JPH11125903A - Color image forming material, photosensitive liquid for color image forming, photosensitive element, production of color image and production of color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color image forming material which consists of a photosensitive resin having dispersion of pigments and which does not cause coating defects such as pinholes, to provide a photosensitive liquid and a photosensitive element containing this material, to provide a producing method of a color image, and to provide a color filter having a coating film of pixels without coating defects such as pinholes. SOLUTION: This color image forming material contains a resin, pigments, monomers containing one or more photopolymerizable unsatd. bonds in the molecule, a photoinitiator and a nonionic surfactant. As the nonionic surfactant, a polyoxyethylene alkylphenol or the like is used. The photosensitive liquid is prepared by incorporating an org. solvent into the color image forming material and dissolving or dispersing other components. The photosensitive element is produced by forming a photosensitive layer containing the color image forming material on a supporting body. The producing method of a color image includes processed to form a photosensitive layer containing the color image forming material on a substrate and to expose and to develop the layer.

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, when a liquid photosensitive material is applied on the entire surface to form pixels on a substrate and a coating film is formed, pinhole-shaped non-applied portions are generated, which causes a problem of poor coating. Was.

[0004]

The invention according to claims 1 to 3 is to provide a colored image forming material comprising a photosensitive resin in which a pigment is dispersed and having no pinhole coating failure. The invention according to claim 4 provides a photosensitive liquid comprising a colored image forming material which is made of a photosensitive resin in which a pigment is dispersed and has no pinhole coating failure.
The invention according to claim 5 or 6 is to provide a photosensitive element having a photosensitive layer comprising a colored image forming material which is made of a photosensitive resin in which a pigment is dispersed and has no pinhole coating failure. The invention according to claim 7 provides a method for producing a colored image which is made of a photosensitive resin in which a pigment is dispersed, and has no pinhole coating failure. Claim 8
The invention in comprises a photosensitive resin in which a pigment is dispersed,
An object of the present invention is to provide a color filter having a coating film of a pixel having no coating failure of a pinhole.

[0005]

SUMMARY OF THE INVENTION The present invention provides a resin, a pigment,
In a colored image forming material containing a monomer containing one or more photopolymerizable unsaturated bonds in a molecule, a photoinitiator and a nonionic surfactant, the nonionic surfactant is polyoxyethylene alkylphenol, The present invention relates to a colored image forming material which is a xylene alkyl ether or a polyoxyethylene phosphate. The present invention also relates to the above-mentioned colored image forming material, wherein the resin is a resin having 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]

BEST MODE FOR CARRYING OUT THE INVENTION The weight average molecular weight of the resin in the present invention is preferably in the range of 1,500 to 200,000, more preferably in the range of 5,000 to 100,000. 10,000-50,000
It is preferably within the range of 0. If the weight average molecular weight is less than 1,500, the dispersion stability of the pigment tends to decrease, and if it exceeds 200,000, the viscosity becomes high when the composition is made into a photosensitive liquid, and the coating properties, especially when spin coating, are increased. The coatability tends to decrease. 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.

The above resin has an acid value in the range of 20 to 300, preferably 40 to 200, more preferably 60 to 200, from the viewpoint that the photosensitive layer has alkali developability after exposure. It is preferably in the range of 150.
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.

The resin has an unsaturated equivalent of 600.
~ 3,000, preferably 800 ~
More preferably, it is in the range of 2,000. When the unsaturated equivalent is less than 600, the pigment tends to partially cure at the time of dispersion of the pigment, and when it exceeds 3,000, the effect of improving the photosensitivity tends to decrease. Here, the unsaturated equivalent means the molecular weight of the resin per unsaturated bond.

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; ethyldiethylene glycol methacrylate; butyltriethylene glycol methacrylate; methyldipropylene Alkyl polyalkylene glycol methacrylates such as glycol methacrylate, alkyl polyalkylene glycol acrylates such as ethyl diethylene glycol acrylate, butyl triethylene glycol acrylate, and methyl dipropylene glycol acrylate; aryl polyalkylene glycol methacrylates such as phenylhexaethylene glycol methacrylate; Hexaethylene glycol acrylate arylpolycarboxylic et polyalkylene glycol acrylate, dicyclopentanyl methacrylate, dicyclopentanyl acrylate, isobornyl methacrylate,
Fluorinated alkyl methacrylates such as methoxylated cyclodecatriene methacrylate, isobornyl acrylate, methoxylated cyclodecatriene acrylate, glycerol methacrylate, glycerol acrylate, heptadecafluorodecyl methacrylate, and the like; fluorinated alkyl acrylates such as heptadecafluorodecyl acrylate; -Hydroxyethyl methacrylate, 2-hydroxyethyl acrylate and the like.

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 monomer having two or more photopolymerizable unsaturated bonds in the molecule further includes a compound 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 nonionic surfactant in the present invention comprises:
Polyoxyethylene alkylphenol, polyoxyethylene alkyl ether or polyoxyethylene phosphate is used. The polyoxyethylene alkylphenol is specifically represented by the general formula (III)

Embedded image (In the formula, R is a linear or branched alkyl group having 1 to 100 carbon atoms, and may be substituted with an aryl group such as a phenyl group, and n represents an integer of 8 to 15.) It is a compound represented by these.

The polyoxyethylene alkyl ether is
Specifically, the general formula (IV)

Embedded image (However, in the formula, R is a linear or branched alkyl group having 1 to 100 carbon atoms, and may be substituted with an aryl group such as a phenyl group, and n represents an integer of 4 to 30.) It is a compound represented by these.

The polyoxyethylene phosphate is specifically represented by the general formula (V)

Embedded image (Wherein, R is a linear or branched alkyl group having 1 to 100 carbon atoms, which may be substituted with an aryl group such as a phenyl group, and R 'is hydrogen or R- (CH ₂ CH
₂ O) _n- , where n is an integer of 8 to 15).

The resin, pigment, monomer having at least one photopolymerizable unsaturated bond in the molecule, photoinitiator and nonionic surfactant used in the colored image forming photosensitive liquid are as follows. (A) resin is preferably 10 to 85% by weight, more preferably 20 to 60% by weight, particularly preferably 25 to 50% by weight, and (b) pigment is
Preferably 5 to 70% by weight, more preferably 10 to 60%
% By weight, particularly preferably 15 to 50% by weight, and (c) a monomer having at least one photopolymerizable unsaturated bond in a molecule.
Preferably 2 to 50% by weight, more preferably 5 to 40% by weight, particularly preferably 10 to 30% by weight, (d) the photoinitiator is preferably 0.01 to 20% by weight, more preferably 2 to 15% by weight. % By weight, particularly preferably 5 to 10% by weight,
(E) The nonionic surfactant is preferably used in an amount of 1 to 40% by weight, more preferably 20 to 40% by weight, and particularly preferably 30 to 40% 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. If the amount of the photoinitiator is too small, the photosensitivity tends to decrease, and if the amount is too large, the adhesiveness tends to decrease. Further, if the amount of the nonionic surfactant is too small, the effect of suppressing pinholes is lost, and if the amount is too large, the photosensitive properties and coatability tend 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 includes a resin, a dye, a monomer containing at least one photopolymerizable unsaturated bond in a molecule in a photosensitive solution,
The total solid content including the photoinitiator and the nonionic surfactant is 5 to 5.
Preferably, it is used so as to be in the range of 40% by weight. When the total solid content exceeds 40% by weight, the viscosity increases,
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 at least one photopolymerizable unsaturated bond in the molecule, the photoinitiator and the nonionic surfactant may be mixed before the dispersion treatment 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; 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 dispersion treatment, the entire 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 of 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.

As a method of applying the photosensitive liquid to the substrate, there are 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 carried out 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.

After the above exposure, a developing 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 step. In particular, in a method of manufacturing a color filter, it is preferable to repeat the colored image forming step 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.

[0043]

The present invention will be described below with reference to examples. (1) Resin used: Copolymer A: 50 mol% of styrene-monomaleic acid (3
-Methacryloyloxy-2-hydroxy-propyl)
Ester 30 mol% -Maleic acid derivative A 20 mol%
, Having a weight average molecular weight of 11,000 and an acid value of 66.
3. Copolymer of unsaturated group equivalent 564.7 The repeating unit based on the maleic acid derivative A has the following structure.

Embedded image

Preparation Example 1 of Photosensitive Liquid 40 g of Copolymer A as resin, 25 g of Pigment Red 177 and 5 of Pigment Yellow 139 as pigments
g and propylene glycol monomethyl ether 200
g were mixed, and the resulting mixture was subjected to a dispersion treatment using a bead mill for 2 hours. To 200 g of the resulting dispersion, 13 g of copolymer A, 27 g of trimethylolpropane triacrylate as a monomer, 6 g of benzophenone as a photoinitiator, 2 g of N, N'-tetraethyl-4,4'-diaminobenzophenone, and 2 g of propylene glycol monomethyl 292 g of ether was added and mixed to obtain a photosensitive solution for forming a colored image.

Preparation Example 2 of Photosensitive Liquid 60 g of Copolymer A as a resin, 22 g of CI Pigment Green 36 by a color index name as a pigment, and
8 g of CI Pigment Yellow 83 and 250 g of propylene glycol monomethyl ether were mixed, and the resulting mixture was subjected to a dispersion treatment using a bead mill for 2 hours. To 220 g of the obtained dispersion, 35 g of pentaerythritol tetraacrylate, and benzophenone 6 as a photoinitiator.
g, 3 g of N, N'-tetraethyl-4,4'-diaminobenzophenone and 125 g of propylene glycol monomethyl ether were added and mixed to obtain a photosensitive solution for forming a colored image.

Preparation Example 3 of Photosensitive Liquid 20 g of a copolymer A as a resin, 24 g of CI Pigment Blue 15: 6 by a color index name as a pigment,
1 g of CI Pigment Violet 23 and 216 g of propylene glycol monomethyl ether were mixed, and the resulting mixture was subjected to a dispersion treatment using a bead mill for 2 hours. In 140 g of the obtained dispersion, 38.5 g of the copolymer was added.
35 g of 1,4-butanediol diacrylate, 6 g of benzophenone as a photoinitiator, 2 g of N, N'-tetraethyl-4,4'-diaminobenzophenone and 262.5 g of propylene glycol monomethyl ether are added and mixed to form a colored image. A photosensitive solution was obtained.

Preparation Example 3 of Photosensitive Liquid As a resin, 38 g of copolymer A, Pigment Black 7
Was mixed with 176 g of propylene glycol monomethyl ether, and the resulting mixture was subjected to a dispersion treatment using a bead mill for 2 hours. In 200 g of the obtained dispersion,
38.5 g of the copolymer, 27 g of trimethylopropane triacrylate, 6 g of benzophenone as a photoinitiator, 2 g of N, N'-tetraethyl-4,4'-diaminobenzophenone and 280 g of propylene glycol monomethyl ether were added and mixed. A photosensitive liquid for formation was obtained.

Comparative Examples 1 to 4 Preparation of Photosensitive Liquids The glass substrates on which the photosensitive liquids obtained in Examples 1 to 4 were chromium-deposited (Corning Co., trade names 7059 and 30)
(0 mm × 200 mm) by spin coating, left at room temperature for 1 minute, and then heated at 90 ° C. for 1.5 minutes. Thereafter, the amount of pinhole-like defects generated was examined in units of ten sheets. The number of occurrences per sheet is shown in Table 1.

[0049]

[Table 1]

Example 1 A nonionic surfactant, polyoxyethylene alkylphenol (trade name: Nonal 912A, manufactured by Toho Chemical Industry Co., Ltd.) was added to the photosensitive solution shown in Preparation Example 1 for a total of 100 parts by weight of a colored image forming material. 1 part by weight, 5 parts by weight, 20 parts by weight
Parts by weight, 30 parts by weight and 40 parts by weight,
A photosensitive solution was prepared. The prepared photosensitive solution was evaluated in the same manner as in Comparative Example 1, and the evaluation results are shown in Table 2.

[0051]

[Table 2]

Example 2 A photosensitive solution prepared in the same manner as in Example 1 was prepared in the same manner as in Example 1 with respect to the photosensitive solution shown in Preparation Example 2, and the evaluation results are shown in Table 3.

[0053]

[Table 3]

Example 3 A photosensitive solution prepared in the same manner as in Example 1 was prepared in the same manner as in Example 1 with respect to the photosensitive solution shown in Photosensitive Solution Preparation Example 3, and the evaluation results are shown in Table 4.

[0055]

[Table 4]

Example 4 The photosensitive solution prepared in the same manner as in Example 1 was evaluated in the same manner as in Example 1 with respect to the photosensitive solution shown in Photosensitive Solution Preparation Example 4, and the evaluation results are shown in Table 5.

[0057]

[Table 5]

Example 5 A nonionic surfactant polyoxyethylene alkyl ether (trade name: KC-498, manufactured by Toho Chemical Industry Co., Ltd.) was added to the photosensitive solution shown in Preparation Example 1 for a total weight of 100% of the colored image forming material. The photosensitive solution is prepared by adding 1 part by weight, 5 parts by weight, 20 parts by weight, 30 parts by weight, and 40 parts by weight to the parts by weight. The prepared photosensitive solution was evaluated in the same manner as in Comparative Example 1, and the evaluation results are shown in Table 6.

[0059]

[Table 6]

Example 6 A photosensitive solution prepared in the same manner as in Example 5 was prepared in the same manner as in Example 5 with respect to the photosensitive solution shown in Photosensitive Solution Preparation Example 2, and the evaluation results are shown in Table 7.

[0061]

[Table 7]

Example 7 A photosensitive liquid prepared in the same manner as in Example 5 was prepared in the same manner as in Example 5 with respect to the photosensitive liquid shown in Preparation Example 3, and the evaluation results are shown in Table 8.

[0063]

[Table 8]

Example 8 A photosensitive solution prepared in the same manner as in Example 5 was prepared in the same manner as in Example 5 with respect to the photosensitive solution shown in Photosensitive Solution Preparation Example 4, and the evaluation results are shown in Table 9.

[0065]

[Table 9]

Example 9 A nonionic surfactant polyoxyethylene phosphate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Plysurf A212E) was added to the photosensitive solution shown in Preparation Example 1 for the entire colored image forming material. 1 part by weight, 5 parts by weight,
20 parts by weight, 30 parts by weight, and 40 parts by weight are added to prepare a photosensitive solution. Comparative Example 1
Table 10 shows the results of the evaluation.

[0067]

[Table 10]

Example 10 A photosensitive solution prepared in the same manner as in Example 9 was evaluated in the same manner as in Example 9 with respect to the photosensitive solution shown in Photosensitive Solution Preparation Example 2, and the evaluation results are shown in Table 11.

[0069]

[Table 11]

Example 11 A photosensitive solution prepared in the same manner as in Example 9 was evaluated by the same method as in Example 9 with respect to the photosensitive solution shown in Photosensitive Solution Preparation Example 3, and the evaluation results are shown in Table 12.

[0071]

[Table 12]

Example 12 A photosensitive solution prepared in the same manner as in Example 9 was prepared in the same manner as in Example 9 by using the photosensitive solution shown in Photosensitive Solution Preparation Example 4, and the evaluation results are shown in Table 13.

[0073]

[Table 13]

Example 13 A photosensitive solution containing 30 parts by weight of the nonionic surfactant obtained in Example 1 was applied onto a 6 μm-thick polyethylene terephthalate film by a gravure coating method.
The film was dried at a temperature of 2 ° C. for 2 minutes to form a film having a thickness of 2.0 μm, and then coated 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. Laminating conditions were as follows: glass substrate temperature 40 ° C., laminating roll temperature 110 ° C., laminating pressure 3.5 kgf / cm ² , laminating speed 1.5 m / min. Next, through a negative mask, an image of 10 mJ / cm ² was exposed imagewise from above the polyethylene terephthalate film using an ultra-high pressure mercury lamp,
Next, after peeling off the polyethylene terephthalate film, 0.5% by weight of polyoxyethylene nonylphenyl ether (Nonal 912A, manufactured by Toho Chemical Co., Ltd.) was used.
And an aqueous solution containing 0.3% by weight of potassium hydroxide,
Development was performed to obtain a red colored image. Further, using the photosensitive solution containing 30 parts by weight of the nonionic surfactant obtained in Example 2 and the photosensitive solution containing 30 parts by weight of the nonionic surfactant obtained in Example 3, respectively, A green colored image and a blue colored image were obtained in the same manner as described above.

When any of the above photosensitive elements was used, there was no pinhole in the image, and an excellent colored image was obtained.

Example 14 Example 1 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 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 13. 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 13. 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. There was no pinhole in the obtained color filter.

[0077]

The colored image forming material according to any one of claims 1 to 3 is made of a photosensitive resin in which a pigment is dispersed, and has no pinhole coating failure. The colored image forming photosensitive liquid according to claim 4 is made of a photosensitive resin in which a pigment is dispersed, and contains a colored image forming material having no pinhole coating failure. The photosensitive element according to the fifth or sixth aspect is made of a photosensitive resin in which a pigment is dispersed, and has a photosensitive layer containing a colored image forming material free from pinhole coating failure. In the method for producing a colored image according to claim 7, the colored image is made of a photosensitive resin in which a pigment is dispersed, and a colored image having no pinhole coating failure can be obtained. According to the method for manufacturing a color filter according to the eighth aspect, a color filter having a coating film of a pixel made of a photosensitive resin in which a pigment is dispersed and having no pinhole coating failure can be obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/004 505 G03F 7/004 505 // C09D 171/02 C09D 171/02 (72) Inventor Tetsuya Okazaki Goi, Ichihara-shi, Chiba 14 South Coast, Hitachi Chemical Co., Ltd., Goi Plant (72) Inventor Shinya Kato 14 Goi South Coast, Ichihara-shi, Chiba Prefecture, Hitachi Chemical Co., Ltd., Goi Plant (72) Inventor Tomohiro Nagoya, Goi-minami Coast, Ichihara, Chiba Prefecture 14 Hitachi Chemical Co., Ltd. Goi Plant

Claims (8)

[Claims] 1. A colored image forming material containing a resin, a pigment, a monomer containing at least one photopolymerizable unsaturated bond in a molecule, a photoinitiator and a nonionic surfactant,
A colored image forming material in which the nonionic surfactant is polyoxyethylene alkylphenol, polyoxyethylene alkyl ether or polyoxyethylene phosphate. 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.