JPH07244377A - Colored image forming material, production of photosensitive solution, photosensitive element and color filter using same and color filter - Google Patents

Abstract

PURPOSE:To obtain a colored image forming material having high adhesion to a substrate and high photosensitivity. CONSTITUTION:This colored image forming material contains a resin (a) having an acid value of 20-300 and a wt. average mol.wt. of 1,500-200,000, a pigment (b), a monomer (c) having two or more photopolymerizable unsatd. bonds in one molecule, a photopolymn. initiator (d) and a macromonomer (e) having one polymerizable unsatd. group at one terminal of a dimethylsiloxane polymer. The objective photosensitive soln., photosensitive element and color filter are produced using this colored image forming material.

Description

Detailed Description of the Invention

[0001]

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

On the other hand, when forming a pixel on a substrate, there is a problem that the pixel is peeled off during development because the adhesion of the photosensitive film containing the pigment to the substrate is low. Therefore, conventionally, a silane coupling agent has been added to the composition to improve the adhesiveness, but the addition of the silane coupling agent reduces the dispersibility of the pigment, and the improvement of the adhesiveness is also unsatisfactory. Was enough. Further, it has been known that a general silane coupling agent has low stability and loses its effect particularly when exposed to high humidity, so that an image pattern cannot be obtained.

[0005]

DISCLOSURE OF THE INVENTION The present invention remarkably improves the adhesion to a substrate, which is a problem of a light-sensitive material in which a pigment is dispersed, and is not affected by the environment at the time of exposure and has a good photosensitivity. The present invention provides a colored image-forming material having, a photosensitive solution using the same, a photosensitive element, a method for producing a color filter, and a color filter.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that by using a special macromonomer,
The present inventors have found that the adhesion of the photosensitive material to the substrate can be improved without lowering the dispersibility of the pigment, and that the effect can be maintained for a long period of time, leading to the present invention.

That is, the present invention provides (a) an acid value of 20 to 3
00, a resin having a weight average molecular weight of 1,500 to 200,000, (b) a pigment, (c) a monomer containing two or more photopolymerizable unsaturated bonds in the molecule, (d) a photoinitiator and (e) ) A colored image-forming material containing a macromonomer having one polymerizable unsaturated group at one end of a polymer of dimethylsiloxane, a photosensitive solution containing the colored image-forming material, a layer containing the colored image-forming material, and a support. A photosensitive element having a body film.

Further, the present invention comprises the steps of forming a film of the colored image forming material on a substrate, irradiating an actinic ray imagewise, photocuring the exposed portion, and removing the unexposed portion by development.
The present invention relates to a method for producing a color filter, which is characterized in that pixels are formed by repeatedly performing the colored image forming materials of different colors, and a color filter produced by the method.

The present invention will be described in detail below. (A) component having an acid value of 20 to 300 and a molecular weight of 1,500 to 20
There are no particular restrictions on the 50,000 resin as long as the acid value and molecular weight are within this range. For example, a carboxyl group-containing polymerizable monomer such as (meth) acrylic acid or itaconic acid and a (meth) acrylic acid ester. A typical example thereof is a copolymer with a polymerizable monomer such as styrene.
The resin as the component (a) may have a photopolymerizable unsaturated bond. Examples of such a resin include a high acid value carboxyl group-containing resin, glycidyl methacrylate,
Glycidyl group-containing unsaturated compounds such as allyl glycidyl ether, resins reacted with unsaturated alcohols such as allyl alcohol, 2-hydroxyacrylate, and 2-hydroxymethacrylate, carboxyl group-containing resins having hydroxyl groups, and free isocyanate group-containing unsaturated compounds Resin reacted with epoxy resin, addition reaction product of polybasic acid anhydride with addition reaction product of epoxy resin and unsaturated carboxylic acid, addition of conjugated diene polymer or conjugated diene copolymer with unsaturated dicarboxylic acid anhydride A typical resin is a resin obtained by reacting a reaction product with a hydroxyl group-containing polymerizable monomer.

The acid value of the resin of component (a) is 20 to 300,
Preferably 40-200, more preferably 60-150
The range is. When the acid value is less than 20, the alkali developability is lowered, and when it exceeds 300, the shape of the image pattern becomes unclear.

The molecular weight of the resin of component (a) is 1,5
00-200,000, preferably 5,000-10
10,000, more preferably 10,000 to 500,000
The range is 00. When the molecular weight is less than 1,500, the dispersion stability of the pigment becomes poor, and when it exceeds 200,000, the viscosity of the photosensitive solution becomes high and the coating property at the time of spin coating deteriorates.

The amount of the resin as the component (a) used is (a),
It is preferably 10 to 85% by weight based on the total amount of the components (b), (c), (d) and (e), and 20 to 6
More preferably 0% by weight, 25 to 50% by weight
Is particularly preferable. If the amount used is less than 10% by weight, the dispersion stability of the pigment tends to decrease, and
When the content is more than 5% by weight, the viscosity of the photosensitive solution becomes high, and the coating property during spin coating tends to deteriorate.

Next, the pigment as the component (b) will be described. There are inorganic pigments and organic pigments, and black carbon black (inorganic pigment) and organic pigments are preferable in terms of rich color tone. Examples of the organic pigment include azo type, phthalocyanine type, indigo type, anthraquinone type, perylene type, quinacridone type, methine / azomethine type, isoindolinone type and the like.

When the colored image forming material of the present invention is applied to a color filter, pigment systems suitable for colored images such as red, green, blue and black are used. For the red colored image, a single red pigment system may be used, or a yellow pigment system may be mixed with the red pigment system for toning. Examples of red pigments include Pigment Red 9, 123, 155, 168, 177, and 18 under the color index name.
0, 217, 220, 224 and the like. As a yellow pigment type, for example, with a color index name,
Pigment Yellow 20, 24, 83, 93, 109, 1
10, 117, 125, 139, 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. Examples of green pigments include Pigment Green 7 with a color index name,
36, 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 system, for example, Pigment Blue 15, 15:
3, 15: 4, 15: 6, 22, 60 and the like.
Further, as the purple pigment system, for example, Pigment Violet 19, 23, 29, 3 and 3 by the color index name
7, 50 and the like. These blue and purple pigments may be used as a mixture of two or more kinds.
When the blue pigment system and the violet pigment system are mixed and used, the violet pigment system is 100 in total amount of the blue pigment system and the violet pigment system.
It is preferable to use 50 parts by weight or less with respect to parts by weight. For a black colored image, for example, carbon black,
Black pigments such as titanium carbon, black iron and manganese dioxide are used.

The amount of the component (b) pigment used is (a),
The total amount of the components (b), (c), (d) and (e) is preferably 5 to 50% by weight, and 10 to 40% by weight.
It is more preferable to set it as a weight%, and it is especially preferable to set it as 15 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 50% by weight, the photosensitivity tends to decrease.

Examples of the monomer (c) having two or more photopolymerizable unsaturated bonds in the molecule include, for example, EO-modified bisphenol A diacrylate (here, EO means ethylene oxide, and the same applies hereinafter), ECH-modified bisphenol A diacrylate (where ECH means epichlorohydrin; the same applies below), bisphenol A dimethacrylate, 1,4-butanediol 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 40
0 diacrylate, polypropylene glycol 400 dimethacrylate, tetraethylene glycol diacrylate, ECH modified 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, EO modified phosphoric acid triacrylate, EO modified trimethylolpropane Triacrylate, PO-modified trimethylolpropane triacrylate (where PO means propylene oxide, the same applies below), tris (methacryloxyethyl)
Isocyanurate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate,
Examples include dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate. These monomers may be used alone or in combination of two or more.

The monomer of the component (c) is (a),
The total amount of components (b), (c), (d) and (e) is preferably 2 to 50% by weight, more preferably 5 to 40% by weight, and 10 to 30% by weight. Is particularly preferable. If the proportion of the monomer is less than 2% by weight, the photosensitivity tends to be low, and if it exceeds 50% by weight, the dispersion stability of the pigment tends to decrease.

Examples of the photoinitiator as the component (d) include benzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, benzyl and 2,2-di Ethoxyacetophenone, 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
Examples thereof include-(o-chlorophenyl) -4,5-diphenylimidazole dimer. These photoinitiators may be used alone or in combination of two or more.

The amount of the (d) component photoinitiator used is
The amount is preferably 0.01 to 20% by weight, more preferably 2 to 15% by weight, based on the total amount of the components (a), (b), (c), (d) and (e). , 5 to 1
It is particularly preferable to set it to 0% by weight. This usage is 0.
If it is less than 01% by weight, the photosensitivity tends to be low, and if it exceeds 20% by weight, the adhesion tends to be lowered.

As the macromonomer having one polymerizable unsaturated group at one end of the dimethylsiloxane polymer as the component (e), for example, SILAPLANE FM07.
21, SILAPLANE FM0725, SILAP
LANE FM0711, SILAPLANE FM0
701 (above, product name of Nitrogen Co., Ltd.) and the like. These macromonomers may be used alone or in combination of two or more.

The number average molecular weight of the macromonomer as the component (e) is preferably in the range of 1,500 to 200,000, more preferably in the range of 3,000 to 50,000. When the number average molecular weight is less than 1,500,
The effect of improving the adhesion tends to be insufficient, and 2
If it exceeds 0,000, the compatibility with the resin of component (a) tends to decrease.

The amount of the macromonomer used as the component (e) is
It is preferably 0.2 to 20% by weight based on the total amount of the components (a), (b), (c), (d) and (e),
More preferably, it is 0.5 to 15% by weight.
It is particularly preferable to set it to 0 to 10% by weight. If the amount used is less than 0.2% by weight, the effect of improving the adhesion tends to be insufficient, and if it exceeds 20% by weight (a).
The compatibility of the components with the resin tends to decrease.

In the colored image-forming material of the present invention, in addition to the essential components (a), (b), (c), (d) and (e), hydroquinone and hydroquinone for suppressing the dark reaction. A variety of thermal polymerization inhibitors such as monomethyl ether, pyrogallol, t-butyl catechol, fluorine-based, silicon-based and hydrocarbon-based surfactants for improving the smoothness of the film, UV absorbers, antioxidants, etc. Additives can be used as needed.

The colored image-forming material of the present invention is prepared by adding a suitable organic solvent to form a photosensitive solution, which 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.

Next, a method of using the colored image forming material of the present invention as a photosensitive liquid will be described below. First, it is necessary to disperse the component (b) pigment. This method is usually
The resin and the pigment as the component (a) can be mixed with an organic solvent, and the mixture can be obtained by using a dispersing / kneading device such as an ultrasonic disperser, a three-roll mill, a ball mill, a sand mill, a bead mill, a homogenizer, and a kneader.

The organic solvent used at this time is not particularly limited, and examples thereof include ketone solvents, cellosolve solvents, alcohol solvents, aromatic solvents and the like. Specifically, acetone, methyl ethyl ketone, cyclohexanone, methyl cellosolve, ethyl cellosolve, butyro cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyro cellosolve acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol dimethyl ether, Diethylene glycol ethyl ether, triethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, 3-methyl-3
-Methoxybutanol, 3-methyl-3-methoxybutyl acetate, N-methyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, tetrahydrofuran, dioxane, benzene Organic solvents such as toluene, xylene, and ethyl acetate. These are used alone or in combination of two or more.

At this time, a polycarboxylic acid type polymer activator,
Anionic pigment dispersants such as polysulfonic acid type polymer activators, pigment dispersants such as nonionic pigment dispersants such as polyoxyethylene / polyoxypropylene block polymers, anthraquinone type, perylene type, phthalocyanine type, quinacridone type, etc. Addition of a carboxyl group, a sulfonic acid group, a sulfonate group, a carboxylic acid amide group, a sulfonic acid amide group, or a derivative of an organic dye having a substituent such as a hydroxyl group to an organic dye may improve the dispersibility or dispersion stability of the pigment. It is good and preferable.

These pigment dispersants and organic dye derivatives 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), (d) and (e) may be added at the time of dispersing the pigment, and (c),
You may add (d) and (e) component. The entire amount of the resin as the component (a) may be used together with the pigment during the dispersion, or a part of the resin may be added after the dispersion. However, the resin is pigment 10.
It is preferable to use 20 parts by weight or more when dispersed, with respect to 0 parts by weight. If it is less than 20 parts by weight, the dispersion stability of the pigment tends to decrease.

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, it is preferable to use 100 parts by weight or more of the organic solvent at the time of dispersion with respect to 100 parts by weight of the total amount of the pigment and the resin at the time of dispersion. If 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,
It is preferably used so that the total solid content including the components (b), (c), (d) and (e) is in the range of 5 to 40% by weight. Then, when the photosensitive solution thus obtained is directly applied to the substrate, for example, roll coater coating, spin coater coating, spray coating, whaler coating, dip coater coating, curtain flow coater coating, wire bar coater coating , Gravure coater coating, air knife coater coating and the like. The substrate used in this case is selected depending on the application, but for example, transparent glass substrate such as white plate glass, blue plate glass, silica-coated blue plate glass, synthetic resin such as polyester resin, polycarbonate resin, acrylic resin, vinyl chloride resin, etc. Examples thereof include a sheet, a film or a substrate, a metal substrate such as an aluminum plate, a copper plate, a nickel plate, and a stainless plate, a ceramic substrate, a semiconductor substrate having a photoelectric conversion element, and the like. After coating, a film can be obtained by usually drying at a temperature of 50 to 130 ° C. for 1 to 30 minutes.

On the other hand, a layer containing a colored image-forming material is coated and dried once on a support without directly coating the photosensitive solution on the substrate (the thickness of this layer is usually 0.1 to 300 μm, preferably 0). 2 to 30 μm, more preferably 0.2 to 5 μm
It is also possible to form a colored image forming material film on the substrate by, for example, forming a photosensitive element and laminating the photosensitive element on 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 coating, a film can be obtained by drying at a temperature of 50 to 130 ° C. for 1 to 30 minutes as described above. Further, for the purpose of preventing dust from adhering to the surface of the layer, it is desirable to laminate a peelable cover film on the surface of the layer.

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 used rather 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, it is preferable to heat and press-bond while superposing the substrate and the layer containing the colored image-forming material of the present invention. 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 thus formed on the surface of the substrate is appropriately determined depending on the application, but is usually in the range of 0.1 to 300 μm. When used for a color filter, it is usually used in the range of 0.2 to 5 μm.

Next, a method for 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 applying a photosensitive solution to a substrate, an oxygen shielding film such as polyvinyl alcohol is added to the surface of the film in an amount of 0.5 to 30.
It may be formed with a thickness of 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, a developing step, that is, an inorganic alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium metasilicate, monoethanolamine,
The unexposed part was removed by spraying an aqueous solution containing an organic base or salt such as diethanolamine, triethanolamine, tetramethylammonium hydroxide, triethylamine, n-butylamine, etc., or removing the unexposed portion to correspond to the image. A colored image pattern of the cured film can be obtained. 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 post-heated at a temperature of 60 to 200 ° C. for 1 to 60 minutes. The image pattern becomes stronger, which is preferable. Illustrating a method for producing a color filter used for a liquid crystal display device, by using the colored image-forming material according to the present invention on a glass substrate, by repeating the above-described method, red,
After forming colored pixels such as green and blue, a method of forming a black colored image as a black matrix in a gap between the colored pixels, or after forming a black matrix by chrome vapor deposition or a black colored image, As above, red,
There is a method of forming a color filter by forming colored pixels such as green and blue.

[0041]

EXAMPLES The present invention will be described below with reference to examples.

Resin Synthesis Example Methyl methacrylate 42 g, butyl acrylate 33
g, 25 g of acrylic acid and 2 g of azobisisobutyronitrile, a propylene glycol monomethyl ether 90 which was kept at 110 ° C. in a nitrogen gas atmosphere.
It was dripped in 2 g over 2 hours. After the dropping, the mixture was kept warm for 3 hours with stirring, and then 1 g of azobisdimethylvaleronitrile and 1 of propylene glycol monomethyl ether.
A mixture of 2 g was added dropwise over 20 minutes and then 4
The mixture was kept warm with stirring for a time to obtain a high acid value acrylic resin (acid value 193) solution. Next, 24 g of glycidyl methacrylate, 0.1 g of hydroquinone and 0.8 g of tetraethylammonium bromide were added to this solution and reacted at 105 ° C. for 6 hours while blowing air to obtain a resin solution having a photopolymerizable unsaturated group. . The acid value of the resin is 8
8, the weight average molecular weight was 45,000. The solid content of the resin solution was 55% by weight.

Example 1 As the component (a), the resin solution 7 obtained in the above synthesis example was used.
3 g (solid content 40 g), as a component (b), with a color index name, 25 g of Pigment Red 177 and 5 g of Pigment Yellow 139 and a component (e),
Macromonomer (manufactured by Nissin Corporation, trade name SILAPLANE F
3 g of M0721) was added to 167 g of propylene glycol monomethyl ether, and this was dispersed for 2 hours using a bead mill. To 200 g of this dispersion, the above resin solution 2 was added.
4 g (solid content 13 g), 27 g of trimethylolpropane triacrylate as component (c), 6 g of benzophenone as component (d), N, N'-tetraethyl-4,
2 g of 4'-diaminobenzophenone and 280 g of propylene glycol monomethyl ether were added and mixed to obtain a photosensitive solution containing the colored image forming material of the present invention. A glass substrate (made by Corning, product name 7059)
A film having a thickness of 2.0 μm was formed by applying the composition by spin coating and further drying at 80 ° C. for 5 minutes. The obtained film was imagewise exposed to 150 mJ / cm ² through a negative mask with an ultrahigh pressure mercury lamp, and then developed with an aqueous solution containing 6% by weight of triethanolamine. The evaluation results of the obtained red image pattern are shown in Table 1.

Example 2 As the component (a), the resin solution 1 obtained in the above synthesis example was used.
As a component (b), 10 g (solid content 60 g), 22 g of Pigment Green 36 and 8 g of Pigment Yellow 83 were added to 200 g of propylene glycol monomethyl ether by a color index name, and this was dispersed for 2 hours using a bead mill. To 220 g of this dispersion, (c)
35 g of pentaerythritol tetraacrylate as a component, 6 g of benzophenone as a component (d), N,
3 g of N′-tetraethyl-4,4′-diaminobenzophenone, 1 g of macromonomer (manufactured by Nissin Corporation, trade name SILAPLANE FM0711) and 125 g of propylene glycol monomethyl ether were added as components (e) and mixed, A photosensitive solution containing the colored image forming material of 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. The evaluation results of the obtained green image pattern are shown in Table 1.

Example 3 As the component (a), the resin solution 3 obtained in the above synthesis example was used.
6 g (solid content 20 g), as component (b), 24 g of Pigment Blue 15-6 and 1 g of Pigment Violet 23 were added to 200 g of propylene glycol monomethyl ether by a color index name, and this was dispersed for 2 hours using a bead mill. . To 140 g of this dispersion,
70 g of the above resin solution (solid content 38.5 g), 1,4-butanediol diacrylate 35 as the component (c)
g, (d) component as benzophenone 6g, N, N '
-Tetraethyl-4,4'-diaminobenzophenone 2
g, macromonomer as component (e) (Nitrogen Co., Ltd.)
(Trade name: SILAPLANE FM0701) (trade name) and 230 g of propylene glycol monomethyl ether were added and mixed to obtain a photosensitive solution containing the colored image forming material of the present invention.
This photosensitive solution was coated on a glass substrate in the same manner as in Example 1,
It was dried to form a film having a thickness of 2.0 μm. The obtained film was exposed and developed by the same method and conditions as in Example 1. The evaluation results of the obtained blue image pattern are shown in 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.
m of the colored image-forming material was formed, and a 40 μm-thick polyethylene film was coated thereon to obtain a photosensitive element. After peeling off 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 60 mJ / cm ² was performed on the polyethylene terephthalate film with an ultra-high pressure mercury lamp, and then the polyethylene terephthalate film was peeled off, followed by development in the same manner and conditions as in Example 1. It was The evaluation results of the obtained red image pattern are shown in Table 1.

Example 5 A red image pattern was formed on the glass substrate used in Example 1 on which a black matrix had been 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 on 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 Example 1 is the same as Example 1 except that the component (e) is not used.
A photosensitive solution was obtained with the same composition, method, and conditions as in. Using this photosensitive liquid, a film thickness of 2.
A 0 μm film was formed, and further exposed and developed. The results are shown in Table 1.

Comparative Example 2 Instead of using the macromonomer as the component (e) in Example 1, a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd.,
Example 1 except that 3 g of product name KBM1003) is used
A photosensitive solution was obtained with the same composition, method, and conditions as in. Using this photosensitive liquid, a film thickness of 2.
A film having a thickness of 0 μm was formed, and further exposed and developed. The results are shown in Table 1.

[0051]

[Table 1]

From Table 1, the adhesion of the film is extremely poor when no substance which improves the adhesion, such as the macromonomer of the component (e) or the silane coupling agent in the present invention, is added (Comparative Example 1). Therefore, it can be seen that the image pattern is peeled off during development and an image cannot be obtained. Further, when the silane coupling agent was added (Comparative Example 2), the dispersion stability was lower than when the silane coupling agent was not added (Comparative Example 1). On the other hand, the adhesion of the film is improved as compared with Comparative Example 1, but it is not perfect. Therefore, in the image pattern obtained by development, fine lines are peeled off and only the image pattern having a wide width remains, resulting in low resolution. It was also found that when the exposure was performed under high humidity, the image pattern was completely peeled off and an image could not be obtained.

On the other hand, in the case of Examples 1, 2 and 3 in which the macromonomer as the component (e) within the scope of the present invention was used, the adhesion of the film was significantly improved without impairing the dispersion stability. It is possible to obtain an image pattern with high sensitivity and high resolution. Further, unlike Comparative Example 2, no decrease in photosensitivity was observed even under high humidity. on the other hand,
When the photosensitive element shown in Example 4 is used,
The photosensitivity was further improved, and even at an exposure amount of 60 mJ / cm ² , the photosensitivity and resolution equivalent to those in Example 1 were exhibited. As described above, the color filters (Examples 5 and 6) produced by using the colored image-forming material having good characteristics which have never existed in the past are excellent in optical characteristics with depolarization of 500 or more, and are effective as an image display device. I confirmed that there is.

[0054]

INDUSTRIAL APPLICABILITY The photosensitive liquid and the photosensitive element using the colored image forming material of the present invention remarkably improve the adhesion to the substrate, and are not affected by the environment at the time of exposure and have good photosensitivity. It is an excellent thing to maintain. Further, the color filter manufactured by the method for manufacturing a color filter of the present invention using these photosensitive liquid or photosensitive element can be used as an image display device having excellent optical characteristics.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03F 7/033 7/075 511 // C08F 290/06 MRY (72) Inventor Koji Yamazaki Hitachi, Ibaraki Prefecture 4-13-1, Higashimachi, Ichi, Ibaraki Laboratory, Hitachi Chemical Co., Ltd. (72) Inventor, Satoshi Akahori, 4-13-1, Higashimachi, Hitachi City, Ibaraki Prefecture, Ibaraki Laboratory, Hitachi Chemical (72) Inventor, Sato Tsutomu, Ichihara City, Chiba Prefecture, 14 Goi Minami Coast, Hitachi Chemical Co., Ltd., Goi Plant (72) Inventor, Yoichi Kimura, 14 Ichihara City, Chiba Prefecture, Goi Minami Coast, Hitachi Chemical Co., Ltd.

Claims (7)

[Claims] 1. A resin having (a) an acid value of 20 to 300 and a weight average molecular weight of 1,500 to 200,000, (b) a pigment,
(C) a monomer containing two or more photopolymerizable unsaturated bonds in the molecule, (d) a photoinitiator, and (e) a macromonomer having one polymerizable unsaturated group at one end of the polymer of dimethylsiloxane. A colored image forming material containing the same. 2. A photosensitive liquid containing the colored image-forming material according to claim 1. 3. A photosensitive element having a support film and a layer containing the colored imaging element of claim 1. 4. The photosensitive element according to claim 3, further comprising a peelable cover film laminated on a layer containing a colored image forming material. 5. A step of forming a film of the colored image-forming material according to claim 1 on a substrate, irradiating an actinic ray imagewise, photocuring the exposed portion, and removing the unexposed portion by development, A method for producing a color filter, wherein the colored image forming material according to claim 1 having a plurality of different colors is repeatedly formed to form pixels. 6. The method for producing a color filter according to claim 5, wherein red, green and blue pixels are formed using the colored image forming material according to claim 1. 7. A color filter manufactured by the manufacturing method according to claim 6.