JPS6132842A - Manufacture of photosensitive resin having high sensitivity - Google Patents

Abstract

PURPOSE:To form a photosensitive layer developable with an aqueous alkali developer by reacting a precursor of (modified) polyester resin having photosensitive unsatd. double bonds each adjacent to an aromatic ring and carboxyl groups in the molecule with a monoepoxy compound having a photosensitive unsatd. double bond. CONSTITUTION:Polycarboxylic acid components contg. photosensitive unsatd. dicarboxylic acid or a deriv. thereby by 15-100mol% of the total amount of the components and polyol components such as ethylene glycol are charged into a reactor in a prescribed blending ratio, and after adding a catalyst such as zinc acetate and an inhibitor such as hydroquinone, they are brought into a reaction at 150-250 deg.C. The resulting precursor or (modified) polyester resin having 20- 215 acid value is reacted with a monoepoxy compound having a photosensitive unsatd. double bond such as cinnamic acid to obtain a photosensitive resin. This resin is dissolved in a solvent, mixed with a sensitizer, a pigment, etc., and applied to a support such as an Al or Zn plate with a spinner or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a photosensitive resin, and more particularly to a method for producing a highly sensitive photosensitive resin used in a photosensitive layer of a photosensitive image forming material.

[Conventional technology]

Because of the unique photodimerization reaction, studies have been conducted on mild photosensitive resins in which a cinnamic acid skeleton is introduced into the side chain or main chain of the molecule. 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 described above, an image forming material using a photosensitive polyester resin having a cinnamic acid skeleton in the molecular main chain produced by condensation of phenylene diacrylic acid or its alkyl ester and glycold. is said to have relatively high photosensitivity, but the sensitivity is not necessarily sufficient to meet current practical requirements. On the other hand, attempts have been made to increase the sensitivity of image forming materials using the above photosensitive polyester resins by using polyfunctional cinnamic acid esters as crosslinking agents, but such crosslinking agents are generally It also has poor compatibility with resins.

The increased sensitivity of the image forming material is also insufficient.

Furthermore, in recent years, a simplified plate-making method has been proposed in which an image is directly printed on a photosensitive layer from an electrical image signal using a laser beam, instead of printing the image through a halftone film. However, the current photosensitive image forming materials have insufficient photosensitivity, and the reality is that a large, high-output laser must be used. For this reason, photosensitive image forming materials with even higher sensitivity are desired.

Photosensitive resins used in image-forming materials are generally produced by a polycondensation reaction between a polyhydric carboxylic acid component having a cinnamic acid skeleton and a polyhydric alcohol component, and as the molecular weight increases, its photosensitivity improves. It is known that it is difficult to do.

However, in the case of polycondensation reactions, it is generally difficult to obtain polymers with high molecular weight, and when the polycondensation reaction is carried out at high temperatures for a long time to increase the molecular weight, it is difficult to obtain polymers with high molecular weight due to the presence of the cinnamic acid skeleton. Branching and crosslinking are likely to occur as side reactions,
Gels that are insoluble in solvents tend to form. These facts or phenomena adversely affect the developability, resolution, printing characteristics, etc. of image forming materials using the resin.

Furthermore, since these photosensitive resins generally 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, there are many problems in terms of development workability, safety and health of the working environment, economic efficiency, and prevention of air pollution and other pollution. Therefore, it is also desired to develop a photosensitive resin that can be developed with an aqueous developer.

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-52-150897) have been developed. etc.), but such conventional resins can be developed with an aqueous developer when used as a photosensitive material for a printing plate.

However, it is still insufficient in terms of light sensitivity), tackiness of the plate due to moisture, and oil sensitivity during printing, and improvements are desired.

[Problem that the invention seeks to solve]

An object of the present invention is to provide a method for producing a photosensitive resin having high photosensitivity.

Another object of the present invention is to provide a method for producing a highly sensitive photosensitive resin that can form a photosensitive layer that can be developed with an aqueous alkaline developer.

[Failure to solve the problem]

In the molecule, there is a photosensitive unsaturated double bond adjacent to the aromatic nucleus,
A monoepoxy compound having a photosensitive unsaturated double bond (hereinafter referred to as a photosensitive monoepoxy compound) is added to a precursor consisting of a polyester or modified polyester resin containing a carboxyl group (hereinafter referred to as a (modified) polyester resin precursor). The above objective is achieved by reacting .

The (modified) polyester resin precursor used in the present invention is
It can be derived from a polyhydric carboxylic acid component containing a dicarboxylic acid having a photosensitive unsaturated double bond adjacent to an aromatic nucleus (hereinafter referred to as photosensitive unsaturated dicarboxylic acid) and a polyhydric alcohol component. For example, (1)... A method in which the reaction is carried out at a ratio in which the amount of carboxyl groups is in excess of the amount of hydroxyl groups (one-stage method), (2)... A method in which the amount of hydroxyl groups is in excess of the amount of carboxyl groups. A method in which a polyester containing hydroxyl groups is once produced by reacting in an excessive proportion, and then an acid anhydride is added to the hydroxyl groups contained in this resin (two-step method), (3) --- as described above. In the two-step method, when adding an acid anhydride to the hydroxyl groups to be added to the polyester, the amount of hydroxyl groups contained in one polyester is added in excess of the amount of acid anhydride groups in the acid anhydride, and carboxyl groups are added. A polyester containing a hydroxyl group is synthesized together with a compound having two or more functional groups in the molecule that can react with the hydroxyl group (hereinafter referred to as a chain extender).
(three-stage method).

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

Examples of photosensitive unsaturated dicarboxylic acids include dicarboxylic acids represented by the following general formulas +11 to (7), and derivatives of these dicarboxylic acids include dialkyl esters of these dicarboxylic acids such as dimethyl ester and diethyl ester. , di(ethylene glycol) ester% di(alkylene glycol) ester such as di(propylene glycol) ester, and dicarboxylic acid halide such as dicarboxylic acid chloride.

(In the above general formulas (1) to (7), h R1 and R; each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and 1 carbon number
~4 alkoxyl group, halogen atom or nitro group, s''l represents an alkylene group having 2 to 4 carbon atoms, and !
represents an integer from 1 to 5, and n and n' each independently represent an integer from 1 to 5.
represents an integer of 4, and m represents an integer of 1 to 5. ) As a preferable example of the above dicarboxylic acid or its derivative, p
-phenylene diacrylic acid, m-phenylene diacrylic acid, 2,5-dimethoxy-p-phenylene diacrylic acid, 2-nitro p-phenylene diacrylic acid, p-carboxycinnamic acid, cinnamylidenemalonic acid, bis( Dicarboxylic acids such as p-cinnamic acid) diethylene glycol ether, bis(P-carboxybenzal)cyclohexanone, bis(p-carboxybenzal)cyclopentanone, and p,p'-chalcone dicarboxylic acid or derivatives thereof can be mentioned. .

In the production of the (modified) polyester resin precursor, other polycarboxylic acids or derivatives thereof can be used together with the above photosensitive unsaturated dicarboxylic acids or derivatives thereof. Examples of such compounds include cono-phosphoric acid, adipic acid, etc. , azelaic acid, sepatic acid, phthalic acid, inphthalic acid, -terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, tetrabromophthalic acid, tetrachlorophthalic acid, 1
．． Dicarboxylic acids such as 4-cyclohexanedicarboxylic acid, maleic acid, fumaric acid, itaconic acid, 5-sodium sulfoinphthalic acid, etc.; polyhydric carboxylic acids such as trimellitic acid, or their anhydrides or ester derivatives, etc. can all be used. .

However, the use of large amounts of these other polyhydric carboxylic acids or their derivatives should be avoided since it causes a decrease in the photosensitivity of the resin. In order to obtain sufficiently high photosensitivity,
It is desirable that the amount of the photosensitive unsaturated dicarboxylic acid or its derivative used be 15 to 100 mol% of the total polyhydric carboxylic acid component.

On the other hand, as the polyhydric alcohol component, various types can be used without particular limitation, such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, .3-butylene glycol, 1,6-hexanediol, 2-butene-1,4-diol, 2.2.
4-trimethyl-1,3-bentanediol, 1.4-
Bis-β-hydroxyethoxycyclohexane, cyclohexane dimetatool, tricyclodecane dimetatool, hydrogenated bisphenol A, hydrogenated bisphenol F1 Ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, ethylene oxide of bisphenol F adduct, propylene oxide adduct of bisphenol F, ethylene oxide adduct of hydrogenated bisphenol A, propylene oxide adduct of hydrogenated bisphenol A, 3-methylpentane-1,
Examples thereof include 3,5-) diol, glycerin, trimethylolpropane, trimethylolethane, and pentaerythritol.

Polyester synthesis is generally readily prepared by means known in the art. In other words, it can be produced by combining the polyhydric carboxylic acid component and the polyhydric alcohol component in a predetermined mixing ratio, and then reacting (esterification reaction or transesterification) in the presence of a catalyst and inhibitor that are added as needed. , the reaction temperature is preferably 15"0 to 250°C. In addition, when a relatively low molecular weight glycol is used in the synthesis of polyester in the two-step method and the three-step method, the glycol component may be present in excess of the predetermined amount. It can also be produced by blending and allowing the entire reaction to proceed, and after the completion of the reaction, gradually reducing the pressure in the reactor to distill out excess glycol.

Examples of the catalyst used for the reaction between the polyhydric carboxylic acid component and the polyhydric alcohol component include tetraisoglobyl titanate, tetrabutoxytitanate, diptyltin oxide, dibutyltin laurate, lyticum ethoxide, zinc acetate, manganese acetate, Organic metal compounds such as calcium acetate; inorganic metal compounds such as titanium dioxide, antimony trioxide, calcium oxide, and zinc chloride can be used.

The amount used is 50 to 10,000 pp as a metal component.
m is preferred.

Inhibitors are used to minimize the crosslinking and branching of ethylenically unsaturated groups that tend to occur during polycondensation reactions, such as phenothiazine, etc.
Hydroquinone, hydroquinone monomethyl ether, 2
, 6-ditart-7'thyl-p-cresol, p-
Benzoquinone etc. can be used. The amount used is 50 to 2
,000 ppm is preferred.

Examples of the acid anhydrides used in the two-step process and the six-step process include succinic anhydride, octadecylsuccinic anhydride, camphoric anhydride, maleic anhydride, phthalic anhydride, 4-methylphthalic anhydride, and 3-nitrophthalic anhydride. 5.3
',4.4'-benzophenonetetracarboxylic dianhydride, 3.3',4.4'-diphenyltetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1 ,4,5.8-naphthalenetetracarboxylic dianhydride, 4,4'-Xkhonyldiphthalic dianhydride, 2,2-bis(5,4-dicarboxyphenyl)propanihydride, bis(6,4 -dicarboxyphenyl)ether dianhydride, 4,4'-C3
, 3'-(alkylphosphoryldiphenylene)-bis(
5-(2 , 5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride (Dainippon Ink Chemicals KK#!, Evicron B-4400), 1,2
, 3.4-cyclopentanetetracarboxylic dianhydride,
Alicyclic tetracarboxylic dianhydrides such as 1,2,4.5-cyclohexanetetracarboxylic dianhydride, tetrahydrofuran tetracarboxylic dianhydride; 1,2,3,
4-butanetetracarboxylic dianhydride, 1.2, 4.5
-Aliphatic tetracarboxylic dianhydrides such as pentane tetracarboxylic dianhydride can be used.

The reaction between polyester and acid anhydride can be carried out by: ■ Adding a predetermined amount of cyclic acid anhydride to the molten polyester, or ■ Dissolving the polyester in an organic solvent and adding a predetermined amount of acid anhydride. and perform the reaction. The reaction temperature is preferably room temperature or higher and 220°C or lower, and the reaction time is 5
Minutes or more is preferable.

Organic solvents used in the above reaction include: chlorine-based solvents such as methylene chloride, chloroform, trichloroethane, trichloroethylene, chlorobenzene, dichlorobenzene, and carbon tetrachloride; ether-based solvents such as tetrahydrofuran and dioxane; glycol methyl Ester solvents such as ether acetate, glycol ethyl ether acetate, ethyl acetate, etc. Ketone solvents such as methyl ethyl ketone, methyl imbutyl ketone, cyclohexanone, 4-methyl-4-methoxy-2-pentanone, etc.; dimethyl formamide, dimethyl acetamide, N-
Nitrogen-containing solvents such as methylpyrrolidone and nitrobenzene; dimethylsulfoxide and the like; 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, and N-acylimidazole groups.

Examples include those having functional groups such as a silanol group, a furoxane group, an aziridine group, one aziridine group, a vinyl ether group, a ketene acetal group, an unsaturated cycloacetal group, and a carbodiimide group. Chain extenders having all of these functional groups minerals, such as diaryl phthalate compounds, diaryl phthalate compounds, diaryl carbonate compounds, bis(N-acyllactam) compounds, bis(N-acylimide) compounds,
Bisbenzoxazinone compound, polyisocyanate compound, bisoxacilone compound, bis(N-acylimidazole) compound, alkoxysilane compound, sila/-
compound, furoxane compound, bisaziridine compound,
There are compounds such as polyinthiocyanate compounds, divinyl ether compounds, diketene acetal compounds, unsaturated cycloacetal compounds, biscarbodiimide compounds, etc. Polyesters containing hydroxyl groups as well as carboxyl groups in the three-step process (hereinafter referred to as hydroxyl group-containing polyesters) The reaction between the polyester and the chain extender can be carried out under the same conditions as the reaction between the acid anhydride and the polyester described above.

The reaction ratio between the hydroxyl group-containing polyester and the chain extender is 0.2 to 1.5 equivalents, preferably 0.5 equivalents of functional groups capable of reacting with the hydroxyl groups in the chain extender per 1 equivalent of hydroxyl groups in the hydroxyl group-containing polyester. It is desirable to select a bar weight in the range of ~12 bar. If the number of equivalents of the functional groups in the chain extender is less than 0.2 per equivalent of hydroxyl groups in the hydroxyl-containing polyester, it is difficult to increase the molecular weight of the resulting resin to the molecular weight required to obtain high photosensitivity. If it exceeds 9.1.5, even if the proportion of the chain extender is increased, further increases in the molecular weight and photosensitivity of the resulting resin cannot be expected, and gelation is more likely to occur. So I don't like it.

For the reaction between the hydroxyl group-containing polyester and the chain extender, a catalyst may be used if necessary, such as organometallic compounds such as dibutyltin oxide, diptyltin dilaurate, tetra-n-butyl titanate, dimethyl Examples include tertiary amines such as benzylamine and trimethylbenzylammonium chloride, and quaternary ammonium salts.

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

By the means described above, it is possible to produce a (modified polyester resin precursor) having an acid value of 20 to 215.
The use of modified) polyester resin precursors is preferred.

Next, the (modified) polyester resin precursor thus produced is reacted with a monoepoxy compound having a photosensitive unsaturated double bond (hereinafter referred to as a photosensitive monoepoxy compound).

Examples of photosensitive monoepoxy compounds include monoepoxy compounds represented by the following general formulas (8) to a4.

C)l, =C-coocn, -CB-C)l,
----aso (In the general formulas (8) to I, R1 is a hydrogen atom, and has 1 carbon number)
-4 alkyl group, C1-4 alkoxyl group, norogen atom or nitro group, R1 is a hydrogen atom,
Represents a methyl group, phenyl group or cyano group; %4 represents an alkyl group having 1 to 10 carbon atoms or a phenyl group b
RIla hydrogen atom, methyl group or phenyl group s
"8 represents an alkylene group or an arylene group," I represents a hydrogen atom or a methyl group, 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. Was. ) Suitable examples of the photosensitive monoepoxy compounds include cinnamic acid, α-cyano 4u[, p-methoxycinnamic acid, 4-chloro-α-phenylidene 4fi, cinnamylideneacetic acid, α-cyanocinnamylideneacetic acid, 2-nitro Glycidyl esters such as cinnamylidene acetic acid pP-phenylene diacrylic acid monomethyl ester, p-) unilene diacrylic acid monoethyl ester, p-phenylene diacrylic acid monophenyl ester, p-phenylene diacrylic acid mono-2-ethyl ester ester, m-phenylene diacrylic acid monoethyl ester, 2,5-dimethoxy-p
Glycidyl esters such as -722 diacrylic acid heptanoethyl ester and 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-valeric acid, α-phenylmaleimido-6-caproic acid, α-phenylmaleimido-p-benzoic acid, etc.; glycidyl esters of acrylic acid, methacrylic acid: 4-hydroxychalcone, 4 Examples include glycidyl ether of '-hydroxychalcone.

(The reaction between the modified polyester resin precursor and the photosensitive monoepoxy compound is based on the reaction system in which a predetermined amount of the photosensitive monoepoxy compound is added to a solution of the (modified) polyester resin precursor dissolved in an inert organic solvent, or @ melted (denatured)
This can be carried out in a reaction system in which a predetermined amount of a photosensitive monoepoxy compound is added to a polyester resin precursor. Preferred reaction conditions naturally vary depending on the presence or absence of a catalyst, but
Generally speaking, the reaction temperature is preferably 50 to 150°C.

The reaction between the (modified) polyester resin precursor and the photosensitive monoepoxy compound varies depending on the acid value of the (modified) polyester resin precursor and the molecular weight of the monoepoxy compound, but in general, solvent development type photosensitive image formation In the case of photosensitive resins used in materials, it is desirable to react 0.5 to 1 equivalent of epoxy groups in a photosensitive monoepoxy compound per 100 carboxyl groups in the (modified) polyester resin precursor. Preferably, in the case of photosensitive resins used in aqueous alkaline developer-developable photosensitive image forming materials, % (modification)
The epoxy group of the photosensitive monoepoxy compound is 0.2 to 1 equivalent of the carboxyl group of the polyester resin precursor.
The catalyst used in the reaction includes quaternary ammonium salts such as triethylbenzylammonium chloride, triethylbenzylammonium bromide, etc.;
Tertiary amines such as dimethylbenzylamine, tri-n-butylamine, triethylamine%2-methylimidazole, etc.; inorganic salts such as lithium chloride, sodium chloride, etc.; organic phosphorus compounds such as triphenylphosphine, 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.1. Ru.

The photosensitive resin obtained in this way may be
Purification is achieved by re-precipitation using conventional means. The precipitants used in this case include alcohols such as methanol and ethanol; petroleum ether, n-hexane,
Petroleum-based hydrocarbons such as refloin; water, etc. may be mentioned.

In addition, in the photosensitive resin produced in this way, an acid anhydride is reacted with the hydroxyl group generated when the photosensitive monoepoxy compound 'ft (modified) polyester resin precursor is added to the acid value of the photosensitive resin. It is also possible to increase the developability with an aqueous alkaline developer.

According to the method described above, photosensitive resins with various acid values can be produced by adjusting the blending ratio etc. As for the resin, it is preferable to use a photosensitive resin having an acid value of 15 or more for an image forming material that can be developed with an aqueous alkaline developer.

The photosensitive resin produced according to the present invention is usually a composition dissolved in a suitable solvent, or further contains sensitizers, pigments, dyes, fillers, stabilizers, crosslinking agents, and plasticizers as necessary. It is used as a composition with additives such as. Suitable solvents vary depending on the composition and molecular weight of the resin, but are generally organic solvents used in the reaction of oligoesters and acid anhydrides as described above; such as tetrahydrofurfuryl alcohol, benzyl alcohol, diacetone alcohol, etc. Alcohol solvent; ethylene gelcol monophenyl ether, etc. The above solvents may be used alone or in combination of two or more.

As the sensitizer, any one that can be used in this field can be used, including benzophenone conductors, benzanthrone derivatives, quinones, aromatic nitro compounds, naphthothiazoline derivatives, benzothiazoline derivatives, totocoumarin compounds, and the like. Pyrylium mounds, thiapyrylium salts, etc. can be used. Examples of such sensitizers include Michler's ketone, diethylaminoethylbenzophenone, benzanthrone, (6-methyl-1,3-diaza-1,
9-benz) anthrone biclamide, 6,11-dichlorobenzanthrone, 6-phenyl-benzanthrone % 1.8-dimethoxyanthraquinone, 1,2-benzanthraquinone, 5-nitroacenaphthene, 2-nitrofluorene, 2. 7-cinitrofluorene, 1-nitronaphthalene, 1.5-dinitronaphthalene, p-nitrodiphenyl, 2-dibenzoylmethylene-3-methylnaphthothiazoline, 2-benzoylmethylene-1-methylnaphthothiazoline, 2-bis( 70yl) methylene-
3-methylbenzothiazoline, 2-benzoylmethylene-3-methylbenzothiazoline, 3,3-carbonyl-
Bis(7-ethylaminocoumarin), 2,4゜6-triphenylthiavirylium perchlorate, 2,6-bis(p-ethoxyphenyl)4-(p-n-amyloxyphenyl)-thiapyrylium There are barchlorate, etc.

The above-mentioned photosensitive resin composition is applied to a support by a well-known coating method such as waller coating, derag coating, curtain coating, roll coating, spray coating, air knife coating, doctor knife coating, or spinner coating.

Specific examples of supports 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; Examples include paper coated with a synthetic resin solution, composite materials in which a metal layer is provided on a synthetic resin using techniques such as vacuum deposition or lamination; silicon wafers, etc.

As a support for the image forming material, a mechanically, chemically, or electrochemically roughened metal plate made of aluminum, copper, zinc, etc. is used, and on this is usually a A thick photosensitive layer 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 and dissolving and removing the unexposed areas, a corresponding image can be formed on the support.

When an aqueous alkaline developer is used during development, the aqueous alkaline developer contains water as a main component and water-soluble inorganic materials such as alkaline metal silicates, bicarbonates, carbonates, or hydroxides. A compound containing an amine tA''ffk may be used, and if necessary, a compound containing a 4aWj medium, a surfactant, or other additives may be used.

Suitable light sources for use in fog light include carbon arc lamps, mercury lamps, xenon lamps, metallolide lamps, lasers, and the like.

The present invention will be specifically explained below using examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

(Two-step method) ■ Manufacture of polyester An acid component and an alcohol component having the composition listed in Table 1 are combined with a catalyst (diptyltin oxide) and an inhibitor (phenothiazine), 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 to completely distill off the ethanol produced by the two reactions to obtain a polyester.

(2) Manufacture of (modified) polyester resin precursor The polyester of (1) above (heated to 1201't-140°C, charged with the acid anhydride listed in Table 1 while stirring,
Step method) ■ Production of hydroxyl group-containing polyester Ester (120,9
) was heated to 140° C., all of the acid anhydrides listed in Table 1 were charged with stirring, and stirring was continued for 2 hours at normal pressure under a nitrogen atmosphere to obtain a hydroxyl group-containing polyester.

■ Production of (modified) polyester resin precursor Monochlorobenzene 400I was added to the hydroxyl group-containing polyester (1001) to make a 20% solution by weight, and as a chain extender, 4,4'-diphenylmethane diisocyanate gold and the hydroxyl group of the hydroxyl group-containing polyester were added. Prepared at a ratio such that the number of equivalents of the functional group of the chain extender per equivalent is 1.0, 60
After continuing stirring at ℃ for 3 hours, the temperature inside the vessel was lowered to room temperature, and 46.71' of N,N-dimethylformamide was added to 20 g of the photosensitive resin of [1] to make a 60% by weight solution. To the solution, add 1.8 g of triethylbenzylammonium chloride and the photosensitive monoepoxy compound listed in Table 1 and the reaction catalyst, and charge it into the same reaction vessel as in [1] above, and continue stirring at 120 ° C. for 5 hours. After
The temperature inside the vessel was lowered to room temperature, the produced resin solution was taken out, poured into a large amount of methanol, the produced resin was precipitated, taken out, and dried under reduced pressure at 60 ° C. to obtain a photosensitive resin. The photosensitive resin of [2] was diluted with cyclohexanone to prepare a 4% by weight solution, and 2-benzoylmethylene-1-methyl-β-7tocyanoline (5% by weight based on the resin) and phthalocyanine pigment were added to this solution. (10% by weight based on the resin) to prepare a photosensitive composition. After this composition was grained, it was coated on an anodized aluminum plate and dried to prepare a photosensitive plate having a photosensitive layer having a thickness of 1 μm.

A step wedge with a height difference of 0.15 was completely attached to the photosensitive plate obtained in (5)-1 above, and a metal halide lamp with an output of 1Kw (Iwasaki Electric Co., Ltd.
The above-mentioned photosensitive plate was exposed to light using Idol Fin 1000J) t', manufactured by Co., Ltd.

Next, the sample was immersed in the following developer for 30 seconds, and then developed by wiping it off with a cellulose sponge, and its developability was evaluated. In addition, the photosensitivity is determined by the exposure time required to insolubilize the fifth stage of the step wedge after development. The contents and results of each side above are summarized in Table 1.

In addition, 1) in Table 1 is as shown below.

(1) The number of epoxy groups is the number of equivalents of epoxy groups in the photosensitive epoxy compound reacted with one equivalent of carboxyl group in the (modified) polyester resin precursor.

〔Effect of the invention〕

The photosensitive resin produced by the production method of the present invention has 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. C,
It has high photosensitivity.

The production method of the present invention can produce a photosensitive resin that can be dissolved or swelled in a Maruki-based alkaline developer by adjusting the blending ratio of raw materials.

Therefore, by applying the photosensitive resin produced according to the present invention to an image forming material, it is possible to produce both a solvent-developed image forming material and an aqueous alkaline developer-developed image forming material. These image forming materials have high photosensitivity and are particularly excellent as photosensitive materials for photosensitive lithographic printing plates.

The use of the photosensitive resin of the present invention is not necessarily limited to the photosensitive layer of a photosensitive lithographic printing plate, for example, IC,!
It can also be used as a photoresist for microfabrication required when manufacturing electronic parts such as J-frames and connectors.

Claims (1)

[Claims] 1. A precursor consisting of a polyester or modified polyester resin containing a photosensitive unsaturated double bond adjacent to an aromatic nucleus and a carboxyl group in the molecule; 1. A method for producing a highly sensitive photosensitive resin, which comprises reacting a monoepoxy compound having a monoepoxy compound. 2. The manufacturing method according to claim 1, wherein 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). ▲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) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(4) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(5) ▲Mathematical formulas, chemical formulas, There are tables, etc.▼・・・・・・(6) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(7) (In the general formulas (1) to (7) above, R_1 and R_1' each independently represents a hydrogen atom, 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_2 represents an alkylene group having 2 to 4 carbon atoms, and l is 1 5, n and n' each independently represent an integer of 1 to 4, and m represents an integer of 1 to 5.) 3. A monoepoxy compound having a photosensitive unsaturated double bond , the manufacturing method according to claim 1 or 2, which is a monoepoxy compound represented by the following general formulas (8) to (14). ▲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
) ▲There are 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
) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(14
) (In the 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. ) 4. The precursor made of polyester or modified polyester resin has an acid value of 20 or more, and the epoxy group of the monoepoxy compound having a photosensitive unsaturated double bond is 0 per equivalent of carboxyl group of this precursor. The manufacturing method according to claims 1 to 3, wherein .2 to 0.9 equivalents are reacted.