JPH11310714A - Red resin composition, photosensitive red resin composition, photosensitive fluid for formation of red image, production of colored image, and production of color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a red resin composition improved in light transmittance in which a pigmented photosensitive material is problematic, a photosensitive red resin composition having improved light transmittance, a red image formation photosensitive fluid having improved light transmittance, a process for producing a color image having improved light transmittance, and a process for producing a color filter containing a red image having excellent light transmittance. SOLUTION: There are provided a red resin composition prepared by dispersing a red pigment and C.I. Pigment Orange 43 in a resin; a photosensitive red resin composition containing a red pigment, C.I. Pigment Orange 43, a resin, a monomer containing at least one photopolymerizable unsaturated bond in the molecule, and a photoinitiator; a red image formation photosensitive fluid containing the photosensitive resin composition and an organic solvent; a process for producing a color image comprising the steps of: laying a photosensitive layer comprising the color image formation material on a support, and forming a color image by exposure and development; and a process for producing a color filter comprising the step of forming a red image thereby.

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. Therefore, recently, a method using a photosensitive material in which a pigment is dispersed for the purpose of improving heat resistance and light resistance has attracted attention, and much research has been conducted. According to this method, the manufacturing method is simplified, and the obtained color filter is known to be stable and have a long life.

However, 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 According to the first aspect of the present invention, there is provided a red resin composition which improves the light transmittance which is a problem of a photosensitive material in which a pigment is dispersed, and which solves the problems of the prior art. To provide. The invention according to claim 2 or 3 provides a photosensitive red resin composition having improved light transmittance. The invention described in claim 4 provides a photosensitive liquid for forming a red image with improved light transmittance.
Claim 5 or 6 provides a method for producing a colored image with improved light transmittance. The invention described in claim 7 provides a method for producing a color filter including a red image having excellent light transmittance.

[0005]

The present invention provides a red pigment and C.I.
I. a red resin composition obtained by dispersing Pigment Orange 43 in a resin. The present invention also provides a red pigment, CI
Pigment Orange 43, a resin, a monomer having at least one photopolymerizable unsaturated bond in the molecule, and a photosensitive red resin composition containing a photoinitiator. The present invention also relates to the photosensitive red resin composition, wherein the resin has an acid value of 20 to 300 and a weight average molecular weight of 1500 to 200,000.
And a photosensitive red resin composition. 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. The present invention also relates to a method for producing a color filter, which comprises a step of forming a red image by the method for producing a colored image.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, pigments include
A yellow pigment or an orange pigment is used in combination with the red pigment, and CI pigment orange 43 (color index name) is used as an essential component for the yellow or orange pigment.

[0007] As the yellow or orange pigment in the present invention, other yellow or orange pigments can be used in addition to CI Pigment Orange 43. 0-90% by weight
And more preferably 0 to 50% by weight. If the amount of the yellow or orange pigment other than CI Pigment Orange 43 is too large, the light transmittance tends to decrease. As other yellow or orange pigments,
For example, CI Pigment Yellow 20, 24, 83, 9
3, 109, 110, 117, 125, 139, 14
Commonly known ones such as 7, 154 can be used.

The above-mentioned red pigments include, for example, CI Pigment Reds 9 and 12 by color index names.
3, 155, 168, 177, 180, 217, 22
0, 224 and the like.

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

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 it is used as a colored image forming material. 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 (mean 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 preferred.

The monoalkyl maleate is preferably one having 1 to 12 carbon atoms in the alkyl.
Monomethyl maleate, monoethyl maleate, mono-n-propyl maleate, monoisopropyl maleate,
Mono n-butyl maleate, mono n-hexyl maleate, mono n-octyl maleate, mono 2-maleate
Examples include ethylhexyl, mono-n-nonyl maleate, and mono-n-dodecyl maleate. As the citraconic acid monoalkyl ester, alkyl having 1 carbon atom
To 12, preferably monomethyl citraconic acid, monoethyl citraconic acid, mono-n-propyl citraconic acid, monoisopropyl citraconic acid, mono-n-butyl citraconic acid, mono-n-hexyl citraconic acid, mono-n-octyl citraconic acid, citraconic acid Mono 2-ethylhexyl, mono-n-nonyl citraconic acid, mono-n-dodecyl citraconic acid and the like can be mentioned. As the styrene derivative, α-methylstyrene, m- or p-methoxystyrene, p-hydroxystyrene, 2-methoxy-4-
Hydroxystyrene, 2-hydroxy-4-methylstyrene and the like.

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 one compound each having one ethylenically unsaturated bond, allyl alcohol, 2-buten-4-ol, furfuryl alcohol, oleyl alcohol, cinnamyl alcohol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol A resin obtained by reacting a compound (unsaturated alcohol) having one hydroxyl group and one ethylenically unsaturated bond, such as acrylamide,
A resin in which a carboxyl group-containing resin having a hydroxyl group is reacted with a free isocyanate group-containing unsaturated compound, a resin in which an addition reaction product of an epoxy resin and an unsaturated carboxylic acid is reacted with a polybasic anhydride, a conjugated diene polymer or Resins obtained by reacting a hydroxyl group-containing polymerizable monomer with an addition reaction product of a conjugated diene copolymer and an unsaturated dicarboxylic anhydride are exemplified.

The unsaturated equivalent of these resins is 200 to 3
000, preferably 230 to 1000
And more preferably in the range of 250 to 75
It is preferably set to 0. If the unsaturated equivalent is too small, there is a tendency to partially cure when adjusting the photosensitive material, particularly when dispersing the pigment in the resin, and if the unsaturated equivalent is too large, sufficient photopolymerizability is imparted by the introduction of unsaturated groups. Not done. Here, the unsaturated equivalent means the molecular weight of the resin per unsaturated bond.

When the resin has photopolymerizability by itself, or when it is given photosensitivity as a composition such as a photosensitive red resin composition as described below, 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 1,
It is preferably in the range of 500 to 200,000, more preferably in the range of 5,000 to 100,000, and particularly preferably in the range of 10,000 to 50,000. Weight average molecular weight of 1,50
If it is less than 0, the dispersion stability of the pigment tends to decrease, and if it exceeds 200,000, the viscosity becomes high when it is made into a photosensitive solution, and the coatability, especially the coatability when spin-coating, tends to decrease. There is. In the present specification, the weight average molecular weight is a value measured by gel permeation chromatography and converted using a calibration curve of standard polystyrene.

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)

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

Embedded image (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 having 1 to 1 carbon atoms. 1
2) represents a repeating unit represented by formula (I) / general formula (II) in a ratio of 1/1 to 5/1 (molar ratio).
Is particularly preferred in terms of the 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, and 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, a repeating unit in which R ⁶ 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 group having a photoreactive unsaturated bond, a repeating unit in which R ⁶ is a hydrogen atom, and (iv) a general formula (II) )), R ⁴ and R ⁵ are each independently a hydrogen atom or a group having a photoreactive unsaturated bond, and at least one of them is a group having a photoreactive unsaturated bond;
It is preferable that R ⁶ has a repeating unit that is an alkyl group having 1 to 12 carbon atoms.

As a method for producing a resin having a repeating unit represented by the general formula (I) and a 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.) Is produced by an addition reaction.

As a precursor of the resin 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 monoalkyl maleate (for example, 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, mono-n-hexyl maleate, and maleic acid. Mono-n-octyl, mono-2-ethylhexyl maleate, mono-n maleate
-Nonyl, 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, mono-n-hexyl citraconic acid, citraconic acid Mono-n
Octyl, mono-2-ethylhexyl citraconic acid,
Mono-n-nonyl citraconic acid, mono-n citraconic acid
-Dodecyl 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 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 at least one photopolymerizable unsaturated bond 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 polymerizable unsaturated bond used in the above-mentioned colored image forming material or colored image forming photosensitive liquid has one molecule in its 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 ether) such as (meth) acrylic acid ester of (hexaethylene glycol phenyl ether), and (polyalkylene glycol aryl ether) such as (hexaethylene glycol phenyl ether) acrylate. 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 is further represented by the general formula (a):

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

Embedded image (Where m and n are each independently 1 to 10
Epichlorohydrin modified product of bisphenol A and addition esterified product of acrylic acid, bisphenol A dimethacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol dimethacrylate represented by
Glycerol dimethacrylate, neopentyl glycol diacrylate, general formula (c)

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

Embedded image (Where m and n are each independently 1 to 10
Phthalic acid modified epichlorin modified product and acrylic acid addition esterified product, polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, tetraethylene glycol diacrylate represented by the general formula (e):

Embedded image (Where m and n are each independently 1 to 20
1,6-hexanediol and an addition esterified product of acrylic acid (having two aquilyl groups in one molecule), trimethylolpropane triacrylate, pentaerythritol triacrylate, General formula (f)

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

Embedded image (Wherein, R represents an ethylene group or a propylene group, m, m ′ and m ″ each independently represent an integer of 1 to 20). Triacrylate of an alkylene oxide adduct of trimethylolpropane , Tris (methacryloxyethyl) isocyanurate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and the like.
More than one species can be used in combination.

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. Specific examples include ketone compounds such as acetone, methyl ethyl ketone, cyclohexanone, and dioxane.Alkylene glycol ether compounds include methyl cellosolve, ethyl cellosolve, butizolecellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, and 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 And Tel acetate e. Examples of the polyethylene glycol alkyl ether acetate compounds, diethylene glycol methyl ether acetate,
Diethylene glycol ethyl ether acetate, diethylene glycol propyl ether acetate, diethylene glycol iso-propyl 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 iso-propyl ether acetate, triethylene glycol butyl ether acetate, triethylene glycol tert-butyl ether acetate and the like, as the alcohol compound, methyl alcohol,
Ethyl alcohol, isopropyl alcohol, n-butyl alcohol, 3-methyl-3-methoxybutanol,
Tetrahydrofuran and the like; aromatic compounds such as benzene, toluene, xylene, N-methyl-2-pyrrolidone and N-hydroxymethyl-2-pyrrolidone; and others, 3-methyl-3-methoxybutyl acetate, acetic acid Organic solvents such as ethyl are exemplified. These can be used alone or in combination of two or more.

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

When 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. When 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, and when the amount is too large, the light sensitivity tends to be low. If the amount of the monomer having one or more photopolymerizable unsaturated bonds in the molecule is too small, the photosensitivity tends to be low, and if it is too large, the dispersion stability of the pigment tends to be low. Furthermore, when the photoinitiator is too small, the photosensitivity tends to decrease, and when too large, the adhesion tends to decrease.

The organic solvent is a resin, a pigment, a monomer having at least one photopolymerizable unsaturated bond in a molecule and a photoinitiator in the photosensitive liquid for forming a red image having 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 red resin composition or the photosensitive liquid for forming a red image in the present invention contains a thermal polymerization inhibitor (hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, etc.) for suppressing a dark reaction, and a substrate. Titanate coupling agent for improving adhesiveness with silane (silane coupling agent having vinyl group, epoxy group, amino group, mercapto group, etc., 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 dispersed with an ultrasonic disperser, a three-roll mill, a ball mill, a sand mill, a bead mill, a homogenizer, a kneader, or the like.
The dispersion treatment is preferably performed by kneading using a kneading apparatus. At this time, it is preferable to use at least 20 parts by weight of the resin 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 with respect to 100 parts by weight of the total amount of the pigment and the resin at the time of dispersion. If the amount is less than 100 parts by weight, the viscosity at the time of dispersion is too high, and dispersion may be difficult particularly when the dispersion is carried out by a ball mill, a sand mill, a peas mill or the like. 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 red image, a monomer having two or more photopolymerizable unsaturated bonds in a molecule and a photoinitiator are further 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 mixing ratio in the photosensitive red resin composition or the photosensitive liquid for forming a red image and 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. 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 whole amount of the resin may be used together with the pigment at the time of the dispersion treatment, or a part of the resin may be added after the dispersion treatment. However, it is preferable to use at least 20 parts by weight of the resin for 100 parts by weight of the pigment during the dispersion treatment. If it is less than 20 parts by weight, the dispersion stability of the pigment tends to decrease. Similarly, the entire amount of the organic solvent may be used together with the pigment during the dispersion treatment, or a part of the organic solvent may be added after the dispersion treatment. However, the organic solvent is
It is preferable to use at least 100 parts by weight at the time of the dispersion treatment based on 100 parts by weight of the total amount of the pigment and the resin at the time of the dispersion treatment. If the amount is less than 100 parts by weight, the viscosity at the time of the dispersion treatment is too high, and particularly when the dispersion is performed by a ball mill, a sand mill, a bead mill or the like, the dispersion may be difficult.

In producing the color filter of the present invention, each pigment system suitable for a colored image such as red, green, blue and black is used. When the photosensitive colored resin composition or the photosensitive liquid for forming a colored image of the present invention is used for the production of a color filter, each pigment system suitable for a colored image such as red, green, blue and black is used. The above-mentioned red pigments are used, but the following pigments are used as other pigments.

For a green colored image, a single green pigment system may be used, or a yellow pigment system may be mixed with a green pigment system for toning. As the green pigment, any of an inorganic pigment and an organic pigment can be used, but an organic pigment is preferable from the viewpoint of abundant color tone and the like. Examples of the organic pigment include phthalocyanine-based pigments, for example, Pigment Green 7, 36, and 37 under the color index name. As the yellow pigment, for example, CI Pigment Yellow 20, 24, 83, 93, 109, 11 under the color index name
0, 117, 125, 139, 147, 154 and the like. These green pigment system and yellow pigment system can be used as a mixture of two or more kinds. In addition,
When using a mixture of green and yellow pigments,
The yellow pigment is preferably used in an amount of 50 parts by weight or less based on 100 parts by weight of the total of the green pigment and the yellow pigment.

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. As blue pigments, for example, CI Pigment Blue 15, 15:
3, 15: 4, 15: 6, 22, 60 and the like.
Examples of purple pigments include CI Pigment Violet 19, 23, 29, 3 by color index name.
7, 50 and the like. These blue pigments and violet pigments can be used as a mixture of two or more kinds. When a mixture of a blue pigment and a violet pigment is used, the violet pigment is preferably used in an amount of 50 parts by weight or less based on 100 parts by weight of the total of the blue pigment and the violet pigment. .

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

Formulation of a colored resin composition, a photosensitive colored resin composition and a photosensitive liquid for forming a colored image when a pigment system other than the red pigment system is used, and preparation of components, compositions or photosensitive solutions other than pigments The method and the like are determined according to the red resin composition, the photosensitive red resin composition and the photosensitive liquid for forming a red image.

In order to laminate 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 substrate is selected depending on the application, for example, a transparent glass plate such as white plate glass, blue plate glass, silica coated blue plate glass, a polyester resin, a polycarbonate resin, an acrylic resin, a synthetic resin sheet such as a vinyl chloride resin, Examples include a film or plate, a metal plate such as an aluminum plate, a copper plate, a nickel plate, and 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.

As a method of applying the photosensitive liquid to the substrate, there are 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 film composed of the colored image forming material can be obtained. The thickness of the photosensitive layer formed in this manner is appropriately determined depending on the application, but is preferably 0.1 to 3 mm.
It is preferably in the range of 00 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 in which a film is laminated on the substrate and pressure-bonded 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.

Exposure to the photosensitive layer laminated on the substrate can be performed by irradiating the photosensitive layer with actinic rays in an image-like manner. Thereby, the film in the exposed portion can be cured. At the time of exposure, an oxygen barrier film such as polyvinyl alcohol may be formed on the surface of the film with a thickness of 0.5 to 30 μm, and the film may be exposed from above. As the light source of the actinic ray, for example, a 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 Langsten lamp, a visible light laser and the like are suitable. Using these light sources, actinic rays are irradiated imagewise by pattern exposure through a photomask, direct drawing by scanning, or the like.

Following the above exposure, a development step is performed. An aqueous solution containing an inorganic alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium metasilicate, an organic base such as monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, triethylamine, 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 is formed by such a colored image forming process. In particular, in a method of manufacturing a color filter, a colored image forming process is performed in a different three to four colors including a red image forming process. Is preferably repeated. 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.

[0046]

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 mol% of maleic acid monopropyl ester-maleic acid derivative 3
A copolymer composed of 0 mol%, having a weight average molecular weight of 11,000 and an acid value of 65 (hereinafter referred to as copolymer A). (2) The repeating unit based on the maleic acid derivative has the following structure.

Embedded image

Example 1 (1) Production of Red Colored Resin Composition To 200 g of diethylene glycol dimethyl ether, 30 g of copolymer A as a resin, 16 g of CI Pigment Red 177 and 9 g of CI Pigment Orange 43 as a pigment were added, and a bead mill was used. For 2 hours 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 200 g of diethylene glycol dimethyl ether as an organic solvent were added and mixed. Thus, a red colored image forming photosensitive liquid was obtained.

(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 obtained film was exposed to an image of 700 mJ / cm ^{2 with} an ultrahigh 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 To 200 g of diethylene glycol dimethyl ether, 30 g of copolymer A as a resin, 20 g of CI Pigment Red 254 and 6 g of CI Pigment Orange 43 as pigments were added, and a bead mill was used. For 2 hours to obtain a red colored resin composition. To this red resin dispersion, 35 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 200 g of diethylene glycol dimethyl ether as an organic solvent were added and mixed. Thus, a red colored photosensitive liquid for forming an image was obtained.

(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 obtained film was exposed to an image of 700 mJ / cm ^{2 with} an ultrahigh pressure mercury lamp through a negative mask, and then developed with an aqueous solution containing 0.3% by weight of potassium hydroxide. Table 1 shows the reflectance and chromaticity of the obtained red pixels.

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 14 g of CI Pigment Red 254 as a pigment, and CI Pigment Orange 43
Was added and 2 g of CI Pigment Yellow 83 was added thereto, and the mixture was dispersed using a bead mill for 2 hours to obtain a red colored resin composition. This red resin composition, 32 g of trimethylolpropane triacrylate as a monomer, 6 g of benzophenone as a photoinitiator and N, N'-tetraethyl-
2,4 g of 4,4'-diaminobenzophenone and 200 g of diethylene glycol dimethyl ether as an organic solvent
Was dispersed using a bead mill for 2 hours.

(2) Production of Colored Image The obtained red photosensitive solution is applied to a 6 μm thick polyethylene terephthalate film by a gravure code 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 a glass substrate similar to that used in Example 1. Laminating conditions are
Glass substrate temperature 40 ° C, laminating roll temperature 110
C., a laminating pressure of 3.5 kgf / cm ² and a laminating 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 using an ultra-high pressure mercury lamp, and then the polyethylene terephthalate film was peeled off.
Development was performed in the same manner and under the same conditions as in Example 1. Table 1 shows the reflectance and chromaticity of the obtained red pixels.

Example 4 (1) Production of Green Colored Resin Composition and Photosensitive Liquid 30 g of Copolymer A as a resin, 21 g of CI Pigment Green 36 as a pigment, 9 g of CI Pigment Yellow 83, and diethylene glycol dimethyl ether 2
In addition to 00g, a dispersion treatment was performed for 2 hours using a bead mill to prepare a green colored resin composition. To this, 32 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 to obtain a green colored image forming photosensitive solution.

(2) Preparation of Blue Colored Resin Composition and Photosensitive Liquid To 30 g of copolymer A as a resin, 17 g of CI Pigment Blue 15-6 as a pigment, 1 g of CI Pigment Violet 23, and 200 g of diethylene glycol dimethyl ether, and use a bead mill. For 2 hours to prepare a blue colored resin composition. In addition, pentaerythritol hexaacrylate 34 as a monomer
g, 6 g of benzophenone as a photoinitiator and N, N'-
Tetraethyl-4,4'-diaminobenzophenone 2 g
Further, 200 g of diethylene glycol dimethyl ether was added and mixed as an organic solvent to obtain a blue colored photosensitive liquid for image formation.

(3) Production of Color Filter A red image pattern was formed on a glass substrate on which a black matrix was formed with chromium in the same manner and under the same conditions as in Example 1, and then heated at 180 ° C. for 10 minutes. .
Next, Example 1 was performed using the above-mentioned red photosensitive liquid for image formation.
A red image pattern was formed next to the red pixel pattern in the same manner and under the same conditions as described above, and then heating was performed at 180 ° C. for 10 minutes. Next, a blue image pattern was formed next to the red 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 μm ×
A mosaic color filter composed of 100 μm green, red and blue colors was prepared.

Comparative Example 1 CI Pigment Orange 43 as a yellow or orange pigment
Except that CI Pigment Yellow 83 was used in place of the above, a red photosensitive solution 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 reflectance, chromaticity and transmission curve were measured. The results are shown in Table 1 and FIG.

[0057]

[Table 1]

The reflectance and chromaticity are measured by a color techno system.
The measurement was performed using a spectrocolorimeter JP7200F manufactured by 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 reflectance and x and y are Chromaticity.

From Table 1, it can be seen that the use of CI Pigment Orange 43 as a yellow or orange pigment gives a high chromaticity Y value and good color purity (Examples 1 to 3).
On the other hand, when CI Pigment Orange 43 is not used (Comparative Examples 1 and 2), it is recognized that the value of the chromaticity Y is low and the light transmittance is not good. FIG. 1 shows a transmission curve of a red pixel, curve 1 shows a transmission curve of a red pixel of Example 1, and curve 2 shows a transmission curve of a red pixel of Comparative Example 1.
As is clear from FIG. 1, the light transmittance of Example 1 is superior to that of Comparative Example 1. Thus, it was confirmed that the color filter (Example 4) produced by using a red photosensitive liquid and a photosensitive element having a higher light transmittance than ever before had excellent optical characteristics and was effective as an image display device.

[0060]

According to the present invention, the red resin composition according to the present invention is excellent in light transmittance, and the red image based on the photosensitive liquid for forming a red image is excellent in light transmittance. According to the method for producing a colored image according to claim 5 or 6, a red image having excellent light transmittance can be obtained. According to the manufacturing method of claim 7, 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 transmission curve.

[Explanation of symbols]

 1 ... Red pixel light transmission curve prepared in Example 1 2 ... Red pixel light transmission curve prepared in Comparative Example 1

 ──────────────────────────────────────────────────の Continuing on the front page (72) Koji Yamazaki, 14, Goi-minamikachi, Ichihara-shi, Chiba Hitachi Chemical Co., Ltd. Goi Plant Co., Ltd. (72) Inventor Seigo Yokochi 14 Goi South Coast, Ichihara City, Chiba Pref.

Claims (7)

[Claims] 1. A red pigment and CI Pigment Orange 43
A red resin composition obtained by dispersing a resin in a resin. 2. Red pigment, CI Pigment Orange 4
3. A photosensitive red resin composition comprising a resin, a monomer containing at least one photopolymerizable unsaturated bond in a molecule, and a photoinitiator. 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 1500 to 200,000. 4. A photosensitive liquid for forming a red image, comprising the photosensitive resin composition according to claim 2 and an organic solvent. 5. A method for producing a colored image, comprising a colored image forming step of laminating a photosensitive layer comprising the colored image forming material according to claim 2 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 liquid according to claim 5. 7. A method for producing a color filter, comprising the step of forming a red image by the method for producing a colored image according to claim 5. Description: