
Amylamine, dipropylamine, dibutylamine, cyamylamine, tripropylamine, tributylamine, methyldiethylamine, ethylenediamine, trimethylenediamine, tetramethylenediamine, polyethyleneimine, hensylamine, N,N-dimethylbenzylamine, NN-jethylhensylamine , N,N-dipropylbenzylamine, 0- or m- or p-methoxy or methylbenzylamine, N,N-di(methoxyhensyl)amine, β-phenylethylamine, ε, δ
-Phenylamylamine, γ-phenylpropylamine, cyclohexylamine, aniline, monomethylaniline, dimethylaniline, toluidine, benzidine, α-
or β-naphthylamine, 0- or m- or p-
Fuynylene diamine, pyrrolidine, piperazine, morpholine, urotropin, diazabicycloundecane, pyrrole, pyridine, quinoline, hydrazine, phenylhydrazine, N,N'-diphenylhydrazine, hydroxylamine, semicarbazide, tetraalkylammonium hydroxide, aminobenzoic acid acid, formamide, acetamide, N,N-dimethylformamide, N,N-dimethylaniline 1~, acetanilide, monoethanolamine,
jetanolamine, triethanolamine, 2-(2
-aminoethyl)ethanolonope 2-amino-2-methyl-1,3-propanediol, 2-amino-1,3-
Amine compounds such as propanediol, 2-amino-2-hydroxymethyl-1,3-propanediol (primary, secondary, tertiary amines, monoamines, diamines, triamines, tetraamines to polyamines, aliphatic button amines, amine conductors such as aliphatic cyclic amines, aromatic amines, petrocyclic amines) and acid amides, or salts of carboxylic acids and amines (for example, salts of octanoic acid and monoethanolamine, jetanolamine, etc.). can give.

Also, sodium methylate, sodium ethylate,
Alkali metal alcoholades such as sodium propylade, potassium methylate, potassium ethylate, potassium propylate, lithium methylate, lithium ethylate, alkali metal amides such as sodium, potassium, and lithium amides, ethylamide, dipropylamide, etc. are used. It will be done. Inorganic bases include sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, calcium carbonate, barium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and sodium phosphate. , hydroxides, carbonates, bicarbonates, phosphates, silicates, metasilicates of alkali metals and alkaline earth metals such as potassium phosphate, sodium silicate, potassium silicate, sodium metasilicate, etc. Can be mentioned.

Among these, sodium silicate and potassium silicate are particularly preferred.

The processing method of the present invention involves imagewise exposing a photosensitive lithographic printing plate that does not require dampening water and containing a quinonediazide compound as a primer layer, and then performing a development step, and then processing the image area with a processing solution containing a basic substance to develop color. However, it is preferable to add a basic substance to the developer to make it more stable, and to develop the color at the same time as the development with the developer.

Further, when processing with a processing liquid containing a basic substance, the pH of the processing liquid is preferably 11 or more, and more preferably 12 to 135.

Furthermore, the treatment liquid containing basic substances is mainly composed of water,
The amount of basic substance contained therein is 0.1% by weight to 2% by weight.
0% by weight, preferably 1% to 10% by weight.

The photosensitive lithographic printing plate that does not require dampening water and is used in the present invention is preferably washed with water after being treated with a treatment liquid containing a basic substance, or after being treated with a treatment liquid simultaneously with a developer.

The treatment liquid containing a basic substance used in the present invention contains 50% water.
It is preferable to contain water in an amount of 0% by weight or more, and more preferably 8011% by weight or more.

In addition, color development can be improved by adding an organic solvent, a surfactant, etc. to the treatment liquid containing a basic substance, and it is particularly preferable to use a sparingly water-soluble organic solvent as the organic solvent.

The water soluble organic solvent used as this additive is 2
An organic solvent having a solubility in water at 0°C of 10% by weight or less, such as diisobutyl ketone, acetophenone, isophorone, diethyl succinate, methyl benzoate, diethyl oxalate, dimethyl phthalate, inbutyl acetate,
Benzyl benzoate, ethylene glycol monophenyl ether, ethylene glycol dibutyl ether, ethylene glycol benzyl ether, diethylene glycol di-n-butyl ether, diethylene glycol diacetate, n-amyl alcohol, benzyl alcohol,
Cyclohexanone, cyclohexanol, N-benzylethanolamine, anisyl alcohol, dimethylbenzylcarpitol 2-N-ethylanilinoethanol,
Examples include propylene glycol monophenyl ether and N-phenylethanolamine.

Among these, ethylene glycol monophenyl ether, ethylene glycol hensyl ether, hensyl alcohol, cyclohexanone, cyclohexanol, N
-Benzylethanolamine, anisyl alcohol, dimethylbenzylcarpitol, 2-N-ethylanilinoethanol, propylene glycol monophenyl ether, and N-phenylethanolamine are particularly effective.

The amount of organic solvent used in the present invention is 1% by weight to 1% by weight.
0% by weight, preferably 2% to 631% by weight is preferred.

One or more organic solvents used in the present invention can be used in combination.

The photosensitive layer of the photosensitive lithographic printing plate that does not require dampening water used in the present invention is preferably of a type that removes the photosensitive layer in the portion that will become the image area during development.

The following margin: Either a positive-working photosensitive composition or a negative-working photosensitive composition can be used in the photosensitive layer used in the processing method of the present invention for a photosensitive lithographic printing plate that does not require dampening water. As a positive photosensitive composition, a polymer compound containing an orthoquinonediazide group is mainly used. Here, the polymer compound containing an orthoquinonediazide group is a combination of a compound containing an orthoquinonediazide group and an alkali-soluble resin. It is used in the meaning of either or both of a reaction product and a mixture of a compound containing an orthoquinonediazide group and an alkali-soluble resin.

Typical examples will be explained below.

As a polymer compound containing an orthoquinone cyacyto group,
For example, ester compounds of 0-naphthoquinonediazide sulfonic acid and polycondensation resins of phenols and aldehydes or ketones may be mentioned.

Examples of the phenols include phenol, 0
-cresol, m-cresol, p-cresol, 3.
Examples include m-phenols such as 5-xylenol, carvacrol, and thymol, dihydric phenols such as catechol, resorcinol, and hydroquinone, and trihydric phenols such as pyrogallol and phloroglucin.

Examples of the aldehyde include formaldehyde, benzaldehyde, acetaldehyde, crotonaldehyde,
Examples include furfural.

Preferred among these aldehydes are formaldehyde and benzaldehyde.

Furthermore, examples of the above-mentioned ketones include acetone, methyl ethyl ketone, and the like.

Specific examples of the polycondensation resin include phenol/formaldehyde resin, m-cresol/formaldehyde resin, m-, o-mixed cresol/formaldehyde resin, resorcinol/henzaldehyde resin, pyrogallol/acetone resin, and the like.

The condensation rate (0) of the 0-naphthoquinone cyasito sulfonic acid with respect to the O)I group of the phenol in the 0-naphthoquinone cyasito compound (reaction rate per 1 group) is 15 to 80.
%, more preferably 20 to 45%.

Further, as the O-quinonediazide compound used in the present invention, compounds described in JP-A-58-43451 can also be used.

Among the above 0-quinonediazide compounds, 1,2-penzoquinone diazitosulfonyl chloride or 1,2-naphthoquinone cyasitosulfonyl chloride is reacted with a pyrogallol acetone condensation resin or 2,3,4-trihydroxybenzophenone. The resulting O-quinonediazide ester compound is most preferred.

As the ○-quinonediazide compound used in the present invention, each of the above compounds may be used alone, or 2 fi!
The above compounds may be used in combination.

Used in the present invention. - The polymer compound containing quinonediazide preferably has a molecular weight of 1,500 or more, more preferably 2,000 or more, in consideration of coating properties.

The above-mentioned 0-quinonediazide compound is preferably used in combination with an alkali-soluble resin. Examples of alkali-soluble resins include novolac resins, vinyl polymers having phenolic hydroxyl groups, and condensation resins of polyhydric phenols and aldehydes or ketones described in JP-A-55-57841. Examples of the novolac resin include phenol-formaldehyde resin, cresol-formaldehyde resin, phenol-cresol-formaldehyde copolycondensation resin as described in JP-A-55-57841, and phenol-cresol-formaldehyde copolycondensation resin as described in JP-A-55-127553. Examples include copolycondensation resins of p-substituted phenol and phenol or cresol and formaldehyde as described above.

Moreover, the vinyl polymer having a phenolic hydroxyl group is a polymer having a unit having the phenolic hydroxyl group in its molecular structure, and is a polymer having the following general formula [I] to -numerical formula [
Polymers containing at least one structural unit of V] are preferred.

-Mathematical formula [ ] General formula [+1] (CR+ R2-C,R.

Mo→ Yau-0H General formula [II+] General formula [] General formula [V] +CR3 CR4) H [In the formula, R1 and R2 each represent a hydrogen atom, an alkyl group or a carboxyl group, preferably a hydrogen atom. R3 represents a hydrogen atom, a halogen atom, or an alkyl group, preferably a hydrogen atom or an alkyl group such as a methyl group or an ethyl group, R4 represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, preferably a hydrogen atom , A represents an alkylene group which may have a substituent and which connects a nitrogen atom or an oxygen atom and an aromatic carbon atom, m represents an integer of O to 10, and B has a substituent. represents a phenylene group which may have a substituent or a naphthylene group which may have a substituent. ] The polymer used in the photosensitive composition of the present invention preferably has a copolymer-type structure, and can be used in combination with the structural units represented by formulas [I] to [V] above. Examples of monomer units that can be used include ethylenically unsaturated olefins such as ethylene, propylene, imbutylene, butadiene, and isoprene, such as styrene, α-methylstyrene,
Styrene necks such as p-methylstyrene and p-chlorostyrene, acrylic acids such as acrylic acid and methacrylic acid, unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid, and maleic anhydride, such as methyl acrylate, acrylic Ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, acrylic acid
Esters of α-methylene aliphatic monocarboxylic acids such as 2-chloroethyl, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, and ethyl ethacrylate; nitriles such as acrylonitrile and methacrylonitrile; Amides such as acrylamide, e.g. acrylanilide, p-chloroacrylanilide, m-nitroacrylanilide, ω
- anilides such as methoxyacrylanilide, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, inbutyl vinyl ether, β-chloroethyl vinyl ether, Vinyl chloride, vinylidene chloride, vinylidene cyanite, such as 1-methyl-1-methoxyethylene, 1,1-dimethoxyethylene, 1,2-dimethoxyethylene, 1,1-dimethoxycarbonylethylene,
Ethylene conductors such as 1-methyl-1-nitroethylene, such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone, N-
There are N-vinyl caramers such as vinylpyrrolidone. These vinyl-based caramers exist in polymer compounds with a structure in which unsaturated double bonds are cleaved.

Among the above monomers, aliphatic monocarboxylic acid esters and nitriles exhibit excellent performance for the purpose of the present invention and are therefore preferred.

Considering the applicability of these alkali-soluble resins,
Those having a molecular weight of 1,500 or more are preferable, and those having a molecular weight of 2,000 or more are more preferable.

In addition to the above-mentioned materials, these photosensitive compositions also contain pigments such as dyes and pigments, sensitizing agents, plasticizers, surfactants, organic acids, acid anhydrides, and acidic substances when exposed to light. A compound etc. that can generate can be added.

There are various types of negative photosensitive materials used in the present invention, and representative ones will be described below.

(1) Photosensitive composition containing diazo resin The diazo resin represented by the condensate of p-diazodiphenylamine and formaldehyde may be water-soluble or water-insoluble, but is preferably
7 and No. 57-43890, etc., which are water-insoluble and soluble in ordinary organic solvents are used. Particularly preferred is a diazo resin represented by the following general formula [I].

General formula [lco[wherein RI, R2 and R3 represent a hydrogen atom, an alkyl group or an alkoxy group, and R4 represents a hydrogen atom, an alkyl group or a phenyl group.

X represents PF6 or BF4, and Y represents -NH--5- or -0-. ] The diazo resin is preferably used in combination with a film-forming resin, particularly a lipophilic polymer compound having a hydroxyl group. In addition to those listed above, such lipophilic polymer compounds include monomers having an aliphatic hydroxyl group in the side chain, such as 2
Copolymers of -hydroxyethyl acrylate or 2-hydroxyethyl methacrylate and other copolymerizable monomers can be mentioned. In addition to these, polyvinyl butyral resins, polyurethane resins, polyamide resins, epoxy resins, novolac resins, natural resins, etc. may be added as necessary.

Various polymeric compounds can be used as the binder used in combination with the diazonium salt, but preferably, JP-A-54-9
Monomers having an aromatic hydroxyl group as described in Japanese Patent No. 8613, such as N-(4-hydroxyphenyl)acrylamide, N-(4-hydroxyphenyl)methacrylamide, o+, m-, or p- Copolymers of hydroxystyrene, o-, m-, or p-hydroxyphenyl methacrylate and the like with other monomers, hydroxyethyl acrylate units as described in U.S. Pat. No. 4,123,276 or a polymer containing hydroxyethyl methacrylate units as a main repeating unit Natural resins such as shellac and rosin, polyvinyl alcohol, polyamide resins described in U.S. Patent No. 3,751,257, U.S. Patent No. 3,66
0.097, a phthalated polyvinyl alcohol resin, an epoxy resin condensed from bisphenol A and epichlorohydrin, and celluloses such as cellulose acetate and cellulose acetate phthalate.

Examples of the alkali-soluble resin include novolac resin, vinyl polymer having a phenolic hydroxyl group, and JP-A-55-5
Examples include condensation resins of polyhydric phenols and aldehydes or ketones described in Japanese Patent No. 7841. Examples of novolac resins include phenol/formaldehyde resin, cresol/formaldehyde resin, and JP-A-5
Phenol-cresol-formaldehyde copolycondensation resin as described in JP-A No. 5-57841, p as described in JP-A-55-127553
Examples include copolycondensation resins of -substituted phenol and phenol or cresol and formaldehyde.

In addition to the above-mentioned materials, these photosensitive compositions may also contain colorants such as dyes and pigments, sensitizing agents, plasticizers, surfactants, organic acids, acid anhydrides, and acids that can be removed by exposure to light. Compounds that may be generated can be added.

These binders are present in the solid content of the photosensitive composition in an amount of 40 to 99%.
It is contained in an amount of 50 to 95% by weight. The diazo resin is contained in an amount of 1 to 60% by weight, preferably 3 to 30% by weight.

Other dyes, pigments such as pigments, fat-sensitizing agents, plasticizers, surfactants, etc. can be added to these photosensitive compositions.

(2) In the main chain or side chain of the polymer -C)I-C)i-C-
Photosensitive composition containing a polymer compound having groups Examples of such polymer compounds include polyesters, polyamides, and polycarbonates containing -CH-CH-C- as a photosensitive group in the main or side chain of the polymer. (e.g., U.S. Patent No. 3,
No. 030,208, No. 3707.373 and No. 3,453,237)
; those whose main components are photosensitive polyesters derived from (2-probeliden) malonic acid compounds such as cinnamylidene malonic acid and difunctional glycols (for example, U.S. Pat. No. 2,956,878 and No. 3.173.78
7), cinnamate esters of hydroxyl-containing polymers such as polyvinyl alcohol, starch, cellulose, and the like (e.g., U.S. Pat. No. 2,690,966). , same No. 2,752,37
2, No. 2,732,301, etc.).

These photosensitive compositions may contain other sensitizers, stabilizers, plasticizers, pigments, dyes, and the like.

(3) Photopolymerizable composition comprising an addition polymerizable unsaturated compound This composition preferably comprises (a) a vinyl monomer having at least two terminal vinyl groups, (b) a photopolymerization initiator, and ( C) Consists of a polymer compound as a binder.

As the vinyl caramer of this component (a),
No. 5093, No. 35-14719, No. 44-2872
It is described in each publication No. 7.

Acrylic or methacrylic esters of polyols, such as diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, or methylene bis(meth)acrylamide , bis(meth)acrylamides such as ethylene bis(meth)acrylamide, or unsaturated monomers containing urethane groups, such as di(2'-methacryloxyethyl)-2,4-tolylene diurethane, di( Diol mono(meth) such as 2-acryloxyethyl) trimethylene diurethane etc.
Examples include reaction products of acrylate and diisocyanate.

As the photopolymerization initiator of component (b), the compound represented by the above general formula [1] can be used, but other types can also be used. For example, carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, as described in "Light Sensitive Systems", Vol.
These include halogen compounds and photoreducible dyes. More specifically, it is disclosed in British Patent No. 1,459,563.

Furthermore, various known polymers can be used as the binder for component (C). Details of specific binders are described in US Pat. No. 4,072,527.

These photopolymerizable compositions contain thermal polymerization inhibitors, plasticizers,
A dye, B1, etc. can be contained.

(4) Photosensitive composition containing an azide group As the photosensitive azide compound, an aromatic azide compound in which the azide group is bonded to an aromatic ring directly or via a carbonyl group or a sulfonyl group is preferably used.

For example, boriasitostyrene, polyvinyl-p as described in U.S. Pat. No. 3,096,311;
-Azidohensiatate, polyvinyl-p-azidobenzal, reaction product of azidoarylsulfonyl chloride and unsaturated hydrocarbon polymer described in Japanese Patent Publication No. 45-9613, and Japanese Patent Publication No. 43-21017, No. 44
No.-229, No. 44-22954, No. 45-2491
Polymers having sulfonyl azide or carbonyl azide as described in each publication of No. 5 can be mentioned.

A liposensitizing agent and a surfactant added to the photosensitive composition,
The amount of additives such as sensitizers, stabilizers, thermal polymerization inhibitors, plasticizers, and pigments such as dyes and pigments varies depending on the type, but in general, they are included in the photosensitive composition contained in the photosensitive coating solution. 0.01 to 20% by weight, preferably 0.05 to 20% by weight based on the product
10% by weight is suitable.

Dyes preferably used in the present invention include basic dyes and oil-soluble dyes. Specifically, Victoria Pure Blue BOH, Victoria Blue BH, Methyl Violet, Eisen Malachite Green (manufactured by Hodogaya Chemical Industry), Patent Pure Blue
Basic dyes such as Vx10-Damine B, Methylene Blue (manufactured by Sumitomo Chemical), Sudan Blue 111, Victoria Blue F4R (BA,
Oil-soluble dyes include Oil Blue #603, Oil Blue BOS, and Oil Blue IIN (manufactured by Orient Chemical Industries).

The silicone rubber used in the present invention is a linear organic polymer having a repeating unit represented by the following general formula [I] and having a molecular weight of several thousand to hundreds of thousands and a hydroxyl group in the main chain or at the end of the main chain. Those containing siloxane as a main component are preferred.

General formula [11% formula% where n is an integer of 2 or more, R is an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, an alkoxyl group, a vinyl group, an aryl group, a silanol group (OH group), ,R
Preferably, 60% or more of the methyl groups are methyl groups. The silanol group (OH group) may be located either in the main chain or at the end of the main chain, but is preferably located at the end.

The silane coupling agent (or silicone crosslinking agent) used in the present invention is RnS + These groups may also have functional groups such as halogen, amine, hydroxy, alkoxy, aryloxy, and thiol.

X is -0H1-CH2, -0AC1-o-N-c,
Represents a substituent such as -cp, -Br, -■, etc. Here R2
, R3 represent the same as R above, and R2 and R3 may be the same or different. Moreover, Ac represents an acetyl group. ) is a silane compound represented by

That is, the silicone rubber useful in the present invention is obtained by a synthetic reaction between such a silicone haze polymer and a silicone crosslinking agent such as those listed above.

Specific examples of the silane coupling agent used in the present invention include HN [(CH2) 3si (OMe) 3] 2
, vinyltriethoxysilane, Cj! (CH2) 3
sj (OMe) 3, CH35i (OAc) 3,
Examples include R5(CH2)ssi(OMe)3, vinyltris(methylethylketoxime)silane, and the like.

The silicone rubber mentioned above can be manufactured manually as a commercially available product, such as YE-3085 manufactured by Toshiba Silicone Co., Ltd. In addition, other useful silicone rubbers can be produced by reacting the above-mentioned base polymer with a silicone oil having a repeating unit represented by the following general formula [11], or by reacting R
It can also be obtained by an addition reaction with a base polymer of silicone, about 3% of which is vinyl groups, or by reaction between the silicone oils.

General formula [, 11co HR (wherein, R has the same meaning as R, which is a substituent of the polymer represented by general formula [1], m is an integer of 2 or more, and n is O or an integer of 1 or more ) In order to obtain silicone rubber by such a crosslinking reaction, the crosslinking reaction is carried out using a catalyst. This catalyst includes tin, zinc, cobalt, lead,
Organic carboxylates of metals such as calcium, manganese, etc.
For example, dibutyltin laurate, tin(II) octoate, cobalt naphthenate, or chloroauric acid may be used.

Additionally, fillers can be mixed in to improve the strength of the silicone rubber and to obtain a silicone rubber that can withstand the frictional forces generated during printing operations. Silicone rubber mixed with filler in advance is commercially available as silicone rubber stock or silicone rubber dispersion, and when it is preferable to obtain a silicone rubber film by coating as in the present invention, RTV
Alternatively, dispersion of LTV silicone rubber is preferably used. An example of this is 5ylOff 23.5RX-257, S H manufactured by Toray Silicone.
There are silicone rubber dispersions for vapor coating such as 237.

In the present invention, it is preferable to use condensation and crosslinking type silicone rubber.

The silicone rubber layer preferably contains a silane coupling agent having an amino group in order to further improve adhesiveness.

Examples of preferable silane coupling agents include the following.

(a) H2NCH2CH2NH(CH2) ssi
(OC+(3).

(b) H2NCE2CH2NH(CH2) 3Si
(QC) 13) 2 (CH3) (C) 82N (C
)12) ssl (OEj).

The silicone rubber layer used in the present invention may further contain a small amount of photosensitizer.

The silicone rubber layer used in the present invention is prepared by dissolving silicone rubber in a suitable solvent, applying it onto the photosensitive layer, and drying it.

The support of the present invention is preferably one that is flexible enough to be set in a normal lithographic printing machine and that can withstand the load applied during printing, such as metal plates such as aluminum, zinc, copper, and steel, and metal plates such as chromium, zinc, Examples include metal plates plated or vapor-deposited with copper, nickel, aluminum, iron, etc., paper, plastic films, glass plates, resin-coated paper, paper covered with metal foil such as aluminum, and the like.

Among these, aluminum plates are preferred.

The treatment for the support itself to improve the adhesion is not particularly limited, and includes various surface roughening treatments.

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 0.5-5 μm, silicone rubber layer 0.1-10 μm
m1 is preferably 0.5 to 2 μm.

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

In the following, the present invention will be specifically explained with reference to examples, but the present invention is not limited by these examples.

Example 1 A primer layer composition having the following composition was coated on a smooth aluminum plate degreased in a conventional manner to a dry weight of 2.0 g/m'' and cured by heating at 120° C. for 5 minutes.

[Primer layer composition Koebicoat 1001 (bisphenol A epoxy resin manufactured by Shell Chemical, equivalent weight 450-500) 100 parts by weight Adeka Hartner EH700 (manufactured by Asahi Denka Co., Ltd., acid anhydride curing agent) 347f 1 part Adeka Heartner EHC30 (manufactured by Asahi Denka Co., Ltd., tertiary amine curing accelerator) 10 parts by weight naphthoquinone
Ester compound of (1,2)-diazide-(2)-5-sulfonic acid chloride and pyrogallol acetone resin (compound described in Synthesis Example 2 of JP-A-60-143345) 50 parts by weight ethyl cellosolve 1500 parts by weight Methyl cellosolve 800 parts by weight Next, on the primer layer, a photosensitive composition having the following composition was added to the dry weight:
sg/m'' and dried at 90°C to form a photosensitive layer.

[Photosensitive layer composition Cop-diazodiphenylamine paraformaldehyde condensate hexafluorophosphate 50 parts by weight 2-hydroxyethyl methacrylate, N-(4-hydroxyphenyl) methacrylamide, methacrylic acid molar ratio 40157/3 copolymer resin of
50 parts by weight Victoria Pure Blue BOH (manufactured by Hodokugaya Chemical Co., Ltd., dye) 1 part by weight Methyl Cellosolve 900 parts Next, the following silicone rubber composition was applied to the photosensitive layer to a dry weight of 1.8 g/m''. The silicone rubber layer was formed by coating the silicone rubber layer and drying it at 90° C. for 10 minutes.

[Silicone rubber layer composition] Dimethylpolysiloxane having hydroxyl groups at both ends (molecular weight 82,000) 100 parts by weight Triacetoxysilane 10 parts by weight Dibutyltin laurate 08 parts by weight Isopar E (manufactured by Esso Chemical) 9001 parts by weight Furthermore, the above silicone A single-sided matted polypropylene film having a thickness of 8 μm was laminated on the rubber layer to obtain an ice-free photosensitive lithographic printing plate.

A positive film was vacuum-adhered onto the silicone rubber layer of the photosensitive lithographic printing plate thus obtained, and then exposed using a metal halide lamp as a light source.

Next, this plate material was charged with a developing solution containing the following basic compound into the developing section of an automatic processor at 30° C., and after the temperature was adjusted to 30° C., the brush peripheral speed was set at 120 m/min in the developing section.
The film was developed for 100 seconds to remove the silicone rubber layer in the exposed area. Further, 101% of an aqueous solution containing 1% by weight of sodium lauryl sulfate and 5% by weight of citric acid was charged into the rinsing section.

[Developer] (p) 113.0) Potassium silicate aqueous solution (Si (h: 26% by weight,
0:14% by weight) 20wt potassium hydroxide 3wt water
100 weight As described above, the exposed plate material was treated with a developer containing a basic compound and then rinsed, so that the photosensitive layer in the image area from which the silicone rubber layer was removed developed a reddish-brown color. Visible image quality after development was provided.

In the present invention, a visible image can be obtained without a dyeing process, so there is no need to stain hands or clothes with a dyeing solution, and a dyeing process using a dyeing solution is not required.
The automatic developing machine has been made more compact.

When printing was carried out using the printing plate thus obtained, it showed good image reproducibility from shadows to highlights, and was also excellent in chemical resistance to plate cleaners and the like.

Examples 2 to 6 Waterless photosensitizers produced in exactly the same manner as in Example 1 except that the developer used in Example 1 was changed to a developer containing the additives shown in Table 1. The lithographic printing plate was processed.

Comparative Example 1 A test was conducted in the same manner as in Example 1, except that the primer layer of the waterless photosensitive lithographic printing plate used in Example 1 did not contain a quinonediazide compound.

As is clear from the above Examples 2 to 6 and Comparative Example 1,
In Examples 2 to 6, as shown in Table 1, the image area exhibited a reddish brown color in all cases.

On the other hand, in Comparative Example 1, there was almost no color development in the image area even though it was processed with a developer containing a basic compound, and therefore no visible image was obtained in the image area.

In addition, when the organic solvent of Example 3.5.6 is included, as in the present invention, the coloring property is more excellent, especially when using a poorly water-soluble organic solvent such as benzyl alcohol, it shows excellent coloring property and is also resistant to chemicals. It turned out that he has excellent sex. Comparative Example 1 was extremely sensitive to chemicals such as plate cleaners used during printing.

The following margins [Effects of the invention] The primer layer of the photosensitive lithographic printing plate that does not require dampening water of the present invention contains a quinone diazide compound and is treated with a processing liquid containing a basic compound, thereby changing the coloring of the plate material. Since there is no need for a dyeing process that uses a liquid, work efficiency is improved because hands and clothes do not get dirty during the coloring process, and since there is no need for a dyeing process, the automatic developing machine can be made more compact. It is.

Furthermore, the coating is less likely to deteriorate with respect to various chemicals used during printing, and has excellent chemical resistance.

Claims (1)

[Scope of Claims] 1) A photosensitive lithographic printing plate that does not require dampening water and has a primer layer containing a quinonediazide compound, a photosensitive layer, and a silicone rubber layer in this order on a support is imagewise exposed, and then the photosensitive lithographic printing is performed. A method for processing a photosensitive lithographic printing plate that does not require dampening water, characterized in that the plate is treated with an aqueous processing solution containing a basic substance after or simultaneously with development to develop color in an image-like manner. 2) A method for processing a photosensitive lithographic printing plate that does not require dampening water, characterized in that the aqueous processing solution containing a basic substance according to claim 1 contains 50% by weight or more of water and an organic solvent.