JPH11212264A - Photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the photosensitive composition extremely high in sensitivity and high in resolution and especially useful for forming the black matrix of a color Braun tube and for forming a fluorescent face. SOLUTION: This photosensitive composition comprises a vinyl polymer or copolymer (A1) having repeating units derived from a monomer (a) represented by the formula CH2 =CH-X-NHCOCH3 [X is 1,4-phenylene, sulfonyl, or 1-5C alkylene optionally substituted by one ether, carbonyl, carbonyloxy, or amido group] in an amount of 20-100 mass %; and a water-soluble vinyl polymer or copolymer (A2) having repeating units derived from one or more kinds of water-soluble vinyl monomer (b1) selected from a water-soluble monomer having an aromatic ring and a water-soluble monomer having a hetero ring and an acrylic water-soluble monomer having a molecular weight of >=130, in an amount of (A2) of 0-80 mass %, and this photosensitive composition is composed of the polymer (A)=(A1)+(A2) in an amount of 70-99 mass % and a photosensitive compound (B) selected from an azido compound and a diazo compound in an amount of 1-30 mass %.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition, and more particularly to a photosensitive composition having extremely high sensitivity and high resolution, and a color cathode ray tube using the same.

[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. . As shown here, since the process has a very large number of steps and a long process time, the process is required to be shortened. In particular, the process is required to be shortened at the time of exposure to ultraviolet light, which is rate-limiting. Conventionally, as a photosensitive composition used in the process for solving the above-mentioned problem, for example, a photosensitive composition comprising (1) a polyvinylpyrrolidone and a water-soluble azide compound (Japanese Patent Laid-Open No.
8-79970), (2) a photosensitive composition comprising an acrylamide-diacetone acrylamide copolymer and a water-soluble azide compound (JP-A-50-33764), and (3) acrylamide-diacetoneacrylamide-acryloyl. A photosensitive composition comprising a morpholine copolymer and a water-soluble azide compound (JP-A-6-51509) has been proposed.

On the other hand, for example, the fluorescent screen of a color cathode ray tube has three types of phosphor-containing photosensitive materials in which one of three primary color phosphors of red, green or blue is suspended on a glass panel on which a black matrix is formed. After applying the composition to the entire surface of the glass panel; exposing the exposed portion to water by exposing to ultraviolet light through a photomask; removing the unexposed portion by water spray; After each of the three primary blue phosphors is heated, it is heated in air to oxidatively decompose and remove organic substances.

However, the conventional process uses a photosensitive composition containing a harmful chromium compound, so that it causes environmental pollution and requires only an operation and equipment for removing chromium in a waste liquid. In addition, there is a problem that the stability of the photosensitive component over time is poor, and the reaction gradually proceeds even in a state where it is not directly irradiated with ultraviolet rays such as during storage (this is called a dark reaction). In addition, chromium remains in the phosphor pattern even after the organic substances are decomposed and removed, and there is a problem that the phosphor screen is colored and the emission of the phosphor is inhibited, thereby lowering the brightness of the color cathode-ray tube. There is a need for a photosensitive material containing no compound.

Heretofore, as the phosphor-containing photosensitive composition used in the process for solving the above-mentioned problems, for example, (4) water-soluble polymers such as polyacrylamide and polyvinylpyrrolidone and water-soluble azide Phosphor-containing photosensitive composition comprising a compound (JP-A-49-435)
No. 69), (5) a phosphor-containing photosensitive composition comprising a water-soluble polymer such as polyvinyl alcohol and polyvinylpyrrolidone and a water-soluble diazo compound (JP-A-49-10).
No. 0955), and (6) a phosphor-containing photosensitive composition comprising an aqueous solution of a water-soluble styrylpyridinium-based compound (Japanese Patent Application Laid-Open No. Sho 60-71682).

[0006]

However, all of the photosensitive compositions (1) to (6) have insufficient exposure sensitivity at low illuminance, and thus are not suitable for producing large cathode ray tubes and high definition tubes. When the exposure illuminance is low, not only does the exposure time become extremely long and the productivity decreases, but also it becomes necessary to increase the number of ultraviolet exposure apparatuses, and there are problems such as equipment installation space, equipment maintenance, and equipment costs. Was. Further, in the case of the photosensitive compositions for forming a fluorescent screen according to the above (4) to (6), since the temporal stability of the photosensitive components is not sufficient, deterioration due to a dark reaction is unavoidable. At the time of use, there is a problem that causes a trouble or a decrease in yield.

[0007]

The present inventors have conducted intensive studies to solve the problems of such a conventional photosensitive composition for forming a black matrix and a phosphor screen of a color cathode ray tube, and as a result, have found that Using a composition comprising a vinyl (co) polymer having a repeating unit derived from a monomer having a specific functional group, and an azide compound or a diazo compound as the reactive composition, has extremely high sensitivity and exposure time Was found to be able to be significantly reduced, and the stability with time was high, and the present invention was reached.

That is, the present invention provides a compound represented by the following general formula (1): H ₂ C ＣCH—X—NHCOCH ₃ (1) wherein X is a direct bond, 1,4-phenylene group, sulfonyl group or 5 represents an alkylene group (provided that the alkylene group may have one ether group, carbonyl group, carbonyloxy group, oxycarbonyl group or amide group). A) a monomer represented by the formula:
Vinyl (co) polymer having a repeating unit derived from
1) 20 to 100% by mass of at least one water-soluble vinyl selected from the group consisting of a water-soluble monomer containing an aromatic ring, a water-soluble monomer containing a heterocycle, and an acrylic water-soluble monomer having a molecular weight of 130 or more. Water-soluble vinyl (co) polymer (A2) having a repeating unit derived from a monomer (b1) 0 to 80
A photosensitive composition comprising 70 to 99% by mass of a polymer (A) consisting of 70% by mass and 1 to 30% by mass of a photosensitive compound (B) selected from an azide compound and a diazo compound; Formula (1) H ₂ C ＝ CH—X—NHCOCH ₃ (1) wherein X is a direct bond, a 1,4-phenylene group, a sulfonyl group, or an alkylene group having 1 to 5 carbon atoms (provided that the alkylene group is Represents one ether group, carbonyl group, carbonyloxy group, oxycarbonyl group or amide group.) A) a monomer represented by the formula:
Vinyl (co) polymer having a repeating unit derived from
1) 20 to 100% by mass of at least one water-soluble vinyl selected from the group consisting of a water-soluble monomer containing an aromatic ring, a water-soluble monomer containing a heterocycle, and an acrylic water-soluble monomer having a molecular weight of 130 or more. Water-soluble vinyl (co) polymer (A2) having a repeating unit derived from a monomer (b1) 0 to 80
0.5 to 50% by mass of a polymer (A) composed of 0.5% by mass, 0.002 to 20% by mass of a photosensitive compound (B) selected from an azide compound and a diazo compound, a phosphor, a metal oxide, and a metal water. A photosensitive composition comprising 99.5 to 40% by mass of at least one fine powder (C) selected from the group consisting of oxides, metal salts and pigments; and A color cathode ray tube used for forming a black matrix and / or forming a fluorescent screen.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS A method for forming a vinyl (co) polymer (A1) used in the composition of the present invention will be exemplified below. (1) When X in the general formula (1) is a direct bond: It can be obtained by (co) polymerizing N-vinylacetamide. (2) When X in the general formula (1) is a 1,4-phenylene group: 4-aminostyrene can be obtained by reacting acetic anhydride with pyridine in the presence of pyridine and (co) polymerizing the same. (3) X in the general formula (1) is - (CH ₂₎ when n- of _{H 2 C = CH- (CH 2} ) n-NH 2 (n = 1~5) in pyridine presence, working with acetic anhydride And (co) polymerizing it. (4) X is -O- (CH ₂₎ n-where polyvinyl alcohol derivative of general formula (1), the presence of a base, Br @ -
(CH ₂ ) n-NH ₂ (n = 1 to 5) is reacted, and further reacted with acetic anhydride in the presence of pyridine to obtain
Obtainable. (5) After an esterification reaction of acrylic acid X in the general formula (1) is -COO- (CH ₂₎ when n- of _{HO- (CH 2) n-NH} 2 (n = 1~5), It can be obtained by reacting with acetic anhydride in the presence of pyridine and subjecting it to (co) polymerization. (6) X in the general formula (1) is -OCO- (CH ₂₎ when n- of the polyvinyl alcohol derivative, HOOC- (CH ₂₎
After an esterification reaction of n-NH ₂ (n = 1 to 5),
It can be obtained by reacting with acetic anhydride in the presence of pyridine. (7) In formula X is -CONH- (CH ₂₎ when n- of H ₂ N- (CH ₂₎ pyridine presence in _{n-NH 2 (n = 1~5} ) (1), acts with acetic anhydride After that, it can be obtained by reacting acrylic acid chloride in the presence of pyridine and subjecting it to (co) polymerization. As the monomer (a) represented by the general formula (1), N-vinylacetamide is particularly preferred.

In the polymer (A1), the compound represented by the general formula (1)
The functional group represented by -X-NHCOCH ₃ in the above may be present in the molecule of (A1), and may be obtained by polymerizing a vinyl monomer (a) having the functional group in the molecule. It may be introduced, or may be introduced by a polymer modification reaction to the vinyl polymer.

The (A1) may be a homopolymer or a copolymer with another vinyl monomer (b) as long as it has the above-mentioned functional group in the molecule. . The monomer (b) is not particularly limited as long as it contains a vinyl group and is compatible with the polymer (a) in a polymerization reaction system and can form a copolymer. The (b) is selected from the group consisting of an aromatic ring-containing water-soluble monomer, a heterocyclic ring-containing water-soluble monomer, and an acrylic water-soluble monomer having a molecular weight of 130 or more, preferably 130 to 500. At least one kind of the water-soluble vinyl monomer (b1), the water-soluble vinyl monomer (b2) other than the (b1), and the water-insoluble vinyl monomer (b3).

Examples of (b1) include water-soluble aromatic ring-containing monomers [styrene sulfonic acid or a salt thereof (amine salt, alkali metal salt, etc.), vinylbenzyltrimethylammonium hydroxide, etc.]; Water-soluble monomers [vinyl imidazole, vinyl pyridine, N-vinyl pyrrolidone, N- (meth) acryloyl morpholine, N-((meth) acryloyloxy) ethyl morpholine, etc.]; having a molecular weight of 130 or more (preferably 130 to 500) Acrylic water-soluble monomer (1) Acrylamide monomer [N-alkyl (meth) acrylamide having 5 to 10 carbon atoms in the alkyl group [N-
Pentyl (meth) acrylamide, etc.), N, N-dialkyl (meth) acrylamide [N, N-diisopropyl (meth) acrylamide, etc.] having 3 to 7 carbon atoms in the alkyl group, and 1 to 5 carbon atoms in the alkyl group. N, N, -dialkylaminoethyl (meth) acrylamide [N,
N, -dimethylaminoethyl (meth) acrylamide,
N, N, -diethylaminoethyl (meth) acrylamide, etc.], N, N, -dialkylaminopropyl (meth) acrylamide having 1 to 5 carbon atoms in the alkyl group [N,
N, -dimethylaminopropyl (meth) acrylamide, N, N, -diethylaminopropyl (meth) acrylamide, etc.), N-alkyloxymethyl (meth) acrylamide having 3 to 7 carbon atoms in the alkyl group [N-isopropyloxymethyl (Meth) acrylamide, N-butyloxymethyl (meth) acrylamide, etc.], diacetone (meth) acrylamide, etc.); (2) acrylate monomers [hydroxy or alkoxy group-containing (meth) acrylic esters, for example, 2-hydroxy Ethyl methacrylate, alkyl group having 3 to 3 carbon atoms
And hydroxy-containing (meth) acrylates such as hydroxyalkyl (meth) acrylates (eg, 2-hydroxypropyl (meth) acrylate), glycerol mono (meth) acrylate, and polyethylene glycol mono (meth) acrylate; Formulas 1 to 4) ethers such as 2-ethoxyethyl (meth) acrylate, 2-ethoxypropyl (meth) acrylate, carbitol (meth) acrylate and the like]; (3) sulfonic acid (salt) group-containing monomer [2 -(Meth) acrylamide-2-methylpropanesulfonic acid, 3-sulfopropyl (meth) acrylate, or a salt thereof (eg, an amine salt or an alkali metal salt); (4) a phosphoric acid (salt) group-containing monomer Form [[2-((meth) acryloyloxy) ethyl]] (5) a quaternary ammonium base-containing monomer [eg, [2-((meth) acryloyloxy) ethyl] trimethylammonium chloride]; and the like. No. These can be used alone or in combination of two or more.

The (b2) includes, for example, unsaturated carboxylic acids (salts) [(meth) acrylic acid, crotonic acid, (anhydride) itaconic acid, (anhydride) maleic acid,
Fumaric acid or a salt thereof (such as an amine salt or an alkali metal salt); a hydroxyl-containing acrylate [such as hydroxymethyl acrylate or 2-hydroxyethyl acrylate]; an unsaturated acid amide or a derivative thereof ((meth) acrylamide, diacetone) (Meth) acrylamide, N-alkyl (meth) acrylamide having 1 to 4 carbon atoms in the alkyl group [N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, etc.], alkyl N, N-dialkyl (meth) acrylamide having 1 to 2 carbon atoms [N, N-
Dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, etc.], N-methylol (meth) acrylamide, and N having an alkyl group having 1 to 2 carbon atoms.
-Alkoxymethyl (meth) acrylamide [N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, etc.]; and the like. These can be used alone or in combination of two or more.

Examples of (b3) include: nitrile monomers [(meth) acrylonitrile etc.); aliphatic unsaturated hydrocarbons [α-olefins, isoprene, butadiene etc.]; styrene monomers [styrene, α-methylstyrene,
p-methoxystyrene, vinyltoluene, p-hydroxystyrene, p-acetoxystyrene, etc.]; an alkyl (meth) acrylate having an alkyl group having 1 to 18 carbon atoms [methyl (meth) acrylate, ethyl (meth) acrylate, butyl ( Meth) acrylate, 2-
Ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, etc.]; vinyl ester monomers [vinyl acetate, vinyl propionate, etc.]; vinyl ether monomers [vinyl ethyl ether, vinyl isobutyl ether, etc.] ]; And the like. These can be used alone or in combination of two or more.

The content of the repeating unit derived from the monomer (a) in the (co) polymer (A1) is preferably at least 5 mol%, particularly preferably at least 10 mol%. If it is less than 5 mol%, a sufficient sensitivity improving effect may not be obtained. Further, (b1) and / or (b) in (A1)
2) The content of the unit is preferably from 0 to 95 mol%, particularly preferably from 0 to 90 mol%, and the content of the unit (b3) is preferably from 0 to 10 mol%, particularly preferably from 0 to 5 mol%.

The polymer (A) [(A1) or (A
1) and (A2)] may be either water-soluble or water-insoluble, but are preferably water-soluble when used for forming a black matrix or a fluorescent screen of a color CRT. The weight average molecular weight of (A) is 5
It is preferably from 000 to 2,000,000, and more preferably from 200,000 to 1,500,000. If it is less than 50,000, a sufficient effect of improving sensitivity may not be obtained. If it exceeds 2,000,000, the viscosity may increase, and application unevenness may occur during application.

When the photosensitive composition of the present invention is used for forming a black matrix of a color cathode ray tube, the composition preferably has reciprocity failure characteristics. The reciprocity failure property is a property of forming a stripe or dot pattern having a substantially smaller area than a light irradiation area on a glass surface in the presence of gaseous oxygen. The reciprocity failure property is described in JP-A-48-79970, Poly. En.
g.Sci., 17 (6), 353 (1977). By using a photosensitive composition having reciprocity failure for forming a black matrix of a color CRT, a black matrix having a smaller area than a mask area can be formed. When green, blue, and red phosphor patterns are sequentially formed on the black matrix-formed panel formed in this manner, the area of the phosphor pattern is also substantially smaller than the mask area. Therefore, if a color CRT is created using this mask, the size of the electron beam irradiated through the slits or small holes of the mask is larger than that of the phosphor pattern. It will be better. That is, in order to produce a high-definition and high-quality color CRT, it is preferable to form a black matrix using a photosensitive composition having reciprocity failure characteristics.

When the composition of the present invention has the reciprocity failure property, the polymer (A) used in the composition of the present invention includes the monomer (a), the monomer (b1) and If necessary, a vinyl copolymer (A11) with (b2) and / or (b3), and a water-soluble vinyl (co) having a repeating unit derived from the polymer (A1) and the monomer (b1) A blend with the polymer (A2) is included.

The copolymerization ratio of the monomer (a) and the monomer (b1) in (A11) is such that (a) is 20 to 99 mol%, preferably 30 to 95 mol%, b1) is from 1 to 80 mol%, preferably from 5 to 70 mol%. If the proportion of the monomer (a) exceeds 99 mol%, reciprocity failure characteristics may not be exhibited, and if it is less than 20 mol%, a sufficient sensitivity improving effect may not be exhibited. Also, (b2)
Is 0 to 95 mol%, particularly 0 to 90 mol%, (b
The ratio of 3) is preferably 0 to 10 mol%, particularly preferably 0 to 5 mol%.

The water-soluble polymer (A2) may be a homopolymer of the monomer (b1), but may be copolymerized with another vinyl monomer (b2) and / or (b3). It may be united. (B1) The unit content is 20 mol% or more, particularly 50 mol% or more, (b2) is 0 to 80 mol%, particularly 0 to 50 mol%, and (b3) is 0 to 10 mol%, particularly 0 to 5 mol%. Molar% is preferred. Examples of (A2) include a water-soluble vinyl (co) polymer having a repeating unit derived from an aromatic ring-containing water-soluble monomer [styrene sulfonic acid (co) polymer or a salt thereof (amine salt, alkali metal Salt, etc.); water-soluble vinyl (co) polymer having a repeating unit derived from a heterocyclic-containing water-soluble monomer [vinylpyrrolidone (co)
Polymer, (meth) acryloylmorpholine (co) polymer, vinylimidazole (co) polymer, etc.]; water-soluble having a repeating unit derived from an acrylic water-soluble monomer having a molecular weight of 130 or more (preferably 130 to 500) Vinyl-based (co) polymer [(meth) acrylamide-diacetone (meth) acrylamide copolymer, N-alkyl (meth) acrylamide (co) polymer having 5 to 10 carbon atoms in the alkyl group, carbon number in the alkyl group Is 3 to 7 N,
N-dialkyl (meth) acrylamide (co) polymer,
N, N-dialkylaminoethyl (meth) acrylamide (co) polymer having 1 to 5 carbon atoms in the alkyl group, N, N-dialkylaminopropyl (meth) acrylamide (co) polymer having 1 to 5 carbon atoms in the alkyl group A) polymer, 2- (meth) acrylamido-2-methylpropanesulfonic acid (co) polymer or a salt thereof (amine salt, alkali metal salt, etc.), hydroxyalkyl (meth) having 3 to 7 carbon atoms in the alkyl group Acrylate (co) polymer, 3-sulfopropyl (meth) acrylate (co) polymer or a salt thereof (amine salt, alkali metal salt, etc.); and the like.

When the compound (A2) is contained, the compounding amount of the compound (A2) is usually 80% by mass or less, preferably 2 to 70% by mass, particularly preferably 5 to 5% by mass, based on the mass of the (A).
0% by mass. If the amount of (A2) exceeds 80% by mass, a sufficient sensitivity improving effect may not be exhibited.

In order to exhibit reciprocity failure characteristics, gaseous oxygen needs to be present in the vicinity of the azide compound as described above, and for that purpose, the photosensitive composition coated film must have oxygen permeability. There is. As the polymer component used in the photosensitive composition of the present invention, (A11) and / or (A)
By using the mixture of 1) and (A2), the gaseous oxygen permeability of the coating film is enhanced, and as a result, the photosensitive composition containing the polymer component exhibits reciprocity failure.

The photosensitive compound (B) used in the photosensitive composition of the present invention includes an azide compound and a diazo compound. The azide compound is not particularly limited as long as it is a compound capable of generating nitrene by irradiation with ultraviolet rays and reacting with the (co) polymer (A), but is an aromatic bis azide compound having two azide groups in the molecule. Is preferred. Specific examples include a water-soluble azide compound containing a sulfonic acid (salt) group [4,
4'-diazidostilbene-2,2'-disulfonic acid or a salt thereof, 4,4'-diazidobenzalacetophenone-2-sulfonic acid or a salt thereof, 1,5-penta-3-one-1,4 -Diethenyl-bis (azidobenzenesulfonic acid) or a salt thereof, 2,6-bis (4-azidobenza-2-sulfonic acid) -cyclopentanone or a salt thereof]; a carboxylic acid (salt) group-containing water-soluble azide compound [4
4′-diazidostilbene-α-carboxylic acid or a salt thereof]; water-insoluble azide compound [2,6-bis (4,4′-diazidobenzal) -cyclohexanone, 2,6-bis (4,4′- Diazidobenzal) -4-methylcyclohexanone, 4,4'-diazidostilbene-2,2'-
Bis [N, N-di (2-ethoxyethyl) sulfonamide], 1,3-bis (4'-azidocinnamylidene)-
2-propanone, etc.];

The diazo compound is not particularly limited as long as it is a compound capable of denitrifying by irradiation with ultraviolet rays to generate radicals and reacting with the polymer (A). An aromatic diazo compound having two or more is preferred. Specific examples include benzidine tetrazonium chloride, 3,3′-dimethylbenzidine tetrazonium chloride, 3,3′-dimethoxybenzidine tetrazonium chloride, 4,4′-diaminodiphenylamine tetrazonium chloride,
Examples include 3′-diethylbenzidine tetrazonium sulfate, formalin condensate of diazodiphenylamine, and double salts thereof (salt of zinc chloride, salt of p-toluenesulfonic acid, and the like).

The photosensitive compound (B) may be used alone or as a mixture of two or more. Among them, a water-soluble azide compound containing a sulfonic acid (salt) group is preferable for forming a black matrix or a fluorescent screen of a color cathode ray tube, and 4,4'-diazidostilbene-2,2 is particularly preferable. '-Sodium disulfonate.

The compounding ratio of the polymer (A) and the photosensitive compound (B) in the photosensitive composition of the present invention is such that (A) is usually 70 to 99% by mass, preferably 80 to 99% by mass.
(B) is usually 1 to 30% by mass, preferably 1 to 20% by mass. When the proportion of (B) exceeds 30% by mass, sufficient adhesiveness to the glass surface may not be obtained, and
If the amount is less than mass%, sufficient sensitivity may not be obtained.

Further, the photosensitive composition of the present invention may contain a fine powder (C). Examples of the fine powder (C) include a phosphor [a red phosphor such as Y ₂ O ₂ S: Eu and Y ₂ O ₃ : Eu; ZnS: Cu, Al, ZnS: Au, Cu, A
l, ZnS: green phosphor such as Au, Al; ZnS: A
g, Cl ZnS: blue phosphor such as Ag, Al, etc.]; metal oxide [magnesia, alumina, antimony oxide, titanium oxide, white carbon, diatomaceous earth, iron oxide, etc.]; metal hydroxide [aluminum hydroxide, Magnesium hydroxide, calcium hydroxide, iron hydroxide, metatitanic acid, etc.]; metal salts [silicates such as kaolin, aluminum silicate, clay, talc, mica, asbestos powder, calcium silicate, sericite, bentonite; carbonic acid Carbonates such as calcium, magnesium carbonate, barium carbonate and dolomite; sulfates such as calcium sulfate and barium sulfate]; pigments [CIPigm as color index number
black pigments such as ent Black 1, 6, 7, 9, 10, 11; CI Pigment Red 48, 97, 101, 102, 1
04, 105, 106, 122, 123, 144, 14
9, 166, 168, 177, 178, 180, 18
Red pigments such as 7, 190, 192, 208;
Green pigments such as ent Green 7, 36; CI Pigment Blue
Blue pigments such as 15, 22, 28, 60, 64; CIP
igment Yellow 10, 17, 24, 34, 35, 42,
Yellow pigments such as 48, 83, 86, 93, 94, 108; CI Pigment Violet 19, 23, 29, 30, 3,
Purple pigments such as 2, 37, 40, 50; CI Pigment Or
ange 13,36,43,51,55,59,61,6
Orange pigments such as 4, 65; CI Pigment White 1, 2,
3, 4, 5, 6, 7, 10, 18, 19, 22, 24,
White pigments such as 25, 26 and 27]. Of these, phosphors are preferable.

The average particle size of the fine powder (C) varies greatly depending on the type, but is usually 1 mm or less, preferably 0.01 to 100 μm. The mixing ratio of the polymer (A), the photosensitive compound (B) and the (C) in the photosensitive composition containing the fine powder (C) is (A) 0.5 to 5;
0 mass%, (B) is 0.002 to 20 mass%, and (C) is 99.5 to 40 mass%. The timing of addition of (C) and each component described below is not particularly limited, and may be mixed in advance with (A) and / or (B) or mixed simultaneously with (A) and (B). , (A) and (B).

The composition preferably contains a dispersant (D) in order to uniformly disperse the fine powder (C) in the composition. The dispersant (D) is not particularly limited as long as it has a dispersing action and is compatible with each component, and examples thereof include an anionic dispersant, a nonionic dispersant and a cationic dispersant. Examples of the anionic dispersant include polycarboxylic acid (salt) type dispersants [eg, polyacrylic acid, isobutylene-maleic acid copolymer, styrene-
Maleic acid copolymers, salts thereof (amine salts, alkali metal salts, etc.), etc .; sulfonic acid (salt) type dispersants [eg, dioctyl sulfosuccinate (amine salts, alkali metal salts, etc.), naphthalenesulfonic acid] Formalin condensate]; and the like. Examples of the nonionic dispersant include alkylene oxide addition type dispersants [eg, polyoxyalkylene alkyl ether, polyoxyalkylene higher fatty acid ester, polyoxyalkylene polyhydric alcohol higher fatty acid ester, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene alkyl phenyl ether, Oxyalkylene alkylamino ether, higher fatty acid dialkanolamide, polyoxyethylene / polyoxypropylene block copolymer, etc.]; polyhydric alcohol type dispersant [for example, polyhydric alcohol fatty acid ester or its alkylene oxide adduct,
Polyhydric alcohol alkyl ether or an alkylene oxide adduct thereof]; and the like. Examples of the cationic dispersant include amine salt-type dispersants [eg, N, N-dialkylaminoethyl (meth) acrylate (co) polymer neutralized with inorganic or organic acid (formic acid, acetic acid, lactic acid, etc.)] Quaternary ammonium-type dispersant [tetraalkylammonium halide, quaternized N, N-dialkylaminoethyl (meth) acrylate (co) polymer, etc.]; and the like.

Of these, preferred are anionic dispersants and nonionic dispersants, and particularly preferred are polyacrylic acid or a salt thereof, isobutylene-maleic acid copolymer or a salt thereof, and styrene-maleic acid copolymer. Or a salt thereof, a polyoxyethylene / polyoxypropylene block copolymer, a sorbitan fatty acid ester-ethylene oxide adduct, and a quaternary ammonium salt of an unsaturated acid. When the dispersant (D) is used, the content of the (D) is based on the mass of the fine powder (C).
It is preferably 0.01 to 10% by mass, particularly preferably 0.1 to 10% by mass.
It is from 0.5 to 5% by mass. If the content is less than 0.01% by mass, a sufficient dispersion stabilizing effect may not be obtained, and if it exceeds 10% by mass, sensitivity and developability may be deteriorated.

The composition may optionally contain an adhesion enhancer (E). By adding the adhesion improver (E), the adhesion to glass can be improved. Examples of (E) include a silane coupling agent, a titanium-based coupling agent, an organic carboxylic acid-based compound, an organic phosphoric acid-based compound, and an organic phosphate-based compound, and preferably a silane coupling agent [for example, Vinyl-tris- (β-methoxyethoxy) silane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β- (aminoethyl) -γ
-Aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane,
γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, etc.] and titanium A coupling agent [for example, dihydroxy-bis (lactide) titanium, dialkyl-bis (triethanolaminato) titanium, oxotitaniumbis (monoammonium oxalate, etc.)] When the adhesion improver (E) is added, The addition amount is usually 10% by mass or less, preferably 0.01 to 5% by mass, based on the mass of the polymer (A).

The photosensitive composition of the present invention may contain a water-soluble or water-insoluble solvent or a mixed solvent thereof as a diluent. By containing a diluent,
It becomes possible to adjust the coating properties, storage stability, development characteristics, adhesiveness and the like of the composition. The diluent is not particularly limited as long as it is compatible with each component except the fine powder (C).
For example, water as a water-soluble solvent; alcohol solvents such as methanol, ethyl alcohol, and isopropyl alcohol; methyl cellosolve, ethyl cellosolve, butyl cellosolve, diethylene glycol monomethyl ether;
Glycol solvents such as diethylene glycol monoethyl ether; N-methylpyrrolidone, 2-pyrrolidone,
Amide solvents such as dimethylformamide and N, N-dimethylacetamide.

Examples of the water-insoluble solvent include aliphatic hydrocarbon solvents such as pentane, hexane and cyclohexane; aromatic hydrocarbon solvents such as benzene, toluene and xylene; ethyl acetate, butyl acetate, ethyl lactate and ethyl-3.
Ester solvents such as ethoxypropionate; ketone solvents such as methyl isobutyl ketone and cyclohexanone; and halogen-containing hydrocarbon solvents such as 1,1,1-trichloroethane, trichloroethylene and tetrachloroethylene.

Among these diluents, for forming a black matrix of a color cathode ray tube and for forming a fluorescent screen, a water-soluble solvent is preferable, and water is particularly preferable. The content of the diluent can be arbitrarily set depending on the application conditions of the photosensitive composition and the like. When the fine powder (C) is not contained, the content of the diluent is preferably 2 to 50% by mass relative to the photosensitive composition. When the fine powder (C) is contained, the content of the diluent is preferably 40 to 95% by mass with respect to 5 to 60% by mass of the photosensitive composition.

The composition of the present invention may optionally contain another polymer compound having a weight average molecular weight of 1,000 or more. By adding another polymer compound, it is possible to adjust coatability, sensitivity, development characteristics, adhesiveness, and the like. The other high molecular compound is not particularly limited, for example, vinylpyrrolidone (co) polymer,
(Meth) acrylamide (co) polymer, (meth) acrylamide-diacetone (meth) acrylamide copolymer, vinyl alcohol (co) polymer, JP-A-55-23
No. 163, styrylpyridinium salt compounds,
(Meth) acrylic acid (co) polymer, casein, gelatin, methylcellulose, hydroxypropylcellulose, polyvinylcellulose, polyethylene glycol and the like. When these other polymer compounds are added, the amount of addition can be arbitrarily set, but is usually 50% by mass or less, preferably 30% by mass or less, based on the mass of the (co) polymer (A). It is. If the amount exceeds 50% by mass, the sensitivity may be reduced.

Further, a low molecular compound having a molecular weight of 990 or less and containing a hydroxyl group and / or an iodine atom in the molecule can be added to the composition of the present invention, if necessary. By adding the low molecular compound, development characteristics, adhesion and the like can be adjusted, and sensitivity can be further improved. Examples of low molecular weight compounds having a hydroxyl group in the molecule include, for example, n-butanol, ethylene glycol, diethylene glycol, propylene glycol,
Examples thereof include 1,3-butylene glycol, 1,5-pentanediol, triethanolamine, glycerin, erythritol, pentaerythritol, sorbitol, and hexitol.

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, 3,5-diamino-
Sodium 2,4,6-triiodobenzoate, 3-amino-2,4,6-triiodobenzoic acid, 3-amino-
Sodium 2,4,6-triiodobenzoate, 5-amino-2,4,6-triiodoisophthalic acid, sodium 5-amino-2,4,6-triiodoisophthalate, 5
-Amino-2,4,6-triiodoisophthalamic acid,
Sodium 5-amino-2,4,6-triiodoisophthalamate, 3,5-diiodosalicylic acid, sodium 3,5-diiodosalicylate, 2,3,5-triiodobenzoic acid, 2,3,5 -Sodium triiodobenzoate, tetraalkylammonium iodide, sodium iodide, potassium iodide and the like.

When a low molecular weight compound containing a hydroxyl group and / or an iodine atom in the above molecule is added, the amount of the low molecular weight compound is usually 1 to 2 with respect to the mass of the (co) polymer (A).
00 mass%, preferably 1 to 100 mass%. If the amount is less than 1% by mass, the effect of addition may not be sufficiently obtained.
If it exceeds 00% by mass, development characteristics, resolution and the like may be deteriorated.

A surfactant may be added to the composition of the present invention, if necessary, in order to improve the wettability to the substrate. Surfactant is not particularly limited as long as it is compatible with each component, for example, anionic surfactant,
Nonionic surfactants and cationic surfactants are exemplified. Preferred are nonionic surfactants (for example, sorbitan ester ethylene oxide adduct, alkylphenol ethylene oxide adduct, etc.). When a surfactant is added, the amount thereof is usually 5% by mass or less, preferably 0.05 to 3% by mass, based on the mass of the (co) polymer (A).

As a specific example using the composition of the present invention, the formation of a black matrix and the formation of a fluorescent screen of a color CRT will be described below. As a method for forming a black matrix of a color cathode ray tube, for example, a photosensitive composition of the present invention containing a (co) polymer (A) and a photosensitive compound (B) is usually prepared on a glass panel by 0.1%.
Coating with a thickness of about 2 μm; drying with a hot plate, infrared heater, far infrared heater, etc. to form a coating film; ultraviolet rays such as ultra-high pressure mercury lamp, high pressure mercury lamp, metal halide lamp through a photomask having a desired pattern Is exposed at an illuminance of usually 0.5 to 50 mJ / cm ² ; developed with water to wash and remove unexposed portions to form a resist pattern; applying a black component dispersion such as graphite; hot plate; Examples include a method of performing a series of steps of drying with an infrared heater, a far infrared heater, or the like; oxidizing and decomposing the resist pattern with an oxidizing agent such as hydrogen peroxide; and developing with water. In addition,
(Co) in the photosensitive composition used in the above steps
The polymer (A) and the photosensitive compound (B) are preferably water-soluble.

When the photosensitive composition of the present invention has a reciprocity failure property, the ultraviolet exposure illuminance in the above step is preferably in the range of 0.02 to 1 mW / cm ² . When the exposure illuminance falls below 0.02 mW / cm ² ,
The pattern obtained by ultraviolet irradiation may be extremely small or may not be formed. When the exposure illuminance exceeds 1 mW / cm ² , the exposure time for obtaining a pattern of an appropriate size becomes extremely short. As a result, Swelling and wrinkling of the pattern may occur.

On the other hand, as a method for forming a phosphor screen of a color cathode ray tube, for example, a photosensitive composition of the present invention obtained by suspending a (co) polymer (A), a photosensitive compound (B) and a phosphor is used. Usually 5 to 15 on glass panel with black matrix
Apply with a hot plate, infrared heater, far-infrared heater, etc. to form a coating; apply ultraviolet light from ultra-high pressure mercury lamp, high pressure mercury lamp, metal halide lamp, etc. through a photomask having the desired pattern. Exposure is usually performed at an illuminance of 0.5 to 50 mJ / cm ² ; developing with water to wash and remove unexposed portions to form a phosphor pattern; After performing each process on the body, a method of oxidatively decomposing and removing organic substances by heating (about 400 ° C.) in the air can be exemplified. The (co) polymer (A) and the photosensitive compound (B) in the composition used in the above step are preferably water-soluble.

If necessary, before the above-mentioned steps,
By applying an aqueous solution containing a water-soluble (co) polymer and a water-soluble azide compound on a glass panel in advance to form a thin film, it becomes possible to further enhance the adhesion of the phosphor to the glass surface. . Examples of the water-soluble (co) polymer used for this purpose include vinylformamide (co) polymer, vinylpyrrolidone (co) polymer, (meth) acrylamide (co) polymer, (meth) acrylamide-diacetone (meth) ) Acrylamide copolymer, polyvinyl alcohol and the like. The water-soluble azide compound is not particularly limited, but is preferably 4,
4'-diazidostilbene-2,2'-sodium disulfonate.

[0044]

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”. Note that “exposure” in this embodiment refers to exposure in a state in which a fixed interval (for example, 3.0 mm) is maintained between the photomask and the glass substrate, that is, gap exposure. Furthermore, there are various definitions of "sensitivity". In this embodiment, at a constant illuminance, exposure is performed through a photomask having a mask size of 70 μm, and the width of the formed phosphor pattern reaches 80% (56 μm) of the mask size. Exposure time is defined as sensitivity. In this case, the shorter the exposure time, the higher the sensitivity.

Synthesis Example 1 N-vinylacetamide (68 parts) and diacetone acrylamide (58 parts) were dissolved in ion-exchanged water (1674 parts) and dissolved.
Heated to ° C. Here, "VA-04" is used as a polymerization initiator.
4 "[manufactured by Wako Pure Chemical Industries, Ltd.], 0.15 parts, and the mixture was stirred at 57 ° C for 5 hours to carry out polymerization to prepare a copolymer aqueous solution having a solid content of 7%. The weight average molecular weight of the obtained copolymer by GPC was about 1,300,000.

Synthesis Example 2 68 parts of N-vinylacetamide and 58 parts of sodium p-styrenesulfonate were dissolved in 1674 parts of ion-exchanged water and heated to 56 ° C. Here, “VA” is used as a polymerization initiator.
-044 "[manufactured by Wako Pure Chemical Industries, Ltd.]
Polymerization was performed by stirring at 7 ° C. for 5 hours to prepare a copolymer aqueous solution having a solid content of 7%. The weight average molecular weight of the obtained copolymer by GPC was about 1,200,000.

Synthesis Example 3 N-vinylacetamide (270 parts) was ion-exchanged into water (153).
Dissolve in 0 parts and heat to 55 ° C. 0.25 parts of “VA-044” [manufactured by Wako Pure Chemical Industries, Ltd.] was added as a polymerization initiator, and the mixture was stirred at 55 ° C. for 5 hours to carry out polymerization. A 7% aqueous polymer solution was prepared. The weight average molecular weight of the obtained polymer by GPC was about 1,200,000.

Synthesis Example 4 62.6 parts of acrylamide and 63.4 g of diacetone acrylamide were dissolved in 1,674 g of ion-exchanged water.
Heated to ° C. Here, "VA-04" is used as a polymerization initiator.
4 "[manufactured by Wako Pure Chemical Industries, Ltd.]
Polymerization was carried out by stirring for an hour to prepare a copolymer aqueous solution having a solid content of 7%. The weight average molecular weight of the obtained copolymer by GPC was about 1,400,000.

Synthesis Example 5 A stirred autoclave was charged with triethylamine (1 mol), dimethyl carbonate (1.5 mol) and methanol (2.0 mol) as a solvent, and reacted at a reaction temperature of 110 ° C. for 12 hours. A methanol solution of methyl ammonium carbonate was obtained. A methanol solution of the above triethylmethylammonium carbonate was charged into a 40% isopropyl alcohol solution of an acrylic acid / methyl methacrylate copolymer (molar ratio 70/30) so as to be 70 mol% with respect to 1 mol of carboxyl groups. Next, by-product carbon dioxide gas and methanol were removed to obtain a 40% isopropyl alcohol solution of an acrylic acid / methyl methacrylate copolymer / triethylmethylammonium salt (cationic dispersant). The weight average molecular weight of the obtained copolymer by GPC was about 10,000.

Synthesis Example 6 28.1 g of N-vinylacetamide and 46.9 g of a 50% aqueous acrylamide solution were dissolved in 425 g of ion-exchanged water and heated to 56 ° C. Here, "VA-0" is used as a polymerization initiator.
44 "[manufactured by Wako Pure Chemical Industries, Ltd.] at 56 ° C
After stirring for 5 hours at, polymerization was performed, and 214 g of ion-exchanged water was further added to prepare a copolymer aqueous solution having a solid content of 7%. The weight average molecular weight of the obtained copolymer by GPC was about 1,200,000.

Example 1 A photosensitive composition (1) of the present invention was obtained according to the following formulation. The composition (1) was applied to a thickness of 0.8 μm on a glass substrate by spin coating, and dried on a hot plate at 50 ° C. for 1 minute to form a coating film. This coating film was exposed to ultraviolet light having an exposure illuminance of 0.15 mW / cm ² through a photomask having a line width of 70 μm using an ultra-high pressure mercury lamp, and then developed with water at room temperature to form a resist pattern. It was measured. The sensitivity was 15 seconds (exposure amount: 2.3 mJ / cm ² ). Further, the pattern after development was not disturbed at all, and the mask pattern was faithfully reproduced. The composition also exhibited remarkable reciprocity properties. The entire surface of the glass substrate on which this pattern was formed was covered with a graphite dispersion “Electro-Dug ED-1530”.
(Manufactured by Acheson Japan) was applied by a spin coating method so that the graphite film thickness was 0.8 μm. Further, in an etching solution containing 3% hydrogen peroxide solution and 0.5% sulfuric acid, a glass substrate treated with graphite at room temperature was placed in an etching solution.
It was immersed for 0 second and developed with water at room temperature to form a target black matrix. Even in this black matrix, there was no pattern disturbance at all, and the mask pattern was faithfully reproduced. [Prescription of photosensitive composition (1)] 100 parts of aqueous solution of polymer (solid content: 7%) obtained in Synthesis Example 1 0.7 parts of sodium 4,4'-diazidostilbene-2,2'-disulfonate Surfactant [Nonion LT-221 manufactured by NOF Corporation] 0.04 part N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane 0.08 part Ion-exchanged water 150 parts

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 sensitivity was measured. The result was 17 seconds (exposure amount: 2.6 mJ). / Cm ² ). The composition also exhibited remarkable reciprocity failure characteristics. Further, a black matrix was formed in the same manner as in Example 1, but the pattern was not disturbed at all and the mask pattern was faithfully reproduced. [Prescription of photosensitive composition (2)] 100 parts of aqueous solution of the copolymer obtained in Synthesis Example 2 (solid content: 7%) Sodium 4,4'-diazidostilbene-2,2'-disulfonate 0.7 Part Surfactant [Nonion LT-221 manufactured by NOF Corporation] 0.04 part N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane 0.08 part Ion-exchanged water 150 parts

Example 3 A photosensitive composition (3) of the present invention was obtained according to the following formulation. Using this 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 sensitivity was measured. The result was 17 seconds (exposure amount: 2.6 mJ). / Cm ² ). The composition also exhibited remarkable reciprocity failure characteristics. Further, a black matrix was formed in the same manner as in Example 1, but the pattern was not disturbed at all and the mask pattern was faithfully reproduced. [Prescription of Photosensitive Composition (3)] 70 parts of aqueous solution of polymer (solid content: 7%) obtained in Synthesis Example 3 30 parts of aqueous solution of polyvinyl pyrrolidone (solid content: 7%) 4,4'-diazidostilbene-2 Sodium 2,2'-disulfonate 0.7 part Surfactant [Nonion LT-221 manufactured by NOF Corporation] 0.04 part N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane 0. 08 parts Ion exchange water 150 parts

Example 4 A photosensitive composition (4) of the present invention was obtained according to the following formulation. Using the composition (4), 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 sensitivity was measured. The result was 15 seconds (exposure amount: 2.3 mJ). / Cm ² ). The composition also exhibited remarkable reciprocity failure characteristics. Further, a black matrix was formed in the same manner as in Example 1, but the pattern was not disturbed at all and the mask pattern was faithfully reproduced. [Prescription of Photosensitive Composition (4)] 70 parts of the aqueous polymer solution (solid content 7%) obtained in Synthesis Example 3 30 parts of the aqueous polymer solution (solid content 7%) obtained in Synthesis Example 4 Sodium 4'-diazidostilbene-2,2'-disulfonate 0.7 part Surfactant [Nonion LT-221 manufactured by NOF Corporation] 0.04 part N-β- (aminoethyl) -γ -Aminopropyltrimethoxysilane 0.08 parts Deionized water 150 parts

Example 5 A photosensitive composition (5) of the present invention was obtained according to the following formulation. Using this composition (5), 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 sensitivity was measured. The result was 15 seconds (exposure: 2.3 mJ). / Cm ² ). The composition also exhibited remarkable reciprocity failure characteristics. Further, a black matrix was formed in the same manner as in Example 1, but the pattern was not disturbed at all and the mask pattern was faithfully reproduced. [Prescription of photosensitive composition (5)] 100 parts of aqueous solution of copolymer (solid content: 7%) obtained in Synthesis Example 1 Sodium 4,4'-diazidostilbene-2,2'-disulfonate 0.7 Part Tetramethylammonium iodide 0.3 part Surfactant [Nonion LT-221 manufactured by NOF Corporation] 0.04 part N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane 0.08 Part Ion exchange water 150 parts

Example 6 A photosensitive composition (6) of the present invention was obtained according to the following formulation. Using the composition (6), 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 sensitivity was measured. The result was 15 seconds (exposure amount: 2.3 mJ). / Cm ² ). The composition also exhibited remarkable reciprocity failure characteristics. Further, a black matrix was formed in the same manner as in Example 1, but the pattern was not disturbed at all and the mask pattern was faithfully reproduced. [Prescription of Photosensitive Composition (6)] 70 parts of aqueous solution of copolymer (solid content: 7%) obtained in Synthesis Example 1 polyvinyl alcohol [Denkapovar K-05] manufactured by Denki Kagaku Kogyo Co., Ltd. 30% 4,4'-diazidostilbene-2,2'-disulfonate sodium 0.7 part Surfactant [Nonion LT-221 manufactured by NOF Corporation] 0.04 part N- β- (aminoethyl) -γ-aminopropyltrimethoxysilane 0.08 parts Deionized water 150 parts

Example 7 A phosphor-containing photosensitive composition (7) of the present invention was obtained according to the following formulation. The composition (7) was applied to a thickness of 10 μm on a glass substrate by spin coating, and dried on a hot plate at 50 ° C. for 1 minute to form a coating film. At this time, no unevenness was observed in the coating film. The coating film was exposed to ultraviolet light having an exposure illuminance of 0.40 mW / cm ² through a photomask using an ultra-high pressure mercury lamp, developed with water at normal temperature to form a phosphor pattern, and the sensitivity was measured. The sensitivity was 9 seconds (exposure amount: 3.6 mJ / cm ² ). Further, the pattern after development was not disturbed at all, and the mask pattern was faithfully reproduced. [Prescription of photosensitive composition (7)] 43 parts of aqueous solution of polymer (solid content: 7%) obtained in Synthesis Example 3 0.3 parts of sodium 4,4'-diazidostilbene-2,2'-disulfonate Blue phosphor (ZnS: Ag) 50 parts Dispersant [Sanyo Kasei Kogyo Co., Ltd. "Carribbon L-400"] 0.06 parts Surfactant [Nippon Oil & Fats Co., Ltd. "Nonion LT-221"] 0. 03 parts N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane 0.01 parts Deionized water 87 parts

Example 8 A phosphor-containing photosensitive composition (8) of the present invention was obtained according to the following formulation. The composition (8) was coated on a glass substrate in the same manner as in Example 7, dried, exposed to light, and developed to form a phosphor pattern, and the sensitivity was measured.
Seconds (exposure amount: 3.6 mJ / cm ² ). Further, the pattern after development was not disturbed at all, and the mask pattern was faithfully reproduced. [Prescription of photosensitive composition (8)] 43 parts of the aqueous polymer solution (solid content: 7%) obtained in Synthesis Example 3 0.7 parts of sodium 4,4'-diazidostilbene-2,2'-disulfonate Blue phosphor (ZnS: Ag) 50 parts Cationic dispersant (solid content 40%) obtained in Synthesis Example 5 0.06 parts Surfactant [Nonion LT-221 manufactured by NOF Corporation] 03 parts N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane 0.01 parts Deionized water 87 parts

Example 9 A phosphor-containing photosensitive composition (9) of the present invention was obtained according to the following formulation. Using the composition (9), a phosphor pattern was formed by coating, drying, exposing and developing on a glass substrate in the same manner as in Example 7, and the sensitivity was measured.
Second (exposure amount: 4.0 mJ / cm ² ). Further, the pattern after development was not disturbed at all, and the mask pattern was faithfully reproduced. [Prescription of Photosensitive Composition (9)] 43 parts of aqueous solution of the copolymer obtained in Synthesis Example 1 (solid content: 7%) Sodium 4,4'-diazidostilbene-2,2'-disulfonate 0.3 Part Blue phosphor (ZnS: Ag) 50 parts Dispersant [Sanyo Chemical Industries, Ltd. "Caribbon L-400"] 0.06 parts Surfactant [Nippon Oil & Fats Co., Ltd. "Nonion LT-221"] 0 .03 parts N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane 0.01 parts Deionized water 87 parts

Example 10 A phosphor-containing photosensitive composition (10) of the present invention was obtained according to the following formulation. The composition (10) was coated on a glass substrate, dried, exposed and developed in the same manner as in Example 7 to form a phosphor pattern, and the sensitivity was measured.
13 seconds (exposure amount: 5.2 mJ / cm ² ). Also,
There was no disturbance of the pattern after development, and the mask pattern was faithfully reproduced. [Prescription of photosensitive composition (10)] 43 parts of aqueous solution of copolymer (solid content: 7%) obtained in Synthesis Example 6 Sodium 4,4'-diazidostilbene-2,2'-disulfonate 0.3 Part Blue phosphor (ZnS: Ag) 50 parts Dispersant [Sanyo Chemical Industries, Ltd. "Caribbon L-400"] 0.06 parts Surfactant [Nippon Oil & Fats Co., Ltd. "Nonion LT-221"] 0 .03 parts N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane 0.01 parts Deionized water 87 parts

Comparative Example 1 A comparative photosensitive composition (1) was obtained according to the following formulation. Using the composition (1), 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 sensitivity was measured.
It took 35 seconds at ³ mJ / cm ² . [Prescription of Comparative Photosensitive Composition (1)] Aqueous solution of polyvinylpyrrolidone [“PVP K-90” manufactured by ISP Co., Ltd.] (solid content: 7%) 100 parts 4,4′-diazidostilbene-2,2 Sodium '-disulfonate 0.7 part Surfactant [Nonion LT-221 manufactured by NOF Corporation] 0.04 part N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane 0.08 part 150 parts of ion exchange water

Comparative Example 2 A comparative photosensitive composition (2) 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 sensitivity was measured.
It took 24 seconds at 6 mJ / cm ² . [Prescription of Comparative Photosensitive Composition (2)] Aqueous solution of copolymer obtained in Synthesis Example 4 (solid content: 7%) 100 parts Sodium 4,4'-diazidostilbene-2,2'-disulfonate 0 0.7 parts Surfactant [Nonion LT-221 manufactured by NOF Corporation] 0.04 parts N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane 0.08 parts Ion-exchanged water 150 parts

Comparative Example 3 A comparative phosphor-containing photosensitive composition (3) was obtained according to the following formulation. Using the composition (3), a phosphor pattern was formed by coating, drying, exposing, and developing on a glass substrate in the same manner as in Example 7, and the sensitivity was measured. The exposure amount was 8.0 mJ. It took 20 seconds at / cm ² . [Prescription of comparative photosensitive composition (3)] Polyvinyl alcohol ["Denkapovar K-05" manufactured by Denki Kagaku Kogyo KK] Aqueous solution (solid content 10%) 30 parts Ammonium dichromate 0.3 part Blue fluorescence Body (ZnS: Ag) 50 parts Dispersant [Sanyo Chemical Industries, Ltd. "Caribbon L-400"] 0.06 parts Surfactant [Nippon Oil & Fats Co., Ltd. "Nonion LT-221"] 0.03 parts N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane 0.01 parts Deionized water 100 parts

Comparative Example 4 A comparative phosphor-containing photosensitive composition (4) was obtained according to the following formulation. Using the composition (4), a phosphor pattern was formed by coating, drying, exposing and developing on a glass substrate in the same manner as in Example 7, and the sensitivity was measured. The exposure amount was 10.0 mJ. / Cm ² took 25 seconds. [Prescription of comparative photosensitive composition (4)] Aqueous solution of polyvinylpyrrolidone [“PVP K-90” manufactured by ISP Co., Ltd.] (solid content: 7%) 43 parts 4,4′-diazidostilbene-2,2 Sodium '-disulfonate 0.3 part Blue phosphor (ZnS: Ag) 50 parts Dispersant [Caribbean L-400 manufactured by Sanyo Chemical Industries, Ltd.] 0.06 parts Surfactant [Nippon Oil & Fats Co., Ltd.] "Nonion LT-221"] 0.03 parts N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane 0.01 parts Ion-exchanged water 87 parts

Comparative Example 5 A comparative phosphor-containing photosensitive composition (5) was obtained according to the following formulation. Using the composition (5), a phosphor pattern was formed by coating, drying, exposing, and developing on a glass substrate in the same manner as in Example 7, and the sensitivity was measured. The exposure amount was 8.0 mJ. It took 20 seconds at / cm ² . [Prescription of comparative photosensitive composition (5)] Polyacrylamide [manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight: about 800,000] aqueous solution (solid content: 7%) 43 parts 4,4'-diazidostilbene-2,2 ' -Sodium disulfonate 0.3 part Blue phosphor (ZnS: Ag) 50 parts Dispersant [Caribbean L-400 manufactured by Sanyo Chemical Industry Co., Ltd.] 0.06 part Surfactant [Nippon Oil & Fats Co., Ltd.] Nonion LT-221 "] 0.03 parts N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane 0.01 parts Deionized water 87 parts

[0066]

The photosensitive composition of the present invention has the following effects. 1) Since the sensitivity is extremely high, it greatly contributes to productivity improvement and process cost reduction, such as reduction of the process time and the number of ultraviolet exposure apparatuses. 2) Since it does not contain chromium compounds, which are harmful substances, there is no need to provide equipment for removing chromium in wastewater, and there is no environmental pollution. 3) It can be used in both aqueous and organic solvent systems, and a wide range of diluents can be selected according to the purpose of use. 4) Vinyl-based (co) contained in the photosensitive composition of the present invention
When the polymer is a copolymer with a specific water-soluble vinyl monomer or a blend with a specific water-soluble polymer, the composition has high sensitivity and high resolution and exhibits reciprocity failure characteristics. I do. Therefore, when the photosensitive composition is used for forming a black matrix of a color cathode ray tube, a black matrix having excellent contrast is formed, so that a high definition and high quality color cathode ray tube can be produced. 5) When used for forming a fluorescent screen of a color cathode ray tube, since the composition does not contain a chromium compound, coloring of the fluorescent screen due to the remaining chromium and inhibiting the emission of the fluorescent substance lower the brightness of the color cathode ray tube. I will not let you. For this reason, it is possible to produce an extremely high-quality and high-performance color CRT. 6) Since the photosensitive composition of the present invention containing a phosphor does not deteriorate due to a dark reaction, it has extremely high stability over time and can be stored for a long time as compared with the conventional photosensitive composition containing a phosphor. It is. 7) The photosensitive composition of the present invention containing a phosphor is used not only for forming a fluorescent screen of a color cathode ray tube but also for forming a fluorescent screen of an image display device such as a plasma display, a fluorescent display tube, and a field emission display. It is possible. Due to the above effects, the photosensitive composition of the present invention has an extremely high sensitivity and a high resolution. Therefore, the photosensitive composition is used not only for forming a black matrix and / or for forming a fluorescent screen of a color CRT, but also as an etching resist for forming a shadow mask, Color filter black matrix forming resist, color filter pigment dispersion resist, printed circuit board solder resist, printed circuit board etching resist, printed circuit board dry film resist, interlayer insulating material, liquid crystal transparent conductive film (ITO) patterning Resist, photosensitive printing plate, printing ink, coating material, electromagnetic wave shielding material, etc.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/027 502 G03F 7/027 502 7/30 7/30 H01J 29/32 H01J 29/32

Claims (12)

[Claims] 1. The following general formula (1) H ₂ C ＝ CH—X—NHCOCH ₃ (1) wherein X is a direct bond, a 1,4-phenylene group, a sulfonyl group or an alkylene having 1 to 5 carbon atoms. A group (provided that the alkylene group may have one ether group, carbonyl group, carbonyloxy group, oxycarbonyl group, or amide group). A) a monomer represented by the formula:
Vinyl (co) polymer having a repeating unit derived from
1) 20 to 100% by mass of at least one water-soluble vinyl selected from the group consisting of a water-soluble monomer containing an aromatic ring, a water-soluble monomer containing a heterocycle, and an acrylic water-soluble monomer having a molecular weight of 130 or more. Water-soluble vinyl (co) polymer (A2) having a repeating unit derived from a monomer (b1) 0 to 80
A photosensitive composition comprising 70 to 99% by mass of a polymer (A) consisting of 70% by mass and 1 to 30% by mass of a photosensitive compound (B) selected from an azide compound and a diazo compound. 2. The following general formula (1): H ₂ C ＨCH—X—NHCOCH ₃ (1) wherein X is a direct bond, 1,4-phenylene group, sulfonyl group or alkylene having 1 to 5 carbon atoms. A group (provided that the alkylene group may have one ether group, carbonyl group, carbonyloxy group, oxycarbonyl group, or amide group). A) a monomer represented by the formula:
Vinyl (co) polymer having a repeating unit derived from
1) 20 to 100% by mass of at least one water-soluble vinyl selected from the group consisting of a water-soluble monomer containing an aromatic ring, a water-soluble monomer containing a heterocycle, and an acrylic water-soluble monomer having a molecular weight of 130 or more. Water-soluble vinyl (co) polymer (A2) having a repeating unit derived from a monomer (b1) 0 to 80
0.5 to 50% by mass of a polymer (A) composed of 0.5% by mass, 0.002 to 20% by mass of a photosensitive compound (B) selected from an azide compound and a diazo compound, a phosphor, a metal oxide, and a metal water. A photosensitive composition comprising 99.5 to 40% by mass of one or more fine powders (C) selected from the group consisting of oxides, metal salts and pigments. 3. The composition according to claim 1, wherein said monomer (a) is N-vinylacetamide. 4. The (co) polymer (A1) comprises 20 to 99 mol% of the monomer (a) and the vinyl monomer (b) 1
2. A copolymer comprising from 1 to 80 mol%.
4. The composition according to any one of 3. 5. The composition according to claim 4, wherein said monomer (b) is said monomer (b1). 6. The polymer (A) comprises the polymer (A2)
The composition according to any one of claims 1 to 5, comprising 0% by mass. 7. The composition according to claim 1, wherein said photosensitive compound (B) is an azide compound. 8. The composition according to claim 7, wherein the azide compound is at least one water-soluble azide compound selected from the group consisting of a sulfonic acid (salt) group-containing azide compound and a carboxylic acid (salt) group-containing azide compound. Stuff. Composition. 9. The method according to claim 2, wherein the fine powder (C) is a phosphor.
The composition according to any one of claims 8 to 8. 10. The composition according to claim 2, further comprising 0.01 to 10% by mass of the dispersant (D) based on the mass of the fine powder (C). 11. The composition according to claim 1, further comprising 0.01 to 10% by mass of the adhesion improver (E) based on the mass of the polymer (A). 12. A color cathode ray tube using the photosensitive composition according to claim 1 for forming a black matrix and / or forming a fluorescent screen.