JPH11258794A - Color image forming material, color image forming photosensitive solution, photosensitive element, method for forming color image and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance the dispersibility and photosensitivity of a pigment by incorporating a resin having an acid value and an unsaturated equivalent each in a specified range in the photosensitive solution for forming a color image. SOLUTION: This photosensitive solution for forming an image contains a monomer containing a resin and a dye and a monomer having at least one photopolymerizable unsaturated bond in one molecule and a photoinitiator, and the resin to be used for forming a color image has an acid value of 20-200, preferably, 40-180, and an unsaturated equivalent of 200-1,000, preferably, 230-800, especially, 250-750, and it is not especially limited as far as it has pigment dispersibility and film forming ability and developability in addition to the above properties.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a material for forming a colored image, a photosensitive liquid for forming a colored image, a photosensitive element, a method for producing a colored image, and a method for producing a color filter.

[0002]

2. Description of the Related Art In recent years, color filters have been frequently used in liquid crystal display devices, sensors, color separation devices, and the like.
Conventionally, as a method of manufacturing this color filter, a method of patterning a dyeable resin, for example, natural gelatin or casein, and then dyeing the pattern with a dye to obtain pixels has been used. However, the pixel obtained by this method has a problem that heat resistance and light resistance are low due to restrictions on materials. Therefore, recently, a method of using a photosensitive material in which a pigment is dispersed has been attracting attention for the purpose of improving heat resistance and light resistance, and many studies have been made. According to this method, it is known that the manufacture is simplified, and the obtained color filter is stable and has a long life.

However, techniques for stably dispersing the pigment are difficult, and it is particularly difficult to select a dispersing resin which has a great influence on the dispersibility of the pigment. It is also important to increase the photosensitivity of a photosensitive resin film containing a large amount of pigment.

[0004]

The invention according to claims 1 to 3 provides a colored image forming material which has improved pigment dispersibility and light sensitivity, which are problems of the photosensitive resin in which the pigment is dispersed. Things. The invention according to claim 4 provides a pigment dispersibility, which is a problem of a photosensitive resin in which a pigment is dispersed,
An object of the present invention is to provide a photosensitive liquid containing a colored image forming material having improved light sensitivity. The invention according to claim 5 or 6 is:
An object of the present invention is to provide a photosensitive element having a photosensitive layer containing a colored image forming material with improved pigment dispersibility and photosensitivity, which are problems of a photosensitive resin in which a pigment is dispersed. The invention according to claim 7 provides a method for producing a colored image in which the pigment of the coating film of the pixel is well dispersed and has excellent optical characteristics. An eighth aspect of the present invention is to provide a high-quality color filter in which the pigment of the coating film of the pixel is well dispersed and which has excellent optical characteristics.

[0005]

The present invention provides a resin, a dye,
In a colored image forming photosensitive solution containing a monomer containing one or more photopolymerizable unsaturated bonds in a molecule and a photoinitiator, the resin has an acid value of 20 to 200 and an unsaturated equivalent of 200 to 1
000 resin.
Further, the present invention provides the above-mentioned colored image forming material,
The present invention relates to a colored image forming material in which the resin has a weight average molecular weight of 1,500 to 200,000.

In the present invention, the resin for the colored image forming material may be represented by the following general formula (I):

Embedded image (Wherein, R ¹ represents a hydrogen atom or a methyl group,
R ² and R ³ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms) and the following general formula (I
I)

Embedded image (Wherein, R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a group having a photoreactive unsaturated bond, and R ⁶ represents a hydrogen atom or a carbon atom having 1 to 1 carbon atoms. 1
2) represents a repeating unit represented by formula (I) / general formula (II) in a ratio of 1/1 to 5/1 (molar ratio).
Wherein at least a part of the repeating units represented by the general formula (II) has R ⁴ and R ⁵ in the general formula (II).
At least one of which is a resin which is a repeating unit representing a group having a photoreactive unsaturated bond.

The present invention also relates to a colored image forming photosensitive liquid comprising these colored image forming materials, further containing an organic solvent, and dissolving or dispersing components other than the organic solvent in the organic solvent. The present invention also relates to a photosensitive element having a photosensitive layer containing any of the above-mentioned colored image forming materials laminated on a support. The present invention also relates to a photosensitive element in which a cover film is laminated on a photosensitive layer in the photosensitive element. Further, the present invention relates to a method for producing a colored image, comprising a colored image forming step of laminating a photosensitive layer containing any of the above colored image forming materials on a substrate and exposing and developing the photosensitive layer. The present invention also relates to a method for producing a color filter, wherein a plurality of colored images are produced on the same substrate by the method for producing a colored image.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The resin used for the colored image forming material used in the present invention is a resin having an acid value of 20 to 200 and an unsaturated group equivalent of 200 to 1000. Sometimes has photosensitivity, pigment dispersibility,
There is no particular limitation as long as it has a film forming property and a developing property.
The resin has an acid value in the range of 20 to 200 from the viewpoint that the photosensitive layer has alkali developability after exposure,
It is preferably in the range of 40 to 180, and in particular, 6
It is preferably in the range of 0 to 170. If the acid value is too low, alkali developability tends to decrease, and if the acid value is too high, the shape of the image pattern after alkali development tends to be unclear. If the unsaturated equivalent is too small, it tends to partially cure when adjusting the colored image forming material or the colored image forming photosensitive liquid, particularly when the pigment is dispersed in the resin, and when the unsaturated equivalent is too large, the unsaturated equivalent is unsaturated. Improvement of photosensitivity by the introduction of a group tends to decrease in curing. Here, the unsaturated equivalent means the molecular weight of the resin per unsaturated bond. The unsaturated equivalent of the resin is 200 to
It is within the range of 1000, preferably within the range of 230 to 800, and particularly preferably within the range of 250 to 750.

As such a resin, a resin having a photopolymerizable unsaturated bond for the purpose of photosensitivity is preferably used. Preferred examples of the resin include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, α- Ethyl glycidyl acrylate,
Compounds each having one oxirane ring and one ethylenically unsaturated bond such as crotonyl glycidyl ether and monoalkyl glycidyl itaconate; allyl alcohol; 2-buten-4-ol; furfuryl alcohol;
Resin obtained by reacting a hydroxyl group such as oleyl alcohol, cinnamyl alcohol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide and a compound having one ethylenically unsaturated bond (unsaturated alcohol), a hydroxyl group A resin obtained by reacting a free isocyanate group-containing unsaturated compound with a carboxyl group-containing resin having a resin, a resin obtained by reacting a polybasic anhydride with an addition reaction product of an epoxy resin and an unsaturated carboxylic acid, a conjugated diene polymer or a conjugate Resins obtained by reacting a hydroxyl group-containing polymerizable monomer with an addition reaction product of a diene copolymer and an unsaturated dicarboxylic anhydride are exemplified.

The weight average molecular weight of the resin is 1,
It is preferably in the range of 500 to 200,000, more preferably in the range of 5,000 to 100,000, and particularly preferably in the range of 10,000 to 50,000. Weight average molecular weight of 1,50
If it is less than 0, the dispersion stability of the pigment tends to decrease, and if it exceeds 200,000, the viscosity becomes high when it is made into a photosensitive solution, and the coatability, especially the coatability when spin-coating, tends to decrease. There is. In the present specification, the weight average molecular weight is a value measured by gel permeation chromatography and converted using a calibration curve of standard polystyrene.

As the resin, a repeating unit represented by the general formula (I) and a repeating unit represented by the general formula (II) are preferably used.
Is particularly preferred in terms of pigment dispersion stability and photosensitivity in a ratio of 1/1 to 5/1 (molar ratio).

The following are more preferred as the resin. That is, (i) In the general formula (II), R ⁴ is a group having a photoreactive unsaturated bond, R ⁵ is a hydrogen atom, and R ⁶ is a hydrogen atom. (Ii) In the general formula (II), R ⁴ is a group having a photoreactive unsaturated bond, R ⁵ is a hydrogen atom or a group having a photoreactive unsaturated bond, a repeating unit in which R ⁶ is a hydrogen atom, (iii) in the general formula (II), R ⁴ and R ⁵ is each independently a hydrogen atom or a group having a photoreactive unsaturated bond, at least one of them is a group having a photoreactive unsaturated bond, and R ⁶ is a group having 1 to 12 carbon atoms.
It is preferable that the compound has a repeating unit that is an alkyl group.

As a method for producing a resin having the repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (II), for example, the resin represented by the general formula (I) or (II) Unsaturated alcohols (allyl alcohol, 2-buten-4-ol, furfuryl alcohol, oleyl alcohol, cinnamyl alcohol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate) , N
-Methylol acrylamide), an oxirane ring and ethylene are added to a resin precursor having a repeating unit represented by the general formula (I) and a repeating unit represented by the general formula (II). Compounds each having one unsaturated bond (glycidyl methacrylate,
Glycidyl acrylate, allyl glycidyl ether,
α-ethyl glycidyl acrylate, crotonyl glycidyl ether, monoalkyl monoglycidyl itaconate, etc.), and the like.

As the precursor of the resin having the repeating units represented by the general formulas (I) and (II), styrene or a derivative thereof, maleic anhydride or a monoalkyl maleate (half ester of maleic acid) ) Can be obtained by copolymerizing As the styrene derivative, for example, α-methylstyrene, m or p-
Methoxystyrene, p-hydroxystyrene, 2-methoxy-4-hydroxystyrene, 2-hydroxy-4-
Methylstyrene and the like can be mentioned. As monoalkyl maleate, for example, monomethyl maleate,
Monoethyl maleate, Mono-n-propyl maleate, Mono-isopropyl maleate, Mono-maleate
Examples thereof include n-butyl, mono-n-hexyl maleate, mono-n-octyl maleate, mono-2-ethylhexyl maleate, mono-n-nonyl maleate, and mono-n-dodecyl maleate.

The resin used in the colored image-forming material or the colored image-forming material of the present invention may be a resin having a repeating unit represented by the aforementioned general formula (I) or (II). When used, other resins may be used in combination. As the other resin, a resin other than the resin having the repeating unit represented by the general formula (I) and the general formula (II) among the above-mentioned resins is used, and further, an acrylic resin, an epoxy resin, Urethane resin, melamine resin and the like may be used. The other resin is preferably used in an amount of 50 parts by weight or less based on 100 parts by weight of the total amount of the resin.

As the dye used in the colored image forming material or the colored image forming photosensitive liquid, any of dyes and pigments can be used. However, considering heat resistance and light resistance, pigments are preferred. Is preferred. The pigment includes an inorganic pigment and an organic pigment, and any of them can be used. However, black carbon black (inorganic pigment) and an organic pigment are preferable from the viewpoint of abundant color tone. Examples of the organic pigment include azo-based, phthalocyanine-based, indigo-based, anthraquinone-based, perylene-based, quinacridone-based, methine-azomethine-based, and isoindolinone-based. When producing the color filter of the present invention, each pigment system suitable for colored images such as red, green, blue and black is used. When the photosensitive liquid for forming a colored image of the present invention is used for producing a color filter, each pigment system suitable for a colored image such as red, green, blue, and black is used.

As the red colored image, a single red pigment system may be used, or a yellow pigment system may be mixed with a red pigment system to perform toning. As red pigments, for example, CI Pigment Red 9, 12 by color index name
3, 155, 168, 177, 180, 217, 22
0, 224 and the like. As a yellow pigment, for example, CI Pigment Yellow 20, 24, 83, 93, 109, 110, 117, 1
25, 139, 147, 154 and the like. These red pigment systems and yellow pigment systems may be used as a mixture of two or more types. When a mixture of a red pigment system and a yellow pigment system is used, the yellow pigment system is used.
For a total amount of 100 parts by weight of the red pigment system and the yellow pigment system,
Preferably, it is used in an amount of 50 parts by weight or less.

As a green colored image, a single green pigment system may be used, or the above-mentioned yellow pigment system may be mixed with a green pigment system to perform toning. Examples of green pigments include CI Pigment Green 7, 36, and 37 under the color index name. These green pigment system and yellow pigment system can be used as a mixture of two or more kinds. In addition, when using a mixture of a green pigment system and a yellow pigment system, the yellow pigment system is preferably used in an amount of 50 parts by weight or less based on 100 parts by weight of the total amount of the green pigment system and the yellow pigment system. .

As the blue colored image, a single blue pigment system may be used, or a violet pigment system may be mixed with a blue pigment system for toning. As blue pigments, for example, CI Pigment Blue 15, 1
5: 3, 15: 4, 15: 6, 22, 60 and the like. Examples of purple pigments include CI Pigment Violet 19, 23, 29,
37, 50 and the like. These blue pigments and violet pigments can be used as a mixture of two or more kinds. When a mixture of a blue pigment and a violet pigment is used, the violet pigment is preferably used in an amount of 50 parts by weight or less based on 100 parts by weight of the total of the blue pigment and the violet pigment. .

As the black colored image, for example, black pigments such as carbon black, graphite, titanium carbon, black iron, and manganese dioxide are used.

The photopolymerizable unsaturated bond used in the colored image forming material or the colored image forming photosensitive solution is incorporated in the molecule by one.
Among the monomers having at least one, a monomer having one photopolymerizable unsaturated bond in the molecule includes alkyl methacrylates such as methyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate, methyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. Alkyl acrylates, aralkyl methacrylates such as benzyl methacrylate, aralkyl acrylates such as benzyl acrylate, alkoxyalkyl methacrylates such as butoxyethyl methacrylate,
Alkoxyalkyl acrylates such as butoxyethyl acrylate; aminoalkyl methacrylates such as N, N-dimethylaminoethyl methacrylate; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate; methacrylic acid esters of (diethylene glycol ethyl ether); Methacrylic acid esters of (polyalkylene glycol alkyl ether), such as methacrylic acid esters of (glycol butyl ether), methacrylic acid esters of (dipropylene glycol methyl ether), acrylic acid esters of (diethylene glycol ethyl ether), and (triethylene glycol butyl ether). (Polyalkyl) such as acrylic acid ester and acrylic acid ester of (dipropylene glycol methyl ether) Glycol alkyl ether)
(Polyalkylene glycol aryl ether) such as (meth) acrylic acid ester of (hexaethylene glycol phenyl ether), and (polyalkylene glycol aryl ether) such as (hexaethylene glycol phenyl ether) acrylate. Acrylic acid ester, dicyclopentanyl methacrylate, dicyclopentanyl acrylate, isobornyl methacrylate, methoxylated cyclodecatriene methacrylate, isobornyl acrylate, methoxylated cyclodecatriene acrylate,
Examples include fluorinated alkyl methacrylates such as glycerol methacrylate, glycerol acrylate, and heptadecafluorodecyl methacrylate, fluorinated alkyl acrylates such as heptadecafluorodecyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxyethyl acrylate.

Among monomers having one or more photopolymerizable unsaturated bonds in the molecule, two or more photopolymerizable unsaturated bonds in the molecule are used.
As the monomer having at least one, bisphenol A dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene Glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, tris (methacryloxyethyl) isocyanurate, pentaerythritol tetramethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pen Methacrylate, bisphenol A diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol diacrylate, glycerol diacrylate, neopentyl glycol diacrylate,
Polyethylene glycol diacrylate, polypropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, tris (acryloxyethyl) isocyanurate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol Hexaacrylate, dipentaerythritol pentaacrylate and the like can be mentioned.

The photopolymerizable unsaturated bond used in the colored image-forming material or the colored image-forming photosensitive liquid has two or more in its molecule.
The monomer having at least one monomer represented by the general formula (a)

Embedded image (Wherein, R represents an ethylene group or a propylene group, m and n each independently represent an integer of 1 to 20), a diacrylate of an alkylene oxide adduct of bisphenol A represented by the general formula (b) )

Embedded image (Where m and n are each independently 1 to 10
Epichlorohydrin modified product of bisphenol A and addition esterified product of acrylic acid, bisphenol A dimethacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol dimethacrylate represented by
Glycerol dimethacrylate, neopentyl glycol diacrylate, general formula (c)

Embedded image (Wherein, R represents an ethylene group or a propylene group, m and n each independently represent an integer of 1 to 20), a diacrylate of an alkylene oxide adduct of phosphoric acid represented by the general formula (d )

Embedded image (Where m and n are each independently 1 to 10
Phthalic acid-modified epichloroline and acrylic acid addition ester, polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, tetraethylene glycol diacrylate represented by the general formula (e):

Embedded image (Where m and n are each independently 1 to 20
1,6-hexanediol and an addition esterified product of acrylic acid (having two aquilyl groups in one molecule), trimethylolpropane triacrylate, pentaerythritol triacrylate, General formula (f)

Embedded image (Wherein, R represents an ethylene group or a propylene group, and three m's each independently represent an integer of 1 to 20), a triacrylate of an alkyne oxide adduct of phosphoric acid represented by the general formula ( g)

Embedded image (Wherein, R represents an ethylene group or a propylene group, m, m ′ and m ″ each independently represent an integer of 1 to 20). Triacrylate of an alkylene oxide adduct of trimethylolpropane , Tris (methacryloxyethyl) isocyanurate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and the like.
More than one species can be used in combination.

The photoinitiator used in the colored image forming material or the colored image forming photosensitive solution includes, for example, benzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4 ' -Dimethylaminobenzophenone, benzyl, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether,
Benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4-
(Methylthio) phenyl] -2-morpholino-1-propane, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone , 9,10-phenanthraquinone, 1,2-benzanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2-
(O-chlorophenyl) -4,5-diphenylimidazole dimer and the like. These photoinitiators are used alone or in combination of two or more.

The mixing ratio of the resin, pigment, monomer having one or more photopolymerizable unsaturated bonds in the molecule and photoinitiator used in the colored image forming photosensitive liquid is based on the total amount of these. a) The resin is preferably 10-85% by weight,
More preferably, 20 to 60% by weight, particularly preferably 25% by weight.
(B) the pigment is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, particularly preferably 15 to 30% by weight, and (c) a photopolymerizable unsaturated bond in the molecule. The monomer having one or more is preferably 2 to 50% by weight, more preferably 5 to 40% by weight, particularly preferably 1 to 40% by weight.
0-30% by weight, (d) the photoinitiator is preferably 0.0
The content is 1 to 20% by weight, more preferably 2 to 15% by weight, particularly preferably 5 to 10% by weight.

If the amount of the resin in the colored image forming photosensitive liquid is too small, the dispersion stability of the pigment tends to decrease. If the amount is too large, the viscosity of the photosensitive liquid becomes high, and the coating properties, especially spin coating, are increased. In this case, the applicability tends to decrease. When the amount of the pigment is too small, the color density of the image tends to be low, and when the amount is too large, the light sensitivity tends to be low. If the amount of the monomer having one or more photopolymerizable unsaturated bonds in the molecule is too small, the photosensitivity tends to be low, and if it is too large, the dispersion stability of the pigment tends to be low. Furthermore, when the photoinitiator is too small, the photosensitivity tends to decrease, and when too large, the adhesion tends to decrease.

The colored image-forming material or the colored image-forming photosensitive liquid of the present invention contains a thermal polymerization inhibitor (hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, etc.) for suppressing a dark reaction, a substrate, Titanate coupling agents (such as silane coupling agents having a vinyl group, an epoxy group, an amino group, and a mercapto group, isopropyltrimethacryloyl titanate, and diisopropylisostearoyl-4-aminobenzoyl titanate) for improving the adhesion of Surfactants to improve the smoothness of the film (fluorine, silicon,
Various additives such as a hydrocarbon-based compound) and other additives such as an ultraviolet absorber and an antioxidant can be used as needed.

Examples of the organic solvent used in the photosensitive solution for forming a colored image of the present invention include ketone compounds, alkylene glycol ether compounds, alcohol compounds, aromatic compounds, lactones and the like. Specifically, as a ketone compound, there are acetone, methyl ethyl ketone, cyclohexanone, dioxane, etc., and as an alkylene glycol ether compound, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether,
Diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol mono or dialkyl ether such as diethylene glycol dibutyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, Acetylation product of diethylene glycol monoalkyl ether such as diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl Mono or dialkyl ethers of triethylene glycol such as ether, triethylene glycol monobutyl ether, triethylene glycol dimethyl ether, triethylene glycol methyl ethyl ether, triethylene glycol diethyl ether, triethylene glycol dipropyl ether, triethylene glycol dibutyl ether, propylene Glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol methyl ethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether Propylene glycol monoalkyl ethers such as propylene glycol monoalkyl ether such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate; methyl cellosolve; Ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol mono- or dialkyl ethers such as ethylene glycol dimethyl ether. Alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, 3-methyl-3-methoxybutanol, tetrahydrofuran, and the like. As aromatic compounds, benzene, toluene, xylene, N-methyl-2-pyrrolidone, N-hydroxy Methyl-2-pyrrolidone and the like, and as the lactone, β-lactone, γ-
There are lactone and δ-lactone, and other examples include organic solvents such as 3-methyl-3-methoxybutyl acetate and ethyl acetate. These can be used alone or in combination of two or more.

Among these organic solvents, diethylene glycol mono- or dialkyl ethers, diethylene glycol mono-alkyl ether acetylates, triethylene glycol mono- or dialkyl ethers, propylene glycol mono- or dialkyl ethers, propylene glycol mono-alkyl ether acetylates ,
Lactone compounds are particularly preferred in terms of pigment dispersion stability, coating appearance, and image pattern resolution.

The organic solvent has a total solid content of 5 to 40% by weight including a resin, a dye, a monomer containing one or more photopolymerizable unsaturated bonds in a molecule and a photoinitiator in the photosensitive solution. It is preferably used as follows. If the total solid content exceeds 40% by weight, the viscosity tends to be high and the applicability tends to be poor. If the total solid content is less than 5% by weight, the viscosity tends to be low and the applicability tends to be poor.

Next, a method for producing the photosensitive liquid for forming a colored image used in the present invention will be described. The pigment is mixed and dispersed with a resin, an organic solvent, and, if necessary, a dispersant. At this time, the mixture is preferably subjected to dispersion treatment by kneading using a dispersing / kneading apparatus such as an ultrasonic dispersing machine, a three-roll mill, a ball mill, a sand mill, a bead mill, a homogenizer, and a kneader. The monomer having two or more photopolymerizable unsaturated bonds in the molecule and the photoinitiator may be mixed before or after the dispersion treatment.

Examples of the dispersant include anionic dispersants such as polycarboxylic acid type polymer surfactants and polysulfonic acid type polymer surfactants, and nonionic dispersants such as polyoxyethylene / polyoxypropylene block polymers. An organic dye derivative such as an anthraquinone-based, perylene-based, phthalocyanine-based, or quinacdrine-based organic dye into which a substituent such as a carboxyl group, a sulfonate group, a carboxylic acid amide group, or a hydroxyl group is introduced. It is preferable because the dispersibility and dispersion stability of the pigment are improved. These pigment dispersants and organic dye derivatives are preferably used in an amount of 50 parts by weight or less based on 100 parts by weight of the pigment. If it exceeds 50 parts by weight, the chromaticity tends to shift.

In the above-mentioned dispersion treatment, the whole amount of the resin may be used together with the pigment at the time of the dispersion treatment, or a part of the resin may be added after the dispersion treatment. However, it is preferable to use at least 20 parts by weight of the resin for 100 parts by weight of the pigment during the dispersion treatment. If it is less than 20 parts by weight, the dispersion stability of the pigment tends to decrease. Similarly, the entire amount of the organic solvent may be used together with the pigment during the dispersion treatment, or a part of the organic solvent may be added after the dispersion treatment. However, the organic solvent is
It is preferable to use at least 100 parts by weight at the time of the dispersion treatment based on 100 parts by weight of the total amount of the pigment and the resin at the time of the dispersion treatment. If the amount is less than 100 parts by weight, the viscosity at the time of the dispersion treatment is too high, and particularly when the dispersion is performed by a ball mill, a sand mill, a bead mill or the like, the dispersion may be difficult.

In order to laminate a photosensitive layer on a substrate using the colored image forming photosensitive liquid according to the present invention, the photosensitive liquid is applied directly to the substrate or the photosensitive liquid is applied to a support once to form a film. After that, it can be performed by laminating on a substrate or the like. The above substrate is selected depending on the application,
For example, white plate glass, blue plate glass, transparent glass plate such as silica-coated blue plate glass, polyester resin, polycarbonate resin, acrylic resin, synthetic resin sheet such as vinyl chloride resin, film or plate, aluminum plate, copper plate,
Examples include a metal plate such as a nickel plate and a stainless steel plate, other ceramic plates, and a semiconductor substrate having a photoelectric conversion element. On these substrates, a black matrix may be formed in advance by chromium evaporation or the like.

The method of applying the photosensitive liquid to the substrate includes roll coater coating, spin coater coating, spray coating, wicker coating, dip coater coating, curtain flow coater coating, wire bar coater coating, gravure coater coating, air knife coater coating, and the like. There is.
After application, it is preferable to dry at a temperature of 50 to 130 ° C. for 1 to 30 minutes. Thus, a film composed of the colored image forming material can be obtained. The thickness of the photosensitive layer formed in this manner is appropriately determined depending on the application, but is preferably 0.1 to 3 mm.
It is preferably in the range of 00 μm. When used for a color filter, the thickness is preferably in the range of 0.2 to 5 μm.

A photosensitive element can be prepared by forming a photosensitive layer on a support in the same manner as described above.
As the support, a polyethylene film, an acrylic resin film, a polyester film, or the like can be used. Further, a peelable cover film can be laminated on the photosensitive layer. As the peelable cover film, a polyethylene film, a Teflon film, a polypropylene film, surface-treated paper, or the like is used, and when peeling, the adhesive strength between the photosensitive layer and the cover film is smaller than the adhesive strength between the photosensitive layer and the support. The smaller one is selected and used. In order to laminate the photosensitive layer of the photosensitive element on the above-mentioned substrate, there is a method in which, if a cover film is provided, the photosensitive layer is laminated on the substrate after the cover film is peeled or while the cover film is peeled off, and then pressed through a roller. At this time, it is preferable to slightly heat the roller. Further, it is preferable to perform the pressure bonding under reduced pressure. The support is preferably peeled off after the photosensitive layer is laminated on the substrate.

The exposure of the photosensitive layer laminated on the substrate can be performed by irradiating the photosensitive layer with actinic rays in an image-like manner. Thereby, the film in the exposed portion can be cured. At the time of exposure, an oxygen barrier film such as polyvinyl alcohol may be formed on the surface of the film with a thickness of 0.5 to 30 μm, and the film may be exposed from above. As the light source of the actinic ray, for example, a carbon arc lamp, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a Langsten lamp, a visible light laser and the like are suitable. Using these light sources, actinic rays are irradiated imagewise by pattern exposure through a photomask, direct drawing by scanning, or the like.

Following the above exposure, a development step is performed. An aqueous solution containing an inorganic alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium metasilicate, an organic base such as monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, triethylamine, n-butylamine, or a salt. (Alkaline developer), a non-exposed portion is removed by spraying a developer such as an organic solvent or dipping in a developer to obtain a colored image pattern of a cured film corresponding to an image. After development, post-baking is preferably performed to further harden the colored image pattern. The post-bake temperature is preferably from 60 to 280C, and the heating time is preferably from about 1 to 60 minutes.

A colored image is formed by such a colored image forming process. In particular, in a method of manufacturing a color filter, it is preferable to repeat the colored image forming process for three to four different colored images. In the present invention, three to four different colored images are three colors of red, green, and blue when a red, green, and blue colored image is formed on a black matrix previously formed by chromium evaporation or the like. Shown, after forming a black matrix using a black colored image forming material, when forming a red, green, blue colored image, or after forming a red, green, blue colored image, these colored images When a black matrix is formed using a black image forming material in the gaps, black, red, green,
Shows four colors of blue. The order of forming the red, green, and blue colored images is arbitrary. The colored image is adapted to form pixels for each color.

[0040]

The present invention will be described below with reference to examples. (1) Resin to be used: Copolymer A: 50 mol% of styrene-monomaleic acid (2
-Acryloyloxyethyl) ester 30 mol% -A maleic acid derivative A 20 mol% copolymer having a weight average molecular weight of 9000, an acid value of 91 and an unsaturated equivalent of 264 The repeating unit based on the maleic acid derivative A is as follows: It has a structure.

Embedded image Copolymer B: styrene 75 mol% -maleic acid mono (2
-Acryloyloxyethyl) ester 20 mol% -Maleic acid derivative A 5 mol%, weight average molecular weight 10,000, acid value 76, unsaturated equivalent 495 copolymer

Copolymer C: 50 mol% of styrene-35 mol% of maleic acid mono (2-methacryloyloxyethyl) ester-15 mol% of maleic acid derivative B,
Copolymer having a weight average molecular weight of 12,000, an acid value of 106 and an unsaturated equivalent of 285 The repeating unit based on maleic acid derivative B has the following structure.

Embedded image

Copolymer D: styrene 75 mol% -maleic acid mono (2-acryloyloxyethyl) ester 2
5 mol%, weight average molecular weight 7000, acid value 1
06, a copolymer having an unsaturated equivalent of 526 Copolymer E: 83 mol% of styrene-monomaleic acid (2
-Acryloyloxyethyl) ester having a weight average molecular weight of 8,000, an acid value of 76, and an unsaturated equivalent of 734. Copolymer F: α-methylstyrene 50 mol% -mono (2-acryloyl maleate) Oxyethyl) ester 50
Mol%, weight average molecular weight of 12,000, acid value of 1
62, a copolymer having an unsaturated equivalent of 346

Copolymer G: 50 mol% of styrene-30 mol% of citraconic acid mono (2-acryloyloxyethyl) ester-20 mol% of citraconic acid derivative C, having a weight average molecular weight of 9000, an acid value of 86 and an unsaturated equivalent The repeating unit based on the citraconic acid derivative C has the following structure.

Embedded image (One of R and R 'is a hydrogen atom and the other is a methyl group) Copolymer H: α-methylstyrene 75 mol% -citraconic acid mono (2-acryloyloxyethyl) ester 4
0 mol%-10 mol% of citraconic acid derivative C,
Weight average molecular weight 10,000, acid value 79, unsaturated equivalent 4
74 copolymer

Copolymer I: A copolymer comprising 75 mol% of styrene-25 mol% of mono (2-acryloyloxyethyl) citraconic acid, having a weight average molecular weight of 7000, an acid value of 104 and an unsaturated equivalent of 540. Merged J: styrene 75 mol% -maleic acid mono (n
-Propyl) ester 25 mol%, weight average molecular weight 8000, acid value 119 copolymer K: styrene 75 mol% -maleic acid mono (n
(Propyl) ester, 25 mol%, weight average molecular weight: 8000, copolymer having an acid value of 116 Copolymer L: 16 mol% methacrylic acid-58 mol% methyl methacrylate-26 mol% butyl acrylate, weight average Copolymer having a molecular weight of 20,000 and an acid value of 85

Example 1 40 g of copolymer A as a resin, 25 g of Pigment Red 177 and 25 of Pigment Yellow 83 as pigments
g, 200 g of diethylene glycol dimethyl ether as an organic solvent, and this was subjected to a dispersion treatment for 2 hours using a bead mill. 30 g of trimethylolpropane triacrylate as a monomer, 6 g of benzophenone as a photoinitiator and N, N'-tetraethyl-
2,4 g of 4,4'-diaminobenzophenone and 280 g of diethylene glycol dimethyl ether as an organic solvent
Was added and mixed to obtain a photosensitive liquid for forming a colored image. When the obtained photosensitive solution was allowed to stand at 25 ° C., the number of days until secondary aggregation started to occur was defined as dispersion stability. The results are shown in Table 1. Further, the obtained photosensitive solution was applied on a glass substrate (Corning Co., trade name: 7059) by a spin coating method, and then dried at 80 ° C. for 5 minutes to form a film having a thickness of 2.0 μm.
Was formed. The appearance of the coating film at the time of application was visually evaluated, and the results are shown in Table 1.

The resulting film was imagewise exposed to 100 mJ / cm ² by means of an ultra-high pressure mercury lamp through a negative mask, and then 0.5% of polyoxyethylene nonylphenyl ether (Nonal 912A, manufactured by Toho Chemical Co., Ltd.) was added. weight%
And an aqueous solution containing 0.3% by weight of potassium hydroxide,
Development was performed to obtain a red image pattern. Table 1 shows the results of evaluating the light sensitivity, resolution, and pattern shape of the obtained red image pattern by the following test methods.

Test Method Photosensitivity: Evaluation was performed using a 21-stage step tablet in which the optical density was set to the first stage and the optical density was increased by 0.15 for each stage. The larger the value, the better the light sensitivity. Resolution: Evaluated using a negative mask having a pattern having the same line and space width (μm). It is indicated by the minimum line and space width (μm) that could be completely developed, and the smaller the value, the better the resolution. Pattern shape: The surface state and cross-sectional shape of the image pattern were evaluated. The more uniform the surface and the nearer the cross-sectional shape is, the better the pattern shape becomes.

Example 2 60 g of Copolymer B as a resin, 22 g of CI Pigment Green 36 with a color index name as a pigment, and
8 g of CI Pigment Yellow 83 and 250 g of diethylene glycol dimethyl ether as an organic solvent were added to a solvent, which was subjected to a dispersion treatment for 2 hours using a bead mill. To this dispersion, 32 g of pentaerythritol tetraacrylate as a monomer, 6 g of benzophenone and 3 g of N, N'-tetraethyl-4,4'-diaminobenzophenone as photoinitiators and 125 g of diethylene glycol dimethyl ether as an organic solvent were added and mixed. Was obtained. The dispersion stability of the obtained photosensitive solution was measured in the same manner as in Example 1. Using the obtained photosensitive liquid, a film thickness of 2.0 was obtained in the same manner as in Example 1.
A μm film was formed, the appearance of the coating film was evaluated, and the light sensitivity, resolution, and pattern shape of the image pattern were evaluated.
The results are shown in Table 1.

Example 3 25 g of copolymer C as a resin, 24 g of CI Pigment Blue 15-6 as a pigment and 1 g of CI Pigment Violet 23 as a pigment, and 200 g of diethylene glycol dimethyl ether as an organic solvent were added to a bead mill. For 2 hours. 30 g of dipentaerythritol hexaacrylate as a monomer, 6 g of benzophenone as a photoinitiator and N, N'-tetraethyl-4,4'-
2 g of diaminobenzophenone and 230 g of diethylene glycol dimethyl ether as an organic solvent were added and mixed to obtain a blue colored image forming photosensitive liquid. The dispersion stability of the obtained photosensitive solution was measured in the same manner as in Example 1. Using the obtained photosensitive liquid, a film thickness of 2.
A film having a thickness of 0 μm was formed, the appearance of the coating film was evaluated, and the light sensitivity, resolution and pattern shape of the image pattern were evaluated. The results are shown in Table 1.

Comparative Example 1 A photosensitive solution was obtained under the same composition and conditions as in Example 2 except that Copolymer J was used instead of Copolymer B. The dispersion stability of the obtained photosensitive solution was measured in the same manner as in Example 1. Using the obtained photosensitive liquid, a film having a thickness of 2.0 μm was formed in the same manner as in Example 1, the appearance of the coating film was evaluated, and the light sensitivity, resolution and pattern shape of the image pattern were evaluated. . The results are shown in Table 1.

Comparative Example 2 A photosensitive solution was obtained under the same composition and conditions as in Example 2 except that copolymer L was used instead of copolymer B. The dispersion stability of the obtained photosensitive solution was measured in the same manner as in Example 1. Using the obtained photosensitive liquid, a film having a thickness of 2.0 μm was formed in the same manner as in Example 1, the appearance of the coating film was evaluated, and the light sensitivity, resolution and pattern shape of the image pattern were evaluated. . The results are shown in Table 1.

Comparative Example 3 Instead of using copolymer C, polyvinylpyrrolidone (trade name k-90, manufactured by GAF) was used, except that
A photosensitive solution was obtained under the same composition, method, and conditions as in Example 3.
The dispersion stability of the obtained photosensitive solution was measured in the same manner as in Example 1. Using the obtained photosensitive liquid, a film having a thickness of 2.0 μm was formed in the same manner as in Example 1, the appearance of the coating film was evaluated, and the light sensitivity, resolution and pattern shape of the image pattern were evaluated. . The results are shown in Table 1.

Comparative Example 4 A photosensitive solution was prepared in the same manner as in Example 3 except that cellulose acetate phthalate (polymerization degree: 100, manufactured by Wako Pure Chemical Industries) was used instead of the copolymer C. I got The dispersion stability of the obtained photosensitive solution was measured in the same manner as in Example 1. Using the obtained photosensitive liquid, in the same manner as in Example 1,
A film having a thickness of 2.0 μm was formed, the appearance of the coating film was evaluated, and the light sensitivity, resolution and pattern shape of the image pattern were evaluated. Table 1 shows the results.

[0054]

[Table 1]

Table 1 shows that when a resin having no photoreactive unsaturated bond different from the resin of the present invention was used (Comparative Examples 1, 2, 3, and 4), the photosensitivity was inferior to the examples. . When a resin having a main skeleton different from the resin in the present invention was used (Comparative Examples 2, 3, and 4), the dispersion stability of the photosensitive solution and the appearance of the obtained film were all inferior to those of the Examples. I understand. On the other hand, when the resin according to the present invention is used (Examples 1, 2 and 3), the dispersion stability of the photosensitive solution remains stable without any change even after 30 days, and the appearance of the film is good. And the film thickness was also uniform. Also, the photosensitivity was extremely high as compared with Comparative Examples 1, 2, 3 and 4,
High resolution image patterns were obtained. Further, when a resin having high hygroscopicity was used as in Comparative Examples 3 and 4, the resin was easily affected by humidity at the time of exposure, and when exposed in an environment where the humidity was 75% RH or more, the light sensitivity was significantly reduced to one step or less. However, there is a problem that an image pattern cannot be obtained. In contrast, Examples 1, 2 and 3 using the resin of the present invention
Is not affected by humidity, even when exposed under high humidity,
It was confirmed that there was a feature that a sufficiently high sensitivity equivalent to the result in Table 1 could be obtained.

Example 4 The photosensitive solution obtained in Example 1 was coated on a 6 μm-thick polyethylene terephthalate film by a gravure coating method, dried at 100 ° C. for 2 minutes, and dried to a thickness of 2.0 μm.
Was formed and coated thereon with a polyethylene film having a thickness of 40 μm to obtain a photosensitive element. After the polyethylene film was peeled off from the obtained photosensitive element, it was laminated on a glass substrate similar to that used in Example 1. The laminating condition is a glass substrate temperature of 40.
° C., the temperature of the laminate roll 110 ° C., lamination pressure 3.5 kgf / cm ^2, was carried out at a laminating speed 1.5 m / min. Next, through a negative mask, one image was formed on the polyethylene terephthalate film using an ultra-high pressure mercury lamp.
After exposing to 0 mJ / cm ² and peeling off the polyethylene terephthalate film, development was carried out under the same method and conditions as in Example 1 to obtain a red colored image. Further, using the photosensitive liquid obtained in Example 2 and the photosensitive liquid obtained in Example 3, a photosensitive element was produced in the same manner as described above, and a green colored image and a blue colored image were produced in the same manner as above. A colored image was obtained. When any of the above photosensitive elements was used, the light sensitivity was further improved as compared with the corresponding Examples 1, 2 and 3, respectively, and even when the exposure amount was 10 mJ / cm ² , Examples 1 and 2 were used. And 3, the same number of steps and resolution were shown.

Example 5 A black matrix was formed on the same glass substrate as used in Example 1 by vapor deposition of chromium.
After an image pattern was formed in red by the same method and under the same conditions as described above, a heat treatment was performed at 200 ° C. for 20 minutes. Then
Using the substrate, under the same method and conditions as in Example 2,
A green image pattern was formed next to the red image pattern. After that, heat treatment was performed at 200 ° C. for 20 minutes. Next, using the substrate, a blue image pattern was formed next to the green image pattern under the same method and conditions as in Example 3. After that, heat treatment was performed at 200 ° C. for 20 minutes. As described above, one pixel is 30 μm × 10
A color filter in which pixels were arranged in a mosaic of O μm consisting of three colors of red, green and blue was produced.

Example 6 A black matrix was formed on the same glass substrate as used in Example 1 by vapor deposition of chromium, and a red photosensitive element was used to obtain a red color using the same method and conditions as in Example 4. After forming the image pattern, a heat treatment was performed at 200 ° C. for 20 minutes. Next, a green image pattern was formed next to the red image pattern on the substrate by using the green photosensitive element in the same manner and under the same conditions as in Example 4. After that, heat treatment was performed at 200 ° C. for 20 minutes. Next, a blue image pattern was formed next to the green image pattern on the substrate by using the blue photosensitive element and using the same method and under the same conditions as in Example 4.
After that, heat treatment was performed at 200 ° C. for 20 minutes. As described above, a color filter in which one pixel was arranged in a mosaic of three colors of red, green, and blue of 30 μm × 1OO μm was produced.

As in Examples 5 and 6, the color filters prepared by using a photosensitive liquid having a better dispersion stability than ever before have excellent depolarizing properties of 1000 or more, exhibit excellent optical characteristics, and are suitable for image display. It was confirmed that the device was excellent.

Example 7 The procedure of Example 1 was repeated except that the copolymer D was used instead of the copolymer A as the resin. Table 2 shows the results of tests on the dispersion stability of the obtained colored image forming photosensitive liquid, the appearance of the coating film when applied, the photosensitivity, resolution and pattern shape of the image pattern.

Example 8 The procedure of Example 2 was repeated except that the copolymer E was used instead of the copolymer B as the resin. Table 2 shows the results of testing the dispersion stability of the obtained photosensitive liquid for forming a colored image, and the light sensitivity, resolution, and pattern shape of the external appearance image pattern of the coating film when applied.

Example 9 The procedure of Example 3 was repeated except that the copolymer F was used instead of the copolymer C as the resin. Table 2 shows the results of testing the dispersion stability of the obtained photosensitive liquid for forming a colored image, and the light sensitivity, resolution, and pattern shape of the external appearance image pattern of the coating film when applied.

[0063]

[Table 2]

As can be seen from Table 2, when the resin according to the present invention was used (Examples 6, 7 and 8), the dispersion stability of the photosensitive solution was 3
Even after the elapse of 0 days, there was no change at all, it was stably present, the appearance of the film was good, and the film thickness was uniform. In addition, the photosensitivity was extremely high, and a high-resolution image pattern was obtained. In the case of Examples 6, 7 and 8 using the resin according to the present invention, it was confirmed that there was a characteristic that a sufficient high sensitivity was obtained even when exposed under high humidity without being affected by humidity.

Example 10 A photosensitive element was prepared in the same manner as in Example 4, except that the photosensitive solution obtained in Example 7 was used instead of the photosensitive solution obtained in Example 1. Using the obtained photosensitive element, a red colored image was obtained according to Example 4. Further, using the photosensitive liquid obtained in Example 8 and the photosensitive liquid obtained in Example 9, photosensitive elements were respectively produced in the same manner as described above, and a green colored image and a blue colored image were produced in the same manner as above. Was obtained. When any of the above photosensitive elements was used, the corresponding Examples 7, 8, and 9 were used, respectively.
The light sensitivity was further improved as compared with the case of Example 1, and the number of steps and the resolution were the same as those of Examples 7, 8 and 9 even at the exposure amount of 10 mJ / cm ² .

Example 11 Example 7 was repeated except that a black matrix was formed on the same glass substrate used in Example 1 by chromium evaporation.
After forming an image pattern in red by the same method and under the same conditions as above, a heat treatment was performed at 200 ° C. for 20 minutes. Then
Using the substrate, under the same method and conditions as in Example 8,
A green image pattern was formed next to the red image pattern. After that, heat treatment was performed at 200 ° C. for 20 minutes. Next, using the substrate, a blue image pattern was formed next to the green image pattern under the same method and conditions as in Example 9. After that, heat treatment was performed at 200 ° C. for 20 minutes. As described above, one pixel is 30 μm × 10
A color filter in which pixels were arranged in a mosaic of O μm consisting of three colors of red, green and blue was produced.

Example 12 A black matrix was formed on the same glass substrate as used in Example 1 by vapor deposition of chromium, and a red photosensitive element was used to obtain a red color using the same method and conditions as in Example 10. After the image pattern is formed,
Heat treatment was performed for minutes. Then, using the substrate,
A green image pattern was formed next to the red image pattern in the same manner and under the same conditions as in Example 10 using the green photosensitive element. After that, heat treatment was performed at 200 ° C. for 20 minutes. Next, a blue image pattern was formed next to the green image pattern on the substrate by using the blue photosensitive element and using the same method and under the same conditions as in Example 10. After that, heat treatment was performed at 200 ° C. for 20 minutes. As described above, one pixel is 30 μm × 100 μm
A color filter having pixels arranged in a mosaic of three colors of red, green and blue was prepared.

As in Examples 11 and 12, the colored image and the color filter prepared by using a photosensitive liquid having good dispersion stability, which has not been obtained in the past, have a depolarizing property of 1000.
As described above, the optical characteristics were excellent, and it was confirmed that the image display device was excellent.

Example 13 Example 13 was repeated except that copolymer A was used as the resin instead of copolymer A. Table 3 shows the results of testing the dispersion stability of the obtained photosensitive liquid for forming a colored image and the photosensitivity, resolution, and pattern shape of the appearance image pattern of the coating film when applied.

Example 14 The same procedure as in Example 2 was carried out except that copolymer H was used instead of copolymer B as the resin. Table 3 shows the results of testing the dispersion stability of the obtained photosensitive liquid for forming a colored image and the photosensitivity, resolution, and pattern shape of the appearance image pattern of the coating film when applied.

Example 15 The same procedures as in Example 3 were carried out except that copolymer I was used instead of copolymer C as the resin. Table 3 shows the results of testing the dispersion stability of the obtained photosensitive liquid for forming a colored image and the photosensitivity, resolution, and pattern shape of the appearance image pattern of the coating film when applied.

Comparative Example 5 A photosensitive solution was obtained under the same composition and conditions as in Example 2, except that Copolymer J was used instead of Copolymer B. The dispersion stability of the obtained photosensitive solution was measured in the same manner as in Example 1. Using the obtained photosensitive liquid, a film having a thickness of 2.0 μm was formed in the same manner as in Example 1, the appearance of the coating film was evaluated, and the light sensitivity, resolution and pattern shape of the image pattern were evaluated. . The results are shown in Table 3.

[0073]

[Table 3]

As can be seen from Table 3, when the resin according to the present invention was used (Examples 13, 14 and 15), the dispersion stability of the photosensitive solution was stable without any change even after 30 days. And the film thickness was uniform. In addition, the photosensitivity was extremely high, and a high-resolution image pattern was obtained. In the case of Examples 13, 14, and 15 using the resin according to the present invention, it was confirmed that there was a characteristic that a sufficient high sensitivity was obtained even when exposed under high humidity without being affected by humidity.
In contrast, Comparative Example 5 was inferior in light sensitivity, resolution, and pattern formability.

Example 16 A photosensitive element was prepared in the same manner as in Example 4, except that the photosensitive solution obtained in Example 13 was used instead of the photosensitive solution obtained in Example 1. Using the obtained photosensitive element, a red colored image was obtained according to Example 4. Also,
Using the photosensitive solution obtained in Example 14 and the photosensitive solution obtained in Example 15, a photosensitive element was prepared in the same manner as described above, and a green coloring image and a blue coloring were formed in the same manner as above. Image obtained. In the case of using any of the above photosensitive elements, the corresponding Example 13 and
Light sensitivity is further improved as compared with the cases of 14 and 15, and 10
Even with the exposure amount of mJ / cm ^2, the same number of steps and resolution as those of Examples 13, 14, and 15 were shown.

Example 17 The same method as in Example 1 except that a black matrix was formed on the same glass substrate as used in Example 1 by chromium evaporation.
After forming an image pattern in red under the same method and conditions as in No. 3, a heat treatment was performed at 200 ° C. for 20 minutes. Next, using the substrate, a green image pattern was formed next to the red image pattern under the same method and conditions as in Example 14. After that, heat treatment was performed at 200 ° C. for 20 minutes. Next, using the substrate, a blue image pattern was formed next to the green image pattern under the same method and conditions as in Example 15. After that, heat treatment was performed at 200 ° C. for 20 minutes. As described above, one pixel is 30 μm ×
A color filter in which pixels were arranged in a mosaic of 100 μm in three colors of red, green and blue was produced.

Example 18 A black matrix was formed on the same glass substrate as used in Example 1 by vapor deposition of chromium. After the image pattern is formed,
Heat treatment was performed for minutes. Then, using the substrate,
A green image pattern was formed next to the red image pattern in the same manner and under the same conditions as in Example 16 using the green photosensitive element. After that, heat treatment was performed at 200 ° C. for 20 minutes. Next, a blue image pattern was formed next to the green image pattern on the substrate by using the blue photosensitive element and using the same method and under the same conditions as in Example 16. After that, heat treatment was performed at 200 ° C. for 20 minutes. As described above, one pixel is 30 μm × 100 μm
A color filter having pixels arranged in a mosaic of three colors of red, green and blue was prepared.

As in Examples 17 and 18, the colored image and the color filter produced by using a photosensitive solution having a good dispersion stability, which has not been obtained before, have a depolarizing property of 1000.
As described above, the optical characteristics were excellent, and it was confirmed that the image display device was excellent.

[0079]

The colored image-forming material according to any one of claims 1 to 3 has high dispersibility and dispersion stability of the pigment, has good photosensitivity, and can provide a film having an excellent coating film appearance.
The photosensitive liquid for forming a colored image according to the fourth aspect contains a material for forming a colored image in which the dispersibility of the pigment and the photosensitivity are improved. The photosensitive element according to claim 5 or 6,
A pigment having high dispersibility and dispersion stability, good photosensitivity, and a film having excellent coating appearance can be obtained. Claim 7
According to the production method described in 2, the pigment in the coating film of the pixel is well dispersed, and a colored image having excellent optical characteristics is provided.
The color filter according to the eighth aspect provides a high-quality optical film with excellent dispersion of the pigment of the coating film of the pixel.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C09D 4/00 C09D 4/00 (72) Inventor Seigo Yokochi 14 Goi Minamikaigan, Ichihara City, Chiba Prefecture Hitachi Chemical Co., Ltd. Goi Plant (72) Inventor Shinya Kato 14 Goi South Coast, Ichihara City, Chiba Prefecture Hitachi Chemical Co., Ltd. Goi Plant (72) Inventor Tomohiro Nagoya 14 Goi South Coast, Ichihara City, Chiba Prefecture Hitachi Gosei Plant (72) Inventor Yuji Kobayashi 14 Goi South Coast, Ichihara City, Chiba Prefecture, Hitachi Chemical Co., Ltd., Goi Plant (72) Inventor Akira Sasaki 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture, Hitachi Chemical Co., Ltd.

Claims (8)

[Claims] 1. A colored image forming photosensitive solution containing a resin, a dye, a monomer containing at least one photopolymerizable unsaturated bond in a molecule, and a photoinitiator, wherein the resin has an acid value of 20 to 20.
A colored image forming material which is a resin having 0 and an unsaturated equivalent of 200 to 1,000. 2. The resin has a weight average molecular weight of 1,500 to 2,
The colored image forming material according to claim 1, which is a resin of 000. 3. The resin represented by the following general formula (I): (Wherein, R ¹ represents a hydrogen atom or a methyl group,
R ² and R ³ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms) and the following general formula (I
I) (Wherein, R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a group having a photoreactive unsaturated bond, and R ⁶ represents a hydrogen atom or a carbon atom having 1 to 1 carbon atoms. 1
2) represents a repeating unit represented by formula (I) / general formula (II) in a ratio of 1/1 to 5/1 (molar ratio).
Wherein at least a part of the repeating units represented by the general formula (II) has R ⁴ and R ⁵ in the general formula (II).
The colored image forming material according to claim 1, wherein at least one of the resins is a resin that is a repeating unit representing a group having a photoreactive unsaturated bond. 4. A colored image forming photosensitive liquid comprising the colored image forming material according to claim 1, further comprising an organic solvent, wherein components other than the organic solvent are dissolved or dispersed in the organic solvent. 5. A photosensitive element obtained by laminating a photosensitive layer containing the colored image forming material according to claim 1 on a support. 6. The photosensitive element according to claim 5, further comprising a cover film laminated on the photosensitive layer. 7. A method for producing a colored image, comprising a colored image forming step of laminating a photosensitive layer containing the colored image forming material according to claim 1 on a substrate and exposing and developing the photosensitive layer. 8. A method for producing a color filter, comprising: producing a plurality of colored images on the same substrate by the method for producing a colored image according to claim 7.