JPH11172144A - Coloring matter-dispersing composition and photosensitive colored resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition providing a dispersed type coloring pattern while keeping spectrum characteristics of a water-soluble dye, and useful for an image displaying device such as a TV by dispersing a salt of a water-soluble coloring matter and a specific amine in an organic solvent. SOLUTION: The objective composition is obtained by dispersing a salt of (A) a water-soluble coloring matter having a sulfonic acid group and (B) an amine having a skeleton structure of formula I, preferably a primary amine of formula II R1 to R5 are each H or a 1-5C alkyl; (x) is 1-8; (y) is 1-[8-(x)]; (m) is 1-3; (n) is 1-6} in an organic solvent (preferably an organic solvent without an alcoholic hydroxy group). The salt can be obtained by dissolving the component A in water if necessary by heating, regulating the pH of the solution of the component A so as to be 5-9 by a basic aqueous solution of sodium hydroxide or the like or an acidic aqueous solution of hydrochloric acid or the like, adding an aqueous solution obtained by dissolving the component B in an acid such as acetic acid to the above obtained solution with pH 5-9 under stirring, and filtering, washing and drying the precipitated product.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a color display device for a television, a video monitor, a computer, etc.
Color sensor, camera, organic solvent dispersion of a new salt useful as a dye for a color filter used in an imaging device such as a video camera, a photosensitive colored resin composition using the same, and a colored image comprising the same, and further having the same The present invention relates to an image display device and / or an image sensor.

[0002]

2. Description of the Related Art Conventionally, a color filter used for a material such as a liquid crystal display device or a solid-state imaging device is formed by dyeing a pattern on a dyeable resin by using a photoresist, or forming a pattern by dyeable photoresist. And then dyed. However, this method has problems such as difficulty in cost reduction due to complicated steps due to the dyeing step and difficulty in step management such as pH and temperature control of the dyeing bath.

Therefore, for example, Japanese Patent Application Laid-Open No. 58-100107
In Japanese Patent Application Laid-Open Publication No. Hei 9 (1999) -175, a method of forming a color filter using a material in which a dye is dispersed in a silver halide emulsion is proposed. In this method, since a dye is added in advance, a colored image can be obtained by irradiating radiation and then performing a development treatment, which is promising for simplifying the process. But this material,
Although the spectral characteristics can be satisfied because the dyes used in the conventional dyeing method can be used as they are, there are disadvantages such as the expensive silver halide and the need for special equipment in the process.

[0004] On the other hand, many non-silver salt materials using a soluble dye coloring matter have been proposed. For example, JP-A-57-16
No. 407 and JP-A-57-74707 report a material in which a water-soluble dye is dissolved in an aqueous resist material and an oil-soluble dye is dissolved in an organic solvent-based resist material.
Other examples using dyes soluble in organic solvents are disclosed in JP-A-1-501973 and JP-A-2-127.
602, JP-A-4-128703, JP-A-6-9891, JP-A-6-51115, JP-A-6-59114, JP-A-6-220339, JP-A-6-230210 Gazette, JP-A-6-30
No. 0913, JP-A-7-84114, JP-A-7-72323 and the like.

[0005] However, when a dye having low solubility is used, it may be precipitated during long-term storage, and is unsuitable especially for producing a color filter for a solid-state imaging device requiring high resolution. In addition, in the method using an oil-soluble dye having a relatively high solubility, precipitation of the dye during storage can be prevented, but after forming the pattern of the first color, when further applying a different coloring composition, or overcoat layer In the providing step or the like, the dye may cause bleeding or migration, causing color mixing or contamination, which may cause a reduction in color purity.

Further, JP-A-61-77804, JP-A-61-180202, and JP-A-61-1802
The composition described in Japanese Patent Publication No. 03 is obtained by dissolving a dye in a polyimide precursor. However, these compositions use a high-boiling solvent such as N-vinylpyrrolidone to dissolve the dye and the polyimide precursor, and obtain a film of the composition on a substrate on which a color filter is to be formed. Has the disadvantage that the temperature must be increased in order to remove the solvent in the pre-baking step.

In the case of a composition containing a water-soluble dye, the dye may be eluted from the pattern in the developing step with water after the irradiation of the pattern, resulting in uneven color.

Therefore, for example, Japanese Patent Application Laid-Open No. 60-237403.
Japanese Patent Application Laid-Open No. HEI 4-163552 proposes a method of forming a pattern using a photoresist in which a pigment is dispersed and directly forming a color filter. In this method, since a colored insoluble pigment is added in advance, a colored pattern is obtained by irradiating ultraviolet rays and then removing the uncured portion with a developing solution, which is promising for simplifying the process. However, the pigments used in these have a drawback that the types are small and the spectral characteristics cannot be satisfied.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to develop a material capable of obtaining a dispersed colored pattern while maintaining the spectral characteristics of a water-soluble dye.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention. That is, the present invention relates to (1) a water-soluble dye having a sulfonic acid group and the following formula (1)

[0011]

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A dye dispersion composition, wherein a salt with an amine having a skeletal structure represented by the following formula (1) is dispersed in an organic solvent: (2) the amine is a primary amine (1). The dye dispersion composition, (3) the primary amine is represented by the following formula (2)

[0013]

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(Wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each represent a hydrogen atom or a C ₁ -C ₅ alkyl group;
x is an integer of 1 to 8, y is an integer of 1 to (8-x), m is 1
An integer of 1 to 3, and n is an integer of 1 to 6. And (4) the primary amine is a compound represented by the following formula (3):

[0015]

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The dye dispersion composition of (2), which is a compound represented by the formula (5), which is dissolved in an organic solvent having an alcoholic hydroxy group (5): A dye dispersion composition according to any one of (6) to (5), an alkali-soluble resin, a photosensitive colored resin composition containing a compound capable of causing a crosslinking reaction by radiation, (7) A color filter having a cured layer of the nonvolatile component of the photosensitive colored resin composition according to (6), (8) an image display device or an image pickup device having the color filter according to (7), (9)
(6) A colored image forming method, wherein a colored pattern is formed by a photolithographic method using the photosensitive colored resin composition described in (6).

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The salt used in the present invention comprises a water-soluble dye having a sulfonic acid group and an amine having a skeleton represented by the above formula (1). The amine having a skeletal structure represented by the above formula (1) is a compound in which a primary amino group is bonded to the skeleton structure represented by the above formula (1) directly or via a bonding chain. Examples of the bonding chain include a C1 to C5 alkylene chain such as methylene, ethylene, propylene, butylene, and pentylene, and methylene is preferable. This amine is a compound that is soluble in acidic water and hardly soluble in alkaline water.

Examples of the amine having a skeletal structure represented by the above formula (1) include a compound represented by the above formula (2). R ₁ , R ₂ , R ₃ , R ₄ , R in the formula (2)
Examples of the alkyl group in ₅ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a ter-butyl group, an n-pentyl group, and an isoamyl group.

In the above formula (2), R ₁ , R ₂ ,
As a preferable combination of R ₃ , R ₄ , R ₅ , m, n, x, and y, R ₁ and R ₃ are a methyl group, R ₂ and R ₄ are a hydrogen atom, R ₅ is an isopropyl group, and m, n, x, and y are all 1. Specifically, abiethylamine represented by the above formula (3) can be mentioned.

Examples of the water-soluble dye having a sulfonic acid group used in the present invention include acid dyes and direct dyes. When acid dye is exemplified by color index number,

C. I. Acid Yellow 1,3,4,5,7,7: 1,9,11,14,17,
17: 1, 18, 19, 23, 23: 1, 24, 25,
25: 1, 27, 29, 29: 1, 34, 36, 38,
40, 40: 1, 41, 42, 44, 48, 49, 5
3,54,56,57,59,60,61,63,6
4, 65, 65: 1, 72, 73, 75, 76, 78,
79, 83, 96, 98, 99, 104, 105, 10
7,110,112,114,116,116: 1,1
17, 119, 123, 127, 128, 131, 13
2,133,135,136,137,141,14
2,143,151,155,157,158: 1,1
59, 161, 165, 166, 167, 169, 17
2,174,176,184,185,189,19
3,194,196,197,199,200,20
3,204,207,208,214,215: 1,2
16, 218, 219, 219: 1, 220, 221,
228, 230, 231, 232, 235, 236, 2
37,239,240,241,242,243,24
4,245,246,247,248,249,25
0,251,252

C. I. Acid Orange 1,3,5,6,7,8,10,10: 1,11,1
2,14,17,19,20,24,25,28,3
3, 39, 43, 45, 47, 51, 51: 1, 52,
56, 60, 61, 62, 63, 64, 67, 69, 7
0, 74, 77, 78, 80, 81, 82, 85, 8
6,87,87: 1,88,88: 1,89,93,9
4,95,96,102,105,106,107,1
08, 116, 122, 124, 127, 128, 13
0,134,135,140,141,142,14
4,145,149,154,155,156,15
9,160,161,162,166,168,17
0,171,172,173

C. I. Acid Red 1,4,5,6,7,8,9,10,13,14,1
7, 18, 24, 26, 27, 29, 32, 33, 3
5,37,40,41,42,44,49,50,5
1,51: 1,52,56,57,66,70,73,
80, 82, 85, 87, 88, 89, 91, 92, 9
3,94,95,97,98,99,106,111,
114, 115, 116, 117, 118, 119, 1
19: 1, 127, 128, 129, 131, 134,
135,137,138,141,143,145,1
48,150,151,154,158,167,17
0,174,176,179,180,182,18
3,184,186,191,194,195,19
9, 201, 209, 211, 211: 1, 213, 2
13: 1, 214, 215, 217, 219, 221
225, 225: 1, 226, 227, 228, 23
4,246,247,249,251,252,25
4,256,257,259,260,261,26
2,263,264,265,266,274,27
6,277,278,279,281,282,28
3,289,296,299,300,301,30
3,307,308,310,314: 1,315,3
16,316: 1,317,318,321,322
331,336,337,341,353,354,3
55, 356, 357, 359, 360, 361, 36
2,364,366,374,382,383,38
4,388,389,392,395,396,39
7,399,400,403,404,405,40
7,410,412,413,414,415,41
6,417,418,419,420,421,42
2,423,424,425,426,427,42
8,429,430,431,432,433

C. I. Acid Violet 1,3,5: 1,6,7,9,12,13,15,1
7, 19, 21, 31, 34, 41, 42, 43, 4
7, 48, 49, 54, 56, 58, 66, 68, 7
5,78,80,84,85,87,89,90,9
7, 102, 103, 104, 105: 1, 106, 1
09, 120, 121, 122, 126, 128, 12
9

C. I. Acid Blue 1,3,4,5,6,7,9,13,15,20,2
2,23,25,27,29,40,41,43,4
5, 47, 48, 59, 61: 1, 62, 72, 74,
78, 80, 82, 83, 89, 90, 92, 93, 9
3: 1,100,102,103,104,106,1
10, 112, 113, 116, 118, 119, 12
0, 123, 126, 127, 127: 1, 129, 1
29: 1, 133, 134, 138, 140, 142,
145, 147, 151, 156, 158, 158:
1,158: 2,161,167,168,170,1
71,172,175,177,182,183,18
5,191,192,193,198,199,20
1,203,204,205,207,208,20
9,213,220,221,224,225,22
7,229,229: 1,230,231,232,2
34,235,239,243,245,247,24
9,250,254,258,260,264,27
0,274,276,277,278,279,28
0, 281, 283, 284, 285, 288, 29
0,296,298,300,312,314,31
5,317,321,324,327,328,33
0,331,333,335,336,338,34
0,341,342,343,344,345,34
6,348,349,350,351,352

C. I. Acid Green 1,3,5,9,12,16,19,20,25,2
6, 27, 28, 35, 40, 40: 1, 41, 43,
50, 51, 52, 53, 60, 61, 65: 1, 6
6,68: 1,70: 1,73,79,81,82,8
4,87: 1,91,92,94,99,100,10
2,103,104,106,107,108,10
8: 1, 109, 111, 112, 114, 115, 1
17, 118, 119, 120

C. I. Acid Brown 2,4,6,10,11,13,14,15,17,1
9, 19: 1, 20, 21, 24, 28, 30, 37,
40, 43, 44, 45, 46, 47, 48, 50, 5
2,53,58,59,64,65,68,69,7
0, 71, 72, 73, 74, 75, 77, 78, 8
0,83,84,85,88,96,97,98,10
0, 101, 102, 103, 104, 105, 10
6,107,107: 1,108,108: 1,11
0,110: 1,112,112: 1,113,11
3: 1, 119, 121, 122, 125, 126, 1
27,133,134,135,136,137,13
8,139,140,141,142,147,15
6,157,159,160,161,162,16
5,167,174,175,188,188: 1,1
89, 191, 194, 196, 213, 214, 21
5,216,216: 1,217,218,223,2
24,226,227,228,231,232,23
5,237,238,239,240,248,25
1,253,254,258,264,266,26
7,268,270,276,282,282: 1,2
83,284,286,287,289,290,29
4,297,298,298: 1,301,303,3
04,311,314,321,322,324,32
5,326,327,328,330,331,33
2,332: 1,333,338,341,342,3
43,343: 1345,347,348,349,3
51,354,355,356,357,358,35
9,360,361,362,363,364,36
5,366,373,380,381,382,38
3,384,386,387,390,392,39
5,396,397,402,403,404,40
6,408,409,413,414,415,41
6,417,418,419,420,422,42
5,427,428,429,430,431,43
2,433,434,435,436,437,43
8,439,440

C. I. Acid Black 1,2,7,9,21,24,26,29,31,4
1, 47, 48, 50, 52, 52: 1, 58, 60,
60: 1, 61, 62, 63, 63: 1, 63: 2, 6
4,65,71,75,76,77,78,79,8
2,83,84,92,94,102,107,10
9,110,112,113,115,118,11
9, 121, 122, 127, 128, 131, 13
1: 1,132,139,140,155,157,1
59,164,170,172,173,179,18
0,187,187: 1,189,191,192:
2,194,196,197,199,207,20
8,209,210,213,215,217,21
8,220,221,222,224,225,22
6,227,228 and the like, but is not limited thereto.

As a direct dye, a color index number is exemplified.

C. I. Direct Yellow 1,2,4,5,6,6: 1,8,9,11,12,1
4,17,22,24,26,27,28,29,3
0, 33, 34, 39, 44, 48, 49, 50, 5
0: 1, 53, 54, 58, 68, 83, 84, 86,
87, 93, 95, 96, 98, 99, 100, 10
3,105,105: 1,106,107,109,1
10, 118, 126, 127, 130, 132, 13
3,134,137,137: 1,138,139,1
42, 144, 147, 148, 148: 1, 149,
150, 152, 153, 154, 157, 159, 1
60, 161, 162, 163, 164, 165

C. I. Direct Orange 1,6,7,8,10,15,17,25,26,2
9, 29: 1, 32, 34, 35, 37, 37:13
9, 40, 41, 46, 49, 51, 57, 61, 6
2: 1, 70, 72, 73, 80, 102, 106, 1
07, 108, 118, 121

C. I. Direct Red 1,2,4,7,9,10,11,13,16,17,
20, 21, 22, 23, 24, 26, 28, 31, 3
6, 37, 38, 39, 4445, 46, 47, 54,
59, 62, 63, 67, 72, 75, 76, 79, 8
0, 81, 83, 83: 1, 84, 89, 92, 95,
99, 107, 111, 112, 118, 121, 12
3,126,127,127: 1,149,153,1
55,173,176,184,187,195,20
5,207,209, 211,212,216,21
7,218,221,223,224,225,22
6,227,230,232,233,236,23
8,239,240,241,242,243,25
0, 251, 252, 253, 254, 255, 25
7,258,259,260,261

C. I. Direct Violet 1,6,7,9,12,14,21,22,35,4
0, 41, 46, 47, 48, 51, 53, 56, 6
2,66,83,93,94,95,98,100,1
02, 103, 104

C. I. Direct Blue 1,2,3,6,8,8: 1,9,10,14,15,
21, 22, 25, 35, 54, 55, 59, 65, 6
7, 68, 70, 71, 74, 75, 76, 77, 7
8,80,80: 1,81,84,85,86,87,
90,94,95,96,98,100,106,10
8, 109, 120, 120: 1, 121, 126, 1
50, 151, 154, 158, 158: 1, 160,
162,165,168,173,189,191,1
92,193,199,200,201,202,20
3,207, 211, 212, 213, 214, 21
5,218,219,222,225,229,23
6,237,243,244,248,249,25
1,252,253,255,256,257,26
1,262,265,267,270,273,27
4,277,278,281,283,284,28
5,286,288,289,290,291,29
2,293,294,295,296,297

C. I. Direct Green 1,6,8,8: 1,26,27,28,29,30,
31, 47, 51: 1, 59, 66, 67, 68, 6
9, 80, 83, 84, 85, 85: 190, 92, 9
4,95,96,97,98,99

C. I. Direct Brown 1,1: 2,2,6,14,25,27,30,31,
33, 39, 44, 44: 1, 51, 53, 57, 5
9, 61, 78, 79, 80, 95, 100, 101,
103, 106, 111, 112, 113, 115, 1
16, 154, 157, 169, 170, 172, 18
4,195,200,208,209,210,21
2,214,218,219,221,222,22
3,225,229,230,231,232,23
5,238,240,241

C. I. Direct Black 4,5,9,11,14,17,19,19: 1,2
2,28,29,32,36,38,49,51,5
6,62,71,74,75,80,91,94,10
1,103,108,112,113,115,11
7, 118, 121, 122, 132, 146, 15
0,154,155,159,160,161,16
2: 1,163,164,165,168,169,1
70,171,173,174,175,176,17
7, 178, 179, 180, etc., but are not limited thereto.

The salt used in the present invention can be obtained, for example, as follows. That is, the dye having a sulfonic acid group is dissolved in water by heating if necessary, and a basic aqueous solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, , Hydrochloric acid, sulfuric acid, acetic acid
H is adjusted to 5 to 9, and then, while stirring the solution, an aqueous solution in which an amine having a skeleton structure represented by the above formula (1) is dissolved with an acid such as acetic acid has a sulfonic acid group equivalent per molecule of the dye. More than one minute, the precipitated product is collected by filtration, washed with water,
It may be dried.

The obtained salt is soluble in an organic solvent having an alcoholic hydroxy group. However, benzene solvents such as benzene, toluene and xylene, cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and butyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate and the like Propylene glycol monoalkyl ether acetates, methyl methoxypropionate, methyl ethoxypropionate, propionates such as ethyl ethoxypropionate, methyl acetate, ethyl acetate, acetates such as amyl butyl acetate, acetone, methyl ethyl ketone, Organic solvents without alcoholic hydroxy groups such as ketones such as methyl butyl ketone and pure water Shows little solubility Te.

The dye dispersion composition of the present invention is prepared by dispersing the above salt and a dispersant such as an anionic, cationic or nonionic polymer surfactant in an organic solvent having no alcoholic hydroxy group as exemplified above. And dispersing using a dispersing machine such as a ball mill, a sand mill, a dissolver, a two-roll or a three-roll. The amount of the dispersant added at this time depends on the particle size of the pigment and the molecular weight of the dispersant, but is 1 to 40% by weight based on the above-mentioned salt. When a polymer dispersant which may gel by heat during dispersion is used, a thermal polymerization inhibitor such as hydroquinone may be added as necessary.

The photosensitive colored resin composition of the present invention contains the above-described dye dispersion composition, an alkali-soluble resin, and a compound capable of causing a crosslinking reaction by radiation. Examples of the alkali-soluble resin used here include a polymer compound having a phenolic hydroxy group such as polyvinyl phenol and a novolak resin, and a resin having a carboxyl group.

Examples of the resin having a carboxyl group include a compound having a (meth) acrylic acid unit, a hydrolyzate of a copolymer compound of maleic anhydride and another monomer, and the copolymer compound into alcohols and amines. And a resin having a partial ester or partial amide unit obtained by ring opening. Examples of the copolymerized compound of maleic anhydride and another monomer used to obtain the resin include, for example, a copolymerized compound of a monomer of styrenes such as styrene and α-alkylstyrene or a derivative thereof and maleic anhydride. can give. Examples of alcohols used to obtain a resin having a partial ester unit include alcohols such as methanol, ethanol, and propanol, 2-hydroxyethyl (meth) acrylate, pentaerythritol triacrylate, and polyethylene glycol mono (meth) acrylate. (Meth) acrylic acid esters in which an alcoholic hydroxy group remains. Examples of amines used to obtain a resin having a partial amide unit include aniline and benzylamine.

Examples of the compound having a (meth) acrylic acid unit include (meth) acrylic acid alone or monomers such as ethylene, vinyl acetate, styrene, (meth) acrylonitrile, and (meth) acrylic acid ester. Compounds obtained by copolymerizing (meth) acrylic acid by a method such as radical polymerization or ionic polymerization can be used.

Compounds capable of causing a crosslinking reaction by radiation used in the photosensitive colored resin composition of the present invention include:
Bisphenol-A type epoxy resin, bisphenol-
F type epoxy resin, bisphenol-S type epoxy resin, novolak type epoxy resin, polycarboxylic acid glycidyl ester, polyol glycidyl ester, aliphatic or alicyclic epoxy resin, amino epoxy resin, triphenol methane type epoxy resin, dihydroxybenzene type Epoxy (meth) acrylate resin obtained by reacting a glycidyl group such as epoxy resin with (meth) acrylic acid, lower alcohol such as methanol, ethanol, propanol, or (poly) ethylene glycol, (poly) propylene glycol, glycerin, Acrylate resins obtained by reacting polyhydric alcohols such as methylolpropane, pentaerythritol and dipentaerythritol with (meth) acrylic acid, N-methylolmelamine, N-methylol Azoguanamine, acrylate resin obtained by reacting (poly) N-methylol (meth) acrylamide with (meth) acrylic acid, (di) azidobenzophenone, (di) azidochalcone, (di) azidostilbene, (di) (Di) azide compounds such as azidobenzalcyclohexanone and the like. These compounds can be used alone or in combination of two or more as necessary.

The photopolymerization initiator used in the photosensitive colored resin composition of the present invention includes benzyl, benzoin methyl ether, benzoin isopropyl ether, benzoin butyl ether, benzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzoyl Benzoic acid, esterified product of benzoylbenzoic acid, 4-benzoyl-4′-methyldiphenylsulfide, benzyldimethylketal, 2-butoxyethyl-4-methylaminobenzoate, chlorothioxanthone, methylthioxanthone, ethylthioxanthone, isopropylthioxanthone, dichlorothioxanthone , Dimethylthioxanthone, diethylthioxanthone, diisopropylthioxanthone, dimethylaminobenzoate, dimethylaminobenzoate isoamyl Ester, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane-1-
On, 1-hydroxycyclohexyl phenyl ketone,
2-hydroxy-2-methyl-1-phenylpropane-
1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, methylbenzoyl isoformate, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane- 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′- Tetraphenylbisimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (4-methoxyphenyl) bisimidazole, 2,4-bis (trichloromethyl) -6- ( 4'-methoxyphenyl) -1,
3,5-s-triazine, 2,4,6-tris (trichloromethyl) -1,3,5-s-triazine, 2,4-
Bis (tribromomethyl) -6- (4′-methoxyphenyl) -1,3,5-s-triazine, 2,4,6-tris (tribromomethyl) -1,3,5-s-triazine, Tribromomethylphenylsulfone and the like. These compounds can be used alone or in combination of two or more as necessary.

The amount of each component used in the photosensitive colored resin composition of the present invention is such that the total solid content contained in the composition is 100%.
In terms of parts by weight, the salt is 1 to 30 parts by weight, preferably 5 to 25 parts by weight, and the alkali-soluble resin is
0 parts by weight, preferably 20 to 70 parts by weight, 2 to 50 parts by weight, preferably 5 to 40 parts by weight of a compound capable of causing a crosslinking reaction by radiation, and 0 to 40 parts by weight of a photopolymerization initiator.
Parts by weight, preferably 0 to 30 parts by weight are desirable.

Using the obtained photosensitive colored resin composition, a colored pattern can be obtained by a photolithographic method. That is, on a substrate such as a chromium substrate, a glass substrate, and a silicon wafer, by a spin coating method, a roll coating method, a printing method, a coating method such as a bar coating method, so that the film thickness is usually 0.3 to 10 μm. Apply, surface temperature 5
Soft-baking is performed on a hot plate at 0 to 130 ° C. to form a colored photosensitive film. This film is irradiated with light (for example, X-rays, ultraviolet rays, visible rays, etc.) through a mask on which a desired pattern such as a dot pattern or a stripe pattern is drawn using an exposure apparatus such as a projection aligner or a stepper. Next, development processing is performed with alkaline water to remove unirradiated portions to form a colored pattern. Thereafter, processing such as post-exposure and post-baking is performed to obtain a colored image of the present invention.

The color filter comprising a colored image of the present invention is obtained by providing a cured layer of the nonvolatile component of the above-mentioned photosensitive colored resin composition on a substrate. Using a photosensitive colored resin composition containing a dye of each color of cyan, magenta, and yellow having a complementary color relationship with green, blue, or their complementary colors, the above-described photolithographic method can be repeated for each color.

An image display device having a color filter of the present invention is, for example, a liquid crystal display device in which a backlight portion, a polarizing film portion, a liquid crystal portion, a color filter portion of the present invention, a polarizing film portion, and the like are laminated in this order. In the case of an image pickup device, the color filter portion of the present invention is formed on a charge transfer device formed on a semiconductor such as silicon, a phototransistor, a protective layer for protecting a photodiode, and the like, and is manufactured. You.

[0050]

EXAMPLES The present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 (Cyan Dye Dispersion Composition) To a 10 l beaker was added 3400 ml of water. I. Ac
Add 180 g of id Blue 185, and raise the temperature to 65.
The temperature was raised to ℃ to completely dissolve. Then the pH of this solution was adjusted to 8
And 1010 g of a solution composed of 140 g of the compound of the formula (3), 30 g of acetic acid, and 700 g of water was gradually added. After completion of the dropwise addition, the mixture was further stirred for 2 hours, and the precipitated product was collected by filtration, washed with hot water, dried and pulverized to obtain a salt used in the present invention. 10 g of this salt, Solsperse 24000 (trade name: manufactured by Zeneca)
Polymer dispersant) 2 g, cyclohexanone 11.5 g, propylene glycol monomethyl ether acetate 2
6.5 g was dispersed in a bead mill to obtain a dye dispersion composition of the present invention.

Example 2 (Yellow Dye Dispersion Composition) To a 5 l beaker was added 2000 ml of water. I. Aci
180 g of Yellow 110 was added, and the temperature was 7
The temperature was raised to 0 ° C. to dissolve completely. Next, the pH of this solution was adjusted to 9, and 140 g of the compound of the formula (3), 30 g of acetic acid,
710 g of a solution consisting of 700 g of water was slowly added. After completion of the dropwise addition, the mixture was further stirred for 2 hours, and the precipitated product was collected by filtration, washed with hot water, dried and pulverized to obtain a salt used in the present invention. 10 g of this salt, Solsperse 24000 (trade name: manufactured by Zeneca)
Polymer dispersant) 2 g, cyclohexanone 11.5 g, propylene glycol monomethyl ether acetate 2
6.5 g was dispersed in a bead mill to obtain a dye dispersion composition of the present invention.

Example 3 (Yellow Dye Dispersion Composition) To a 5 l beaker was added 2000 ml of water. I. Dir
ect Yellow 142 was added, and the temperature was raised to 70 ° C. to complete dissolution. Then the pH of this solution
Was adjusted to 8, 140 g of the compound of the formula (3), and acetic acid 30
g and a solution consisting of 700 g of water were gradually added to 1000 g. After completion of the dropwise addition, the mixture was further stirred for 2 hours, and the precipitated product was collected by filtration, washed with hot water, dried and pulverized to obtain a salt used in the present invention. 10 g of this salt, Solsperse 24000 (trade name:
Zeneca polymer dispersant 2 g, cyclohexanone 1
1.5 g and propylene glycol monomethyl ether acetate (26.5 g) were dispersed in a bead mill to obtain a dye dispersion composition of the present invention.

Example 4 (Red Dye Dispersion Composition) To a 5 l beaker was added 1000 ml of water. I. Aci
200 g of d Red 257 was added, and the temperature was raised to 70 ° C. to complete dissolution. Next, the pH of this solution was adjusted to 8, and 140 g of the compound of the formula (3), 30 g of acetic acid, and 70 g of water were added.
820 g of a solution consisting of 0 g was gradually added. After completion of the dropwise addition, the mixture was further stirred for 2 hours, and the precipitated product was collected by filtration, washed with hot water, dried and pulverized to obtain a salt used in the present invention. This salt 10
g, Solsperse 24000 (trade name: polymer dispersant manufactured by Zeneca), 21.5 g, cyclohexanone 11.5 g, propylene glycol monomethyl ether acetate 26.5
g was dispersed in a bead mill to obtain a dye dispersion composition of the present invention.

Example 5 (Magenta dye dispersion composition) 1250 ml of water was added to a 5 l beaker, and C.I. I. Aci
100 g of d Red 289 was added, and the temperature was raised to 60 ° C. to complete dissolution. Next, the pH of this solution was adjusted to 9, and 320 g of the compound of the formula (3), 30 g of acetic acid, and 70 g of water were added.
710 g of a solution consisting of 0 g was gradually added. After completion of the dropwise addition, the mixture was further stirred for 2 hours, and the precipitated product was collected by filtration, washed with hot water, dried and pulverized to obtain a salt used in the present invention. This salt 10
g, Solsperse 24000 (trade name: polymer dispersant manufactured by Zeneca), 21.5 g, cyclohexanone 11.5 g, propylene glycol monomethyl ether acetate 26.5
g was dispersed in a bead mill to obtain a dye dispersion composition of the present invention.

Example 6 (Photosensitive magenta resin composition) Benzyl methacrylate 7 was used as an alkali-soluble resin.
4.6 g of a polymer compound having a weight average molecular weight of 30,000 consisting of 0 mol% and 30 mol% of methacrylic acid, and a compound capable of causing a crosslinking reaction by radiation, Kayarad DP
HA (brand name: Nippon Kayaku acrylate resin) 4.2
g parts by weight, Irgacure 369 as a photopolymerization initiator
(Product name: Ciba Geigy photopolymerization initiator) 1.5 g,
0.75 g of Kayacure DETX-S (trade name: Nippon Kayaku photopolymerization initiator) and 0.75 g of biimidazole (trade name: Kurokin Kasei Co., Ltd.) are added to 45 g of propylene glycol monomethyl ether acetate, and then 7.5 g of the magenta dye dispersion composition obtained in Example 5
Was added and mixed well, and after further adding Surflon S-383 (trade name: a surfactant manufactured by Seimi Chemical Co., Ltd.),
The mixture was filtered through a filter having a pore size of 2.5 μm to obtain a photosensitive colored resin composition (magenta) of the present invention.

Example 7 (Magenta color image formation) Kayamirror UC-1 (trade name: Nippon Kayaku thermosetting protective film) was applied to a thickness of 1 μm on a bare silicon wafer, and hot surface temperature of 220 ° C. Heating was performed on the plate for 5 minutes to form a protective film layer. The photosensitive colored resin composition obtained in Example 6 was spin-coated on this protective film so as to have a thickness of 1 μm, and soft-baked on a hot plate having a surface temperature of 80 ° C. for 90 seconds. Next, the film was exposed to contact using a chrome mask on which a resolution test pattern was drawn. As a light source, a UV-35 filter and a V-42 filter made by Toshiba Glass were attached to a 500 W ultra-high pressure mercury lamp, and a wavelength of 365 nm was taken out. The irradiation energy was 150 mJ / cm ² . Next, after developing with Kayamirror DVL-T50D (trade name: Nippon Kayaku organic alkali developing solution) at a temperature of 25 ° C for 60 seconds, washing with water and post-baking for 5 minutes on a hot plate having a surface temperature of 200 ° C. Was performed to obtain a cured film.
Observation with an optical microscope revealed that a 2 μm pattern without residue was resolved. Further, when the color characteristics were measured, they showed very good spectral characteristics.

Example 8 (Preparation of Complementary Color Filter) The color filter dye obtained in Example 1 or the color filter dye obtained in Example 2 was replaced with the color filter dye of Example 6, respectively. Cyan and yellow photosensitive colored resin compositions were obtained. Using these photosensitive colored resin compositions, a complementary color filter was produced. That is, on the magenta pattern obtained in Example 7, a cyan photosensitive resin composition was applied, and soft bake, pattern exposure, development, and post bake were performed. Further, yellow was applied on the magenta and cyan patterns. The photosensitive resin composition was applied and the same operation was performed to obtain a complementary color filter. Observation with an optical microscope revealed that the color filter was excellent in color purity without mixing and decolorization.

[0059]

According to the present invention, a dispersion-type colored pattern can be obtained while maintaining the spectral characteristics of the water-soluble dye. The color filter produced using the photosensitive colored resin composition using the dye dispersion composition of the present invention has no color mixing, excellent color purity, and excellent spectral characteristics. , Color filters used for color display devices, image sensors such as color sensors, video cameras, digital cameras, etc. can be manufactured with good quality.

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁶ Identification code FI G03F 7/004 505 G03F 7/004 505

Claims (9)

[Claims] 1. A water-soluble dye having a sulfonic acid group and the following formula (1): Wherein a salt with an amine having a skeletal structure represented by the formula: is dispersed in an organic solvent. 2. The dye dispersion composition according to claim 1, wherein the amine is a primary amine. 3. The method of claim 1, wherein the primary amine has the following formula (2): (Wherein, R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ each represent a hydrogen atom or a C ₁ -C ₅ alkyl group, x is an integer of 1-8, and y is 1- (8-x ), M is an integer of 1-3,
n is an integer of 1 to 6. 3. The dye dispersion composition according to claim 2, which is a compound represented by the formula: 4. The primary amine is represented by the following formula (3): ## STR3 ## The dye dispersion composition according to claim 2, which is a compound represented by the formula: 5. The pigment dispersion composition according to claim 1, wherein the organic solvent is an organic solvent having no alcoholic hydroxy group. 6. A photosensitive colored resin composition comprising the dye dispersion composition according to claim 1, an alkali-soluble resin, and a compound capable of causing a crosslinking reaction by radiation. 7. A color filter having a cured layer of a nonvolatile component of the photosensitive colored resin composition according to claim 6. 8. An image display device or an image sensor having the color filter according to claim 7. 9. A method for forming a colored image, comprising forming a colored pattern by photolithography using the photosensitive colored resin composition according to claim 6.