JPH03198046A - Developing solution for colored image forming material - Google Patents

Abstract

PURPOSE:To enable stable processing for a long period without causing precipitation even at the time of a lot of colored image forming material by incorporating a chelating agent and a basic compound and water in the developing solution. CONSTITUTION:This developing solution is used for developing the colored image-forming material provided on a transparent substrate treated to enhance releasabilty with a colored photosensitive layer containing a photosensitive composition and a colorant, and the developing solution contains the basic compound in such an amount as holding pH of the developing solution in the range of 10-13.5 and the chelating agent and water, thus permitting stable processing to be ensured without causing precipitation even when a large amount of colored image-forming materials are processed.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a developer for colored image-forming materials, and in particular, a colored photosensitive layer containing at least a photosensitive composition and a colorant on a release-treated transparent support. The present invention relates to a developer used for developing a colored image forming material having the following properties.

[Conventional technology]

It is desired that a developer for a colored image forming material is stable even when a large amount of the material to be processed is developed, and therefore capable of stable processing for a long period of time. Colored image-forming materials are sometimes used, for example, as color proofs for proofing during color printing, but in such cases it is highly desirable that the developer is stable and that good colored images can be stably produced over a long period of time. .

However, in the conventional technology, this is not always satisfied, and when a large amount of colored image forming material is processed, a precipitate may be formed in the developer, making it impossible to perform stable processing.

Further, since such a developer is used to obtain a desired image by dissolving the non-image area of the image forming material, it is basically required to have excellent elution properties of the non-image area. Furthermore, not only that, but it is also required that no background stains appear. This is because if background smear appears, a proper dye image cannot be reproduced.

This problem can be said to be particularly important in the case of color proof development as described above.

However, the reality is that it is quite difficult to obtain a developer for colored image forming materials that satisfies all of the above requirements.

For example, JP-A No. 59-97140 states that adding a surfactant and an organic solvent to an aqueous alkaline developer is effective for improving wettability and shortening development time.
Japanese Patent Publication No. 56-501217 discloses a technique in which a surfactant is added to an aqueous alkaline developer, but there is no statement that the above-mentioned problems can be solved, and it is difficult to use these conventional techniques. Even if a large amount of colored image-forming material is processed, a precipitate will form in the developer, and this will adhere to the colored image-forming material, causing stains and clogging the filter of the developing machine, resulting in long-term problems. It is considered that stable processing of the period cannot be performed.

[Purpose of the invention]

The present invention solves the above problems, does not cause precipitation even when a large amount of colored image forming material is processed, enables stable processing for a long period of time, has excellent elution properties in non-image areas, and eliminates background stains. It is an object of the present invention to provide an advantageous developer solution for colored image-forming materials that does not generate any color.

[Means and effects for solving the problems] The object of the present invention is to develop a colored image-forming material having a colored photosensitive layer containing at least a photosensitive composition and a colorant on a release-treated transparent support. This is achieved by a developer for colored image forming materials, which is characterized by containing (a) a basic compound, (b) a chelating agent, and (C) water.

This configuration solves the problems of the prior art described above, and although its effect is not necessarily clear, the above (a)
It is considered that the contents of ) to (C) as a whole bring about the effects of the present invention and form a developer that solves the problems. For the inventors of the present invention, the effects of the present invention were not necessarily expected, and the present invention was achieved as a result of various studies.

The present invention will be explained in detail below.

It is essential that the developer of the present invention contains the above-mentioned (a) to (c), of which (a) the basic compound will be explained first.

In the present invention, the basic compound is a compound exhibiting basicity in the sense of the term used in the ordinary chemical field (hereinafter also simply referred to as "base").

This can be either an inorganic or organic base.

When using an organic base, ammonia, hydrazine, hydroxyamine, or an organic base having 1 to 30 carbon atoms is 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, benzylamine, N.

N-dimethylbenzylamine, N,N-diethylbenzylamine, N,N-dipropylbenzylamine, 0- or m- or p-methoxy or methylbenzylamine, N,N-di(methoxybenzyl)amine, β- Phenylethylamine, ε.

δ-phenylamylamine, T-phenylpropylamine, cyclohexylamine, aniline, monomethylaniline, dimethylaniline, toluidine, benzidine, α
- or β-naphthylamine, 0- or m- or p
- Phenylenediamine, pyrrolidine, piperidine, piperazine, morpholine, urotropin, diazabicycloundecane, pyrrole, pyridine, quinoline, hydrazine, phenylhydrazine, N,N''-diphenylhydrazine, hydroxylamine, semicarbazide, tetraalkylammonium hydroxide, amino Benzoic acid, formamide, acetamide, N,N-dimethylformamide, N,
N-dimethylacetamide, acetanilide, monoethanolamine, diethanolamine, triethanolamine, 2-(2aminoethyl)ethanol, 2-amino-
2-methyl-1,3-propanediol, 2-amino-
Amine compounds such as 1,3-propanediol, 2-amino-2hydroxymethyl-1,3-propanediol (primary, secondary, tertiary amines, monoamines, diamines, triamines, tetraamines to polyamines, aliphatic chains) formula amines, aliphatic cyclic amines, aromatic amines, heterocyclic amines), amine derivatives such as acid amides, or salts of carboxylic acids and amines (for example, salts of octanoic acid, monoethanolamine, jetanolamine, etc.) ), etc.

Also, sodium methylate, sodium ethylate,
Using alkali metal alcoholades such as sodium propylade, potassium methylate, potassium ethylate, potassium propylate, lithium methylate, lithium ethylate, alkali-substituted amides of sodium, potassium, and lithium, and alkali-substituted amides such as ethylamide, dipropylamide, etc. You can also do that.

Inorganic bases include sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate,
Lithium carbonate, calcium carbonate, barium carbonate, sodium bicarbonate, potassium bicarbonate, sodium phosphate,
Sodium triphosphate, sodium diphosphate, potassium phosphate, potassium triphosphate, potassium diphosphate,
Hydroxides, carbonates, and bicarbonates of alkali metals and alkaline earth metals such as ammonium phosphate, tertiary ammonium phosphate, diammonium diphosphate, sodium silicate, potassium silicate, ammonium silicate, and sodium metasilicate. , phosphates, silicates, metasilicates, etc.

Among these, alkali silicates are most preferred because they have good development stability.

The content of these basic compounds in the developing solution cannot be determined unconditionally depending on the basicity of the compound, the degree of solubility, etc., but the pH of the solution used is preferably 8.5 to 11.
5, more preferably pH 10 to 13.5. - For boat fishing, the content of the basic compound in the developer is preferably in the range of 0.05 to 20 weight percent, more preferably in the range of 0.1 to 10 weight percent. , is used in an appropriate amount to adjust the pH of the developer to a desired value.

Next, the chelating agent (b) contained in the developer of the present invention will be explained.

In the present invention, a chelating agent refers to a substance that coordinates with a metal ion to form a chelate compound.

Preferred chelating agents contained in the developer of the present invention are those that are soluble in an alkaline aqueous solution and capable of sequestering calcium ions and/or magnesium ions in the alkaline aqueous solution. More preferably, the blocking rate at the pH value of the developer is 50% or more, and more preferably the blocking rate at pH 10.0 to 13.5 is 50%.
It is preferable to use the above chelating agents. Here, the sequestration rate is expressed as a percentage to what extent the metal ions are trapped, and can be determined by titration or the like.

Examples of chelating agents that can be used in the present invention include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid,
Hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, 1.3
- Aminopolycarboxylic acids such as diamino 2-propatol tetraacetic acid and their sodium salts and potassium salts, 2-phosphonobutane-1,2,, 11-licarboxylic acid, 2-phosphonobutane-2,3,4-tricarboxylic acid,
1-phosphonoethane-1,2,2-tricarboxylic acid, 1-
Examples include organic phosphonic acids or phosphotricarboxylic acids such as hydroxyethane-1,1 diphosphonic acid, aminodo (methylene phosphonic acid), and their sodium and potassium salts.

The amount of the above-mentioned chelating agents added is usually preferably 0.001 to 1% by weight, more preferably 0.01 to 0.2% by weight, based on the total amount of the developer composition, and they are used alone or in combination. be able to.

Furthermore, these chelating agents may be added to the developer composition in advance, or may be added to the developer composition during development to perform the development process.

Next, as the water (c) used in the developer of the present invention, water normally used for preparing this type of developer may be used, pure water may be used, but ordinary tap water may be used.

The developing solution of the present invention must contain the above-mentioned (a) to (C), but in addition to these, it can also contain (d) an organic solvent having a solubility in water of 20% by weight or less. The solubility referred to here is at room temperature (20°C).

When containing an organic solvent, examples of those that can be preferably used include diisobutyl ketone, acetophenone, isophorone, diethyl succinate, methyl benzoate, diethyl oxalate, dimethyl phthalate, isobutyl acetate,
Benzyl benzoate, ethylene glycol monophenyl ether, ethylene glycol dibutyl ether, ethylene glycol benzyl ether, diethylene glycol di-n-butyl ether, ethylene glycol diacetate, propylene glycol monobutyl ether, n-
Examples include amyl alcohol and benzyl alcohol. However, it is not limited to these.

Among these, diethyl succinate, dimethyl phthalate, benzyl benzoate, ethylene glycol monophenyl ether, diethylene glycol diacetate, propylene glycol motsubutyl ether, and benzyl alcohol are particularly effective.

The content of these organic solutions in the developer is 1 to 3
It is preferably 0% by weight, more preferably 2 to 20% by weight.

Furthermore, the developer of the present invention may contain (e) a surfactant. The surfactant used may be anionic, nonionic, cationic, or amphoteric, and anionic surfactants and nonionic surfactants can be particularly advantageously used.

Examples of anionic surfactants that can be used include fatty acid salts, abietate salts, hydroxyalkanesulfonate salts, alkanesulfonate salts, dialkylsulfosuccinates, linear alkylbenzene sulfonate salts, branched chain alkylbenzene sulfonate salts, Alkylnaphthalene sulfonates, alkyldiphenyl ether sulfonates, alkylphenoxy polyoxyethylene propyl sulfonates, polyoxyethylene alkyl sulfophenyl ether salts, N-methyl-N-oleyl taurine sodium, N-alkyl sulfosuccinic acid monoamide Sodium salts, petroleum sulfonates,
Sulfated castor oil, sulfated beef leg oil, sulfate ester salts of fatty acid alkyl esters, alkyl sulfate ester salts, polyoxyethylene alkyl ether sulfate ester salts,
Aliphatic monoglyceride sulfate ester salts, polyoxyethylene alkyl phenyl ether sulfate ester salts, polyoxyethylene styrylphenyl ether 1m ester salts, alkyl phosphate ester salts, polyoxyethylene alkyl ether phosphate ester salts, polyoxyethylene alkyl phenyl ether phosphate ester salts , partially saponified products of styrene-maleic anhydride copolymers, partially saponified products of olefin-maleic anhydride copolymers, naphthalene sulfonate formalin condensates, and the like.

Among these, alkylnaphthalene sulfonates, alkyldiphenyl ether sulfonates, linear alkylbenzene sulfonates, and polyoxyethylene alkylphenyl ether sulfate salts can be particularly preferably used.

In addition, nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene polystyrylphenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, glycerin fatty acid partial esters, Sorbitan fatty acid partial esters, pentaerythritol fatty acid partial esters, propylene glycol monofatty acid esters, sucrose fatty acid partial esters, polyoxyethylene sorbitan fatty acid partial esters, polyoxyethylene sorbitol fatty acid partial esters, polyethylene glycol fatty acids Esters, polyglycerin fatty acid partial esters, polyoxyethylenized castor oil, polyoxyethylene glycerin fatty acid partial esters, fatty acid jetanolamides, N,N-bis2-hydroxyalkylamines, polyoxyethylenealkylamines , triethanolamine fatty acid esters, trialkylamine oxides, etc. can be used. Among them, polyoxyethylene alkylphenyl ethers, polyoxyethylene-polyoxypropylene block polymers, etc. can be preferably used.

As the cationic surfactant, alkylamine salts, quaternary ammonium salts, polyoxyethylene alkylamine salts, polyethylene polyamine derivatives, etc. can be used.

The content of the surfactant in the developer of the present invention is preferably 0.01 to 30% by weight, more preferably 0.1 to 20% by weight.

Next, the developer for colored image-forming materials of the present invention is a developer used for developing colored image-forming materials having a colored photosensitive layer containing at least a photosensitive composition and a colorant on a release-treated transparent support. However, details of such colored image-forming materials to be processed will be described below.The developer for colored image-forming materials of the present invention is for forming a colored image on a release-treated support.

Here, the release-treated support is used to facilitate the separation of the support after transfer when the formed image is transferred from the support to a transfer material. Refers to a support that is constructed by subjecting the surface of the support to a mold release treatment or by providing a mold release layer on the surface of the support in order to improve the mold releasability during the process.

Such a release-treated support can be constructed by subjecting the surface of the support to release treatment with a suitable oil-repellent substance, or by providing a release layer on the support.

Although the material of the support used is arbitrary, a transparent support is preferably used. As the transparent support, a polyester film, particularly a biaxially oriented polyethylene terephthalate film, is preferred in terms of dimensional stability against water and heat. In addition, acetate film, polyvinyl chloride film,
Polyethylene film, polypropylene film, polyethylene film, etc. can be used.

As the oil-repellent substance for performing the above mold release treatment on the support, for example, silicone resin, fluororesin, fluorine surfactant, polyolefin, polyamide, etc. can be used. Alcohol-soluble polyamide, alcohol-soluble nylon, blend of partially esterified resin of copolymer of styrene and maleic anhydride and methoxymethylated nylon, polyvinyl acetate,
Polyacrylate, copolymer of polymethyl methacrylate and acrylate, polyvinyl chloride, copolymer of vinyl chloride and vinyl acetate, polyvinyl butylade, cellulose acetate phthalate, methylcellulose, ethylcellulose, cellulose diacetate, cellulose triacetate, polyvinyl Alcohol, butyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, cyanoethyl cellulose, cellulose acetate, cellulose triacetate, cellulose acetate butyrate, hydroxybrobyl methyl cellulose phthalate, hydroxypropyl methyl cellulose hexahydrophthalate, or mixtures thereof can be used.

The thickness of the release layer is preferably in the range of 0.01 μm to 10 am, particularly preferably in the range of 0.1 μm to 5 μm.

In order to improve mold releasability, a particularly preferable example B includes an example in which a polypropylene layer or a polyethylene layer thinner than the thickness of the support is provided.

The method for forming a polypropylene layer or polyethylene layer on a support is as follows: (1) A solution of polyvinyl acetate, polyvinyl chloride, epoxy resin, polyurethane resin, natural rubber, synthetic rubber, etc. dissolved in an organic solvent is used as an adhesive. After applying these adhesives on a support and drying with hot air or heating, a polypropylene film or a polyethylene film is overlaid and laminated by pressing under heat.
So-called dry lamination method; (2) Using a copolymer of ethylene and vinyl acetate, a copolymer of ethylene and acrylic ester, polyamide resin, petroleum resin, rosin, wax, or a mixture thereof as an adhesive, these adhesives After applying the material onto a support by a doctor blade method, roll coating method, gravure method, reverse roll method, etc. while keeping it in a molten state by heating it as it is,
The so-called hot-melt lamination method, in which polypropylene or polyethylene films are immediately laminated together and laminated by heating at a high temperature if necessary and then cooling; (3) The polypropylene or polyethylene is kept in a molten state and then extruded. This is the so-called extrusion lamination method, in which the film is extruded into a film, and while it is still in a molten state, a support is bonded and laminated; Examples include a so-called co-extrusion method in which a polypropylene layer or a polyethylene layer is formed on a support Fino C by molding with polypropylene or polyethylene in a molten state two times.

In the present invention, the colored photosensitive layer is one that is colored for image formation and has photosensitivity, and any such layer may be used. For example, using what is called a photopolymer as a photosensitive material,
A colored photosensitive layer can be constituted by this, a coloring agent, and an appropriate solvent.

Here, photopolymer refers to polymerization, crosslinking, and
Changes such as dimerization, bridge rupture, decomposition, and rearrangement occur, resulting in increases and decreases in solubility in solvents, changes in hydrophilicity and hydrophobicity, and changes in softening point. It is a photosensitive material with specific properties, and includes those that have been conventionally used as photosensitive agents for plate making, photoresists, photosensitive resins, etc.

There are two types of photopolymers: negative type (for example, those whose solubility decreases when exposed to light) and positive type (for example, those whose solubility increases when exposed to light), and the following examples are known.

<Examples of negative photopolymers> l) Photosensitive photopolymers that give group-group ions upon light irradiation, such as ferric ammonium citrate, ferric ammonium tartrate, ferric ammonium oxalate, and ferric sodium oxalate. A composition comprising a diiron salt and a hydrophilic polymer such as gelatin, modified gelatin, polyvinyl alcohol partially saponified polyvinyl acetate, polyacrylic and its copolymers, polyacrylamide and its homologs.

2) Tetrazonium salts of hydrophilic polymers such as gelatin, fish glue, gum arabic, polyvinyl alcohol, polyacrylamide, carboxymethyl cellulose, hydroxyethyl cellulose, copolymers of polyvinyl methyl ether and maleic anhydride, and diamino compounds such as benzidine and dianisidine. , and a composition comprising a diazo resin obtained by condensing p-diazodiphenylamine and paraformdehyde.

3) A diazo resin in which a diazo compound such as p-diazodiphenylamine and paraformaldehyde are combined.

4) Azide compounds such as sodium 4.4°-diazidostilbene-2,2′disulfonate and sodium 4-azidohenzalaceto-2-sulfonate, polyacrylamide, polyvinylpyrrolidone, gelatin, modified gelatin, casein, A composition comprising a polymer such as acrylonitrile-grafted polyvinyl alcohol and N-alkoxymethylated nylon.

5) 4.4'-Diazidobenzalacetone, 4°4°-
A composition consisting of an azide compound such as diazidobenzal or methylcyclohexanone and a polymer such as cyclized rubber or synthetic rubber.

6] A composition comprising a cinnamic acid ester or furyl acrylic acid ester of polyvinyl alcohol and a sensitizer such as 5-nitroacenaphthene or 1,2-benzanthraquinone.

7) A composition comprising a polymer of a vinyl monomer having a photosensitive group, such as cinnamic acid p-vinylphenyl ester, or a copolymer with other monomers, and a sensitizer such as 5-nitroacenaphthene.

8) Vinyl monomers such as acrylamide, methylenebisacrylamide, acrylic acid, acrylic esters, triethylene glycol diacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, cellulose derivatives, or polyvinyl A composition comprising an alcohol derivative and a photopolymerization initiator.

9) A composition comprising an acrylamide such as methylenebisacrylamide or N,N'-hexamethylenebismethacrylamide, an alcohol-soluble nylon, and a photopolymerization initiator.

10) Ethylenically unsaturated compounds such as acrylamide, acrylic acid, N,N'-methylene acrylamide, and ferric ammonium citrate, ferric ammonium tartrate, ferric ammonium oxalate, ferric sodium oxalate. Photosensitive ferric salts such as gelatin, modified gelatin, polyvinyl alcohol, partially saponified polyvinyl acetate,
A composition comprising a hydrophilic polymer such as polyacrylic acid and its copolymers, polymethacrylic acid and its copolymers, polyacrylamide and its homologs.

11) Ethylenically unsaturated monomers such as acrylamide and acrylic acid, photoreducible dyes such as thionine, riboflavin, and methylene blue, and reducing agents such as ascorbic acid, triethanolamine, thiourea, and sodium ethylenediamine-tetraacetate. A composition comprising a hydrophilic polymer such as gelatin, polyvinyl alcohol, or polyacrylamide, and optionally a crosslinking agent such as calcium acrylate, barium acrylate, or N,N'-methylenebisacrylamide.

Among these, the examples shown in 5) to 9) can be particularly advantageously used when utilizing changes in softening point due to light.

<Examples of positive type photopolymers> 1) Quinonediazide compounds such as o-naphthoquinonediazide-sulfonic acid esters or sulfonic acid amides.

or mixtures of these quinonediazide compounds with alkali-soluble resins such as novolak-phenolic resins.

2) Reaction product of polynuclear anion of heteropolyacid or isopolyacid and diazonium salt (published in Japanese Patent Publication No. 39-7663) 3
) Compounds having an 0-nitrobenzaldehyde group such as bis-(3-aldehyde-4-nitrophenyl)-phthalate and 3-aldehyde-4-nitrophenyl carbonate.

4) Ethylenedioxy-5,5'-resorcinol.

The above-mentioned photopolymers are of a type whose solubility changes with light, and the following are examples of photopolymers whose hydrophilicity or hydrophobicity changes with light.

1) Reaction product of diazo resin and yellow blood salt.

2) A composition in which a diazo compound, an azide compound, carbon tetrabromide, iron oxide, etc. are added as a catalyst to an aggregate of high molecular weight polyethylene oxide and a phenol resin.

For more information on photopolymers, including those discussed here, see J. Kosar, Light Sensit.
iveSystem” (Wiley & 5ons+
New York+ 1965) and Color Materials Association Magazine No. 44
(1971), pages 116 to 137.

In the present invention, particularly preferred colored photosensitive layers are as follows (1)
) to (IV).

(1) A photosensitive composition containing an o-quinonediazide compound and a polymer compound (A) having a carboxylic acid vinyl ester polymerized unit represented by the following general formula in its molecular structure.

RCOOCH=CH! However, R represents an alkyl group having 1 to 17 carbon atoms.

(If) A photosensitive composition containing a diazo compound and/or an azide compound, and the above-mentioned polymer compound (A).

(III) A photosensitive composition containing a vinyl compound and/or vinylidene compound, a photopolymerization initiator, and the above-mentioned polymer compound (A).

(IV) A photosensitive composition containing a photoacid generator, a compound having at least one bond that can be decomposed by an acid, and the above-mentioned polymer compound (A).

Photosensitive composition (I) which describes these photosensitive compositions (1) to (IV)> The 0-quinonediazide compound contained in this photosensitive composition (1) is any compound that can function as a photosensitizer. , any one can be used, specifically, for example, 1.
2-benzoquinonediazide-4-sulfonyl chloride, 1.2-naphthoquinonediazide-4-sulfonyl chloride, 1゜2-naphthoquinonediazide-5-sulfonyl chloride, or 1.2-naphthoquinonediazide-
A compound obtained by condensing 6-sulfonyl chloride with a compound containing a hydroxyl group and/or an amino group is preferably used.

Examples of the hydroxyl group-containing compound in this case include trihydroxybenzophenone, dihydroxyanthraquinone,
Examples include bisphenol A1 phenol novolac resin, resorcin benzaldehyde condensation resin, and pyrogallol acetone condensation resin.

In addition, examples of amino group-containing compounds include aniline,
p-aminodiphenylamine, p-aminobenzophenone, 4,4'-diaminodiphenylamine, 4,4°
-Diaminobenzophenone, etc.

Further information regarding quinonediazide compounds, including those described herein, can be found in J. Kosar [Light Sensitive Systems J (Light 5ensi
New York City, John Wiley & Sons, Inc., published in 1965), and Yonematsu,
Co-authored with Inui “Photosensitive Polymer” (Kodansha, published in 1977)
You can follow what is described in .

Further, this photosensitive composition (1) contains a polymer compound (A) having a carboxylic acid vinyl ester polymerized unit represented by the following general formula in its molecular structure.

RCOOCH=CH However, R represents an alkyl group having 1 to 17 carbon atoms.

Any polymer compound having the above structure can be used, but as the carboxylic acid vinyl ester monomer for constituting the polymerized unit represented by the above general formula, the following examples are preferable. The name and chemical formula are also shown.

■Vinyl acetate ■Vinyl propionate ■Vinyl butyrate ■Vinyl pivalate ■Vinyl caproate ■Vinyl caprylate ■Vinyl caprate ■Vinyl laurate ■Vinyl myristate [Phase] Vinyl Valmitate ■Vinyl stearate @vinyl versatate CH.

CHscOOcH=C8z CHsCHiCOOCH=CHz CHa(CHthCOOCH=CHz (CH3) 3CCOOCH=CII□CHs(CHz
)4cOOcH=c)IzCTo(CHz)bcOOc
H=cHzCHz(CHz)scOOcH=c)IzC
H3(CHI)+. C00CH= C8zCH3(CH
2) l□C00CH= CHIC)Is(CHz)+
4COOCH=CHzCHi(CHz)+i, C00C
H=CHzR' CC00C) l=cHz t (pl, R2 is an alkyl group, and the sum of the carbon numbers is 7. In other words, it is in the form of R'+R""CJ+a) As a carboxylic acid vinyl ester monomer, More preferably, the carboxylic acid has 1 to 4 carbon atoms in its main chain. especially,
Vinyl acetate is preferred.

Note that the above R also includes an alkyl group having a substituent, that is, a vinyl ester of a substituted carboxylic acid is also included in the polymerization unit.

The polymer compound (A) is 1 of carboxylic acid vinyl ester.
It may be a polymer obtained by polymerizing seeds, a polymer obtained by copolymerizing two or more types of carboxylic acid vinyl ester, or a polymer obtained by copolymerizing two or more types of carboxylic acid vinyl ester, or an arbitrary component ratio of carboxylic acid vinyl ester and other monomers that can be copolymerized with it. It may be a copolymer of

Examples of monomer units that can be used in combination with the polymerized unit represented by the above general formula include ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene, such as styrene, α-methylstyrene, P - Styrenes such as 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 diethyl maleate and maleic acid. Diesters of unsaturated dicarboxylic acids such as dibutyl, di-2-ethylhexyl maleate, dibutyl fumarate, di-2-ethylhexyl fumarate, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid dodecyl, 2-chloroethyl acrylate,
α-methylene aliphatic monocarboxylic acid esters such as phenyl acrylate, α-methyl chloroacrylate, methyl methacrylate, and ethyl methacrylate; Nitriles such as acrylonitrile and methacrylonitrile; Amides such as acrylamide; e.g. acrylic anilide, p-chloroacrylanilide, m-nitroacrylanilide, m-methoxyacrylanilide, etc., e.g. evamethyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether,
Vinyl ethers such as β-chloroethyl vinyl ether, vinyl chloride, vinylidene chloride, vinylidene cyanide, such as l-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,
There are vinyl monomers such as N-vinyl compounds such as N-vinylindole, N-vinylpyrrolidone, and N-vinylpyrrolidone. These vinyl monomers exist in the polymer compound (A) in a structure in which unsaturated double bonds are cleaved.

Particularly preferred as the polymer compound (A) is one having a vinyl acetate polymerization unit in its molecular structure. Among them, those having 40 to 95@t% of vinyl acetate polymerization units and those having a number average molecular weight (MN) of 1,000 to 100,0
00, weight average molecular weight (MW) is s, ooo ~ 5
00,000 is preferred.

More preferably, vinyl acetate polymerized units (especially 40
~95 wt%) and polymeric compounds having a carboxylic acid vinyl ester polymer unit with a longer chain than vinyl acetate are preferred, especially those with a number average molecular weight (MN) of 2.000 to 60.0.
00, weight average molecular weight (MW) is 10,000 to 150
．． 000 is preferred.

In this case, the monomer that copolymerizes with vinyl acetate to form a polymer compound having vinyl acetate polymerized units may be any monomer that can form a copolymer, such as among the monomers listed above. You can arbitrarily choose from.

Copolymers that can be used as the polymer compound (A) in carrying out the present invention are listed below by indicating their monomer components. However, it goes without saying that the invention is not limited to the following examples.

■Vinyl acetate-ethylene ■Vinyl-styrene acetate ■Vinyl acetate-crotonic acid ■Hinyl acetate-maleic acid ■Vinyl acetate-2-ethylhexyl acrylate ■Vinyl acetate-2-ethylhexyl maleate ■Vinyl acetate-methyl vinyl ether ■Vinyl acetate-vinyl chloride■ Vinyl acetate-N-vinylpyrrolidone [phase] Vinyl acetate-vinyl propionate ■Vinyl acetate-
Vinyl pivalate @ Vinyl acetate Rubersatate ■ Vinyl acetate - Vinyl laurate [Phase] Vinyl acetate - Vinyl stearate ■ Vinyl acetate -
Vinyl versatate - ethylene ■ Vinyl acetate Rubber vinyl versatate - 2-ethylhexyl acrylate ■ Vinegar 1 Vinyl rubber Versatate - Vinyl laurate [Phase] Vinyl acetate Rubersatic acid and Nyl-crotonic acid ■ Vinyl louver propionate Vinyl satiate @ Vinyl propionate - Vinyl versatate - Crotonic acid ■ Pivalic acid - Vinyl stearate - Maleic acid <Photosensitive composition (■)> The photosensitive composition (It) is a diazo compound and/or an azide compound , and a polymer compound (A). Here, the term diazo compound refers to at least one diazo group in the molecule.
It refers to a compound that has an individual property, and includes a chain diazo compound and an aromatic diazo compound, but a diazo resin described later is preferable. Moreover, the azide compound refers to a compound having at least one N group in the molecule.

The photosensitive composition (I[) may contain one or more diazo compounds, or may contain any combination of one or more diazo compounds and azide compounds.

The content of the diazo compound and/or azide compound in the photosensitive composition (II) is 0 in the solid component of the photosensitive composition.
．． It is preferably 5 to 30% by weight, more preferably 5 to 20% by weight.

Any diazo compound or azide compound can be used as long as it can function as a photosensitizer, and specific examples include the following.

Diazo compounds that can be used include diazo resins represented by condensates of aromatic diazonium salts and, for example, active carbonyl-containing compounds, especially formaldehyde. Among these, organic solvent-soluble diazo resins are preferred.

Examples of diazo resins include organic solvent-soluble reaction products of condensates of P-diazophenylamine and formaldehyde or acetaldehyde, and hexafluorophosphates, tetrafluoroborates, perchlorates, and periodates. diazo resin inorganic salts, also U.S. Patent No. 3.300.3
09, the above condensates and sulfonic acids such as para-toluenesulfonic acid or its salts, phosphinic acids such as benzenephosphinate or its salts, hydroxyl group-containing compounds such as 2.4 dihydroxyhensiphenone, etc. , 2-hydroxy 4-methoxy-
Examples include organic solvent-soluble diazo resin organic acid salts which are reaction products of benzophenone-5-sulfonic acid or its salts.

Further, as the azide compound that can be used, the following compounds can be specifically mentioned.

4.4' diazidiphenylmethane 2,6-dichloro-4-nitro-azidobenzene 4,4
゛Diazidobenzophenone 4.4'-Diazidodiphenylmethane 3'-dimethoxy4.4''-diazidophenyl 4.4 -Diazidostilbene 4' Methoxy-4-azidodiphenylamine 4.4' Diazidochalcone 4.4°-di Azidodiphenylamine 2.6-di(4"-azidobenzal)dichlorohexane 3.3°-dimethyl-4,4"-diazidodiphenyl 2.6-di(4"-azidobenzal)-4-methylcyclohexanone 4.4° -diazidophenylazonaphthalene HI 4' nitrophenylazobenzene-4-azide The photosensitive composition (n) also contains a polymer compound (A), which is similar to the photosensitive composition (1) -azidopyrene <Photosensitive composition (■)> The photosensitive composition (DI) contains a vinyl compound and/or a vinylidene compound, a photopolymerization initiator, and a polymer compound (A).

The content ratio of the vinyl compound (and/or vinylidene compound) to the polymer compound (A) is such that the weight ratio of vinyl compound (and/or vinylidene compound)/polymer compound (A) is 0.1 to 2. A range of 0 is preferable.

Further, the content of the photopolymerization initiator is preferably 0.01 to 20.0 wt% based on the total of the photopolymerization compound and the vinyl compound (and/or vinylidene compound).

In the photosensitive composition (III), any of various vinyl compounds or vinylidene compounds can be used.

Suitable vinyl or vinylidene compounds that can be used include, for example, unsaturated esters of polyols, especially esters of acrylic acid or methacrylic acid, such as ethylene glycol diacrylate, glycerol triacrylate, polyacrylates, ethylene glycol dimethacrylate, 1,3-propanediol. Dimethacrylate, polyethylene glycol dimethacrylate, 1,2,4-butane trio-trimethacrylate, trimethylolethane triacrylate, pentaerythritol di, tri, and tetramethacrylate, pentaerythritol di, tri, and tetraacrylate, dipentaerythritol - polyacrylates, 1,3-propanediol-diacrylate, 1,5-pentanedi-roodimethacrylate, bis-acrylates and bis-methacrylates of polyethylene glycol with 200 to 400 molecules and similar compounds; unsaturated amides, Particular mention may be made of unsaturated amides of acrylic and methacrylic acid and ethylene bis-methacrylamide with α,ω-diamines whose alkylene chains may be opened by carbon atoms. However, it is not limited to these.

Further, as the photopolymerization initiator that can be used, those having low absorption in the visible region are more preferable, and examples thereof include the following compounds. However, it is not limited to these. Namely, benzophenone, Michler's ketone (Mi
chler's ketone.

The chemical names are r4,4'-bis-(dimethylamino)benzophenone J), 4,4'-bis(diethylamino)benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-ethylanthraquinone, phenanthraquinone, and other aromatic ketones, benzoin, hengeine ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether, methylbenzoin, ethyl hengeine and other hengeynes, and 2- (0-chlorophenyl)-4,5-diphenylimidazole duplex, 2-(o-chlorophenyl)-
4,5-(m-methoxyphenyl)imidazole doublet, 2-(o-fluorophenyl)-4,5-diphenylimidazole doublet, 2-(o-methoxyphenyl)-
4,5-diphenylimidazole duplex, 2-(p-methoxyphenyl)-4,5-diphenylimidazole duplex, 2,4-di(p-methoxyphenyl)-5phenylimidazole duplex, 2-( 2,4-dimethoxyphenyl)-4,5-diphenylimidazole duplex, 2-
(p-methylmercaptophenyl)-4,5-diphenylimidazole duplex and U.S. Pat. No. 3,479.1
85, GB 1,047,569 and U.S. Pat. No. 3,784,557. I can do it.

Polymer compound (A) contained in the photosensitive composition (I[[)
The same ones as those explained in the photosensitive composition (I) can be used.

<Photosensitive composition (■)> The photosensitive composition (IV) is a photoacid generator, a compound having at least one bond that can be decomposed by an acid (hereinafter sometimes abbreviated as "acid decomposable compound") , and a polymer compound (A).

The content of the photoacid generator in the photosensitive composition (IV) is preferably 0.1 to 10% by weight, and 0.2 to 5% by weight based on the total solid content of the photosensitive composition. It is more preferable. The content of acid-decomposed compounds is also 5 to 70% by weight.
It is preferable that it is, and it is more preferable that it is 10 to 50 weight%. In addition, the polymer compound has the same <30 to 95
It is preferably 50 to 90% by weight, more preferably 50 to 90% by weight.

Here, the photoacid generator refers to a compound that can generate acid upon irradiation with actinic rays. Such photoacid generators include many known compounds and mixtures, such as diazonium salts, phosphonium salts, sulfonium salts, and iodonium BF,\PF.

Salts such as SbF, -, SiF@"-1C204-, organic halogen compounds, orthoquinonediazide sulfonyl chloride, etc. can be used, and organometallic/organic halogen compounds can also be used to form or separate acids upon irradiation with actinic rays. It can be used as an actinic light-sensitive ingredient.

In principle, all organic halogen compounds known as free-radical-forming photoinitiators can be used as photoacid generators capable of forming hydrohalic acids. Examples of such compounds are U.S. Pat.
No. 36,489, No. 3,779,778 and West German Patent Application No. 2.243.621.

Also, for example, West German Patent Publication No. 2,610゜8
No. 42, JP-A-54-74728, JP-A No. 55-7774
Compounds that generate acids by photolysis, as described in Japanese Patent No. 2, No. 57-16323, and No. 60-3626, can also be used.

Furthermore, 0-naphthoquinonediazide-4-sulfonic acid halide described in JP-A-50-36209 can also be used.

This photosensitive composition (IV) contains an acid decomposition compound along with the photoacid generator. Examples of compounds having a bond that can be decomposed by an acid upon receiving an acid generated by the action of such a photoacid generator (acid-decomposed compound) include:
Examples include compounds having -c-o-C,: bond and 2S i -0-C.< bond.

,, c-o-C; Specific compounds having a bond include, for example, a compound having an acetal or ketal group, an orthocarboxylic acid ester group and/or a carboxylic acid amide acetanol described in JP-A-51-120714; Compounds having groups, polymers having acetal or ketal groups in the main chain described in JP-A-53-133429, compounds containing enol ether groups as described in JP-A-55-12995, JP-A-55 -126236
Examples include compounds having an N-acylimino carbonate group as described in Japanese Patent Publication No. 17345/1984, and polymers having an orthocarboxylic acid ester group in the main chain as described in Japanese Patent Application Laid-Open No. 17345/1984.

Further, specific compounds having an =st-oCζ bond include, for example, compounds described in JP-A-60-37549, JP-A-60-52845, and JP-A-60-121446.

Further, specific examples of compounds having an ester group include compounds described in JP-A-60-3625 or JP-A-60-10247.

Among these compounds having a bond that can be decomposed by an acid, compounds having an "E S t -0-Cmi bond are preferable. Among them, compounds having an E S t -0-Cmi bond of Particularly preferred are compounds having at least one bond and at least one hydrophilic group.

These acid-decomposable compounds may be used alone or in combination of two or more.

Further, as the acid-decomposed compound, a compound containing at least one orthocarbonate group represented by the following general formula [X] can be suitably used.

General formula [X] A compound containing at least one such orthocarbonate group (hereinafter referred to as an orthocarbonate compound).

), for example, at least one phenolic O
A compound that can be synthesized by carrying out a transesterification reaction of at least one compound having an H group and/or at least one alcoholic OR group (hereinafter referred to as an OH group-containing compound) and tetraalkoxymethane in one or more steps. can be mentioned.

For this transesterification reaction, for example, 5vens
K. Kes, Tidskr, 65.10 (1953
) can be used.

Examples of the OH group-containing compounds include monohydric alcohols, dihydric alcohols, trihydric alcohols, tetravalent or higher alcohols, monovalent phenolic compounds, divalent phenolic compounds, and trivalent phenolic compounds. Examples include compounds, phenolic compounds having a valence of four or more, or compounds having both a phenolic OH group and an alcoholic OH group.

Examples of the monohydric alcohol include n-propyl alcohol, n-butyl alcohol, n-pentyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decyl alcohol, and n-dodecyl alcohol. , n-tetradecyl alcohol, n-hexadecyl alcohol, n-octadecyl alcohol, isopropyl alcohol, isobutyl alcohol, 5ec-butyl alcohol, tert-butyl alcohol, isopentyl alcohol, activated amyl alcohol, tert-pentyl alcohol, cyclopene Tanol, cyclohexanol, allyl alcohol, crotyl alcohol, methyl vinyl carbinol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,
Aliphatic alcohols such as triethylene glycol monomethyl ether and triethylene glycol monoethyl ether, and aromatic alcohols such as benzyl alcohol, α-phenylethyl alcohol, β-phenylethyl alcohol, diphenyl carbinol, triphenyl carbinol, and cinnamyl alcohol. etc. can be mentioned.

As the dihydric alcohol, for example, JP-A-53133
Pentane-1,5-diol, n, described in Publication No. 429
-hexane-1,6-diol, 2-ethyl-hexane-1,6-diol, 2,3-dimethyl-hexane-1
, 6-diol, heptane-17-diol, cyclohexane-1,4-diol, nonane-1,7-diol, nonane-1,9-diol, 3,6-dimethyl-nonane-1,9-diol, decane -1,10-diol,
Dodecane l, 12-diol, 1,4-bis-(hydroxymethyl)-cyclohexane, 2-ethyl-1,4-
Bis-(hydroxymethyl)-cyclohexane, 2-methyl-cyclohexane-1,4-jetanol, 2-methyl-cyclohexane-1,4-dibrobanol, thio-
Dipropylene glycol, 3-methyl-pentane-1,
5-diol, diptylene glycol, oxypivalic acid-neopentyl glycol ester, 4,8-bis-
(Hydroxymethyl)-tricyclodecane, n-butene-(2)-1,4-diol, n-budo-2-yn-1
, 4-diol, n-hex-3-yne-2,5-diol, 1,4-bis-(2-hydroxyethoxy)-futhidi(2), p-xylylene glycol, 25-dimethyl-hex -3-yne-2,5 diol, bis=(2
-hydroxyethyl)-sulfide, 2,2,4.4
Aliphatic alcohols and p -xylylene glycol, aromatic alcohols such as 2-methyl-2-phenyl-1,3-propanediol, and the like.

As the trihydric alcohol, for example, JP-A-56173
Glycerol, butane-1°2.4- described in Publication No. 45
) diol, 2-hydroxymethyl-butane-1,4-
Diol, pentane-L 2,5 triol, 2-hydroxymethyl-pentane 15-diol, hexane-
1,2,5-triol, 2-hydroxymethyl-hexane-1°6-diol, hexane-1,2,6-triol, 4-ethyl-hexane-1,4,5-1-diol, heptane-1 ,4,5-triol,1(1,2
-dihydroxyethyl)-4-hydroxymethyl-benzene, 2,4.6-triethyl-5propyl-heptane-1,3,7-triol, 1-(2,3-dihydroxy-propoxy)-4-hydroxymethyl- Benzene, 1-(2,3-dihydroxypropyl)-4-hydroxymethyl-benzene, off-chie 3-nin-1.7.
8-) Diol, octane-1,2,8-triol,
Octane-1,3,8-1-diol, Nonane-1,4
, 5-triol, 3-(1-hydroxy-1-methylethyl)-5-oxa-octane-2,8-diol,
2,6.8-1-dimethyl-3-hydroxymethyl-nonane-6,7-diol, 2-hydroxymethyl-3-
Aliphatic or aromatic alcohols such as oxa-hebutane-1,7-diol and hexadecane-1,2,16-)diol can be mentioned.

Examples of the tetrahydric or higher alcohol include aliphatic alcohols such as pentaerythritol, threitol, bentitol, sorbitol, and polyvinyl alcohol. It may also be an aromatic alcohol.

Examples of monovalent phenolic compounds include phenol, O-cresol, m-cresol, p-cresol, 3
, 5-xylenol, carvacrol, thymol, α-
Examples include naphthol and β-naphthol.

Divalent phenolic compounds include catechol, resorcinol, hydroquinone, 2.2-bis(4-hydroxyphenyl)butane, bis(p-hydroxyphenyl)methane, 2.2-bis(4-hydroxyphenyl)propyne,
Examples include 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene.

Examples of trivalent phenolic compounds include pyrogallol and phloroglucin.

As a phenolic compound having a valence of 4 or more, 1°4.9.
Examples include 10-tetrahydroxyanthracene.

A compound having both phenolic OH and alcoholic OH is 2-(bis(4-hydroxyphenyl)
Methyl)benzyl alcohol and the like can be mentioned.

As the above-mentioned tetraalkoxymethane, for example, tetramethoxymethane or tetraethoxymethane is generally used.

Tetraethoxymethane, for example, Organic Synthesis Collect, Pornium IV (OrganicSy
nthenes Co11. Vol, IV) 45
7 (1963) using chloropicrin and sodium ethoxide. Other tetraalkoxymethanes can also be synthesized by similar methods. Also Journal of Organic
Chemistry〇, Org, Chem, )36.11
76 (1971) or the method described in the Journal of Organic Chemistry (J.
It can also be synthesized by a method similar to that described in Org, Chew, ) 37.4198 (1972).

The above-mentioned ortho carbonic acid ester compound can be prepared, for example, by combining the tetraalkoxymethane and the OH group-containing compound at a temperature of 60 to 170°C, preferably 80 to 150°C, without using a solvent.
It can be obtained by reaction at a temperature of °C. The liberated lower alcohol is optionally distilled off. At this time, an acidic catalyst,
For example, it is preferable to carry out the reaction in the presence of P-)luenesulfonic acid or sulfuric acid. Further, depending on the case, the reaction may be carried out under reduced pressure. Further, solvents that are inert under the above reaction conditions, such as benzene, toluene, xylene, dioxane, chlorinated hydrocarbons, etc., can also be used as the reaction solvent. The liberated lower alcohol is optionally distilled off together with a portion of the solvent.

The quantitative ratio in the reaction of the tetraalkoxymethane and the 0■ group-containing compound is generally such that the total amount of OH groups is 4 moles per 1 mole of tetraalkoxymethane, but in some cases, A quantity ratio different from this may also be used.

In addition, when two types of OH group-containing compounds are used, a total of three of the tetraalkoxymethane and two types of OH group-containing compounds may be reacted at the same time, or in some cases, first the tetraalkoxymethane and one of the OH group-containing compounds may be reacted simultaneously. The compounds may be reacted and then the product may be reacted with another OH group-containing compound.

The reaction can be carried out in the same manner when three or more types of 0)1g-containing compounds are used.

Also chemical berichte (Chew, Ber,) 54
4 (1961) or a similar method. For example, it was obtained by the method described in this document.

Examples include a method of reacting chloromethane with the above-mentioned OH group-containing compound.

The product obtained by the above method is an orthocarbonate compound, and examples thereof include a compound containing one of the following orthocarbonate group units, a compound containing two or more, or a mixture thereof.

0-C-0 = Below margin, Jl, ;/ The above R+, R1, R+, and R1 each represent an alkyl group, an aryl group, an aralkyl group, an alkenyl group, or the like. It includes those having substituents of these alkyl groups, aryl groups, aralkyl groups, and alkenyl groups. Furthermore, at least two of R1 to R4 may be bonded to each other to form a ring.

Furthermore, the bond portion may be further bonded to the same or other orthocarbonate group unit mentioned above via a substituted or unsubstituted alkylene group, arylene group, aralkylene group, alkenyl group, etc. .

The compound having at least one orthocarbonate group unit is preferably one having 1 to 50 orthocarbonate group units in its molecule.

Specific examples of compounds having at least one orthocarbonate group are shown below.

Exemplary compounds NO,1(C1,0), C and HO(CH,CHzOh
Reaction product with H Nα2 (CH30) 4C and 80 (CHzCHzO
The reaction product with hH (CHiO) 4c and HOClhCH(OH)(, H6
Reaction product with CH20H (CiHso) 4C and) IO (CHzCHzOhH Reaction product (CIl:10) 4C and (HOClb) Reaction product with 4c No, 3 No, 5 Nα4 Nα6 (CJsO) 4C and HOCHzCH (OH)CI(O
H) Reaction product with CHzOH, 9 (n Reaction product with CJwOCHzCHiOhC u) Reaction product with Nα13 HO (CHzCHzOhH (CH30) 4C and HO(C)lICH, Reaction product between OhH and Ho(cozcHzOhH) Reaction product No, 15 CCHzO) of product Nα14 (n-C4HqO) ac and IO (CHtCH2OhH HOCH2CH(OH)C3H,CH,OH) aC and HO(CB, CH,0hH(H
Reaction product with OCHriC (CHzCHzOhH Reaction product with Nα21 (CH30) aC and HO (C1lICH!0hl (No, 17) In the present invention, in the photosensitive composition (1), the polymer compound (A) contained in the reaction product photosensitive composition (IV) is a reaction product with the reaction product HO (CHzCHzOhH).
The colored photosensitive layer can be constructed by dissolving the above-mentioned photopolymer or photosensitive composition in an appropriate solvent and adding a coloring agent thereto.

As the solvent, any solvent that can dissolve or disperse the photosensitive composition etc. can be used. For example, methyl cellosolve, ethyl cellosolve ``P・''L/''
t, 0/Jlz7'7"1"L/"t, 0/Jlz7'
Other solvents can be used, such as methanol, dimethylformamide, dimethyl sulfoxide, alcohols, water, or mixtures thereof.

The colored photosensitive layer is colored by containing an appropriate coloring agent. As the coloring agent, arbitrary dyes and pigments can be added and used. In particular, when used for color proofing, the usual colors required are yellow, magenta, cyan,
Pigments and dyes with a tone that matches black are required, but
Other metal powders, white pigments, fluorescent pigments, etc. are also used. When applying the present invention to color proofing, the following:
Many pigments and dyes known in the art can be used.

(C0I means color index).

Victoria Pure Blue (C, I 42595) Auramine (C, I 41000) Cathylone Brilliant Flavin (C, I Basic 13) Rhodamine 6 GCP (C, I 45160) Rhodamine B (C, I 45170'') Safranin OK
2O: 100 (C, I 50240”) Erioglaucine X (C, I 42080) Fast Black HB (C, I 26150) No. 1201
Lionor Yellow o-(C,I 21090) Lionor Yellow GRO (C,I 21090'') Shimla Fast Yellow 8CF (C,I 21105) Benzidine Yellow 4T-564D (C,I 21095) Shimla Raf Puth Red 4015 (C,I 12355) Lionor Red 7 B12O3 (C, 115830)
First Gen Blue TGR-L (C, I 74160) Lionor Blue SM (C, I 26150) Mitsubishi Carbon Black MA-100 Mitsubishi Carbon Black #30. #40. #50 Among the above pigments, anionic or cationic pigments are preferable, and for example, it is preferable to use pigments containing inert salts such as sulfonic acids, carboxylic acids, and amines. Such pigments may be obtained by converting the soluble groups of water-soluble dyes into inert salts, or may be obtained from lecithin, naphthenic acid metal salts, alkylbenzene sulfonates, dialkylnaphthalene sulfonates, mono- or dialkylnaphthalenes. sulfonates, mono- or dialkyl sulfosuccinates, dialkyl phosphate salts, rosinates,
Alternatively, it may be a processed anion or cation pigment treated with a treatment agent such as an organic amine.

The colored photosensitive layer of the image forming material used in the method of the present invention may be composed of a single layer consisting of a colorant, a photosensitive composition, and a binder (polymer compound), or may be composed of a colorant and a binder. It can also be divided into two layers: a colored layer made of a photosensitive composition and a photosensitive layer made of a photosensitive composition. When using two layers, it does not matter which layer is placed on the support side.

In the present invention, the ratio of colorant/binder in the colored photosensitive layer can be determined as appropriate. For example, in the case of dyes, the content is preferably 5% to 75% by weight, and in the case of pigments, the content is preferably 5% to 90% by weight.

In addition, the thickness of the colored photosensitive layer applied to the release support can be determined as appropriate depending on the target optical density, the type of colorant (dye, pigment, carbon black), and its content, but within an acceptable range. If so, the thinner the coating layer is, the higher the resolution and the better the image quality. Therefore, the film thickness is preferably 0.1 g/rrr to 5 g
It is usually used within the range of /rrf.

When carrying out the present invention, plasticity and coating properties improvers and the like may be added to the colored photosensitive layer, if necessary.

Plasticizers include various low-molecular compounds such as phthalate esters, triphenyl phosphates, maleate esters, and coating properties improvers include surfactants such as fluorine surfactants and ethyl cellulose polyalkylene ether. Examples include nonionic surfactants.

When an image obtained using the developer of the present invention is embodied, for example, as a multicolor transfer image forming method, the basic methods can be roughly divided into the following methods (1) and (n).

(1) Lay the first colored image-forming material having a colored image-forming layer for the first color on the support onto the transfer material, transfer at least the colored image-forming layer to the transfer material, and peel off the support. do. Next, image exposure is performed through a first color film original corresponding to the first color, and then development processing is performed to form a colored image of the first color on the transfer material.

Next, at least a colored image forming layer of a second colored image forming material having a colored image forming layer of a second color different in tone from the first color is transferred onto the first colored colored image layer on the transfer material. Then, an alignment image of the second color film original corresponding to the second color (generally called a registration mark image is used)
is registered with the first color registration mark image, image exposure is performed through the second color film original, followed by development processing to obtain a two color matched image on the transferred material. Thereafter, similar processing is performed for the third and fourth colors to obtain a multicolor image.

This method is known from Japanese Patent Publication No. 47-27441, Japanese Patent Publication No. 56-501217, etc.

(II) A first color colored image is formed on a first color colored image forming material, at least the colored image is transferred to a transfer material, and the support is peeled off. In addition, a second colored image forming material is added to the second colored image forming material.
After forming a colored image, a second image formed along with this is formed.
While registering the color register mark image with the first color register mark image on the transfer material, the second colored image is transferred onto the first color colored image, and the support is peeled off, and the two colors are registered. Get the image. Similarly, colored images of the third color and the fourth color are also transferred onto the transfer material to obtain a multicolor image. In some cases, this multicolor image may be indirectly transferred onto another transfer material,
Multicolor images may also be obtained.

This type of method is disclosed in Japanese Patent Application Laid-open Nos. 47-41830, 59-97140, 60-28649 and US Pat. No. 3,775,113.

〔Example〕

Examples of the present invention and comparative examples will be described below.

It should be noted that, as a matter of course, the present invention is not limited only to the embodiments described below, but can take various forms.

Example 1 A colored photosensitive composition dispersion having the following composition was dried using a wire bar on the polypropylene surface of a support obtained by dry laminating a 25 μm thick polypropylene film on a 50 μm thick polyethylene terephthalate film. After coating to a film thickness of 1 μm, it was dried to produce four colored image forming materials.

Vinyl acetate-hinyl laurate (80: 20 parts by weight) copolymer M N =20. OOO MW=55.000 Dishes black: Carbon black MA-100 (manufactured by Mitsubishi Kasei) 0.99g cyanide
Nidianin Blue 4920 (manufactured by Dainichiseika) 0.55 g Magenta:
Seika Fast Carmine 1483 (manufactured by Dainichiseika Chemicals) 0.68 g Yellow: Seiryoku Fast Yellow H-1055 (manufactured by Dainichiseika Chemicals) 0.68 g or more on the polyethylene terephthalate film surface of the four-color colored image forming material obtained The color separation mesh positive films of each color were superimposed, image exposure was carried out for 20 seconds from a distance of 50 mm using a 4:1 metal halide lamp, and the following developer was used.
Development was performed using an automatic developing machine as follows to form colored images in four colors.

<Developer> In other words, add 20% developer to the development processing section of the automatic processor. The developer temperature was adjusted to 30°C.

The conveyance speed of the automatic developing machine was set so that the developing time was 30 seconds. Further, in order to perform water washing as a step of the developing process, 10ffi of water was put into the washing tank.

The above-mentioned image-exposed colored image-forming material was passed through the above-mentioned automatic developing machine, and 2 pieces of 950 mm x 650 mm size were processed.
Processing continued at a rate of 0 sheets/day. At this time, it was investigated on what day the spray nozzle of the automatic developing machine would become clogged or precipitation would occur in the developing solution during processing.

The colored image forming material thus developed and washed with water was transferred onto paper, and stains in non-image areas were measured using a reflection densitometer.

The above results are shown in Table 1 below. Note that the stain in the non-image area (background stain) was measured for the transferred image of the cyan colored image forming material.

In this example, the image surface of the black image obtained as described above and art paper were brought into close contact with each other, and the surface was moved between a pair of heated nip rolls at a pressure of 5 kg/d at a rate of 50 cm/day. When the support was peeled off after passing at a speed of 10 minutes, the peeling was easily performed and only the black image area was transferred onto the art paper.

Subsequently, colored images were transferred in the order of cyan, magenta, and yellow, thereby obtaining a color proofing image consisting of four colors on art paper. As a result, in this example, only the image area was transferred, and the finished product was very similar to the actual printed matter.

Example 2 A release layer solution having the following composition was applied onto a biaxially stretched polyethylene terephthalate film having a thickness of 75 μm using a wire bar so as to have a dry film thickness of 0.5 μm, and dried.

Next, a heat-adhesive layer solution having the following composition was applied onto the release layer to a dry film thickness of 7 μm and dried.

Next, a colored photosensitive layer dispersion having the following composition was applied onto the heat-adhesive layer using a wire bar so that the dry film thickness was 1 μm.
Dry.

Vinyl acetate-vinyl versatate (80:20 parts by weight) copolymer M N = 22.000 MW = 60000 A color separation net positive film is superimposed on the polyethylene terephthalate film surface of the colored image forming material obtained above, 50C with a 4kW metal halide lamp! Image exposure was performed for 20 seconds from a distance of 1, and development was performed in the same manner as in Example 1 using the following developer, and the same evaluation was performed.

<Developer> The image surface of the obtained colored image and high-quality paper are superimposed, and a 5 kg /
The colored image was transferred onto the high-quality paper by passing the CD under pressure at a speed of 50 cm/min, and when the support of the colored image forming material was peeled off, the colored image, the heat-fusible layer, and A release layer was transferred onto the wood-free paper.

Regarding this example, the same data as Example 1 are shown in Table-1.

Example 3 A release layer solution having the following composition was applied onto a polyethylene terephthalate film having a thickness of 75 μm so that the dry film thickness was 0.5 μm to prepare a support having a releasable surface.

(Release layer solution) Torezin F-30 (alcohol-soluble nylon, manufactured by Toshi) 10 g methanol 90 g Next, four colored photosensitive composition dispersions having the following composition were prepared, and the dry film thickness was 1.
It was coated on the release layer so as to have a thickness of .mu.m, thereby producing four-color image forming materials.

Vinyl acetate-vinyl versatate-vinyl laurate-crotonic acid (55:20:20:5 parts by weight) copolymer M
N=32. OOO MW=72,000 1L” Black: Carbon black MA-100 (manufactured by Mitsubishi Kasei) 0.99g Cyan Nidianin Blue 4920 (manufactured by Dainichiseika) 0.55g Magenta: Seika First Carmine 1483 (manufactured by Dainichiseika) 0.68g Yellow: Seika First Yellow H-7055 (manufactured by Dainichiseika) 0.68g A color separation mesh positive film of each color was superimposed on the colored photosensitive layer surface of the obtained four-color colored image forming material, and the film was heated using a 4kW metal halide lamp. Image exposure was performed for 60 seconds from a distance of 50c11, and development was performed in the same manner as in Example 1 using the following developer.
We conducted an evaluation.

<Developer> Next, an image-receiving layer solution having the following composition was coated on another polyethylene terephthalate film to a dry film thickness of 20 μm and dried to prepare an image-receiving sheet.

(Image receiving layer solution) Vinyl chloride/vinyl acetate copolymer (composition ratio 75:25, MPR-T-5 manufactured by Nissin Chemical Co., Ltd.)
) 18g Pentaerythritol Tetraacrylate 1g
Michler's ketone 0.1 g Benzophenone 0.64 g Paramethoxyphenol 0.018 g Methyl ethyl ketone 44 g The previously obtained yellow image was brought into close contact with the image-receiving layer surface of the image-receiving sheet, and the image was passed between a pair of heated nip rolls at a speed of 5 kg/c.
The yellow image was transferred onto the image-receiving layer by passing at a speed of 50 cm/min under the pressure conditions of d, and the polyethylene terephthalate film on the color image side was peeled off.

Subsequently, the colored image is transferred in the order of magenta, cyan, and black, and the image side of the image-receiving sheet is brought into close contact with art paper, and the image-receiving sheet is passed between a pair of nip rolls under the same conditions as described above. 50 with a metal halide lamp of 4 to 50 on the polyethylene terephthalate film surface.
Full exposure was given for 30 seconds from a distance of 1.5 cm, after which the polyethylene terephthalate film of the image receiving sheet was peeled off.

A multicolor proofing image was formed on the art paper.

Table 1 shows the same data as in each of the above examples.

Example 4 A colored photosensitive layer dispersion having the following composition was applied onto the polypropylene surface of a support obtained by dry laminating a 25 μm thick polypropylene film on a 50 μm thick polyethylene terephthalate film using a wire bar. It was applied to a thickness of 1 μm and dried.

(Colored photosensitive layer dispersion liquid composition) 2.3.4-) Lyhydroxybenzophenone naphthoquinone-1,2 diazide sulfonic acid ester 0.616 g The following binder polymer 4.384 g The following pigment The following amount Ethyl cellosolve 39. 6 g Fluorine surfactant (FC-430 manufactured by 3M) 0.25 g Binary polymer monomer vinyl acetate-hinyl stearate (70: 30 parts by weight) copolymer M N = 51,000 MW = 95 ,000 Dishes black carbon black MA-100 (manufactured by Mitsubishi Kasei) 0.99g Cyan Nidianin Blue 4920 (manufactured by Dainichiseika) 0.55g Magenta: Seiriki First Carmine 1483 (manufactured by Dainichiseika) 0.68 g Yellow:
Seika First Yellow H-7055 (manufactured by Dainichiseika) 0.68 g Next, an adhesive layer coating solution with the following composition was applied onto the colored photosensitive layer using a wire bar to a dry film thickness of 5 μm, and dried. Four colored image forming materials were prepared.

(Adhesive layer coating liquid composition) Alicyclic saturated hydrocarbon resin Alcon P-90 (manufactured by Kanyo Kagaku, softening point 90°C) 12 g
Alicyclic saturated hydrocarbon resin Alcon P-100 (manufactured by Kanyo Kagaku, softening point 100°C) 3g
Styrene-butadiene block copolymer Tuffrene A (manufactured by Asahi Kasei Industries) 5g toluene 100m! ! Among the colored image forming materials of each color created as described above, the adhesive layer surface of the colored image forming material using a pigment with a tone matching cyan, and the water-resistant white synthetic paper (Peachco manufactured by Nisshinbo Co., Ltd.)
WEK-110) and a pair of heated nip rolls under a pressure of 5 kg/ci.
The cyan colored imaging material was adhered onto the white synthetic paper via the adhesive layer.

Next, a color separation mesh positive film corresponding to cyan is superimposed on the support surface of a colored image forming material using a pigment of a tone matching that of cyan, which is adhered onto white synthetic paper, and the film is adhered by a vacuum adhesion method. Image exposure was performed for 20 seconds from a distance of 50 cm using a 4KW metal halide lamp, and then the support was peeled off from the cyan colored image forming material after image exposure, and development was performed in the same manner as in Example 1 using the following developer. A cyan colored image was formed on white synthetic paper.

Further, the same evaluation as in Example 1 was performed.

Developer Solution> Next, a colored image forming material using a pigment of a tone matching magenta is adhered to the white synthetic paper on which a cyan colored image has been formed via an adhesive layer, and then the same operation as above is performed. By doing this, a magenta colored image is formed, and the same operation is repeated for yellow and black.
A color proofing image consisting of four colors was formed on white synthetic paper.

Table 1 shows the same data as in each of the above examples.

Comparative Example 1 In Example 1, a comparative developer having the same composition as in Example 1 was used except for the chelating agent tetrasodium ethylenediaminetetraacetate. Other aspects were carried out and evaluated in exactly the same manner as in Example 1.

Comparative Example 2 In Example 2, a comparative developer having the same composition as in Example 2 except for the chelating agent tetrasodium ethylenediaminetetraacetate was used. Other aspects were carried out and evaluated in exactly the same manner as in Example 2.

Examples 1 to 4 described above. Comparative Examples 1 and 2 Evaluation Table 1 As can be seen from Table 1, in Examples 1 to 4 of the present invention, no nozzle clogging or precipitation was observed even on the 7th day. On the other hand, in the comparative example, it occurred on the 3rd, 7th, or 5th day. Further, it can be seen that while the stains in the non-image areas are undetectable in Examples 1 to 4, considerable stains occur in Comparative Examples 1 to 2.

〔Effect of the invention〕

As mentioned above, the developer for colored image-forming materials of the present invention does not easily cause precipitation even when a large amount of colored image-forming materials are processed, can be processed stably for a long period of time, and has excellent elution properties in non-image areas. It is excellent and has the effect of not causing background stains.

Claims (1)

[Scope of Claims] 1. A developer used for developing a colored image-forming material having a colored photosensitive layer containing at least a photosensitive composition and a colorant on a release-treated transparent support, comprising: (a) A developer for a colored image forming material, comprising a basic compound (b) a chelating agent and (c) water.