JPH08171214A - Method for processing photosensitive planographic printing plate - Google Patents

Abstract

PURPOSE: To provide a method for processing a photosensitive planographic printing plate exhibiting excellent stability even when the negative and positive ones are developed. CONSTITUTION: A photosensitive planographic printing plate having a photosensitive layer on a substrate having a hydrophilic surface is image-exposed and then developed using an aq. alkali developer and a liq. developing replenishment. In this case, the developer and replenishment are an aq. soln. of an alkali metal silicate, the SiO2 concn. is controlled to 1.0-4.0wt.%, the SiO2 concn. is kept constant in a running developer, and an alkali-soluble resin is incorporated into the developer by 0.1-20wt.%. Meanwhile, the SiO2 content of the developer is controlled to 3.0-7.0wt.%, (SiO2 )/(M) (where (SiO2 ) is the molarity of SiO2 , and (M) is the molarity of alkali metal) is controlled to 0.5-1.5, the SiO2 content of the aq. alkali. developing replenishment is adjusted to 0.5-3.0wt.%, and (SiO2 )/(M) is regulated to 0.15-0.8.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for treating a photosensitive lithographic printing plate.

[0002]

2. Description of the Related Art There are negative type and positive type photosensitive lithographic printing plates for obtaining lithographic printing plates, both of which are used.

Conventionally, in order to obtain a lithographic printing plate having sufficient performance by processing these negative photosensitive lithographic printing plates and positive photosensitive lithographic printing plates, negative photosensitive lithographic printing plates are For the developer and the positive photosensitive lithographic printing plate, it was necessary to use a separate developer for the positive developer.

Therefore, it is necessary to separately prepare a processing device for processing each of the negative photosensitive lithographic printing plate and the positive photosensitive lithographic printing plate, resulting in a large installation space of the processing device. There was a problem of being lost. Further, if the negative photosensitive lithographic printing plate and the positive photosensitive lithographic printing plate are processed by one processing device, the installation space of the processing device can be reduced, but it is necessary to replace the developer. This time, there arises a problem that workability deteriorates.

In order to solve these problems, a method for developing a positive type photosensitive lithographic printing plate and a negative type photosensitive lithographic printing plate in common by using a common developing solution in one developing machine has been developed. However, it is necessary to replenish these developing solutions with a large amount of developing replenishing solution, and the cost of the processing agent is high,
Further, there was a problem that the amount of waste liquid was inevitably increased. Also,
Development stability is poor, and in long-term running processing,
Occasionally, defective ink deposition and background stains occurred.

Although it has been proposed to use a highly alkaline developing solution and a more alkaline developing replenishing solution, the alkali activity fluctuates greatly and the development stability is insufficient. In particular, there was a big problem in a long-term running process. Further, in the method of measuring the activity of the developing solution by some method and feeding back the result, for example, in the method of judging the activity of the developing solution by measuring the electric conductivity and feeding back the result to replenish it, The conductivity value and the activity of the developing solution do not necessarily correspond to each other, and it is inevitable that the solution sensitivity varies.

[0007]

SUMMARY OF THE INVENTION Accordingly, the object of the present invention is to obtain stable gradation even after long-term running treatment, to prevent the occurrence of background stains and defective ink replenishment, and to replenish liquid and waste liquid. Of the developing solution is measured and the result is fed back to improve the replenishment accuracy in the replenishing method, and moreover, the negative photosensitive lithographic printing plate and the positive photosensitive lithographic printing plate can be improved. It is an object of the present invention to provide a method for processing a photosensitive lithographic printing plate which exhibits excellent stability even when both are developed.

[0008]

The above objects of the present invention are as follows: (1) Imagewise exposing a photosensitive lithographic printing plate having a photosensitive layer on a support having a hydrophilic surface, and then using an aqueous alkaline developer and a development replenisher. In the processing method of developing treatment, the aqueous alkaline developer and the developing replenisher are aqueous solutions of alkali metal silicates, and the concentration of SiO ₂ contained in the aqueous alkaline developer and the developing replenisher is 1.0 to 4.0. Wt% and in the running developer SiO
_A method for treating a photosensitive lithographic printing plate, characterized in that the density of ₂ is kept constant. (First Invention) (2) In a processing method of image-exposing a photosensitive lithographic printing plate having a photosensitive layer on a support having a hydrophilic surface, and then performing development processing using an aqueous alkaline developer and a development replenisher. A photosensitive lithographic printing plate characterized in that the aqueous alkaline developer and the developing replenisher are aqueous solutions of alkali metal silicates, and the aqueous alkaline developer contains 0.1 to 20% by weight of an alkali-soluble resin. Processing method. (Second invention) (3) In a processing method in which a photosensitive lithographic printing plate having a photosensitive layer on a support having a hydrophilic surface is imagewise exposed, and then development processing is carried out using an aqueous alkaline developer and a development replenisher. The aqueous alkaline developer and the development replenisher are aqueous solutions of alkali metal silicates, and the concentration of SiO ₂ contained in the aqueous alkaline developer is 3.0 to 7.0% by weight, [S
iO ₂ ] / [M] (wherein [SiO ₂ ] represents the molar concentration of SiO ₂ and [M] represents the molar concentration of alkali metal) is 0.5 to 1.5; The concentration of SiO ₂ contained in the aqueous alkaline developing replenisher is 0.5 to 3.0% by weight,
[SiO ₂ ] / [M] is 0.15 to 0.8. A method for treating a photosensitive lithographic printing plate. (Third invention)

The present invention will be described in detail below.

First, the aqueous alkaline developer and development replenisher used in the present invention will be described.

In the first invention, the aqueous alkaline developing solution and the developing replenishing solution are alkaline aqueous solutions of alkali metal silicates, and the concentration of SiO ₂ contained in the aqueous alkaline developing solution and the developing replenishing solution is 1.0. .About.4.0% by weight, and the concentration of SiO _{2 in} the running developer is kept constant.

Examples of the alkali metal silicate used in the first invention include potassium silicate, sodium silicate, sodium metasilicate, potassium metasilicate and the like. The alkali metal is preferably potassium.

The aqueous alkaline developer and the developing replenisher include
An alkali agent other than alkali silicate can be contained. As such an alkaline agent, potassium hydroxide,
Sodium hydroxide, lithium hydroxide, sodium phosphate tribasic, sodium phosphate dibasic, potassium phosphate tribasic, potassium phosphate dibasic, ammonium phosphate tribasic, ammonium phosphate dibasic, sodium bicarbonate, sodium carbonate ,
Examples thereof include inorganic alkali agents such as potassium carbonate and ammonium carbonate, organic alkali agents such as mono-, di- or triethanolamine and tetraalkylammonium hydroxide, and organic ammonium silicates. As the alkaline agent, potassium compounds such as potassium hydroxide, potassium triphosphate, dibasic potassium phosphate and potassium carbonate are preferable.

The concentration of SiO ₂ contained in the aqueous alkaline developer is preferably 2.0 to 4.0% by weight. [SiO ₂ ] / [M] in the aqueous alkaline developer
(In the formula, [SiO ₂ ] represents the molar concentration of SiO ₂ ,
[M] indicates the molar concentration of the alkali metal. ) Is 0.5
It is preferable that it is ~ 1.0.

SiO contained in the aqueous alkaline developing replenisher
The concentration of ₂ is preferably 2.0 to 4.0% by weight. Further, [SiO ₂ ] / [M] in the aqueous alkaline developer and the developer replenisher is preferably 0.15 to 0.75.

In the present invention, the constant concentration of SiO ₂ in the running developer does not mean that there is no change, but that the concentration of SiO ₂ is almost constant in the running developer. Means that the SiO ₂ concentration during running development is ± 0.3% by weight.
It should be in the range of.

[0017] To keep the concentration of SiO ₂ in the constant in the running developer, may be a concentration of SiO ₂ in the developer replenisher substantially the same as SiO ₂ concentration of the developing solution (mother liquor).

A nonionic surfactant may be added to the aqueous alkaline developer and the developer replenisher. The amount of the nonionic surfactant added is in the range of 0.01 to 10% by weight, preferably 0.02 to 2% by weight.

The pH of the developer (25 ° C., the same below) is 1
2.5 to 13.0 is preferable, and the pH of the developing replenisher is 1.
It is preferably 3.1 to 13.8, and the pH of the developer replenisher is preferably 0.3 or more higher than the pH of the developer.

In the second invention, the aqueous alkaline developer and the developing replenisher are aqueous solutions of alkali metal silicates, and the aqueous alkaline developer contains an alkali-soluble resin of 0.1.
It is contained in an amount of 1 to 20% by weight.

Examples of the silicate used in the second invention include the silicates shown in the first invention. The preferred silicate is potassium silicate.

The aqueous alkaline developing solution and the developing replenishing solution include
Similar to the first invention, an alkali agent other than alkali silicate can be contained. Examples of the alkaline agent other than these alkali silicates include the alkaline agents shown in the first invention. Further, preferred alkaline agents are potassium compounds such as potassium hydroxide, potassium triphosphate, potassium diphosphate, potassium carbonate and the like.

The concentration of SiO ₂ contained in the aqueous alkaline developer is preferably 1.0 to 5.0% by weight. [SiO ₂ ] / [M] in the aqueous alkaline developer
Is preferably 0.3 to 1.2.

SiO contained in the aqueous alkaline developing replenisher
The concentration of ₂ is preferably 1.0 to 5.0% by weight. Further, [SiO ₂ ] / [M] in the aqueous alkaline developer and the developer replenisher is preferably 0.15 to 0.75.

Examples of the alkali-soluble resin added to the aqueous alkali developer include novolac resins and vinyl resins having alkali-soluble groups such as hydroxyl groups and carboxyl groups.

Examples of the novolak resin used in the present invention include resins obtained by condensing phenols with formaldehyde or ketone in the presence of an acid catalyst. Examples of the phenols include phenol, o-cresol, Examples include m-cresol, p-cresol, 3,5-xylenol, 2,4-xylenol, 2,5-xylenol, carvacrol, thymol, catechol, resorcin, hydroquinone, pyrogallol, phloroglucin, and the aldehyde is formaldehyde. , Benzaldehyde, acetaldehyde, crotonaldehyde, furfural and the like. Preferred of these are formaldehyde and benzaldehyde. In addition, examples of the ketone include acetone and methyl ethyl ketone.

The above phenol compounds may be used alone or in combination of two or more to condense with formaldehyde or a ketone to obtain a resin. Among these, preferred novolak resins are resins obtained by copolycondensing at least one selected from phenol, m-cresol, o-cresol and p-cresol with formaldehyde, and examples thereof include phenol-formaldehyde resin and m. −
Cresol / formaldehyde resin, o-cresol /
Formaldehyde resin, phenol / p-cresol /
Formaldehyde copolymer resin, m-cresol, p-
Cresol / formaldehyde copolycondensate resin, o-cresol / p-cresol / formaldehyde copolycondensate resin, phenol / m-cresol / p-cresol / formaldehyde copolycondensate resin, phenol / o-
Examples thereof include cresol / p-cresol / formaldehyde copolycondensation resin. Further, among the above novolak resins, phenol / m-cresol / p-cresol / formaldehyde resin is preferable. In addition, pyrogallol
Acetone resin is also preferred.

In the present invention, the above-mentioned novolak resin may be used alone or in combination of two or more kinds.

The molecular weight (polystyrene standard) of the above novolak resin is 2.0 × 10 9 as the weight average molecular weight Mw.
^{3 to} 2.0 × 10 ⁴ and number average molecular weight Mn of 7.0 × 10
A value within the range of ^{2 to} 5.0 × 10 ³ is preferable,
Furthermore, preferably, Mw is 3.0 × 10 ^{3 to} 6.0 × 1.
0 ³ and Mn are values in the range of 7.7 × 10 ^{2 to} 1.2 × 10 ³ . The molecular weight of the novolak resin in the present invention is measured by GPC (gel permeation chromatography method).

The above novolak resins may be used alone or in combination of two or more kinds.

Examples of the vinyl-based resin having an alkali-soluble group such as a hydroxyl group and a carboxyl group include polymers containing at least one structural unit represented by the following general formulas (X) to (XV).

[0032]

Embedded image

In the general formulas (X) to (XV), R
₁ and R ₂ each represent a hydrogen atom, an alkyl group or a carboxyl group, and preferably a hydrogen atom. R ₃ 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. R ₄ and R ₅ represent a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and preferably a hydrogen atom. A connects a nitrogen atom or an oxygen atom and an aromatic carbon atom,
Represents an alkylene group which may have a substituent, and m is 0
Represents an integer of 10 and B represents a phenylene group which may have a substituent or a naphthylene group which may have a substituent.

The vinyl polymer having a phenolic hydroxyl group used in the present invention preferably has a copolymer type structure, and the structural unit represented by each of the general formulas (X) to (XV) is As the monomer to be copolymerized with, for example, ethylene, propylene, isobutylene, butadiene, isoprene and other ethylenically unsaturated olefins, for example, styrene, α-methylstyrene,
Styrenes such as p-methylstyrene and p-chlorostyrene, for example, acrylic acids such as acrylic acid and methacrylic acid, for example, unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid and maleic anhydride, for example acrylic acid Methyl, ethyl acrylate, -n-butyl acrylate,
Esters of α-methylene aliphatic monocarboxylic acids such as isobutyl acrylate, dodecyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate and ethyl methacrylate For example, nitriles such as acrylonitrile and methacrylonitrile, amides such as acrylamide, and anilides such as acrylanilide, p-chloroacrylanilide, m-nitroacrylanilide, and m-methoxyacrylanilide, such as acetic acid. Vinyl esters such as vinyl, vinyl propionate, vinyl benzoate and vinyl acetate, for example, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether and β-chloroethyl vinyl ether. , Vinyl chloride, vinylidene chloride, vinylidene cyanide, for example, 1-methyl-1-methoxyethylene, 1,1-dimethoxyethylene, 1,2-dimethoxyethylene, 1,1-dimethoxycarbonylethylene, 1-methyl-1- Ethylene derivatives such as nitroethylene, such as N-vinylpyrrole,
N-vinylcarbazole, N-vinylindole, N-
There are N-vinyl monomers such as vinylpyrrolidene and N-vinylpyrrolidone. These vinyl-based monomers are present in the polymer compound with a structure in which the unsaturated double bond is cleaved.

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

These monomers may be bonded to the polymer used in the present invention in either a block or random state.

The alkali-soluble resin is preferably contained in the aqueous alkaline developer in an amount of 0.5 to 10% by weight.

A nonionic surfactant may be added to the aqueous alkaline developer and the developer replenisher. The amount of the nonionic surfactant added is in the range of 0.01 to 10% by weight, preferably 0.02 to 2% by weight.

The pH of the developer (25 ° C., the same applies hereinafter) is 1
2.5 to 13.0 is preferable, and the pH of the developing replenisher is 1.
It is preferably 3.1 to 13.8, and the pH of the developer replenisher is preferably 0.3 or more higher than the pH of the developer.

In the third invention, the aqueous alkaline developer and the developing replenisher are alkaline aqueous solutions of silicate, and the concentration of SiO ₂ contained in the aqueous alkaline developer is 3.0 to 7.0% by weight. [SiO ₂ ] / [M] is 0.5
~ 1.5, S contained in the aqueous alkaline developing replenisher
iO ₂ concentration is 0.5 to 3.0% by weight, [SiO ₂ ] /
[M] is 0.15 to 0.8.

Examples of the silicate used in the third invention include the silicates shown in the first invention. The preferred silicate is potassium silicate.

The aqueous alkaline developing solution and the developing replenishing solution include
Similar to the first invention, an alkali agent other than alkali silicate can be contained. Examples of the alkaline agent other than these alkali silicates include the alkaline agents shown in the first invention. Further, preferred alkaline agents are potassium compounds such as potassium hydroxide, potassium triphosphate, potassium diphosphate, potassium carbonate and the like.

The concentration of SiO ₂ contained in the aqueous alkaline developer is preferably 3.5 to 5.5% by weight. [SiO ₂ ] / [M] in the aqueous alkaline developer
Is preferably 0.6 to 1.2.

SiO contained in the aqueous alkaline developing replenisher
The concentration of ₂ is preferably 1.0 to 3.0% by weight. In addition, the [Si
O ₂ ] / [M] is preferably 0.2 to 0.65.

A nonionic surfactant may be added to the aqueous alkaline developer and the developer replenisher. The amount of the nonionic surfactant added is in the range of 0.01 to 10% by weight, preferably 0.02 to 2% by weight.

The pH of the developer (25 ° C., the same below) is 1
2.5 to 13.0 is preferable, and the pH of the developing replenisher is 1.
It is preferably 3.1 to 13.8, and the pH of the developer replenisher is preferably 0.3 or more higher than the pH of the developer.

Next, the photosensitive lithographic printing plate having a photosensitive layer on the support having a hydrophilic surface used in the present invention will be described.

The photosensitive lithographic printing plate which can be processed by the processing method of the present invention may be a negative photosensitive lithographic printing plate or a positive photosensitive lithographic printing plate, both of which are It can be mixed and processed.

The negative type photosensitive lithographic printing plate is a negative type photosensitive composition such as a photopolymerization type photosensitive composition, a photocrosslinking type photosensitive composition or a diazo compound on a support having a hydrophilic surface. A positive-working photosensitive lithographic printing plate is obtained by applying a coating solution prepared by dissolving a photosensitive composition containing a solvent in a solvent to form a photosensitive layer. It can be obtained by coating a photosensitive composition, for example, a photosensitive composition containing an o-quinonediazide compound in a solvent, to form a photosensitive layer.
These negative photosensitive lithographic printing plates and positive photosensitive lithographic printing plates are known, and any of them can be processed in the present invention.

As a solvent for dissolving the photosensitive composition,
Methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol monoisopropyl ether, propylene glycol, propylene glycol monoethyl ether acetate, Propylene glycol monobutyl ether,
Dipropylene glycol monomethyl ether, dipropylene glycol dicarboxylic acid methyl ether, dipropylene glycol methyl ethyl ether, ethyl formate, propyl formate, butyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, propione Ethyl acid, methyl butyrate, ethyl butyrate,
Dimethylformamide, dimethyl sulfoxide, dioxane, acetone, methyl ethyl ketone, cyclohexanone, methylcyclohexanone, diacetone alcohol,
Examples include acetylacetone and γ-butyrolactone. These solvents may be used alone or in combination of two or more.

As the coating method, conventionally known methods such as spin coating, wire bar coating, dip coating, air knife coating, roll coating, blade coating and curtain coating can be used.

The concentration of the coating solution is preferably in the range of 1 to 50% by weight. The coating amount of the coating liquid may be about 0.2 to 10 g / m ² as a solid content.

As the support of the photosensitive lithographic printing plate, paper,
Plastic (for example, polyethylene, polypropylene, polystyrene, etc.) laminated paper, aluminum (including aluminum alloys), metal plates such as zinc, copper, cellulose diacetate, cellulose triacetate, cellulose propionate, polyethylene terephthalate, polyethylene, Films of plastics such as polypropylene, polycarbonate, polyvinyl acetal, etc.
Examples include papers or plastic films laminated or vapor-deposited with the metals as described above, and steel plates plated with aluminum or chrome. Of these, aluminum and aluminum-coated composite supports are particularly preferable.

Further, surface treatment such as surface roughening treatment and anodizing treatment is carried out for the purpose of imparting hydrophilicity to the surface of the aluminum material, improving adhesion to the photosensitive layer, and enhancing surface strength. .

Examples of the surface roughening method include generally known brush polishing method, ball polishing method, electrolytic etching, chemical etching, liquid honing, sand blasting and the like and combinations thereof, preferably brush polishing method,
Electrolytic etching, chemical etching and liquid honing are mentioned, of which the roughening method involving the use of electrolytic etching is particularly preferred. Further, as the electrolytic bath used in the electrolytic etching, an aqueous solution containing an acid, an alkali or a salt thereof or an aqueous solution containing an organic solvent is used, and among these, an electrolytic solution containing hydrochloric acid, nitric acid or a salt thereof is particularly used. Liquids are preferred. Further, the surface-roughened aluminum plate is desmutted with an acid or alkali aqueous solution, if necessary. The aluminum plate thus obtained is preferably anodized, and particularly preferably, a method of treating with a bath containing sulfuric acid or phosphoric acid can be mentioned. Further, if necessary, surface treatment such as treatment with an alkali silicate or hot water or immersion in a water-soluble polymer compound or an aqueous solution of potassium fluorozirconate can be performed to enhance hydrophilicity.

Next, specific examples of the photosensitive composition for forming a photosensitive layer by coating on a support having a hydrophilic surface will be described. 1) Photopolymerizable photosensitive resin composition As the photopolymerizable photosensitive resin composition, for example, (a) a vinyl monomer having at least two terminal vinyl groups,
Examples thereof include a photocrosslinking photosensitive composition composed of a polymer compound as a photopolymerization initiator (b) and a binder (c).

As the vinyl monomer of the above component (a),
For example, Japanese Examined Patent Publication Nos. 35-5093 and 35-14719.
And the acrylic acid or methacrylic acid esters of polyols [for example, diethylene glycol di (meth)] are used.
Acrylate, triethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate], methylenebis (meth) acrylamide, bis (meth) acrylamides such as ethylenebis (meth) acrylamide , And an unsaturated monomer containing a urethane group, for example, di- (2′-methacryloxyethyl)-
Examples include reaction products of diol mono (meth) acrylate and diisocyanate such as 2,4-tolylene diurethane and di- (2-acryloxyethyl) trimethylene diurethane.

Examples of the photopolymerization initiator as the component (b) include carbonyl compounds as described in Chapter 5 of "Light Sensitive Systems" by J. Kosar,
Examples thereof include organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, and photoreducible dyes. Specific photopolymerization initiators are disclosed in British Patent No. 1,459,563, and the photopolymerization initiators disclosed herein can be used in the present invention.

As the binder of the component (c), various known polymers can be used. For details of specific binders, see US Pat. No. 4,072,52.
No. 7 specification.

Further, for example, polyester resin, vinyl chloride-vinyl acetate copolymer, acrylic resin, vinyl chloride resin, polyamide resin, polyvinyl butyral resin, epoxy resin, acrylate copolymer, vinyl acetate copolymer, phenoxy. Resin, polyurethane resin, polycarbonate resin, polyacrylonitrile butadiene, polyvinyl acetate, lipophilic polymer compound having a hydroxyl group (for example, a monomer having an aliphatic hydroxyl group in the side chain, for example,
A copolymer of 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate with another copolymerizable monomer), a monomer having an aromatic hydroxyl group as described in JP-A-54-98613. Body (eg, N- (4-hydroxyphenyl) acrylamide,
N- (4-hydroxyphenyl) methacrylamide, o
-, M- or p-hydroxystyrene, o-, m- or p-hydroxyphenylmethacrylate) with other copolymerizable monomers, U.S. Pat.
Polymers containing hydroxyethyl acrylate units or hydroxyethyl methacrylate units as main repeating units described in 3,276, natural resins such as shellac and rosin, polyvinyl alcohol,
Polyamide resin described in US Pat. No. 3,751,257, linear polyurethane resin described in US Pat. No. 3,660,097, phthalated resin of polyvinyl alcohol, and bisphenol A. Epoxy resin condensed with epichlorohydrin, alkali-soluble resin (for example, novolac resin, vinyl polymer having phenolic hydroxyl group, JP-A-55-57841)
And a polycondensation resin of an aldehyde or a ketone) and the like described in Japanese Patent Laid-Open Publication No. 2004-242242. Examples of the novolac resin include phenol / formaldehyde resin, cresol / formaldehyde resin, JP-A-5
Phenol / cresol / formaldehyde copolycondensation resin as described in JP-A-5-57841, p as described in JP-A-55-127553
-A copolycondensation resin of substituted phenol and phenol or cresol and formaldehyde, etc. may be mentioned.

(A) a vinyl monomer having at least two terminal vinyl groups, (b) a photopolymerization initiator and (c) a polymer compound as a binder are contained in the solid content of the photopolymerizable photosensitive material ( a) is 20 to 80% by weight, and (b) is 0.1 to
It is preferable that 20% by weight and 20 to 80% by weight of (c) are contained.

The photopolymerizable photosensitive resin composition may contain a diazo compound, a thermal polymerization inhibitor, a plasticizer, a dye or a pigment. 2) Photocrosslinkable photosensitive composition The photocrosslinkable photosensitive composition contains a compound having a photodimerizable group.

Examples of the compound having a photodimerizable group include
For example, the compound which has the structure shown by the following general formula (I)-(VIII) can be mentioned.

[0064]

Embedded image

[0065]

Embedded image

[0066]

[Chemical 4] In the general formula (I), the general formula (II) and the general formula (III), R ₁ represents an aryl group or a heterocyclic group, which are an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a nitro group or an amino group. It may have an alkoxycarbonyl group, an acyloxy group, an alkanoyl group, a cyano group or an azido group. R ₂ represents hydrogen or an alkyl group having 1 to 10 carbon atoms, and R ₃ represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkanoyl group or a cyano group. n shows the integer of 0-5.

[0067]

Embedded image

[0068]

[Chemical 6] In the general formula (VI), Ar represents an aryl group and R ₄
Represents hydrogen, halogen, an alkyl group having 1 to 10 carbon atoms, or a cyano group.

[0069]

[Chemical 7] Examples of the compound having such a structure include cinnamic acid ester, β-furyl acrylic acid ester, α-cyanocinnamic acid ester, p-azidocinnamic acid ester, β-styryl acrylic acid ester, α-cyano-β-styryl acrylic acid. Acid ester, p-phenylenediacrylic acid ester, p- (2-benzoylvinyl) -cinnamic acid ester, β-naphthyl acrylic acid ester, cinnamylidene pyruvate ester, α-methyl-β-styryl acrylic acid ester, α-phenyl-β-styryl acrylic acid ester, α-cyano-β-furyl acrylic acid ester, p-dimethylaminocinnamic acid ester, amide corresponding to the above ester, chalcone, benzylideneacetone, stilbazole, stilbene, α-phenylmaleimide, coumarin, pi Emissions, anthracene, dibenzazepine, or These induction, and the like, but is not limited thereto.

These compounds having a photodimerizable group can be used alone or in admixture of two or more kinds.

In the photocrosslinking photosensitive composition, a sensitizer is used in addition to the compound having a photodimerizable group.

Typical examples of the sensitizer include 2,4,7-
Trinitro-9-fluorenone, 5-nitroacenaphthene, p-nitrodiphenyl, p-nitroaniline, 2-
Nitrofluorenone, 1-nitropyrene, N-acetyl-4-nitro-1-naphthylamine, N-benzoyl-
4-nitro-1-naphthylamine, Michler's ketone,
N-butylacridone, 5-benzoylacenaphthene,
1,8-phthaloylnaphthalene, 1,2-benzanthracene, 9,10-phenanthraquinone, chlorobenzanthron, N-phenylthioacridone, 1,2-benzanthraquinone, N-methyl-2- Examples thereof include, but are not limited to, benzoylmethylene-β-naphthothiazole, 2-chlorotioxaton, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, eosin, erythosine and picramide. . The use of these sensitizers is not essential, but they are used for the purpose of increasing the light utilization efficiency on the longer wavelength side.

If necessary, an inorganic powder or a polymer may be mixed with the photocrosslinking photosensitive composition for the purpose of providing shape retention.

What is useful as the above-mentioned inorganic powder is one that can be dispersed in the photocrosslinking photosensitive composition.
Colloidal silica, calcium carbonate, titanium oxide and the like can be mentioned. Further, as the above-mentioned polymer, a compound having a photodimerizable group, and further, an ordinary vinyl polymer as long as it has a property of being mixed with a sensitizer,
(Meth) acrylic acid ester polymer, unvulcanized rubber, polyether, polyamide, polyester, polyurethane, epoxy resin, urea resin, alkyd resin, melamine resin, phenol resin, gum rosin, polyterpene,
The coumarone-indene resin, as well as mixtures thereof, can be widely used.

Further, the photocrosslinking photosensitive composition may contain a diazo compound. 3) Photosensitive composition containing diazo compound Among these diazo compounds, a diazo resin which is a condensate of p-diazodiphenylamine and formaldehyde is typical, and those which are insoluble in water and soluble in an organic solvent are preferable. For example, water-insoluble and ordinary organic solvent-soluble compounds described in JP-B-47-1167 and JP-A-57-43890 can be mentioned.

An example of the diazo resin is the diazo resin represented by the following general formula (IX).

[0077]

Embedded image [In the formula, R ¹ , R ² and R ³ each represent a hydrogen atom, an alkyl group or an alkoxy group, and R ⁴ represents a hydrogen atom, an alkyl group or a phenyl group. X represents a PF ₆ or BF _4, Y is -NH -, - shows S- or -O-. In the diazo resin, examples of the diazo monomer include 4-
Diazo-diphenylamine, 1-diazo-4-N, N-
Dimethylaminobenzene, 1-diazo-4-N, N-diethylaminobenzene, 1-diazo-4-N-ethyl-
N-hydroxyethylaminobenzene, 1-diazo-4
-N-methyl-N-hydroxyethylaminobenzene,
1-diazo-2,5-diethoxy-4-benzoylaminobenzene, 1-diazo-4-N-benzylaminobenzene, 1-diazo-4-N, N-dimethylaminobenzene, 1-diazo-4-morpholinobenzene , 1-diazo-2,5-dimethoxy-4-p-tolylmercaptobenzene, 1-diazo-2-ethoxy-4-N, N-dimethylaminobenzene, p-diazo-dimethylaniline, 1
-Diazo-2,5-diethoxy-4-morpholinobenzene, 1-diazo-2,5-diethoxy-4-morpholinobenzene, 1-diazo-2,5-dimethoxy-4-morpholinobenzene, 1-diazo-2, 5-diethoxy-4
-P-Tolylmercaptobenzene, 1-diazo-4-N
-Ethyl-N-hydroxyethylaminobenzene, 1-
Diazo-3-ethoxy-4-N-methyl-N-benzylaminobenzene, 1-diazo-3-chloro-4-N, N
-Diethylaminobenzene, 1-diazo-3-methyl-
4-pyrrolidinobenzene, 1-diazo-2-chloro-4
-N, N-dimethylamino-5-methoxybenzene, 1
-Diazo-3-methoxy-4-pyrrolidinobenzene, 3
-Methoxy-4-diazodiphenylamine, 3-ethoxy-4-diazodiphenylamine, 3- (n-propoxy) -4-diazodiphenylamine, 3- (isopropoxy) -4-diazodiphenylamine and the like can be mentioned.

Examples of the aldehyde used as the condensing agent with the diazo monomer include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, and benzaldehyde.

The diazo resin used in the present invention is a co-condensed diazo resin containing an aromatic compound having at least one group selected from the group consisting of a carboxyl group and a hydroxyl group and an aromatic diazonium compound as a constituent unit in the molecule. Resins are preferred.

The aromatic compound having at least one group selected from the group consisting of a carboxyl group and a hydroxyl group means an aromatic ring substituted with at least one carboxyl group and / or an aromatic ring substituted with at least one hydroxyl group. An aromatic ring is included in the molecule, and in this case, the carboxyl group and the hydroxyl group may be substituted with the same aromatic ring.

The aromatic ring is preferably an aryl group, for example, a phenyl group or a naphthyl group.

The above-mentioned carboxyl group or hydroxyl group may be directly bonded to the aromatic ring, or may be bonded via some bonding group (hereinafter, simply referred to as a joint).

In the above case, the number of carboxyl groups bonded to one aromatic ring is preferably 1 or 2, and the number of hydroxyl groups bonded to one aromatic ring is preferably 1 to 3. Furthermore, examples of the joint include an alkylene group having 1 to 4 carbon atoms.

Specific examples of the aromatic compound having at least one group selected from the group consisting of the above-mentioned carboxyl group and hydroxyl group include benzoic acid, (o, m, p) -chlorobenzoic acid, phthalic acid and terephthalate. Acid, diphenylacetic acid, phenoxyacetic acid, p-methoxyphenylacetic acid, p-
Methoxybenzoic acid, 2,4-dimethoxybenzoic acid, 2,
4-Dimethylbenzoic acid, p-phenoxybenzoic acid, 4-
Anilinobenzoic acid, 4- (m-methoxyanilino) benzoic acid, 4- (p-methoxybenzoyl) benzoic acid, 4-
(P-Methylanilino) benzoic acid, 4-phenylsulfonylbenzoic acid, phenol, (o, m, p) -cresol, xylenol, resorcin, 2-methylresorcin, (o, m, p) -methoxyphenol, m-ethoxy. Phenol, catechol, phloroglysin, p-hydroxyethylphenol, naphthol, pyrogallol,
Hydroquinone, p-hydroxybenzyl alcohol, 4
-Chlororesorcin, biphenyl 4,4'-diol,
1,2,4-benzenetriol, bisphenol A,
2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, p-hydroxyacetophenone, 4,4'-dihydroxydiphenyl ether,
4,4'-dihydroxydiphenylamine, 4,4'-
Dihydroxydiphenyl sulfide cumylphenol,
(O, m, p) -chlorophenol, (o, m, p)-
Bromophenol, salicylic acid, 4-methylsalicylic acid, 6-methylsalicylic acid, 4-ethylsalicylic acid, 6
-Propyl salicylic acid, 6-lauryl salicylic acid, 6-
Stearyl salicylic acid, 4,6-dimethyl salicylic acid,
p-Hydroxybenzoic acid, 2-methyl-4-hydroxybenzoic acid, 6-methyl-4-hydroxybenzoic acid, 2,
6-dimethyl-4-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,4-dihydroxy-6-methylbenzoic acid, 2,6-dihydroxybenzoic acid, 2,6-dihydroxy-4-methylbenzoic acid, 4-chloro-2,6
-Dihydroxybenzoic acid, 4-methoxy-2,6-dioxybenzoic acid, gallic acid, phloroglucin carboxylic acid,
2,4,5-Trihydroxybenzoic acid, m-galloyl gallic acid, tannic acid, m-benzoyl gallic acid, m-
(P-toluyl) gallic acid, protocatechuoyl-gallic acid, 4,6-dihydroxyphthalic acid, (2,4-dihydroxyphenyl) acetic acid, (2,4-dihydroxyphenyl) acetic acid, (3,4,5-5- Trihydroxyphenyl)
Acetic acid, p-hydroxymethylbenzoic acid, p-hydroxyethylbenzoic acid, 4- (p-hydroxyphenyl) methylbenzoic acid, 4- (o-hydroxybenzoyl) benzoic acid, 4- (2,4-dihydroxybenzoyl) benzoic acid Acid, 4- (p-hydroxyphenoxy) benzoic acid, 4-
(P-Hydroxyanilino) benzoic acid, bis (3-carboxy-4-hydroxyphenyl) amine, 4- (p-
Hydroxyphenylsulfonyl) benzoic acid, 4- (p-
Hydroxyphenylthio) benzoic acid and the like can be mentioned, of which salicylic acid, p-hydroxybenzoic acid, p-methoxybenzoic acid, and metachlorobenzoic acid are particularly preferable.

Examples of the aromatic diazonium compound forming the constitutional unit of the above-mentioned co-condensed diazo resin include, for example, JP-B-49-
Although diazonium salts such as those listed in Japanese Patent No. 48001 can be used, in particular, diphenylamine-
4-diazonium salts are preferred.

The diphenylamine-4-diazonium salts are derived from 4-amino-diphenylamines, and such 4-amino-diphenylamines include 4-amino-diphenylamine and 4-amino-3-.
Methoxy-diphenylamine, 4-amino-2-methoxy-diphenylamine, 4-amino-2'-methoxy-
Diphenylamine, 4-amino-4'-methoxy-diphenylamine, 4-amino-3-methyldiphenylamine, 4-amino-3-ethoxy-diphenylamine, 4
-Amino-3-β-hydroxy-ethoxydiphenylamine, 4-amino-diphenylamine-2-sulfonic acid, 4-amino-diphenylamine-2-carboxylic acid,
4-amino-diphenylamine-2'-carboxylic acid and the like can be mentioned, and 4-amino-4'-methoxy-diphenylamine and 4-amino-diphenylamine are particularly preferable.

The co-condensed diazo resin can be obtained by a known method, for example, Photographic Science and Engineering (Photo.Sci.Eng.) Vol. 17, p. 33 (1973), US Pat. No. 2,063, According to the method described in each of No. 631, No. 2,679,498, in a sulfuric acid, a phosphoric acid, or a hydrochloric acid, a diazonium salt, an aromatic compound having a carboxyl group and / or a hydroxyl group, an aromatic diazo compound, and It is obtained by polycondensing aldehydes such as paraformaldehyde, acetaldehyde, benzaldehyde or ketones such as acetone and acetophenone.

The aromatic compound having a carboxyl group and / or a hydroxyl group in the molecule, the aromatic diazo compound and the aldehydes or ketones can be freely combined with each other, and two or more kinds of them can be mixed and co-condensed. It is also possible to do so.

The molar ratio of the aromatic compound having at least one of the carboxyl group and the hydroxyl group to the aromatic diazo compound is usually 1: 0.1 to 0.1:
1, preferably 1: 0.5 to 0.2: 1, more preferably 1: 1 to 0.2: 1. In this case, the total molar ratio of aromatic compounds and aromatic diazo compounds having at least one of a carboxyl group and a hydroxyl group and aldehydes or ketones is usually 1: 0.6.
To 1.5, preferably 1: 0.7 to 1.2, and the reaction is carried out at a low temperature for a short time, for example, for about 3 hours to obtain a co-condensed diazo resin.

A counter anion is used in the above co-condensed diazo resin. The counter anion includes an anion that stably forms a salt with the diazo resin and makes the resin soluble in an organic solvent. These include organic carboxylic acids such as decanoic acid and benzoic acid, organic phosphoric acids such as phenylphosphoric acid and sulfonic acids, and typical examples include methanesulfonic acid,
Chloroethanesulfonic acid, dodecanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, mesitylenesulfonic acid, and anthraquinonesulfonic acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, hydroxysulfonic acid, 4-acetylbenzenesulfonic acid, Aliphatic and aromatic sulfonic acids such as dimethyl-5-sulfoisophthalate, 2,2 ', 4,4'-tetrahydroxybenzophenone, 1,2,3-trihydroxybenzophenone, 2,2', 4-trihydroxy Examples thereof include, but are not limited to, hydroxyl group-containing aromatic compounds such as benzophenone, halogenated Lewis acids such as hexafluorophosphoric acid and tetrafluoroboric acid, and perhalogen acids such as ClO ₄ and IO ₄ . Among these, particularly preferred are hexafluorophosphoric acid, tetrafluoroboric acid, and 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid.

The above-mentioned co-condensation diazo resin can be obtained as an arbitrary value for the molecular weight by variously changing the molar ratio of each monomer and the condensation conditions, but it is effectively used for the intended purpose of the present invention. In order to have a molecular weight of about 400-10
It is generally selected from the range of 000, but is preferably about 800 to 5000.

The diazo compound is usually contained in the solid content of the photosensitive composition in an amount of 1 to 20% by weight, preferably 2 to 10% by weight. 4) Photosensitive composition containing orthoquinonediazide compound Examples of the orthoquinonediazide compound include ester compounds of o-naphthoquinonediazide sulfonic acid and a polycondensation resin of phenols and aldehydes or ketones.

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

Examples of the aldehyde include formaldehyde, benzaldehyde, acetaldehyde, crotonaldehyde, furfural and the like. Preferred of these are formaldehyde and benzaldehyde. In addition, examples of the ketone include acetone and methyl ethyl ketone.

Specific examples of the polycondensation resin include phenol / formaldehyde resin, m-cresol / formaldehyde resin, m-, p-mixed cresol / formaldehyde resin, resorcin / benzaldehyde resin, pyrogallol / acetone resin and the like. To be

In the o-naphthoquinonediazide compound, the condensation rate of o-naphthoquinonediazide sulfonic acid with respect to the OH groups of phenols (reaction rate with respect to one OH group) is preferably 15 to 80%, more preferably 2
0 to 45%.

Further, as the orthoquinonediazide compound, the following compounds described in JP-A-58-43451 can also be mentioned. That is, for example, known 1,2-benzoquinone diazide sulfonic acid ester, 1,2-naphthoquinone diazide sulfonic acid ester, 1,2-benzoquinone diazide sulfonic acid amide, 1,2-naphthoquinone diazide sulfonic acid amide, etc. -Quinonediazide compounds, more specifically Jei Cosar (J.
Kosar) "Light Sensitive Systems"("L
ight-Sensitive Systems ”) pages 339-352 (19)
1965, John Willy and Sons (John W)
iley & Sons) (New York) and W.S.
1,2-Benzoquinonediazide-4-sulfonic acid described in "Photoresist", Volume 50, (1975) by WS De Forest, McGraw-Hill (New York). Phenyl ester, 1,2,1 ', 2'-di- (benzoquinonediazide-4-sulfonyl) -dihydroxybiphenyl, 1,2-benzoquinonediazide-4- (N
-Ethyl-N-β-naphthyl) -sulfonamide, 1,
2-naphthoquinonediazide-5-sulfonic acid cyclohexyl ester, 1- (1,2-naphthoquinonediazide-
5-sulfonyl) -3,5-dimethylpyrazole, 1,
2-naphthoquinonediazide-5-sulfonic acid-4 ″ -hydroxydiphenyl-4 ″ -azo-β-naphthol ester, N, N-di- (1,2-naphthoquinonediazide-
5-sulfonyl) -aniline, 2- (1,2-naphthoquinonediazide-5-sulfonyloxy) -1-hydroxy-anthraquinone, 1,2-naphthoquinonediazide-
5-sulfonic acid-2,4-dihydroxybenzophenone ester, 1,2-naphthoquinonediazide-5-sulfonic acid-2,3,4-trihydroxybenzophenone ester, 1,2-naphthoquinonediazide-5-sulfonic acid chloride 2 mol And 4,4'-diaminobenzophenone 1
2 moles of condensate, 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 4,4'-dihydroxy-
1,1'-diphenylsulfone 1 mol condensate, 1,2
Examples include 1,2-quinonediazide compounds such as a condensate of 1 mol of naphthoquinonediazide-5-sulfonic acid chloride and 1 mol of purpurogallin and 1,2-naphthoquinonediazide-5- (N-dihydroabietyl) -sulfonamide. it can. In addition, Japanese Examined Patent Publication Nos. 37-1953 and 3
7-3627, 37-13109, 40-26
No. 126, No. 40-3801, No. 45-5604,
45-27345, 51-13013, JP-A-48-96575, 48-63802, 48-.
The 1,2-quinonediazide compounds described in Japanese Patent No. 63803 can also be mentioned.

Of the above o-quinonediazide compounds,
An o-quinone diazide ester compound obtained by reacting 1,2-benzoquinone diazide sulfonyl chloride or 1,2-naphthoquinone diazide sulfonyl chloride with pyrogallol-acetone condensation resin or 2,3,4-trihydroxybenzophenone is particularly preferable.

In the present invention, each of the above compounds may be used alone as the o-quinonediazide compound,
Moreover, you may use it in combination of 2 or more type.

It is preferable to mix an alkali-soluble resin in the photosensitive composition containing the orthoquinonediazide compound. Examples of these alkali-soluble resins include novolac resins, vinyl polymers having a phenolic hydroxyl group, 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, JP-A-55. Examples thereof include a copolycondensation resin of p-substituted phenol and phenol or cresol and formaldehyde as described in JP-A-127553.

The molecular weight of the novolac resin (polystyrene standard) is preferably 3.00 × 10 in terms of number average molecular weight Mn.
^{2 to} 7.50 × 10 ³ , weight average molecular weight Mw of 1.00 ×
10 ^{3 to} 3.00 × 10 ⁴ , more preferably Mn of 5.0
0 × 10 ^{2 to} 4.00 × 10 ³ , Mw of 3.00 × 10 ^3.
˜2.00 × 10 ⁴ .

The above novolak resins may be used alone or in combination of two or more kinds.

The proportion of the novolak resin in the photosensitive composition is preferably 5 to 95% by weight.

The above-mentioned vinyl polymer having a phenolic hydroxyl group used in the present invention is a polymer having a unit having a phenolic hydroxyl group in its molecular structure, and is at least one of the following general formulas (X) to (XV). Polymers containing one structural unit are preferred.

[0106]

[Chemical 9]

In the general formulas (X) to (XV), R
₁ and R ₂ each represent a hydrogen atom, an alkyl group or a carboxyl group, and preferably a hydrogen atom. R ₃ 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. R ₄ and R ₅ represent a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and preferably a hydrogen atom. A connects a nitrogen atom or an oxygen atom and an aromatic carbon atom,
Represents an alkylene group which may have a substituent, and m is 0
Represents an integer of 10 and B represents a phenylene group which may have a substituent or a naphthylene group which may have a substituent.

The vinyl polymer having a phenolic hydroxyl group used in the present invention preferably has a copolymer type structure, and the structural unit represented by each of the general formulas (X) to (XV) can be used. As the monomer to be copolymerized with, for example, ethylene, propylene, isobutylene, butadiene, isoprene and other ethylenically unsaturated olefins, for example, styrene, α-methylstyrene,
Styrenes such as p-methylstyrene and p-chlorostyrene, for example, acrylic acids such as acrylic acid and methacrylic acid, for example, unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid and maleic anhydride, for example acrylic acid Methyl, ethyl acrylate, -n-butyl acrylate,
Esters of α-methylene aliphatic monocarboxylic acids such as isobutyl acrylate, dodecyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate and ethyl methacrylate For example, nitriles such as acrylonitrile and methacrylonitrile, amides such as acrylamide, and anilides such as acrylanilide, p-chloroacrylanilide, m-nitroacrylanilide, and m-methoxyacrylanilide, such as acetic acid. Vinyl esters such as vinyl, vinyl propionate, vinyl benzoate and vinyl acetate, for example, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether and β-chloroethyl vinyl ether. , Vinyl chloride, vinylidene chloride, vinylidene cyanide, for example, 1-methyl-1-methoxyethylene, 1,1-dimethoxyethylene, 1,2-dimethoxyethylene, 1,1-dimethoxycarbonylethylene, 1-methyl-1- Ethylene derivatives such as nitroethylene, such as N-vinylpyrrole,
N-vinylcarbazole, N-vinylindole, N-
There are N-vinyl monomers such as vinylpyrrolidene and N-vinylpyrrolidone. These vinyl-based monomers are present in the polymer compound with a structure in which the unsaturated double bond is cleaved.

Of the above monomers, aliphatic monocarboxylic acid esters and nitriles are preferable because they exhibit excellent performance for the purpose of the present invention.

These monomers may be bonded to the polymer used in the present invention in either a block or random state.

The proportion of the vinyl polymer having a phenolic hydroxyl group in the photosensitive composition is preferably 0.5 to 70% by weight.

As the vinyl polymer having a phenolic hydroxyl group, the above polymers may be used alone or in combination of two or more kinds. It can also be used in combination with other polymer compounds.

The orthoquinonediazide compound accounts for 6% of the orthoquinonediazide compound in the photosensitive material.
-60% by weight is preferable, and particularly preferable is 10-5.
0% by weight.

If necessary, a plasticizer, a surfactant, an organic acid, an acid anhydride and the like can be added to the photosensitive composition containing the orthoquinonediazide compound.

Further, in order to improve the oil sensitivity of the photosensitive composition, a photosensitive layer containing an orthoquinonediazide compound as a photosensitive material may contain, for example, p-tert-butylphenolformaldehyde resin or pn-octylphenolformaldehyde. It is also possible to add a resin or a sensitizer such as a resin in which these resins are partially esterified with an o-quinonediazide compound.

A printout material capable of forming a visible image upon exposure can be added to the photosensitive composition which is coated on a support having a hydrophilic surface to form a photosensitive layer. The printout material is used with a compound that produces an acid or a free radical upon exposure to light and changes its color tone by interacting with the acid or free radical generated from the compound upon exposure to form a color image. For the printout material, a dye that changes its color tone by interacting with the above-mentioned acid or free radical generated by exposure is used.

As the dye, those which change the color tone by reacting with free radicals or acids can be preferably used.
Here, "the color tone changes" includes any change from colorless to colored color tone, and from colored to colorless or different colored color tone. Preferred dyes are those which form a salt with an acid to change the color tone.

For example, Victoria Pure Blue BOH
[Hodogaya Chemical Co., Ltd.], Oil Blue # 603 [Orient Chemical Co., Ltd.], Patent Pure Blue [Sumitomo Mikuni Chemical Co., Ltd.], Crystal Violet, Brilliant Green, Ethyl Violet, Methyl Violet, Methyl Green, Erythrosin B, Basic Fuchsin ,
Triphenylmethane-based, diphenylmethane-based, oxazine-based, xanthene-based represented by malachite green, oil red, m-cresol purple, rhodamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, cyano-p-diethylaminophenylacetanilide and the like. , An iminonaphthoquinone-based, azomethine-based, or anthraquinone-based dye is mentioned as an example of a color-changing agent that changes from a colored color to a colorless or different colored color tone.

On the other hand, examples of the changing agent that changes from colorless to colored include leuco dyes and triphenylamine,
Diphenylamine, o-chloroaniline, 1,2,3-
Triphenylguanidine, naphthylamine, diaminodiphenylmethane, p, p'-bis-dimethylaminodiphenylamine, 1,2-dianilinoethylene, p,
p ', p "-tris-dimethylaminotriphenylmethane, p, p'-bis-dimethylaminodiphenylmethylimine, p, p', p" -triamino-o-methyltriphenylmethane, p, p'-bis -Dimethylaminodiphenyl-4-anilinonaphthylmethane, p, p ', p "
-Primary or secondary arylamine dyes represented by triaminotriphenylmethane.

Particularly preferred are triphenylmethane-based and diphenylmethane-based dyes, more preferred are triphenylmethane-based dyes, and particularly Victoria Pure Blue BOH.

The above dye is usually contained in the solid content of the photosensitive composition in an amount of 0.5 to 10% by weight, preferably about 1 to 5%.
It is contained by weight%.

Various additives can be further added to the photosensitive composition which is coated on a support having a hydrophilic surface to form a photosensitive layer.

For example, alkyl ethers (eg, ethyl cellulose, methyl cellulose) for improving coating properties, fluorochemical surfactants, and nonionic surfactants (eg, Pluronic L-64 (Asahi Denka Co., Ltd.)
A), a plasticizer for imparting flexibility and abrasion resistance to the coating film (for example, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate,
Tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or methacrylic acid oligomers and polymers), an oil sensitizer for improving the oil sensitivity of the image area (for example, JP-A-55) -527-styrene-maleic anhydride copolymer alcohol-based half-esterified products), stabilizers [eg phosphoric acid, phosphorous acid, organic acids (citric acid, oxalic acid, benzenesulfonic acid, naphthalenesulfone) Acid, 4-methoxy-2-hydroxybenzophenone-5-sulfonic acid, tartaric acid, etc.), a development accelerator (eg, higher alcohol, acid anhydride, etc.) and the like.
The addition amount of these additives varies depending on the intended purpose of use, but is generally 0.
It is from 01 to 30% by weight.

When the photosensitive composition is a photopolymerization type photosensitive composition or a photocrosslinking type photosensitive composition, in order to prevent the polymerization inhibiting action by oxygen in the air, for example, polyvinyl alcohol, acidic celluloses and the like are used. A protective layer made of such a polymer having an excellent oxygen barrier property may be provided on the surface of the photosensitive lithographic printing plate.

Image exposure of a photosensitive lithographic printing plate having a photosensitive layer on a support having a hydrophilic surface is carried out through a transparent original image having a line image, a halftone image and the like. As a source of active light suitable for exposure, a carbon arc lamp, a mercury lamp,
Examples include xenon lamps, metal halide lamps and strobes.

[0126]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1 << Positive-type photosensitive lithographic printing plate sample >> JI having a thickness of 0.24 mm
An S-1050 aluminum plate was immersed in a 2% sodium hydroxide aqueous solution, degreased, electrochemically roughened in a dilute nitric acid solution, thoroughly washed, and then anodized in a dilute sulfuric acid solution. Then, an oxide film of 2.5 g / m ² was formed on the surface of the aluminum plate. The aluminum plate thus treated was washed with water, dried, and then coated with a photosensitive composition coating solution having the following composition so that the dry weight was 2.2 g / m ² , and dried to obtain a positive photosensitive lithographic printing plate. A sample was obtained.

<Photosensitive Composition Coating Solution> An ester compound of naphthoquinone- (1,2) -diazide- (2) -5-sulfonic acid chloride and pyrogallol-acetone resin (Japanese Patent Application Laid-Open No. 60-143345). Compound described in 2.) 2.5 parts by weight Copolycondensation resin of phenol and m-, p-mixed cresol and formaldehyde (molar ratio of phenol, m-cresol and p-cresol charged is 10:54:36, Weight average molecular weight 4800) 7.0 parts by weight Novolak resin synthesized from p-tert-octylphenol and formaldehyde Ester compound of naphthoquinone- (1,2) -diazide- (2) -5-sulfonic acid chloride (condensation) Ratio: 50 mol%, Mw = 1700) 0.1 parts by weight Polyethylene glycol # 2000 0.1 parts by weight Amount: naphthoquinone- (1,2) -diazide- (2) -4-sulfonic acid chloride 0.05 part by weight Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.08 part by weight Ethyl Cellosolve 80 parts by weight Methyl Cellosolve 20 parts by weight << Sample of negative photosensitive lithographic printing plate >> 3% of aluminum plate
It was degreased with sodium hydroxide, and this was degreased in a 11.5 g / liter hydrochloric acid bath at 25 ° C. and a current density of 80 A / dm ²
Second electrolytic etching, washing with water, 30 ° C in 30% sulfuric acid bath,
Anodization was performed for 15 seconds under the condition of 11.5 A / dm ² . Next, it was treated with a 1% sodium metasilicate aqueous solution at 85 ° C. for 30 seconds, washed with water and dried to obtain an aluminum plate for a lithographic printing plate. After filtering the photosensitive composition coating solution having the following composition on the aluminum plate thus treated, it was coated on a support using a bar coater to a dry weight of 2.0 g / m ² , and dried. A negative photosensitive lithographic printing plate sample was obtained.

<Photosensitive Composition Coating Liquid> Trimethylolpropane triacrylate 0.3 g Poly (N- (4-hydroxyphenyl) methacrylamide / acrylonitrile / methylmethacrylate / methacrylic acid) copolymer Molar ratio 25/25 / 42/8 copolymer (Mw: 42000) 0.3 g Nippon Kayaku Co., Ltd. DETX (the following structure) 0.03 g

[0130]

[Chemical 10] Nippon Kayaku Co., Ltd. EPA (the following structure) 0.03g

[0131]

[Chemical 11] Diazo resin-1 0.024 g Victoria blue BOH (trade name, manufactured by Hodogaya Chemical Co., Ltd.) 0.012 g JULIMER AC-10L (trade name, manufactured by Nippon Pure Chemical Co., Ltd.) 0.012 g Methyl Cellsolve 8.0 g , Diazo resin-1 is synthesized by the following.

3.5 g (25 mmol) of p-hydroxybenzoic acid and p-diazodiphenylamine sulfate 2
1.75 g (75 mmol) was dissolved in 90 g concentrated sulfuric acid under ice cooling. To this solution 2.7 g (90 mmol)
Paraformaldehyde was slowly added. On this occasion,
The reaction temperature was added so as not to exceed 10 ° C. After stirring the reaction solution for 2 hours, the mixture was added dropwise to 1 liter of ethanol, the generated precipitate was filtered off, and washed with ethanol. The precipitate was dissolved in 200 ml of pure water, and an aqueous solution in which 10.5 g of zinc chloride was dissolved was added. The generated precipitate was filtered, washed with ethanol, and then dissolved in 300 ml of pure water. An aqueous solution in which 13.7 g of ammonium hexafluorophosphate was dissolved was added to this solution. The formed precipitate is filtered off, washed with water and ethanol, and then washed with 25
It was dried at C for one day to obtain diazo resin-1. When the molecular weight of this diazo resin was measured by gel permeation chromatography (hereinafter abbreviated as GPC), the weight average molecular weight was about 2300.

The positive-working photosensitive lithographic printing plate sample and the negative-working photosensitive lithographic printing plate sample obtained as described above were added to an original film having a pattern of corresponding halftone dots and a step tablet for measuring sensitivity (Eastman).・ A 21-step gray scale (No. 2, density difference 0.15, manufactured by Kodak Co., Ltd.) was adhered and exposed with a 2 kW metal halide lamp as a light source under a condition of 8.0 mW / cm ² from a distance of 70 cm for 60 seconds.

Next, a developing solution and a developing replenishing solution having the following compositions were charged in an automatic developing machine under the following developing replenishing conditions to obtain the image-exposed positive-working photosensitive lithographic printing plate and negative-working photosensitive lithographic printing plate. Development processing was performed at 30 ° C. for 12 seconds.

<Development replenishment conditions> Replenishment of processing: 18 mm
Torr / m², Replenishment over time: 58 ml / h, daily replenishment
(Replenishment during non-working time of automatic processor): 55 millilitres
/ H <Developer> A Potassium silicate (SiO ₂: 26% by weight, K₂O: 13% by weight) 80 parts by weight Potassium hydroxide 12 parts by weight Water 620 parts by weight <Development replenisher> A Potassium silicate (SiO ₂: 26% by weight, K₂O: 13% by weight) 50 parts by weight Potassium hydroxide 30 parts by weight Water 350 parts by weight The order of processing is positive photosensitive lithographic printing plate and negative photosensitive
The total number of lithographic printing plates is 100 for each chrysanthemum size per day.
The 200th plate was processed in a total of 1200 plates in one week. fine
The processing order is random, but the total number of editions per day is
I made it the 100th edition.

The printing plates obtained by processing after 1 week from the time of fresh solution all showed good image reproducibility, and many good prints were obtained.

Further, a printing plate obtained by processing after one week from the time of fresh solution was filled with ink and evaluated for stains and inking according to the following evaluation criteria. The results obtained are shown in Table 1. = Staining = ○; No ink buildup on the non-image area △; Light ink buildup on the non-image area = Inking = ○; Ink buildup on the image area is sufficient △; Image Inking of the ink on the image area is slightly insufficient. X: Inking of the ink on the image area is poor. Example 2 In Example 1, the developing solution and the developing replenishing solution were changed to the following, and development was performed. Exposure and development were performed in the same manner except that the replenishment conditions were changed as described below, and stains and inking were evaluated in the same manner as in Example 1. The results obtained are shown in Table 1.

<Development replenishment conditions> Processing replenishment: 30 milliliters
Torr / m², Replenishment over time: 54 ml / h, daily replenishment
(Replenishment during non-operating time of automatic processor): 50 millilitres
/ H <Developer> A Potassium silicate (SiO ₂: 26% by weight, K₂O: 13% by weight) 50 parts by weight Potassium hydroxide 10 parts by weight Copolycondensation resin of phenol and m-, p-mixed cresol and formaldehyde (phenol, m-cresol and p-cresol were charged at a molar ratio of 10:54). : 36, weight average molecular weight 4800) 5 parts by weight water 620 parts by weight <Development replenisher> A potassium silicate (SiO 2 ₂: 26% by weight, K₂O: 13% by weight) 60 parts by weight Potassium hydroxide 20 parts by weight Water 350 parts by weight Further, the printing plates obtained after the treatment for one week are all
Shows good image reproducibility and produces many good prints.
Was.

Example 3 The same procedure as in Example 1 was carried out except that the developing solution and the developing replenisher were changed to the following, and the developing replenishing conditions were changed as follows. Then, the dirt and the inking were evaluated. The results obtained are shown in Table 1.

<Development replenishment conditions> Replenishment of processing: 23 ml / m ² , replenishment with time: 56 ml / h, replenishment for a day (replenishment during non-operating time of automatic processor): 50 ml / h.

<Developer> A potassium silicate (SiO 2 ₂: 26% by weight, K₂O: 13% by weight) 130 parts by weight Potassium hydroxide 17 parts by weight Water 620 parts by weight <Development replenisher> A Potassium silicate (SiO ₂: 26% by weight, K₂O: 13% by weight) 30 parts by weight Potassium hydroxide 20 parts by weight Water 350 parts by weight Further, the printing plates obtained after the treatment for one week are all
Shows good image reproducibility and produces many good prints.
Was.

Comparative Example << Negative-type photosensitive lithographic printing plate comparative sample >> A negative-type photosensitive lithographic printing plate sample was prepared in the same manner as in the negative-type photosensitive lithographic printing plate sample described in Example 1 except that the following photosensitive composition coating liquid was used. A photosensitive lithographic printing plate comparison sample was prepared.

<Photosensitive Composition Coating Liquid> Hexafluorophosphate 1 part by weight of a condensation product of p-diazodiphenylamine and paraformaldehyde N-4-hydroxyphenylmethacrylamide copolymer (Japanese Patent Publication No. 57-43890). 10 parts by weight Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts by weight Methyl cellosolve 100 parts by weight.

The positive-working photosensitive lithographic printing plate sample described in Example 1 and the negative-working photosensitive lithographic printing plate comparison sample obtained as described above were used to prepare an original film having a pattern of corresponding halftone dots and a sensitivity. A step tablet for measurement (Eastman Kodak Co., No. 2, 21-step gray scale with a density difference of 0.15 each with 21 steps of gray scale) was adhered, and a 2 kW metal halide lamp was used as a light source at a condition of 8.0 mW / cm ²
It was exposed for 60 seconds from a distance of 0 cm.

Next, a developing solution and a developing replenishing solution having the following compositions were charged into an automatic developing machine under the following developing replenishing conditions to obtain the image-exposed positive-working photosensitive lithographic printing plate and negative-working photosensitive lithographic printing plate. Development processing was performed at 30 ° C. for 12 seconds.

<Development replenishment conditions> Replenishment of processing: 50 milliliters
Torr / m², Replenishment over time: 100 ml / h, daily supplement
Charge (replenishment during non-working time of automatic processor): 90 mm
Torr / h <Developer> A Potassium silicate (SiO ₂: 26% by weight, K₂O: 13% by weight) 2.2 parts by weight Potassium hydroxide 1.5 parts by weight β-anilinoethanol 0.3 parts by weight Propylene glycol 0.3 parts by weight 2-hydroxy-3-naphthoic acid 0.6 parts by weight p -Tert-Butylbenzoic acid 1.2 parts by weight Emulgen 147 (Kao Corporation) 0.05 parts by weight potassium sulfite 0.9 parts by weight water 90 parts by weight <Development replenisher> A potassium silicate (SiO2) ₂: 26% by weight, K₂O: 13% by weight) 2.2 parts by weight Potassium hydroxide 2.0 parts by weight β-anilinoethanol 0.3 parts by weight Propylene glycol 0.3 parts by weight 2-hydroxy-3-naphthoic acid 0.6 parts by weight p -Tert-Butylbenzoic acid 1.2 parts by weight Emulgen 147 (Kao Co., Ltd.) 0.03 parts by weight potassium sulfite 0.9 parts by weight water 90 parts by weight sex
The total number of lithographic printing plates is 100 for each chrysanthemum size per day.
The 200th plate was processed in a total of 1200 plates in one week. fine
The processing order is random, but the total number of editions per day is
I made it the 100th edition.

The performance of the printing plate obtained by processing after 1 week from the time of fresh solution was not usable.

Further, the printing plate obtained by processing after one week from the time of fresh solution was filled with ink and evaluated for stains and inking in the same manner as in Example 1. The results obtained are shown in Table 1.

[0149]

[Table 1]

[0150]

According to the processing method of the present invention, stable gradation can be obtained even after a long-term running processing, and the occurrence of background stains and defective ink replenishment can be prevented. Is improved and the replenishment accuracy is improved in the replenishment system, and it is excellent even when both the negative photosensitive lithographic printing plate and the positive photosensitive lithographic printing plate are developed. Shows good stability.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ryoji Hattori 1 Sakura-cho, Hino-shi, Tokyo Konica stock company (72) Inventor Akio Kasakura 1000 Kamoshida-cho, Aoba-ku, Yokohama, Kanagawa Mitsubishi Chemical Yokohama Research Institute In-house (72) Inventor Kenshi Kaneda 1000 Kamoshida-cho, Aoba-ku, Yokohama-shi, Kanagawa Mitsubishi Chemical Corporation Yokohama Research Institute

Claims (3)

[Claims] 1. A processing method in which a photosensitive lithographic printing plate having a photosensitive layer on a support having a hydrophilic surface is imagewise exposed and then subjected to development processing using an aqueous alkaline developer and a development replenisher. The solution and the development replenisher are aqueous solutions of alkali metal silicates, and the concentration of SiO ₂ contained in the aqueous alkaline developer and the development replenisher is 1.0 to
A method for treating a photosensitive lithographic printing plate, which comprises 4.0% by weight and keeps the concentration of SiO ₂ constant in a running developer. 2. A processing method in which a photosensitive lithographic printing plate having a photosensitive layer on a support having a hydrophilic surface is imagewise exposed and then subjected to development processing using an aqueous alkaline developer and a development replenisher. Solution and developing replenisher are aqueous solutions of alkali metal silicates, and the aqueous alkaline developer contains 0.1 to 20% by weight of an alkali-soluble resin. . 3. A processing method in which a photosensitive lithographic printing plate having a photosensitive layer on a support having a hydrophilic surface is imagewise exposed and then subjected to development processing using an aqueous alkaline developer and a development replenisher. The developer and the developer replenisher are aqueous solutions of alkali metal silicates, and the concentration of SiO ₂ contained in the aqueous alkali developer is 3.0 to 7.0% by weight, [SiO ₂ ] / [M] (equation Inside, [SiO ₂ ] is Si
The molar concentration of O ₂ is shown, and [M] is the molar concentration of alkali metal. ) Is 0.5 to 1.5, the concentration of SiO ₂ contained in the aqueous alkaline developing replenisher is 0.5 to 3.0% by weight, and [SiO ₂ ] / [M] is 0.15 to 0.8. A method for treating a photosensitive lithographic printing plate, characterized in that