JPH11109623A - Photosensitive solution for forming color image, production of color filter using same and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photosensitive soln. for forming a color image dispensing with an oxygen shield film and excellent in photosensitive characteristics and to produce a color filter using the photosensitive soln. SOLUTION: The photosensitive soln. for forming a color image contains a resin, a pigment, a monomer contg. one or more photopolymerizable unsatd. bonds in the molecule and a photopolymn. initiator contg. 30-100 wt.% carbazole photopolymn. initiator, e.g. represented by the formula (where R<3> is preferably H or 1-20C alkyl, each of R<1> and R<2> is preferably H, 1-5C alkyl or 6-14C aryl and X<1> is preferably amino, 1-5C alkylamino, di-1-3C alkylamino or morpholino).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive liquid for forming a colored image used for producing a color filter used for a liquid crystal display device, a sensor, a color separation device and the like, a method for producing a color filter using the same, and The present invention relates to a color filter obtained by the method.

[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 for producing this color filter, a dyeable resin, for example, a material obtained by imparting photosensitivity to natural gelatin or casein is subjected to pattern exposure and development.
A method of forming a colored pixel by mainly dyeing with a dye has been adopted. However, the pixel obtained by this method has a problem that heat resistance and light resistance are low due to restrictions on materials. Therefore, recently, for the purpose of improving heat resistance and light resistance, a method of forming a colored image by pattern exposure and development using a colored photosensitive resin material in which a pigment is dispersed has attracted attention, and many studies have been made. Began to take place. According to this method, it is known that the method for producing a color filter is also simplified, and the obtained color filter is stable and has a long life.

However, in a colored photosensitive resin material conventionally used in the production of a color filter, curing inhibition by oxygen occurs on the surface of the film of the photosensitive resin material,
There is a problem that the sensitivity at the time of exposure is reduced.

[0004]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art and provides an oxygen-blocking film by adding a photopolymerization initiator to a photosensitive resin material which is hardly inhibited by curing by oxygen. It is an object of the present invention to provide a photosensitive liquid for forming a colored image which is excellent in photosensitive characteristics without requiring any of the above.

Another object of the present invention is to provide a method for producing a color filter using the photosensitive solution for forming a colored image, and a color filter obtained by the method.

[0006]

Means for Solving the Problems As a result of repeated studies to solve the above-mentioned problems, the present inventors can prevent curing inhibition by oxygen by using a photopolymerization initiator having a carbazole structure, They have found that photosensitivity can be improved without providing an oxygen barrier film, and based on this finding, have completed the present invention.

That is, the present invention comprises (a) a resin, (b) a pigment, (c) a monomer containing at least one photopolymerizable unsaturated bond in a molecule, and (d) a photopolymerization initiator. In the photosensitive liquid for forming a colored image, the photopolymerization initiator (d) is a carbazole-based photopolymerization initiator represented by the following general formula (I), (II) or (III) in an amount of 30 to the total amount of the photopolymerization initiator.
To provide a photosensitive liquid for forming a colored image, characterized in that the photosensitive liquid contains 0.1 to 100% by weight.

[0008]

Embedded image (Wherein, R ¹ and R ² each independently represent a hydrogen atom,
An alkyl group having 20 or an aryl group having 6 to 14 carbon atoms; or R ¹ and R ² are bonded to each other to represent an alkylene group having 4 to 7 carbon atoms; R ³ is a hydrogen atom; Represents an alkyl group or an acyl group having 2 to 11 carbon atoms, and X ¹ represents

[0009]

Embedded image R ⁵ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 3 to 18 carbon atoms, and R ⁶ and R ⁷
Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a hydroxyalkyl group having 2 to 4 carbon atoms;
⁶ and R ⁷ are bonded to each other to form an alkylene group having 4 to 7 carbon atoms,
An oxadialkylene group having 3 to 4 carbon atoms or 3 to 4 carbon atoms
Represents an imino dialkylene group, Y ¹ is a hydrogen atom or

[0010]

Embedded image Wherein Y ² represents a hydrogen atom, a halogen atom or a nitro group, R ⁴ represents a direct bond or an alkylene group having 1 to 10 carbon atoms, and X ² represents —O—R ⁸ —O— or

[0011]

Embedded image R ⁸ represents an alkylene group having 2 to 10 carbon atoms,
R ⁹ each independently represents an alkyl group having 1 to 20 carbon atoms,
Or two R ⁹ are combined with each other represents an alkylene group having 1 to 4 carbon atoms. Further, in the present invention, the above-mentioned photosensitive liquid for forming a colored image is applied on a substrate, and then dried to form a film, and the film is irradiated with actinic rays in an image-like manner to cure the exposed portion. A plurality of pixels of different colors characterized by repeating the step of forming pixels by removing unexposed portions by development using a plurality of colored image forming photosensitive liquids of different colors. And a method for producing a color filter having the following.

Further, the present invention provides a color filter obtained by the production method of the present invention.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

[Photosensitive Liquid for Forming a Colored Image] The resin as the component (a) of the photosensitive solution for forming a colored image of the present invention has an acid value of 20 to 20.
300, weight average molecular weight of 1,500 to 200,000
Are preferred, a carboxyl group-containing resin, for example,
Copolymerization of carboxyl group-containing polymerizable monomers such as acrylic acid, methacrylic acid and itaconic acid with polymerizable monomers such as acrylates such as methyl acrylate and ethyl acrylate, methacrylates such as methyl methacrylate and ethyl methacrylate, and styrene. Coalescence is a typical example.

From the viewpoint of improving the photosensitivity of the photosensitive solution, a preferred example of the resin (a) is a carboxyl group-containing resin having a photopolymerizable unsaturated bond.

Examples of the carboxyl group-containing resin having a photopolymerizable unsaturated bond include a resin obtained by reacting a carboxyl group-containing resin having a hydroxyl group with an unsaturated compound having a free isocyanate group, and a resin obtained by reacting an epoxy resin with an unsaturated carboxylic acid. Resin obtained by reacting a polybasic acid anhydride with an addition reaction product, resin obtained by reacting a hydroxyl group-containing polymerizable monomer with an addition reaction product of a conjugated diene polymer or a conjugated diene copolymer and an unsaturated dicarboxylic anhydride, carboxyl Group-containing resins, for example,
Glycidyl group-containing unsaturated compounds such as glycidyl methacrylate and allyl glycidyl ether, and resins obtained by reacting the above-mentioned carboxyl group-containing resin with unsaturated alcohols such as allyl alcohol, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate. ,
Consisting of a repeating unit (IV) represented by the following general formula (IV) and a repeating unit (V) represented by the following general formula (V), the molar ratio of the repeating unit (IV) to the repeating unit (V) is represented by ( (IV) / (V) is from 1 to 5, and from the viewpoint of improving the heat resistance of the pixel and the dispersibility of the pigment, the resin containing the repeating units (IV) and (V) is included. Are preferred.

[0017]

Embedded image (In the above general formula, R ¹⁰ represents a hydrogen atom or a methyl group;
R ¹¹ represents a hydrogen atom, a hydroxyl group or an alkyl group or an alkoxy group having 1 to 12 carbon atoms, and R ¹² is a group having a photopolymerizable unsaturated bond. As a method for producing a resin comprising the above repeating units (IV) and (V), for example, a photopolymerizable unsaturated bond is added to an acid anhydride group of a copolymer of styrene or a derivative thereof and maleic anhydride. And a method of ring-opening addition of the alcohol.

Specifically, styrene such as styrene, α-methylstyrene, m or p-methoxystyrene, p-hydroxystyrene, 2-methoxy-4-hydroxystyrene, 2-hydroxy-4-methylstyrene or a derivative thereof To the acid anhydride group of the copolymer of
A resin obtained by ring-opening addition of -hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, or the like becomes a basic skeleton. At this time, the ratio (molar ratio) of styrene or its derivative to maleic anhydride is in the range of 1: 1 to 1: 5.

At this time, a compound obtained by esterifying an unsaturated alcohol with (anhydride) maleic acid may be used,
If a compound having an oxirane ring and a compound having an ethylenically unsaturated bond is added and copolymerized with styrene or a styrene derivative, the unsaturated groups react during polymerization and tend to gel, which is not preferable.

The unsaturated equivalent in the dispersion resin thus obtained is preferably in the range of 300 to 3,000, more preferably in the range of 350 to 2,000. When the unsaturated equivalent is less than 300, the pigment tends to be partially cured when the pigment is dispersed, and when it exceeds 3,000, the effect of improving the photosensitivity tends to decrease. Here, the unsaturated equivalent means the molecular weight of the resin per unsaturated bond. Further, the molar ratio (IV) / (V) of the repeating unit (IV) and the repeating unit (V) is 1 to 5, and more preferably 1 to 3. If this molar ratio is less than 1, the heat resistance of the pixel may be reduced,
If it exceeds, the solubility of the coating film may decrease.

The acid value of the resin (a) is preferably from 20 to 300, more preferably from 40 to 200, and more preferably from 60 to 1
More preferably, it is 50. If the acid value is less than 20, the alkali developability tends to decrease.
If it exceeds 0, the shape of the image pattern tends to be unclear.

The weight-average molecular weight of the resin (a) (measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve) may be from 1,500 to 200,000. It is more preferably from 3,000 to 100,000, and still more preferably from 5,000 to 50,000. If the weight-average molecular weight is less than 1,500, the dispersion stability of the pigment tends to decrease.
If it exceeds 0, the viscosity when it is made into a photosensitive solution will be high, and the applicability at the time of coating on a substrate will be reduced, and it tends to be difficult to obtain a uniform coating film.

The above various resins exemplified as the resin (a) may be used alone or in combination of two or more.

The amount of the resin (a) used in the present invention is 10 to 85% by weight based on the total amount of the resin (a), the pigment (b), the monomer (c) and the photopolymerization initiator (d). Preferably, the content is more preferably 20 to 60% by weight,
It is particularly preferred that the content be 5 to 50% by weight. If the amount is less than 10% by weight, the dispersion stability of the pigment tends to decrease. If the amount exceeds 85% by weight, the viscosity of the photosensitive liquid becomes high, and the coatability decreases, resulting in a uniform coating film. Is difficult to obtain.

The pigment (b) used in the present invention includes:
Either inorganic pigments or organic pigments can be used, but usually organic pigments are preferred from the viewpoint of abundant color tone, except for black carbon black (inorganic pigment) and graphite (inorganic pigment).

Examples of the organic pigment include azo, phthalocyanine, indigo, anthraquinone, perylene, quinacridone, methine-azomethine, isoindolinone, and the like.

When the colored image forming photosensitive liquid of the present invention is applied to a color filter, pigments suitable for colored images such as red, green, blue and black are preferably used.

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

The red pigments include, for example, C.I. I. Pingment Red 9, 12
3, 155, 168, 177, 180, 217, 22
0, 224 and the like.

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

These red pigments and yellow pigments can be used as a mixture of two or more kinds. In addition,
When a mixture of a red pigment system and a yellow pigment system is used, the yellow pigment system 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 red pigment system and the yellow pigment system.

For 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. In addition,
When using a mixture of a green pigment system and a yellow pigment system, it is preferable to use 50 parts by weight or less of the yellow pigment system based on 100 parts by weight of the total amount of the green pigment system and the yellow pigment system.

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.

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, C.I. I. Pigment Violet 19,
23, 29, 37, 50 and the like.

These blue pigments and purple pigments can be used as a mixture of two or more kinds. In addition,
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 amount of the blue pigment and the violet pigment.

For a black colored image, for example, a black pigment system such as carbon black, graphite, titanium carbon, black iron, and manganese dioxide is used.

The amount of the pigment (b) used in the present invention is 5 to 70% by weight based on the total amount of the resin (a), the pigment (b), the monomer (c) and the photopolymerization initiator (d). More preferably, it is more preferably 10 to 50% by weight,
It is particularly preferred that the content be 40 wt%. If the amount used is less than 5% by weight, the color density of the image tends to decrease, and if it exceeds 70% by weight, the light sensitivity tends to decrease.

The monomer (c) having one or more photopolymerizable unsaturated bonds in the molecule used in the present invention includes, for example, methyl methacrylate, lauryl methacrylate,
Benzyl methacrylate, butoxyethyl methacrylate, butoxyethyl acrylate, butoxytriethylene glycol acrylate, ECH-modified butyl acrylate (here, ECH means epichlorohydrin; the same applies hereinafter), dicyclopentanyl acrylate, dicyclopentenyloxyethyl methacrylate ,
N, N-dimethylaminoethyl methacrylate, ethyl diethylene glycol acrylate, 2-ethylhexyl acrylate, glycerol methacrylate, heptadecafluorodecyl acrylate, 2-hydroxyethyl methacrylate, caprolactone-modified 2-hydroxyethyl acrylate, isobornyl acrylate, methoxydipropylene Glycol acrylate, methoxylated cyclodecatriene acrylate, phenoxyhexaethylene glycol acrylate, EO-modified phosphate acrylate (here, EO means ethylene oxide).
The same applies to the following. ), Caprolactone-modified tetrahydrofurfuryl acrylate, EO-modified bisphenol A diacrylate, EOH-modified bisphenol A diacrylate, bisphenol dimethacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol dimethacrylate, Glycerol dimethacrylate, neopentyl glycol diacrylate, stearyl methylene diacrylate, myristyl methylene diacrylate, EO-modified phosphate diacrylate, ECH-modified phthalate diacrylate, polyethylene glycol 400 diacrylate,
Polypropylene glycol 400 dimethacrylate, tetraethylene glycol diacrylate, ECH-modified 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, EO-modified phosphate triacrylate,
EO-modified trimethylolpropane triacrylate, P
O-modified trimethylolpropane triacrylate (where PO means propylene oxide; the same applies hereinafter), tris (methacryloxyethyl) isocyanurate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate And acrylates such as dipentaerythritol pentaacrylate, and methacrylates corresponding thereto.
These monomers are used alone or in combination of two or more.

The amount of the monomer (c) used in the present invention is 2 to 50% by weight based on the total amount of the resin (a), the pigment (b), the monomer (c) and the photopolymerization initiator (d). More preferably, it is more preferably 5 to 40% by weight,
It is particularly preferred that the content be 10 to 30% by weight. When the proportion of the monomer is less than 2% by weight, the light sensitivity tends to be low.
If it exceeds 50% by weight, the dispersion stability of the pigment tends to decrease.

In the present invention, the weight ratio (a) / (c) of the compounding amount of the resin (a) and the monomer (c) is 0.5 to 5.0.
It is preferably 0, more preferably 0.7 to 3.5, and particularly preferably 1.0 to 2.5. If this ratio is less than 0.5, the surface tackiness of the dried coating film tends to deteriorate, and if it exceeds 5.0, the light sensitivity tends to decrease.

Photopolymerization initiator (d) used in the present invention
Must contain a carbazole-based photopolymerization initiator represented by the general formulas (I), (II), and (III). The carbazole-based photopolymerization initiator represented by the general formula (I), (II) or (III) is used alone or in combination of two or more.

The compound represented by the general formula (I), (II) or (II)
In the carbazole-based photopolymerization initiator represented by I),
R¹, R^Two, R^Three, R^Five, R⁶, R⁷And R⁹Carbon represented by
Examples of the alkyl group of Formulas 1 to 20 include methyl, ethyl,
Ropyl, isopropyl, butyl, sec-butyl, te
rt-butyl, isobutyl, amyl, hexyl, octyl
, Isooctyl, 2-ethylhexyl, nonyl, deci
, Dodecyl, tridecyl, tetradecyl, nonadeci
And eicosyl. R¹And R^TwoRepresented by
Examples of the aryl group having 6 to 14 carbon atoms include phenyl and bif
Enyril, naphthyl, anthryl, phenanthryl, etc.
No. R¹And R^TwoHaving 4 to 7 carbon atoms
Examples of the alkylene group include tetramethylene and pentamethyl.
Len, hexamethylene, heptamethylene and the like.
You. R^ThreeAs an acyl group having 2 to 11 carbon atoms represented by
Is acetyl, propionyl, butyroyl, 2-ethyl
Hexanoyl, acryloyl, methacryloyl, benzo
Yl, tert-butylbenzoyl, chlorobenzoyl
And the like. R^FiveAl having 3 to 18 carbon atoms represented by
Examples of the kenyl group include allyl and octadecenyl.
It is. R⁶And R⁷C2-4 hydroxy represented by
Hydroxyalkyl, 2-hydro
Xypropyl, 2-hydroxybutyl and the like.
R⁶And R⁷Having 4 to 7 carbon atoms formed by bonding
Group, an oxadialkylene group having 3 to 4 carbon atoms or 3 carbon atoms
As the iminodialkylene groups of (4) to (4), tetramethylene
, Pentamethylene, hexamethylene, oxadiethylene
And iminodiethylene. Y ^TwoRepresented by
Halogen atoms include chlorine, bromine, fluorine and iodine
Is mentioned. R^FourAlkyl having 1 to 10 carbon atoms represented by
Methylene, ethylene, trimethylene,
Tetramethylene, hexamethylene, decamethylene, etc.
I can do it. R⁸An alkylene having 2 to 10 carbon atoms represented by
As the group, ethylene, propylene, 2,2-dimethyl
Propylene, 1,4-butylene, hexamethylene, deca
Methylene and the like;⁹Combine to form
Examples of the alkylene group having 1 to 4 carbon atoms include ethylene,
Pyrene, butylene and the like.

Among the various carbazole-based photopolymerization initiators represented by the general formulas (I), (II) and (III), preferred are those represented by the following general formula (VI). .

[0047]

Embedded image In various carbazole-based photopolymerization initiators represented by the general formula (VI), R ³ is preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ¹ and R ² are preferably a hydrogen atom, An alkyl group having 1 to 5 carbon atoms or 6 carbon atoms
And X ¹ is preferably an amino group, an alkylamino group having 1 to 5 carbon atoms, a di-C _1-3 alkylamino group or a morpholino group.

Representative examples of the carbazole-based photopolymerization initiator represented by the general formula (I), (II) or (III) include the following. (1): 3- (2-methyl-2-dimethylaminopropionyl) carbazole (2): 3- (2-methyl-2-morpholinopropionyl) -9-methylcarbazole (3): 3,6-bis (2 -Methyl-2-morpholinopropionyl) -9-methylcarbazole (4): 3- (2-methyl-2-morpholinopropionyl) -9-butylcarbazole (5): 3- (2-ethyl-2-piperidino) Propionyl) -9-butylcarbazole (6): 3- (2-methyl-2-diethanolaminopropionyl) -9-methylcarbazole (7): 3- (2-methyl-2-dibutylaminopropionyl) -9-chloro Carbazole (8): 3- (2-methyl-2-piperazinopropionyl) -6-nitro-9-methylcarbazole (9): 3- 2-methyl-2-morpholinopropionyl) -9-acetylcarbazole (10): 3,6-bis (2-methyl-2-morpholinopropionyl) -9-benzoylcarbazole (11): 3- (2-methyl-2) -Hydroxypropionyl) -9-methylcarbazole (12): 3- (2-methyl-2-methoxypropionyl) -9-methylcarbazole (13): 3- (2-methyl-2-allyloxypropionyl) -9- Methylcarbazole (14): 3- (1-hydroxycyclohexylcarbonyl) -9-butylcarbazole (15): 1,4-bis (9-butyl-3-carbazolyl) -2,3-dihydroxybutane-1,4- Dione (16): 1,6-bis (diethylamino) hexane-
1,6-dione (17): 1,4-bis [1- (9-methyl-3-carbazolylcarbonyl) isopropyl] piperazine (18): N, N′-dimethyl-N, N-bis [1 −
(9-methyl-3-carbazolyloyl) isopropyl]
Ethylenediamine (19): 2,7-bis [1- (9-butyl-3-carbazolylcarbonyl) isopropyl] -2,7-dimethyl-3,6-dioxaoctane (20): 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-butylcarbazole (21): 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-octylcarbazole (22): 3,6 -Bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole Table represented by the general formula (I), (II) or (III) in the total amount of the photopolymerization initiator (d) used in the present invention. The ratio of the carbazole-based photopolymerization initiator to be used is 30 to 100% by weight, preferably 40 to 100% by weight, particularly preferably 50 to 100% by weight. When the ratio of the carbazole-based photopolymerization initiator is less than 30% by weight, when the photosensitive liquid is exposed, curing inhibition due to oxygen on the surface is apt to occur, and the sensitivity and resolution are reduced.

Other photopolymerization initiators that can be used in combination with the carbazole-based photopolymerization initiator are not particularly limited and can be appropriately selected from known ones. For example, benzophenone, N, N'-tetraethyl-4 Benzophenone-based photopolymerization initiators such as 4,4'-diaminobenzophenone and 4-methoxy-4'-dimethylaminobenzophenone are preferably used. Also, for example, a benzyl-based photopolymerization initiator such as benzyl, a ketal-based photopolymerization initiator such as benzyldimethyl ketal, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone,
-Methyl-1- [4- (methylthio) phenyl] -2-
Acetophenone-based photopolymerization initiators such as morpholinopropan-1-one and α-hydroxyisobutylphenone; benzoin-based photopolymerization initiators such as benzoin, benzoin methyl ether and benzoin isobutyl ether; A polymerization initiator, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone,
3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,2-benzoanthraquinone, 1,4
-Anthraquinone-based photopolymerization initiators such as -dimethylanthraquinone and 2-phenylanthraquinone; naphthoquinone-based photopolymerization initiators such as 1,4-naphthoquinone; and phenanthraquinone-based photopolymerization initiators such as 9,10-phenanthraquinone. , 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer and the like can also be used. These photopolymerization initiators other than the carbazole-based photopolymerization initiator are used alone or in combination of two or more.

The amount of the photoinitiated weight part mixture (d) used in the present invention is 0.01 to 0.01% of the total amount of the resin (a), the pigment (b), the monomer (c) and the photopolymerization initiator (d). 20% by weight
, Preferably 2 to 15% by weight, particularly preferably 5 to 10% by weight. If the amount is less than 0.01% by weight, the photosensitivity tends to decrease, and if it exceeds 20% by weight, the adhesion to the substrate tends to decrease.

When the photosensitive liquid for forming a colored image of the present invention containing the above resin (a), pigment (b), monomer (c) and photopolymerization initiator (d) as essential components is used for coating, Usually, it is used as a coating liquid in which the essential components (a), (b), (c) and (d) are dissolved and decomposed in an organic solvent. Examples of the organic solvent that can be used in the colored image forming photosensitive liquid of the present invention include:
For example, ketone-based, cellosolve-based, alcohol-based, aromatic-based solvents and the like can be mentioned. Specifically, acetone, methyl ethyl ketone, cyclohexanone, methyl cellosolve (ethylene glycol monomethyl ether), ethyl cellosolve (ethylene glycol monoethyl ether),
Butyrocellosolve, Methylcellosolve acetate, Ethyl cellosolve acetate, Butyellosolve acetate, Ethylene glycol monopropyl ether, Ethylene glycol monohexyl ether, Ethylene glycol dimethyl ether, Diethylene glycol ethyl ether, Triethylene glycol dimethyl ether, Propylene glycol monomethyl ether, Propylene glycol dimethyl ether Propylene glycol monoethyl ether, propylene glycol diethyl ether, propylene glycol monopropyl ether, propylene glycol diisopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutanol, 3- Tyl-3-methoxybutyl acetate, N-methyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, tetrahydrofuran, dioxane, benzene, toluene, xylene, acetic acid Organic solvents such as ethyl are exemplified. These organic solvents are used alone or in combination of two or more.

When the colored image forming photosensitive liquid of the present invention contains an organic solvent, the amount of the organic solvent is such that the proportion of the organic solvent in the colored image forming photosensitive liquid is 60 to 95% by weight. Is preferred. When the amount of the organic solvent exceeds 95% by weight, drying of the coating film of the colored image forming photosensitive liquid containing the organic solvent tends to take a long time, and the amount of the organic solvent is 60% by weight.
If it is less than 3, the viscosity of the photosensitive solution tends to be too high, and the coatability tends to decrease.

The photosensitive liquid for forming a colored image of the present invention contains the essential components of resin (a), pigment (b), monomer (c),
And a photopolymerization initiator (d), a thermal polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, pyrogallol, and t-butylcatechol for suppressing a dark reaction, a vinyl group for improving adhesion to a substrate, Epoxy group, amino group, silane coupling agent having a mercapto group, etc., titanate coupling agent such as isopropyltrimethacryloyl titanate, diisopropylisostearoyl-4-aminobenzoyl titanate, fluorine-based, silicon for improving the smoothness of the film Various additives such as a surfactant, a hydrocarbon surfactant, and other additives such as an ultraviolet absorber and an antioxidant can be appropriately used as needed. The total amount of these additives is usually (a),
It is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the total solid content consisting of (b), (c) and (d).

The photosensitive liquid for forming a colored image of the present invention contains a resin outside the range of the resin of the component (a), such as an acrylic resin, an epoxy resin, a urethane resin, and a melamine resin.
The component (a) can be used in an amount of 50 parts by weight or less based on 100 parts by weight of the resin. If the amount exceeds 50 parts by weight, the dispersion stability and photosensitivity of the pigment tend to be reduced.

The general method for preparing the photosensitive liquid for forming a colored image of the present invention is described below.

First, in order to disperse the pigment (b), the resin (a) and the pigment (b) are mixed with an organic solvent (e), and the mixture is mixed with an ultrasonic disperser, a three-roll mill, a ball mill, a sand mill, The dispersion is performed using a dispersing / kneading apparatus such as a bead mill, a homogenizer, and a kneader.

In the dispersing step, anionic pigment dispersants such as polycarboxylic acid type polymer activators, polysulfonic acid type polymer activators, nonionic pigment dispersants such as polyoxyethylene / polyoxypropylene block polymers, etc. Pigment dispersants, anthraquinone-based, perylene-based, phthalocyanine-based, and quinacridone-based organic pigments are introduced with a substituent such as a carboxyl group, a sulfonic acid group, a sulfonate group, a carboxamide group, a sulfonamide group, or a hydroxyl group. Addition of a derivative of an organic pigment or the like is preferable because the dispersibility and dispersion stability of the pigment are improved.

These pigment dispersants and organic pigment derivatives are
It is preferable to use 50 parts by weight or less based on 100 parts by weight of the pigment.

Further, the monomer (c) and the photopolymerization initiator (d) may be added at the time of dispersing the pigment, and the monomer (c) and the photopolymerization initiator (d) may be added after dispersing the pigment.

The entire amount of the resin (a) may be used together with the pigment at the time of dispersion, or a part of the resin may be added after the dispersion. However, it is preferable to use at least 20 parts by weight of the resin at the time of dispersion with respect to 100 parts by weight of the pigment. If the amount of the resin used is less than 20 parts by weight at the time of dispersion, the dispersion stability of the pigment tends to decrease.

Similarly, the organic solvent (e) may be used in its entirety when the pigment is dispersed, or a part of the organic solvent may be added after the dispersion. However, 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. When the amount of the organic solvent used is less than 100 parts by weight at the time of dispersion, the viscosity at the time of dispersion is too high, and dispersion may be difficult particularly when the dispersion is carried out by a ball mill, a sand mill, a bead mill or the like.

Next, a method for producing the color filter of the present invention will be described.

[Production Method of Color Filter] In the production method of the color filter of the present invention, the photosensitive liquid for forming a colored image of the present invention is coated on a substrate and then dried to form a film. The step of forming a pixel by irradiating the exposed portion with an image and curing the exposed portion by light, and removing the unexposed portion by development is performed by using a plurality of colored image forming photosensitive liquids of different colors. To form pixels of a plurality of different colors on the substrate.

Examples of the method of applying the colored image-forming photosensitive liquid of the present invention on a substrate include roll coater coating, spin coater coating, spray coating, white coater coating, dip coater coating, curtain flow coater coating, and wire bar coating. It is performed by a coater coating, a gravure coater coating, an air knife coater coating, or the like.

The substrate used at this time is selected depending on the application. For example, a transparent glass substrate such as white plate glass, blue plate glass, silica-coated blue plate glass, polyester resin, polycarbonate resin, acrylic resin, vinyl chloride resin, etc. Examples include a synthetic resin sheet, film or substrate, a metal substrate such as an aluminum plate, a copper plate, a nickel plate, and a stainless steel plate, other ceramic substrates, and a semiconductor substrate having a photoelectric conversion element.

After the coating, the coating is preferably dried by blowing heated air (dry air) on the coating or by placing the substrate on a heated hot plate. . The heating temperature of the drying air or the hot plate is usually preferably from 30 to 200 ° C, particularly preferably from 50 to 150 ° C, and the film can be formed by heating for 1 to 30 minutes. The heating temperature may be kept constant during drying, but may be increased stepwise.

The thickness of the dried coating film formed on the substrate surface in this way is appropriately determined depending on the application, but is usually 0.2
-5 μm, preferably 0.5-1.5 μm.

Next, the film on the substrate obtained by the above-described method is irradiated with actinic rays imagewise to cure the film in the exposed portion. At this time, an oxygen barrier film such as polyvinyl alcohol having a thickness of 0.5 to 30 μm may be formed on the surface of the film on the substrate, and exposure may be performed 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 preferably used. Using these light sources, an active light beam is irradiated in an image form by pattern exposure through a photomask, direct drawing by scanning, or the like. Exposure light amount is usually 10 to 1,000 m
J / cm ² , preferably 50 to 500 mJ / cm ² .

Subsequently, a colored image pattern of the cured film corresponding to the image can be obtained by a developing step of removing the unexposed portions.

As the developing method, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate and sodium metasilicate, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, triethylamine, n-
Examples thereof include a method of spraying an aqueous solution containing an organic base such as butylamine and a salt, and a method of dipping in an aqueous solution.

After development, the colored image pattern is further subjected to high-pressure water
0.5 to 5 J / cm using silver lamp etc. ^TwoIrradiate the amount of light
Post-exposure or after 1-60 minutes at 60-200 ° C
Preferably, heating is performed. After this exposure and post-heating
Therefore, the image pattern becomes stronger.

By repeating the above steps using a plurality of colored image forming photosensitive liquids of a plurality of different colors, a color filter having pixels of a plurality of different colors can be manufactured.

As a specific example, a method for producing a color filter used in a liquid crystal display device is illustrated. For example, by repeating the above-described method using the colored image forming material of the present invention on a glass substrate, After forming a colored pixel of blue or the like, a method of forming a black colored image as a black matrix in the gap between the colored pixels, or after forming a black matrix by chromium vapor deposition or a black colored image first, and Similarly, there is a method of forming a color filter by forming colored pixels such as red, green, and blue.

[0075]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples of the present invention and Comparative Examples thereof, but the present invention is not limited to these Examples.

Example 1 Resin (25 g) having repeating units (IV) and (V) shown in Table 1 as resin (a) and carbon black (40 g) as pigment (b) were mixed with propylene glycol as an organic solvent. In addition to dimethyl ether (200 g),
This was dissolved and dispersed using a bead mill for 2 hours. In this dispersion, pentaerythritol tetraacrylate (19 g) as a monomer (c) and 3- (2-methyl-carbazole-based photopolymerization initiator represented by the general formula (I) as a photopolymerization initiator (d) are added. 2-dimethylaminopropionyl) carbazole (10 g) and N, N'-tetraethyl-4,4'-diaminobenzophenone (6 g);
In addition, ethylene glycol monoethyl ether (200 g) was added and mixed as an organic solvent to obtain a black colored image forming photosensitive liquid. Table 2 shows the amounts and ratios of the respective materials.

The obtained photosensitive liquid was applied on a glass substrate (Corning Co., trade name: 7059) by spin coating, and then dried at 100 ° C. for 10 minutes on a hot plate to give a film thickness of 1.0 μm. A dried coating film was formed.

Next, the dried coating film was imagewise exposed to light of 200 mJ / cm ^{2 using} a super-high pressure mercury lamp through a negative mask, and then developed with an aqueous solution containing 3% by weight of triethanolamine to obtain a black image pattern. Was.
The optical density of the obtained black image pattern was 2.5.

The sectional shape of the obtained image pattern was evaluated and the results are shown in Table 3. The closer the cross-sectional shape is to a rectangle, the better the pattern shape is.

Further, the photosensitivity and resolution of the dried coating film were evaluated by the following methods, and the results are shown in Table 3.

Light sensitivity: The optical density of 0.00 is the first stage,
A step tablet having 41 steps in which the optical density is increased by 0.05 for each step is prepared, and the step tablet is placed on the dried coating film with a super-high pressure mercury lamp for 200 steps.
Exposure was performed at mJ / cm ² , and then development was performed using an aqueous solution containing 3% by weight of triethanolamine, and the state of the film under the step tablet at the time of exposure was observed. Table 3 shows the maximum number of steps that did not hinder the curing of the dried coating film during exposure and did not cause dissolution or flow due to the development of the portion that was under the tablet. The greater the value of the number of steps, the better the light sensitivity.

Resolution: A plurality of striped negative masks having the same line and space width (μm) (line and space width: 1 μm, 3 μm, 5 μm, 1 μm)
(0 μm, 20 μm, 30 μm), exposure was performed at 200 mJ / cm ² using ultrahigh pressure mercury or the like, and then development was performed using an aqueous solution containing 3% by weight of triethanolamine. The evaluation of the resolution is shown in Table 3 with the minimum line and space width (μm) that could be completely developed. The smaller the value, the better the resolution.

Example 2 Resin B (35 g) having repeating units (IV) and (V) shown in Table 1 as resin (a) and C.I. I. Pigment Red 17
7 (21 g) and C.I. I. Pigment Yellow 139
(4 g) was added to propylene glycol diethyl ether (250 g) as an organic solvent, and this was dissolved and dispersed using a bead mill for 2 hours. In the dispersion, the above resin (5 g), trimethylolpropane triacrylate (32 g) as a monomer (c), and a carbazole-based photopolymerization initiator represented by the general formula (I) as a photopolymerization initiator (d) 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole (4 g) and N, N'-tetraethyl-4,4'-diaminobenzophenone (4 g) as an organic solvent Propylene glycol diisopropyl ether (50 g)
And ethylene glycol monomethyl ether acetate (100 g) were added and mixed to obtain a red colored image forming photosensitive liquid. Table 2 shows the compounding amounts and ratios of the respective materials.

A dried coating film having a thickness of 2.0 μm was formed from the obtained photosensitive liquid in the same manner as in Example 1, and the light sensitivity, resolution and pattern shape of the red colored image of the obtained dried coating film were determined as follows. Evaluation was performed in the same manner as in Example 1, and the results are shown in Table 3.

Example 3 Resin C (40 g) having repeating units (IV) and (V) shown in Table 1 as resin (a) and C.I. I. Pigment Green 3
6 (15 g) and C.I. I. Pigment Yellow 83 (6
g) was added to propylene glycol monomethyl ether (200 g) as an organic solvent, and this was dissolved and dispersed using a bead mill for 2 hours. In this dispersion, pentaerythritol tetraacrylate (31 g) as a monomer (c) and 3,6-bis which is a carbazole-based photopolymerization initiator represented by the general formula (I) as a photopolymerization initiator (d) are added. (2-Methyl-2-morpholinopropionyl-9-n
-Octylcarbazole) (8 g), and propylene glycol monomethyl ether (200 g) as an organic solvent.
g) was added and mixed to obtain a green colored image forming photosensitive liquid. Table 2 shows the compounding amounts and ratios of the respective materials.

A dried coating film having a thickness of 2.0 μm was formed from the obtained photosensitive liquid in the same manner as in Example 1, and the light sensitivity, resolution, and pattern shape of the green colored image of the obtained dried coating film were determined as follows. Evaluation was performed in the same manner as in Example 1, and the results are shown in Table 3.

Example 4 Acrylic resin D (38 g) shown in Table 1 as resin (a)
And C.I. and C.I. I.
Pigment Blue 15: 6 (17 g) and C.I. I. Pigment Violet 23 (1 g) was added to propylene glycol monomethyl ether (260 g) as an organic solvent, and this was dissolved and dispersed using a bead mill for 2 hours. In this dispersion, trimethylolpropane triacrylate (36 g) as a monomer (c) and 3- (2-methyl) which is a carbazole-based photopolymerization initiator represented by the general formula (I) as a photopolymerization initiator (d) are added. -2-dimethylaminopropionyl) carbazole (3 g) and N, N'-
Tetraethyl-4,4'-diaminobenzophenone (5
g) and ethylene glycol monomethyl ether (140 g) as an organic solvent were added and mixed to obtain a blue colored image forming photosensitive liquid. Table 2 shows the amount and ratio of each material.
Shown in

A dried coating film having a thickness of 2.0 μm was formed from the obtained photosensitive liquid in the same manner as in Example 1, and the photosensitivity, resolution, and pattern shape of the blue colored image of the obtained dried coating film were determined as follows. Evaluation was performed in the same manner as in Example 1 except that the development was performed using an aqueous solution containing 0.5% by weight of sodium carbonate. The results are shown in Table 3.

Comparative Example 1 A black colored image forming photosensitive liquid was obtained in the same manner as in Example 1 except that the carbazole-based photopolymerization initiator used in Example 1 was changed to benzophenone. Table 2 shows the compounding amounts and ratios of the respective materials.

A dried coating film was formed from the obtained photosensitive liquid in the same manner as in Example 1. The light sensitivity, resolution, and pattern shape of the black colored image of the obtained dried coating film were the same as those in Example 1. The results were evaluated by the method and the results are shown in Table 3.

Comparative Example 2 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n which is a carbazole-based photopolymerization initiator represented by the general formula (I) as the photopolymerization initiator (d) -Dodecylcarbazole (2 g) and N, N'-tetraethyl-
A red colored image forming photosensitive liquid was obtained in the same manner as in Example 2 except that 4,4'-diaminobenzophenone (6 g) was used. Table 2 shows the compounding amounts and ratios of the respective materials.

Using the obtained photosensitive liquid, a dried coating film having a thickness of 2.0 μm was formed in the same manner as in Example 2, and the light sensitivity, resolution and pattern shape of the red colored image of the obtained dried coating film were determined. The evaluation was performed in the same manner as in Example 1, and the results are shown in Table 3.

[0093]

[Table 1]

[0094]

[Table 2] d1: carbazole-based photopolymerization initiator (1): 3- (2-methyl-2-dimethylaminopropionyl) carbazole (22): 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n- Dodecylcarbazole (21): 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-octylcarbazole d2: benzophenone-based photopolymerization initiator PGDME: propylene glycol dimethyl ether EGEE: ethylene glycol monoethyl ether PGDEE: Propylene glycol diethyl ether PGDiso-PE: propylene glycol diisopropyl ether EGMEA: ethylene glycol monomethyl ether acetate PGME: propylene glycol monomethyl ether EGME: ethylene glycol Monomethyl ether

[0095]

[Table 3] From Table 3, it can be seen that the photosensitive liquids for colored image formation (Comparative Examples 1 and 2) in which the carbazole-based photopolymerization initiator in the present invention was not used at all or the carbazole-based photopolymerization initiator was not used in the concentration in the present invention were used. It can be seen that the light sensitivity was low and no image pattern or pixel could be obtained.

On the other hand, the photosensitive liquids for forming a colored image using the carbazole-based photopolymerization initiator of the present invention at the concentration of the present invention (Examples 1 to 4) have good photosensitive characteristics without providing an oxygen barrier film. Both the sensitivity and the resolution were high, and the obtained pattern shape was rectangular and good.

Example 5 After a black matrix was formed on the glass substrate used in Example 1 by chromium evaporation, a red image pattern was formed in the same manner as in Example 2. Thereafter, post-heating was performed on a hot plate at 180 ° C. for 10 minutes.

Next, using the substrate, a green image pattern was formed next to the red image pattern in the same manner as in Example 3, and then post-heating was performed at 180 ° C. for 10 minutes in the same manner as described above. .

Next, using the substrate, a blue image pattern is formed between the green image pattern and the red image pattern in the same manner as in Example 4, and then at 200 ° C. for 10 minutes in the same manner as described above. Post heating was performed.

By the above operation, each was 30 μm × 100
A high-quality color filter in which pixels of three colors of red, green and blue having a size of μm were arranged in a mosaic pattern was produced.

Example 6 After a black image pattern (black matrix) was formed on the glass substrate used in Example 1 in the same manner as in Example 1, post-heating was performed at 205 ° C. for 20 minutes in the same manner as described above. Was done.

Next, pixels were formed in the order of red, green and blue in the same manner as in Example 5, and each pixel was 30 μm × 100 μm
A high-quality color filter in which pixels of three colors of red, green and blue having a size of are arranged in a mosaic pattern.

The depolarization of the color filters obtained in Examples 5 and 6 was measured with an illuminometer at a light intensity ratio of 0 ° and 90 ° with the color filter interposed between two polarizing plates.

Since the dried coating films formed in Examples 5 and 6 have extremely high resistance to curing inhibition by oxygen as compared with the case where a conventional photosensitive liquid is used, the obtained color filter Have a depolarizing property of 5
It was confirmed to be excellent as an image display device, having excellent optical characteristics of at least 00.

[0105]

The photosensitive solution for forming a colored image according to the present invention exhibits good photosensitive characteristics without providing an oxygen barrier film, and has a sensitivity and
Both resolutions are excellent.

The color filter produced by the method of producing a color filter of the present invention using the photosensitive solution for forming a colored image has excellent optical properties and high quality.
It is excellent as an image display element.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Go Uchida 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Inside Hitachi Chemical Co., Ltd. Ibaraki Research Laboratories (72) Inventor Yukiko Muramatsu 4--13 Higashicho, Hitachi City, Ibaraki Prefecture 1 Ibaraki Research Laboratory, Hitachi Chemical Co., Ltd. (72) Inventor Yoichi Kimura 14 Goi South Coast, Ichihara City, Chiba Prefecture Inside the Goi Plant, Hitachi Chemical Co., Ltd. (72) Inventor Koji Yamazaki 14 Goi South Coast, Ichihara City, Chiba Prefecture Address Hitachi Chemical Industry Co., Ltd.

Claims (5)

[Claims] 1. A colored image formation comprising (a) a resin, (b) a pigment, (c) a monomer containing at least one photopolymerizable unsaturated bond in a molecule, and (d) a photopolymerization initiator. In the photosensitive liquid for use, the photopolymerization initiator (d) has the following general formula (I)
A photosensitive liquid for forming a colored image, comprising the carbazole-based photopolymerization initiator represented by (II) or (III) in an amount of 30 to 100% by weight based on the total amount of the photopolymerization initiator (d). Embedded image (Wherein, R ¹ and R ² each independently represent a hydrogen atom,
An alkyl group having 20 or an aryl group having 6 to 14 carbon atoms; or R ¹ and R ² are bonded to each other to represent an alkylene group having 4 to 7 carbon atoms; R ³ is a hydrogen atom; X ¹ represents an alkyl group or an acyl group having 2 to 11 carbon atoms, and X ¹ represents R ⁵ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 3 to 18 carbon atoms, and R ⁶ and R ⁷
Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a hydroxyalkyl group having 2 to 4 carbon atoms;
⁶ and R ⁷ are bonded to each other to form an alkylene group having 4 to 7 carbon atoms,
An oxadialkylene group having 3 to 4 carbon atoms or 3 to 4 carbon atoms
Wherein Y ¹ is a hydrogen atom or Y ² represents a hydrogen atom, a halogen atom or a nitro group, R ⁴ represents a direct bond or an alkylene group having 1 to 10 carbon atoms, and X ² represents —O—R ⁸ —O— or R ⁸ represents an alkylene group having 2 to 10 carbon atoms,
R ⁹ each independently represents an alkyl group having 1 to 20 carbon atoms,
Or two R ⁹ are combined with each other represents an alkylene group having 1 to 4 carbon atoms. ) 2. The resin (a) has an acid value of 20 to 300, a weight average molecular weight of 1,500 to 200,000, and a repeating unit (IV) represented by the following general formula (IV) and the following general formula: Consisting of a repeating unit (V) represented by (V),
A molar ratio of the repeating unit (IV) to the repeating unit (V),
The photosensitive liquid for forming a colored image according to claim 1, wherein the photosensitive liquid contains a resin having (IV) / (V) of 1 to 5. Embedded image (In the above general formula, R ¹⁰ represents a hydrogen atom or a methyl group,
R ¹¹ represents a hydrogen atom, a hydroxyl group, an alkyl group or an alkoxy group having 1 to 12 carbon atoms, and R ¹² is a group having a photopolymerizable unsaturated bond. ) 3. A colored image forming photosensitive liquid according to claim 1 or 2 is coated on a substrate, and then dried to form a film. A plurality of steps of forming a pixel by photocuring and removing unexposed areas by development using a plurality of colored image forming photosensitive liquids of different colors. A method for manufacturing a color filter having color pixels. 4. The method according to claim 3, wherein a color filter having red pixels, green pixels, blue pixels and black pixels is manufactured by using four types of photosensitive liquids for forming colored images of red, green, blue and black, respectively. Law. 5. A color filter produced by the production method according to claim 3.