JPH10104825A - Photosensitive solution for forming colored 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 colored image capable of giving a dry coating film having a thin uniform thickness, a uniform chromaticity distribution and low tackiness and the produce a high guality of color filter excellent in optical characteristics by using the photosensitive soln. SOLUTION: This photosensitive soln. for forming a colored image contains a resin having an acid value of 20-300 and a wt. average mol.wt. of 1,500-200,000, a pigment, a monomer contg. one or more photopolymerizable unsatd. bonds in the molecule, a photoinitiator and an org. solvent. When the rate of evaporation of n-butyl acetate is represented as 1.00, that of the org. solvent is 0.1-0.4. A color filter is produced by using the solution.

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.

In recent years, attention has been paid to a method of forming a colored image by using a photosensitive resin material which is colored by dispersing a pigment, and exposing and developing the photosensitive resin material in order to improve heat resistance and light resistance. Many considerations have been taken. 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.

On the other hand, in order to form a colored image with the photosensitive liquid for forming a colored image, a photosensitive material for forming a colored image dissolved or dispersed in an organic solvent is applied to the surface of the substrate, dried, and the colored layer is formed on the substrate. Must be provided. At that time, it is necessary to provide a colored layer having a uniform thickness in order to exhibit the performance of the colored resist, for example, color characteristics such as uniform color density.

However, in the case of spin coater coating,
The thickness distribution of the colored layer tends to be non-uniform due to the influence of the air current.

Further, even in the drying step, the thickness of the colored layer tends to be non-uniform, and it is very difficult to obtain a uniform thickness especially when the colored layer is a thin film. That is, conventionally, in the drying step, a solvent was evaporated and dried by blowing air with humidity control on the substrate coated with the photosensitive liquid for forming a colored image to evaporate and dry the solvent to obtain a color layer. The unevenness of the thickness distribution of the dried colored layer occurs due to the flow and turbulence of the heated air.

[0007] The unevenness of the thickness of the colored layer not only gives a bad impression in appearance, but also causes a variation in chromaticity after exposure and development processing, a decrease in reproducibility of the original pattern, and the like.

In order to prevent this unevenness, it is necessary to carry out the drying promptly. A method of drying over a long period of time by setting the drying air speed to a very low speed, giving a temperature gradient to the drying air temperature, A method in which the temperature is set to be low and the temperature is set to be high in the latter stage drying, or a method in which a solvent having a high boiling point is added to a solvent which dissolves and disperses the photosensitive material for forming a colored image, is used.

However, in these methods, it is difficult to completely prevent uneven film thickness distribution due to dry air, and in the case of producing a colored image forming material industrially, a belt-shaped support is transported. However, since the coating and drying are continuously performed, the length and the complexity of the drying equipment are increased. When a solvent having a high boiling point is used, a problem of tackiness of the colored layer after drying occurs.

[0010]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and has a thin and uniform film thickness and chromaticity distribution by being applied on a substrate and then dried. Another object of the present invention is to provide a colored image forming photosensitive liquid capable of obtaining a dried coating film having low tackiness.

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.

[0012]

Means for Solving the Problems As a result of repeated studies to solve the above problems, the present inventors have used an organic solvent having a specific evaporation rate as an organic solvent for dissolving and dispersing a photosensitive agent for forming a colored image. As a result, it has been found that a colored layer having a thin film thickness and a uniform chromaticity distribution can be obtained without increasing the tackiness of a coating film (colored layer) formed by applying and drying a photosensitive solution. Was completed.

That is, the present invention relates to (a) an acid value of 20 to 30.
0, a resin having a weight average molecular weight of 1,500 to 200,000, (b) a pigment, (c) a monomer containing at least one photopolymerizable unsaturated bond in a molecule, (d) a photoinitiator, and (e) )
In a colored image forming photosensitive solution containing an organic solvent, the organic solvent (e) has an evaporation rate of 0.1 or more and 0.4 or less when the evaporation rate of n-butyl acetate is 1.00. A photosensitive liquid for forming a colored image.

Further, in the present invention, the above-mentioned photosensitive solution for forming a colored image is coated on a substrate, and then dried to form a film. Curing, and removing a non-exposed portion by development to form a pixel, repeatedly using a plurality of colored image forming photosensitive liquids of different colors, wherein a plurality of different colors are used. The present invention provides a method for producing a color filter having pixels.

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

[0016]

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

[Photosensitive Liquid for Forming a Colored Image] The photosensitive solution for forming a colored image of the present invention has an acid value of 20 to 300, which is the component (a);
The resin having a weight-average molecular weight of 1,500 to 200,000 is not particularly limited as long as the acid value and the weight-average molecular weight fall within the above ranges, but carboxyl group-containing resins such as acrylic acid and methacrylic acid , Carboxyl group-containing polymerizable monomers such as itaconic acid, and acrylates such as methyl acrylate and ethyl acrylate;
Representative examples include a copolymer with a polymerizable monomer such as methacrylate or styrene, such as methyl methacrylate or ethyl methacrylate.

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 a free isocyanate group-containing unsaturated compound, and a resin obtained by reacting an epoxy resin with an unsaturated carboxylic acid. A resin obtained by reacting a polybasic acid anhydride with an addition reaction product, a resin obtained by reacting a hydroxyl group-containing polymerizable monomer with an addition reaction product of a conjugated diene polymer or a conjugated diene copolymer and an unsaturated dicarboxylic acid anhydride, 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. ,
The repeating unit (I) represented by the following general formula (I), the repeating unit (II) represented by the following general formula (II), and the repeating unit (III) represented by the following general formula (III)
And a repeating unit (I) and a repeating unit (II)
And the molar ratio to the sum of (III), (I) / ｛(II)
+ (III)} from 1 to 5, among which the above-mentioned repeating units (I), (II) and (III) are used from the viewpoint of improving the heat resistance of the pixel and the dispersibility of the pigment. Resins are preferred.

[0020]

Embedded image (In the above formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom, a hydroxyl group or an alkyl group or an alkoxy group having 1 to 12 carbon atoms, and R ³ each independently represent a 1 to 1 carbon atom.
12 represents an alkyl group, and R ⁴ represents a group having a photopolymerizable unsaturated bond. As a method for producing a resin comprising the above repeating units (I), (II) and (III), for example, a precursor resin comprising the repeating units (I) and (II) may be added to an unsaturated alcohol such as allyl alcohol. , 2-buten-4-ol, furfuryl alcohol, oleyl alcohol, cinnamyl alcohol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N-methylol acrylamide and the like, and the above precursor Compounds each having one oxirane ring and one ethylenically unsaturated bond in the resin, for example, glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, α-ethyl glycidyl acrylate, crotonyl glycidyl ether, monoalkyl monoglycidyl itaconate And a method of manufacturing by addition reaction of esters in a ratio of equimolar or less and the like.

The precursor resin composed of the repeating units (I) and (II) is composed of styrene or a derivative thereof and a monoalkyl maleate (half ester of maleic acid).
Can be obtained by copolymerizing

Examples of the styrene derivative include α-methylstyrene, m or p-methylstyrene, m or p-methylstyrene.
Methoxystyrene, p-hydroxystyrene, 2-methoxy-4-hydroxystyrene, 2-hydroxy-4-
Methylstyrene and the like can be mentioned.

The monoalkyl maleate includes, for example, mono-C _1-12 alkyl maleate, for example, monomethyl maleate, monoethyl maleate, mono-n-propyl maleate, mono-maleate.
Isopropyl, mono-n-butyl maleate, mono-n-hexyl maleate, mono-n-octyl maleate, mono-2-ethylhexyl maleate, mono-n-nonyl maleate, mono-n-maleate Dodecyl and the like.

The thus obtained resin comprising repeating units (I), (II) and (III) preferably has an unsaturated equivalent of from 600 to 3,000,
It is more preferably set to 00 to 2,000. If the unsaturated equivalent is less than 600, it tends to be partially cured when dispersed with the pigment, and if it exceeds 3,000, the effect of improving photosensitivity tends to be reduced. Here, the unsaturated equivalent means the molecular weight of the resin per unsaturated bond. Further, the molar ratio of the repeating unit (I) to the total of the repeating units (II) and (III), (I) / ｛(II) +
(III)｝ is 1 to 5, more preferably 1 to 3. If the molar ratio is less than 1, the heat resistance of the pixel may decrease, and if it exceeds 5, the solubility of the coating film may decrease.

The acid value of the resin (a) is from 20 to 300, preferably from 40 to 200, and more preferably from 60 to 15
More preferably, it is set to 0. If the acid value is less than 20, the alkali developability decreases, and if it exceeds 300, the shape of the image pattern becomes unclear.

The resin (a) has a weight average molecular weight (gel permeation chromatography (GPC)).
And converted using a standard polystyrene calibration curve) are 1,500 to 200,000,
000 to 100,000, preferably 10,
More preferably, it is set to 000 to 50,000. When the weight average molecular weight is less than 1,500, the dispersion stability of the pigment is reduced. When the weight average molecular weight is more than 200,000, the viscosity when used as a photosensitive liquid is increased, and the coating property when coating on a substrate is reduced. However, it becomes difficult to obtain a uniform coating film.

The above various resins exemplified as the resin of the component (a) may be used alone or in combination of two or more. When a resin having a photopolymerizable unsaturated group comprising the above repeating units (I), (II) and (III) is used for the purpose of improving the heat resistance of the pixel and the dispersibility of the pigment, the component (a) The ratio of the resin having a photopolymerizable unsaturated group to the total amount of the resin is 10 to 100.
% By weight, more preferably 30 to 100% by weight.

As the pigment of the component (b) used in the present invention, any of inorganic pigments and organic pigments can be used, but usually black carbon black (inorganic pigment), graphite (inorganic pigment) and the like are usually used. Organic pigments are preferred from the viewpoint of rich color tone.

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

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 to perform toning.

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

As the blue pigments, 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 violet 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 the black colored image, for example, a black pigment system such as carbon black, graphite, titanium carbon, black iron, and manganese dioxide is used.

Examples of the monomer having at least one photopolymerizable unsaturated bond as the component (c) used in the present invention include methyl methacrylate, benzyl methacrylate, butoxyethyl methacrylate, butoxyethyl acrylate, and butoxytriethylene. Glycol acrylate, ECH-modified butyl acrylate (where E
CH means epichlorohydrin. The same applies to the following. ), Dicyclopentanyl acrylate, dicyclopentenyloxyethyl methacrylate, N, N-dimethylaminoethyl methacrylate, ethyldiethylene 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 hereinafter. ), Caprolactone-modified tetrahydrofurfuryl acrylate, EO-modified bisph Nool A diacrylate, ECH-modified bisphenol A diacrylate, bisphenol A dimethacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol diacrylate, EO Modified phosphate diacrylate, EC
H-modified phthalic acid diacrylate, polyethylene glycol 400 diacrylate, polypropylene glycol 4
00 dimethacrylate, tetraethylene glycol diacrylate, ECH-modified 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, EO-modified phosphate triacrylate, EO-modified trimethylolpropane triacrylate, PO-modified tri Methylolpropane triacrylate (where PO means propylene oxide; the same applies hereinafter), tris (methacryloxyethyl) isocyanurate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipenta Typical examples include acrylates such as erythritol pentaacrylate and methacrylates corresponding thereto. . These monomers are used alone or in combination of two or more.

As the photoinitiator of the component (d) used in the present invention, for example, benzophenone, 2-benzyl-2
-Dimethylamino-1- (4-morpholinophenyl)
Butan-1-one, 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-chloro Thioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-
[4- (methylthio) phenyl] -2-morpholino-1
-Propane, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-
Chlor-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 1,2-benzoanthraquinone, 1,4-
Examples thereof include dimethylanthraquinone, 2-phenylanthraquinone, and 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer. These photoinitiators are used alone or in combination of two or more.

The organic solvent of the component (e) used in the present invention, when the evaporation rate of n-butyl acetate is 1.00,
It is essential that the evaporation rate of the organic solvent (e) be 0.1 to 0.4. When the evaporation rate of the organic solvent (e) is larger than 0.4, it tends to be difficult to obtain a coating film having a uniform film thickness and a concentration distribution at a film thickness of 1.5 μm or less. The problem that the tackiness of a coating film becomes high arises.

Of course, the organic solvent (e) used in the present invention
Is capable of dissolving the resin (a), the monomer (c) and the photoinitiator (d), and dispersing or dissolving the pigment (b).

Here, the evaporation rate of n-butyl acetate is set to 1.
The evaporation rate of the organic solvent (e) when it is set to 00 is obtained as follows.

First, n-butyl acetate Amg is evaporated at 25 ° C. and normal pressure, and the time t until the evaporation completely evaporates.
Measure _n-BuA . Next, the same amount (Amg) of the organic solvent (e) is evaporated under the same conditions, and the time t _sol until complete evaporation is measured. The evaporation rate of the organic solvent (e) when the evaporation rate of n-butyl acetate is set to 1.00 is calculated by the equation (t _n-BuA / t _sol ).

In the present invention, the evaporation rate of the organic solvent (e) means the evaporation rate of one kind of the organic solvent when the organic solvent (e) comprises only one kind of the organic solvent. When e) is a mixed solvent composed of two or more organic solvents, it means the evaporation rate of the mixed solvent.

When a mixed solvent is used as the organic solvent (e), if the evaporation rate of the mixed solvent is 0.1 or more and 0.4 or less, what kind of evaporation rate of each solvent constituting the mixed solvent has However, each is usually 0.1 or more.
A mixed solvent composed of an organic solvent having an evaporation rate of 4 or less is preferably used.

Further, for example, the organic solvent comprises at least one organic solvent having an evaporation rate of less than 0.1 and at least one organic solvent having an evaporation rate of 0.1 or more, and has an evaporation rate of less than 0.1. % By weight, preferably 3 to 25% by weight,
A mixed solvent comprising 70 to 99% by weight, preferably 75 to 97% by weight of an organic solvent having an evaporation rate of 0.1 or more is also suitably used. The evaporation rate of the organic solvent having an evaporation rate of 0.1 or more in the mixed solvent is not particularly limited as long as the evaporation rate is 0.1 or more, but is usually preferably 0.1 or more and less than 0.4.

Assuming that the evaporation rate of n-butyl acetate is 1.00, the organic solvent having an evaporation rate of 0.1 to 0.4 is, for example, ethylene glycol monoethyl ether (evaporation rate 0.32). Propylene glycol tertiary butyl ether (evaporation rate 0.25), propylene glycol methyl ether acetate (evaporation rate 0.34), ethylene glycol ethyl ether acetate (evaporation rate 0.20), propylene glycol ethyl ether acetate (evaporation rate 0.20). 19), 3-methyl-3-methoxybutyl acetate (evaporation rate 0.1
0), diethylene glycol dimethyl ether (evaporation rate 0.36), dipropylene glycol methyl ether (evaporation rate 0.12) and the like. In particular, dipropylene glycol methyl ether (evaporation rate 0.12),
Diethylene glycol dimethyl ether (evaporation rate 0.
36), propylene glycol ethyl ether acetate (evaporation rate 0.19) and propylene glycol methyl ether acetate (evaporation rate 0.34) are preferred.

Further, the evaporation rate of n-butyl acetate was set to 1.0
Organic solvents having an evaporation rate of less than 0.1 when 0 is used include, for example, ethylene glycol monobutyl ether (evaporation rate 0.09), 3-methyl-3-methoxybutanol (evaporation rate 0.07), diethylene glycol Ethyl ether (evaporation rate <0.01), diethylene glycol butyl ether (evaporation rate <0.01), tripropylene glycol methyl ether (evaporation rate <0.
01).

The amount of the resin (a) used in the present invention is 10 to 85% by weight, preferably 10 to 85% by weight, based on the total amount of the resin (a), the pigment (b), the monomer (c) and the photoinitiator (d). 2
0 to 60% by weight, more preferably 25 to 50% by weight. If the amount is less than 10% by weight, the dispersion stability of the pigment tends to decrease, and if it exceeds 85% by weight, the viscosity of the photosensitive liquid becomes high, and the pigment is applied onto a substrate by spin coating. The applicability when forming a film decreases,
It becomes difficult to obtain a uniform coating film.

The amount of the pigment used as the component (b) 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 photoinitiator (d). Is preferably, more preferably 10 to 40% by weight, and
It is particularly preferred that the content be 5 to 30% by weight. 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 of the component (c) in the present invention is 2 to 50% by weight, preferably 5 to 5% by weight based on the total amount of the resin (a), the pigment (b), the monomer (c) and the photoinitiator (d). -40% by weight, more preferably 10-30% 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.

The amount of the photoinitiator (d) used in the present invention is 0.01 to 20% by weight based on the total amount of the resin (a), the pigment (b), the monomer (c) and the photoinitiator (d). %, More preferably 2 to 15% by weight, and 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 tends to decrease.

In the present invention, the organic solvent as the component (e) is
In the total amount of the resin (a), the pigment (b), the monomer (c), the photoinitiator (d) and the organic solvent (e), (a)
It is preferable to use the solid content of (b), (c) and (d) in an amount such that the proportion of the total solid content is 5 to 40% by weight. When the proportion of the total solid content is less than 5% by weight, it takes a long time to dry the coating film. When the proportion exceeds 40% by weight, the viscosity of the photosensitive solution tends to be too high, and the coating property tends to be reduced.

The photosensitive liquid for forming a colored image of the present invention comprises, as essential components, (a) a resin, (b) a monomer, (c) a pigment,
In addition to (d) a photoinitiator and (e) an organic solvent, a thermal polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, pyrogallol, and t-butylcatechol for suppressing a dark reaction, and for improving adhesion to a substrate. Silane coupling agents having a vinyl group, an epoxy group, an amino group, a mercapto group, etc., isopropyltrimethacryloyl titanate, diisopropylisostearoyl-4
-Titanate coupling agents such as aminobenzoyl titanate, fluorine-based, silicon-based, and hydrocarbon-based surfactants for improving the smoothness of the film, and other additives such as ultraviolet absorbers and antioxidants. It can be used as needed. Usually, the total amount of these additives is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the total solid content consisting of (a), (b), (c) and (d), More preferably, the amount is 0.5 to 5 parts by weight.

The photosensitive liquid for forming a colored image of the present invention contains a resin other than the resin of the component (a), such as an acrylic resin, an epoxy resin, a urethane resin, or 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.

In the case where the above-mentioned additives and resins other than the resin (a) are added to the colored image forming photosensitive liquid of the present invention,
The organic solvent (e) is the total amount of the solid content of the resin (a), the other resin, the pigment (b), the monomer (c), the photoinitiator (d), and the additives in the total amount of the photosensitive liquid for forming a colored image. Is preferably used in such an amount that the ratio becomes 5 to 40% by weight.

A general method for preparing the photosensitive solution for forming a colored image of the present invention will be described below.

First, in order to disperse the pigment of the component (c),
The resin of the component (a) and the pigment of the component (b) are mixed with the organic solvent of the component (e), and the mixture is dispersed in an ultrasonic disperser, a three-roll mill, a ball mill, a sand mill, a bead mill, a homogenizer, a kneader, or the like. Disperse using a kneading device.

In the dispersion step, anionic pigment dispersants such as polycarboxylic acid type polymer activators and 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 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.

The monomer of component (c) and the photoinitiator of component (d) may be added at the time of pigment dispersion, and the monomer of component (c) and the photoinitiator of component (d) may be added after pigment dispersion. Is also good.

The resin of the component (a) may be used in its entirety 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 of the component (e) may be used in its entirety at the time of dispersion of the pigment, or a part of the organic solvent may be added after the dispersion. However, at least one organic solvent is used 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.
It is preferable to use at least 00 parts by weight. 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 applied 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.

In some cases, good results can be obtained by dehumidifying dry air. The drying air is applied to the coating film at a rate of 0.1 m / sec to 30 m / sec, particularly 0.5 m / sec to 20 m / sec.
It is preferred to supply at a rate of / s.

The thickness of the dried coating film formed on the substrate surface in this manner is appropriately determined depending on the application, but is usually 0.2
-5 μm, preferably 0.5-1.5 μm. According to the method of the present invention, a dried coating film having a thickness of 1.5 μm or less can be formed to a uniform thickness.

According to the present invention, the unevenness of the film thickness of the coating film, which has conventionally occurred in the drying step, is eliminated, the performance as an image forming material is made uniform, and the coating and drying conditions in an extremely wide range. It is possible to obtain a colored layer (coating film) having a uniform film thickness and concentration below, thereby simplifying the drying equipment. Also, the tackiness of the colored layer obtained after drying can be reduced.

Next, the film on the substrate obtained by the above method is irradiated with actinic rays in an image-like manner 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 1000 mJ
/ 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 the development, the colored image pattern is further
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 for 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, red, green, 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.

[0085]

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 As the resin (a), the repeating units (I) and (I) shown in Table 1 were used.
Resin (a-1) having I) and (III) (15 g)
And carbon black (35 g) as the pigment (b),
The organic solvent (e) was added to dipropylene glycol methyl ether (evaporation rate: 0.12) (200 g) (200 g), and this was dissolved and dispersed using a bead mill for 2 hours. In this dispersion, pentaerythritol tetraacrylate (35 g) was used as the monomer (c), and 2-pentamer was used as the photoinitiator (d).
Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (10 g) and N, N '
-Tetraethyl-4,4'-diaminobenzophenone (5 g) and dipropylene glycol methyl ether (evaporation rate 0.12) (200) as an organic solvent (e)
g) was added and mixed to obtain a black colored image forming photosensitive liquid.

The obtained photosensitive liquid was applied on a glass substrate (Corning Co., trade name: 7059) by spin coating, followed by drying at 80 ° C. for 10 minutes (dry air supply speed: 1.0 m / sec). Was performed to form a dried coating film having a thickness of 1.0 μm.

The appearance of the dried coating film was evaluated by visual observation of transmitted light from the backlight, and the results are shown in Table 2. In Table 2, "good"
Means that the dried coating is uniform and has no coating unevenness,
“Defective” means that uneven coating due to dry air or the like is clearly visible.

Further, the substrates with the dried coating film are overlapped so that the obtained dried coating films are on the inside, and 1 kg
Was placed at 40 ° C. for 4 hours and then peeled off to evaluate tackiness. Table 2 shows the results. In Table 2,
`` Good '' means that the dried coatings can be easily peeled off without adhesion, and `` Poor '' means that the dried coatings are completely adhered, and a Means the sound was heard.

Next, the dried coating film was imagewise exposed to light of 300 mJ / cm ² by means of an ultra-high pressure mercury lamp through a negative mask, and then developed with an aqueous solution containing 3% by weight of triethanolamine to form a black image pattern. Obtained. The optical density of the obtained black image pattern was 2.5.

The surface state and cross-sectional shape of the obtained image pattern were evaluated and are shown in Table 2. The more uniform the surface and 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 2.

Light sensitivity: The optical density of 0.05 was set as the first step, and a 21-step tablet was prepared in which the optical density increased by 0.15 for each step, and this step tablet was placed on the dried coating film. 3 with an ultra-high pressure mercury lamp
Exposure was performed at 00 mJ / cm ² , and then development was performed with 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 2 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 processing of the portion 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, 40 μm, and 50 μm), exposure was performed at 300 mJ / cm ² using an ultra-high pressure mercury lamp, and then development was performed using an aqueous solution containing 3% by weight of triethanolamine. The evaluation of the resolution was shown by the minimum line and space width (μm) that could be completely developed. The smaller the value, the better the resolution.

Example 2 As the resin (a), the repeating units (I) and (I) shown in Table 1 were used.
Resin (a-2) having I) and (III) (30 g)
And C.I. and C.I. I.
Pigment Red 177 (21 g) and C.I. I. Pigment Yellow 139 (4 g) was mixed with diethylene glycol dimethyl ether as an organic solvent (e) (evaporation rate: 0.1 g).
36) (200 g), and this was dissolved and dispersed using a bead mill for 2 hours. This dispersion was added to the above resin (a
-2) (5 g), dipentaerythritol hexaacrylate (30 g) as monomer (c), and 2-benzyl-2-dimethylamino-1- as photoinitiator (d).
(4-morpholinophenyl) butan-1-one (8
g) and N, N'-tetraethyl-4,4'-diaminobenzophenone (2 g) and propylene glycol ethyl ether acetate (evaporation rate 0.19) (200 g) as an organic solvent (e) were added and mixed. Was obtained.

Using the obtained photosensitive liquid, a dried coating film having a thickness of 1.5 μm was formed in the same manner as in Example 1, and the appearance of the dried coating film was evaluated by visual observation of transmitted light from the backlight. Table 2
It was shown to. The tackiness of the obtained dried coating film was evaluated in the same manner as in Example 1. The results are shown in Table 2.

The same procedure as in Example 1 was carried out except that the light sensitivity, resolution, and pattern shape of the red colored image of the obtained dried coating film were changed to an exposure amount of 100 mJ / cm ² at the time of exposure with an ultrahigh pressure mercury lamp. And the results are shown in Table 2.

Example 3 As the resin (a), the repeating units (I) and (I) shown in Table 1 were used.
Resin (a-3) having I) and (III) (35 g)
And C.I. and C.I. I.
Pigment Green 36 (15 g) and C.I. I. Pigment Yellow 83 (5 g) was added to propylene glycol methyl ether acetate (evaporation rate 0.34) (200 g) as an organic solvent (e), and the mixture was dissolved and dispersed for 2 hours using a bead mill. To this dispersion, trimethylolpropane triacrylate (35 g) as a monomer (c) and 2-benzyl-2- as a photoinitiator (d) were added.
Dimethylamino-1- (4-morpholinophenyl) butan-1-one (8 g) and N, N'-tetraethyl-
4,4'-diaminobenzophenone (2 g), and diethylene glycol dimethyl ether (evaporation rate 0.36) (160 g) and diethylene glycol ethyl ether (evaporation rate <0.01) as organic solvents (e) (4)
0g) was added and mixed to obtain a green colored image forming photosensitive liquid.

Using the obtained photosensitive liquid, a dried coating film having a thickness of 1.5 μm was formed in the same manner as in Example 1, and the appearance of the dried coating film was evaluated by visual observation of transmitted light from the backlight. Table 2
It was shown to. The tackiness of the obtained dried coating film was evaluated in the same manner as in Example 1. The results are shown in Table 2.

The same procedure as in Example 1 was carried out except that the light sensitivity, resolution, and pattern shape of the green colored image of the obtained dried coating film were changed to an exposure amount of 100 mJ / cm ² at the time of exposure with an ultrahigh pressure mercury lamp. And the results are shown in Table 2.

Example 4 As the resin (a), the repeating units (I) and (I) shown in Table 1 were used.
Resin (a-4) having I) and (III) (35 g)
And C.I. and C.I. I.
Pigment Blue 15: 6 (18 g) and C.I. I. Pigment Violet 23 (2 g) was added to diethylene glycol dimethyl ether (evaporation rate 0.36) (200 g) as an organic solvent (e), and the mixture was dissolved and dispersed using a bead mill for 2 hours. To this dispersion, trimethylolpropane triacrylate (35 g) as a monomer (c) and 2-benzyl-2- as a photoinitiator (d) were added.
Dimethylamino-1- (4-morpholinophenyl) butan-1-one (8 g) and N, N'-tetraethyl-
4,4'-diaminobenzophenone (2 g) and diethylene glycol dimethyl ether (evaporation rate 0.36) (180 g) and tripropylene glycol methyl ether (evaporation rate <0.01) as organic solvent (e)
(20 g) were added and mixed to obtain a blue colored image forming photosensitive liquid.

Using the obtained photosensitive liquid, a dried coating film having a thickness of 1.5 μm was formed in the same manner as in Example 1, and the appearance of the dried coating film was evaluated by visual observation of transmitted light from the backlight. Table 2
It was shown to. The tackiness of the obtained dried coating film was evaluated in the same manner as in Example 1. The results are shown in Table 2.

The photosensitivity, resolution, and pattern shape of the blue colored image of the obtained dried coating film were set to an exposure amount of 100 mJ / cm ² at the time of exposure with an ultra-high pressure mercury lamp, and the development was performed for 1 hour.
Evaluation was carried out in the same manner as in Example 1 except that the test was performed using an aqueous solution containing sodium carbonate by weight, and the results are shown in Table 2.

Comparative Example 1 A black colored image forming photosensitive liquid was obtained in the same manner as in Example 1 except that the organic solvent (e) was changed to ethylene glycol monomethyl ether (evaporation rate: 0.47).

Using the obtained photosensitive liquid, a dried coating film having a thickness of 1.0 μm was formed in the same manner as in Example 1, and the appearance of the dried coating film was evaluated by visual observation of transmitted light from the backlight. Table 2
It was shown to. The tackiness of the obtained dried coating film was evaluated in the same manner as in Example 1. The results are shown in Table 2.

The photosensitivity, resolution and pattern shape of the black colored image of the obtained dried coating film were evaluated in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 2 A red colored image forming photosensitive liquid was obtained in the same manner as in Example 2 except that all of the organic solvent (e) was changed to diethylene glycol monoethyl ether (evaporation rate <0.01).

Using the obtained photosensitive liquid, a dried coating film having a thickness of 1.5 μm was formed in the same manner as in Example 2, and the appearance of the dried coating film was evaluated by visual observation of transmitted light from the backlight. Table 2
It was shown to. The tackiness of the obtained dried coating film was evaluated in the same manner as in Example 1. The results are shown in Table 2.

The same procedures as in Example 1 were carried out except that the photosensitivity, resolution, and pattern shape of the red colored image of the obtained dried coating film were changed to an exposure amount of 100 mJ / cm ² at the time of exposure with an ultrahigh pressure mercury lamp. And the results are shown in Table 2.

[0110]

[Table 1]

[0111]

[Table 2] Table 2 shows that the coating film obtained by applying the photosensitive liquid for forming a colored image formed using an organic solvent outside the range of the organic solvent (e) in the present invention has poor appearance (Comparative Example 1). It was found that the tackiness was poor (Comparative Example 2). Films having poor appearance of the coating film also had poor photosensitive characteristics, low photosensitivity and low resolution, and had problems with the resulting pattern shapes.

On the other hand, the coating film obtained by applying the photosensitive liquid for forming a colored image prepared by using the organic solvent (e) according to the present invention has an extremely uniform appearance and a good tackiness, and has a low tackiness. It was good. Similarly, the photosensitive properties of the coating film were good, the photosensitivity and the resolution were both 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 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 190 ° 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.

[0116] By the above operation, 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 180 ° 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 depolarizing properties of the color filters obtained in Examples 5 and 6 were 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 both had a very good coating appearance as compared with the case where a conventional photosensitive liquid was used, all of the color filters obtained were not used. It was confirmed that the depolarizing property was 900 or more, which was excellent in optical characteristics and excellent as an image display device.

[0121]

The photosensitive liquid for forming a colored image of the present invention has a good appearance even when applied and dried on a substrate by a method such as spin coater coating or hot air drying under the influence of airflow. A coating film having extremely excellent uniformity of the film thickness and the concentration distribution can be formed. The method for producing a color filter of the present invention uses the above-described photosensitive liquid for forming a colored image of the present invention, and when coating and drying the photosensitive liquid for forming a colored image, the film thickness and concentration distribution of the coating film are not uniform. No special operation or device is required to prevent the formation of a color filter. Therefore, according to the production method of the present invention, a color filter having excellent optical characteristics can be efficiently produced.

The color filter of the present invention produced by the above-described method using the photosensitive liquid for forming a colored image of the present invention has excellent optical characteristics, high quality, and is excellent as an image display device.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/033 G03F 7/033 7/038 7/038 // C08F 2/50 C08F 2/50 C09D 4/06 C09D 4/06 201/00 201/00 (72) Inventor Hiroyuki Sonobe 4-13-1, Higashicho, Hitachi City, Ibaraki Prefecture Inside Hitachi Chemical Co., Ltd.

Claims (8)

[Claims] 1. A resin having (a) a resin having an acid value of 20 to 300 and a weight average molecular weight of 1,500 to 200,000, (b) a pigment, and (c) one or more photopolymerizable unsaturated bonds in a molecule. When the organic solvent (e) has an evaporating rate of n-butyl acetate of 1.00 in a colored image forming photosensitive liquid containing the contained monomer, (d) photoinitiator and (e) organic solvent. A photosensitive liquid for forming a colored image having an evaporation rate of 0.1 to 0.4. 2. The organic solvent (e) is a mixed solvent comprising at least two kinds of organic solvents having an evaporation rate of 0.1 or more and 0.4 or less, assuming that an evaporation rate of n-butyl acetate is 1.
2. The colored image forming photosensitive liquid according to claim 1, wherein an evaporation rate of the mixed solvent is 0.1 or more and 0.4 or less. 3. An organic solvent (e) having an evaporation rate of n-butyl acetate of 1 to 1 to 30% by weight of an organic solvent having an evaporation rate of less than 0.1 and an organic solvent having an evaporation rate of 0.1 or more. 2. The photosensitive liquid for forming a colored image according to claim 1, wherein the mixed solvent comprises 70 to 99% by weight of the solvent, and the evaporation rate of the mixed solvent is 0.1 to 0.4. 4. An organic solvent (e) having an evaporation rate of n-butyl acetate of 1 to 1 to 30% by weight of an organic solvent having an evaporation rate of less than 0.1 and an evaporation rate of 0.1 to 0.1. A mixed solvent comprising 70 to 99% by weight of an organic solvent of 4 or less;
2. The colored image forming photosensitive liquid according to claim 1, wherein an evaporation rate of the mixed solvent is 0.1 or more and 0.4 or less. 5. A resin (a) comprising a repeating unit (I) represented by the following general formula (I), a repeating unit (II) represented by the following general formula (II), and a resin represented by the following general formula (III): And the molar ratio of the repeating unit (I) to the total of the repeating units (II) and (III), (I) / {(II) + (III)} is 1 to 5.
The photosensitive liquid for forming a colored image according to any one of claims 1 to 4, wherein the photosensitive liquid contains a resin that is: Embedded image (In the above formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom, a hydroxyl group or an alkyl group or an alkoxy group having 1 to 12 carbon atoms, and R ³ each independently represent a 1 to 1 carbon atom.
12 represents an alkyl group, and R ⁴ represents a group having a photopolymerizable unsaturated bond. ) 6. A photosensitive solution for forming a colored image according to claim 1, which is applied on a substrate, and then dried to form a film, and the film is exposed to actinic rays to form an image. Wherein the step of forming a pixel by photo-curing the part and removing the unexposed part by development is repeated using a plurality of colored image forming photosensitive liquids of different colors. A method for manufacturing a color filter having pixels of a plurality of colors. 7. The method for producing a color filter according to claim 6, wherein the thickness of the film formed by applying the photosensitive liquid for forming a colored image on a substrate and then drying is 1.5 μm or less. 8. A color filter produced by the method according to claim 6.