JPH11209632A - Red resin composition, photosensitive red resin composition, red image-forming photosensitive solution, production of colored image, and production of color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition desirable to produce a color filter improved in the saturation of red and light transmittance by dispersing C.I. Pigment Red 254 and a yellow or orange pigment in a resin. SOLUTION: The resin used is desirably one having an acid value of 20-300 and a weight-average molecular weight of 1,500-200,000 and is especially desirably one having a formula I/formula II ratio of 1/1 to 5/1 by mole. In the formulae, R<1> is H or methyl; R<2> and R<3> are each an alkyl or an alkoxyl; R<4> and R<5> are each H, an alkyl or a photo-reactive unsaturation-containing group; and R<6> is H or an alkyl. The red pigment/yellow pigment ratio is desirably 90/10 to 40/60 by weight. This composition may further contain a monomer having at least one photopolymerizable unsaturation, a photoinitiator, etc. It is dissolved in an organic solvent for forming a photosensitive solution.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a red resin composition,
The present invention relates to a photosensitive red resin composition, a photosensitive liquid for forming a red image, a method for producing a colored image, and a method for producing a color filter.

[0002]

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

However, when a pigment is used as compared with a dye, there is a problem that the light transmittance is low.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a red image forming material suitable for producing a color filter having improved red color saturation and light transmittance. It is another object of the present invention to provide a color filter which has excellent chroma and light transmittance especially in red color, whereby a high definition and low power consumption color display can be manufactured. .

[0005]

According to the present invention, there is provided a C.I. I. Pigment Red 254 and a toning pigment such as yellow or orange in a resin, a red resin composition, a photosensitive red resin composition, a photosensitive liquid using the composition, and the photosensitive red resin composition. Alternatively, the present invention relates to a method for producing a colored image using a photosensitive liquid and a method for producing a color filter.

That is, the present invention relates to (a) a resin, (b)
Color Index (CI) Pigment Red 25
And a red resin composition comprising a yellow pigment or an orange pigment dispersed therein.

Further, the present invention provides (a) a resin, (b) a color index (CI) pigment red 254,
A photosensitive red resin composition comprising a yellow pigment or an orange pigment, (c) a monomer having at least one photopolymerizable unsaturated bond in a molecule, and (d) a photoinitiator. A resin having an acid value of 20 to 300 and a weight average molecular weight of 1,500 to 20,000, or a resin represented by the following general formula (I):

[0008]

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

[0010]

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(Wherein, R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a group having a photoreactive unsaturated bond, and R ⁶ represents a hydrogen atom or a carbon atom (Representing an alkyl group of Formulas 1 to 12) represented by the following general formula (I) / general formula (II):
The present invention relates to a photosensitive red resin composition which is a resin having a ratio of (molar ratio) / 1.

The present invention also relates to a photosensitive liquid for forming a red image containing the photosensitive resin composition and an organic solvent.

The present invention also relates to a method for producing a colored image, comprising a colored image forming step of laminating a photosensitive layer comprising the above-described photosensitive red resin composition on a substrate, and exposing and developing the photosensitive layer. The present invention also relates to a method for producing a colored image, wherein the photosensitive layer is formed from the above-described photosensitive liquid for forming a red image.

Further, according to the present invention, a colored image forming material using the above-described photosensitive red resin composition or photosensitive solution is formed as a film on a substrate, actinic rays are irradiated imagewise, and an exposed portion is irradiated with light. The present invention relates to a method for producing a color filter, wherein a step of curing and removing an unexposed portion by development is repeatedly performed on colored image forming materials of a plurality of different colors to form pixels.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, pigments include
A pigment such as yellow or orange is used in combination with the red pigment, and C.I. I. Pigment Red 254 (color index name) is used as an essential component.

As the red pigment in the present invention, C.I. I.
Other red pigments besides Pigment Red 254 can be used, but the amount of the red pigment is preferably 0 to 90% by weight based on the whole red pigment, and 0 to 5% by weight.
More preferably, it is 0% by weight. C. I. If the amount of the red pigment other than Pigment Red 254 is too large, the light transmittance tends to decrease. Other red pigments include, for example, C.I. I. Pigment Red 9, 123,
155, 168, 177, 180, 217, 220, 2
24 and the like can be used.

Examples of the yellow pigment include C.I. I. Pigment Yellow 20, 24, 83, 93, 109, 11
0, 117, 125, 139, 147, 154 and the like. Examples of the orange pigment include C.I. I. Pigment Orange 43, 71 and the like.

In the present invention, the mixing ratio of the red pigment and the yellow pigment is such that the weight ratio of the red pigment / the yellow pigment is 90/10 to 10%.
40/60, preferably 80/20 to 50
/ 50 is more preferable.

The resin used in the red resin composition used in the present invention is not particularly limited as long as it has a pigment dispersibility when used as a colored image forming material, and a resin having a film forming property is preferable. Further, those which do not hinder photosensitivity and have developability are preferable. As such a resin, carboxymethylhydroxyethylcellulose, cellulose resins such as hydroxyethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone and the like can be used, but methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate Acrylates or methacrylates such as acrylate, propyl acrylate, butyl acrylate, etc., homopolymers or copolymers of styrene, styrene derivatives and other polymerizable monomers, (meth) acrylic acid (means acrylic acid and methacrylic acid The same applies hereinafter), itaconic acid,
Carboxyl group-containing polymerizable monomers such as maleic acid, maleic anhydride, monoalkyl maleate, citraconic acid, citraconic anhydride, monoalkyl citraconic acid and (meth) acrylic acid ester, styrene,
Styrene derivatives and copolymers with other polymerizable monomers are particularly desirable.

The monoalkyl maleate is preferably an alkyl monoalkyl ester having 1 to 12 carbon atoms.
Monomethyl maleate, Monoethyl maleate, Mono-n-propyl maleate, Monoisopropyl maleate, Mono-n-butyl maleate, Mono-n maleate
-Hexyl, mono-n-octyl maleate, mono-2-ethylhexyl maleate, mono-n-nonyl maleate, mono-n-dodecyl maleate and the like.
As the citraconic acid monoalkyl ester, those having 1 to 12 carbon atoms in alkyl are preferable, and monomethyl citraconic acid, monoethyl citraconic acid, mono-n-propyl citraconic acid, monoisopropyl citraconic acid,
Mono-n-butyl citraconic acid, mono-n citraconic acid
-Hexyl, mono-n-octyl citraconic acid, mono-2-ethylhexyl citraconic acid, mono-citraconic acid-
n-nonyl, mono-n-dodecyl citraconic acid and the like.

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. Preferable examples of such a resin include oxiranes such as glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, α-ethyl glycidyl acrylate, crotonyl glycidyl ether, and monoalkyl glycidyl ether of itaconate as a high acid value carboxy-containing resin. A compound having one ring and 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 200 to
3,000, preferably 230 to 1,
000, more preferably 250
It is preferably set to 750. When the unsaturated equivalent is less than 200, the pigment tends to partially cure when the pigment is dispersed in the resin during the preparation of the photosensitive material, and when the unsaturated equivalent exceeds 3,000, the photopolymerizability due to the introduction of the unsaturated group is insufficient. Is not granted to Here, the unsaturated equivalent means the molecular weight of the resin per unsaturated bond.

When the resin has photopolymerizability by itself, or when the composition is given photosensitivity as in the case of a photosensitive red resin composition as described later, it exhibits alkali developability after exposure. From the viewpoint of having an acid value of 20 to
Preferably, the acid value is in the range of 300.
It is preferably within a range of from 200 to 200, and particularly preferably from 60 to 1
It is preferably in the range of 70. 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 above resin has a weight average molecular weight of 1,
It is preferably in the range of 500 to 200,000, and particularly preferably in the range of 10,000 to 50,000. If the weight average molecular weight is less than 1,500, the dispersion stability of the pigment tends to decrease.
If it exceeds 000, the viscosity becomes high when it is made into a photosensitive solution,
The applicability, particularly the applicability during spin coating, tends to decrease.

In the present invention, the weight average molecular weight is a value measured by gel permeation chromatography and converted using a calibration curve of standard polystyrene.

As the resin having an acid value of 20 to 300 and a weight average molecular weight of 1,500 to 200,000, in particular, the following general formula (I)

[0028]

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

[0030]

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(Wherein, R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a group having a photoreactive unsaturated bond, and R ⁶ represents a hydrogen atom or a carbon atom (Representing an alkyl group of Formulas 1 to 12) represented by the following general formula (I) / general formula (II):
Resins having a ratio of / 1 (molar ratio) are particularly preferred in terms of pigment dispersion stability and photosensitivity.

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

As a method for producing a resin having the repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (II), for example, the repeating unit represented by the general formula (I) As a precursor of the resin having a repeating unit represented by the general formula (II), unsaturated alcohols (allyl alcohol, 2-buten-4-ol, furfuryl alcohol, oleyl alcohol, cinnamyl alcohol,
Hydroxyacrylate, 2-hydroxymethacrylate, N-methylolacrylamide, etc.) and a resin having a repeating unit represented by the general formula (I) and a repeating unit represented by the general formula (II) Compounds each having one oxirane ring and one ethylenically unsaturated bond (glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, α-ethyl glycidyl acrylate, crotonyl glycidyl ether, monoalkyl monoglycidyl itaconate, etc.) And a method of manufacturing by adding the compound.

As a resin precursor having a repeating unit represented by the general formula (I) and a repeating unit represented by the general formula (II), styrene or a derivative thereof and a maleic acid monoalkyl ester (maleic acid (Half ester) and monoalkyl citraconic acid (half ester of 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.

Examples of the monoalkyl maleate include monomethyl maleate, monoethyl maleate, mono-n-propyl maleate, mono-isopropyl maleate, mono-n-butyl maleate, and mono-n-hexyl maleate. And mono-n-octyl maleate, mono-2-ethylhexyl maleate, mono-n-nonyl maleate, mono-n-dodecyl maleate and the like.

Examples of the monoalkyl citraconic acid ester include monomethyl citraconic acid, monoethyl citraconic acid, mono-n-propyl citraconic acid, mono-isopropyl citraconic acid, mono-n-butyl citraconic acid, and mono-n-hexyl citraconic acid. Mono-n-octyl citraconic acid, mono-2-ethylhexyl citraconic acid, mono-n-nonyl citraconic acid, mono-n-dodecyl citraconic acid, and the like.

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

The red resin composition may further contain a monomer having two or more photopolymerizable unsaturated bonds in a molecule, a photoinitiator, and the like to form a photosensitive red resin composition. A photosensitive solution can be prepared by incorporating an organic solvent.

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

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

The above-mentioned monomer having two or more photopolymerizable unsaturated bonds in the molecule further includes a compound represented by the general formula (a):

[0043]

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

[0045]

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(Wherein m and n each independently represent an integer of 1 to 10), an epichlorohydrin-modified bisphenol A and an addition ester of acrylic acid, bisphenol A dimethacrylate, 4
-Butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol diacrylate, general formula (c)

[0047]

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

[0049]

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(Wherein, m and n each independently represent an integer of 1 to 10), an epichloroline-modified phthalic acid and an addition ester of acrylic acid, a diacrylate of polyethylene glycol, a polypropylene Glycol dimethacrylate, tetraethylene glycol diacrylate, general formula (e)

[0051]

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(Wherein, m and n each independently represent an integer of 1 to 20) and an epichloroline-modified product of 1,6-hexanediol and an addition esterified product of acrylic acid (an acryloyl group is Having two in one molecule), trimethylolpropane triacrylate, pentaerythritol triacrylate, general formula (f)

[0053]

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

[0055]

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(Wherein, R represents an ethylene group or a propylene group, and m, m ′ and m ″ each independently represent
A triacrylate of an alkylene oxide adduct of trimethylolpropane represented by an integer of 1 to 20)
Tris (methacryloxyethyl) isocyanurate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate and the like can be mentioned.

These monomers can be used alone or in combination of two or more.

Examples of the photoinitiator include benzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, benzyl, 2,2-diethoxyacetophenone, Benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2 -Morpholino-1-propane, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-
2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 1,2-benzoanthraquinone, 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.

Examples of the organic solvent include ketone compounds, alkylene glycol ether compounds, alcohol compounds, aromatic compounds and the like. Specifically, ketone compounds include acetone, methyl ethyl ketone, cyclohexanone, etc., and alkylene glycol ether compounds include methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, ethylene glycol monopropyl ether,
Ethylene glycol monohexyl ether, ethylene glycol 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, etc., and alcohol compounds such as methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, 3-methyl-3-methoxybutanol, etc. There are 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, and dioxane are exemplified. These can be used alone or in combination of two or more.

The mixing ratio of the resin, pigment, monomer having two or more photopolymerizable unsaturated bonds in the molecule and photoinitiator used in the photosensitive red resin composition or the photosensitive liquid for forming a red image is as follows. Based on the total amount, (a) the resin is preferably 10 to 85% by weight, more preferably 20 to 60% by weight, particularly preferably 25 to 50% by weight, and (b) the pigment is
Preferably 5 to 50% by weight, more preferably 10 to 40%
% By weight, particularly preferably 15 to 30% by weight, and (c) a monomer having two or more photopolymerizable unsaturated bonds in a molecule.
Preferably 2 to 50% by weight, more preferably 5 to 40% by weight, particularly preferably 10 to 30% by weight, (d) the photoinitiator is preferably 0.01 to 20% by weight, more preferably 2 to 15% by weight. %, Particularly preferably 5 to 10% by weight.

If the amount of the resin in the photosensitive red resin composition or the photosensitive liquid for forming a red image is too small, the dispersion stability of the pigment tends to decrease. If the amount is too large, the viscosity of the photosensitive liquid becomes high. There is a tendency that the coatability, particularly the coatability during spin coating, decreases.

When the content of the pigment is less than 5% by weight, the color density of the image tends to decrease, and when the content exceeds 50% by weight, the light sensitivity tends to decrease.

If the amount of the monomer having two or more photopolymerizable unsaturated bonds in the molecule is less than 2% by weight, the photosensitivity tends to decrease, and if it exceeds 50% by weight, the dispersion stability of the pigment tends to decrease. There is.

Further, if the photoinitiator is less than 0.01% by weight, the photosensitivity tends to decrease, and if it exceeds 20% by weight, the adhesion tends to decrease.

The organic solvent may be a resin, a pigment, a monomer having at least one photopolymerizable unsaturated bond in a molecule thereof in a red image forming photosensitive solution, and a total solid content including a photoinitiator of 5 to 40% by weight. Is preferably used. 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 applicability tends to be poor.

In the present invention, the photosensitive red resin composition or the photosensitive liquid for forming a red image includes a thermal polymerization inhibitor (hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, etc.) for suppressing a dark reaction, Titanate coupling agent for improving adhesiveness with silane (silane coupling agent having vinyl group, epoxy group, amino group, mercapto group, etc., isopropyltrimethacryloyl titanate, diisopropylisostearoyl-4-aminobenzoyl titanate, etc.) ,
Surfactants (fluorine-based,
Various additives such as silicon-based and hydrocarbon-based) and other additives such as an ultraviolet absorber and an antioxidant can be used as needed.

Next, a method for producing the red resin composition, the photosensitive red resin composition and the photosensitive liquid for forming a colored image used in the present invention will be described.

The pigment is mixed and dispersed with a resin, an organic solvent and, if necessary, a dispersant. At this time, the mixture is preferably subjected to dispersion treatment by kneading using a dispersing / kneading apparatus such as an ultrasonic dispersing machine, a three-roll mill, a ball mill, a sand mill, a paste mill, a homogenizer, and a kneader. At this time, it is preferable to use at least 20 parts by weight of the resin with respect to 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 less than 100 parts by weight, the viscosity at the time of dispersion is too high,
In particular, when dispersing by a ball mill, a sand mill, a bead mill, or the like, dispersion may be difficult. As described above, a red resin composition can be produced.

In order to prepare a photosensitive red resin composition or a photosensitive liquid for forming a colored image, a monomer having at least two photopolymerizable unsaturated bonds in a molecule and a photoinitiator are mixed. Mixing may be performed before the dispersion treatment, or may be performed after the dispersion treatment. The whole 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 the colored image forming photosensitive liquid.

The amount of each component used is adjusted from the time of production of the red resin composition so that it finally becomes the compounding ratio in the photosensitive red resin composition or the photosensitive liquid for forming a red 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 the like. An organic dye such as an anthraquinone-based, perylene-based, phthalocyanine-based, or quinacridone-based organic dye may be a derivative of an organic dye obtained by introducing a substituent such as a carboxyl group, a sulfonate group, a carboxylic acid amide group, or a hydroxyl group. It is preferable because the dispersibility and dispersion stability of the pigment are improved. These pigment dispersants and organic dye derivatives are preferably used in an amount of 50 parts by weight or less based on 100 parts by weight of the pigment. If it exceeds 50 parts by weight, the chromaticity tends to shift.

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

Similarly, the entire amount of the organic solvent may be used together with the pigment during the dispersion treatment, or a part of the organic solvent may be added after the dispersion treatment. However, it is preferable to use at least 100 parts by weight of the organic solvent at the time of dispersion treatment, based on 100 parts by weight of the total amount of the pigment and the resin at the time of dispersion treatment. 10
If the amount is less than 0 parts by weight, the viscosity at the time of the dispersion treatment is too high, and the dispersion may be difficult particularly when the dispersion is performed by a ball mill, a sand mill, a bead mill or the like.

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 of the present invention or the photosensitive solution for forming a colored image is used for the production of a color filter, each pigment system suitable for a colored image such as red, green, blue or black is used. Is done. The above-mentioned red pigments are used, but the following pigments are used as other pigments.

For a green colored image, a single green pigment may be used, or a yellow pigment system may be mixed with a green pigment system for toning.

The green pigments include, for example, C.I. I. Pigment Green 7, 36,
37 and the like.

The yellow pigments include, for example, C.I. I. Pigment Yellow 20, 2
4, 83, 93, 109, 110, 117, 125, 1
39, 147, 154 and the like.

These green pigments and yellow pigments can be used as a mixture of two or more kinds. When a mixture of a green pigment type and a yellow pigment type is used, the yellow pigment type is used in a total amount of 10 parts for the green pigment type and the yellow pigment type.
It is preferable to use 50 parts by weight or less based on 0 parts by weight.

For a blue colored image, a single blue pigment system may be used, or a violet pigment system may be mixed with a blue pigment system for toning.

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

The purple pigments include, for example, C.I. I. Pigment Violet 19,
23, 29, 37, 50 and the like.

These blue pigments and purple 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 replaced by a total amount of the blue pigment and the violet pigment of 10%.
It is preferable to use 50 parts by weight or less based on 0 parts by weight.

For a 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 red pigment system was used,
The colored resin composition, the composition in the photosensitive colored resin composition and the photosensitive solution for forming a colored image, the components used other than the pigment, the method of preparing the composition or the photosensitive solution, and the like are a red resin composition, a photosensitive red resin composition, It is determined according to the photosensitive liquid for forming a red image.

For laminating a photosensitive layer on a substrate using a colored image forming material, a colored image forming photosensitive liquid is directly applied to a substrate, or the photosensitive liquid is once applied to a support to form a film. And lamination on a substrate.

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.

Examples of the method of applying the photosensitive liquid to the substrate include roll coater coating, spin coater coating, spray coating, whey coater coating, dip coater coating, curtain flow coater coating, wire bar coater coating, gravure coater coating, air knife coater coating, and the like. There is.
After application, it is preferable to dry at a temperature of 50 to 130 ° C. for 1 to 30 minutes. Thus, a film composed of the colored image forming material can be obtained.

The thickness of the photosensitive layer formed in this manner is appropriately determined depending on the application, but is preferably in the range of 0.1 to 300 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 laminate 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 peeled off after the photosensitive layer is laminated 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 laminated on the substrate can be carried out by irradiating the photosensitive layer with actinic rays in an image-like manner. Thereby, the film in the exposed portion can be cured. At the time of exposure, an oxygen barrier film such as polyvinyl alcohol may be formed on the surface of the film with a thickness of 0.5 to 30 μm, and the film may be exposed from above.

As the light source of the actinic ray, for example, a carbon arc lamp, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a 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 step. In particular, in a method of manufacturing a color filter, the colored image forming step is repeated for three to four different colored images including a red image forming step. It is preferred to do so. For example, red, green, and blue colored images are formed on a black matrix previously formed by chromium evaporation or the like. After a black matrix is formed 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 between the colored images using a black image forming material. The order of forming the red, green, and blue colored images is arbitrary. The colored image is adapted to form pixels for each color.

[0097]

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: 50 mol% of styrene
-20% by mole of maleic acid monopropyl ester-30% by mole of maleic acid derivative, having a weight average molecular weight of 11
(2) A repeating unit based on the maleic acid derivative has the following structure.

[0099]

Embedded image

Example 1 (1) Production of Red Colored Resin Composition In 200 g of diethylene glycol dimethyl ether, 30 g of copolymer A as a resin and C.I. I. Pigment Red 254 and C.I. I. Pigment Yellow 139 was added and dispersed for 2 hours using a bead mill to obtain a red colored resin composition.

To this red resin dispersion, 32 g of dipentaerythritol hexaacrylate as a monomer, 6 g of benzophenone and 2 g of N, N'-tetraethyl-4,4'-diaminobenzophenone as a photoinitiator and diethylene glycol dimethyl ether 2 as an organic solvent.
00g was added and mixed to obtain a red colored image forming photosensitive liquid.

(2) Production of Colored Image This photosensitive liquid was applied on a glass substrate (Corning Co., Ltd., trade name: 7059) by spin coating, and further dried at 110 ° C. for 5 minutes to form a film having a thickness of 2. A 0 μm film was formed.

The obtained film was exposed to an image of 700 mJ / cm 2 using a super-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 red pixel.

Example 2 (1) Production of Red Colored Resin Composition In 200 g of diethylene glycol dimethyl ether, 30 g of copolymer A as a resin and C.I. I. Pigment Red 254 and C.I. I. Pigment Yellow 83 was added thereto, and dispersed for 2 hours using a bead mill to obtain a red colored resin composition.

To this red resin dispersion, 35 g of dipentaerythritol hexaacrylate as a monomer, 6 g of benzophenone as a photoinitiator and 2 g of N, N′-tetraethyl-4,4′-diaminobenzophenone, and diethylene glycol dimethyl ether 2 g as an organic solvent.
00g was added and mixed to obtain a red colored image forming photosensitive liquid.

(2) Production of Colored Image This photosensitive liquid was applied on a glass substrate (Corning Co., Ltd., trade name: 7059) by spin coating, and further dried at 110 ° C. for 5 minutes. A 0 μm film was formed.

The obtained film was exposed to an image of 700 mJ / cm ^{2 using} a super-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 red pixel.

Example 3 (1) Production of Red Colored Resin Composition In 200 g of diethylene glycol dimethyl ether, 30 g of copolymer A as a resin and C.I. I. Pigment Red 254 (19 g), C.I. I. Pigment Red 177 (2 g), C.I. I. Pigment Yellow 83 was added and dispersed for 2 hours using a bead mill to obtain a red colored resin composition.

To this red resin composition were added 32 g of trimethylolpropane triacrylate as a monomer, 6 g of benzophenone and 2 g of N, N'-tetraethyl-4,4'-diaminobenzophenone as a photoinitiator and diethylene glycol dimethyl ether 20 g as an organic solvent.
0 g was added and mixed to obtain a red colored image forming photosensitive liquid.

(2) Production of Colored Image The obtained red photosensitive liquid was applied to a 6 μm-thick polyethylene terephthalate film by a gravure coating method, and dried at 100 ° C. for 12 minutes to form a 20 μm-thick red image. Forming a layer containing the material, and having a thickness of 40
A photosensitive element was obtained by coating with a polyethylene film of μm.

After the polyethylene film was peeled off from the obtained photosensitive element, it was laminated on the same glass substrate as that used in Example 1. Lamination conditions were as follows: glass substrate temperature 40 ° C., laminating roll temperature 11
The lamination was performed at 0 ° C., a lamination pressure of 3.5 kgf / cm ² , and a lamination speed of 1.5 m / min.

Next, through a negative photomask, a 60 mJ / cm ² pixel-like exposure was performed from above the polyethylene terephthalate film with an ultra-high pressure mercury lamp, and then the polyethylene terephthalate film was peeled off. Development was performed under the conditions. Table 1 shows the reflectance and chromaticity of the obtained red pixels.

Example 4 (1) Production of green colored resin composition and photosensitive solution 30 g of copolymer A as a resin and C.I. I. Pigment Green 36 and C.I. I. Pigment Yellow 83 and 9 g of diethylene glycol dimethyl ether were dispersed in a bead mill for 2 hours to prepare a green colored resin composition. To this, 32 g of pentaerythritol hexaacrylate as a monomer, 6 g of benzophenone as a photoinitiator and N,
2 g of N'-tetraethyl-4,4'-diaminobenzophenone and 200 g of diethylene glycol dimethyl ether as an organic solvent were added and mixed to obtain a green colored image forming photosensitive liquid.

(2) Production of blue colored resin composition and photosensitive solution 30 g of copolymer A as a resin and C.I. I. Pigment Blue 15-6 and C.I. I. Pigment Violet 23 was added to 200 g of diethylene glycol dimethyl ether, and dispersed for 2 hours using a bead mill to prepare a blue colored resin composition. To this, 34 g of pentaerythritol hexaacrylate as a monomer, 6 g of benzophenone and 2 g of N, N'-tetraethyl-4,4'-diaminobenzophenone as a photoinitiator and 200 g of diethylene glycol dimethyl ether as an organic solvent were added and mixed. A photosensitive liquid for formation was obtained.

(3) Production of Color Filter A red image pattern was formed on a glass substrate having a black matrix formed of chromium by the same method and under the same conditions as in Example 1, and then heated at 180 ° C. for 10 minutes. .
Next, using the above-described green image forming photosensitive liquid, under the same method and conditions as in Example 1, next to the red pixel pattern,
After forming a green image pattern, heating was performed at 180 ° C. for 10 minutes. Next, a blue image pattern was formed next to the green image pattern under the same method and conditions as in Example 1 using the above-described blue image forming photosensitive liquid, and then heated at 180 ° C. for 10 minutes. From the above, one pixel is 30 pixels.
A mosaic color filter composed of three colors of green, red and blue having a size of μm × 100 μm was prepared.

[Comparative Example 1] The red pigment was C.I. I. Pigment Red 254 and C.I. I. Pigment Red 1
Except that 77 was used, a red image forming photosensitive liquid was blended by the same method and conditions as in Example 1, and a red image pattern was formed by the same method and conditions as in Example 1. The degree and transmission curve were measured. The results are shown in Table 1 and FIG.

[0117]

[Table 1]

The reflectance and the chromaticity were measured by using a spectral colorimeter JP7200F manufactured by Color Techno System Co., Ltd.
The measured values Y, x, and y are the Y value, x value, and y value based on the XYZ (Yxy) color system, which is the CIE standard color system, where the Y value is the transmittance, and x and y are Chromaticity.

From Table 1, it can be seen that C.I. I. By using Pigment Red 254, it can be seen that the value of the chromaticity Y is large and the color purity is good. Further, it can be seen from the transmission curve (FIG. 1) that the light transmittance is greatly improved.
In contrast, C.I. I. When Pigment Red 254 is not used (Comparative Example 1), it is recognized that the value of Y of the chromaticity is low and the light transmittance is not good.

Thus, the color filter (Example 4) prepared using the photosensitive liquid for forming a red image and the photosensitive element having a higher light transmittance than ever before has excellent optical characteristics.
It was confirmed that it was effective as an image display device.

[0121]

The red image based on the red resin composition of the present invention, the photosensitive red resin composition, and the photosensitive liquid for forming a red image has excellent light transmittance. According to the method for producing a colored image of the present invention, a red image having excellent light transmittance can be obtained.
Further, a color filter having a red pixel with excellent light transmittance can be manufactured.

[Brief description of the drawings]

FIG. 1 is a graph showing a red pixel light transmittance curve.

[Explanation of symbols]

 1 ... red pixel light transmittance curve created in Example 1 2 ... red pixel light transmittance curve created in Comparative Example 1

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 25/02 C08L 25/02 35/00 35/00 G02B 5/20 101 G02B 5/20 101 5/22 5/22 G03F 7 / 004 505 G03F 7/004 505 7/027 502 7/027 502 511 511 7/033 7/033 7/30 7/30 (72) Inventor Tetsuya Okazaki 14 Goi South Coast, Ichihara City, Chiba Prefecture Hitachi Chemical Co., Ltd. (72) Inventor Seigo Yokochi 14 Goi South Coast, Ichihara City, Chiba Prefecture Hitachi Chemical Co., Ltd.Goi Plant (72) Inventor Shinya Kato 14 Goi South Coast, Ichihara City, Chiba Prefecture Hitachi Chemical Goi Co., Ltd. in the factory

Claims (9)

[Claims] 1. A red resin composition comprising (a) a resin and (b) a color index (CI) pigment red 254 and a yellow or orange pigment dispersed therein. 2. A resin, (b) a color index (CI) pigment red 254, a toning pigment containing at least yellow or orange, and (c) a photopolymerizable unsaturated bond in the molecule. A photosensitive red resin composition comprising: (d) a photoinitiator having at least one monomer. 3. The photosensitive red 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. The resin is represented by the following general formula (I): (Wherein, R ¹ represents a hydrogen atom or a methyl group,
R ² and R ³ each independently represent a hydrogen atom, a carbon number of 1 to 1;
An alkyl group of 2 or an alkoxy group having 1 to 12 carbon atoms) and the following general formula (II): (Wherein, in the formula, R ⁴ and R ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a group having a photoreactive unsaturated bond, and R ⁶ represents a hydrogen atom or a carbon atom having 1 to 1 carbon atoms.
A repeating unit represented by the following formula:
The photosensitive red resin composition according to claim 2, which is a resin having the formula (I) / the formula (II) in a ratio of 1/1 to 5/1 (molar ratio). 5. A resin, (b) a color index (CI) pigment red 254, a toning pigment containing at least yellow or orange, and (c) a photopolymerizable unsaturated bond in the molecule. A monomer having at least one monomer, (d) a photoinitiator,
(E) A photosensitive liquid for forming a red image, comprising an organic solvent. 6. A colored image forming step of laminating a photosensitive layer comprising a colored image forming material using the photosensitive resin composition according to claim 2, on a substrate, and exposing and developing the photosensitive layer. Method for producing a colored image. 7. A method according to claim 6, wherein the photosensitive layer is formed from the photosensitive solution according to claim 5. 8. A colored image forming material is formed as a film on a substrate by using the photosensitive red resin composition according to claim 2, 3 or 4, or the photosensitive liquid according to claim 5, and actinic light is formed into an image. A method for producing a color filter, wherein the steps of irradiating, light-curing an exposed portion, and removing an unexposed portion by development are repeatedly performed on colored image forming materials of a plurality of different colors to form pixels. 9. The method according to claim 8, wherein the pixels according to claim 6 are red, green and blue pixels.