JP3421424B2 - Photosensitive solution containing colored image forming material, photosensitive element and method for producing color filter using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive solution containing a colored image forming material, a photosensitive element using the same and a method for producing a color filter.

[0002]

2. Description of the Related Art In recent years, color filters have been widely used in liquid crystal display devices, sensors, color separation devices and the like. As a method for producing this color filter, conventionally, a method has been used in which a dyeable resin, for example, natural gelatin or casein is patterned, and dyed there mainly with a dye to obtain pixels. However, the pixel obtained by this method has a problem that the heat resistance and the light resistance are low due to the limitation of the material. Therefore, recently, for the purpose of improving heat resistance and light resistance, a method using a photosensitive material in which a pigment is dispersed has attracted attention and many studies have been conducted. It is known that according to this method, the manufacturing method is simplified, and the obtained color filter is stable and has a long life. However, it is difficult to stably disperse the pigment, and it is particularly difficult to select a dispersion resin and a solvent that most affect the dispersibility of the pigment.

[0003]

As described above, the present invention remarkably improves the dispersion stability of the pigment, which is a problem of the photosensitive material in which the pigment is dispersed, and solves the problems of the prior art. Provided are a photosensitive solution containing a forming material, a photosensitive element using the same, and a method for producing a color filter.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventors have selected a dispersion resin and an organic solvent so that the viscosity of a solution consisting of the dispersion resin and the organic solvent falls within a specific range. The inventors have found that the stability of a photosensitive solution containing a pigment can be remarkably improved and have reached the present invention.

That is, the present invention provides (a) an acid value of 20 to 3
No. 00 dispersion resin, (b) pigment, (c) monomer having at least one photopolymerizable unsaturated bond in the molecule, and (d) a colored image forming material containing a photoinitiator, an organic solvent was added. In the photosensitive liquid, the viscosity of the solution (resin concentration 10% by weight) consisting of the dispersed resin and the organic solvent at 25 ° C.
The present invention relates to a photosensitive solution containing a colored image-forming material, wherein a combination of a dispersion resin and an organic solvent is selected so as to be in the range of 3.0 mPa · s to 12.0 mPa · s, and a photosensitive element using the same.

The present invention also relates to a photosensitive element having a support film and a layer containing a colored image forming material prepared by using a photosensitive solution containing the above-mentioned colored image forming material.

In the present invention, the colored image forming material is formed as a film on a substrate using the photosensitive liquid containing the colored image forming material or the photosensitive element described above, and actinic rays are imagewise irradiated. The present invention relates to a method for producing a color filter, wherein the steps of photo-curing the exposed portion and removing the unexposed portion by development are repeated for colored image forming materials of different colors to form pixels.

The present invention will be described in detail below. The dispersion resin having an acid value of 20 to 300 as the component (a) has a solution viscosity of 3.0 to 12 when combined with an organic solvent described later.
There is no particular limitation as long as it is within the range of 0 mPa · s, but for example, a carboxyl group-containing polymerizable monomer such as (meth) acrylic acid or itaconic acid and a polymerizable monomer such as (meth) acrylic acid ester or styrene. And a polyester resin, a resin having a photopolymerizable unsaturated bond (for example, a glycidyl methacrylate containing a high acid value carboxyl group-containing resin, a glycidyl group-containing unsaturated compound such as allyl glycidyl ether, allyl alcohol, 2- A resin obtained by reacting an unsaturated alcohol such as hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, a resin obtained by reacting a carboxyl group-containing resin having a hydroxyl group with a free isocyanate group-containing unsaturated compound, an epoxy resin and an unsaturated carboxylic acid Resin, conjugated by reacting polybasic acid anhydride with addition reaction product A preferable resin is a resin obtained by reacting a hydroxyl group-containing polymerizable monomer with an addition reaction product of a diene polymer or a conjugated diene copolymer and an unsaturated dicarboxylic acid anhydride).

Among them, the following general formula (I)

[Chemical 2] (In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom, a hydroxyl group, an alkyl group or an alkoxy group having 1 to 12 carbon atoms, and R ³ represents an alkyl group having 1 to 12 carbon atoms. , R ⁴ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a group having a photoreactive unsaturated bond which may have one hydroxyl group, and m and n are 1 ≦ m / n ≦ 5. The resin represented by the formula (1) is an integer of 1 or more selected so that the sensitivity can be increased. The basic resin of the dispersion resin represented by the general formula (I) is a copolymer of styrene or its derivative and a maleic acid monoalkyl ester.
At this time, if (anhydrous) maleic acid is used instead of maleic acid monoalkyl ester, the yield of the copolymer is low, which is not preferable.

Specifically, styrene such as styrene, α-methylstyrene, m- or p-methoxystyrene, p-hydroxystyrene, 2-methoxy-4-hydroxystyrene, 2-hydroxy-4-methylstyrene and the like or derivatives thereof. And 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-dodecyl maleate, etc. The copolymer with the maleic acid monoalkyl ester of is the basic skeleton. A resin having a ratio m / n of styrene or a derivative thereof and a maleic acid monoalkyl ester in the range of 1 to 5 is used.

To introduce a photoreactive unsaturated bond into the resin represented by the general formula (I), a copolymer of styrene or a derivative thereof and a maleic acid monoalkyl ester is added to allyl alcohol. , 2-butene-4-
Oar, furfuryl alcohol, oleyl alcohol,
It can be obtained by esterifying an unsaturated alcohol such as cinnamyl alcohol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and N-methylol acrylamide. Further, glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, α-ethyl glycidyl acrylate, crotonyl glycidyl ether, itaconic acid monoalkyl monoglycidyl ester and other compounds having an oxirane ring and one ethylenically unsaturated bond, respectively, It can be obtained by addition reaction with a copolymer of styrene or a derivative thereof and a maleic acid monoester.

At this time, styrene or its derivative is prepared by using a compound in which the above-mentioned unsaturated alcohol is monoesterified with (anhydrous) maleic acid or a compound having an oxirane ring and an ethylenically unsaturated bond is added. Copolymerization with is not preferable because unsaturated groups may react during the polymerization to cause gelation.

The thus obtained (a) acid value of 20 to
The unsaturated equivalent in the dispersion resin of 300 is 600 to 3,000.
The range of 0 is preferable, and the range of 800 to 2,000 is particularly preferable. If the unsaturated equivalent weight is less than 600, there is a possibility that the pigment will partially cure during dispersion with the pigment described below.
When it exceeds 3,000, the effect of improving the photosensitivity decreases. The unsaturated equivalent in the present invention means the molecular weight of the resin per unsaturated bond.

Further, it is necessary to leave a carboxyl group in the above-mentioned (a) dispersion resin having an acid value of 20 to 300, and the acid value thereof is 20 to 300, preferably 40 to 200, and particularly preferably 60 to 150. It is a range. When the acid value is less than 20, the alkali developability is deteriorated, and when it exceeds 300, the shape of the image pattern tends to be unclear, which is not preferable.

(A) The molecular weight of the dispersion resin having an acid value of 20 to 300 is preferably 1,500 to 30,000, and particularly,
More preferably, it is 4,000 to 15,000. If the molecular weight is less than 1,500, the dispersion stability of the pigment will be poor, and if it exceeds 30,000, the viscosity of the photosensitive solution will be high, and the coating property during spin coating will tend to be reduced.

These (a) dispersion resins having an acid value of 20 to 300 may be used alone or in combination of two or more.
The dispersion resin of the component (a) is 10 to 10 with respect to the total amount of the colored image forming material consisting of (a), (b), (c) and (d).
It is used in an amount of 85% by weight, preferably 20 to 60% by weight, particularly preferably 25 to 50% by weight. (A) When the ratio of the dispersing resin is less than 10% by weight, the dispersion stability of the pigment is lowered, and when it exceeds 85% by weight, the viscosity of the photosensitive solution becomes high and the coating property at the time of spin coating is lowered. Tend to do.

Next, the pigment as the component (b) will be described. There are inorganic pigments and organic pigments, but generally, organic pigments are used except for black carbon black or the like due to its rich color tone. As an organic pigment,
For example, azo, phthalocyanine, indigo, anthraquinone, perylene, quinacridone, methine
Examples include azomethine type and isoindolinone type.

When the colored image forming material of the present invention is applied to a color filter, each pigment system suitable for colored images such as red, green, blue and black is 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. As the red pigment system, for example, Pigment Red 9, 123, 15 with a color index name
5, 168, 177, 180, 217, 220, 224
Etc. As the yellow pigment type, for example, Pigment Yellow 20, 2 with a color index name
4, 83, 93, 109, 110, 117, 125, 1
39, 147, 154 and the like. These red and yellow pigments may be used as a mixture of two or more kinds. When the red pigment system and the yellow pigment system are mixed and 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 the green colored image, a single green pigment system may be used, or the above yellow pigment system may be mixed with the green pigment system for toning. As a green pigment system, for example,
The color index name is Pigment Green 7, 3
6, 37 and the like. These green and yellow pigments may be used as a mixture of two or more kinds. When the green pigment system and the yellow pigment system are mixed and used, the total amount of the yellow pigment system and the green pigment system is 1
It is preferable to use 50 parts by weight or less with respect to 00 parts by weight.

For a blue colored image, a single blue pigment system may be used, or a purple pigment system may be mixed with a blue pigment system for toning. As the blue pigment type, for example, with a color index name, Pigment Blue 15, 15: 3,
15: 4, 15: 6, 22, 60 and the like. Further, as the purple pigment system, for example, with a color index name, pigment violet 19, 23, 29, 37,
50 etc. are mentioned. These blue and purple pigments may be used as a mixture of two or more kinds. Also,
When the blue pigment system and the violet pigment system are mixed and used, it is preferable to use 50 parts by weight or less of the violet pigment system to 100 parts by weight of the total amount of the blue pigment system and the violet pigment system.

For the black colored image, for example, black pigments such as carbon black, titanium carbon, black iron and manganese dioxide are used. The pigment of the component (b) according to the present invention is 5 to 50% by weight, preferably 10 to 40% by weight based on the total amount of the colored image forming material consisting of (a), (b), (c) and (d). %, Particularly preferably 15 to 30% by weight. When the proportion of the pigment is less than 5% by weight, the color density of the image is too low, and when it exceeds 50% by weight, the light density tends to decrease.

Examples of the monomer having at least one photopolymerizable unsaturated bond as the component (c) in the present invention include, for example, methyl methacrylate, benzyl methacrylate, butoxyethyl methacrylate, butoxyethyl acrylate, butoxytriethylene glycol acrylate. , ECH-modified butyl acrylate (ECH means epichlorohydrin; the same shall apply hereinafter), dicyclopentanyl acrylate, EO-modified dicyclopentenyl acrylate (EO means ethylene oxide; also hereinafter), N, N-dimethylaminoethyl Methacrylate, ethyldiethylene glycol acrylate, 2-ethylhexyl acrylate, glycerol methacrylate, heptadecafluorodecyl acrylate, 2-hydroxyethyl methacrylate DOO, caprolactone-modified 2-
Hydroxyethyl acrylate, isobornyl acrylate, methoxydipropylene glycol acrylate,
Methoxylated cyclodecatriene acrylate, phenoxyhexaethylene glycol acrylate, EO modified phosphoric acid acrylate, caprolactone modified tetrahydrofurfuryl acrylate, EO modified bisphenol A diacrylate, ECH modified bisphenol A diacrylate, bisphenol A dimethacrylate, 1,4-butane Diol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol diacrylate, EO modified phosphoric acid diacrylate, ECH modified phthalic acid diacrylate, polyethylene glycol 400 diacrylate, polypropylene glycol 400 Dimethacrylate, tetraethylene glycol diacreyl , ECH modified 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, E
O-modified phosphoric acid triacrylate, EO-modified trimethylolpropane triacrylate, PO-modified trimethylolpropane triacrylate (PO means propylene oxide, the same shall apply hereinafter), tris (methacryloxyethyl) isocyanurate, pentaerythritol tetraacrylate, Examples thereof include dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate. These monomers are used alone or in combination of two or more.

The monomer of the component (c) in the present invention is
2 to 50% by weight, preferably 5 to 40% by weight, particularly preferably 10 to 30% by weight, based on the total amount of the colored image-forming material comprising the components (a), (b), (c) and (d). Used in the range of. If the proportion of the monomer is less than 2% by weight, the photosensitivity is too low, and if it exceeds 50% by weight,
The dispersion stability of the component (b) pigment tends to decrease.

Examples of the photoinitiator of the component (d) in the present invention include benzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, benzyl,
2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone,
2-Methyl-1- [4- (methylthio) phenyl] -2
-Morpholino-1-propane, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone,
2-ethylanthraquinone, 1,4-naphthoquinone,
9,10-phenanthraquinone, 1,2-benzanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2- (o-chlorophenyl)-
Examples include 4,5-diphenylimidazole dimer. These photoinitiators are used alone or in combination of two or more.

The photoinitiator of the component (d) in the present invention is
0.01 to 20% by weight, preferably 2 to 15% by weight, particularly preferably 5 to 10% by weight based on the total amount of the colored image-forming material comprising the components (a), (b), (c) and (d). Used in the range of wt%. If the proportion of the photoinitiator is less than 0.01% by weight, the photosensitivity is too low, and if it exceeds 20% by weight, the adhesion tends to be lowered.

The colored image forming material in the present invention includes
In addition to the essential components (a), (b), (c), and (d), a thermal polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, pyrogallol, and t-butylcatechol for suppressing dark reaction, and a substrate. To improve the adhesion of vinyl group, epoxy group, amino group, silane coupling agent having a mercapto group or the like isopropyl trimethacryloyl titanate, diisopropyl isostearoyl-4-aminobenzoyl titanate titanate coupling agent, Fluorine-based, silicon-based, hydrocarbon-based surfactants and the like for improving the smoothness of the film, and various additives such as an ultraviolet absorber and an antioxidant can be appropriately used as necessary.

In addition, a resin that does not have a carboxyl group or has a acid group of less than 20 and serves as an ordinary binder, such as an acrylic resin, an epoxy resin, a urethane resin, and a melamine resin, is dispersed in a pigment. Not limited to this, 50 parts by weight or less may be used per 100 parts by weight of the dispersion resin of the component (a) according to the present invention. If it exceeds 50 parts by weight, the dispersion stability and photosensitivity of the pigment are lowered, which is not preferable.

The colored image-forming material in the present invention is made into a photosensitive solution by adding an appropriate organic solvent, and the photosensitive solution is directly coated on the substrate, or once coated on a support and then laminated on the substrate. It is formed as a film on the surface. Then, exposure and development are performed to obtain a desired image pattern.

The method of using the colored image forming material as a photosensitive liquid in the present invention will be described below. First, the dispersion resin of the component (a) and the pigment of the component (b) are mixed with an organic solvent, and this mixture is subjected to various dispersion and kneading using an ultrasonic disperser, a three-roll mill, a ball mill, a sand mill, a bead mill, a homogenizer, a kneader, etc. It can be performed using the device. The organic solvent that can be used at this time is not particularly limited, and examples thereof include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol dibutyl ether. Diethylene glycol monoalkyl ether such as diethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, etc. Ether acetate, ethylene glycol, propylene glycol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dialkyl ethers of ethylene glycol such as ethylene glycol dipropyl ether, beta-lactone, gamma
-Lactones such as lactone and δ-lactone, and others such as methyl methoxy propionate, ethyl methoxy propionate, ethyl ethoxy propionate, methyl ethoxy propionate, methyl ethyl ketone, tetrahydrofuran, dioxane, toluene, N-methyl pyrrolidone, etc. Can be mentioned. These are used alone or in combination of two or more.

The features of the present invention will now be described. The feature of the present invention resides in optimizing the combination of the above-mentioned component (a) dispersion resin and the above-mentioned organic solvent.
It is to remarkably enhance the stability of the photosensitive solution containing a pigment.

For the optimum combination of the dispersing resin and the organic solvent, the parameter of the viscosity of the solution found for the first time by the present invention is used. That is, a dispersion resin (when two or more kinds of dispersion resins are used in the photosensitive solution, a mixed resin having the same ratio as the ratio of each dispersion resin used) and an organic solvent (when two or more kinds of organic solvents are used in the photosensitive solution, The viscosity of a solution (resin concentration 10% by weight) consisting of only a mixed solvent having the same ratio as the ratio of each organic solvent used is 3.0 mP at 25 ° C.
a · s to 12.0 mPa · s, preferably 5 mPa · s to 10 m
The essence of the present invention is to select the dispersion resin and the organic solvent so as to be in the range of Pa · s, more preferably 6 mPa · s to 8 mPa · s. As a result, the stability of the photosensitive liquid containing the pigment can be remarkably enhanced as compared with the conventional one. Therefore,
As the above-mentioned dispersion resin and organic solvent, when the dispersion resin is specified, an organic solvent which falls within the above viscosity range is selected, and when the organic solvent is specified, a dispersion resin which falls within the above viscosity range is selected. In that way, the combination is optimized. Solution consisting of dispersed resin and organic solvent only (resin concentration 1
0 wt%) has a viscosity of 3.0 mPa · s at 25 ° C.
A photosensitive solution using a dispersion resin and an organic solvent in a combination that is out of the range of 12.0 mPa · s is not preferable because the stability of the photosensitive solution containing the pigment, which is the object of the present invention, is significantly reduced.

In dispersing the pigment, anionic pigment dispersants such as polycarboxylic acid type polymer activators and polysulfonic acid type polymer activators, nonionic pigment dispersants such as polyoxyethylene and polyoxypropylene block polymers, etc. Introducing a substituent such as a carboxyl group, a sulfonic acid group, a sulfonic acid group, a carboxylic acid amide group, a sulfonic acid amide group, or a hydroxyl group into a pigment dispersant or an organic dye such as anthraquinone type, perylene type, phthalocyanine type, quinacridone type Addition of a derivative of an organic dye is preferable because the dispersibility and dispersion stability of the pigment are further improved.

Derivatives of these pigment dispersants and organic dyes are
It is preferable to use 50 parts by weight or less with respect to 100 parts by weight of the pigment. Further, the components (c) and (d) may be added when the pigment is dispersed, or the components (c) and (d) may be added after the pigment is dispersed.

The total amount of the dispersion resin as the component (a) may be used together with the pigment during dispersion, or a part of the dispersion resin may be added after dispersion. However, it is preferable to use at least 20 parts by weight or more of the dispersion resin at the time of dispersion with respect to 100 parts by weight of the pigment. If it is less than 20 parts by weight, the dispersion stability of the pigment is lowered. Similarly, the total amount of the organic solvent may be used when the pigment is dispersed, or a part of the organic solvent may be added after the dispersion. However, the organic solvent is 100% of the total amount of pigment and dispersion resin at the time of dispersion.
It is preferable to use at least 100 parts by weight or more when dispersed, with respect to parts by weight. If it is less than 100 parts by weight, the viscosity at the time of dispersion is too high, and it may be difficult to disperse particularly when it is dispersed by a ball mill, a sand mill, a bead mill or the like.

The organic solvent is (a) in the photosensitive solution,
The total solid content including the components (b), (c) and (d) is 5 to 4
It is preferably used so as to be in the range of 0% by weight.

When the photosensitive solution thus obtained is directly coated on the substrate, for example, roll coater coating, spin coater coating, spray coating, whaler coating, dip coater coating, curtain flow coater coating, wire coating It is performed by bar coater coating, gravure coater coating, air knife coater coating, or the like.

The substrate used in this case is selected depending on the application, but for example, transparent glass substrates 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 synthetic resin sheets, films or substrates, metal substrates such as aluminum plates, copper plates, nickel plates, and stainless steel plates, other ceramic substrates, semiconductor substrates having photoelectric conversion elements, and the like.

After coating, usually at a temperature of 50 to 130 ° C., 1
The film can be obtained by drying for ~ 30 minutes.

On the other hand, it is possible to form a film on the surface of the substrate by directly applying it to the support and then laminating it on the substrate, instead of directly applying it to the substrate. As a method of applying the photosensitive solution to the support, knife coater coating, gravure coater coating, roll coater coating, spray coater coating and the like can be used. Examples of the support used at this time include films such as polyester film, polyimide film, polyamideimide film, polypropylene film and polystyrene film. After application, as before, as usual,
The film can be obtained by drying at a temperature of 50 to 130 ° C. for 1 to 30 minutes. Further, it is desirable to laminate a peelable cover film on the surface of the film for the purpose of preventing dust from adhering to the surface of the film.

Examples of the peelable cover film include polyethylene film, Teflon film, polypropylene film, surface-treated paper, and the like. When peeling the cover film, the film and the cover are more adhesive than the adhesive force between the film and the support. Any adhesive having a smaller adhesive force with the film may be used.

As a method for laminating the photosensitive element thus obtained on a substrate, the substrate and the film containing the colored image-forming material of the present invention are superposed on each other.
It is preferable to perform thermocompression bonding. In this case, the atmosphere may be atmospheric pressure or reduced pressure.

The thickness of the film containing the colored image-forming material of the present invention formed on the surface of the substrate in this manner is appropriately determined depending on the application, but is usually used in the range of 0.1 to 300 μm. When used for a color filter, 0.2-
It is often used in the range of 5 μm.

Next, a method of forming an image pattern will be described. The film on the substrate obtained by the above method is imagewise irradiated with an actinic ray to cure the film in the exposed portion. At this time, when the film is formed using the photosensitive element,
The exposure may be performed from above with the support attached, or the support may be peeled off and then exposed. Even when a film is formed by directly coating the substrate with a photosensitive solution, an oxygen shielding film such as polyvinyl alcohol having a thickness of 0.5 to 5 is formed on the surface of the film.
It may be formed with a thickness of 30 μm and exposed from above.

As the light source of the actinic ray, for example, a carbon arc lamp, an ultrahigh 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. Actinic rays are irradiated in an image form by pattern exposure using a photomask using these light sources or direct drawing by scanning.

Subsequently, in the developing step, that is, inorganic alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium metasilicate, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, triethylamine, n-butylamine. The unexposed portion can be removed by spraying an aqueous solution containing an organic base or salt such as the above or immersing in an aqueous solution to obtain a colored image pattern of the cured film corresponding to the image. At this time, when exposure is carried out with the support attached, the support is peeled off and then development is carried out. After development, the colored image pattern is post-exposed to a light amount of 0.5 to 5 J / cm ² using a high pressure mercury lamp or the like, or 60 to 200
Post-heating at a temperature of 1 ° C. for 1 to 60 minutes is preferable because the image pattern becomes stronger.

As an example of a method for producing a color filter used for a liquid crystal display device, the above-mentioned method is repeated by directly or indirectly using a photosensitive solution comprising a colored image forming material of the present invention and an organic solvent on a glass substrate. By doing
After forming colored pixels of red, green, blue, etc., a method of forming a black colored image as a black matrix in the gaps between the colored pixels, or forming a black matrix by vapor deposition of chromium or a black colored image first. Later, as above,
There is a method of forming a color filter by forming colored pixels of red, green, blue and the like.

[0048]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto. Example 1 45 g of the resin represented by the general formula (I) shown in Table 1 as the component (a), Pigment Red 177, 23 g and Pigment Yellow 139, 6 g by the color index name as the component (b) were methyl methoxyproton. Peonate 1
A mixed solvent of 50 g and 100 g of N-methylpyrrolidone was added, and this was dispersed for 2 hours using a bead mill. In 200 g of this dispersion, 20 g of tetraethylene glycol diacrylate as component (c), 5 g of pentaerythritol triacrylate, 6 g of benzophenone as component (d), 2 g of N, N'-tetraethyl-4,4'-diaminobenzophenone and 230 g of methyl methoxypropionate was added and mixed to obtain a photosensitive solution containing the colored image forming material of the present invention. This photosensitive solution was applied onto a glass substrate (Corning Co., Ltd., trade name 7059) by spin coating and further dried at 80 ° C. for 5 minutes to give a film thickness of 2.0.
A μm film was formed. The obtained film was imagewise exposed to 80 mJ / cm ² through a negative pressure mask with an ultra-high pressure mercury lamp, and then developed with an aqueous solution containing 6% by weight of triethanolamine. Table 2 shows the evaluation results of sensitivity and pattern shape.

Example 2 As component (a), acrylic acid / methyl methacrylate / butyl acrylate (= 30/40/30 wt% ratio)
Copolymer (molecular weight 36,000) with glycidylmethacrylate added, acid value 78, unsaturated equivalent weight 720, 65 g of resin, (b) component as color index name,
Pigment Green 36, 19 g and Pigment Yellow 139, 4 g were mixed with ethyl ethoxypropionate 230.
g and 30 g of methyl ethyl ketone were added to the mixed solvent, and this was dispersed for 2 hours using a bead mill. This dispersion 21
0 g, as component (c), trimethylolpropane triacrylate 28 g, polyethylene glycol 400
5 g of diacrylate, 6 g of benzophenone, 2 g of N, N'-tetraethyl-4,4'-diaminobenzophenone and 130 g of ethylethoxypropionate as component (d) were added and mixed to contain the colored image forming material of the present invention. A photosensitive solution was obtained. This photosensitive solution was applied onto a glass substrate and dried in the same manner as in Example 1 to form a film having a thickness of 2.0 μm. The obtained film was exposed and developed under the same method and conditions as in Example 1, and Table 2 shows the evaluation results of the photosensitivity and pattern shape of the obtained green image pattern.

Example 3 As the component (a), 50 g of the resin represented by the general formula (I) shown in Table 1, and as the component (b), Pigment Blue 15-6, 21 g and Pigment Violet 23 under the color index name. 3 g was added to a mixed solvent of 200 g of methyl methoxypropionate and 40 g of dioxane, and this was dispersed for 2 hours using a bead mill. This dispersion 2
To (00 g), 20 g of ECH-modified 1,6-hexanediacrylate as component (c), 10 g of dipentaerythritol pentaacrylate, and 6 g of benzophenone as component (d), N, N'-tetraethyl-4,4'-diaminobenzophenone. A mixed solvent of 2 g and 150 g of ethyl ethoxy propionate and 40 g of methyl ethyl ketone was added and mixed to obtain a photosensitive solution containing the colored image forming material of the present invention. This photosensitive solution was applied onto a glass substrate and dried in the same manner as in Example 1 to form a film having a thickness of 2.0 μm. The obtained film was exposed and developed under the same methods and conditions as in Example 1, and Table 2 shows the evaluation results of the photosensitivity and the pattern shape of the obtained green image pattern.

[0051]

[Table 1]

Example 4 The photosensitive solution obtained in Example 1 was applied onto a polyethylene terephthalate film having a thickness of 6 μm by a gravure coating method and dried at 100 ° C. for 2 minutes to give a film thickness of 2.0 μm.
The film of No. 2 was formed and covered with a polyethylene film having a thickness of 40 μm to obtain a photosensitive element.

After removing the polyethylene film from the obtained photosensitive element, it was laminated on the same glass substrate as used in Example 1. The laminating conditions are a glass substrate temperature of 40 ° C. and a laminating roll temperature of 11
It was carried out at 0 ° C., laminating pressure 3.5 kgf / cm ² , and laminating speed 1.5 m / min.

Next, through a negative mask, imagewise exposure of 40 mJ / cm ² was carried out from the polyethylene terephthalate film with an ultra-high pressure mercury lamp, and then the polyethylene terephthalate film was peeled off, followed by the same method and conditions as in Example 1. It was developed.

Example 5 A red image pattern was formed on the glass substrate used in Example 1 on which a black matrix was formed by vapor deposition of chromium by the same method and conditions as in Example 1, and then at 150 ° C. for 1 hour.
After heating for 0 minutes. Then, using that substrate,
By the same method and conditions as in Example 2, a green image pattern was formed next to the red image pattern. After that, 150 ℃
After heating for 10 minutes. Next, using the substrate, a blue image pattern was formed next to the green image pattern by the same method and conditions as in Example 3. Then 15
Post heating was carried out at 0 ° C. for 10 minutes. As described above, a color filter in which one pixel is arranged in a mosaic pattern of three colors of red, green and blue of 30 μm × 100 μm was produced.

Example 6 A red image pattern was formed on the glass substrate used in Example 1 in which a black matrix was formed by vapor deposition of chromium by the same method and conditions as in Example 4, and then at 150 ° C. for 1 hour.
After heating for 0 minutes. Next, using the photosensitive liquid obtained in Example 2, a photosensitive element was produced by the same method and conditions as in Example 4. This photosensitive element was laminated on the above-mentioned substrate by the same method and conditions as in Example 4, further exposed to light, and after peeling off the polyethylene terephthalate film, development was carried out by the same method and condition as in Example 2. A green image pattern was formed next to the red image pattern. Then, after-heating was performed at 150 ° C. for 10 minutes. Then, using the photosensitive liquid obtained in Example 3,
A photosensitive element was produced by the same method and conditions as in Example 4. This photosensitive element was laminated on the above-mentioned substrate by the same method and conditions as in Example 4, further exposed to light, and after peeling off the polyethylene terephthalate film, development was carried out by the same method and condition as in Example 3. A blue image pattern was formed next to the green image pattern.
Then, after-heating was performed at 150 ° C. for 10 minutes. As described above, a color filter in which one pixel is arranged in a mosaic pattern of three colors of red, green and blue of 30 μm × 100 μm was produced.

Comparative Example 1 In the photosensitive liquid composition of Example 1, the organic solvent used for dispersing the pigment was 150 g of methyl methoxypropionate and N-.
Ethyl cellosolve was used instead of the mixed solvent of 100 g of methylpyrrolidone, and dipropylene glycol monobutyl ether was used instead of methyl methoxypropionate after the dispersion, and the same composition, method and conditions as in Example 1 were used. A photosensitive solution was obtained. Using this photosensitive solution, a film having a thickness of 2.0 μm was formed under the same method and conditions as in Example 1, further exposed and developed, and the results are shown in Table 2.

Comparative Example 2 In the photosensitive liquid composition of Example 2, 260 g of methyl ethyl ketone alone was used instead of the mixed solvent of 230 g of ethyl ethoxy propionate and 30 g of methyl ethyl ketone as the organic solvent used for dispersing the pigment, and the organic solvent added after dispersion was A photosensitive solution was obtained in the same composition, method and conditions as in Example 2 except that methyl ethyl ketone was added instead of ethyl ethoxy propionate. Using this photosensitive solution, a film having a thickness of 2.0 μm was formed under the same method and conditions as in Example 1, further exposed and developed, and the results are shown in Table 2.

Comparative Example 3 In the photosensitive liquid composition of Example 3, the dispersion resin was methacrylic acid / methyl methacrylate / butyl acrylate (= 1).
2/50/38 wt% ratio) copolymer (molecular weight 4600
A photosensitive solution was obtained in the same composition, method and conditions as in Example 3 except that the acid value was 0 and the acid value was 78).

Using this photosensitive solution, a film having a thickness of 2.0 μm was formed by the same method and conditions as in Example 1, and further 300
Exposure and development were carried out at mJ / cm ² , and the results are shown in Table 2. Further, the viscosity of the solution (solid content 10% by weight) composed of the dispersion resin and the organic solvent used in Examples 1, 2, and 3 and Comparative Examples 1, 2, and 3 was measured at 25 ° C. using an E-type viscometer. It was measured. The results, the dispersion stability of the photosensitive solution, and the appearance of the obtained film were evaluated, and the results are also shown in Table 2.

[0061]

[Table 2] From Table 2, the viscosity of the resin solution is 3.0 mPa · s-12.0 m.
In the case of the photosensitive liquids (comparative examples 1, 2 and 3) in which the dispersion resin and the organic solvent which are out of the range of Pa · s are combined, the dispersion stability is remarkably low, and the films prepared using these photosensitive liquids are It can be seen that the appearance and photosensitivity are also inferior. On the other hand, in the photosensitive liquids (Examples 1, 2 and 3) in which the dispersion resin and the organic solvent are combined such that the viscosity of the resin solution is in the range of 3.0 mPa · s to 12.0 mPa · s, the dispersibility is Even after 50 days, it did not change at all and remained stable. Along with that, the film produced using these photosensitive solutions had a good appearance and a uniform film thickness. Further, the photosensitivity was higher than that of Comparative Examples 1, 2 and 3, and a high resolution image pattern was obtained. Furthermore, when the photosensitive element shown in Example 4 is used, the photosensitivity is further improved as compared with the cases of Examples 1, 2 and 3, and even when the exposure amount is 40 mJ / cm ² , The number of steps and the resolution are the same as in the case of 1. As described above, the color filters (Examples 5 and 6) produced by using the photosensitive liquid having high sensitivity and good dispersion stability, which are unprecedented in the past, are excellent in optical characteristics with depolarization of 500 or more, and image display is excellent. It was confirmed to be effective as a device.

[0062]

INDUSTRIAL APPLICABILITY The present invention uses a dispersion resin and an organic solvent selected so that the viscosity of a solution consisting of the dispersion resin and the organic solvent falls within a specific range. The dispersion stability of the photosensitive liquid can be remarkably improved. The present invention also provides a photosensitive element using such a photosensitive solution, and further a color filter, and a color filter produced using such a photosensitive solution or a photosensitive element has excellent optical characteristics. It can be used as an image display device.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Koji Yamazaki 4-13-1, Higashimachi, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Ibaraki Research Institute (72) Satoshi Akahori, 4-13-1, Higashimachi, Ibaraki Prefecture Hitachi Chemical Co., Ltd.Ibaraki Research Institute (72) Inventor Tsutomu Sato 14 Goi Minamikaigan, Ichihara, Chiba Hitachi Chemical Co., Ltd. Goi Factory (72) Inventor Yoichi Kimura 14 Goi Minamikaigan, Ichihara, Chiba Hitachi Chemical Co., Ltd. Goi factory (56) Reference JP-A-5-224417 (JP, A) JP-A-5-295057 (JP, A) JP-A-2-4201 (JP, A) JP-A 5-61196 (JP, A) JP-A-54-137085 (JP, A) JP-A-62-212603 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03F 7/00 -7/42

Claims (7)

(57) [Claims] 1. A dispersion resin having an acid value of 20 to 300,
In a photosensitive solution obtained by adding an organic solvent to a colored image-forming material containing (b) a pigment, (c) a monomer having one or more photopolymerizable unsaturated bonds in the molecule, and (d) a photoinitiator,
The viscosity of the solution (resin concentration 10% by weight) consisting of the dispersed resin and the organic solvent is 3.0 mPa · s at 25 ° C.
A photosensitive liquid containing a colored image forming material, characterized in that a combination of a dispersion resin and an organic solvent is selected so as to be in a range of 12.0 mPa · s. 2. The (a) dispersion resin having an acid value of 20 to 300 comprises:
The photosensitive liquid containing the colored image-forming material according to claim 1, which has an unsaturated equivalent of 600 to 3,000. 3. A dispersion resin (a) having an acid value of 20 to 300 comprises:
The following general formula (I): (In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom, a hydroxyl group, an alkyl group or an alkoxy group having 1 to 12 carbon atoms, and R ³ represents an alkyl group having 1 to 12 carbon atoms. , R ⁴ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a group having a photopolymerizable unsaturated bond which may have one hydroxyl group, and m and n are 1 ≦ m / n ≦ 5. A photosensitive liquid containing the colored image-forming material according to claim 1 or 2, which is a resin represented by the formula (1) is an integer of 1 or more. 4. A photosensitive element having a support film and a layer containing a colored image-forming material produced by using the photosensitive solution according to claim 1. Description: 5. The photosensitive element according to claim 4, further comprising a peelable cover film laminated on a layer containing a colored image forming material. 6. A colored image forming material is formed as a film on a substrate using the photosensitive solution according to claim 1, 2 or 3 or the photosensitive element according to claim 4 or 5, and actinic rays are imaged. A method for producing a color filter, wherein the steps of irradiating, photo-curing the exposed portion and removing the unexposed portion by development are repeated for colored image forming materials of different colors to form pixels. 7. The method for manufacturing a color filter according to claim 6, wherein the pixels according to claim 6 are red, green and blue pixels.