JPH1144953A - Photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water-soluble or water-dispersible photosensitive compsn. which does not cause dropping of PVA in a hardened part during development with water, by constituting the compsn. of a vinylalcohol-based polymer having specified double bonds, unsatd. monomers having ethylene-type double bonds, and a photopolymn. initiator. SOLUTION: This photosensitive compsn. contains a vinylalcohol polymer having double bonds expressed by the formula, unsatd. monomers having ethylene-type double bonds, and a photopolymn. initiator. In the formula, A is a <=20C hydrocarbon group having ethylene type unsatd. double bonds which may be interrupted by oxygen atoms, nitrogen atoms or sulfur atoms. The upper limit of the carbon number of the hydrocarbon group is <=20, and preferably <=15, and more preferably <=10. The PVA used for this photosensitive compsn. is selected so as to use the reaction of aromatic amino groups and unsatd. monomers having epoxy groups and ethylene-type double bonds. Since the reaction is efficiently carried out in water, the PVA itself can be used as a photosensitive compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a water-soluble or water-dispersible photosensitive composition.

[0002]

2. Description of the Related Art Compositions containing a vinyl alcohol polymer, an unsaturated monomer having an ethylenic double bond, and a photopolymerization initiator are widely used as photosensitive compositions in letterpress materials for printing and the like. . The photosensitive composition is formed into a sheet (hereinafter, referred to as a “photosensitive resin plate”) on a support such as a metal plate or a film plate, and then exposed to light and developed to form a resin relief plate. Vinyl alcohol polymer (hereinafter "PVA")
The photosensitive composition using (hereinafter abbreviated as) can be easily extracted with water after the exposure, and is easy to use in plate making, and thus has been used in the printing field. However, conventional PV
The photosensitive composition using A has a serious drawback that the PVA of the cured portion is also removed at the time of development when the uncured portion is washed away with water after exposure. The performance is significantly impaired.

In order to solve such problems, a modified PVA having a radically polymerizable ethylenically unsaturated double bond has been proposed. JP-A-03-192103 proposes a method of reacting a carboxylic acid-modified vinyl alcohol-based polymer with glycidyl methacrylate in acidic hot water. However, in this method, it is necessary to react in acidic hot water for a long time, and since the reactivity between the carboxylic acid and the glycidyl group is low, a large amount of glycidyl methacrylate is required. Therefore, in this method, the introduction amount of the ethylenically unsaturated double bond is low,
It is not enough to solve the problem. Also, JP-A-04-30384
No. 2 proposes a method of reacting an amino group-modified vinyl alcohol polymer with a compound containing an epoxy group and an ethylenically unsaturated double bond (eg, glycidyl methacrylate). However, the amino group-modified PVA used for the reaction is difficult to synthesize industrially, and has a somewhat low reactivity with an epoxy group, has a long time to complete the reaction, and is not efficient.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a water-soluble or water-dispersible photosensitive composition which does not have the disadvantage of the conventional photosensitive composition using PVA that the PVA does not fall off from the cured portion during water development. It is to provide an ionic composition.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies in view of the above problems, and as a result, have found that a vinyl alcohol polymer having a double bond represented by the following chemical formula (5) or (6), an ethylenic double bond A photosensitive composition comprising an unsaturated monomer having the formula (1) and a photopolymerization initiator was found, and the present invention was completed.

[0006]

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[0007]

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(Where A represents a hydrocarbon group having 20 or less carbon atoms and having an ethylenically unsaturated double bond which may be interrupted by an oxygen atom, a nitrogen atom or a sulfur atom, S represents a sulfur atom, B represents a hydrocarbon group having 20 or less carbon atoms which may contain an oxygen atom, a nitrogen atom or a sulfur atom.)

Further, a vinyl alcohol polymer containing an aromatic group substituted by an amino group represented by the following formula (7) or (8), a compound having an epoxy group and an ethylenically unsaturated double bond, A photosensitive composition comprising an unsaturated monomer having a double bond and a photopolymerization initiator has been found.

[0010]

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[0011]

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(Provided that C represents a primary amino group or a secondary amino group, S represents a sulfur atom, and B represents a carbon atom having 20 or less carbon atoms which may contain an oxygen atom, a nitrogen atom or a sulfur atom. Represents a hydrogen group.)

[0013]

A in Chemical Formulas 5 and 6 is a hydrocarbon group having 20 or less carbon atoms and having an ethylenically unsaturated double bond which may be interrupted by an oxygen atom, a nitrogen atom or a sulfur atom. . The upper limit of the carbon number of the hydrocarbon group is 20
Or less, preferably 15 or less, more preferably 10 or less, and particularly preferably 8 or less. The lower limit of the carbon number of the hydrocarbon group is preferably 4 or more, more preferably 5 or more, and particularly preferably 6 or more. Among A, those represented by the following chemical formula 9 are preferable.

[0014]

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R ^{1 to} R ⁷ in Chemical Formula 9 are hydrogen or a hydrocarbon group having 8 or less carbon atoms, preferably hydrogen or a methyl group. n is an integer of 1 to 6, and 1 to 3 is more preferable. Among X in Chemical formula 9, a linking group selected from the following Chemical formulas 10 to 12, or a hydrocarbon group having 8 or less, preferably 3 or less carbon atoms which may be interrupted by an oxygen atom, a nitrogen atom or a sulfur atom is preferable.

[0016]

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(However, the carbon / oxygen double bond side in Chemical formula 10 is linked to the carbon constituting the double bond represented by Chemical formula 9)

[0018]

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(However, the carbon-oxygen double bond side in Chemical formula 11 is connected to the carbon constituting the double bond represented by Chemical formula 9. R ⁸ is hydrogen or hydrogen or a carbon number of 8 or less, preferably 3 or less. Represents a hydrocarbon group.)

[0020]

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(However, the methylene group side in Chemical formula 12 is
It is linked to the carbon constituting the double bond represented by Chemical formula 9. )

As the aromatic ring represented by the formula (5) or (6), in addition to the benzene ring, hydrogen, a methyl group, a methoxy group,
It may have a substituent selected from a nitro group and a hydroxy group. Further, a naphthalene ring to which a benzene ring is further bonded may be used. A in Chemical formulas 5 and 6 may be any position of ortho, meta and para.

B in Chemical formula 6 is a hydrocarbon group having 20 or less carbon atoms which may contain an oxygen atom, a nitrogen atom or a sulfur atom. The upper limit of the carbon number of the hydrocarbon group is 20 or less, preferably 15 or less, more preferably 10 or less, and particularly preferably 8 or less. Among B, the following chemical formula 13
Those represented by are preferred.

[0024]

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(Where R ⁹ represents a divalent hydrocarbon group which may have a nitrogen atom, an oxygen atom or a sulfur atom,
R ¹⁰ to R ¹² is hydrogen or not more than 8 carbon atoms, preferably represents more than 3 hydrocarbon group, S is a sulfur atom. R ⁹ represents a hydrocarbon group having a carbon number of 20 or less, preferably 15 or less, and specifically, —CH ₂ OCH ₂ — and —OCH
_2- , -CONH-φ-OCH _2- , -CONHCH
_{2 -, - CONHCH 2 OCH 2} -, - CONHCH 2 OC
_{H 2 CH 2 -, - CONHCH} 2 OCH 2 CH 2 CH 2 -, -
CONHCH ₂ OCH ₂ CH ₂ CH ₂ CH _2- , -CONH
CH ₂ -φ (CH ₃ ) ₂ -CH _2- and the like. In addition,
φ means a phenylene group.

The structure having a double bond represented by Chemical Formula 5 or Chemical Formula 6 may be bonded to the side chain or terminal of PVA, but is preferably bonded to the side chain. This structure may be directly bonded to the main chain of PVA, or may be bonded to the main chain via some kind of spacer.

The content of the structure having a double bond in the PVA of the present invention is usually 0.01 to 30 mol%, preferably 0.1 to 20 mol%, more preferably 0.5 to 1 mol%.
0 mol%. When the content is extremely low, the object of the present invention cannot be sufficiently achieved, and when the content is extremely high, characteristics such as water solubility inherent of the vinyl alcohol polymer are lost.

Although the molecular weight of the PVA of the present invention is not particularly limited, 4% dimethyl sulfoxide (DMSO) of the PVA is used.
It is preferably 3 to 10,000 mPa · S, more preferably 3 to 5000 mPa · S, and more preferably 5 to 10 mV · S, expressed as the viscosity of the solution at 20 ° C. (measured with a Brookfield viscometer).
00 mPa · S is more preferable. The saponification degree of the PVA of the present invention is not particularly limited as long as it is water-soluble or water-dispersible, but is usually 65 mol% or more, preferably 80 mol%.
That is all.

The PVA of the present invention substantially comprises a vinyl alcohol unit or a vinyl alcohol unit and a vinyl ester unit, except for a copolymer unit containing a structure having a double bond. Examples of the vinyl ester unit include vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl trifluoroacetate, vinyl 2-ethylhexanoate and the like, and usually vinyl acetate is used.

The monomer units other than these may be contained as long as the gist of the present invention is not impaired. Examples of such units include olefins such as ethylene, propylene, 1-butene, and isobutene; and non-olefins such as acrylic acid, methacrylic acid, crotonic acid, (anhydrous) phthalic acid, (anhydrous) maleic acid, and (anhydrous) itaconic acid. Saturated acids or salts thereof or mono- or dialkyl esters having 1 to 18 carbon atoms; acrylamide, N- having 1 to 18 carbon atoms;
Acrylamides such as alkylacrylamide, N, N-dimethylacrylamide, 2-acrylamidopropanesulfonic acid or a salt thereof, acrylamidopropyldimethylamine or an acid salt thereof or a quaternary salt thereof; methacrylamide, an N-alkyl having 1 to 18 carbon atoms Methacrylamides such as methacrylamide, N, N-dimethylmethacrylamide, 2-methacrylamidopropanesulfonic acid or a salt thereof, methacrylamidopropyldimethylamine or an acid salt thereof or a quaternary salt thereof; N-vinylpyrrolidone, N-vinyl N-vinylamides such as formamide and N-vinylacetamide; vinyl cyanides such as acrylonitrile and methacrylonitrile; alkyl vinyl ethers having 1 to 18 carbon atoms; Ethers, vinyl ethers such as alkoxides comb alkyl vinyl ethers; vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl halides such as vinyl bromide; vinylsilane such as trimethoxyvinylsilane, allyl acetate,
Allyl chloride, allyl alcohol, dimethylallyl alcohol and the like can be mentioned. The content of these monomer units is not particularly limited, as long as the polymer is water-soluble or water-dispersible.

The PVA of the present invention comprises a vinyl alcohol polymer having an aromatic group substituted with an amino group (hereinafter abbreviated as “aromatic amino group”), an epoxy group and an ethylenically unsaturated double bond. It is obtained by reacting with a contained compound. The vinyl alcohol polymer containing an aromatic amino group is hydrolyzed after reacting a thiol or thioester containing an aromatic amino group with a copolymer of a vinyl ester monomer and a vinyl monomer having an epoxy group. Is obtained by

Examples of the method of copolymerizing the vinyl ester monomer and the monomer having an epoxy group include known methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Among them, a bulk polymerization method or a solution polymerization method in which polymerization is carried out without a solvent or in a solution such as an alcohol is usually employed, and when a polymer having a high degree of polymerization is obtained, an emulsion polymerization method is employed. Examples of the alcohol used as a solvent during the solution polymerization include lower alcohols such as methyl alcohol, ethyl alcohol, and propyl alcohol. Examples of the initiator used for the copolymerization include α, α′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, and n-propyl peroxycarbonate. And known initiators such as azo initiators and peroxide initiators. There is no particular limitation on the polymerization temperature, but -10 ° C to 150 ° C.
Is appropriate.

Examples of the vinyl monomer having an epoxy group used for copolymerization with a vinyl ester monomer include allyl glycidyl ether, methallyl glycidyl ether, butadiene monoepoxide, 1,2-epoxy-5-hexene, and 1,2-epoxy- 7-octene, 1,2-epoxy-9-decene, 8-hydroxy-6, 7-epoxy-1-octene, 8-acetoxy-6, 7-epoxy-1-octene, N- (2,3-epoxy ) Propylacrylamide, N- (2,3-epoxy) propylmethacrylamide, 4-acrylamidophenylglycidyl ether, 3-acrylamidophenylglycidylether, 4-methacrylamidophenylglycidylether, 3-methacrylamidophenylglycidylether, N-glycidol Methyl acrylamide, N- glycidoxy methyl methacrylamide, N- glycidoxyethyl acrylamide, N- glycidoxy methacrylamide, N- glycidoxypropyl acrylamide,
N-glycidoxypropyl methacrylamide, N-glycidoxybutyl acrylamide, N-glycidoxybutyl methacrylamide, 4-acrylamidomethyl-2,
5-dimethyl-phenylglycidyl ether, 4-methacrylamidomethyl-2,5-dimethyl-phenylglycidyl ether, acrylamidopropyldimethyl (2,3-epoxy) propylammonium chloride,
Examples include methacrylamidopropyldimethyl (2,3-epoxy) propylammonium chloride and glycidyl methacrylate.

As a method of reacting a thiol or thioester containing an aromatic amino group with a copolymer of a vinyl ester monomer and a monomer having an epoxy group, a reaction between a thiol group or a thioester group and an epoxy group is used. Use. The reaction is carried out without a solvent or in a solvent that dissolves or swells a compound having a thiol group or a thioester group and a copolymer having an epoxy group. Examples of such a solvent include alcohols such as methanol, ethanol, n-propyl alcohol and n-butyl alcohol; aromatics such as benzene, toluene and xylene; ethers such as tetrahydrofuran, dioxane and diethyl ether; and n-hexane. And the like. These solvents are used alone or as a mixture. The reaction conditions vary depending on the structure of the epoxy group and the structure of the thiol group or the thioester group. However, when a solvent is used, the concentration of the copolymer is usually 5 to 90%, and the concentration of the thiol group or the thioester group / The epoxy group concentration (molar ratio) = 1.0-5.0, the reaction temperature is 0-250 ° C., and the reaction time is 0.1.
01 to 20 hours. In the reaction with a thiol group, basic compounds such as tertiary amines (eg, triethylamine, pyridine, etc.), phosphines (eg, tributylphosphine, triphenylphosphine, etc.), sodium hydroxide, tetraethylammonium hydroxide, sodium methylate, and sodium acetate Basic compounds such as sodium and sodium carbonate are effective as reaction catalysts. In the reaction with a thioester group, a quaternary ammonium salt such as tributylammonium chloride and tributylammonium bromide is effective as a reaction catalyst. In order to prevent oxidation of the thiol group, the reaction system may be degassed or replaced with nitrogen, or an antioxidant may be added.

Examples of the thiol containing an aromatic amino group to be reacted with the copolymer having an epoxy group include 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, and 2- (N-methyl) amino. Thiophenol, 3- (N-methyl) aminothiophenol,
4- (N-methyl) aminothiophenol, 2-amino-3-methoxythiophenol, 2-amino-4-methoxythiophenol, 4-amino-2-methoxythiophenol, 4-amino-3-methoxythiophenol ,
2-amino-3-hydroxythiophenol, 2-amino-4-hydroxythiophenol, 4-amino-2-
Hydroxythiophenol, 4-amino-3-hydroxythiophenol, 2-amino-3-nitrothiophenol, 2-amino-4-nitrothiophenol, 4-amino-2-nitrothiophenol, 4-amino-3- Nitrothiophenol, 2,3-diaminothiophenol,
Examples thereof include 2,4-diaminothiophenol, 3,4-diaminothiophenol, and 2-aminothionaphthol. Further, esters such as these acetates and benzoates can also be used.

For the hydrolysis subsequent to the reaction between the thiol group or thioester group and the epoxy group, a saponification reaction using a basic catalyst or an acid catalyst commonly used in saponification of polyvinyl ester can be applied. That is, using a basic catalyst such as sodium hydroxide, potassium hydroxide or sodium methylate or an acidic catalyst such as p-toluenesulfonic acid, the reaction is carried out using an alcohol or glycol such as methanol, ethanol, propanol, butanol or ethylene glycol as a solvent. Is performed. In this case, a solvent such as tetrahydrofuran, dioxane, dimethyl sulfoxide, diethylene glycol dimethyl ether, toluene, acetone, or water is appropriately mixed and used in order to improve the solubility of the vinyl ester polymer and the catalyst. In some cases, a radical polymerization inhibitor such as hydroquinone or p-methoxyphenol may be added. The conditions of the saponification reaction are appropriately adjusted depending on the structure of the vinyl ester polymer used and the desired degree of saponification of the vinyl alcohol polymer. Usually, the saponification catalyst concentration / vinyl ester unit concentration (molar ratio) = 0.001 to 1.2, the reaction temperature is 20 to 180 ° C, and the reaction time is 0.1 to 20 hours. .

The reaction between the aromatic amino group-modified PVA and the compound having an epoxy group and an ethylenically unsaturated double bond utilizes the reaction between the aromatic amino group and the epoxy group.
The reaction is carried out without solvent or in a solvent that dissolves or swells the aromatic amino group-modified PVA and the compound having an epoxy group and an ethylenically unsaturated double bond. Examples of such a solvent include water, dimethyl sulfoxide, N, N-dimethylacetamide, alcohols such as methanol, ethanol, n-propyl alcohol and n-butyl alcohol, aromatics such as benzene, toluene and xylene, and tetrahydrofuran. And ethers such as dioxane and diethyl ether, and hydrocarbons such as n-hexane. These solvents are used alone or as a mixture. The reaction conditions were aromatic amino group-modified PVA.
In general, when a solvent is used, the concentration of the aromatic amino group-modified PVA is 1 to 9
0%, epoxy group concentration / amino group concentration = (molar ratio) 1.0 to 5.0, the reaction temperature is 0 to 250 ° C., and the reaction time is 0.01 to 40 hours. In some cases, a radical polymerization inhibitor such as p-methoxyphenol or hydroquinone is added during the reaction. Here, in the reaction between the amino group and the epoxy group, tertiary amines (eg, triethylamine, pyridine, etc.), phosphines (eg, tributylphosphine, triphenylphosphine, etc.), sodium hydroxide, tetraethylammonium hydroxide, sodium methylate, etc. Basic compounds, weakly basic compounds such as sodium acetate and sodium carbonate, Lewis acids such as titanium tetrachloride and boron fluoride, and quaternary ammonium salts such as tributylammonium chloride and tributylammonium bromide are effective as reaction catalysts. .

Examples of the compound having an epoxy group and an ethylenic double bond used in the reaction with the aromatic amino group-modified PVA include epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate, and N-glycidyl. Epoxy group-containing (meth) acrylamides such as xymethyl (meth) acrylamide, N-glycidoxymethyl-N-methyl (meth) acrylamide, epoxy group-containing vinyl ethers such as glycidyl vinyl ether, and epoxy such as allyl glycidyl ether Epoxy group-containing α-olefins such as group-containing allyl ethers, butadiene monooxide, hexadiene monooxide, and octadiene monooxide.

The PVA of the present invention can be isolated in the presence of a radical polymerization inhibitor or the like, but in many cases, it is convenient to use the one obtained by reacting in a solvent as it is. For example, an aromatic amino group-modified PVA in water,
An aqueous solution of a vinyl alcohol-based polymer having an ethylenic double bond obtained by reacting a compound having an epoxy group and an ethylenically unsaturated double bond is mixed with an unsaturated monomer having an ethylenic double bond and light. It is preferable to mix the polymerization initiator and use it as it is as the photosensitive composition.

The radically polymerizable unsaturated monomer having an ethylenic double bond (hereinafter abbreviated as “polymerizable monomer”) used in the photosensitive composition of the present invention is one which is radically polymerizable by a photoinitiator. Can be used. Such examples include 2-hydroxyethyl (meth) acrylate, ethylene glycol (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol (Meth) acrylate, polyethylene glycol di (meth) acrylate, β-oxypropyl (meth) acrylate, β-oxyethyl (meth) acrylate, and N-β-oxyethylacrylamide, N
-Oxymethylacrylamide, N-γ-oxypropylacrylamide, Np-oxyphenylacrylamide, N-β-oxyethyl N′-methylacrylamide, methacrylamide derivatives thereof, and the like. Further, acrylamide, methacrylamide, m-phenylenebisacrylamide, ethylenediaminebisacrylamide, hexamethylenediaminebismethacrylamide and the like can also be mentioned.

As the photopolymerization initiator used in the photosensitive composition of the present invention, for example, benzophenone, benzoin, p,
p'-dimethylbenzoin, benzoin methyl ether, benzoin isopropyl ether, acyloin, nucleus-substituted aromatic acyloin, acyloin alkyl ether,
Diacetyl compound, benzyl compound, ketoaldonyl compound, 1,1′-azocyclohexanecarbonitrile,
Azonitrile compound, 9,10-anthroquinone, chloranthraquinone, 1,4-naphthoquinone, 9,10-
Phenanthroquinone and the like.

The photosensitive composition of the present invention may contain a thermal polymerization inhibitor or a storage stabilizer for the purpose of improving the storage stability. If necessary, a coloring agent, a pigment, a plasticizer, etc. may be added. May be contained.

[0043]

The present invention will be described in detail below with reference to examples and comparative examples. In the following Examples and Comparative Examples, "parts" and "%" mean by weight unless otherwise specified.

(Synthesis Example of Vinyl Ester Polymer Having Epoxy Group) Polymer 1 1000 parts of vinyl acetate monomer, allyl glycidyl ether 13 were placed in a reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet and a thermometer. 0.4 parts and methanol 400
Then, nitrogen gas was bubbled for 15 minutes to degas. Separately, an initiator solution prepared by dissolving 4.3 parts of 2,2′-azoisobutyronitrile in 29 parts of methanol was prepared, and nitrogen was replaced by bubbling with nitrogen gas. The temperature of the reactor was raised, and when the internal temperature reached 60 ° C., a separately adjusted initiator solution was added to initiate polymerization. After polymerization at 60 ° C. for 5 hours, the polymerization was stopped by cooling. The solid content at this time was 45.1%. Subsequently, unreacted vinyl acetate monomer was removed while occasionally adding methanol at 30 ° C. under reduced pressure to obtain a methanol solution of polyvinyl acetate copolymer (concentration: 44.5%). A part of this methanol solution was put into ether to recover the polymer, which was purified by reprecipitation twice with acetone-ether, and then dried at 40 ° C. under reduced pressure. Proton NMR (GSX-27 manufactured by JEOL Ltd.) using CDCl ₃ as a solvent for this purified polymer
0) Measurement and intrinsic viscosity measurement in acetone (JIS) were performed to calculate the viscosity average molecular weight. As a result, vinyl acetate having a viscosity average molecular weight of 82 × 10 ³ containing 1.0 mol% of allyl glycidyl ether unit (epoxy group) was obtained. It was a copolymer. This copolymer is referred to as polymer 1.

Polymer 2 to Polymer 4 Amount of vinyl ester, amount of methanol, type and amount of initiator,
A vinyl ester polymer having an epoxy group shown in Table 1 was prepared in the same manner as in Polymer 1, except that the type, amount, and addition method of the compound having an epoxy group and an ethylenically unsaturated double bond were appropriately changed. Obtained.

[0046]

[Table 1]

(Synthesis Example of PVA Having Aromatic Amino Group) Polymer a A methanol solution of polymer 1 (concentration: 40.2) was placed in a reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet, and a thermometer.
%), Weighed out 100 parts, bubbled nitrogen gas for 15 minutes, and charged a solution of 2.2 parts of 2-aminothiophenol and 0.07 part of sodium acetate in 32 parts of methanol. After reacting at 50 ° C. for 2 hours with stirring, the mixture was cooled to 40 ° C. and saponified by adding 9.4 parts of a 10% strength methanol solution of sodium hydroxide. After leaving at 40 ° C. for 1 hour, pulverized, neutralized by adding acetic acid, washed with a Soxhlet extractor for 48 hours or more, and dried at 60 ° C. for 20 hours or more to obtain an aromatic amino group-modified PVA. . Was measured for IR and proton NMR (d ₆ -DMSO) of the PVA, epoxy groups completely disappeared, confirmed the introduction of 1.0 mol% of aniline groups, vinyl alcohol content of 97.4 mole %Met. A 4% DMSO solution of the PVA was prepared, and its viscosity (using a Brookfield viscometer) measured at 20 ° C. was 64.2 mPa · S. This PV
A is a polymer a.

Polymers b to g In the same manner as in the case of the polymer a, the polymer b was reacted by using the polymers 1 to 4 under the conditions shown in Table 2.
~ Polymer g was obtained.

[0049]

[Table 2]

Polymer A In a reactor equipped with a stirrer, a reflux condenser and a thermometer, 90 parts of dimethyl sulfoxide (DMSO) and polymer a
Was added and dissolved by heating at 90 ° C. for 1 hour. After cooling the solution temperature to 50 ° C., 0.24 parts of p-methoxyphenol was added, followed by 1.6 parts of glycidyl methacrylate (GMA) to react. During the reaction, unreacted GMA was measured by gas chromatography, and the change with time was monitored. As a result, no change was observed after 24 hours. The obtained reaction solution was added to a large amount of a methanol solution (containing 1% p-methoxyphenol), and unreacted GMA was added.
After drying, the polymer was dried under reduced pressure at 20 ° C. to obtain a polymer A. IR and proton NMR of polymer A (d ₆ -D
As a result, the introduction of 0.9 mol% of an ethylenically unsaturated double bond derived from GMA was confirmed. Further, a 4% DMSO solution of the PVA was prepared, and the viscosity (using a Brookfield viscometer) measured at 20 ° C. was 68.1 mPa · S. The PVA is referred to as a polymer A.

Polymer B to Polymer J In the same manner as for Polymer A, using Polymers b to g,
The reaction was carried out under the conditions shown in Table 3 to obtain Polymers B to J.

[0052]

[Table 3]

Comparative Polymers (A) to (E) By a known method, the base PVA shown in Table 4 was reacted with a compound having an epoxy group and an ethylenic double bond to obtain Comparative Polymers (A) to (E). Combined (E) was synthesized.

[0054]

[Table 4]

Example 1 70 parts of polymer A and 0.25 part of hydroquinone were added to water 20
In addition to 0 parts, the mixture was dissolved under heating at 90 ° C., and 100 parts of 2-hydroxyethyl acrylate and 3 parts of benzoin isopropyl ether were added. After defoaming this solution,
Apply to aluminum plate, dry at 80 ° C for 30 minutes, 0.5m
m was obtained. Subsequently, a high-pressure mercury lamp was irradiated from a distance of 75 cm for 10 minutes to form a cured film. The obtained cured film is 90
It was immersed in hot water of 2 ° C. for 2 hours, and the extraction ratio into hot water was determined by the following equation. Extraction rate (%) = ((W−W ₁ ) − (W ₂ + W ₃ )) / W ×
100 W: Weight of cured film before extraction W ₁ : Weight of cured film after extraction W ₂ : Weight of inhibitor W ₃ : Weight of photoinitiator The extraction rate is indicated by the following symbols. ：: Extraction rate is less than 2% △: Extraction rate is 2% or more and less than 5% ×: Extraction rate is 5% or more

Examples 2 to 9 In the same manner as in Example 1 except that Polymers B to J were used, cured films were prepared by the method shown in Table 5, and an extraction test in hot water was performed. Was. Table 5 shows the results.

Comparative Examples 1 to 5 A cured film was prepared by the method shown in Table 5 in the same manner as in Example 1 except that Comparative Polymers (A) to (E) were used. An extraction test was performed. Table 5 shows the results.

[0058]

[Table 5]

Example 11 To an aqueous solution obtained by dissolving 70 parts of the polymer a in 200 parts of water, 1.4 parts of hydroquinone and 33 parts of glycidyl methacrylate were added, reacted at 60 ° C. for 2 hours, cooled to room temperature, and cooled to room temperature.
100 parts of hydroxyethyl acrylate was added, and 3 parts of benzoin isopropyl ether was further added. After detreatment, evaluation was performed in the same manner as in Example 1. Table 6 shows the results.

Examples 12 to 13 In the same manner as in Example 11, tests were performed under the conditions shown in Table 6. Table 6 shows the results.

Comparative Example 6 A test was conducted in the same manner as in Example 11 under the conditions shown in Table 6. Table 6 shows the results.

[0062]

[Table 6]

[0063]

According to the present invention, the photosensitive composition of the present invention can be prepared by using conventional PVA.
Compared to those using
It is very excellent with little dropout of A. The PVA used in the photosensitive composition of the present invention utilizes a reaction between an aromatic amino group and an unsaturated monomer having an epoxy group and an ethylenic double bond. The reaction proceeds efficiently in water. Therefore, it can be used as it is as a photosensitive composition. That is, in the presence of a polymerizable monomer and a photopolymerization initiator, PVA having an aromatic amino group and an unsaturated monomer having an epoxy group and an ethylenic double bond can be reacted in water. It can be used as a photosensitive composition and is very efficient.

Continued on the front page (72) Inventor Naoki Fujiwara 1621 Sakurazu, Kurashiki-shi, Okayama Prefecture Inside Kuraray Co., Ltd. (72) Inventor Toshiaki Sato 1621 Sakurazu, Kurashiki-shi, Okayama Prefecture Kuraray Co., Ltd.

Claims (4)

[Claims] 1. A photosensitive composition comprising a vinyl alcohol polymer having a double bond represented by the following chemical formula 1, an unsaturated monomer having an ethylenic double bond, and a photopolymerization initiator. Embedded image (However, A represents a hydrocarbon group having 20 or less carbon atoms having an ethylenically unsaturated double bond which may be interrupted by an oxygen atom, a nitrogen atom or a sulfur atom.) 2. A photosensitive composition comprising a vinyl alcohol polymer having a double bond represented by the following chemical formula 2, an unsaturated monomer having an ethylenic double bond, and a photopolymerization initiator. Embedded image (However, A represents a hydrocarbon group having 20 or less carbon atoms having an ethylenically unsaturated double bond which may be interrupted by an oxygen atom, a nitrogen atom or a sulfur atom, S represents a sulfur atom, and B represents an oxygen atom Represents a hydrocarbon group having 20 or less carbon atoms which may contain an atom, a nitrogen atom or a sulfur atom.) 3. A vinyl alcohol polymer having an aromatic group substituted by an amino group represented by the following chemical formula 3, a compound having an epoxy group and an ethylenically unsaturated double bond, A photosensitive composition comprising an unsaturated monomer and a photopolymerization initiator. Embedded image (However, C represents a primary amino group or a secondary amino group.) 4. A vinyl alcohol polymer having an aromatic group substituted by an amino group represented by the following chemical formula 4, a compound having an epoxy group and an ethylenically unsaturated double bond, A photosensitive composition comprising an unsaturated monomer and a photopolymerization initiator. Embedded image (Where C represents a primary amino group or a secondary amino group,
S represents a sulfur atom, and B represents a hydrocarbon group having 20 or less carbon atoms which may contain an oxygen atom, a nitrogen atom or a sulfur atom. )