JP2002212438A - Green resin composition, photosensitive green resin composition, photosensitive liquid for formation of green image, and manufacturing methods of green-colored image and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a green resin composition where light transmittance is improved by dispersing a pigment, a photosensitive green resin composition where light transmittance is improved, a photosensitive liquid for formation of a green image where light transmittance is improved, and manufacturing methods of a green-colored image where light transmittance is improved and a color filter containing the green-colored image excellent in light transmittance. SOLUTION: A green resin composition comprises dispersing a green pigment and a pigment pulverized represented by general formula (1) (X is selected from H, Cl, Br and I which may be different) wherein an average particle size is in not more than 70 nm, into a resin, and manufacturing methods of a green-colored image, etc., use the resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a green resin composition,
The present invention relates to a photosensitive green resin composition, a photosensitive liquid for forming a green image, a method for producing a green 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 dyeing the same with a dye mainly to obtain pixels has been adopted. 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. There was a problem that the rate was low.

[0003]

DISCLOSURE OF THE INVENTION The present invention relates to (1) a green resin composition obtained by dispersing a green pigment and a pigment represented by the general formula (1) having an average particle diameter of 70 nm or less into a resin. ,

[0004]

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(2) Green pigments, pigments represented by the general formula (1) having a fine average particle diameter of 70 nm or less, resins, monomers having at least one photopolymerizable unsaturated bond in a molecule, and light A photosensitive green resin composition containing an initiator, (3)
The resin has an acid value of 20 to 300 and a weight average molecular weight of 1,5.
(2) a photosensitive green resin composition comprising a photosensitive green resin composition and an organic solvent, wherein the photosensitive green resin composition comprises a photosensitive green resin composition and an organic solvent;
(5) A method for producing a green colored image in which a photosensitive layer comprising the photosensitive green resin composition according to (2) or (3) is formed on a substrate and exposed to light, and (6) the photosensitive layer is formed as a green image according to (4). The present invention relates to (5) a method for producing a green colored image formed from the photosensitive liquid for formation and (7) a method for producing a color filter for forming a green colored image by the method for producing a colored image according to (5) or (6).

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, pigments include
The pigment represented by the above general formula (1) having an average particle size of 70 nm or less is used as an essential component. X in the formula is selected from H, Cl, Br and I, which may be different. By setting the average particle size to 70 nm or less, a green colored image having excellent light transmittance can be obtained. this,
The average particle size is preferably 10 nm or more and 70 nm or less, and 2
The thickness is more preferably from 0 nm to 40 nm. In the present invention, a green pigment and a yellow pigment are used in combination for adjusting chromaticity. The ratio of the general formula (1) is not particularly limited, and is preferably 5 to 100% by weight based on the pigment component. The higher the ratio, the higher the degree of improvement in transmittance, and conversely, the lower the ratio, the lower the degree of improvement in transmittance.

[0007] These pigments used for adjusting chromaticity include, for example, C.I. I. Pigment Green, 36, 37, C.I. I. Pigment Yellow 17, 20, 24, 83, 93, 109, 110, 1
17, 125, 128, 129, 139, 147, 15
0, 154, 180, 185 and the like. These green pigments and yellow pigments can be used as a mixture of two or more kinds.

The resin used in the present invention is not particularly limited as long as it has pigment dispersibility when used as a green image forming material. Further, a resin having a film forming property is preferable, and it does not hinder photosensitivity. And those having developability are preferred. Examples of such a resin include cellulosic resins such as carboxymethylhydroxyethylcellulose and hydroxyethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone and the like, and include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, glycidyl methacrylate, bis・ Glycidyl methacrylate, dimethylaminoethyl methacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, lauryl methacrylate, stearyl methacrylate, benzyl methacrylate, benzyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate,
Butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl methacrylate, hexyl acrylate,
Homopolymers or copolymers of acrylates or methacrylates such as octyl methacrylate, octyl acrylate, and phosphorus-containing methacrylate, styrene, styrene derivatives, and other polymerizable monomers; (meth) acrylic acid (acrylic acid and methacrylic acid) The same applies hereinafter), carboxyl group-containing polymerizable monomers such as itaconic acid, maleic acid, maleic anhydride, monoalkyl maleate, citraconic acid, citraconic anhydride and monoalkyl citraconic acid, and (meth) acrylic acid. Esters, styrene, styrene derivatives, and copolymers with other polymerizable monomers are preferred.

The monoalkyl maleate is preferably an alkyl group having 1 to 12 carbon atoms in the alkyl group, such as monomethyl maleate, monoethyl maleate, mono-n-propyl maleate, monoisopropyl maleate and monoisopropyl maleate. -N-butyl, maleic acid mono-
n-hexyl, mono-n-octyl maleate, mono-2-ethylhexyl maleate, mono-n-maleate
Nonyl, mono-n-dodecyl maleate and the like can be mentioned. As the citraconic acid monoalkyl ester,
Those having 1 to 12 carbon atoms in the alkyl group are preferred, and monomethyl citraconic acid, monoethyl citraconic acid, mono-n-propyl citraconic acid, monoisopropyl citraconic acid, mono-n-butyl citraconic acid, mono-n-hexyl citraconic acid Mono-n-octyl citraconic acid,
Examples thereof include mono-2-ethylhexyl citraconic acid, mono-n-nonyl citraconic acid, and mono-n-dodecyl citraconic acid. Examples of the styrene derivative include α-methylstyrene, m- or p-methoxystyrene, p-hydroxystyrene, 2-methoxy-4-hydroxystyrene, 2-hydroxy-4-methylstyrene, and the like.

Further, as the resin, a resin having a photopolymerizable unsaturated bond may be used. Preferred examples of such a resin include oxirane rings such as glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, α-ethyl glycidyl acrylate, crotonyl glycidyl ether, and monoalkyl glycidyl ether itaconate in a high acid value carboxy group-containing resin. And a compound having one ethylenically unsaturated bond, allyl alcohol, 2-buten-4-ol, furfuryl alcohol, oleyl alcohol, cinnamyl alcohol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N- One each of a hydroxyl group such as methylol acrylamide and an ethylenically unsaturated bond
Resin obtained by reacting a compound having a carboxylic acid group (unsaturated alcohol), resin obtained by reacting a carboxyl group-containing resin having a hydroxyl group with an unsaturated compound having a free isocyanate group, polyaddition to an addition reaction product of an epoxy resin and an unsaturated carboxylic acid Examples thereof include a resin obtained by reacting an acid anhydride, and a resin obtained by reacting a hydroxyl group-containing polymerizable monomer with an addition reaction product of a conjugated diene polymer or a conjugated diene copolymer with an unsaturated dicarboxylic anhydride.

The unsaturated equivalent of these resins is from 600 to 3
000, preferably 800 to 2000
It is more preferable to be within the range. If the unsaturated equivalent is too small, there is a tendency to partially cure when preparing the photosensitive material, particularly when dispersing the pigment in the resin, and if the unsaturated equivalent is too large, sufficient photopolymerizability is imparted by the introduction of unsaturated groups. Not done. In addition, the unsaturated equivalent here means the molecular weight of the resin per one unsaturated bond.

The above resin is said to have alkali developability after exposure when it has photopolymerizability itself or when it is given photosensitivity as a composition such as a photosensitive green resin composition described later. From the viewpoint, the acid value is 20 to 300.
, Preferably in the range of 40 to 200, and more preferably in the range of 60 to 150. If the acid value is less than 20, alkali developability tends to decrease, and if it exceeds 300, the shape of the pixel pattern after alkali development tends to be unclear.

The weight average molecular weight of the resin is 1,
It is preferably in the range of 500 to 200,000, more preferably in the range of 5,000 to 100,000, and even more preferably in the range of 10,000 to 50,000. Weight average molecular weight of 1,50
If it is less than 0, the dispersion stability of the pigment tends to decrease, and if it exceeds 200,000, the viscosity increases when it is made into a photosensitive solution, and the coatability, especially the coatability when spin-coating, tends to decrease. There is.

In the present specification, the weight average molecular weight is a value measured by gel permeation chromatography and converted using a calibration curve of standard polystyrene. An acid value of 20 to 300 and a weight average molecular weight of 1.5
In particular, as the resin of 00 to 200,000, (meth)
An acrylic resin, at least two of which are monomer components (I) 2-hydroxyethyl methacrylate and (II)
Methacrylic acid, which is obtained using a copolymerizable (meth) acrylic monomer having at least one benzene ring in the unit molecule (III), and copolymerizing (I), (II) and (III) When the resin is 100 parts by weight, the (meth) acrylic resin obtained by polymerizing 3 to 30 parts by weight of (I), 5 to 50 parts by weight of (II) and 20 to 92 parts by weight of (III) is stable in dispersion of the pigment. It is preferable from the viewpoints of properties and light sensitivity.

As the resin used in the green resin composition of the present invention, other resins may be used in combination with the above-mentioned resins. As another resin, an epoxy resin, a urethane resin, a melamine resin, or 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. The green resin composition may further contain a monomer having one or more photopolymerizable unsaturated bonds in a molecule and a photoinitiator to form a photosensitive green resin composition, and further contain an organic solvent. To form a photosensitive solution.

Examples of the monomer having one or more photopolymerizable unsaturated bonds in a molecule include methyl methacrylate, benzyl methacrylate, butoxyethyl methacrylate, butoxytriethylene glycol acrylate, ECH (epichlorohydrin) -modified butyl acrylate, Cyclopentanyl acrylate, EO (ethylene oxide) -modified dicyclopentenyl acrylate,
N, N-dimethylaminoethyl methacrylate, ethyl diethylene glycol acrylate, 2-ethylhexyl acrylate, glycerol methacrylate, heptadecafluorodecyl acrylate, 2-hydroxyethyl methacrylate, caprolactone-modified 2-hydroxyethyl acrylate, isobornyl acrylate, methoxydipropylene Glycol acrylate, methoxylated cyclodecatriene acrylate, phenoxyhexaethylene glycol acrylate, EO-modified phosphate acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, EO-modified bisphenol A diacrylate, ECH-modified bisphenol A diacrylate, bisphenol A dimethacrylate, 1, 4-butanediol diacrylate, , 3-butylene glycol diacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol di acrylate, EO-modified phosphoric acid diacrylate, EC
H-modified phthalic acid diacrylate, polyethylene glycol 400 diacrylate, polypropylene glycol 4
00 dimethacrylate, tetraethylene glycol diacrylate, ECH-modified 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, EO-modified phosphate triacrylate, EO-modified trimethylolpropane triacrylate, PO (propylene) Oxide) modified trimethylolpropane triacrylate, tris (methacryloxyethyl) isocyanurate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, acrylates such as dipentaerythritol pentaacrylate, and methacrylates corresponding thereto. Is mentioned. These monomers can be used alone or in combination of two or more.

Examples of the photoinitiator include benzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, benzyl, 2,2-diethoxyacetophenone and 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
-Butyl anthraquinone, 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. As the organic solvent, for example,
Ketone compounds, alkylene glycol ether compounds,
Examples include alcohol compounds and aromatic compounds. Specific examples include ketone compounds such as acetone, methyl ethyl ketone, and cyclohexanone.Alkylene glycol ether compounds include methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, ethylene glycol monopropyl ether, and ethylene glycol. Glycol monohexyl ether, ethylene glycol dimethyl ether, diethylene glycol ethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate , Diethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol propyl ether acetate, diethylene glycol isopropyl ether acetate, diethylene glycol butyl ether acetate, diethylene glycol-t-butyl ether acetate, triethylene glycol methyl ether acetate, triethylene glycol ethyl ether acetate, triethylene glycol propyl Ether acetate, triethylene glycol isopropyl ether acetate, triethylene glycol butyl ether acetate, triethylene glycol-t-butyl ether acetate, and the like. Propyl alcohol, n- butyl alcohol, there are 3-methyl-3-methoxybutanol and the like, aromatic compounds, benzene,
Toluene, xylene, N-methyl-2-pyrrolidone, N
-Hydroxymethyl-2-pyrrolidone and the like, and as others, 3-methyl-3-methoxybutyl acetate,
Organic solvents such as ethyl acetate, tetrahydrofuran, dioxane and the like can be mentioned. These can be used alone or in combination of two or more.

The resin, pigment, monomer having at least one photopolymerizable unsaturated bond in the molecule, and the photoinitiator used in the photosensitive green resin composition or the photosensitive liquid for forming a green image are as follows. Based on the total amount, (a) the resin is preferably 10 to 85% by weight, more preferably 20 to 60% by weight,
More preferably 25 to 50% by weight, (b) the pigment is preferably 5 to 70% by weight, more preferably 10 to 40% by weight, even more preferably 15 to 30% by weight, and (c) a photopolymerizable unsaturated bond. Is preferably 2 to 50% by weight, more preferably 5 to 40% by weight, even more preferably 10 to 30% by weight, and (d) the photoinitiator is preferably 0.01% by weight. -20% by weight, more preferably 2-15% by weight, even more preferably 5-10% by weight.

When the amount of the resin in the photosensitive green resin composition or the photosensitive liquid for forming a green image is too small, the dispersion stability of the pigment tends to decrease. Properties, especially the applicability during spin coating, tend 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. Further, when the amount of the monomer having one or more photopolymerizable unsaturated bonds in the molecule is too small, the photosensitivity tends to decrease, and when the amount is too large, the dispersion stability of the pigment tends to decrease.

Further, when the amount of the photoinitiator is too small, the photosensitivity tends to decrease, and when the amount is too large, the adhesiveness tends to decrease. Organic solvent is a resin in a green image forming photosensitive liquid,
It is preferably used so that the total solid content including the pigment, a monomer containing one or more photopolymerizable unsaturated bonds in the molecule and the photoinitiator is in the range of 5 to 40% by weight. If the total solid content exceeds 40% by weight, the viscosity tends to be high, and the coatability tends to be poor. If the total solid content is less than 5% by weight, the viscosity tends to be low and the coatability tends to be poor.

The photosensitive green resin composition or the photosensitive liquid for forming a green image according to the present invention contains a thermal polymerization inhibitor (hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, etc.) for suppressing a dark reaction, and a substrate. Titanate coupling agent for improving adhesiveness with silane (silane coupling agent having vinyl group, epoxy group, amino group, mercapto group, etc., isopropyltrilotacryloyl titanate, diisopropylisostearoyl-4-aminobenzoyl titanate, etc.) ,
Surfactants (fluorine-based,
Various additives such as silicon-based and hydrocarbon-based), ultraviolet absorbers, and antioxidants can be used as needed.

Next, a method for producing the green resin composition, the photosensitive green resin composition and the photosensitive liquid for forming a colored image according to 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 dispersed with an ultrasonic disperser, a three-roll mill, a ball mill, a sand mill, a bead mill, a homogenizer, a kneader, or the like.
The dispersion treatment is preferably performed by kneading using a kneading apparatus. At this time, it is preferable to use at least 20 parts by weight of the resin based on 100 parts by weight of the pigment. If the amount of the resin is too small, the dispersion stability of the pigment tends to decrease.
It is preferable to use at least 100 parts by weight of the organic solvent at the time of dispersion based on 100 parts by weight of the total amount of the pigment and the resin at the time of dispersion. If it is less than 100 parts by weight, the viscosity at the time of dispersion is too high, and dispersion may be difficult particularly when the dispersion is carried out by a ball mill, a sand mill, a bead mill or the like. As described above, a green resin composition can be produced.

In order to prepare a photosensitive green resin composition or a photosensitive liquid for forming a colored image, a monomer having at least one photopolymerizable unsaturated bond in a molecule and a photoinitiator are mixed.
These may be mixed before the dispersion treatment or may be mixed after the dispersion treatment. The entire amount of the resin may not be used at the time of the dispersion, and the remainder may be mixed later, particularly at the time of producing a colored image forming photosensitive liquid. The amount of each component used is adjusted from the time of production of the green resin composition so that it finally becomes the mixing ratio in the photosensitive green resin composition or the photosensitive liquid for forming a green image.

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, and anthraquinone. , Perylene, phthalocyanine, quinacridone-based organic dyes such as carboxyl group, sulfonate group,
Derivatives of organic dyes into which substituents such as carboxylic acid amide groups and hydroxyl groups have been introduced. It is preferable because the dispersibility and dispersion stability of the pigment are improved. These 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 dye tends to shift.

In the above-mentioned dispersion treatment, the whole amount of the resin may be used together with the pigment at the time of the dispersion treatment, or a part of the resin may be added after the dispersion treatment. However, it is preferable to use at least 20 parts by weight of the resin for 100 parts by weight of the pigment during the dispersion treatment. If it is less than 20 parts by weight, the dispersion stability of the pigment tends to decrease. Similarly, the entire amount of the organic solvent may be used together with the pigment at the time of the dispersion treatment, or a part of the organic solvent may be added after the dispersion treatment. However, it is preferable to use at least 100 parts by weight of the organic solvent 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.

When 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 photosensitive colored resin composition or the photosensitive liquid for forming a colored image 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. The above-mentioned green pigments are used, but the following pigments are used as other pigments.
For a red colored image, a single red pigment may be used,
Toning may be performed by mixing a yellow pigment and an orange pigment with a red pigment.

The red pigments include, for example, C.I. I. Pigment Red 9, 123,
155, 168, 177, 180, 217, 220, 2
24, 254, etc., as a yellow pigment or an orange pigment,
C. I. Pigment Yellow 20, 24, 83, 93,
109, 110, 117, 125, 139, 147, 1
54, C.I. I. Pigment Oranges 71, 43 and the like can be used. These red pigments, yellow pigments and orange pigments can be used as a mixture of two or more kinds. For a blue colored image, a single blue pigment system may be used, or the blue pigment system may be mixed with a violet pigment system to perform toning.

Examples of the blue pigment include, for example, C.I. I. Pigment Blue 15, 15:
3, 15: 4, 15: 6, 22, 60 and the like.
Examples of purple pigments include C.I. I. Pigment Violet 19, 23, 2
9, 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. .

For the black colored image, for example, black pigments such as carbon black, graphite, titanium carbon, black iron, and manganese dioxide are used. When a pigment system other than the green pigment system is used, the coloring resin composition, the composition in the photosensitive coloring resin composition and the photosensitive solution for forming a colored image, the components used other than the pigment, the composition or the method of preparing the photosensitive solution are as follows. , A green resin composition, a photosensitive green resin composition, and a photosensitive liquid for forming a green image. In order to form a photosensitive layer on a substrate using a colored image forming material, the colored image forming photosensitive liquid is directly applied to the substrate, or the photosensitive liquid is once applied to a support to form a film, and then the substrate is coated on the substrate. It can be performed by forming.

The above-mentioned substrate is selected depending on the application. For example, a transparent glass plate such as a white plate glass, a blue plate glass, a silica-coated blue plate glass, or a synthetic resin such as a polyester resin, a polycarbonate resin, an acrylic resin, and a vinyl chloride resin. Sheet, film or plate, aluminum plate,
Examples include a metal plate such as a copper plate, a nickel plate, and a stainless steel plate, other ceramic plates, and a semiconductor substrate having a photoelectric conversion element. A black matrix may be formed on these substrates in advance by chromium evaporation or the like.

As a method of applying the photosensitive liquid to the substrate, roll coating, spin coating, spray coating,
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. 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 300.
It is preferably in the range of μm. When used for a color filter, the thickness is preferably in the range of 0.2 to 5 μm.

A photosensitive layer can be formed on a support in the same manner as described above. In order to form the photosensitive layer on the substrate, there is a method of laminating a film on the substrate and pressing the film 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 separated after forming a photosensitive layer on the substrate. As the support, a polyethylene film, an acrylic resin film, a polyester film, or the like can be used.

The exposure of the photosensitive layer formed on the substrate can be performed by irradiating the photosensitive layer with actinic rays in an image-like manner. Thereby, the film in the exposed portion can be cured. At the time of exposure, an oxygen barrier film such as polyvinyl alcohol may be formed on the surface of the film with a thickness of 0.5 to 30 μm, and the film may be exposed from above. As the light source of the actinic ray, for example, a Kabon 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. By performing pattern exposure through a photomask or direct drawing by scanning using these light sources, an actinic ray is irradiated in an image form.

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, or an organic base such as monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, triethylamine, or 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 can be obtained by such a colored image forming process,
In particular, in the method of manufacturing a color filter, it is preferable that the colored image forming step is repeatedly performed for three to four different colored images including a green image forming step. For example, red, green, and blue colored images are formed on a black matrix previously formed by chromium evaporation or the like. Also,
After forming a black matrix using a black colored image forming material, red, green and blue colored images are formed. Further, after forming the red, green and blue colored images, a black matrix is formed in the gaps between these colored images using a black image forming material. The order of forming red, green, and blue colored images is arbitrary. The colored image is adapted to form pixels for each color.

[0037]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. (1) Resin used: 70 mol% of benzyl methacrylate-2-15 mol% of hydroxyethyl methacrylate
A copolymer having a polymerization average molecular weight of 25,000 and an acid value of 96, obtained by polymerizing 15 mol% of methacrylic acid (hereinafter referred to as copolymer A).

Example 1 (1) Preparation of Photosensitive Liquid for Forming a Green Colored Image In 250 g of diethylene glycol dimethyl ether, 60 g of copolymer A as a resin and the above-mentioned general formula (1) in which the average particle diameter was reduced to 45 nm were used. Wherein X is a chlorine atom, 18 g of a pigment represented by C.I. I. Pigment Green 36 was added, and the mixture was dispersed for 2 hours using a bead mill. To 220 g of this dispersion, 35 g of dipentaerythritol hexaacrylate as a monomer, 6 g of benzophenone and 3 g of N, N'-tetraethyl-4,4'-diaminobenzophenone as a photoinitiator, and diethylene glycol dimethyl ether 125 as an organic solvent
g was added and mixed to obtain a green colored image forming photosensitive liquid.

(2) Production of Green Colored Image This photosensitive liquid was applied to a glass substrate (Corning Co., trade name 7).
059) by spin coating, and then 11
Drying was performed at 0 ° C. for 5 minutes to form a film having a thickness of 2.0 μm. The obtained film was exposed to an image of 700 mJ / cm ² through an ultra-high pressure mercury lamp through a negative mask, and then developed with an aqueous solution containing 0.3% by weight of potassium hydroxide. Table 1 and FIG. 1 show the reflectance, chromaticity, and transmission curve of the obtained green colored image.

Comparative Example 1 (1) Preparation of Photosensitive Liquid for Forming Green Colored Image In 250 g of diethylene glycol dimethyl ether, 60 g of copolymer A as a resin and an average particle diameter of 200 nm were used.
18 g of a pigment represented by the general formula (1) wherein X is a chlorine atom; I. Pigment Green 36 was added, and the mixture was dispersed for 2 hours using a bead mill. To 220 g of this dispersion, 35 g of dipentaerythritol hexaacrylate as a monomer, 6 g of benzophenone and 3 g of N, N'-tetraethyl-4,4'-diaminobenzophenone as a photoinitiator and 125 g of diethylene glycol dimethyl ether as an organic solvent were added and mixed. Thus, a green colored photosensitive liquid for image formation was obtained.

(2) Production of Green Colored Image This photosensitive liquid was applied to a glass substrate (Corning Co., trade name 7).
059) by spin coating, and then 11
Drying was performed at 0 ° C. for 5 minutes to form a 2.0 μm thick film. The obtained film was exposed to an image of 700 mJ / cm ² through an ultra-high pressure mercury lamp through a negative mask, and then developed with an aqueous solution containing 0.3% by weight of potassium hydroxide. Table 1 and FIG. 1 show the reflectance, chromaticity, and transmission curve of the obtained green colored image.

[0042]

[Table 1]

The reflectance and the chromaticity were measured using a spectrocolorimeter JP7200F manufactured by Color Techno System Co., Ltd.
Y, x, and y after the measurement are a Y value, an x value, and a y value based on the XYZ (Yxy) color system, which is the CIE standard color system. From Table 1, it can be seen that the use of the pigment represented by the general formula (1), which has been refined to 45 nm according to the present invention, has a large chromaticity Y value and good color purity (Example 1). Further, it can be seen from the transmission curve (FIG. 1) that the light transmittance is greatly improved. On the other hand, a pigment represented by the general formula (1) having an average particle diameter of 200 nm (Comparative Example 1)
It is recognized that the value of Y of the chromaticity is low and the transmittance is not good. From the above, it can be confirmed that the examples have excellent optical characteristics and are effective as image display elements.

[0044]

The green colored image formed by the green resin composition, photosensitive green resin composition, and photosensitive liquid for forming a green image according to the present invention has excellent light transmittance. According to the method for producing a green colored image according to the present invention, a green image having excellent light transmittance can be obtained. Further, by the method for manufacturing a color filter according to the present invention, a color filter having green pixels having excellent light transmittance can be manufactured.

[Brief description of the drawings]

FIG. 1 is a graph showing light transmission curves of green coloring images of pixels obtained in Examples and Comparative Examples.

[Explanation of symbols]

 Example 1 Green Pixel Light Transmittance Curve Created in Example 1 Comparative Example 1 Green Pixel Light Transmittance Curve Created in Comparative Example 1

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/07 C08K 5/07 G02B 5/20 101 G02B 5/20 101 G03F 7/004 505 G03F 7/004 505 (72) Inventor Liu Shunbayashi 14 Goi South Coast, Ichihara City, Chiba Prefecture, Hitachi Chemical Industry Co., Ltd.Goi Office (72) Inventor Koji Yamazaki 14 Goi South Coast, Ichihara City, Chiba Prefecture, Hitachi Chemical Co., Ltd. Goi Office (72) Inventor Tetsuya Okazaki 14 Goi South Coast, Ichihara City, Chiba Prefecture Hitachi Chemical Co., Ltd. Goi Office (72) Inventor Seiji Haruhara 14 Goi South Coast, Ichihara City, Chiba Prefecture Hitachi Chemical Co., Ltd. Goi Office F-term (Reference) 2H025 AA04 AA10 AA11 AB13 AC01 AD01 BC13 BC42 CA00 CB42 CB55 CB56 CC03 CC12 FA17 2H048 BA45 BA 47 BA48 BB42 4J002 AB021 BC031 BE011 BG031 BG071 BJ001 EE046 FD096 GQ00 4J011 QA03 QA05 QA06 QA07 QA33 QA34 QA38 QA46 RA03 RA04 RA09 RA10 SA01 SA06 SA21 SA25 SA31 SA41 SA64 SA02 BA03 A01 BA01 A26 A01 BA01 A26 A01 BA01

Claims (7)

[Claims] 1. A green resin composition obtained by dispersing a green pigment and a pigment represented by the general formula (1) whose average particle diameter is reduced to 70 nm or less in a resin. Embedded image 2. A green pigment, a pigment represented by the general formula (1) having an average particle diameter of 70 nm or less, a resin, a monomer having at least one photopolymerizable unsaturated bond in a molecule, and photoinitiation. Green photosensitive resin composition containing an agent. 3. The photosensitive green resin composition according to claim 2, wherein the resin has an acid value of 20 to 300 and a weight average molecular weight of 1,500 to 200,000. 4. A photosensitive liquid for forming a green image, comprising the photosensitive green resin composition according to claim 2 and an organic solvent. 5. A method for producing a green colored image in which a photosensitive layer comprising the photosensitive green resin composition according to claim 2 or 3 is formed on a substrate and an exposure phenomenon occurs. 6. The method for producing a green colored image according to claim 5, wherein the photosensitive layer is formed from the photosensitive liquid for forming a green image according to claim 4. 7. A method for producing a color filter, comprising the step of forming a green colored image by the method for producing a colored image according to claim 5.