JP2000258911A - Photosensitive colorable resin composition, photosensitive fluid for forming colored image, photosensitive element, production of colored image, production of panel for color filter and production of color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive colorable resin composition excellent in photosensitive characteristics such as photosensitivity, attaining efficient coloring or discoloring by heat treatment after patterning by exposure and development, suitable for use particularly in the formation of the black matrix of a color filter and capable of forming a black matrix excellent in light shielding property, low reflexivity and insulating property with good resolution. SOLUTION: The photosensitive colorable resin composition that colors or discolors under heat contains (A) a photosetting resin component, (B) a fluorane compound, (C) a thermally acid generating agent and (D) a compound containing one or more epoxy groups in one molecule. An organic solvent is added to the photosensitive colorable resin composition to obtain the objective photosensitive fluid for forming a colored image. A photosensitive layer comprising the photosensitive colorable resin composition is formed on a substrate to obtain the objective photosensitive element.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive coloring resin composition, a photosensitive liquid for forming a colored image, a photosensitive element, a method for producing a colored image, a method for producing a color filter panel, 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 devices, sensors, color separation devices, and the like.
This color filter is composed of red, green, blue or cyan, magenta, and yellow pixels, and a light-shielding black matrix corresponding to a gap between these pixels. Conventionally, as a method for producing a black matrix, a method has been employed in which chromium metal is deposited on a glass substrate and etched. The black matrix produced by this method has a problem that the light shielding property is high but the reflectance is high and the visibility is poor. As a means for solving the problem, a low reflection chromium having a chromium oxide / chromium metal bilayer structure has been devised. However, this method has a problem that the cost is high.

[0003] Recently, attention has been paid to a method using a photosensitive material in which a pigment is dispersed, and many studies have been made. According to this method, it is known that the manufacturing method is also simplified and the reflectance is reduced. However, on the other hand, in order to increase the light-shielding property, the pigment content must be increased, and there has been a problem that the photosensitive characteristics are reduced. Further, when carbon black is used, there is also a problem that the specific resistance is reduced.

Further, in general, when a photosensitive resin composition contains a dye, there is a problem that the photosensitive characteristics are deteriorated due to light absorption by the dye, particularly when the content of the dye is large.

Further, generally, a resin composition which is colored only after a specific treatment is expected to be used in various fields.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photosensitive colored resin composition which has excellent photosensitive characteristics such as photosensitivity and which can be efficiently colored or discolored by heat treatment after patterning.

Another object of the present invention is to provide a photosensitive solution containing a photosensitive coloring resin composition which has excellent photosensitive characteristics such as photosensitivity and which efficiently develops or changes its color by heat treatment after patterning.

Another object of the present invention is to provide a photosensitive element containing a photosensitive coloring resin composition which is excellent in photosensitive characteristics such as photosensitivity and which develops or changes its color by heat treatment.

Another object of the present invention is to provide a method for producing a colored image in which an image can be colored or discolored by heat treatment after exposure and development, and the photosensitive characteristics such as photosensitivity at the time of exposure are improved. Aim.

Further, according to the present invention, a photosensitive layer is formed on a substrate by using the above-mentioned photosensitive liquid for forming a colored image or a photosensitive element, and after exposure and development, heat treatment is carried out to form a color or change the color. It is an object of the present invention to provide a method for producing a color filter panel having a black matrix having excellent properties, low reflectivity, and insulating properties.

Another object of the present invention is to provide a color filter having a black matrix excellent in light-shielding properties, low reflectivity, insulating properties, and the like, and a plurality of pixels of different chromatic colors.

[0012]

The present invention comprises (A) a photocurable resin component, (B) a fluoran compound, (C) a thermal acid generator and (D) at least one epoxy group in a molecule. Provided is a photosensitive coloring resin composition which contains a compound and develops or discolors by heat.

Further, the present invention provides, as one embodiment of the photosensitive coloring resin composition of the present invention, (A) a photocurable resin component,
(B) a fluoran compound, (C) a thermal acid generator, (D) a compound containing at least one epoxy group in a molecule, and (E)
Provided is a photosensitive coloring resin composition which contains a dye and which develops or changes color to an achromatic color by heat.

Further, according to the present invention, as one embodiment of the photosensitive coloring resin composition of the present invention, (A) a photocurable resin component comprises
Provided is a photosensitive coloring resin composition containing (a) a polymer, (b) a monomer containing at least one photopolymerizable unsaturated bond in a molecule, and (c) a photopolymerization initiator.

In one embodiment of the present invention, the polymer (a) has an acid value of 20.
Weight average molecular weight of 1,500 to 200,000
The present invention provides a photosensitive coloring resin composition which is a polymer.

The present invention also provides a photosensitive liquid for forming a colored image, which further comprises (F) an organic solvent in the photosensitive coloring resin composition of the present invention.

Further, the present invention provides a photosensitive element obtained by forming a photosensitive layer comprising the photosensitive coloring resin composition of the present invention on a support.

The present invention also provides a method for producing a colored image in which a photosensitive layer comprising the photosensitive coloring resin composition of the present invention is laminated on a substrate, and is exposed and developed.

Further, the present invention provides, as one embodiment of the above-mentioned method for producing a colored image, a method of heat-treating a photosensitive layer after exposure to form a color or change its color.

Further, the present invention provides, as one embodiment of the above-mentioned method for producing a colored image, a method of applying the photosensitive liquid for forming a colored image of the present invention on a substrate and drying it to laminate a photosensitive layer.

The present invention also provides, as one embodiment of the above-mentioned method for producing a colored image, a method of transferring the photosensitive layer of the photosensitive element of the present invention onto a substrate and laminating the photosensitive layer on the substrate. I do.

Further, according to the present invention, a photosensitive layer comprising the photosensitive coloring resin composition of the present invention is laminated on a substrate, and the photosensitive layer is irradiated with actinic rays in an image-like manner to cure the exposed portions with light. A method for producing a color filter panel, comprising forming a black matrix by removing an exposed portion by development and heat-treating a photocured photosensitive layer to form a color or change its color.

The present invention also provides, as an embodiment of the above-mentioned method for producing a color filter panel, a method of coating the photosensitive liquid for forming a colored image of the present invention on a substrate and drying it to laminate a photosensitive layer. I do.

According to another aspect of the present invention, there is provided a method of manufacturing a color filter panel, comprising: transferring the photosensitive layer of the photosensitive element of the present invention onto a substrate and laminating the photosensitive layer on the substrate. I will provide a.

In the present invention, a photosensitive layer comprising the photosensitive coloring resin composition of the present invention is laminated on a substrate, and the photosensitive layer is irradiated with actinic rays in an image-like manner to cure the exposed portions with light. The exposed part is removed by development, and the photo-cured photosensitive layer is subjected to heat treatment to form a color or discoloration to form a black matrix to produce a color filter panel, and a plurality of different color filter panels are formed on the color filter panel. Provided is a method for manufacturing a color filter, wherein a plurality of different chromatic pixels are formed using a chromatic colored image forming material.

Further, the present invention provides, as one embodiment of the above-mentioned method for producing a color filter, a method of applying the photosensitive liquid for forming a colored image of the present invention on a substrate and drying it to laminate a photosensitive layer.

Further, the present invention provides, as one embodiment of the above-mentioned method for producing a color filter, a method of transferring the photosensitive layer of the photosensitive element of the present invention onto a substrate and laminating the photosensitive layer on the substrate. I do.

Further, the present invention provides, as one embodiment of the above-mentioned method for producing a color filter, a method in which the pixel is composed of a red pixel, a green pixel and a blue pixel.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION (1) Photosensitive Colorable Resin Composition In the photosensitive colorable resin composition of the present invention, (A) a photocurable resin component preferably has a film-forming property. Those having pigment dispersibility are preferable, and further,
Those which do not hinder photosensitivity and have developability are preferred.

The photocurable resin component (A) used in the present invention includes, for example, (I) a polymer, (b) a monomer containing at least one photopolymerizable unsaturated bond in a molecule, and c) a combination of a photoinitiator; (II) a combination of a (d) polymer and (e) a crosslinking agent; and (III) a photocrosslinkable polymer.

As the polymer (a) of the combination (I), for example, (meth) acrylic acid (meaning acrylic acid and methacrylic acid; the same applies hereinafter), itaconic acid, maleic acid, maleic anhydride, monoalkyl maleate Carboxyl group-containing vinyl polymerizable monomers such as esters, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate,
(Meth) acrylates such as butyl acrylate,
Representative examples include copolymers with vinyl polymerizable monomers such as styrene and styrene derivatives. 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, mono-n-octyl maleate, Mono-2-ethylhexyl maleate, mono-n-nonyl maleate, mono-n-dodecyl maleate and the like can be mentioned. As the styrene derivative,
α-methylstyrene, m- or p-methoxystyrene,
p-hydroxystyrene, 2-methoxy-4-hydroxystyrene, 2-hydroxy-4-methylstyrene and the like.

As the polymer (a) of the combination (I), a polymer containing one or more photopolymerizable unsaturated bonds in the molecule can also be used. As such a polymer, for example, a carboxylic acid group-containing resin having a high acid value (for example, one having a high acid value among the above-mentioned polymers), glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, α-ethyl glycidyl acrylate, Compounds each having one oxirane ring and one ethylenically unsaturated bond, such as crotonyl glycidyl ether and monoalkyl glycidyl ether itaconate; allyl alcohol, 2-buten-4-ol, furfuryl alcohol, oleyl alcohol, and cinamyl Free isocyanate is added to a resin obtained by reacting an unsaturated alcohol such as alcohol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide, or a carboxyl group-containing resin having a hydroxyl group. Resins obtained by reacting an over preparative group-containing unsaturated compound,
A resin obtained by reacting an addition reaction product of an epoxy resin and an unsaturated carboxylic acid with a polybasic acid anhydride, a conjugated diene copolymer or an addition reaction product of a conjugated diene copolymer and an unsaturated dicarboxylic anhydride. Examples of the resin include a resin obtained by reacting a hydroxyl group-containing polymerizable monomer.

The polymer (a) of the combination (I) preferably has an acid value of 20 to 300, and more preferably 40 to 200.
Is more preferable, and the weight average molecular weight (standard polystyrene conversion value by gel permeation chromatography) is preferably 1,500 to 200,000, more preferably 10,000 to 50,000. .

The monomer having one or more photopolymerizable unsaturated bonds (b) in the combination (I) is not particularly limited, and examples thereof include methyl methacrylate, benzyl methacrylate, butoxyethyl methacrylate, and butoxytriethylene. Glycol acrylate, ECH
(Epichlorohydrin) modified butyl acrylate, dicyclopentenyl 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 bisphe Lumpur A diacrylate, ECH
Modified bisphenol A diacrylate, bisphenol A dimethacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate,
Diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol diacrylate, EO modified phosphate diacrylate, ECH modified phthalic diacrylate, polyethylene glycol 400 diacrylate, polypropylene glycol 400 dimethacrylate, tetraethylene glycol diacrylate, ECH modified 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, EO-modified phosphate triacrylate, EO-modified trimethylolpropane triacrylate, PO-modified trimethylolpropane triacrylate (PO means propylene oxide. Same), tris (methacryloxyethyl) isocyanurate, pentaerythr Tall tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, acrylate such as dipentaerythritol pentaacrylate, etc. methacrylates corresponding to these. These monomers can be used alone or in combination of two or more.

The photoinitiator (c) of the combination (I) is not particularly limited. For example, benzophenone, N,
N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, benzyl, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyldimethyl ketal, α- Hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 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, 2
-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, and a triazine-based photoinitiator. These photoinitiators can be used alone or in combination of two or more.

In the combination (I), the amount of the monomer (b) containing one or more photopolymerizable unsaturated bonds in the molecule is from 1 to 300 parts by weight based on 100 parts by weight of the polymer (a).
It is preferable that the amount be 10 parts by weight, more preferably 10 to 200 parts by weight. (C) the amount of photoinitiator is (a)
0.00 with respect to 100 parts by weight of the total amount of the component and the component (b)
1 to 50 parts by weight, preferably 0.01 to 40 parts by weight.
It is more preferred to be parts by weight.

The polymer (d) of the combination (II) includes, for example, casein, gelatin, polyvinyl alcohol, polyvinylpyrrolidone and the like, and the crosslinking agent (e) includes, for example, dichromate, diazonium salt,
Bisazide compounds and the like can be mentioned. Combination (II)
In (e), the amount of the crosslinking agent is (d) the amount of the polymer 100
The amount is preferably 0.01 to 50 parts by weight, more preferably 0.1 to 40 parts by weight based on parts by weight.

(III) The photocrosslinkable polymer is not particularly limited, and examples thereof include polyvinyl cinnamate and polycinnamylidene vinyl acetate.

The various types of (A) photocurable resin components exemplified above may be used alone or in combination of two or more.

The fluoran compound (B) used in the present invention includes, for example, 3-diethylamino-7- (2-
Chloroanilino) fluoran, 3-dibutylamino-7
-(2-chloroanilino) fluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3-dibutylamino-6-methyl-7-anilinofluoran, 3
-Dipentylamino-6-methyl-7-anilinofluoran, 3-diethylamino-7,8-benzofluoran, 3-diethylamino-6-methoxy-7-benzofluoran, 1,3-dimethyl-6-diethylamino Fluorane, 2-bromo-3-methyl-6-dibutylaminofluoran, 2-N, N-dibenzylamino-6-diethylaminofluoran, 3- (N-ethyl-N-isopentylamino) -6 Methyl-7-anilinofluoran, 3- [N-ethyl-N- (4-methylphenyl) amino] -6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-xylidino Fluoran and the like.

The (C) thermal acid generator used in the present invention is not particularly limited as long as it is a material capable of generating an acid when heated. For example, 80-300 ° C,
A material that generates an acid under a heating condition of preferably 100 to 280 ° C for 1 second to 24 hours, preferably 1 second to 10 hours is preferable. Examples of the (C) thermal acid generator include, for example, nitrobenzyl tosylate (for example, 2-nitrobenzyl tosylate), benzylanilinium sulfonate, bissulfonyldiazomethane, arylsulfinic acid, hexafluoroantimonate (for example, 2 -Butenyltetramethylenesulfonium hexafluoroantimonate, 3-methyl-2-butenyltetramethylenesulfonium hexafluoroantimonate), trifluoromethanesulfonate, trihaloacetates (eg, trifluoroacetates) and the like Can be As the acid generated by heating, sulfonic acids such as p-toluenesulfonic acid and trifluoromethanesulfonic acid, hexanefluoroantimonic acid, trifluoroacetic acid, and hydrochloric acid are preferable.

The (C) thermal acid generator is preferably blended in such an amount that the molar ratio of (B) fluoran compound / (C) thermal acid generator is 0.2 to 5.0, and 0.5 to 5.0. It is more preferable to mix in an amount of 2.0, particularly preferably 0.9 to 1.5. When this compounding ratio is 0.
When the ratio is out of the range of 2 to 5.0, the coloring ability tends to decrease.

The compound containing one or more epoxy groups (D) used in the present invention is not particularly limited. For example, glycidyl (meth) acrylate, 3,4
Monomers having one epoxy group in the molecule such as epoxymethyl (meth) acrylate, vinyl epoxy cyclohexane, biphenyl type epoxy resin, bisphenol A type epoxy resin, orthocresol novolak type epoxy resin, glycidylamine type epoxy resin, fat Epoxy resins having two or more epoxy groups in the molecule, such as cyclic epoxy resins, heterocyclic epoxy resins, and aliphatic epoxy resins, polyglycidyl (meth) acrylate, glycidyl (meth) acrylate / methyl (meth) Copolymers of glycidyl (meth) acrylates such as acrylate copolymers and glycidyl (meth) acrylate / benzyl (meth) acrylate copolymers with monomers containing at least one unsaturated bond copolymerizable in the molecule, etc. Is mentioned. When an epoxy resin or other copolymer is used among the above examples of the component (D), their weight average molecular weight (gel permeation chromatography) is 500 to
It is preferable to use those of 200,000,
It is more preferable to use one having a thickness of 100 to 100,000. These (D) compounds containing one or more epoxy groups in the molecule have the effect of stabilizing the hue after (B) the fluoran compound develops color by the action of an acid generated from the thermal acid generator by heating (C). Having.

(D) The amount of the compound containing one or more epoxy groups in the molecule is as follows: (A), (B), (C) and (D)
The total amount of the components is preferably 0.01 to 10% by weight, more preferably 0.1 to 5.0% by weight.
If the amount is less than 0.01% by weight, the hue stability of the fluoran compound after color development tends to decrease. If the amount exceeds 10% by weight, the developability of the photosensitive coloring resin composition of the present invention after curing is reduced. Tends to worsen.

The photosensitive coloring resin composition of the present invention may optionally contain (E) a dye. (E)
The pigment is not particularly limited, but a chromatic dye or pigment can be used.

As the red pigment, for example, Pigment Red 9, 123, 155, 1
68, 177, 180, 217, 220, 224 and the like.

Examples of the yellow pigments include, for example, Pigment Yellow 17, 20, 24, and 8 under the color index name.
3, 93, 109, 110, 117, 125, 128,
129, 138, 139, 147, 154 and the like.

The green pigments include, for example, Pigment Greens 7, 36, and 37 under the color index name.

Examples of blue pigments include, for example, Pigment Blue 15, 15: 3 and 15:
4, 15: 6, 22, 60 and the like.

Examples of purple pigments include, for example, Pigment Violet 19, 23, 2
9, 37, 50 and the like.

Further, pigments of colors other than those described above can be used.

(E) By blending a dye, a photosensitive coloring resin composition which develops or changes into a chromatic or achromatic color other than the dye due to heating can be obtained.
For example, (B) obtaining a photosensitive coloring resin composition which develops or changes color in an achromatic color by heating by blending a colorant having a complementary color to the color after the fluoran compound has developed color by the action of an acid Can be.

The total amount of the (B) fluoran compound and the (E) dye is 5 to 70% by weight based on the total amount of the components (A), (B), (C), (D) and (E). Is preferably set to 10 to 60% by weight, more preferably 15 to 50% by weight. If the amount is less than 5% by weight, the light-shielding property of the image after heating tends to decrease, and if it exceeds 70% by weight, the light sensitivity tends to decrease. Also, (E) the amount of the dye used is
The content is preferably 90% by weight or less, and more preferably 80% by weight based on the total amount of the (B) fluoran compound and (E) dye.
It is more preferably at most 70% by weight, particularly preferably at most 70% by weight. If this amount exceeds 90% by weight, the light sensitivity tends to decrease. Further, in order to obtain the effect of mixing the dye (E), the content is preferably 1% by weight or more, more preferably 5% by weight or more. Further, for example, in the case where (B) the fluoran compound develops or discolors to a color complementary to the color of the dye (E) due to the acid generated by heating, photosensitive coloring that develops or discolors to black upon heating. In order to obtain a conductive resin composition, the amount of the (E) dye is preferably 1 to 90% by weight, and more preferably 5 to 70% by weight based on the total amount of the (B) fluoran compound and the (E) dye. Is preferred.

As the black pigment, black pigments such as carbon black, graphite, titanium carbon, black iron oxide, and manganese dioxide can be used. The amount of the black pigment used is preferably 90% by weight or less based on the total amount of the (B) fluoran compound and the (E) pigment.
More preferably 80% by weight or less, 70% by weight
It is particularly preferable to set the following. If this amount exceeds 90% by weight, the light sensitivity tends to decrease. In order to obtain the effect of blending the black pigment, the content is preferably 1% by weight or more, more preferably 5% by weight or more.

In the photosensitive coloring resin composition of the present invention, the essential components (A), (B), (C) and (D),
And, in addition to the component (E) used as needed,
Further, thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, pyrogallol, and t-butylcatechol for suppressing dark reaction, and silane coupling agents (vinyl group, epoxy group, amino group, etc.) for improving adhesion to a substrate. Group, a silane coupling agent having a mercapto group or the like), a titanate coupling agent (such as isopropyltrimethacryloyl titanate or diisopropylisostearoyl-4-aminobenzoyl titanate), or a surfactant for improving the smoothness of the film ( Various additives such as a fluorine-based surfactant, a silicon-based surfactant, and a hydrocarbon-based surfactant), an ultraviolet absorber, and an antioxidant can be appropriately used as needed.

(2) Photosensitive Liquid for Forming a Colored Image The photosensitive solution for forming a colored image of the present invention is obtained by further adding (F) an organic solvent to the above-mentioned photosensitive coloring resin composition. The colored image forming photosensitive liquid of the present invention is directly applied to a substrate and dried, or once applied to a support and dried to form a film, and then formed as a film on the substrate surface by laminating the substrate or the like. . Thereafter, exposure and development are performed to obtain a target image pattern.

The organic solvent (F) used in the photosensitive solution for forming a colored image of the present invention is not particularly limited.
Examples include ketone solvents such as ethylene glycol solvents, propylene glycol solvents, lactone solvents, lactam solvents, etc., cellosolve solvents, alcohol solvents, ether solvents, ester solvents, and aromatic solvents.
Specific examples of these organic solvents include, for example, acetone,
Methyl ethyl ketone, cyclohexanone, methyl cellosolve, ethyl cellosolve, butyrocellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyrocellosolve acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol dimethyl ether, diethylene glycol ethyl ether, triethylene glycol Dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, diethylene glycol dimethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol di Isopropyl ether, propylene glycol monomethyl ether acetate, 3-methyl -
3-methoxybutanol, 3-methyl-3-methoxybutyl acetate, N-methyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, methyl alcohol,
Organic solvents such as ethyl alcohol, isopropyl alcohol, n-butyl alcohol, tetrahydrofuran, dioxane, benzene, toluene, xylene, and ethyl acetate are exemplified. These organic solvents are used alone or in combination of two or more.

These organic solvents have a total solid content of 5 to 40% by weight including the components (A), (B), (C), (D) and (E) in the photosensitive solution. Preferably, it is used in such a manner as to be in the range of 10 to 30% by weight. 5% by weight of total solids
If it is less than 40%, it takes a long time to dry the coating film. If it exceeds 40% by weight, the viscosity of the photosensitive solution is too high, and the coating property is undesirably reduced.

The method for preparing the photosensitive liquid for forming a colored image of the present invention is described below. When (B) a fluoran compound and (E) a dye are soluble in (F) an organic solvent, (A)
The components (E) to (E) are all mixed, and an organic solvent (F) is added thereto to obtain a photosensitive solution.

When there is a component insoluble in the organic solvent (F) in the fluoran compound (B) and the dye (E), it is necessary to disperse the insoluble component. As a method of dispersing, usually, the dispersing resin and the (B) fluoran compound and the insoluble component in the (E) dye are mixed with (F) an organic solvent (one kind may be used alone, or two or more kinds may be used in combination. And a method of mixing the mixture using various dispersing / kneading apparatuses such as an ultrasonic disperser, a three-roll mill, a ball mill, a sand mill, a bead mill, a homogenizer, and a kneader. As the dispersion resin, a part or all of the photocurable resin component (A) may be used. Also, anionic pigment dispersants such as polycarboxylic acid type polymer activators and polysulfonic acid type polymer activators, pigment dispersants such as nonionic pigment dispersants such as polyoxyethylene / polyoxypropylene block polymers, and anthraquinone type , A perylene-based, phthalocyanine-based, quinacridone-based organic dye, and 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. This is preferable because the dispersibility and dispersion stability of the pigment are improved.

The soluble component of the (B) fluoran compound and the (E) dye may be added at the time of dispersion of the insoluble component or after the dispersion. Similarly, the organic solvent (F) may be used in its entirety at the time of dispersion of the insoluble component, or a part of the organic solvent (F) may be added after the dispersion. However, it is preferable that at least 100 parts by weight of the organic solvent (F) is used based on 100 parts by weight of the total amount of the insoluble component and the dispersed resin when the insoluble component is dispersed. If the amount is less than 100 parts by weight, the viscosity at the time of dispersion may be too high, and dispersion may become difficult particularly when dispersed by a ball mill, a sand mill, a bead mill or the like.

(3) Photosensitive Element The photosensitive element of the present invention has a photosensitive layer formed of the photosensitive coloring resin composition of the present invention and a support for supporting the same. It can be produced by applying the colored image-forming photosensitive solution of the present invention on a body and drying. The thickness of the photosensitive layer is generally 0.1 to 300 μm, preferably 0.2 to 30 μm, more preferably 0.2 to 5 μm.
m.

As the support, for example, a film that can be peeled off at the time of use after forming the photosensitive layer, such as a polyester film, a polyimide film, a polyamideimide film, a polypropylene film, and a polystyrene film, is suitably used. The thickness of the support is preferably from 10 to 500 μm, more preferably from 20 to 300 μm.

Examples of the method of applying the photosensitive liquid for forming a colored image on a support include knife coater application, gravure coater application, roll coater application, spray coater application, and the like. After the application, the photosensitive layer composed of the photosensitive coloring resin composition of the present invention can be formed by drying usually at a temperature of 50 to 100 ° C. for 1 to 30 minutes. However, the temperature and time conditions for drying must be such that the thermal acid generator in the photosensitive solution does not generate an acid.
In order to prevent dust from adhering to the surface of the photosensitive layer, it is preferable to laminate a peelable cover film on the surface of the film.

Examples of the peelable cover film include polyethylene film, Teflon film, polypropylene film, surface-treated paper, and the like. When the cover film is peeled off, the adhesive strength between the photosensitive layer and the support is smaller than the adhesive strength. Preferably, the adhesive strength between the photosensitive layer and the cover film is smaller.

(4) Method for Producing a Colored Image and Method for Producing a Panel for Color Filter A colored image is prepared by laminating a photosensitive layer comprising the photosensitive colored resin composition of the present invention on a substrate, exposing and developing. Can be manufactured.

The substrate is selected depending on the application.
For example, transparent glass substrates such as white plate glass, blue plate glass, silica-coated blue plate glass, and the like, sheets or films or substrates made of synthetic resins such as polyester resin, polycarbonate resin, acrylic resin, and vinyl chloride resin, aluminum plates, copper plates, nickel plates, and stainless steel Examples include a metal substrate such as a plate, another ceramic substrate, and a semiconductor substrate having a photoelectric conversion element. When manufacturing a color filter panel, a transparent substrate is usually used.

A method for laminating a photosensitive layer on a substrate is as follows.
For example, there are a method of directly applying the photosensitive liquid for forming a colored image of the present invention on a substrate and drying, and a method of transferring the photosensitive layer of the photosensitive element of the present invention onto the substrate.

Examples of the method of directly applying the photosensitive liquid for forming a colored image to a substrate include roll coater coating, spin coater coating, spray coating, white coater coating, dip coater coating, curtain flow coater coating, wire bar coater coating, and gravure coating. Coater coating, air knife coater coating, and the like. After coating, usually 50-100 ° C
By drying at a temperature of 1 to 30 minutes, a photosensitive layer can be formed. However, the temperature and time conditions for drying must be such that the thermal acid generator in the photosensitive solution does not generate an acid.

As a method for transferring the photosensitive layer of the photosensitive element onto the substrate, it is preferable to heat and press the photosensitive layer of the photosensitive element while overlapping the photosensitive layer on the substrate. Usually, the temperature during thermocompression bonding is preferably 50 to 100 ° C., and the pressure is preferably 0.6 to 6 kgf / cm ² . However, the temperature and time conditions during the thermocompression bonding must be such that the thermal acid generator in the photosensitive layer does not generate an acid. The atmosphere during the thermocompression bonding may be normal pressure or reduced pressure.

The thickness of the photosensitive layer containing the photosensitive coloring resin composition of the present invention thus formed on the substrate surface is determined depending on the use, but is usually in the range of 0.1 to 300 μm. When used for a color filter, the thickness is usually 0.2 to 5 μm.

The formation of an image by exposing and developing the photosensitive layer on the substrate can be generally carried out as follows.

The photosensitive layer on the substrate formed by the above method is irradiated imagewise with actinic rays to cure the exposed portion of the photosensitive layer.
When a photosensitive layer is formed using a photosensitive element,
Exposure may be performed from above with the support attached, or after the support is peeled off, exposure may be performed. In the case where the photosensitive layer is formed by directly applying a colored image forming photosensitive liquid to the substrate, an oxygen barrier film such as polyvinyl alcohol is applied to the surface of the photosensitive layer.
It may be formed with a thickness of 5 to 30 μm, and then 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 tungsten lamp, a visible light laser and the like are suitable. An actinic ray is irradiated imagewise by pattern exposure through a photomask using these light sources, or by direct drawing by scanning.

Subsequently, development is performed. The development is performed using an aqueous alkaline solution, a solvent, or the like, depending on the type of the photocurable resin component (A). For example, when a combination of the above (I) is used as the photocurable resin component (A), an alkaline aqueous solution is preferably used. As the alkaline aqueous solution,
There is no particular limitation, for example, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium metasilicate, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium An aqueous solution containing an organic base such as hydroxide, triethylamine, n-butylamine, or a salt can be used. The solvent is not particularly limited and includes, for example, ethylene glycol solvents, propylene glycol solvents, lactone solvents, lactam solvents, ketone solvents, cellosolve solvents, alcohol solvents, ester solvents, aromatic solvents, Water can be used. An unexposed portion is removed by spraying or dipping the developer, and an image pattern of a cured film corresponding to an image can be obtained. At this time, when exposure is performed with the support, the development is performed after the support is removed.

After development, the temperature at which the thermal acid generator generates an acid,
Preferably for 1 minute to 24 hours at a temperature of 80 to 300 ° C, more preferably for 1 to 60 minutes at a temperature of 100 to 280 ° C.
By post-heating, the image pattern is colored or discolored.

For example, as described above, an image pattern is formed on a transparent substrate such as a glass substrate using the photosensitive coloring resin composition of the present invention which develops or changes color to black upon heating, and is heated to form an image. By coloring or discoloring the pattern to black, a color filter panel in which a black matrix is formed can be manufactured.

(5) Method for Producing a Color Filter In the method for producing a color filter of the present invention, a color filter panel with a black matrix is produced as described above, and a plurality of different color filters are provided on the color filter panel. A color filter is manufactured by sequentially forming a plurality of different chromatic pixels using a colored image forming material. As the plurality of different chromatic pixels, for example, red, green, and blue pixels are formed. For these chromatic pixels, for example, instead of the photosensitive coloring resin composition of the present invention, a photosensitive layer is laminated, exposed, and developed on a color filter panel using another photosensitive coloring image forming material. May be formed. As such a photosensitive colored image forming material, for example, those containing the above (A) photocurable resin component and (E) dye can be used. When such a photosensitive colored image forming material is used, post-heating after exposure is not essential.

A color filter can also be manufactured by forming a chromatic pixel on a substrate and then forming a black matrix using the photosensitive coloring resin composition of the present invention.

[0080]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

Example 1 23.3 g of a dispersing resin represented by the formula (1), 30 g of dipentaerythritol hexaacrylate, 1.2 g of a photoinitiator represented by the structural formula (2), and a compound represented by the structural formula (3) 4. 2 g of a photoinitiator to be obtained,
6 g, 3- (N-ethyl-N-isopentylamino)-
50 g of 6-methyl-7-anilinofluoran and 2.4 g of 2-nitrobenzyl tosylate (manufactured by Midori Kagaku Co., Ltd., trade name NB-101), biphenyl type epoxy resin (manufactured by Yuka Shell Epoxy, trade name) YX-4000)
4.5 g of diethylene glycol dimethyl ether 4
The mixture was added to 67 parts and mixed to prepare a photosensitive solution containing a black matrix forming material. The color of this photosensitive solution was pale yellow.

The obtained photosensitive solution was applied on a glass substrate (Corning Co., trade name: 7059) by spin coating and dried at 80 ° C. for 5 minutes to form a film having a thickness of 1.0 μm. The obtained film is exposed to an image of 100 mJ / cm ² by an ultra-high pressure mercury lamp through a negative mask, and then polyoxyethylene nonylphenyl ether (manufactured by Toho Chemical Co., Ltd., name: Nonal 912A)
Development was carried out with an aqueous solution containing 0.5% by weight and 0.3% by weight of potassium hydroxide, and a heating and color development treatment was performed at 200 ° C. for 30 minutes to form a black matrix pattern.

[0083]

Embedded image Example 2 23.3 g of a dispersion resin represented by the formula (1), 30 g of dipentaerythritol hexaacrylate, 1.2 g of a photoinitiator represented by the formula (2), and light represented by the formula (3) 4. Initiator 1.2 g, photoinitiator represented by structural formula (4)
6 g, 50 g of 3-dipentylamino-6-methyl-7-anilinofluoran and 2.5 g of 2-butenyltetramethylenesulfonium hexafluoroantimonate (trade name CP-66, manufactured by Asahi Denka Kogyo KK) , Glycidyl methacrylate (GMA) / methyl methacrylate (M
MA) Copolymer (copolymerization ratio (weight ratio): GMA / MMA
= 80/20, weight average molecular weight: 21,000) 3.0
g of diethylene glycol dimethyl ether 467 g
To obtain a photosensitive solution containing a black matrix forming material. The color of this photosensitive solution was pale yellow.

The obtained photosensitive solution was applied on a glass substrate (Corning Co., trade name: 7059) by spin coating, and further dried at 80 ° C. for 5 minutes to form a film having a thickness of 1.0 μm.
Was formed. The obtained film is exposed imagewise with an ultra-high pressure mercury lamp through a negative mask at 100 mJ / cm ² , and then polyoxyethylene nonylphenyl ether (Nonal 912A manufactured by Toho Chemical Co., Ltd.)
Development was carried out with an aqueous solution containing 0.5% by weight and 0.3% by weight of potassium hydroxide, and a heating and coloring treatment was performed at 200 ° C. for 30 minutes to form a black matrix pattern.

Example 3 14.2 g of the dispersing resin represented by the formula (1) and 22.5 g of carbon black were added to 200 g of diethylene glycol dimethyl ether, which was dispersed for 2 hours using a bead mill. In 200 g of this dispersion, 10 g of a dispersion resin represented by the formula (1), 30 g of dipentaerythritol hexaacrylate, and a photoinitiator represented by the formula (2) 1.2
g, 1.2 g of a photoinitiator represented by Structural Formula (3), 5.6 g of a photoinitiator represented by Structural Formula (4), 25 g of 3-dipentylamino-6-methyl-7-anilinofluoran , 3
-Methyl-2-butyltetramethylenesulfonium hexafluoroantimonate (manufactured by Asahi Denka Kogyo Co., Ltd.
1.2 g of ortho-cresol novolak epoxy resin (trade name: EOC, manufactured by Nippon Kayaku Co., Ltd.)
N-102S) and 280 g of diethylene glycol dimethyl ether were added and mixed to prepare a photosensitive solution containing a black matrix forming material. The color of this photosensitive solution was black.

The obtained photosensitive liquid was applied on a glass substrate (Corning Co., trade name: 7059) by spin coating, and further dried at 80 ° C. for 5 minutes to form a film having a thickness of 1.0 μm.
Was formed. The obtained film is exposed to an image of 100 mJ / cm ² by an ultra-high pressure mercury lamp through a negative mask, and then polyoxyethylene nonylphenyl ether (trade name: Nonal 912A, manufactured by Toho Chemical Co., Ltd.)
Development was carried out with an aqueous solution containing 0.5% by weight and 0.3% by weight of potassium hydroxide, and a heating and coloring treatment was performed at 200 ° C. for 30 minutes to form a black matrix pattern.

Example 4 The photosensitive solution obtained in Example 1 was coated on a 6 μm thick polyethylene terephthalate film by a gravure coating method, and dried at 100 ° C. for 2 minutes to form a 2.0 μm thick film (photosensitive film). Layer), and the surface was covered with a polyethylene film having a thickness of 40 μm to obtain a photosensitive element.
The color of the photosensitive layer was pale yellow.

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. Lamination was performed under the conditions of a glass substrate temperature of 40 ° C., a laminating roll temperature of 80 ° C., a laminating pressure of 3.5 kgf / cm ² , and a laminating speed of 1.5 m / min. The color of the photosensitive layer after lamination was pale yellow.

Next, the polyethylene terephthalate film was exposed imagewise at 100 mJ / cm ² from the polyethylene terephthalate film using a super-high pressure mercury lamp through a negative mask, and the polyethylene terephthalate film was peeled off.
Developing and heating and coloring were performed in the same manner and under the same conditions as described above to form a black matrix pattern.

Example 5 To 40 g of the dispersing resin represented by the formula (1), 25 g of Pigment Red 177 and 5 g of Pigment Yellow 83 by color index, and 200 g of diethylene glycol dimethyl ether were added and dispersed for 2 hours using a bead mill. . In 200 g of this dispersion, the above-mentioned dispersion resin 1 was added.
0 g, dipentaerythritol hexaacrylate 30
g, 1.2 g of a photoinitiator represented by Structural Formula (2), 1.2 g of a photoinitiator represented by Structural Formula (3), 5.6 g of a photoinitiator represented by Structural Formula (4), and 280 g of diethylene glycol dimethyl ether was added and mixed to obtain a photosensitive solution containing a colored image forming material. The color of this photosensitive solution was red.

The obtained photosensitive liquid was applied on the black matrix substrate obtained in Example 1 by spin coating, and dried at 80 ° C. for 5 minutes to form a film having a thickness of 2.0 μm. The obtained film is exposed to an image of 100 mJ / cm ² by an ultra-high pressure mercury lamp through a negative mask, and then polyoxyethylene nonylphenyl ether (trade name: Nonal 912A, manufactured by Toho Chemical Co., Ltd.)
Development was carried out with an aqueous solution containing 0.5% by weight and 0.3% by weight of potassium hydroxide, followed by heating at 200 ° C. for 30 minutes to form a red image pattern on a black matrix substrate.

To 60 g of the dispersing resin represented by the formula (1), 22 g of Pigment Green 36 and 8 g of Pigment Yellow 83 by color index name, and 250 g of diethylene glycol dimethyl ether were added and dispersed for 2 hours using a bead mill. To 220 g of this dispersion, 10 g of the above dispersion resin, 32 g of dipentaerythritol hexaacrylate, and a photoinitiator represented by the structural formula (2) 1.
6 g, 0.8 g of a photoinitiator represented by Structural Formula (3), 5.8 g of a photoinitiator represented by Structural Formula (4), and 125 g of diethylene glycol dimethyl ether are added and mixed, and a photosensitive material containing a colored image forming material is added. A liquid was obtained. The color of this photosensitive solution was green.

The obtained photosensitive liquid is applied, dried, exposed, developed and post-heated on the above-mentioned black matrix substrate on which a red image pattern is formed under the same conditions as in the case of the red image forming material, to obtain a black matrix. A green image pattern was formed next to the red image pattern on the substrate.

25 g of the dispersion resin represented by the formula (1) and 24 g of Pigment Blue 15: 6 by color index name
And 1 g of Pigment Violet 23 and 200 g of diethylene glycol dimethyl ether, and this was dispersed for 2 hours using a bead mill. 140 g of this dispersion
36 g of the above dispersion resin, 30 g of dipentaerythritol hexaacrylate, 1.9 g of a photoinitiator represented by Structural Formula (2), and 0.9 g of a photoinitiator represented by Structural Formula (3)
g, 6.5 g of a photoinitiator represented by the structural formula (4) and 230 g of diethylene glycol dimethyl ether were added and mixed to obtain a photosensitive liquid containing a colored image forming material. The color of this photosensitive solution was blue.

The obtained photosensitive liquid is applied on the above-mentioned black matrix substrate on which a red image pattern and a green pattern are formed under the same conditions as in the case of the red image forming material.
Drying, exposure, development and post-heating were performed to form a blue image pattern next to the green image pattern on the black matrix substrate. Thus, a color filter in which pixels were arranged in a mosaic of three colors of red, green and blue on a black matrix was produced.

[0096]

The photosensitive coloring resin composition of the present invention and the photosensitive liquid for forming a colored image and the photosensitive element using the same are excellent in photosensitive properties such as photosensitivity, and the pattern produced by using this is heat-treated. It is more efficiently colored or discolored, and is suitable as a colored image forming material.

The method for producing a colored image of the present invention is a method suitable for forming a colored image by forming a cured pattern having a high resolution since a photosensitive layer having excellent photosensitive characteristics such as photosensitivity is used. In addition, the method for producing a colored image of the present invention is suitable for forming a high-resolution colored image because the image is colored or discolored by heat treatment after exposure, so that it has excellent photosensitive characteristics such as light sensitivity at the time of exposure. is there.

According to the method for manufacturing a color filter panel of the present invention, a black matrix having excellent light-shielding properties, low reflection properties, insulation properties and the like can be formed with high resolution.

According to the method of manufacturing a color filter of the present invention, a black matrix having excellent light-shielding properties, low reflection properties, insulation properties and the like is formed with high resolution, and then a plurality of chromatic colored image forming materials are used to form a pixel. Can be formed, so that a color filter having excellent image characteristics can be manufactured.

Continuation of the front page F term (reference) 2H025 AA00 AA01 AA02 AA20 AB13 AC01 AC08 BC12 BC31 BC34 BC43 CA00 CB42 CB43 CB51 CB55 CC03 CC11 CC14 CC17 CC20 EA04 EA08 EA10 FA12 FA17 2H048 BA45 BA48 4J002 AD011 AD021 CD021001 CD053 CD063 CD133 CD191 CD193 CD201 CH052 CK021 DE187 EE037 EE047 EE057 EH039 EH076 EH156 EL030 EL040 EN068 EN078 EN096 EN097 EQ017 EQ037 ES009 EU117 EU187 EU196 EU237 EV209 EV219 EV239 EV317 EY029 FD050 FD070 FD090 FD090 FD090 FD090 FD070 FD070 FD070 FD070 FD070 FD090 FD070 FD090 FD070 FD090 FD090 FD070

Claims (17)

[Claims] 1. A composition containing (A) a photocurable resin component, (B) a fluoran compound, (C) a thermal acid generator and (D) a compound containing at least one epoxy group in a molecule, and develops color by heat. Alternatively, a photosensitive coloring resin composition that changes color. 2. A composition comprising (A) a photocurable resin component, (B) a fluoran compound, (C) a thermal acid generator, (D) a compound containing at least one epoxy group in a molecule, and (E) a dye. And a photosensitive coloring resin composition that develops or changes color to an achromatic color by heat. 3. The photocurable resin component (A) contains (a) a polymer, (b) a monomer containing at least one photopolymerizable unsaturated bond in a molecule, and (c) a photoinitiator. The photosensitive coloring resin composition according to claim 1 or 2, wherein 4. The photosensitive coloring resin composition according to claim 3, wherein (a) the polymer has an acid value of 20 to 300 and a weight average molecular weight of 1,500 to 200,000. 5. A colored image forming photosensitive liquid comprising the photosensitive colored resin composition according to claim 1, further comprising (F) an organic solvent. 6. A photosensitive element obtained by forming a photosensitive layer comprising the photosensitive coloring resin composition according to claim 1 on a support. 7. A photosensitive layer comprising the photosensitive coloring resin composition according to claim 1 is laminated on a substrate, and exposed to light.
A method for producing a colored image to be developed. 8. The method according to claim 7, wherein after exposure, the photosensitive layer is heat-treated to form a color or discolor. 9. The method according to claim 7, wherein the photosensitive liquid for forming a colored image according to claim 5 is applied on a substrate and dried to form a photosensitive layer. 10. The method according to claim 7, wherein the photosensitive layer of the photosensitive element according to claim 6 is transferred onto a substrate to laminate the photosensitive layer on the substrate. 11. A photosensitive layer comprising the photosensitive coloring resin composition according to claim 1, which is laminated on a substrate, and the photosensitive layer is irradiated with actinic rays in an image-like manner to cure the exposed portion. A method for producing a color filter panel, comprising forming a black matrix by removing unexposed portions by development and heat-treating the photocured photosensitive layer to form a color or change its color. 12. A photosensitive liquid for forming a colored image according to claim 5, which is applied on a substrate and dried to form a photosensitive layer.
The method of claim 1. 13. The method according to claim 11, wherein the photosensitive layer of the photosensitive element according to claim 6 is transferred onto a substrate to laminate the photosensitive layer on the substrate. 14. A photosensitive layer comprising the photosensitive coloring resin composition according to any one of claims 1 to 4, which is laminated on a substrate, and the photosensitive layer is irradiated with actinic rays in an image-like manner to cure the exposed portion. Then, the unexposed portions are removed by development, and the photocured photosensitive layer is subjected to heat treatment to form a color or discoloration, thereby forming a black matrix to produce a color filter panel. A method of manufacturing a color filter, comprising forming a plurality of pixels of different chromatic colors using a plurality of colored image forming materials of chromatic colors. 15. The photosensitive liquid for forming a colored image according to claim 5, applied on a substrate and dried to form a photosensitive layer.
4. The method according to 4. 16. The method according to claim 14, wherein the photosensitive layer of the photosensitive element according to claim 6 is transferred onto a substrate to laminate the photosensitive layer on the substrate. 17. The method according to claim 14, wherein the pixels comprise red, green and blue pixels.