JPS6155643A - Photosensitive image forming material developable from aqueous alkaline developer - Google Patents

Abstract

PURPOSE:To enable a development with a high photosensitivity from an aqueous alkaline developer by using a photosensitive layer contg. a specific photosensitive polyester resin. CONSTITUTION:The photosensitive layer comprises the photosensitive polyester resin or the modified polyester resin having a photosensitive unsatd. double bond adjacent to an arom. ring as a main molecular chain, and a photosensitive unsatd. double bond and a carboxyl group as a pendant group. The polyester resin is constituted of >=0.4mol photosensitive unsatd. double bond and the carboxyl group having >=15 acid value per 1,000g polyester resin. The photosensitive unsatd. double bond adjacent to the arom. ring is derived from a dicarboxylic acid shown by the formula I (wherein R1 is a hydrogen atom, a C1-4 alkyl group). The photosensitive unsatd. double bond which is the pendant of the polyester resin is derived from an epoxy resin shown by the formula II (wherein R1 is the same as mentioned above; R3 is a hydrogen atom, methyl, phenyl group). The image forming material has the high photosensitivity and eanble to develop from the aqueous alkaline developer and is suitable for a photosensitive planographic plate and also is useful for a photoresist.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a photosensitive image forming material, and more particularly to a photosensitive image forming material that can be developed with a highly sensitive aqueous alkaline developer.

[Conventional technology]

Because of its unique photodimerization reaction, various photosensitive resins in which a cinnamic acid skeleton is introduced into the side chain or main chain of the molecule have been studied. Examples include polyvinyl alcohol, polyepichlorohydrin, polystyrene, acrylic resins, epoxy resins, and polyesters and polyamides having a cinnamic acid skeleton in the main chain, some of which have been put to practical use. For example, polyvinyl cinnamate produced by the reaction of polyvinyl alcohol and cinnamic acid chloride, polyester produced by the condensation of diethyl phenylene diacrylate and 1,4-di-β-hydroxyethoxycyclohexane. These are used as image forming materials for printing plates, LSI devices, etc.

Among the photodimerizable photosensitive resins mentioned above, photosensitive polyester resins having a cinnamic acid skeleton in the molecular main chain produced by condensation of phenylene diacrylic acid or its alkyl ester with glycol have a relatively high photoresistivity. It is said to be sensitive.

However, since these photosensitive resins exhibit solubility only in organic solvents, organic solvents are used as developing solutions when developing photosensitive layers made from these resins. When using an organic solvent as a developer,
Development of a photosensitive resin that can be developed with an aqueous developer because there are many problems in development workability, safety and health of the working environment, economic efficiency, and prevention of pollution such as air pollution, and it is more expensive than an aqueous developer. is desired.

In recent years, as such resins, photosensitive resins having a phenylene diacrylate group or a cinnamoyloxy group in the main chain and a sulfonate salt group adjacent to an aromatic nucleus (JP-A-58-18625, JP-A-52-130897) have been developed. etc.), but when used as a photosensitive material for printing plates, such conventional resins can be developed with an aqueous developer, but their photosensitivity is insufficient, and the plate resistant to moisture. It is still not sufficient in terms of adhesiveness, oil sensitivity during printing, etc., and improvements are desired.

[Problem that the invention seeks to solve]

An object of the present invention is to provide an image-forming material that has high photosensitivity and is developable with an aqueous alkaline developer.

Another object of the present invention is to provide a photosensitive image forming material that is excellent as a photosensitive lithographic printing plate.

[Means for solving problems]

In order to achieve this purpose, Kinoe Ichinohe has a photosensitive unsaturated double bond adjacent to the aromatic nucleus in the main chain of the molecule, and the photosensitive unsaturated double bond and the carboxyl group are combined into pendant groups. The present invention provides a photosensitive image forming material which can be developed with an aqueous alkaline developer and is characterized in that the photosensitive layer contains a photosensitive polyester or modified polyester resin having the following properties.

The photosensitive polyester or modified polyester resin used in the present invention is first prepared from a polyhydric carboxylic acid component containing a dicarboxylic acid having a photosensitive unsaturated double bond adjacent to an aromatic nucleus and a polyhydric alcohol component. The photosensitive polyester or modified polyester resin precursor can be produced by various methods. For example, (1)
... A method of producing a photosensitive polyester resin precursor by reacting at a ratio in which the amount of carboxyl groups is in excess of the amount of hydroxyl groups (one-stage method), (2) ... The amount of hydroxyl groups is in excess of the amount of carboxyl groups A method of producing a photosensitive polyester resin precursor by once producing a polyester containing a hydroxyl group by reacting at a ratio such that the resin contains an acid anhydride to the hydroxyl group contained in the resin (two-step method), (3)...In the above-mentioned 92-step method, when adding an acid anhydride to the hydroxyl groups contained in the polyester, the amount of hydroxyl groups contained in the polyester is in excess of the amount of acid anhydride groups in the acid anhydride. A polyester containing hydroxyl groups as well as carboxyl groups is synthesized by adding them in a proportion, and a compound having two or more functional groups in the molecule that can react with the hydroxyl groups (hereinafter referred to as a chain extender) is further reacted with this polyester. Method 1 of producing a photosensitive modified polyester resin precursor (three-step method) and the like can be mentioned.

The aforementioned (two-stage method) was proposed by the present applicant in the specification of Japanese Patent Application No. 59-20739, and the (three-stage method) was proposed in the specification of Japanese Patent Application No. 59-46429.

Examples of dicarboxylic acids having a photosensitive unsaturated double bond adjacent to an aromatic nucleus include dicarboxylic acids represented by the following general formulas (11 to (7)) or derivatives thereof, such as dialkyl esters thereof such as dimethyl ester and diethyl ester. ; Can be derived from di(ethylene glycol) ester, di(propylene glycol) ester, !'(alkylene glycol) ester, and the like.

(In the above general formulas (11 to (7), %Rf and R- each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a flucokyfur group having 1 to 4 carbon atoms, a halogen atom, or a nitro group, R2 represents an alkyrev group with carbon if!2 to 4, ! represents an integer of 1 to 5, n represents an integer of 1 to 4, and m represents an integer of 1 to 5.) The above dicarboxylic acid A preferred example of the acid or its derivative is p-
Phenylene diacrylic acid% m-Phenylene diacrylic acid.

2.5-dimethoxy-p-phenylene diacrylic acid, 2
- ditro p-phenylene diacrylic acid, p-carboxycinnamic acid, cinnamylidenemalonic acid 1 bis(p-cinnamic acid) diethylene glycol ether, bis(p-carboxybenzal) cyclohexanone, bis(p-carboxybenzal) Cyclopentanone % dicarboxylic acids such as plp'-chalcone dicarboxylic acid or diesters thereof as mentioned above can be mentioned.

Other polyhydric carboxylic acids can be used in combination with the dicarboxylic acid or derivative thereof having a photosensitive unsaturated double bond adjacent to the aromatic nucleus, and examples of such compounds include succinic acid, adipic acid, azelaic acid, Sepatic acid, phthalic acid, inphthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, tetrabromophthalic acid, tetrachlorophthalic acid, 1,4-cyclohexanedicarboxylic acid, maleic acid, fumaric acid, itaconic acid, carboxynorbornane Polyhydric carboxylic acids such as acetic acid, 5-sodium sulfoisophthalic acid, trimellitic acid, and hemic acid,
Alternatively, its anhydride or its ester derivative can be used.

However, the use of large amounts of these other polyhydric carboxylic acids or their derivatives should be avoided since it will cause a decrease in the photosensitivity of the resin.In order to obtain sufficiently high photosensitivity, it is necessary to avoid using large amounts of these other polycarboxylic acids or their derivatives. It is desirable that the content of the derived units be 15 to 100 mol% of the total polycarboxylic acid units.

On the other hand, as the polyhydric alcohol component, various types can be used without particular limitations, such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol', polypropylene glycol, neopentyl glycol, 1.3 -butylene glycol, 1,6-hexyl diol, 2-butene-1,4-diol, 2,
2.4-) dimethyl-1,3-bentanediol, 1,
4-bis-β-hydroxyethoxycyclohexane, cyclohexane dimetatool, tricyclodecane dimetatool, hydrogenated bisphenol A, 7kfA bisphenol F1 ethylene oxide adduct of bisphenol A,
Propylene oxide adduct of bisphenol A, ethylene oxide adduct of bisphenol F, propylene oxide adduct of bisphenol F, ethylene oxide adduct of hydrogenated bisphenol A, propylene oxide adduct of hydrogenated bisphenol A, tricyclodecane dimetatool Ethylene oxide adduct of tricyclodecane dimetatool, propylene oxide adduct of tricyclodecane dimetatool.

Examples include 5-norbornene-2,3-dimethatool, 5-norboly-no-2,2-dimetatool, trimethylolpropane, and pentaerythritol.

The reaction between the polyhydric alcohol component and the polycarboxylic acid component is
This can generally be easily accomplished by means known in the art. That is, it can be produced by preparing a polyhydric carboxylic acid component and a polyhydric alcohol component in a predetermined blending ratio and reacting (esterification reaction or transesterification) in the presence of a catalyst and an inhibitor that are added as necessary. The temperature is preferably 150 to 250°C.

Examples of the catalyst used for the reaction of the polyhydric carboxylic acid component and the polyhydric alcohol component include organometallic compounds such as diptyltin oxide, diptyltin laurate, diptyltin diacetate, lithium ethoxide, tetraisopropyl titanate, and tetrabutoxytitanate; Inorganic metal compounds such as titanium dioxide, zinc acetate, antimony trioxide, and calcium oxide can be used. The amount used is preferably 5Q.about.110,000 pp as a metal component.

Inhibitors are used to minimize the crosslinking and branching of ethylenically unsaturated groups that tend to occur during polycondensation reactions, such as phenothiazine, nosidoquinone, hydroquinone monomethyl ether,
6-ditert-7'thyl-p-cresol, p-benzoquinone, etc. can be used. The amount used is 5
0 to 2000 ppm is preferred.

Examples of the acid anhydride used in the two-stage method and the six-stage method include succinic anhydride, octadecylconophosphate anhydride, and camphoric anhydride.

Maleic anhydride, 7-talic anhydride, 4-methyl 7-talic anhydride, 3-nitrophthalic anhydride, tetrabromophthalic anhydride, naphthalene dicarboxylic anhydride, 0-sulfobenzoic anhydride, pyromellitic dianhydride anhydride, 3.3',
4.4'-pensiveenonetetracarboxylic dianhydride,
3,3',4,41-diphenyltetracarboxylic dianhydride, 2,3.6,7-su7talentetodicarboxylic dianhydride, 1.4,5.8-naphthalenetetracarboxylic dianhydride , 4,4'-sulfonylsiphthalic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)
Propanihydride, bis(3,4-dicarboxyphenyl)ether dimhydrate, 4,4'-(3,3'-(alkylphosphoryldiphenylene)-bis(iminocarbonyl))cyphthalic dianhydride, Aromatic tetracarboxylic dianhydrides such as adducts of hydroquinone diacetate and trimellitic anhydride, adducts of diacetyldiamine and trimellitic anhydride, etc.; 5-(2,5-dioxotetrahydrofuryl)-6 -Methyl-3,=7chlorhexene-1,2-dicarboxylic acid anhydride (Inu Nippon Ink Chemical Industry K
manufactured by K, Epiclon B-4400), 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4.
Alicyclic tetracarboxylic dianhydrides such as 5-cyclohexanetetracarboxylic dianhydride, tetrahydro-7lanetetracarboxylic dianhydride, etc.;1.2,3,4-butanetetracarboxylic dianhydride;1. Aliphatic tetracarboxylic dianhydrides such as 2,4,5-pentanetetracarboxylic dianhydride and the like can be used.

The reaction between polyester and acid anhydride in the two-step method and three-step method can be carried out either by: (1) adding a predetermined amount of acid anhydride to the molten polyester, or (2) dissolving the polyester in an organic solvent and reacting with the acid anhydride. A predetermined amount of anhydride is added to carry out the reaction. The reaction temperature is preferably from room temperature to 200°C.

Examples of organic solvents used in the above reaction include methylene chloride, chloroform, trichloroethane, trichloroethylene, chlorobenzene, dichlorobenzene, Nishichlorinated carbon, etc.f) Chlorinated solvents; ether solvents such as tetrahydrofuran, dioxane, etc.; ester solvents such as glycol methyl ether acetate, glycol ethyl ether acetate, ethyl acetate, etc.; methyl ethyl ketone,
Ketone solvents such as methylinbutylketone, cyclohexanone, 4-methyl-4-methoxy-2-pentanone, etc.; dimethylformamide, dimethylacetamide, N
- Nitrogen-containing solvents such as methylpyrrolitone and nitrobenzene; and dimethylsulfoxide, etc. The above solvents can be used alone or in combination of two or more.

Chain extenders used in the three-step method include aryl ester groups, aryl carbonate groups, N-acyllactam groups, N-acylimide groups, benzoxazinone groups, incyanate groups, oxazolonyl groups, N-acylimidazole groups, Silanol group, 70-san group, aziridine group,
Examples include those having functional groups such as an inthiocyanate group, a vinyl ether group, a ctene acetal group, an unsaturated cycloacetal group, and a carbodiimide group.

Examples of chain extenders having these functional groups include diaryl oxalate compounds, diaryl 7-thalerate compounds, diaryl carbonate compounds, bis(N-acyllactam) compounds, bis(N-acylimide) compounds,
Bisbenzoxazinone compound, polyisocyanate compound, bisoxacilone compound, bis(N-acylimidazole) compound, alkoxy 7-rane compound, silanol compound, 70xane compound, bisaziridine compound,
There are compounds such as polyinthiocyanate compounds, divinyl ether compounds, diketene acetal compounds, unsaturated cycloacetal compounds, and biscarbodiimide compounds.

The reaction of a polyester containing a hydroxyl group as well as a carboxyl group with a chain extender in the three-step process can be carried out under the same conditions as the reaction of the acid anhydride and polyester described above.

A catalyst can be used as necessary for the reaction between the polyester containing a hydroxyl group as well as a carboxyl group and a chain extender.
Examples of such catalysts include organometallic compounds such as diptyltin oxide, dibutyltin dilaurate, and tetra-n-butyl titanate, 6-class amines such as dimethylbenzylamine and trimethylbenzylammonium chloride, and quaternary ammonium salts. .

As the organic solvent that can be used in the above reaction, the solvent used in the reaction between the polyester and the acid anhydride described above can be used.

Subsequently, in order to introduce a photosensitive unsaturated double bond as a pendant group into the photosensitive polyester or modified polyester resin precursor produced in this way, for example, a photosensitive monoepoxy compound, a photosensitive monoincyanate compound, etc. can be introduced (by reacting).

Photosensitive monoepoxy compounds used in the reaction include:
For example, monoepoxy compounds represented by the following general formulas (8) to α4 may be mentioned, and in this case, the photosensitive polyester or modified polyester resin precursor may have an acid value of 20 to 215.
It is preferable to use those having a hydroxyl value of 15 or less.

R.

CH2= C-Coo CH2-cH-CH2...Song...
-θ2 (In the general formulas (8) to a4, RI is a hydrogen atom,
represents an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a halogen atom or a nitro group, R3 represents a hydrogen atom, a methyl group, a 7-enyl group, or a cyano group;
1 represents an alkyl group having 1 to 10 carbon atoms or a phenyl group, R5 represents a hydrogen atom, a methyl group or a phenyl group, R6 represents an alkylene group or an arylene group, and R?
represents a hydrogen atom or a methyl group, k represents an integer of 1 or 2, ノ represents an integer of 1 to 5, and n represents an integer of 1 to 4. ) Among the above compounds, particularly preferred examples include cinnamic acid,
α-cyanocinnamic acid, p-methoxycinnamic acid, 4-chloro-
Glycidyl esters such as α-phenylcinnamic acid, cinnamylidene acetic acid, α-cyanocynamylidene acetic acid, 2-nitrocinnamylidene acetic acid; p-7 22 diacrylic acid monomethyl ester, p-ph22 diacrylic acid monoethyl ester , p-7 22 diacrylic acid monophenyl ester, p-phenylene diacrylic acid mono-2-ethylhexyl ester, m-phenylene diacrylic acid monoethyl ester, 2,5-dimethoxy-p-phenylene diacrylic acid monoethyl ester esters, glycidyl esters such as 2-nitro-p-phenylene diacrylic acid monoethyl ester; glycidyl esters such as furan acrylic acid and 5-methylfuran acrylic acid; α-phenylmaleimidoacetic acid, α-phenylmaleimido-n-parerianic acid ,
Glycidyl esters such as α-phenylmaleimide-ε-cafuronic acid and α-phenylmaleimide-p-benzoic acid;
Glycidyl ester of acrylic acid and methacrylic acid; 4-
Examples include glycidyl ether of hydroxychalcone and 4'-hydroxychalcone.

The reaction between the photosensitive polyester or modified polyester resin precursor and the photosensitive monoepoxy compound is a reaction in which a predetermined amount of the photosensitive monoepoxy compound is added to a solution in which the (modified) polyester resin precursor is dissolved in an inert organic solvent. It can be carried out under a reaction system in which a predetermined amount of a photosensitive monoepoxy compound is added to a melted (modified) polyester resin precursor. Preferred reaction conditions vary depending on the presence or absence of a catalyst, as well as the acid value of the modified polyester resin precursor and the molecular weight of the monoepoxy compound, but in general, the amount of photosensitive monomer The epoxy group of the epoxy compound is 0.2 to 0. It is desirable to select a range of g equivalents.

Further, the catalyst used in the reaction includes quaternary ammonium halides such as triethylbenzylammonium bromide and triethylbenzylammonium bromide;
Tertiary amines such as dimethylbenzylamine, tri-n-butylamine, triethylamine, 2-methylimidazole, etc.; inorganic groups such as lithium chloride, sodium chloride, etc.; organic phosphorus compounds such as nitriphenylphosphine; and the like.

Examples of the organic solvent used in the reaction include the organic solvents used in the reaction of the polyester and acid anhydride described above.

The fc photosensitive (modified) polyester resin ore thus obtained is purified, if necessary, by re-scattering by conventional means. The precipitant used in this case is
Alcohols such as methanol, ethanol, etc.; petroleum ether.

Petroleum hydrocarbons such as n-hexane, ligroin, etc.;
Examples include water.

In addition, examples of the photosensitive monoisocyanate compound include monoisocyanate compounds represented by the following general formulas α5 to Ql, and in this case, the photosensitive polyester or modified polyester resin precursor has an acid value of 15 to 1.
50, and those having a hydroxyl value of 10 to 100 are preferably used.

(In the above general formula [1-a9, horse is a hydrogen atom or a methyl group; R8 is an alkylene group having 2 to 4 carbon atoms; R4 is an organic diincyanate residue; R3 is a hydrogen atom, a halogen atom, a nitro group carbon Number 1 to 4 alkyl group or alkoxyl group I R6 is a hydrogen atom, methyl group or phenyl group: R7
represents a methylene group or an ethylene group; p represents an integer of 1 or more; q represents an integer of 1 or 2, respectively. ) Particularly preferred series of the above compounds include, for example, β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, 1
, 3-butylene glycol monoacrylate and other hydroxyl group-containing acrylates or methacrylates per mole of tolylene diincyanate, metaphenylene diinocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diincyanate, inphorone diincyanate. A compound obtained by reacting 1 mole of a diisocyanate compound such as acryloyl isocyanate, methacryloyl isocyanate, cinnamoyl incyanate h p-methoxycinnamoyl isocyanate, cinnamylidene isocyanate, the reaction of this precursor with a photosensitive monoisocyanate compound is anhydrous. This can be done by using an inert organic solvent as the reaction solvent.

Examples of the reaction solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-
Pyrrolidone, N-methylcaprolactam, hexamethylphosphorylamide, tetramethylene sulfone, dimethyl sulfone, butyrolactone, trimethyl phosphate,
Benzene, toluene, nitrobenzene, trichlene, ethyl acetate, etc. are preferred, and a) these can be used alone or in combination of two or more. The reaction is desirably carried out in the presence of a catalyst, and known phrethanization catalysts can be used.

In the photosensitive polyester or modified polyester resin produced as described above, the hydroxyl groups generated when adding the photosensitive monoepoxy compound to the photosensitive polyester or modified polyester resin precursor are reacted with an acid anhydride to make the photosensitive polyester resin. It is also possible to increase the acid value of the resin to increase its developability with an aqueous alkaline developer.

The photosensitive polyester or modified polyester resin produced by the method described above has the following components in its resin 1000.9:
0.2 moles or more of photosensitive unsaturated double bonds adjacent to the aromatic nucleus contained in the main chain of the molecule, 0.1 mole or more of photosensitive unsaturated double bonds contained in the pendant groups, and those photosensitive unsaturated double bonds contained in the pendant groups. The total amount of saturated double bonds (the total amount of photosensitive unsaturated double bonds adjacent to the aromatic nucleus contained in the main chain of the molecule and the photosensitive unsaturated double bonds contained in the pendant groups) is 0.4. It is preferable to use such a photosensitive resin in the photosensitive image forming material of the present invention, which has a carboxyl group having an acid value of 15 or more.

The photosensitive image forming material according to the present invention can be produced by using a composition in which the photosensitive resin described above is dissolved in a suitable solvent, or if necessary, a sensitizer, a pigment, a dye, a filler, a stabilizer, This can be carried out by preparing a composition to which additives such as a crosslinking agent and a plasticizer are added, and applying this composition to the surface of the support and drying it.

Suitable solvents vary depending on the composition and molecular weight of the resin, but are usually th solvents used in the reaction of the above polyester and acid anhydride; alcohol-based solvents such as tetrahydrofurfuryl alcohol, benzyl alcohol, diacetone alcohol; glycol; Glycol heptanoalkyl ether solvents such as monomethyl ether and glycol monoethyl ether; ethylene glycol monophenyl ether and the like are examples; these may be used alone or in combination of two or more.

Any sensitizer that can be used in this field may be used, including benzophenone derivatives, benzanthrone derivatives, quinones, aromatic nitro compounds, naphthothiazoline derivatives, benzothiazoline derivatives, ketocoumarin compounds, or pyrylium salts. , thiapyrylium salts, etc. can be used. Examples of such sensitizers include Michler's ketone, diethylaminoethylbenzophenone, benzanthrone, (3-methyl-1,3-diaza-1,
9-benz) anthrone hyclamide, 6.11-dichlorobenzanthrone, 6-quenylupenzanthrone, 1.8-') methoxyanthraquinone, 1,2-benzanthraquinone, 5-nitroacenaphthene, 2-nitrofluorene , 2,7-cinitrofluorene, 1-nitronaphthalene, 1,5-dinitronaphthalene, "p-nitrodiphenyl, 2-dibenzoylmethylene-5-methylnaphthothiazoline, 2-benzoylmethylene-1-methylnandothiazoline, 2-bis(70yl)methylene-6-methylbenzothiazoline, 2-benzoylmethylene-3-methylbenzothiazoline, 3.3-carbonyl-bis(7-dinithylaminocoumarin), 2.4°6-
Dorifhenylthiapyrylium perchlorate, 2,6-
Bis(p-ethoxyphenyl)-4-(p-n-amyloxyphenyl)-thiapyrylium verchlorate and the like.

The photosensitive resin composition described above is applied to a support by a well-known coating method such as whirler coating, dip coating, curtain coating, roll coating, spray coating, air knife coating, doctor knife coating, spinner coating, or the like.

Specific examples of the support include aluminum plates, zinc plates, copper plates, stainless steel plates, and other metal plates; sheets and plates of synthetic resins such as polyethylene terephthalate, polycarbonate, and cellulose derivatives; synthetic resins melt-coated or Examples include paper coated with a synthetic resin solution, composite materials in which a metal layer is provided on a synthetic resin by vacuum deposition, lamination, or other techniques; silicon wafers.

As a support for a printing plate, a mechanically, chemically, or electrochemically roughened metal plate made of aluminum, copper, zinc, etc. is used, and a 0.1 to 2.5 μm thick plate is usually used on this plate. A photosensitive layer with a high temperature is formed.

After image-wise exposing the photosensitive layer of this image-forming material using a negative image to harden and insolubilize the exposed portion of the photosensitive layer,
By developing with an aqueous alkaline developer and dissolving and removing the unexposed areas, a corresponding image can be formed on the support.

In this case, the aqueous alkaline developer is one that has water as its main component, to which are added water-soluble inorganic compounds such as alkaline metal silicates, bicarbonates, carbonates, or hydroxides, and amines. Optionally, those containing additives such as organic solvents and surfactants can be used.

Illustrative light sources used for exposure include carbon arc lamps, mercury lamps, xenon lamps, metal halide lamps, lasers, and the like.

Hereinafter, the present invention will be specifically explained using examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

〔Example〕

Two-stage production method ■ Production of polyester An acid component and an alcohol component having the composition listed in Table 1 are combined with a catalyst (dibutyltin oxtide) and an inhibitor (phenothiazine) together with a stirring device, a nitrogen gas inlet tube, a thermometer, and a distillate. The mixture was charged into a reactor equipped with an outlet tube, and the reaction was started by heating to 190° C. while stirring under a nitrogen gas atmosphere. after that,
Heating and stirring were continued for 3 and a half hours, and the ethanol produced by the reaction was completely distilled off to obtain a polyester.

■ Manufacture of photosensitive polyester resin precursor The polyester (120,!i') of (1) above was heated to 140°C, and the acid anhydrides listed in Table 1 were charged with stirring, and the mixture was heated under nitrogen atmosphere at normal pressure. Stirring was continued under the conditions (reaction time) shown in Table 1 to obtain a photosensitive polyester or modified polyester resin precursor.

Three-step process ■ Production of polyester containing hydroxyl groups as well as carboxyl groups Polyester (1205+) t- of the two-step process ■ described above
The mixture was heated to 140° C., and the acid anhydrides listed in Table 1 were charged with stirring, and stirring was continued for 2 hours at normal pressure in a nitrogen atmosphere to obtain a polyester containing both carboxyl groups and hydroxyl groups.

■ Production of photosensitive modified polyester resin precursor Monochlorobenzene (400 g
) to make a 20% solution by weight, and 4,4 as a chain extender.
'-Diphenylmetal diisocyanate was charged in a ratio such that the number of equivalents of the functional group of the chain extender was 1.0 per equivalent of the hydroxyl group of the polyester containing carboxyl groups and hydroxyl groups, and after continued stirring at 60°C for 3 hours, The internal temperature was lowered to room temperature, and the produced resin solution was taken out and poured into a large amount of methanol to precipitate the produced resin.
It was dried under reduced pressure at °C to obtain a photosensitive modified polyester resin precursor.

N,N-dimethylformamide (46
,7! to make a 30% solution by weight, and add the first
The photosensitive monoepoxy compounds listed in the table and triethylbenzylammonium chloride (0,
Add 1) and charge it into the same reaction vessel as in 1] above.
After continuing stirring at 20°C for 5 hours, the temperature inside the vessel was lowered to the chamber tray, and the produced resin solution was taken out and poured into a large amount of methanol to precipitate the produced resin, taken out and dried under reduced pressure at 60°C. A photosensitive polyester or modified polyester resin was obtained.

[3) - Preparation of 1g base plate The above-mentioned photosensitive polyester or modified polyester resin is diluted with cyclohexanone to prepare an Affi amount % solution, and 2-benzoylmethylene-1-methyl-
A photosensitive composition was prepared by adding β-naphthothiazoline (5% by weight based on the resin) and a phthalocyanine pigment (10% by weight based on the resin). This composition was coated on an aluminum plate which had been grained and anodized, and dried to prepare a photosensitive plate having a photosensitive layer having a thickness of 1 μm.

[a-2 Photosensitivity measurement conditions A step wedge with a step difference of 0.15 was brought into close contact with the photosensitive plate obtained in Taki-1 above, and a metal halide lamp with an output of 1 kW (Iwasaki Electric ■
The above photosensitive plate was exposed using an Idolfin 1000J manufactured by Idolfin Co., Ltd. Next, the sample was immersed in a developer shown in Table 1 below for 30 seconds, and then developed by wiping it gently with a cellulose sponge, and its developability was evaluated. Further, the photosensitivity was expressed as the exposure time required to insolubilize the fifth stage of the step wedge after development.

First expression Image Liquid composition Note 1) Kao Atlas■ Sodium tart-butylnaphthalene sulfonate-based anionic surfactant■ Preparation of printing plate and evaluation of printability by the same method as in (3)-1 above. A negative film with a test pattern was placed in close contact with the prepared photosensitive plate, and a metal halide lamp with an output of 1 kW (Idol Fin 1000J, manufactured by Iwasaki Electric Co., Ltd.) was installed at a position 1 m away from the photosensitive plate.
A printing plate was prepared by exposing the fifth stage of the step wedge to light for the exposure time required to insolubilize it, and then developing with the developer shown in Table 1. The printing plate produced in this way was attached to a four-color lithographic printing machine.

Printing was performed using standard ink for lithographic printing under conditions similar to actual lithographic printing, and printability was evaluated after 50,000 sheets had been printed. A clear image faithful to the original was obtained without any printing defects such as skipping or blurring.

(51 Evaluation of storage stability of photosensitive plate) The photosensitive plate was prepared in the same manner as in (5)-1 above, and then placed in a constant temperature machine (60°C, 60% RH) for 100 minutes as an accelerated test.
Photosensitive plates that were not subjected to the photosensitive temporary payment acceleration test that had been stored for a period of time were prepared, and printing plates were prepared and printed in the same manner as in ①-2 above. There was no difference in developability, photosensitivity, printability, etc. between the accelerated test and the non-accelerated test for either printing plate, indicating that it had good storage stability. .

The contents and results of each of the above examples are summarized in Table 2.

Note that the ax 1) in Table 2 is as shown below. Bone 1)
The concentration of photosensitive groups indicates the number of moles of photosensitive unsaturated double bonds contained in 1000 g of photosensitive polyester or modified polyester resin.

〔Effect of the invention〕

The image forming material of the present invention comprises a photosensitive polyester or modified polyester resin having a photosensitive unsaturated double bond adjacent to an aromatic nucleus in the entire main chain and a photosensitive unsaturated double bond in the side chain. By containing it in the layer, it has high photosensitivity, and at the same time, since the photosensitive polyester or modified polyester resin has a carboxyl group, it can be developed with an aqueous alkaline developer.

The image forming material of the present invention is particularly suitable for use in photosensitive lithographic printing plates, but is not necessarily limited to photosensitive printing plates (for example, for producing electronic components such as ICs, lead frames, connectors, etc.). It can also be used as a photoresist for microfabrication as required.

Claims (1)

[Scope of Claims] 1. A photosensitive polyester or modified polyester having a photosensitive unsaturated double bond adjacent to an aromatic nucleus in the main chain of the molecule, and having a photosensitive unsaturated double bond and a carboxyl group as pendant groups. A photosensitive image forming material that can be developed with an aqueous alkaline developer and is characterized by containing a resin in the photosensitive layer. 2. Photosensitive polyester or modified polyester resin 1.
0.4 mole or more of photosensitive unsaturated double bonds in 000g,
and the image forming material according to item 1, which has a carboxyl group with an acid value of 15 or more. 3. The photosensitive unsaturated double bond adjacent to the aromatic nucleus is derived from a dicarboxylic acid represented by the following general formulas (1) to (7), according to claim 1 or 2. Imaging materials. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(3) ▲Mathematical formulas , chemical formulas, tables, etc. ▼...(4) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼...(5) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼...(6) ▲ Mathematical formulas, chemical formulas , tables, etc. ▼...(7) (In the above general formulas (1) to (7), R_1 and R_1' each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a C 1 to 4 alkyl group. R_2 represents an alkylene group having 2 to 4 carbon atoms, l represents an integer of 1 to 5, and n and n' each independently represent an integer of 1 to 4. , m represents an integer from 1 to 5.) 4. Monoepoxy whose photosensitive unsaturated double bond of the pendant group of the photosensitive polyester or modified polyester resin is represented by the following general formulas (8) to (14) Claims 1 to 3 that are derived from a compound
Manufacturing method described in section. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(8) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(9) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(10) ▲Mathematical formulas , chemical formulas, tables, etc. ▼...(11) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼...(12) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼...(13) ▲ Numerical formulas, chemical formulas , tables, etc.▼...(14) (In the above general formulas (8) to (14), R_1 is a hydrogen atom,
represents an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a halogen atom or a nitro group, R_3 represents a hydrogen atom, a methyl group, a phenyl group or a cyano group,
R_4 represents an alkyl group having 1 to 10 carbon atoms or a phenyl group, R_5 represents a hydrogen atom, a methyl group, or a phenyl group, R_6 represents an alkylene group or an arylene group, R_7 represents a hydrogen atom or a methyl group, and k represents an integer of 1 or 2, l represents an integer of 1 to 5, and n represents an integer of 1 to 4. ) 5. The photosensitive unsaturated double bond of the pendant group of the photosensitive polyester or modified polyester resin has the following general formula (15) to (
19) The manufacturing method according to claims 1 to 4, which is derived from the monoisocyanate compound represented by the following. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(15) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(16) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(17) ▲Mathematical formulas , chemical formulas, tables, etc. ▼...(18) ▲ Numerical formulas, chemical formulas, tables, etc. ▼...(19) (In the above general formulas (15) to (19), R_2 is a hydrogen atom or a methyl Group; R_3 is an alkylene group having 2 to 4 carbon atoms; R_4 is an organic diisocyanate residue; R_5 is a hydrogen atom, a halogen atom, a nitro group, an alkyl group or an alkoxyl group having 1 to 4 carbon atoms; R_6 is a hydrogen atom, a methyl group, or Phenyl group; R_7 is a methylene group or ethylene group; p is an integer of 1 or more; q represents an integer of 1 or 2, respectively.)