JP2001343746A - Photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive composition having proper adhesiveness with respect to a glass surface and in aging stability and is suitable for use in the formation of the black matrix of a color cathode-ray tube. SOLUTION: The photosensitive composition comprises 70-99.5 mass% water- soluble vinyl copolymer (A) comprising the units of a water-soluble monomer (a), having a group selected from among a carboxylic acid group, an acid anhydride group, a sulfonic acid group, a phosphoric acid group and their salts, and N-vinylpyrrolidone units and 0.5-30 mass% water-soluble azido compound (B).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive composition, and more particularly to a water-soluble photosensitive composition useful for forming a black matrix of a color CRT.

[0002]

2. Description of the Related Art Usually, for example, a black matrix of a color cathode ray tube is obtained by applying a water-soluble photosensitive composition to a glass panel over its entire surface; exposing the exposed portion to water by exposing it to ultraviolet light through a photomask; The resist pattern is formed by removing unexposed portions by spraying; applying a black component dispersion such as graphite; decomposing the resist pattern with an oxidizing agent; removing decomposed products by water spraying. . Conventionally, the photosensitive composition used in the process includes, for example, (1) a photosensitive composition comprising polyvinylpyrrolidone and a water-soluble azide compound (JP-A-48-79970), and (2) acrylamide-diamine. A photosensitive composition comprising an acetone acrylamide copolymer and a water-soluble azide compound (JP-A-50-337)
No. 64) has been proposed.

[0003]

However, all of the photosensitive compositions (1) and (2) do not have sufficient adhesive strength to glass, so that an adhesion improver such as a silane coupling agent is added. In this case, in this case,
There was a problem that the silane coupling agent was deactivated over time, and the adhesive strength was significantly reduced in about 3 to 7 days.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the problems of such a conventional photosensitive composition for forming a black matrix of a color CRT, and as a result, the photosensitive composition was identified as a photosensitive composition. The use of a composition comprising a water-soluble vinyl copolymer having a functional group of and a water-soluble azide compound, has a high adhesive force to a glass surface, and also found that the stability with time is extremely high, and the present invention Reached.

That is, the present invention relates to a water-soluble monomer (a) unit having a group selected from the group consisting of a carboxylic acid group, an acid anhydride group, a sulfonic acid group, a phosphoric acid group and a salt thereof, and an N-vinylpyrrolidone unit. A water-soluble photosensitive composition comprising 70 to 99.5% by mass of a water-soluble vinyl copolymer (A) composed of: and 0.5 to 30% by mass of a water-soluble azide compound (B). .

[0006]

DETAILED DESCRIPTION OF THE INVENTION In the composition of the present invention, (a)
A carbon atom having 2 to 20 or more carbon atoms and containing one or two or more groups selected from the group consisting of carboxylic acid groups, acid anhydride groups, sulfonic acid groups, phosphoric acid groups and salts thereof. And specifically, for example, the following. (i) a monomer having a carboxylic acid group; an unsaturated monocarboxylic acid such as (meth) acrylic acid, crotonic acid, cinnamic acid,
Vinylbenzoic acid, alkenoic acid (C 4-12) (for example, vinyl acetic acid, 2-butenoic acid, 3-methyl-3-butenoic acid, 3-pentenoic acid, 4-pentenoic acid, 4-hexenoic acid, 5- Hexenoic acid, etc.); unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, itaconic acid, etc .; monoalkyl (1-8 carbon atoms) esters of unsaturated dicarboxylic acids (above), such as monobutyl maleate Carboxyl group-containing vinyl monomers such as monobutyl ester of fumaric acid, ethyl carbitol monoester of maleic acid, ethyl carbitol monoester of fumaric acid, monobutyl ester of citraconic acid and glycol monoester of itaconic acid; (ii) acid Monomers having an anhydride group; maleic anhydride, itaconic anhydride, citraconic anhydride and the like;

(Iii) a monomer having a sulfonic acid group; an aliphatic or aromatic vinylsulfonic acid having 2 to 30 carbon atoms, for example, vinylsulfonic acid, (meth) allylsulfonic acid; styrenesulfonic acid, α-methylstyrene Sulfonic acid;
(Meth) acrylalkylsulfonic acids [(meth) acryloxypropylsulfonic acid, 2-hydroxy-3-
(Meth) acryloxypropylsulfonic acid, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid, 3- (meth) acryloxyethanesulfonic acid,
2- (meth) acrylamido-2-methylpropanesulfonic acid, 3- (meth) acrylamido-2-hydroxypropanesulfonic acid]; alkyl (3 to 18 carbon atoms)
(Meth) allyl sulfosuccinates and the like; alkene sulfonic acids (3 to 12 carbon atoms), for example, 2-butene-4
Sulfonic acid, 2-butene-3-sulfonic acid and the like; (iv) a monomer having a phosphoric acid group; a phosphoric acid monoester of hydroxyalkyl (meth) acrylate (2 to 6 carbon atoms) [for example, (meth) acryloyl Oxyethyl phosphate etc.], phosphoric acid diester of hydroxyalkyl (meth) acrylate (2-6 carbon atoms) [eg phenyl-2-acryloyloxyethyl phosphate etc.], alkyl (meth) acrylate (2-6 carbon atoms) phosphone (V) salts of these (i) to (iv); alkali metal (sodium, potassium, etc.) salts and alkaline earths of the above (i) to (iv) Metal-like (calcium, magnesium, etc.) salts, amines [ammonia, alkylamines having 1 to 30 carbon atoms (methylamine,
Ethylamine, n-butylamine, etc.), having 6 to 30 carbon atoms.
Aromatic amines (such as aniline))] salts and the like;
(v) may be used in combination of two or more.

Among these, from the viewpoint of adhesive strength to the glass surface, a water-soluble monomer containing a terminal unsaturated group (vinyl group) is preferred, and (meth) acrylic acid,
Vinylbenzoic acid, ψ-alkenoic acid (C4-12),
Vinylsulfonic acid, styrenesulfonic acid, 3-sulfopropyl (meth) acrylate, 2-acryloylamide-2-methylpropanesulfonic acid, 1-alkenesulfonic acid (3 to 12 carbon atoms), 2- (meth) acryloyloxyethyl Phosphates and their salts.

When vinyl polymerization is carried out using (a) and N-vinylpyrrolidone, if necessary, other vinyl monomers (b) may be copolymerized in addition to (a) and N-vinylpyrrolidone. Good. (B) is not particularly limited as long as it is a copolymerizable monomer having a vinyl group, and is usually a water-soluble vinyl monomer (b1) other than (a) or a water-insoluble vinyl monomer. Body (b2).

The above (b1) includes, for example, nonionic monomers and amide monomers [(meth) acrylamide; N-alkyl (C1-4) (meth) acrylamide, for example, N-methyl (meth) acrylamide; ) Acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, etc .; hydroxyalkyl (C 1-4)
(Meth) acrylamide, for example, N-methylol (meth) acrylamide and the like; alkoxy (1 to 4 carbon atoms) alkyl (1 to 5 carbon atoms) (meth) acrylamide, for example, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (Meth) acrylamide, N-butoxymethyl (meth) acrylamide and the like; N, N-dialkyl (C1-5) (meth) acrylamide, for example, N,
N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide and the like; aminoalkyl (C1-5) (meth) acrylamide such as aminoethyl (meth) acrylamide and aminopropyl (meth) acrylamide; -Alkyl (1-5 carbon atoms) aminoalkyl (1-5 carbon atoms) (meth) acrylamide, for example, N-methylaminoethyl (meth) acrylamide, N
-Methylaminopropyl (meth) acrylamide and the like;
N, N-dialkyl (C1-5) aminoalkyl (C1-5) (meth) acrylamide, e.g.
N-dimethylaminoethyl (meth) acrylamide,
N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide; N- (alkyl) aminoalkyl (1-C
5) aminoalkyl (C1-5) (meth) acrylamide, for example, 3-aminopropylaminopropyl (meth) acrylamide, 3-methylaminopropylaminopropyl (meth) acrylamide, etc .; diacetone (meth) acrylamide; N-vinyl Formamide; N-vinylacetamide, etc.];

Acrylate monomers [hydroxyl-containing (meth) acrylates [hydroxyalkyl (C1-5) (meth) acrylates, such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate; 2-hydroxypropyl (meth) acrylate and the like; trihydric to octahydric or higher polyhydric alcohol mono (meth) acrylate, for example, glycerol mono (meth) acrylate and the like; polyalkylene glycol (polymerization degree of 2 to 300 or more) A mono (meth) acrylate having 2 to 4 carbon atoms of an alkylene group, for example, polyethylene glycol mono (meth) acrylate, etc.],
And lower alkyl (1 to 4 carbon atoms) ethers thereof [2-ethoxyethyl (meth) acrylate, 2-ethoxypropyl (meth) acrylate, carbitol (meth) acrylate, etc.], amino group-containing (meth) acrylates [Aminoalkyl (C1-5) (meta)
Acrylates such as aminoethyl (meth) acrylate and aminopropyl (meth) acrylate; N-alkyl (C1-5) aminoalkyl (C1-5)
(Meth) acrylates such as N-methylaminoethyl (meth) acrylate, N-methylaminopropyl (meth) acrylate and the like; N, N-dialkyl (having 1 to 1 carbon atoms)
5) Aminoalkyl (C1-5) (meth) acrylate, for example, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth)
Acrylate, N, N-diethylaminoethyl (meth)
Acrylate; N- (alkyl) aminoalkyl (C1-5) aminoalkyl (C1-5) (meth) acrylate, for example, 3-aminopropylaminopropyl (meth) acrylate, 3-methylaminopropylaminopropyl ( Meth) acrylate and the like];

A vinyl monomer [N-alkyl (C1-5) vinylamine such as N-methylvinylamine; N, N-dialkyl (C1-5) vinylamine such as N, N-dimethyl] N-vinylpyridine; N-vinylimidazole; N- (alkyl) aminoalkyl (C1-5) vinylamine such as 3-aminopropylvinylamine, 3-methylaminopropylvinylamine, etc .; System monomer [N-allylamine; N-alkyl (C1-5) allylamine such as N-methylallylamine; N, N-dialkylallylamine such as N, N-dimethylallylamine];

Cationic monomers • Quaternary ammonium base-containing monomers [(meth) acryloyloxyalkyl (C2 or C3) trialkyl (C1 to C3) ammonium salts, for example, 2- (meth)
Acryloyloxyethyltrimethylammonium chloride; (meth) acrylamidoalkyl (C1
Or 2) a trialkyl (C1-3) ammonium salt, such as (meth) acrylamidomethyltrimethylammonium chloride; vinylbenzyltrialkylammonium salt, such as vinylbenzyltrimethylammonium chloride]; These (b1) can be used alone or in combination of two or more. Among these, preferred are amide-based water-soluble monomers and acrylate-based water-soluble monomers in the nonionic monomers from the viewpoint of sensitivity and resolution.

The above (b2) includes, for example, nitrile monomers [(meth) acrylonitrile and the like]; aliphatic unsaturated hydrocarbons having 2 to 30 carbon atoms [ethylene,
Propylene, isobutylene, isoprene, butadiene, etc.]; a styrene monomer having 8 to 30 carbon atoms [styrene, α-
Methylstyrene, p-methoxystyrene, vinyltoluene, p-hydroxystyrene, p-acetoxystyrene, etc.]; an alkyl (meth) acrylate having an alkyl group having 1 to 18 or more carbon atoms [methyl (meth) acrylate, ethyl ( Meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
Lauryl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, etc.]; vinyl ester monomers having 3 to 30 carbon atoms [vinyl acetate, vinyl propionate, etc.]; vinyl ethers having 3 to 30 carbon atoms Monomers [vinyl ethyl ether, vinyl isobutyl ether, etc.]; These can be used alone or in combination of two or more. Among these, a styrene monomer and an alkyl (meth) acrylate having an alkyl group having 1 to 18 carbon atoms are preferable from the viewpoint of sensitivity and resolution.

As a method for obtaining the water-soluble vinyl copolymer (A), a water-soluble vinyl copolymer having a group selected from the group consisting of the above-mentioned carboxylic acid groups, acid anhydride groups, sulfonic acid groups, phosphoric acid groups and salts thereof. A method of copolymerizing the monomer (a) and N-vinylpyrrolidone is exemplified. In that case, the copolymerization molar ratio of (a) and N-vinylpyrrolidone is usually from 70 to 0.5.
From 5:30 to 99.5, preferably from 70 to 0.5: 50 to 99:50 to 1 from the viewpoint of compatibility between adhesive strength and sensitivity.
When another vinyl copolymer (b) is copolymerized as necessary, the content of the (b1) unit in (A) is preferably 0 to 50 mol%, more preferably 0 to 30 mol%, It is particularly preferably 0 to 20 mol%, and (b) in (A)
2) The unit content is preferably 0 to 10 mol%, more preferably 0 to 5 mol%, particularly preferably 0 to 3 mol%.

In the method of copolymerizing (a) and N-vinylpyrrolidone, the method of polymerization may be a conventionally known method, for example, a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, a reverse phase suspension. A polymerization method, a thin film polymerization method, a spray polymerization method and the like can be mentioned. Examples of the polymerization control method include an adiabatic polymerization method and a temperature-controlled polymerization method. In addition to the method of initiating polymerization with a polymerization initiator, a method of irradiating radiation, an electron beam, ultraviolet light, or the like to initiate polymerization may be employed. A solution polymerization method using an initiator is preferred, and an aqueous solution polymerization method is particularly preferred because there is no need to use an organic solvent or the like and the production cost is advantageous. Suspension polymerization method as a polymerization method,
When the reverse phase suspension polymerization method or the emulsion polymerization method is used, the polymerization is carried out, if necessary, in the presence of a conventionally known dispersant or surfactant. In the case of the reversed-phase suspension polymerization method, polymerization is performed using a conventionally known hydrocarbon solvent such as xylene, normal hexane, and normal heptane.

As the polymerization initiator used in the polymerization using the polymerization initiator, conventionally known initiators can be used. For example, an azo initiator, a peroxide initiator, a redox initiator, And organic halogen compound initiators. Specifically, as the azo initiator, azobisisobutyronitrile, azobiscyanovaleric acid and salts thereof,
2,2'-azobis (2-amidinopropane) hydrochloride, 2,2'-azobis (2-methyl-N-
(2-hydroxyethyl) propionamide and the like; peroxide-based initiators include inorganic peroxides [hydrogen peroxide, ammonium persulfate, potassium persulfate, sodium persulfate, etc.], and organic peroxides [benzoyl peroxide, -T-butyl peroxide, cumene hydroperoxide, succinic peroxide, di (2-ethoxyethyl) peroxydicarbonate, etc .; redox initiators include alkali metal sulfites or bisulfites, ammonium sulfite , Ammonium bisulfite, ferric chloride,
Examples include a combination of a reducing agent such as ferric sulfate and ascorbic acid and an oxidizing agent such as an alkali metal persulfate, ammonium persulfate, hydrogen peroxide, and an organic peroxide.

The halogen of the organic halogen compound initiator includes fluorine, chlorine, bromine and iodine. It is not particularly limited as long as it is an organic halogen compound, but preferably has a halogen number of 1 selected from the group consisting of alkyl halides, alkyl phenyl ketones, alkyl carboxylic acids and alkyl esters of halogenated alkyl carboxylic acids. -10 or more, and an organic halogen compound having 1 to 15 or more carbon atoms, more preferably tetrachloromethane, trichlorobromomethane, trichloroiodomethane, dichloromethylphenylketone, 1-bromo-1-methylethyl Carboxylic acid, alkyl group 1-bromo-1-methylethylcarboxylic acid alkyl ester having 1 to 8 carbon atoms (for example, methyl 1-bromo-1-methylethylcarboxylate, ethyl 1-bromo-1-methylethylcarboxylate, -Bromo-1-methylethylcal Phosphate octyl, 1-bromo-1-methyl carboxylate lauryl), particularly preferably dichloromethyl phenyl ketone, having from 1 to 8 carbon atoms an alkyl radical 1
Bromo-1-methylethylcarboxylic acid alkyl ester. These initiators may be used alone or in combination of two or more.

Among these, the amount of the azo initiator, the peroxide initiator and the redox initiator used is usually 0.0005 to 1% by mass, preferably, 0.0005 to 1% by mass, based on the mass of all monomers. It is 0.01 to 0.5% by mass. The amount of the organic halogen compound initiator used is usually based on the mass of all monomers,
Usually 0.0005 to 10% by mass, preferably 0.001
To 5% by weight, particularly preferably 0.005 to 3% by weight. A chain transfer agent may be used in combination. Examples of such a compound include thiols (n-lauryl mercaptan, mercaptoethanol, mercaptopropanol, triethylene glycol dimercaptan, etc.), thiols (thioglycolic acid, thioapple). Acid, etc.), secondary alcohols (isopropanol, etc.), amines (dibutylamine, etc.), hypophosphites (sodium hypophosphite, etc.), and the like. It is preferably 0.001 to 1% by mass based on the amount of the body.

The polymerization conditions are not particularly limited. For example, the polymerization initiation temperature can be variously changed depending on the type of the catalyst used, but is usually 0 to 160 ° C., preferably 40 to 15 ° C.
0 ° C. The polymerization time is 1 to 60 hours, preferably 3 to
20 hours. The polymerization is preferably aqueous solution polymerization, but may be performed in the coexistence of water and a water-soluble organic solvent if necessary.
As the solvent, the amount of the solvent with respect to water is usually 40% or less, preferably 30% or less on a mass basis. The polymerization concentration may be arbitrarily selected, but is 5 to 100% by weight. The weight average molecular weight of (A) thus obtained (measurement method: GPC
Method) is usually 50,000 or more, preferably 5
000 to 2,000,000, more preferably 2
00,000 to 1,500,000.

The water-soluble azide compound (B) used in the composition of the present invention is not particularly limited as long as it is a compound capable of generating nitrene upon irradiation with ultraviolet rays and reacting with the above-mentioned (A). A water-soluble aromatic bis azide compound having two azide groups is preferred. Specific examples include a sulfonic acid group-containing water-soluble azide compound [4,4′-diazidostilbene-2,2′-disulfonic acid, 4,4 ′
-Diazidobenzalacetophenone-2-sulfonic acid,
1,5-penta-3-one-1,4-diethenyl-bis (azidobenzenesulfonic acid), 2,6-bis (4-azidobenzal-2-sulfonic acid) -cyclopentanone, etc.], containing a carboxylic acid group And water-soluble azide compounds [4,4'-diazidostilbene-α-carboxylic acid and the like], and the above-mentioned salts (amine salts, alkali metal salts, alkaline earth metal salts and the like). Among these, preferred from the viewpoint of solubility are water-soluble azide compounds containing a sulfonic acid (salt) group, and particularly preferred is 4,
4'-diazidostilbene-2,2'-sodium disulfonate.

The water-soluble photosensitive composition of the present invention comprises (A) and (B). (A) and (B) may be used alone or as a mixture of two or more.
The compounding ratio of (A) is usually 70 to 99.5% by mass, preferably 80 to 99% by mass based on the mass of the photosensitive composition.
It is. If (A) is less than 70% by mass, the film-forming properties of the coating film will be reduced, and if it exceeds 99.5% by mass, the sensitivity will be poor.
The blending ratio of (B) is usually 0.5 to 30% by mass, preferably 1 to 20% by mass based on the mass of the photosensitive composition. If (B) is less than 0.5% by mass, the sensitivity becomes poor and 3
If it exceeds 0% by mass, the film-forming properties of the coating film will be reduced. The photosensitive composition of the present invention can be obtained by mixing (A) and (B). The mixing order is not particularly limited,
(A) may be mixed with (B), or (B) may be mixed with (A), and the mixing order of the optional components other than (A) and (B) described below is not limited.

The composition of the present invention may contain a water-soluble solvent as a diluent. By containing a diluent, it becomes possible to adjust the coating properties, storage stability, development characteristics, adhesion and the like of the composition. The diluent is not particularly limited as long as it is compatible with each component. Examples thereof include water; alcohol solvents such as methanol, ethyl alcohol, and isopropyl alcohol; methyl cellosolve, ethyl cellosolve, butyl cellosolve, diethylene glycol monomethyl ether, and diethylene glycol. Glycol ether solvents such as monoethyl ether; N-methylpyrrolidone, 2-pyrrolidone, N, N-dimethylformamide,
Amide solvents such as N, N-dimethylacetamide and the like. Among these, preferred are water and glycol ether solvents from the viewpoint of sensitivity and resolution,
Particularly preferred is water. The content of the diluent can be arbitrarily set depending on the application conditions of the photosensitive composition and the like.
0.8 to 4,000 times, preferably 1.
It is 1 to 3000 times.

The composition of the present invention may contain a surfactant, if necessary, to improve the wettability to the substrate. The surfactant is not particularly limited as long as it is compatible with each component. Examples of the surfactant include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants, for example, those described in US Pat. No. 4,331,447. These may be used alone or in combination of two or more.

The anionic surfactants include those having 8 carbon atoms.
To 24 hydrocarbon ether carboxylic acids or salts thereof,
[Polyoxyethylene (degree of polymerization = 1 to 100) sodium lauryl ether acetate, polyoxyethylene (degree of polymerization = 1 to 100) disodium lauryl sulfosuccinate, etc.], a hydrocarbon sulfate salt having 8 to 24 carbon atoms [lauryl Sodium sulfate, polyoxyethylene (degree of polymerization =
1-100) sodium lauryl sulfate, polyoxyethylene (degree of polymerization = 1-100) triethanolamine lauryl sulfate, polyoxyethylene (degree of polymerization = 1-100)
Coconut oil fatty acid sodium monoethanolamide sulfate,], a hydrocarbon sulfonate having 8 to 24 carbon atoms [such as sodium dodecylbenzene sulfonate], and 8 carbon atoms
To 24 hydrocarbon-based phosphoric acid ester salts [sodium lauryl phosphate, polyoxyethylene (polymerization degree = 1 to 10)
0) Sodium lauryl ether phosphate, etc.], fatty acid salts [sodium laurate, triethanolamine laurate, etc.], acylated amino acid salts [sodium coconut fatty acid methyltaurine, sodium coconut fatty acid sarcosine, coconut fatty acid sarcosine triethanolamine] , N
-Coconut fatty acid acyl-L-glutamate triethanolamine, N-coconut fatty acid acyl-L-glutamate sodium, sodium lauroylmethyl-β-alanine, etc., and others [polyoxyethylene sulfosuccinate (degree of polymerization = 1 to 100)] Lauroylethanolamide 2
Sodium, etc.].

Specific examples of the nonionic surfactant include, for example, an aliphatic alcohol (8 to 24 carbon atoms) alkylene oxide (2 to 8 carbon atoms) adduct (degree of polymerization = 1 to 1).
100) [lauryl alcohol ethylene oxide addition (polymerization degree = 20), oleyl alcohol ethylene oxide addition (polymerization degree = 10), Macko alcohol ethylene oxide addition (polymerization degree = 35), etc.], polyoxyalkylene (carbon number) 2-8, degree of polymerization = 1-100)
Higher fatty acid (C8-24) ester [polyethylene glycol monostearate (degree of polymerization = 20), polyethylene glycol distearate (degree of polymerization = 30)
Etc.], polyhydric (divalent to 10-valent or higher) alcohol fatty acid (8 to 24 carbon atoms) esters [glyceryl monostearate, ethylene glycol monostearate, sorbitan lauric acid (mono / di) ester, sorbitan palmitic acid (Mono / di) ester, sorbitan stearic acid (mono / di) ester, sorbitan oleic acid (mono / di) ester, sorbitan coconut oil (mono / di)
Esters, etc.], polyoxyalkylenes (C 2-8,
Polyhydric (divalent to divalent or higher) alcohol higher fatty acid (C8 to C24) ester [polyoxyethylene (degree of polymerization = 10) sorbitan lauric acid (mono / di) ester; Polyoxyethylene (degree of polymerization = 20) sorbitan palmitic acid (mono / di) ester, polyoxyethylene (degree of polymerization = 15) sorbitan stearic acid (mono / di) ester, polyoxyethylene (degree of polymerization = 10) sorbitan oleic acid (Mono / Di)
Ester, polyoxyethylene (degree of polymerization = 25) lauric acid (mono / di) ester, polyoxyethylene (degree of polymerization = 50) stearic acid (mono / di) ester, polyoxyethylene (degree of polymerization = 18) oleic acid ( Mono / di)
Esters, sorbitan, polyoxyethylene (degree of polymerization = 50) methyl oleic acid methylglucoside, etc.], fatty acid alkanolamides [1: 1 type coconut oil fatty acid diethanolamide, 1: 1 type lauric acid diethanolamide, etc.],
Polyoxyalkylene (C2-8, degree of polymerization = 1-1)
00) alkyl (C 1-22) phenyl ether (polyoxyethylene (degree of polymerization = 20) nonyl phenyl ether, etc.), polyoxyalkylene (C 2-8,
Degree of polymerization = 1-100) alkyl (8-24 carbon atoms) amino ether and alkyl (8-24 carbon atoms) dialkyl (1-6 carbon atoms) amine oxide [lauryl dimethylamine oxide etc.], polydimethylsiloxane polyoxyethylene Adduct, polyoxyethylene / polyoxypropylene block polymer (weight average molecular weight = 150 to 1)
0000).

Examples of the cationic surfactant include quaternary ammonium salt type [stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, distearyldimethylammonium chloride, aminopropylethyldimethylammonium ethyl sulfate lanolin fatty acid], amine salt type [ Stearic acid diethylaminoethylamide lactate, dilaurylamine hydrochloride, oleylamine lactate, etc.]. Examples of the amphoteric surfactant include betaine-type amphoteric surfactants [coconut fatty acid amidopropyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-
Hydroxyethylimidazolinium betaine, laurylhydroxysulfobetaine, sodium lauroylamidoethylhydroxyethylcarboxymethylbetaine hydroxypropylphosphate, etc., and an amino acid type amphoteric surfactant [sodium β-laurylaminopropionate]. Among these, from the viewpoint of stability, nonionic surfactants (for example, sorbitan ester ethylene oxide adduct, alkylphenol ethylene oxide adduct, etc.) are preferred. When a surfactant is contained, the amount is usually 5% by mass or less, preferably 0.05 to 3% by mass, based on the mass of (A) from the viewpoint of the effect of addition and developability.

The composition of the present invention may contain other high molecular weight compounds having a weight average molecular weight of 1,000 to 800,000 or more, if necessary. By including another polymer compound, it becomes possible to adjust coatability, sensitivity, development characteristics, adhesiveness, and the like.
The other polymer compound is not particularly limited, but is preferably a water-soluble one having a weight average molecular weight of 1,000 to 800,000. For example, a vinylpyrrolidone (co) polymer other than (A), (meth) acrylamide (co) ) Polymers,
Alkyl (meth) acrylamide (co) polymer, dialkyl (meth) acrylamide (co) polymer, (meth) acrylamide-diacetone (meth) acrylamide copolymer, acryloylmorpholine (co) polymer, polyvinylformamide (co) poly Copolymer, polyvinylacetamide (co) polymer, sodium styrenesulfonate (co) polymer other than (A), 2-acryloyluramide-2-methylpropanesulfonic acid (co) polymer other than (A), polyvinyl alcohol (Co) polymers, (meth) acrylic acid (co) polymers other than (A), JP-A-55-23163
Patent Document No. styrylpyridinium salt compound, casein, gelatin, methylcellulose, ethylcellulose,
Carboxymethyl cellulose, polyethylene glycol and the like can be mentioned.

Among these, preferred are vinylpyrrolidone (co) polymers other than (A), (meth) acrylamide-diacetone (meth) acrylamide copolymer, and acryloylmorpholine (co) polymer from the viewpoints of sensitivity and resolution. , A polyvinyl formamide (co) polymer, a polyvinylacetamide (co) polymer and a polyvinyl alcohol (co) polymer. When containing these other high molecular compounds, the amount thereof can be arbitrarily set,
The mass of (A) is preferably 50 from the viewpoint of sensitivity.
% By mass or less, more preferably 1% by mass or less
30% by mass.

The composition of the present invention may contain a low molecular weight compound having a molecular weight of 990 or less, containing a hydroxyl group and / or an iodine atom in the molecule, if necessary. By including the low molecular compound, development characteristics, adhesion and the like can be adjusted, and sensitivity can be further improved. Examples of the low molecular compound having a hydroxyl group in the molecule include monohydric alcohols (such as n-butanol) and dihydric alcohols (ethylene glycol, diethylene glycol, propylene glycol, 1,3-butylene glycol, 1,5-pentane) Diol, etc.), 3-8
Or higher polyhydric alcohols (glycerin, erythritol, pentaerythritol, sorbitol, etc.)
And the like.

Examples of the low molecular weight compound containing an iodine atom in the molecule include iodoacetic acid, 3,5-diamino-2,4,6-triiodobenzoic acid (sodium salt), and 3-amino-2,4 , 6-Triiodobenzoic acid (sodium salt), 5-amino-2,4,6-triiodoisophthalic acid (sodium salt), 5-amino-2,
4,6-triiodoisophthalamic acid (sodium salt), 3,5-diiodosalicylic acid (sodium salt),
2,3,5-triiodobenzoic acid (sodium salt), tetraalkylammonium iodide, sodium iodide,
And potassium iodide. Of these, low molecular weight compounds having a hydroxyl group and having a molecular weight of 990 or less are preferable, and ethylene glycol, diethylene glycol and sorbitol are more preferable. When a low molecular weight compound containing a hydroxyl group and / or an iodine atom is contained in the molecule, the amount thereof is preferably from 1 to 100% by mass based on the mass of (A) from the viewpoint of the addition effect and the developability. More preferably, it is 1 to 50% by mass.

As a specific example using the composition of the present invention, formation of a black matrix of a color CRT will be described below. As a method for forming a black matrix of a color cathode ray tube, for example, the photosensitive composition of the present invention containing a water-soluble vinyl polymer (A) and a water-soluble azide compound (B) is usually 0.1 to 2 μm Coating with a hot plate, infrared heater, far infrared heater, etc. to form a coating film; UV light such as ultra-high pressure mercury lamp, high pressure mercury lamp, metal halide lamp, etc. through a photomask having the desired pattern Exposed at an illuminance of 0.5 to 50 mJ / cm2; developed with water to wash and remove unexposed portions to form a resist pattern; coated with a black component dispersion such as graphite; hot plate, infrared heater, Dry with a far-infrared heater etc .; oxidize and decompose the resist pattern with an oxidizing agent such as hydrogen peroxide; develop with water; A method of performing a series of steps can be exemplified.

Further, it is preferable that the illuminance of ultraviolet light exposure in the above step is in the range of 0.02 to 1 mW / cm 2. When the exposure illuminance is less than 0.02 mW / cm 2, the pattern obtained by irradiation with ultraviolet light may be extremely small or the pattern may not be formed.
If the exposure illuminance exceeds 1 mW / cm 2, the exposure time for obtaining a pattern of an appropriate size becomes extremely short, and as a result, the pattern may swell and wrinkle. When the composition of the present invention is irradiated with ultraviolet light, the composition (B)
Is changed to active nitrene, and this nitrene crosslinks (A) to form a resist pattern.

The composition of the present invention contains a carboxylic acid group, an acid anhydride group, a sulfonic acid group and a carboxylic acid group in a water-soluble vinyl copolymer (A).
Since it has a phosphate group and a salt thereof, it has a high adhesive strength to the glass surface due to the interaction between these hydrophilic groups and the glass surface. Therefore, it shows a high adhesive strength to the glass surface without having to add an adhesion improver such as a silane coupling agent. Further, when the conventional silane coupling agent is added, there is a problem that the silane coupling agent is deactivated with time, and the adhesive strength is significantly reduced in about 3 to 7 days. Since the photosensitive composition of the present invention does not require the addition of a silane coupling agent, it has extremely high stability over time compared to a conventional photosensitive composition containing a silane coupling agent.

The water-soluble photosensitive composition of the present invention is not limited to a resist for forming a black matrix of a color CRT, a resist for forming a fine pattern, a resist for patterning a phosphor of a color CRT, a resist for patterning a color CRT pigment filter, a shadow mask. Etching resist for forming, resist for forming color filter black matrix, resist for dispersing color filter pigment, patterning resist for plasma display panel, patterning resist for field emission display, patterning resist for fluorescent display tube, solder resist for printed wiring board, printed wiring board Etching resist, dry film resist for printed wiring board, interlayer insulating material, liquid crystal transparent conductive film (IT
O) Highly useful for resists for patterning, photosensitive printing plates, printing inks, photocurable coating materials, etc., and extremely useful for resists for forming black matrices and fine patterns for color CRTs. high.

[0036]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. In the following, “part” indicates “part by mass” and “%” indicates “% by mass”.

Synthesis Example 1 97.5 parts of N-vinylpyrrolidone and 2.5 parts of sodium acrylate (mole ratio = 97: 3) were mixed with 400 parts of ion-exchanged water.
And heated to 55 ° C. with stirring. Here, “VA-044” [azo polymerization initiator;
0.1 parts of Wako Pure Chemical Industries, Ltd.], and the mixture was stirred at 55 ° C. for 5 hours to carry out polymerization. Then, 500 parts of ion-exchanged water was further added to prepare a 10% solids aqueous solution of the copolymer. The weight average molecular weight of the obtained copolymer was about 800,000.

Example 1 A photosensitive composition (1) of the present invention was obtained according to the following formulation. The composition (1) is applied to a thickness of 1 μm on a glass substrate by spin coating,
The coating was dried at 0 ° C. for 1 minute to form a coating film. Using a proximity exposure machine equipped with a 2 kW ultra-high pressure mercury lamp and a proximity gap of 50 μm, a sharpness test chart No. 1 was used as a photomask. 1 [manufactured by Toppan Printing Co., Ltd.], exposure was performed at an exposure amount of 20 mJ / cm <2>, and the resist pattern was formed by developing with water at normal temperature, and the resolution was measured. Resolution is 3μm
Met. There was no peeling of the pattern at all, and it had a high adhesive strength to the glass surface. In addition, the composition (1)
After storing at 5 ° C. for 3 months, the same evaluation as above was performed, but no decrease in resolution and no peeling of the pattern were observed. [Prescription of photosensitive composition (1)] 30 parts of aqueous solution of copolymer (solid content: 10%) obtained in Synthesis Example 1 sodium 4,4'-diazidostilbene-2,2'-disulfonate 0.3 Part Nonion LT-221 [Tween type nonionic activator, 100%, manufactured by NOF Corporation] 0.03 part Ion exchange water 100 parts

Synthesis Example 2 94.6 parts of N-vinylpyrrolidone and 5.4 parts of sodium p-styrenesulfonate (molar ratio: 97: 3) were dissolved in 400 parts of ion-exchanged water and heated to 55 ° C. with stirring. . To this, 0.1 part of “VA-044” as a polymerization initiator was added, and the mixture was stirred at 55 ° C. for 5 hours to carry out polymerization. Then, 500 parts of ion-exchanged water was further added to obtain a copolymer having a solid content of 10%. An aqueous solution was prepared. The weight average molecular weight of the obtained copolymer was about 700,000.

Example 2 A photosensitive composition (2) of the present invention was obtained according to the following formulation. Using the composition (2), a resist pattern was formed by coating, drying, exposing, and developing on a glass substrate in the same manner as in Example 1, and the resolution was measured. There was no peeling of the pattern at all, and it had a high adhesive strength to the glass surface. The composition (2) was added to 25
After storage at 3 ° C. for 3 months, the same evaluation as in Example 1 was performed, but no reduction in resolution and no peeling of the pattern were observed. [Prescription of photosensitive composition (2)] 30 parts of aqueous solution of copolymer (solid content: 10%) obtained in Synthesis Example 2 Sodium 4,4'-diazidostilbene-2,2'-disulfonate 0.3 Part Nonion LT-221 [Tween type nonionic activator, 100%, manufactured by NOF Corporation] 0.03 part Ion exchange water 100 parts

Synthesis Example 3 94.9 parts of N-vinylpyrrolidone and 5.1 parts of 2-methacryloyloxyphosphate (molar ratio = 97: 3) were dissolved in 400 parts of ion-exchanged water, and a 20% aqueous sodium hydroxide solution was used. PH = 7. 55 with stirring
C. and heated to "VA-044" 0.1 as a polymerization initiator.
After polymerization was carried out by stirring at 55 ° C. for 5 hours, 500 parts of ion-exchanged water was further added to prepare an aqueous copolymer solution having a solid content of 10%. The weight average molecular weight of the obtained copolymer was about 700,000.

Example 3 A photosensitive composition (3) of the present invention was obtained according to the following formulation. Using the composition (3), a resist pattern was formed by coating, drying, exposing, and developing on a glass substrate in the same manner as in Example 1, and the resolution was measured. There was no peeling of the pattern at all, and it had a high adhesive strength to the glass surface. Further, the composition (3) was added to 25
After storage at 3 ° C. for 3 months, the same evaluation as in Example 1 was performed, but no reduction in resolution and no peeling of the pattern were observed. [Prescription of Photosensitive Composition (3)] 30 parts of aqueous solution of copolymer (solid content: 10%) obtained in Synthesis Example 3 Sodium 4,4'-diazidostilbene-2,2'-disulfonate 0.3 Part Nonion LT-221 [Tween type nonionic activator, 100%, manufactured by NOF Corporation] 0.03 part Ion exchange water 100 parts

Comparative Example 1 A comparative photosensitive composition (ratio 1) was obtained according to the following formulation. Using the composition (ratio 1), coating on a glass substrate, drying, exposure, and development were performed in the same manner as in Example 1 to form a resist pattern and measure the resolution. And the resist pattern was not obtained. [Prescription of comparative photosensitive composition (ratio 1)] PVP K-90 [Aqueous solution of polyvinylpyrrolidone (solid content: 10%), manufactured by ISP] 30 parts 4,4'-diazidostilbene-2,2 ' -Sodium disulfonate 0.3 parts Nonion LT-221 [Tween type nonionic surfactant, 100%, manufactured by NOF Corporation] 0.03 parts Ion-exchanged water 100 parts

Comparative Example 2 A comparative photosensitive composition (ratio 2) was obtained according to the following formulation. The composition (ratio 2) was applied to a glass substrate, dried, exposed and developed in the same manner as in Example 1 to measure the formation of a resist pattern and the resolution. However, after storing the photosensitive composition at 25 ° C. for 7 days, the same evaluation as in Example 1 was attempted, but the adhesion to the glass surface was weak, and no resist pattern was obtained. [Preparation of comparative photosensitive composition (ratio 2)] PVP K-90 [Aqueous solution of polyvinylpyrrolidone (solid content: 10%), manufactured by ISP] 30 parts 4,4'-diazidostilbene-2,2 ' -Sodium disulfonate 0.3 parts Nonion LT-221 [Tween type nonionic surfactant, 100%, manufactured by NOF Corporation] 0.03 parts N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane 0. 01 parts Ion exchange water 100 parts

[0045]

The photosensitive composition of the present invention has the following effects. 1) Since the water-soluble vinyl copolymer has a group selected from the group consisting of a carboxylic acid group, an acid anhydride group, a sulfonic acid group, a phosphoric acid group and a salt thereof, the photocured product has an adhesive property to a glass surface. Are better. Therefore, there is no need to add an adhesion improver such as a silane coupling agent, and the resin exhibits high adhesive strength to the glass surface. 2) Since no silane coupling agent is added, the stability with time is extremely high.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/008 G03F 7/008 H01J 9/227 H01J 9/227 DF term (Reference) 2H025 AA14 AB17 AC01 AD01 BA07 BC84 BC85 CB06 CB13 CB16 CB42 CB43 DA18 FA17 4J002 BC121 BG011 BG021 BG071 BG121 BH021 BJ001 BQ001 EQ036 EV246 EV256 FD310 GP03 GQ00 5C028 JJ01

Claims (5)

[Claims] 1. A water solution comprising a water-soluble monomer (a) unit having a group selected from the group consisting of a carboxylic acid group, an acid anhydride group, a sulfonic acid group, a phosphoric acid group and a salt thereof, and an N-vinylpyrrolidone unit. Vinyl copolymer (A) 70-9
9.5 mass%, and water-soluble azide compound (B) 0.5 to
A water-soluble photosensitive composition comprising 30% by mass. 2. The composition according to claim 1, wherein the molar ratio of the unit (a) to the N-vinylpyrrolidone unit is from 70 to 0.5: 30 to 9:
2. The composition according to claim 1, wherein the composition is 9.5. 3. (a) is (meth) acrylic acid, vinylbenzoic acid, ψ-alkenoic acid (C4-12), vinylsulfonic acid, styrenesulfonic acid, 3-sulfopropyl (meth) acrylate, 2- Acryloylamide-2-
Selected from the group consisting of methylpropanesulfonic acid, 1-alkenesulfonic acid (3 to 12 carbon atoms), 2- (meth) acryloyloxyethyl phosphate and salts thereof (alkali metal salts, alkaline earth metal salts, amine salts) 3. The method according to claim 1, wherein at least one kind is selected.
A composition as described. 4. The composition according to claim 1, wherein (B) is at least one member selected from the group consisting of an azide compound containing a sulfonic acid (salt) group and an azide compound containing a carboxylic acid (salt) group. object. 5. The composition according to claim 1, which is used for forming a black matrix of a color CRT.