JP2000298334A - Colored image forming material, photosensitive fluid for forming colored image, photosensitive element, production of colored image and production of color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a colored image forming material excellent in the dispersibility of a pigment, a sensitizing solution containing the colored image forming material and a photosensitive element with a photosensitive layer containing the colored image forming material, to produce a colored image excellent in the dispersibility of the pigment and to produce a color filter with such colored images. SOLUTION: The colored image forming material contains a resin, a pigment, a monomer containing one or more photopolymerizable unsaturated bonds in one molecule, a photopolymerization initiator and a polycaprolactone alkyl ester as a nonionic surfactant. The photosensitive fluid for forming a colored image contains an organic solvent besides the colored image forming material and is obtained by dissolving or dispersing the components except the organic solvent in the organic solvent. The photosensitive element is obtained by laminating a photosensitive layer containing the colored image forming material on a substrate. The colored image is produced through a colored image forming step in which the photosensitive layer containing the colored image forming material is laminated on the substrate, exposed and developed. The color filter is produced by forming such colored image on the same substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a colored image forming material, a colored image forming photosensitive liquid, 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 has been adopted in which a dyeable resin, for example, natural gelatin or casein is patterned and dyed therewith mainly using a dye to obtain pixels. 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 using a photosensitive material in which a pigment is dispersed for the purpose of improving heat resistance and light resistance has attracted attention, and much research has been conducted. According to this method, the manufacturing method is simplified, and the obtained color filter is known to be stable and have a long life. However, on the other hand, a technique for stably dispersing the pigment is difficult, and in particular, it is difficult to select a dispersant that most affects the dispersibility of the pigment.

[0003]

The inventions according to claims 1 to 3 provide a colored image forming material comprising a photosensitive resin in which a pigment is dispersed and having excellent pigment dispersibility.
The fourth aspect of the present invention provides a photosensitive liquid containing a colored image forming material which is made of a photosensitive resin in which a pigment is dispersed and has excellent pigment dispersibility. The invention according to claims 5 and 6 provides a photosensitive element comprising a photosensitive layer containing a colored image forming material which is made of a photosensitive resin in which a pigment is dispersed and has excellent pigment dispersibility. The invention according to claim 7 provides a method for producing a colored image comprising a photosensitive resin in which a pigment is dispersed and having excellent pigment dispersibility.
The invention described in claim 8 provides a method for producing a color filter having a colored image which is made of a photosensitive resin in which a pigment is dispersed and has excellent pigment dispersibility.

[0004]

SUMMARY OF THE INVENTION The present invention provides a resin, a pigment,
In a colored image forming material containing a monomer containing at least one photopolymerizable unsaturated bond in a molecule, a photopolymerization initiator and a nonionic surfactant, the nonionic surfactant is a polycaprolactone alkyl ester. The present invention relates to a colored image forming material. The present invention also relates to the 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 is 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 (However, in the formula, 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
A general formula (I) / a general formula (II) in a ratio of 1/1 to 5/1 (molar ratio), and a general formula (II) Wherein at least a part of the repeating unit represented by the formula (II) is a resin in which at least one of R ⁴ and R ⁵ represents a group having a photoreactive unsaturated bond. For materials.

[0006] The present invention also relates to a colored image forming photosensitive liquid obtained by further containing an organic solvent in the colored image forming material and dissolving or dispersing components other than the organic solvent in the organic solvent. The present invention also relates to a photosensitive element obtained by laminating a photosensitive layer containing the colored image forming material on a support. Further, the present invention further relates to the photosensitive element, wherein a cover film is laminated on the photosensitive layer. The present invention also relates to a method for producing a colored image, comprising a colored image forming step of laminating a photosensitive layer containing the colored image forming material 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.

[0007]

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. 10,000-50,0
It is preferably within the range of 00. 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 solution, and the coatability, especially when spin coating is used. Properties tend to decrease. 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, and more preferably 60 to 150, from the viewpoint that the photosensitive layer has alkali developability after exposure. It is preferably within the range. If the acid value is too low, alkali developability tends to decrease, and if it 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, 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, and R6 is hydrogen. A repeating unit that is an atom; (iii) in the general formula (II), R ⁴ and R ⁵ are each independently a hydrogen atom or a group having a photoreactive unsaturated bond, and at least one of them is a photoreactive It is a group having an unsaturated bond, and preferably has a repeating unit in which R ⁶ is an alkyl group having 1 to 12 carbon atoms.

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 the general formula (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.).

As the precursor of the resin having the repeating units represented by the general formulas (I) and (II), styrene or a derivative thereof and maleic anhydride or a monoalkyl maleic ester (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. Examples of the monoalkyl maleate include monomethyl maleate, monoethyl maleate, mono-n-propyl maleate, mono-isopropyl maleate, mono-n-butyl maleate, mono-n-hexyl maleate, and maleic acid. Mono-n-octyl, mono-2-ethylhexyl maleate, mono-n-nonyl maleate, mono-n-dodecyl maleate and the like can be mentioned.

As the resin used in the colored image forming material or the colored image forming photosensitive liquid of the present invention, a resin having a repeating unit represented by the above-mentioned general formula (I) or (II) may be used. 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 shipping cost of the resin.

The dye used in the colored image forming material or the colored image forming photosensitive liquid may be any of a dye and a pigment, but a pigment is more preferable in consideration of heat resistance and light resistance. 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.

In producing the color filter of the present invention, each pigment system suitable for a colored image such as red, green, blue and black is used. When the colored image forming material of the present invention is used for the production of a color filter, each pigment system suitable for a colored image such as red, green, blue and black is used.

For a red colored image, a single red pigment system may be used, or a yellow pigment system or an orange pigment system may be mixed with a red pigment system to perform toning. Examples of red pigments include, for example, Pigment Red 9, 123, 155, 168, 177, 180, 21 in the color index name.
7, 220, 224, 254 and the like. As a yellow pigment, for example, Pigment Yellow 17, 20, 24, 83, 93, 109, 1
10, 117, 125, 128, 129, 138, 13
9, 147, 150, 154 and the like. Examples of the orange pigments include Pigment Orange 43, 71 and the like with a color index name. These red pigments, yellow pigments, and orange pigments can be used as a mixture of two or more kinds. In the case of using a mixture of a red pigment system and a yellow pigment system or an orange pigment system,
It is preferable to use 90 parts by weight or less of the yellow pigment or the orange pigment based on 100 parts by weight of the total amount of the red pigment, the yellow pigment, and the orange pigment.

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, for example, Pigment Green 7, 3 with a color index name.
6, 37 and the like. These green pigments and yellow pigments may be used in combination of two or more. When a mixture of a green pigment system and a yellow pigment system is used, it is preferable to use 90 parts by weight or less of the yellow pigment system 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. Examples of blue pigments include, for example, Pigment Blue 15, 15:
3, 15: 4, 15: 6, 22, 60 and the like.
Examples of purple pigments include, for example, Pigment Violet 19, 23, 29, 37, 50 under the color index name.
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, it is preferable to use 90 parts by weight or less of the violet pigment based on 100 parts by weight of the total of the blue pigment and the violet pigment.

For the black colored image, for example, black pigments such as carbon black, graphite, titanium carbon, black iron oxide, 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 methacrylates such as N, N-dimethylaminoethyl methacrylate, ethyldiethylene glycol methacrylate, butyltriethylene glycol methacrylate;
Alkyl polyalkylene glycol methacrylate such as methyl dipropylene glycol methacrylate, ethyl diethylene glycol, butyl triethylene glycol acrylate, alkyl polyalkylene glycol acrylate such as methyl dipropylene glycol acrylate, aryl polyalkylene glycol methacrylate such as phenyl hexaethylene glycol methacrylate,
Aryl polyalkylene glycol acrylate such as phenylhexaethylene glycol acrylate, dicyclopentanyl methacrylate, dicyclopentanyl acrylate, isobornyl methacrylate, methoxylated cyclodecatriene methacrylate, isobornyl acrylate, methoxylated cyclodecatriene acrylate, glycerol methacrylate Fluorinated alkyl methacrylates such as 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 monomer having two or more photopolymerizable unsaturated bonds in the molecule further includes a compound represented by the general formula (a):

Embedded image (Where 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 20
An epichlorohydrin modified product of bisphenol A and an addition ester compound of acrylic acid,
Bisphenol A dimethacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol dimethacrylate, 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 p and q are independently 1 to 10
Epoxide hydrin modified phthalic acid and addition esterified acrylic acid, polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, tetraethylene glycol diacrylate, general formula (e)

Embedded image (Where m and n are each independently 1 to 20
Of 1,6-hexanediol and an addition ester of acrylic acid (having two aquilyl groups in one molecule), trimethylolpropane triacrylate, pentaene Erythritol triacrylate, general formula (f)

Embedded image (Wherein, R represents an ethylene group or a propylene group, and three r'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, a, b, and c 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 can be mentioned. These monomers can be used alone or in combination of two or more.

The photopolymerization initiator used in the colored image forming material or the colored image forming photosensitive liquid 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-hydroxycyclohexylphenyl ketone, 2-methyl-1-
[4- (methylthio) phenyl] -2-morpholino-1
-Propane, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-
Chlor-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 1,2-benzoanthraquinone, 1,4-
Examples include dimethylanthraquinone, 2-phenylanthraquinone, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, and the like. These photoinitiators can be used alone or in combination of two or more.

As the nonionic surfactant in the present invention, polycaprolactone alkyl ester is used. The polycaprolactone alkyl ester is specifically represented by the general formula (III)

Embedded image (Wherein, f and g each independently represent an integer of 1 to 30).

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. Based on the total amount, (a) the resin is preferably 10 to 85% by weight, more preferably 20 to 60%, particularly preferably 25 to 50% by weight, and (b) the pigment is preferably 5 to 70% by weight. More preferably 10 to 60%, particularly preferably 15 to 50% by weight, (c) the monomer having one or more photopolymerizable unsaturated bonds in the molecule is preferably 2 to 50% by weight, more preferably 5 to 50% by weight. 40%, particularly preferably 10 to 30% by weight, and (d) the photopolymerization initiator is preferably 0.01 to 20% by weight, more preferably 2 to 15% by weight.
%, Particularly preferably 5 to 10% by weight, (e) the nonionic surfactant is preferably 0.1 to 20% by weight, more preferably 0.5 to 15%, particularly preferably 1 to 10% by weight, It is said.

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. When the amount of the photopolymerization initiator is too small, the photosensitivity tends to decrease. Furthermore, when the amount of the nonionic surfactant is too small, the dispersion stability of the pigment tends to be low,
If the amount is too large, the light sensitivity 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, Coupling agents (having vinyl group, epoxy group, amino group, mercapto group, etc.) and titanate coupling agents (isopropyltrimethacryloyl titanate, diisopropylisostearoyl-4-aminobenzoyl titanate, etc.) ), A surfactant (fluorine-based, silicon-based, hydrocarbon-based, etc.) for improving the smoothness of the film and other various additives such as an ultraviolet absorber and an antioxidant are appropriately used as necessary. Can be.

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, and lactones. Specifically, examples of the ketone compound include acetone, methyl ethyl ketone, cyclohexanone, and dioxane.Examples of the alkylene glycol ether compound include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, and diethylene glycol methyl ethyl. Mono- or dialkyl ethers of diethylene glycol such as ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol Acetylated products of diethylene glycol monoalkyl ethers such as ethyl monopropyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl 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 mono- or dialkyl ethers such as propylene glycol methyl ethyl ether, propylene glycol dipropyl ether and propylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether There are acetylated products of propylene glycol monoalkyl ether such as teracetate and propylene glycol monobutyl ether acetate, and the alcohol compounds include methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, 3-methyl-3-methoxybutanol and the like. There are benzene, toluene, xylene and the like as aromatic compounds, and β-lactone, γ-
Lactone, δ-lactone and the like, and other examples include organic solvents such as tetrahydrofuran, N-methyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, 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 dispersibility, coating film 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,
Total solids content including photoinitiator and nonionic surfactant is 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,
Coating properties deteriorate. If the total solid content is less than 5% by weight, the viscosity tends to be low, and the coatability 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 the resin, the non-ionic surfactant polycaprolactone alkyl ester and the organic solvent. 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 one or more photopolymerizable unsaturated bonds in the molecule and the photoinitiator may be mixed before or after the dispersion treatment.

At this time, a polycarboxylic acid type polymer activator,
Anionic pigment dispersants such as polysulfonic acid type polymer activators, pigment dispersants such as nonionic pigment dispersants such as polyoxyethylene / polyoxypropylene block polymers, anthraquinones, perylenes, phthalocyanines, quinacdrines, etc. When a derivative of an organic dye into which a substituent such as a carboxyl group, a sulfonic acid group, a sulfonic acid group, a carboxylic acid amide group, a sulfonic acid amide group, or a hydroxyl group is introduced is added to the organic dye, the dispersibility and dispersion stability of the pigment are improved. Improved and preferred. 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.

The photosensitive solution for forming a colored image thus obtained is directly applied to a substrate by, for example, roll coater application, spin coater application, spray application,
There are wool coater coat, dip coater coater, curtain flow coater coater, wire bar coater coater, gravure coater coater, air knife coater coater and the like. The substrate used at this time is selected depending on the application, for example, a transparent glass substrate such as a white plate glass, a blue plate glass, a silica-coated blue plate glass, a synthetic resin such as a polyester resin, a polycarbonate resin, an acrylic resin, and a vinyl chloride resin. Examples include a sheet, a film or a substrate, a metal substrate such as an aluminum plate, a copper plate, a nickel plate, and a stainless steel plate, other ceramic substrates, and a semiconductor substrate having a photoelectric conversion element. After coating, usually at a temperature of 50 to 130 ° C.,
The film can be obtained by drying for ３０30 minutes.

On the other hand, the photosensitive liquid for forming a colored image is not applied directly to the substrate, but is first applied onto a support and dried to form a layer containing the colored image forming material (the thickness is usually 0.1 to 30).
0 μm, preferably 0.2 to 30 μm, more preferably 0.2 to 5 μm) to form a photosensitive element, which is then laminated on a substrate to form a film of the colored image forming material on the substrate. It can also be formed. As a method of applying the photosensitive solution to the support, a knife coater application,
Gravure coater coating, roll coater coating, spray coater coating, and the like. As the support used at this time, for example, a film such as a polyester film, a polyimide film, a polyamideimide film, a polypropylene film, and a polystyrene film may be mentioned.

After the application, the film can be dried usually at a temperature of 50 to 130 ° C. for 1 to 30 minutes, similarly to the method of directly applying a colored image forming photosensitive liquid to a substrate. Further, for the purpose of preventing dust from adhering to the surface of the film, it is preferable to laminate a peelable cover film on the surface of the film. Examples of the peelable cover film include, for example, a polyethylene film, a Teflon film, a polypropylene film, surface-treated paper, and the like.When the cover film is peeled, rather than the adhesive force between the film and the support,
It is preferable that the adhesive force between the film and the cover film is smaller.

As a method of laminating the thus obtained photosensitive element on a substrate, it is preferable to heat-press while laminating the substrate and the film containing the colored image forming material of the present invention. In this case, the atmosphere may be normal pressure or reduced pressure. Thus formed on the substrate surface, the thickness of the film containing the colored image forming material of the present invention,
Depends on the application, but is usually 0.1 to 300 μm
Used in the range. When used for a color filter, it is usually used in the range of 0.2 to 5 μm.

Next, a method for forming an image pattern will be described. The film on the substrate obtained by the above method is irradiated with actinic rays in an image-like manner to cure the film in the exposed portion. On this occasion,
When a film is formed using a photosensitive element, exposure may be performed from above with the support attached, or exposure may be performed after removing the support. Further, even when a film is formed by directly applying a photosensitive liquid to the substrate, an oxygen barrier film such as polyvinyl alcohol having a thickness of 0.5 to 30 μm may be formed on the surface of the film, and the film may be exposed from above. As a 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 tungsten 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.

Subsequently, a developing step is performed. That is, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, inorganic alkalis such as sodium metasilicate, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, triethylamine, An unexposed portion is removed by spraying or dipping in an aqueous solution containing an organic base such as n-butylamine or a salt, or the like, so that a colored image pattern of a cured film corresponding to an image can be obtained. At this time, when exposure is performed with the support, the support is peeled off and development is performed. After development, the colored image pattern is further exposed to light of 0.5 to 5 mJ / cm ² using a high-pressure mercury lamp or the like, or is post-heated at a temperature of 60 to 200 ° C. for 1 to 60 minutes to form an image pattern. Is preferred because it is more robust.

As an example of the preparation of a color filter used in a liquid crystal display device, a colored image of red, green, blue or the like can be obtained by repeating the above-mentioned method using the colored image forming material of the present invention on a glass substrate. After forming, a black colored image is formed as a black matrix in the gap between the colored pixels, or after forming a black matrix by chromium vapor deposition or a black colored image first, then red, green, There is a method of forming a color filter by forming a colored pixel such as blue.

[0041]

Next, the present invention will be described with reference to examples.

(1) Resin used: Copolymer A: Styrene 50 mol% -maleic acid mono (3
-Metalloyloxy-2-hydroxypropyl) ester 30 mol% -maleic acid derivative A 20 mol%, a weight average molecular weight of 11,000 and an acid value of 66.3;
A copolymer having an unsaturated equivalent of 564.7. (2) The repeating unit based on the maleic acid derivative has the following structure.

Embedded image

Preparation Example 1 of Photosensitive Liquid 40 g of Copolymer A as a resin, 25 g of CI Pigment Red 177 as a pigment, and CI Pigment Yellow 1
39 and 5 g of diethylene glycol dimethyl ether were mixed, and the resulting mixture was subjected to a dispersion treatment using a bead mill for 2 hours. To 200 g of the obtained dispersion, 13 g of copolymer A, 27 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 292 g of diethylene glycol dimethyl ether as an organic solvent were 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 as a pigment, and CI Pigment Yellow 8
3 g and diethylene glycol dimethyl ether 2
50 g 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 dipentaerythritol hexaacrylate as a monomer, 6 g of benzophenone as a photoinitiator and N,
3 g of N'-tetraethyl-4,4'-diaminobenzophenone and 125 g of diethylene glycol dimethyl ether as an organic solvent were added and mixed to obtain a photosensitive liquid for forming a colored image.

Preparation Example 3 of Photosensitive Liquid 20 g of Copolymer A as a resin, 24 g of CI Pigment Blue 15: 6 as a pigment, 1 g of CI Pigment Violet 23 and 216 g of diethylene glycol dimethyl ether were mixed, and the resulting mixture was subjected to a bead mill. For 2 hours. 140 g of the obtained dispersion
38.5 g of copolymer A, 35 g of dipentaerythritol hexaacrylate as a monomer, 6 g of benzophenone as a photoinitiator and N, N'-tetraethyl-
2 g of 4,4'-diaminobenzophenone and diethylene glycol dimethyl ether 262.
5 g was added and mixed to obtain a colored image forming photosensitive liquid.

Preparation Example 4 of Photosensitive Liquid 38 g of Copolymer A as a resin, 46 g of CI Pigment Black 7 as a pigment and 216 g of diethylene glycol dimethyl ether were mixed, and the resulting mixture was dispersed for 2 hours using a bead mill. Dispersion 2 obtained
38.5 g of copolymer A, 27 g of dipentaerythritol hexaacrylate as a monomer, 6 g of benzophenone as a photoinitiator, 2 g of N, N'-tetraethyl-4,4'-diaminobenzophenone, and diethylene glycol dimethyl ether as an organic solvent 2
80 g was added and mixed to obtain a photosensitive liquid for forming a colored image.

Comparative Examples 1-4 The photosensitive solutions obtained in Preparation Examples 1-4 were prepared at 5 ° C. and 25 ° C.
, And the stability of the viscosity was examined. The results are shown in Table 1.
In addition, the photosensitive liquids obtained in Preparation Examples 1 to 4 were applied to a glass substrate (Corning Co., trade name: 7059) by spin coating, and then dried at 90 ° C. for 5 minutes to obtain a film thickness of 1.
When a 0 μm film was formed and applied, the appearance of the coating film was visually evaluated, and the results are shown in Table 1. The obtained film was exposed to an image of 200 mJ / cm ² by an ultra-high pressure mercury lamp through a negative mask, and then polyoxyethylene nonylphenyl ether (Nonal 912A, manufactured by Toho Chemical Co., Ltd.) was added to the film.
Development was performed with an aqueous solution containing 5% by weight and 0.3% by weight of potassium hydroxide to obtain a colored image pattern. The light sensitivity, resolution, and pattern shape of the obtained colored image pattern were evaluated by the following test methods, and the results are shown in Table 1.

[Test Method] Photosensitivity: An optical density of 0.05 was set as the first step, and evaluation was performed using a 21-step step tablet in which the optical density increased by 0.15 for each step. 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 closer the cross-sectional shape is to a rectangle, the better the pattern shape is.

[0049]

[Table 1]

Example 1 In preparing the photosensitive solution shown in Photosensitive Solution Preparation Example 1, a non-ionic surfactant polycaprolactone (n
# 21) Lauryl ester is colored image forming material total weight 1
0.1 parts by weight, 5 parts by weight, and 20 parts by weight were added to 00 parts by weight to prepare a photosensitive solution. The prepared photosensitive solution was evaluated in the same manner as in Comparative Example 1, and the results are shown in Table 2.

[0051]

[Table 2]

Example 2 A 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 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 evaluated in the same manner as in Example 1 for the photosensitive solution shown in Photosensitive Solution Preparation Example 3, and the evaluation results are shown in Table 4.

[0055]

[Table 4]

Example 4 A 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 photosensitive solution containing 5 parts by weight of the nonionic surfactant obtained in Example 1 was coated on a 6 μm-thick polyethylene terephthalate film by a gravure coating method, and then heated at 100 ° C.
For 2 minutes to form a film having a thickness of 1.0 μm, and then covering 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, a 10 mJ / cm ² exposure was performed in a pixel shape from above the polyethylene terephthalate using an ultra-high pressure mercury lamp, and then the polyethylene terephthalate film was peeled off. An aqueous solution containing 0.5% by weight of Nonal 912A) and 0.3% by weight of potassium hydroxide was used to obtain a red colored image.

The photosensitive solution containing 5 parts by weight of the nonionic surfactant obtained in Example 2, the photosensitive solution containing 5 parts by weight of the nonionic surfactant obtained in Example 3, and the photosensitive solution obtained in Example 4 Using the photosensitive solution containing 5 parts by weight of the obtained nonionic surfactant, photosensitive elements were respectively produced in the same manner as above, and green, blue and black colored images were obtained in the same manner as above. When any of the above photosensitive elements was used, an excellent colored image was obtained.

Example 6 A black matrix was formed by vapor deposition of chromium on the same glass substrate used in Example 1,
A red image pattern was formed in the same manner and under the same conditions as in Example 1 using the photosensitive solution containing 5 parts by weight of the nonionic surfactant obtained in the above, and then heat-treated at 240 ° C. for 20 minutes. Next, using the substrate and a photosensitive liquid containing 5 parts by weight of the nonionic surfactant obtained in Example 2, a green image is formed next to the red image pattern in the same manner and under the same conditions as in Example 2. A pattern was formed. Then, at 240 ° C, 2
Heat treatment was performed for 0 minutes. Then, using the substrate, a photosensitive liquid containing 5 parts by weight of the nonionic surfactant obtained in Example 3 was used under the same method and conditions as in Example 3,
A blue image pattern was formed next to the green image pattern. Thereafter, heat treatment was performed at 240 ° C. for 20 minutes.
As described above, one pixel is 30 μm × 100 μm red,
A color filter in which pixels were arranged in a mosaic of three colors of green and blue was produced. The pixel shape of the obtained color filter was good.

Example 7 The same method and conditions as in Example 4 were used by using a photosensitive solution containing 5 parts by weight of the nonionic surfactant obtained in Example 4 on the same glass substrate as used in Example 4. After a black matrix pattern was formed by heating at 240 ° C., heat treatment was performed at 240 ° C. for 20 minutes. Next, a red image pattern was formed on the substrate using the photosensitive solution containing 5 parts by weight of the nonionic surfactant obtained in Example 1 in the same manner and under the same conditions as in Example 1. Thereafter, heat treatment was performed at 240 ° C. for 20 minutes. Next, using the substrate and a photosensitive solution containing 5 parts by weight of the nonionic surfactant obtained in Example 2, under the same method and conditions as in Example 2, a green image is placed next to the red image pattern. A pattern was formed. Then, at 240 ° C, 2
Heat treatment was performed for 0 minutes. Then, using the substrate, a photosensitive liquid containing 5 parts by weight of the nonionic surfactant obtained in Example 3 was used under the same method and conditions as in Example 3,
A blue image pattern was formed next to the green image pattern. Thereafter, heat treatment was performed at 240 ° C. for 20 minutes.
As described above, one pixel is 30 μm × 100 μm red,
A color filter in which pixels were arranged in a mosaic of three colors of green and blue was produced. The pixel shape of the obtained color filter was good.

Example 8 The same glass substrate as that used in Example 1 except that a black matrix was formed by chromium vapor deposition on Example 5
After forming a red image pattern in the same manner and under the same conditions as above, a heat treatment was performed at 240 ° C. for 20 minutes. Then
Using the substrate, in the same manner and under the same conditions as in Example 5,
A green image pattern was formed next to the red image pattern. Thereafter, heat treatment was performed at 240 ° 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 5. Thereafter, heat treatment was performed at 240 ° 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. The pixel shape of the obtained color filter was good.

[0063]

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 excellent pigment dispersibility. The photosensitive liquid for forming a colored image according to the fourth aspect is made of a photosensitive resin in which a pigment is dispersed, and contains a material for forming a colored image having excellent pigment dispersibility. The photosensitive element according to the fifth and sixth aspects is made of a photosensitive resin in which a pigment is dispersed, and has a photosensitive layer containing a colored image forming material having excellent pigment dispersibility. Claim 7
The method for producing a colored image described above comprises a photosensitive resin in which a pigment is dispersed, and a colored image having excellent pigment dispersibility can be obtained. According to the method for producing a color filter according to the eighth aspect, a color filter comprising a photosensitive resin in which a pigment is dispersed and having a pixel coating film having excellent pigment dispersibility can be obtained.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Koji Yamazaki 14 Goi South Coast, Ichihara City, Chiba Prefecture Inside the Goi Plant of Hitachi Chemical Co., Ltd. (72) Inventor Tetsuya Okazaki 14 Goi South Coast, Ichihara City, Chiba Prefecture Hitachi Chemical Co., Ltd. Inside the Goi Plant (72) Inventor Seigo Yokochi 14 Goi South Coast, Ichihara City, Chiba Prefecture Hitachi Chemical Co., Ltd.The Goi Plant Inside F-term (reference) CA00 CB10 CB16 CB17 CB45 CB55 CC03 CC04 CC12 DA03 EA04 EA08 FA15 2H048 BA45 BA48

Claims (8)

[Claims] 1. A colored image forming material comprising a resin, a pigment, a monomer containing at least one photopolymerizable unsaturated bond in a molecule, a photopolymerization initiator and a nonionic surfactant, wherein A coloring image forming material, wherein the agent is a polycaprolactone alkyl ester; 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) (However, in the formula, 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
A general formula (I) / a general formula (II) in a ratio of 1/1 to 5/1 (molar ratio), and a general formula (II) Is a resin in which at least a part of the repeating unit represented by the formula (II) is a repeating unit in which at least one of R ⁴ and R ⁵ represents a group having a photoreactive unsaturated bond. 2. The colored image forming material according to item 2. 4. 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. Photosensitive liquid. 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.