JP2000338658A - Photosensitive colored resin composition, colored image forming photosensitive fluid using same, photosensitive element, production of colored image and production of color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure high dispersibility and dispersion stability of a pigment, to also ensure high light resistance and to form a coating film excellent in appearance by incorporating at least one of two specified UV absorbing compounds. SOLUTION: At least one of UV absorbing compounds of formulae I and II is incorporated into a photosensitive colored resin composition containing a pigment, a resin, a monomer containing one or more photopolymerizable unsaturated bonds in one molecule and a photoinitiator. In the formula I, X is H or halogen, R1 is H or a 1-6C alkyl, R2 is a 2-12C alkylene and R3 is H or methyl. In the formula II, R4 is H or methyl, R5 is a 2-6C alkylene which may have hydroxy as a substituent, Y is H or a 1-6C alkoxy and Z is H or hydroxy.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[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 the resultant is dyed mainly with 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.

[0003] 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 much research has been conducted. According to this method, the manufacturing method is simplified, and the obtained color filter is known to be stable and have a long life.

[0004] However, the technique for stably dispersing the pigment is difficult, and it is particularly difficult to select a dispersing resin which has a great effect on the dispersibility of the pigment. In addition, there has been a demand for a material for forming a pixel having excellent light fastness, which does not cause a color change even when a backlight is used for a long time.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a photosensitive colored resin composition capable of forming a film having high dispersibility and dispersion stability of a pigment, high light resistance and excellent appearance of a coating film. To provide things.

Another object of the present invention is to provide a colored image forming photosensitive liquid capable of forming a film having high dispersibility and dispersion stability of a pigment, high light resistance and excellent appearance of a coating film. It is in.

Another object of the present invention is to provide a photosensitive element capable of forming a film having high pigment dispersibility and dispersion stability, high light resistance and excellent appearance of a coating film.

It is another object of the present invention to provide a method for producing a colored image in which the pigment of the coating film of the pixel is well dispersed, has high light resistance, and has excellent optical characteristics.

It is another object of the present invention to provide a method for producing a high-quality color filter having a good dispersion of pigment in a coating film of a pixel, high light resistance, and excellent optical characteristics.

[0010]

SUMMARY OF THE INVENTION The present invention provides a pigment, a resin,
In a photosensitive colored resin composition containing a monomer containing at least one photopolymerizable unsaturated bond in a molecule and a photoinitiator, the following general formula (I)

[0011]

Embedded image (Wherein X is a hydrogen atom or a halogen atom, R ¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ² is an alkylene group having 2 to 12 carbon atoms, and R ³ is a hydrogen atom Or a methyl group), and the following general formula (II)

[0012]

Embedded image (Wherein, R ⁴ is a hydrogen atom or a methyl group, R ⁵ is an alkylene group having 2 to 6 carbon atoms which may have a hydroxyl group as a substituent, and Y is a hydrogen atom or an alkoxy group having 1 to 6 carbon atoms. Wherein Z is a hydrogen atom or a hydroxyl group), and a photosensitive colored resin composition containing at least one ultraviolet-absorbing compound selected from ultraviolet-absorbing compounds.

The present invention relates to a colored image forming photosensitive liquid containing the above-mentioned photosensitive colored resin composition and an organic solvent.

The present invention relates to a photosensitive element obtained by laminating a photosensitive layer containing the above-mentioned photosensitive colored resin composition on a support.

The present invention relates to a method for producing a colored image, comprising a colored image forming step of laminating a photosensitive layer containing the above-mentioned photosensitive colored resin composition on a substrate and exposing and developing the photosensitive layer.

The present invention relates to a method for producing a color filter, wherein a plurality of colored images are produced on the same substrate by the above-mentioned method for producing a colored image.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION In the photosensitive colored resin composition of the present invention, the resin is not particularly limited as long as it has pigment dispersibility when used as a colored image forming material. Those having a film forming property are preferable, and those having a developing property without hindering the photosensitivity 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 Homopolymers or copolymers of acrylates or methacrylates such as methacrylate, propyl acrylate and butyl acrylate, styrene, styrene derivatives and other polymerizable monomers, and (meth) acrylic acid (mean acrylic acid and methacrylic acid. The same applies hereinafter.), Itaconic acid, maleic acid, maleic anhydride, monoalkyl maleate, citraconic anhydride, monoalkyl citraconic acid Carboxyl group-containing polymerizable monomer and (meth) acrylic acid esters such as ester, styrene, styrene derivatives, copolymers with other polymerizable monomers are preferred.

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.

The monoalkyl citraconic acid ester preferably has 1 to 12 carbon atoms in the alkyl, and includes monomethyl citraconic acid, monoethyl citraconic acid, mono-n-propyl citraconic acid, monoisopropyl citraconic acid and monoisopropyl citraconic acid. n-butyl, mono-n-hexyl citraconic acid, mono-n-citraconic acid
Octyl, mono-2-ethylhexyl citraconic acid, mono-n-nonyl citraconic acid, mono-n-citraconic acid
Dodecyl and the like.

As the (meth) acrylic acid ester, for example, an alkyl ester of (meth) acrylic acid having 1 to 12 carbon atoms is preferable. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate A) acrylate, isopropyl (meth) acrylate, mono-n-butyl (meth) acrylate, mono-n
-Hexyl (meth) acrylate, mono-n-octyl (meth) acrylate, mono-n-nonyl (meth) acrylate, mono-n-dodecyl (meth) acrylate 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. Preferred examples of such a resin include oxirane rings such as glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, α-ethyl glycidyl acrylate, crotonyl glycidyl ether, and monoalkyl glycidyl ether itaconate in a high acid value carboxyl group-containing resin. And a compound having one ethylenically unsaturated bond and a compound having one ethylenically unsaturated bond (unsaturated alcohol), a carboxyl group-containing resin having a hydroxyl group, and a resin having a free isocyanate group. Resin reacted with a saturated compound, resin obtained by reacting a polybasic anhydride with an addition reaction product of an epoxy resin and an unsaturated carboxylic acid, a conjugated diene polymer or a diene copolymer and an unsaturated dicarboxylic anhydride. Hydroxyl-containing polymerizable in addition reaction product A resin obtained by reacting an Nomar the like.

The unsaturated equivalent of the resin is from 200 to
3,000, preferably 230 to 1,
000, more preferably 250
It is preferably set to 750. When the unsaturated equivalent is too small, the photosensitive material tends to be partially cured during the preparation of the photosensitive material, particularly when the pigment is dispersed in the resin, and when the unsaturated equivalent is too large, the photopolymerizability due to the introduction of the unsaturated group is sufficiently high. Not granted. Here, the unsaturated equivalent means the molecular weight of the resin per unsaturated bond.

When the above resin has photopolymerizability itself, or when it is given photosensitivity as a composition such as a photosensitive colored resin composition as described later, it has an alkali developability after exposure. From the viewpoint of having an acid value of 20 to
It is preferably in the range of 300, more preferably 40 to 2
00, preferably from 60 to 170
Is preferably within the range. If the acid value is less than 20, alkali developability tends to decrease, and if it exceeds 300, the shape of the image pattern after alkali development tends to be unclear.

The weight average molecular weight of the resin is
It is preferably in the range of 1,500 to 200,000, more preferably in the range of 5,000 to 100,000, especially 10,000 to 50,000.
It is preferably within the range of 10,000 to 5
It is preferably in the range of 0.000. If the weight average molecular weight is less than 1,500, the dispersion stability of the pigment tends to decrease, and if it exceeds 200,000, the viscosity becomes high when the composition is made into a photosensitive liquid, and the coating properties, especially when spin coating, are increased. The coatability tends to decrease.

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

As the resin having an acid value of 20 to 300 and a weight average molecular weight of 1,500 to 200,000, particularly, a resin represented by the following general formula (III):

[0028]

Embedded image (Wherein, R ⁶ represents a hydrogen atom or a methyl group,
R ⁷ and R ⁸ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms) and the following general formula (IV)

[0029]

Embedded image (Wherein, in the formula, R ⁹ and R ¹⁰ 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 ¹¹ represents a hydrogen atom or a carbon atom having 1 to 1 carbon atoms.
A resin having a general formula (III) / general formula (IV) (molar ratio) of 1/1 to 5/1 is used to obtain a pigment dispersion stability and light It is preferable in terms of sensitivity.

The following are more preferred as the above-mentioned resin.
Good. That is, (i) In general formula (IV), R
⁹Is a group having a photoreactive unsaturated bond, R^TenIs a hydrogen atom, R
¹¹Is a hydrogen atom, (ii) a compound represented by the general formula (I
In V), R⁹Is a group having a photoreactive unsaturated bond, R
^TenIs a group having a hydrogen atom and a photoreactive unsaturated bond, R¹¹But
A repeating unit that is a hydrogen atom, (iii) a compound represented by the general formula (I)
In V), R⁹Is a group having a photoreactive unsaturated bond, R
^TenIs a hydrogen atom and an alkyl having 1 to 12 carbon atoms or a photoreaction
A group having an unsaturated bond, R ¹¹Is a hydrogen atom
A unit, (iv) in the general formula (IV),⁹And R^Ten
Is a hydrogen atom or a group having a photoreactive unsaturated bond;
¹¹Is a repeating unit having an alkyl group having 1 to 12 carbon atoms.
It is preferable to have one.

The method for producing a resin having a repeating unit represented by the general formula (III) and a repeating unit represented by the general formula (IV) includes, for example, a repeating unit represented by the general formula (III) Unsaturated alcohols (allyl alcohol, 2-buten-4-ol, furfuryl alcohol, oleyl alcohol, cinnamyl alcohol, 2-hydroxyacrylate) may be added to the precursor of the resin having a repeating unit represented by the general formula (IV). 2-hydroxymethacrylate, N-methylolacrylamide, etc.) by esterification reaction, general formula (III)
A compound having one oxirane ring and one ethylenically unsaturated bond (glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether) as a precursor of the resin having the repeating unit represented by the formula (I) and the repeating unit represented by the general formula (IV) , Α-ethyl glycidyl acrylate, crotonyl glycidyl ether, monoalkyl monoglycidyl itaconate, etc.).

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

As the styrene derivative, monoalkyl maleate and monoalkyl citraconic acid, those described above are used.

As the resin used in the photosensitive colored resin composition of the present invention, when a resin having a repeating unit represented by the above-mentioned general formula (III) or (IV) is used, Resins may be used in combination. As the other resin, a resin other than the resin having the repeating unit represented by the general formula (III) and the general formula (IV) among the resins described above is used, and further, an acrylic resin, an epoxy resin, Urethane resin, melamine resin and the like may be used. Other resins are 5 parts per 100 parts by weight of total resin.
It is preferable to use it in an amount of 0 parts by weight or less.

Next, pigments used in the photosensitive colored resin composition or the photosensitive liquid for forming a colored image include inorganic pigments and organic pigments, and both can be used. Black carbon black (inorganic pigments) and organic pigments are preferred. As the organic pigment, for example, azo-based,
Phthalocyanine type, indigo type, anthraquinone type, perylene type, quinacridone type, methine / azomethine type, isoindolinone type and the like can be mentioned.

In producing the color filter of the present invention, each pigment system suitable for colored images such as red, green, blue and black is used.

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

As the red colored image, a single red pigment system may be used, or a yellow pigment system may be mixed with a red pigment system to perform toning.

The red pigments include, for example, C.I. I. Pigment Red 9, 123,
155, 168, 177, 180, 217, 220, 2
24, 254 and the like.

The yellow pigments include, for example, C.I. I. Pigment Yellow 17, 2
0, 24, 83, 93, 109, 110, 117, 12
5, 139, 147, 150, 154 and the like.

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

As a green colored image, a single green pigment system may be used, or the above-mentioned yellow pigment system may be mixed with a green pigment system to perform toning.

The green pigments include, for example, C.I. I. Pigment Green 7, 36,
37 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 and a yellow pigment is used, the yellow pigment is used in an amount of 50 parts by weight or less based on 100 parts by weight of the total weight of the green pigment and the yellow pigment. Is preferred.

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

The 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, Color Index, C.I. I. Pigment Violet 19, 2
3, 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.

As the black colored image, for example, black pigments such as carbon black, graphite, titanium carbon, black iron, and manganese dioxide are used.

The monomer having one or more, preferably two or more, photopolymerizable unsaturated bonds in a molecule used in the photosensitive colored resin composition or the photosensitive liquid for forming a colored image is represented by formula (V):

[0052]

Embedded image (Wherein, R represents an ethylene group or a propylene group, a and b each independently represent an integer of 1 to 20), a diacrylate of an alkylene oxide adduct of bisphenol A represented by the general formula ( VI)

[0053]

Embedded image (Wherein, c and d each independently represent 1 to 10
Epichlorohydrin-modified bisphenol A and addition ester compound of acrylic acid represented by
Bisphenol A dimethacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol diacrylate, general formula (VII)

[0054]

Embedded image (Wherein, R represents an ethylene group or a propylene group, e and f each independently represent an integer of 1 to 20), a diacrylate of an alkylene oxide adduct of phosphoric acid represented by the general formula (VIII) )

[0055]

Embedded image (Where g and h are each independently 1 to 10
Phthalic acid epichlorohydrin modified product and acrylic acid addition ester compound, polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, tetraethylene glycol diacrylate, general formula (IX)

[0056]

Embedded image (Where i and j are independently 1 to 20
1,6-hexanediol-modified epichlorohydrin and acrylic acid adduct ester compound (having two acryloyl groups in one molecule), trimethylolpropane triacrylate, pentaerythritol triacrylate , General formula (X)

[0057]

Embedded image (Wherein, R represents an ethylene group or a propylene group, and three k's each independently represent an integer of 1 to 20) triacrylate of an alkylene oxide adduct of phosphoric acid represented by the general formula ( XI)

[0058]

Embedded image (Wherein, R represents an ethylene group or a propylene group, p, q and r each independently represent an integer of 1 to 20) triacrylate or tris of an alkylene oxide adduct of trimethylolpropane (Methacryloxyethyl) isocyanurate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate and the like.

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

The photoinitiator 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 butyl ether, benzyldimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone,
-Hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-monophorino-1-propanone, t-butylanthraquinone,
-Chloroanthraquinone, 2-ethylanthraquinone,
1,4-naphthoquinone, 9,10-phenanthraquinone, 1,2-benzanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2-
(O-chlorophenyl) -4,5-diphenylimidazole dimer and the like. These photoinitiators are used alone or in combination of two or more.

Next, the photosensitive colored resin composition of the present invention is represented by the following general formula (I) as an ultraviolet absorbing compound:

[0062]

Embedded image (Wherein X is a hydrogen atom or a halogen atom, R ¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ² is an alkylene group having 2 to 12 carbon atoms, and R ³ is a hydrogen atom Or a methyl group), and the following general formula (II)

[0063]

Embedded image (Wherein, R ⁴ is a hydrogen atom or a methyl group, R ⁵ is an alkylene group having 2 to 6 carbon atoms which may have a hydroxyl group as a substituent, and Y is a hydrogen atom or an alkoxy group having 1 to 6 carbon atoms. Wherein Z is a hydrogen atom or a hydroxyl group), and at least one ultraviolet-absorbing compound selected from the group consisting of:

As the ultraviolet absorbing compound represented by the above general formula (I), specifically, 2- [2'-hydroxy-
5'-acryloyloxyethylphenyl] benzotriazole, 2- [2'-hydroxy-5'-methacryloyloxyethylphenyl] benzotriazole, 2-
[2'-hydroxy-5'-methacryloyloxypropylphenyl] benzotriazole, 2- [2'-hydroxy-5'-methacryloyloxyhexylphenyl] benzotriazole, 2- [2'-hydroxy-
3'-t-butyl-5'-methacryloyloxyethylphenyl] benzotriazole, 2- [2'-hydroxy-5'-t-butyl-3'-methacryloyloxyethylphenyl] benzotriazole, 2- [2'- Hydroxy-5'-methacryloyloxyethylphenyl]
-5-chlorobenzotriazole, 2- [2'-hydroxy-5'-methacryloyloxyethylphenyl]-
5-methoxybenzotriazole and the like. These components may be used alone or in combination of two or more.

As the ultraviolet absorbing compound represented by the general formula (II), specifically, 2-hydroxy-4-methacryloyloxybenzophenone, 2-hydroxy-4
-Acryloyloxybenzophenone, 2-hydroxy-4- (2-methacryloyloxy) ethoxybenzophenone, 2-hydroxy-4- (2-methyl-2-methacryloyloxy) ethoxybenzophenone, 2,2 '
-Dihydroxy-4- (2-methacryloyloxy) ethoxy-4'-methoxybenzophenone and 4'-t-butyl-2-hydroxy-4- (2-methacryloyloxy) ethoxybenzophenone. These components may be used alone or in combination of two or more.

The photosensitive liquid for forming a colored image of the present invention contains the photosensitive colored resin composition of the present invention and an organic solvent.

The organic solvent is not particularly limited.
For example, ketone compounds, alkylene glycol ether compounds, alcohol compounds, aromatic compounds and the like can be mentioned. Specifically, ketone compounds include acetone, methyl ethyl ketone, cyclohexanone, and the like, 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 dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, Pyrene 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 tert-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 tert-butyl ether acetate, etc. As compounds,
There are methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, 3-methyl-3-methoxybutanol and the like, and aromatic compounds such as benzene, toluene, xylene, N-methyl-2-pyrrolidone, N-hydroxymethyl- 2-pyrrolidone and the like,
Other examples include organic solvents such as 3-methyl-3-methoxybutyl acetate, ethyl acetate, dioxane, and tetrahydrofuran. These can be used alone or in combination of two or more.

Resin used in the photosensitive colored resin composition,
The mixing ratio of the pigment, the monomer having one or more photopolymerizable unsaturated bonds in the molecule, the photoinitiator and the ultraviolet absorbing compound is such that (a) the resin is preferably 10 to 85 to the total amount thereof. % By weight, more preferably 20 to 60% by weight,
Particularly preferably 25 to 50% by weight, (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 photopolymerizable unsaturated bond. Is preferably 2 to 50% by weight, more preferably 5 to 40% by weight, particularly preferably 10 to 30% by weight, and (d) the ultraviolet absorbing compound is preferably 0.1 to 10% by weight. The content is from 01 to 10% by weight, more preferably from 1 to 7% by weight, particularly preferably from 1.5 to 5% by weight. (E) The photoinitiator is preferably 0.01
-20% by weight, more preferably 2-15% by weight, particularly preferably 5-10% by weight.

If the amount of the resin in the photosensitive colored resin composition or the photosensitive liquid for forming a colored 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 amount of the pigment is too small, the color density of the image tends to be low. If the amount is too large, the light sensitivity tends to decrease.

When the amount of the monomer having one or more photopolymerizable unsaturated bonds in the molecule is too small, the photosensitivity tends to decrease, and when the amount is too large, the dispersion stability of the pigment tends to decrease.

Further, when the amount of the ultraviolet absorbing compound is too small, the light resistance is not improved, and when the amount is too large, the amount of light absorbed by the photoinitiator is reduced, and the film is hardly cured, and the adhesion is reduced.

Further, when the amount of the photoinitiator is too small, the photosensitivity tends to decrease, and when the amount is too large, the adhesiveness tends to decrease.

The organic solvent is a resin, a pigment, a monomer containing at least one photopolymerizable unsaturated bond in a molecule and a photoinitiator in the colored image forming photosensitive solution, and has a total solid content 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 applicability tends to be poor. If the total solid content is less than 5% by weight, the viscosity tends to be low and the applicability tends to be poor.

The photosensitive colored resin composition or the photosensitive liquid for forming a colored image according to the present invention may contain a thermal polymerization inhibitor (hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, etc.) for controlling a dark reaction. Titanate coupling agents (such as silane coupling agents having a vinyl group, an epoxy group, an amino group, and a mercapto group, isopropyltrimethacryloyl titanate, and diisopropylisostearoyl-4-aminobenzoyl titanate) for improving adhesion; and In addition, various additives such as an ultraviolet absorber and an antioxidant can be used as needed.

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

The pigment is mixed and dispersed with a resin, an organic solvent and, if necessary, a dispersant. At this time, the mixture is preferably subjected to dispersion treatment by kneading using a dispersing / kneading apparatus such as an ultrasonic dispersing machine, a three-roll mill, a ball mill, a sand mill, a bead mill, a homogenizer, and a kneader. 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 colored resin composition can be produced.

To prepare a photosensitive colored resin composition or a photosensitive solution for forming a colored image, a monomer having at least one photopolymerizable unsaturated bond in a molecule, an ultraviolet absorbing compound and a photoinitiator are mixed. These may be mixed before the dispersion treatment or may be mixed after the dispersion treatment. The entire amount of the resin may not be used at the time of the dispersion, and the remainder may be mixed later, particularly at the time of producing the photosensitive liquid for forming a colored image.

The amount of each component used is adjusted from the time of production of the colored resin composition so that it finally becomes the compounding ratio in the photosensitive colored resin composition or the photosensitive liquid for forming a colored 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; An organic dye derivative such as an anthraquinone-based, perylene-based, phthalocyanine-based, or quinacdrine-based organic dye into which a substituent such as a carboxyl group, a sulfonate group, a carboxylic acid amide group, or a hydroxyl group is introduced. The use of a dispersant improves the dispersibility and dispersion stability of the pigment. These dispersants 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 whole amount of the resin may be used together with the pigment at the time of the dispersion treatment, or a part of the resin may be added after the dispersion treatment. However, it is preferable to use at least 20 parts by weight of the resin for 100 parts by weight of the pigment during the dispersion treatment. If it is less than 20 parts by weight, the dispersion stability of the pigment tends to decrease.

Similarly, the whole amount of the organic solvent may be used together with the pigment at the time of the dispersion treatment, or a part of the organic solvent may be added after the dispersion treatment. However, it is preferable to use at least 100 parts by weight of the organic solvent in the dispersion treatment based on 100 parts by weight of the total weight of the pigment and the resin in the 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.

The photosensitive element of the present invention can be obtained by forming a photosensitive layer comprising the photosensitive colored resin composition of the present invention on a support. The thickness of the photosensitive layer is usually 0.1 to 3
00 μm, preferably 0.2 to 30 μm, more preferably 0.2 to 5 μm. The photosensitive layer can be formed by applying the colored image forming photosensitive solution of the present invention on a support and drying.

As a method of applying a photosensitive solution to the support,
For example, knife coater coating, gravure coater coating,
Roll coater application, spray coater application and the like can be adopted.

As the support, for example, a film such as a polyester film, a polyamideimide film, a polypropylene film, and a polystyrene film can be used. As such a film, usually, a film having a thickness of 0.2 to 500 μm is preferable,
Those having a thickness of 100 μm are more preferred.

After coating the photosensitive solution on the support, usually 5
The photosensitive layer can be obtained by drying at a temperature of 0 to 130 ° C for 1 to 30 minutes. Further, it is desirable to laminate a peelable cover film on the surface of the photosensitive layer for the purpose of preventing dust from adhering to the surface of the photosensitive layer.

As the peelable cover film, for example, a polyethylene film, a Teflon film, a polypropylene film, a surface-treated paper, or the like can be used. It is only necessary that the adhesive strength between the film and the cover film is smaller.

In the method for producing a colored image of the present invention, a photosensitive layer comprising the photosensitive colored resin composition of the present invention is laminated on a substrate,
It includes a colored image forming step of exposing and developing.

For laminating a photosensitive layer composed of a photosensitive colored resin composition on a substrate, a photosensitive liquid for forming a colored image is directly applied to the substrate, or the photosensitive liquid is temporarily applied to a support to form a film. After the photosensitive element is formed, the photosensitive element can be laminated on a substrate.

The substrate used in the present invention includes:
Depending on the application, for example, transparent glass plate such as white plate glass, blue plate glass, silica-coated blue plate glass, polyester resin, polycarbonate resin, acrylic resin, synthetic resin sheet such as vinyl chloride resin, film or plate, aluminum plate , A copper plate, a nickel plate, a metal plate such as a stainless steel plate, other ceramic plates, and a semiconductor substrate having a photoelectric conversion element. On these substrates, a black matrix may be formed in advance by chromium evaporation or the like.

The method of applying the photosensitive liquid to the substrate includes roll coater coating, spin coater coating, spray coating, wicker coating, dip coater coating, curtain flow coater coating, wire bar coater coating, gravure coater coating, air knife coater coating, and the like. There is. After application, it is preferable to dry at a temperature of 50 to 130 ° C. for 1 to 30 minutes. Thus, a photosensitive layer composed of the photosensitive colored resin composition can be obtained.

The thickness of the photosensitive layer thus formed is determined depending on the intended use, 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 laminated on a substrate using the photosensitive element of the present invention. In order to laminate the photosensitive layer on the substrate, there is a method in which a photosensitive element is overlaid on the substrate and pressure-bonded through a roller. At this time,
Preferably, the roller is heated slightly. 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.

Next, the photosensitive layer laminated on the substrate obtained by the above method is irradiated with actinic rays in an image-like manner to cure the exposed portion of the photosensitive layer. At this time, an oxygen shielding film such as polyvinyl alcohol having a thickness of 0.5 to 30 μm may be formed on the surface of the photosensitive layer 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. 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. The light amount at the time of exposure is usually 10 to 1000 m
J / cm ² is preferable, and 20 to 500 mJ / cm ² is more preferable.

Next, a colored image pattern of a cured film corresponding to an image can be obtained by a developing step of removing an unexposed portion. As a developing method, sodium hydroxide, potassium hydroxide, sodium carbonate, inorganic bases such as sodium metasilicate, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, triethylamine, organic bases such as n-butylamine or An aqueous solution containing a salt (alkali developer), a method of spraying a developer such as an organic solvent, and a method of dipping in a developer are exemplified.

After development, post-baking is preferably performed to further harden the pattern of the colored image. The post-bake temperature is preferably from 60 to 280C, and the heating time is preferably from about 1 to 60 minutes.

The method for producing a color filter of the present invention is characterized by including the step of forming a colored image by the method for producing a colored image of the present invention. That is, it is preferable to perform the colored image forming step by repeatedly performing the colored images of three or four different colors. For example, a red, green, and blue colored image is formed on a black matrix previously formed by chromium vapor deposition or the like. Also, after forming a black matrix using a black colored image forming material, red, green,
A blue colored image is formed. Further, after forming red, green, and blue colored images, a black matrix is formed in a gap between these colored images using a black image forming material.
The order of forming red, green, and blue colored images is arbitrary. The colored image forms pixels for each color.

[0099]

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 repeating units derived from styrene-20 mol% of repeating units derived from monopropyl maleate-30 mol% of repeating units derived from maleic acid derivative, having a weight average molecular weight of 1
Copolymer having 1000 and acid value of 65 (hereinafter referred to as copolymer A) (2) The repeating unit based on the maleic acid derivative has the following structure.

[0100]

Embedded image Example 1 (1) Production of photosensitive liquid for forming a red colored image 40 g of copolymer A as a resin and C.I. I. Pigment Red 177 and C.I. I. Pigment Yellow 83 and 5 g of diethylene glycol dimethyl ether were added to 200 g of diethylene glycol dimethyl ether, and subjected to a dispersion treatment using a bead mill for 2 hours to obtain a red colored resin composition.

This red-colored resin composition, 30 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 2- [2 '-Hydroxy-5'-acryloyloxyethylphenyl] benzotriazole 0.5
g, 0.5 g of 2-hydroxy-4-acryloyloxybenzophenone and 280 g of diethylene glycol dimethyl ether as an organic solvent were added and mixed to obtain a red colored image forming photosensitive liquid. The obtained photosensitive solution is
The number of days until the secondary aggregation started when left at 25 ° C. was defined as dispersion stability, and the results are shown in Table 1. (2) Production of Colored Image This photosensitive liquid was applied to a glass substrate (Corning Co., trade name 7).
059) by spin coating, and
Drying was performed at 5 ° C. for 5 minutes to form a film having a thickness of 2.0 μm.

The resulting film was exposed to 400 mJ / cm ² on the image with 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. The coating appearance and light resistance of the obtained red pixel were evaluated. Table 1 shows the results.

Example 2 (1) Production of green colored resin composition 30 g of copolymer A as a resin and C.I. I. Pigment Green 36, 22 g of C.I. I. Pigment Yellow 83 (8 g) and 250 g of diethylene glycol dimethyl ether as an organic solvent were added thereto, and the mixture was subjected to a dispersion treatment for 2 hours using a bead mill.

220 g of this dispersion, 32 g of pentaerythritol triacrylate as a monomer, 1.0 g of 2- [2'-hydroxy-5'-acryloyloxyethylphenyl] benzotriazole and 2-hydroxy-4-acryloxyl as an ultraviolet absorber 0.2 g of benzophenone, 6 g of benzophenone as a photoinitiator, 2 g of N, N'-tetraethyl-4,4'-diaminobenzophenone, and 125 g of diethylene glycol dimethyl ether as an organic solvent were added and mixed to obtain a green colored image forming photosensitive solution. Obtained. The dispersion stability of the obtained photosensitive solution was measured in the same manner as in Example 1. (2) Production of Colored Image This photosensitive liquid was applied to a glass substrate (Corning Co., trade name 7).
059) by spin coating, and
Drying was performed at 5 ° C. for 5 minutes to form a film having a thickness of 2.0 μm.

The resulting film was exposed to an image of 100 mJ / cm ^{2 using} a super-high pressure mercury lamp through a negative mask, and then developed with an aqueous solution containing 0.6% by weight of sodium carbonate. The coating appearance and light resistance of the obtained green pixel were evaluated. Table 1 shows the results.

Example 3 (1) Production of Blue Colored Resin Composition Copolymer C25 g as a resin and C.I. I. Pigment Blue 15: 6 25g
And C.I. I. Pigment Violet 23, 1 g of diethylene glycol dimethyl ether 2
In addition to 00g, dispersion treatment was performed for 2 hours using a bead mill. To 140 g of this dispersion, 36 g of copolymer C and dipentaerythritol hexaacrylate 3 as a monomer
0 g, 2- [2'-hydroxy-
5'-acryloyloxyethylphenyl] benzotriazole 0.3 g and 2-hydroxy-4-acryloyloxybenzophenone 1.2 g, benzophenone 6 g as photoinitiator and N, N'-tetraethyl-4,4 '
2 g of diaminobenzophenone and 230 g of diethylene glycol dimethyl ether as an organic solvent were added and mixed to obtain a blue colored image forming photosensitive liquid. The dispersion stability of the obtained photosensitive solution was measured in the same manner as in Example 1. (2) Production of Colored Image The obtained blue colored image forming 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 obtain a colored image.
A layer containing a photosensitive colored resin composition having a thickness of 20 μm was formed. The photosensitive element was obtained by coating with a 40 μm thick polyethylene film thereon.

After peeling off the polyethylene film from the obtained photosensitive element, it was laminated on the same glass substrate as that used in Example 1. Laminating 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 minutes.

Next, the pixel was exposed to 60 mJ / cm ² from above the polyethylene terephthalate film by means of an ultra-high pressure mercury lamp through a negative photomask, and then the polyethylene terephthalate film was peeled off. Development was performed under the conditions. The appearance and light resistance of the coating film of the obtained blue pixel were evaluated. Table 1 shows the results.

Comparative Example 1 2- [2'-hydroxy-5 'which is an ultraviolet absorbing compound
-Acryloyloxyethylphenyl] benzotriazole and 0.5 g of 2-hydroxy-4-acryloxybenzophenone were not added, and a photosensitive solution was obtained under the same composition and conditions as in Example 1, and the dispersion stability of the photosensitive solution was improved. The measurement was performed in the same manner as in Example 1.

Further, a film having a thickness of 2.0 μm was formed under the same method and conditions as in Example 1, and the appearance and light resistance of the coating film were evaluated. Table 1 shows the results.

Comparative Example 2 UV-absorbing compound 2- [2'-hydroxy-5 '
[Acryloyloxyethylphenyl] benzotriazole and 0.2 g of 2-hydroxy-4-acryloxybenzophenone except that 1.0 g of benzotriazole and 0.2 g of 2-hydroxy-4-acryloxybenzophenone were not added. The measurement was performed in the same manner as in Example 1.

Further, a film having a thickness of 2.0 μm was formed in the same manner and under the same conditions as in Example 2, and the appearance and light resistance of the coating film were evaluated. Table 1 shows the results.

[0113]

[Table 1] In the light resistance test, a carbon arc lamp (test tank temperature: 40 to 50 ° C, black panel temperature 63 ° C ±
3 ° C.) for a predetermined time, and the color change is ΔE
^* Evaluated from the value of (ab) value. It can be determined that the smaller the value of ΔE ^* (ab), the smaller the color change and the better the light fastness.

ΔE^*(Ab) is a color techno system
L measured using a spectral colorimeter JP7200F manufactured by Co., Ltd.
^*, A^*, B^*Was calculated based on the value of. L of measured value^*, A^*,
And b^*Has been standardized by CIE and
L used in SZ8729)^*, A^*, B^*table
Based on the color system, L^*Is the chromaticity that indicates lightness, hue and saturation
A ^*, B^*Expressed by

A system to which an ultraviolet absorbing compound was added (Example 1)
In (3) to (3), it can be seen that the change in ΔE ^* (ab) is smaller than that in the system without the ultraviolet absorbing compound (Comparative Examples 1 and 2), and the light resistance is improved.

[0116]

According to the photosensitive colored resin composition of the present invention, a film having high pigment dispersibility and dispersion stability, high light fastness, and excellent coating appearance can be obtained.

The photosensitive liquid for forming a colored image of the present invention has high dispersibility and dispersion stability of the pigment, and also has high light resistance, and can provide a film having an excellent coating film appearance.

The photosensitive element of the present invention can provide a film having high pigment dispersibility and dispersion stability, high light resistance, and excellent coating appearance.

According to the method for producing a colored image of the present invention, it is possible to provide a colored image in which the pigment of the coating film of the pixel is well dispersed, the light resistance is high, and the optical characteristics are excellent.

According to the method for producing a color filter of the present invention, it is possible to provide a high-quality color filter in which the pigment of the coating film of the pixel is well dispersed, the light resistance is high, and the optical characteristics are excellent.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Yoichi Kimura 14 Goi South Coast, Ichihara City, Chiba Prefecture Inside the Goi Plant of Hitachi Chemical Co., Ltd. Inside the Goi Plant (72) Inventor Tetsuya Okazaki 14 Goi South Coast, Ichihara City, Chiba Prefecture Hitachi Chemical Industry Co., Ltd. F-term in Goi factory (reference) 2H025 AA00 AA04 AA10 AA18 AB11 AB13 AC01 AC08 AD01 BC12 BC14 BC31 BC34 BC43 BC51 BC54 BC81 BC83 BC86 BC92 CA00 CB04 CB06 CB07 CB10 CB16 CB42 CB55 CC02 CC03 CC12 EA04 BA482048

Claims (7)

[Claims] 1. A photosensitive colored resin composition containing a pigment, a resin, a monomer containing at least one photopolymerizable unsaturated bond in a molecule, and a photoinitiator, comprising a compound represented by the following general formula (I): ] (Wherein X is a hydrogen atom or a halogen atom, R ¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ² is an alkylene group having 2 to 12 carbon atoms, and R ³ is a hydrogen atom Or a methyl group) and an ultraviolet absorbing compound represented by the following general formula (II): (Wherein, R ⁴ is a hydrogen atom or a methyl group, R ⁵ is an alkylene group having 2 to 6 carbon atoms which may have a hydroxyl group as a substituent, and Y is a hydrogen atom or an alkoxy group having 1 to 6 carbon atoms. Wherein Z is a hydrogen atom or a hydroxyl group), and at least one ultraviolet-absorbing compound selected from the ultraviolet-absorbing compounds represented by the formula (I). 2. The resin according to claim 1, wherein the resin has an acid value of 20 to 300 and a weight average molecular weight of 1,500 to 200,000.
The photosensitive colored resin composition as described in the above. 3. A photosensitive liquid for forming a colored image, comprising the photosensitive colored resin composition according to claim 1 and an organic solvent. 4. A photosensitive element obtained by laminating a photosensitive layer containing the photosensitive colored resin composition according to claim 1 on a support. 5. A method for producing a colored image, comprising a colored image forming step of laminating a photosensitive layer containing the photosensitive colored resin composition according to claim 1 on a substrate and exposing and developing the photosensitive layer. 6. The method for producing a colored image according to claim 5, wherein the photosensitive layer is formed from the photosensitive solution according to claim 3. 7. A method for producing a color filter, comprising producing a plurality of colored images on the same substrate by the method for producing a colored image according to claim 6.