JP2001183829A - Colored image forming material, photosensitive fluid using same, photosensitive element, method for producing color filter and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored image forming material having enhanced adhesion to a substrate in spite of a dispersed pigment and having good photosensitivity independently of the environment in exposure, a photosensitive fluid using the material, a photosensitive element, a method for producing a color filter and a color filter. SOLUTION: A film of a colored image forming material containing (a) a resin having an acid value of 20-300 and a weight average molecular weight of 1,500-200,000, (b) a pigment, (c) a monomer containing two or more photopolymerizable unsaturated bonds in one molecule, (d) a photoinitiator and (e) a silane coupling agent having at least one methacryloxypropyl group bonded to Si and at least three methoxy groups bonded to Si in one molecule and a silane coupling agent containing dimethyldimethoxysilane or trimethyltrimethoxysilane is formed on a substrate and imagewise irradiated with active light, the exposed part is photo-cured and the unexposed part is removed by development. These steps are repeatedly carried out using colored image forming materials having different plural colors to form pixels and the objective color filter is produced.

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 liquid 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 frequently used in liquid crystal display devices, sensors, color separation devices, and the like. Conventionally, as a method of producing this color filter, a method of patterning a dyeable resin, for example, natural gelatin or casein, and then dyeing the pattern with a dye to obtain pixels has been used. However, the pixel obtained by this method has a problem that heat resistance and light resistance are low due to restrictions on materials.

[0003] In recent years, attention has been paid to a method using a photosensitive material in which a pigment is dispersed for the purpose of improving heat resistance and light resistance, and many studies have been made. According to this method, it is known that the manufacturing method is simplified, and the obtained color filter is stable and has a long life.

On the other hand, when pixels are formed on a substrate, there is a problem that the pixels are peeled off during development due to low adhesion of a photosensitive film containing a pigment to the substrate. Therefore, conventionally, a silane coupling agent has been added to the composition to improve adhesion, but when a general silane coupling agent is used alone, the stability is low, particularly under high humidity. It has been known that the exposure loses efficacy and no image pattern can be obtained.

[0005]

SUMMARY OF THE INVENTION The present invention significantly improves the adhesion of a photosensitive material in which a pigment is dispersed, which is a problem, to a substrate, and has good photosensitivity without being affected by the environment at the time of exposure. The present invention provides a colored image forming material having the following, 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 specific silane coupling agent in combination, the adhesion of the photosensitive material to the substrate can be improved and its effectiveness can be improved. They have found that they can be maintained over a long period of time, leading to the present invention.

That is, the present invention relates to (a) an acid value of 20 to
300 and 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) methacryloxypropyl bonded to a silicon atom in the molecule. The present invention relates to a colored image-forming material comprising a silane coupling agent having at least one group and at least three methoxy groups bonded to a silicon atom, and a silane coupling agent containing dimethyldimethoxysilane or trimethylmethoxysilane.

The present invention also relates to a photosensitive solution containing the above-mentioned colored image forming material and an organic solvent.

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

[0010] The present invention further relates to the photosensitive element described above, wherein a peelable cover film is laminated on a layer containing a colored image forming material.

The present invention also includes a step of forming a film of the above-mentioned colored image forming material on a substrate, irradiating the film with an actinic ray in an image form, light-curing the exposed portion, and removing the unexposed portion by development. The present invention relates to a method for producing a color filter, characterized in that pixels are formed by repeatedly performing coloring image forming materials of a plurality of different colors.

[0012] The present invention also relates to the present invention, wherein a plurality of different colors are red,
The present invention relates to a method for producing the above-mentioned color filters which are green and blue.

[0013] The present invention also relates to a color filter manufactured by the above manufacturing method.

[0014]

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

The component (a) used in the present invention has an acid value of 20 to 300 and a molecular weight of 1,500 to 200,000.
The resin is not particularly limited as long as the acid value and the molecular weight fall within the above ranges. Examples of the resin include a carboxyl group-containing polymerizable monomer such as acrylic acid, methacrylic acid, and itaconic acid, and methyl methacrylate and butyl acrylate. Representative examples include copolymers with polymerizable monomers such as (meth) acrylic acid esters and styrene. Further, as the resin of the component (a), a resin having a photopolymerizable unsaturated bond may be used. Preferred examples of such a resin include a carboxylic acid group-containing resin having a high acid value, a glycidyl group-containing unsaturated compound such as glycidyl (meth) acrylate and allyl glycidyl ether, allyl alcohol, 2-hydroxyacrylate, and 2-hydroxymethacrylate. A resin reacted with an unsaturated alcohol, a resin obtained by reacting a free isocyanate group-containing unsaturated compound with a carboxyl group-containing resin having a hydroxyl group, and a polybasic anhydride as an addition reaction product between an epoxy resin and an unsaturated carboxylic acid. Typical resins include a reacted resin, 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 with an unsaturated dicarboxylic anhydride.

The acid value of the resin (a) is from 20 to 300,
Preferably 40-200, more preferably 60-150
Range. 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 of 1,500 to 200,000, preferably 5,000.
~ 100,000, more preferably 10,000 ~ 5
The range is 0000. Weight average molecular weight of 1,50
If it is less than 0, the dispersion stability of the pigment becomes poor.
If it exceeds 000, the viscosity when it is made into a photosensitive solution becomes high, and the coating property at the time of spin coating decreases.

Here, the weight average molecular weight is a value measured by gel permeation chromatography and converted using a calibration curve of standard polystyrene.

The amount of the resin (a) used is 10 to 85% by weight based on the total amount of the components (a), (b), (c), (d) and (e). And more preferably 20 to 60% by weight.
It is particularly preferred that the content be 5 to 50% by weight. If the amount is less than 10% by weight, the dispersion stability of the pigment tends to decrease, and if it exceeds 85% by weight, the viscosity when used as a photosensitive liquid increases, and the coating properties during spin coating decrease. Tend.

Next, the pigment of the component (b) will be described. The pigment includes an inorganic pigment and an organic pigment, and any of them can be used. However, black carbon black (inorganic pigment) and an organic pigment are preferable from the viewpoint of abundant color tone. Examples of the organic pigment include azo-based, phthalocyanine-based, indigo-based, anthraquinone-based, perylene-based, quinacridone-based, methine-azomethine-based, and isoindolinone-based.

When the colored image forming material of the present invention is used for the production of a color filter, each pigment system suitable for a colored image such as red, green, blue and black is used.

As the 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.

As red pigments, for example, Pigment Red 9, 123, 155, and
168, 177, 180, 217, 220, 224 and the like.

As the yellow pigments, for example, Pigment Yellow 20, 24,
83, 93, 109, 110, 117, 125, 13
9, 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.

As the 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, Pigment Greens 7, 36, and 37 under the color index name.

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

As the 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.

Examples of blue pigments include, for example, Pigment Blue 15, 15: 3, 1
5: 4, 15: 6, 22, 60 and the like.

As the violet pigments, for example, pigment violet 19, 2
3, 29, 37, 50 and the like.

These blue pigments and purple pigments can be used as a mixture of two or more kinds. In addition,
When a mixture of a blue pigment and a violet pigment is used, the violet pigment is preferably used in an amount of 50 parts by weight or less based on 100 parts by weight of the total of the blue pigment and the violet pigment.

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

The amount of the pigment (b) used in the present invention is 5 to 50 with respect to the total amount of the components (a), (b), (c), (d) and (e). % By weight, more preferably 10 to 40% by weight, and particularly preferably 15 to 30% by weight.
If the amount is less than 5% by weight, the color density of the image tends to decrease, and if it exceeds 50% by weight, the light sensitivity tends to decrease.

Examples of the monomer having two or more photopolymerizable unsaturated bonds in the molecule of the component (c) in the present invention include, for example, EO-modified bisphenol A diacrylate (where EO means ethylene oxide. The same), ECH-modified bisphenol A diacrylate (here, ECH means epichlorohydrin, the same applies hereinafter), bisphenol A dimethacrylate, 1,4-
Butanediol diacrylate, 1,3-butanediol diacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol diacrylate, EO-modified phosphate diacrylate, ECH-modified phthalic acid diacrylate, polyethylene glycol 400 diacrylate, polypropylene glycol 400 dimethacrylate, tetraethylene glycol diacrylate, ECH-modified 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, E
O-modified phosphate triacrylate, EO-modified trimethylolpropane triacrylate, PO-modified trimethylolpropane triacrylate (where PO means propylene oxide; the same applies hereinafter), tris (methacryloxyethyl) isocyanurate, pentaerythritol Examples thereof include tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol pentaacrylate. These monomers can be used alone or in combination of two or more.

In the present invention, the amount of the monomer (c) used is as follows: component (a), component (b), component (c), and component (d).
The amount is preferably 2 to 50% by weight, more preferably 5 to 40% by weight, and particularly preferably 10 to 30% by weight, based on the total amount of the component and the component (e). If the amount of the monomer is less than 2% by weight, the light sensitivity tends to be low, and if it exceeds 50% by weight, the dispersion stability of the pigment tends to decrease.

The photoinitiator of the component (d) in the present invention is not particularly limited. For example, benzophenone, N,
N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, benzyl, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyldimethyl ketal, α- Hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, t-butylanthraquinone, 1-chloroanthraquinone , 2, 3
-Dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 1,2-
Benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer and the like can be mentioned. These photoinitiators are used alone or in combination of two or more.

In the present invention, the amount of the component (d) used as the photoinitiator is as follows: component (a), component (b), component (c) and component (d).
The amount is preferably 0.01 to 20% by weight, more preferably 2 to 15% by weight, and particularly preferably 5 to 10% by weight, based on the total amount of the component and the component (e). 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.

The silane coupling agent (e), which is a component (e) in the present invention, may be referred to as a silane coupling agent (e) in order to improve adhesion to a substrate. A silane coupling agent having at least one methacryloxypropyl group bonded to silane and at least three methoxy groups bonded to a silicon atom (hereinafter sometimes referred to as silane coupling agent (a)) and dimethyldimethoxysilane or trimethylmethoxy It is characterized by containing silane in combination.

Examples of a silane coupling agent having at least one methacryloxypropyl group bonded to a silicon atom and at least three methoxy groups bonded to a silicon atom in the molecule (silane coupling agent (a)) include, for example, γ -Methacryloxypropyltrimethoxysilane and the like. Further, a silane coupling agent other than the silane coupling agent (a) (hereinafter, sometimes referred to as a silane coupling agent (b)) may be added and used. Such materials include vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ
-Glycidoxypropyltrimethoxysilane, β-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-
Examples include aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, and the like. These are used alone or in combination of two or more.

In the present invention, the amount of the component (e) (including the silane coupling agent (b) other than the silane coupling agent (a) when used concurrently) is the amount of the component (a), ), Preferably 0.2 to 20% by weight, more preferably 0.5 to 15% by weight, based on the total amount of the components (c), (d) and (e). It is particularly preferred that the content be 1.0 to 10% by weight. If the amount is less than 0.2% by weight, the effect of improving the adhesion tends to be insufficient, and if it exceeds 20% by weight, the film of the unexposed portion does not peel off when forming a colored image. However, there is a tendency that a good image pattern cannot be obtained.

When a silane coupling agent (b) other than the silane coupling agent (a) is used in common, the total amount of the silane coupling agent (a) and dimethyldimethoxysilane or trimethylmethoxysilane is the same as that of the component (e). The total amount is preferably 75% by weight or more, more preferably 85% by weight or more, and particularly preferably 90% by weight or more. If the amount is less than 75% by weight, the adhesion tends to be insufficient.

In the silane coupling agent (e) of the component (e) in the present invention, the combined ratio (weight ratio) of the silane coupling agent (a) and dimethyldimethoxysilane or trimethylmethoxysilane is 15:85 to 80. : 20, more preferably 25:75 to 70:30, and particularly preferably 40:60 to 60:40. If the combined ratio is out of this range, the combined use effect of the silane coupling agent will be lost, and the adhesion tends to be insufficient.

The colored image forming material of the present invention includes a thermal polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, pyrogallol and t-butylcatechol for suppressing a dark reaction, and a fluorine-based material for improving the smoothness of the film. Various additives such as surfactants such as silicon-based and hydrocarbon-based surfactants, ultraviolet absorbers, and antioxidants 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 liquid, and directly applying it to a substrate, or once applying it to a support and then laminating it on the substrate. A film is formed thereon.
Thereafter, exposure and development are performed to obtain a target 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. As this method, usually, a resin of the component (a) and a pigment of the component (b) are mixed with an organic solvent, and this mixture is dispersed with an ultrasonic disperser, a three-roll mill, a ball mill, a sand mill, a bead mill, a homogenizer, a kneader, or the like. / Using a kneading device.

The organic solvent used at this time is not particularly limited, and examples thereof include ketone solvents, cellosolve solvents, alcohol solvents, and aromatic solvents. Specifically, acetone, methyl ethyl ketone, cyclohexanone, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl 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 And organic solvents such as toluene, xylene and ethyl acetate. These are used alone or in combination of two or more.

At this time, pigment dispersants such as anionic pigment dispersants such as polycarboxylic acid type polymer activators and polysulfonic acid type polymer activators, and nonionic pigment dispersants such as polyoxyethylene / polyoxypropylene block polymers. Additives, anthraquinone-based, perylene-based, phthalocyanine-based, quinacridone-based organic dyes are added with carboxyl groups, sulfonate groups, carboxamide groups, derivatives of organic dyes in which substituents such as hydroxyl groups are introduced, and the like. This is preferable because the properties and dispersion stability are improved.

These pigment dispersants and organic dye derivatives are
It is preferable to use 50 parts by weight or less based on 100 parts by weight of the pigment. If it exceeds 50 parts by weight, the chromaticity tends to shift.

In the pigment dispersion treatment, the components (c), (d) and (e) may be added before the dispersion treatment or after the pigment dispersion treatment.

The resin of the component (a) may be used in its entirety together with the pigment during the dispersion treatment, or a part of the resin may be added after the dispersion treatment. However, it is preferable to use at least 20 parts by weight of the resin at the time of dispersion treatment 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 tends to decrease.

Similarly, the entire amount of the organic solvent may be used at the time of the dispersion treatment of the pigment, or a part of the organic solvent may be added after the dispersion treatment. However, it is preferable to use at least 100 parts by weight of the organic solvent at the time of the dispersion treatment with respect to 100 parts by weight of the total amount of the pigment and the resin at the time of the dispersion treatment. If the amount is less than 100 parts by weight, the viscosity at the time of the dispersion treatment is too high, and particularly when the dispersion treatment is performed by a ball mill, a sand mill, a bead mill or the like, the dispersion treatment may be difficult.

The organic solvent has a total solid content of 5 to 40% by weight including the components (a), (b), (c), (d) and (e) in the photosensitive solution. It is preferably used so that

Next, when the photosensitive solution thus obtained is directly applied to a substrate, for example, a roll coater application, a spin coater application, a spray application, a wooler application, a dip coater application, a curtain flow coater application, a wire coating It is performed by bar coater coating, gravure coater coating, 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 a white sheet glass, a blue sheet glass, a silica-coated blue sheet glass, a synthetic resin such as a polyester resin, a polycarbonate resin, an acrylic resin, and a vinyl chloride resin. Examples 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 steel plate, other ceramic substrates, and a semiconductor substrate having a photoelectric conversion element.

After the application, the temperature is usually 1 to 50 ° C. to 130 ° C.
After drying for about 30 minutes, a film of the colored image forming material can be obtained.

On the other hand, the photosensitive liquid is not applied directly to the substrate, but is first applied onto a support and dried to form a layer containing a colored image forming material (the thickness of this layer is usually 0.1 to 300 μm, preferably 0 to 300 μm, preferably 0 to 300 μm. 0.2-30 μm, more preferably 0.2-5 μm
Can be formed as a film on the surface of the substrate by, for example, laminating the photosensitive element on a substrate. As a method of applying the photosensitive solution to the support, a knife coater application, a gravure coater application, a roll coater application, a spray coater application, or the like can be used. As the support used at this time, for example,
Films such as a polyester film, a polyamideimide film, a polypropylene film, and a polystyrene film are exemplified. After the application, similarly to the above, the film can be dried usually at a temperature of 50 to 130 ° C. for 1 to 30 minutes to obtain a film. 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 a polyethylene film, a Teflon film, a polypropylene film, a surface-treated paper, and the like. What is necessary is just to have a small adhesive force with a film.

As a method of laminating the thus obtained photosensitive element on a substrate, it is preferable to heat-press while laminating the substrate and the layer containing the colored image forming material of the present invention. In this case, the atmosphere may be normal pressure or reduced pressure.

The thickness of the film containing the colored image forming material of the present invention formed on the substrate surface in this way is appropriately determined depending on the use, but is usually preferably in the range of 0.1 to 300 μm. In addition, when used for a color filter, it is usually preferable to set the range to 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 irradiated with actinic rays in an image-like manner to cure the film in the exposed portion. At this time, when a film is formed using a photosensitive element,
Exposure may be performed from above with the support attached, or exposure may be performed after the support has been peeled off. Further, even when a photosensitive liquid is applied directly to the substrate to form a film, an oxygen barrier film such as polyvinyl alcohol is coated on the surface of the film for 0.5 to 30 minutes.
After forming with a thickness of μm, 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, actinic rays are irradiated in an image form by pattern exposure through a photomask, direct drawing by scanning, or the like. The light amount at the time of exposure is usually 10 to 1000 mJ /
cm ² is preferable, and 20 to 500 mJ / cm ² is more preferable.

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. At this time, when exposure is performed with the support, the support is peeled off and development is performed. Examples of the developing method include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium metasilicate; and organic bases such as monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, triethylamine, and n-butylamine. Or a method of spraying an aqueous solution containing salt or dipping in an aqueous solution. The concentration of the inorganic alkali, organic base or salt in the aqueous solution is preferably from 0.01 to 10% by weight, more preferably from 0.1 to 5% by weight.

After development, the colored image pattern is further
0.5-5 J / cm using silver lamp etc. ^TwoPost-exposure
Or post-heating at a temperature of 60-200 ° C for 1-60 minutes.
Then, the image pattern becomes stronger, which is preferable.

In the method for producing a color filter of the present invention,
The above-described process of forming a colored image on the substrate is repeated for a plurality of different colors to form a plurality of pixels of different colors.

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 using a photosensitive liquid or a photosensitive element containing 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 gap between these colored pixels, or forming a black matrix by chromium evaporation or black colored image first Thereafter, as in the above, there is a method of forming a color filter by forming colored pixels of red, green, blue and the like.

[0067]

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.

Synthesis Example 1 of Resin 42 g of methyl methacrylate, 33 of butyl acrylate
g, 25 g of acrylic acid and 2 g of azobisisobutyronitrile in a propylene glycol monomethyl ether 90 kept at 110 ° C. under a nitrogen gas atmosphere.
g in 2 hours. After dropping, with stirring
For 1 hour and then 1 g of azobisdimethyl valeronitrile and 12 g of propylene glycol monomethyl ether
g of the mixture was added dropwise over 20 minutes, and the mixture was kept warm for 4 hours with stirring to obtain a high acid value acrylic resin (acid value 1).
93) A solution was obtained.

Next, 24 g of glycidyl methacrylate, 0.1 g of hydroquinone and 0.8 g of tetraethylammonium bromide were added to this solution, and the mixture was reacted at 105 ° C. for 6 hours while blowing air to obtain a resin solution having a photopolymerizable unsaturated group. I got The acid value of the resin was 88, and the weight average molecular weight was 45,000. The solids content of the resin solution is 5
It was 5% by weight.

Example 1 As the component (a), 73 g (solid content: 40 g) of the resin solution obtained in the above Synthesis Example 1, and as the component (b), 25 g of Pigment Red 177 and Pigment Yellow 139 by a color index name were used. 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, 24 g of the above resin solution (13 g of solid content), 27 g of trimethylolpropane triacrylate as the component (c),
(D) 6 g of benzophenone, 2 g of N, N'-tetraethyl-4,4'-diaminobenzophenone as a component,
As the component (e), γ-methacryloxypropyltrimethoxysilane (Toray Dow Corning Silicone Co., Ltd.)
(Trade name: SZ-6030), 1.5 g and dimethyldimethoxysilane (Dow Corning Toray Silicone Co., Ltd.)
AY43-004) and 280 g of propylene glycol monomethyl ether were added and mixed to obtain a photosensitive solution of the present invention.

This photosensitive solution was applied on a glass substrate (Corning Co., trade name: 7059) by spin coating, followed by drying at 80 ° C. for 5 minutes to form a film having a thickness of 2.0 μm.

The obtained film was exposed to an image of 150 mJ / cm ² by an ultra-high pressure mercury lamp through a negative mask, and then developed with an aqueous solution containing 6% by weight of triethanolamine. Table 1 shows the evaluation results of the obtained red image patterns.

Example 2 As the component (a), 110 g (solid content: 60 g) of the resin solution obtained in Synthesis Example 1 described above, and as the component (b), 22 g of Pigment Green 36 and Pigment Yellow 83 by a color index name were used. Was added to 200 g of propylene glycol monomethyl ether, and this was dispersed for 2 hours using a bead mill. To 220 g of this dispersion,
35 g of pentaerythritol tetraacrylate as the component (c), 6 g of benzophenone as the component (d),
3 g of N, N'-tetraethyl-4,4'-diaminobenzophenone, 0.5 g of γ-methacryloxypropyltrimethoxysilane (trade name SZ-6030, manufactured by Dow Corning Toray Silicone Co., Ltd.) as the component (e) And 0.7 g of dimethyldimethoxysilane (manufactured by Dow Corning Toray Silicone Co., Ltd., trade name: AY43-004),
And propylene glycol monomethyl ether 125
g was added and mixed to obtain a photosensitive solution of the present invention.

This photosensitive solution was applied to 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 in the same manner and under the same conditions as in Example 1. Table 1 shows the evaluation results of the obtained green image patterns.

Example 3 As the component (a), 36 g (solid content: 20 g) of the resin solution obtained in the above-mentioned Synthesis Example 1, and as the component (b), 24 g of Pigment Blue 15: 6 by color index and pigment 1 g of Violet 23 was added to 200 g of propylene glycol monomethyl ether, and this was dispersed for 2 hours using a bead mill. 140 g of this dispersion
The above resin solution 70g (solid content 38.5g),
35 g of 1,4-butanediol diacrylate as the component (c), 6 g of benzophenone as the component (d), N,
2 g of N'-tetraethyl-4,4'-diaminobenzophenone, 3.0 g of γ-methacryloxypropyltrimethoxysilane (manufactured by Dow Corning Toray Silicone Co., Ltd., trade name: SZ-6030) and trimethyl as the component (e) 2.0 g of methoxysilane (AY43-043, manufactured by Dow Corning Toray Silicone Co., Ltd.) and 230 g of propylene glycol monomethyl ether were added and mixed to obtain a photosensitive solution of the present invention.

This photosensitive solution was applied on 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. Table 1 shows the evaluation results of the obtained blue image patterns.

Example 4 The photosensitive solution obtained in Example 1 was applied onto a 6 μm-thick polyethylene terephthalate film by a gravure coating method, and dried at 100 ° C. for 2 minutes to obtain a 2.0 μm-thick film.
m, a layer containing a colored image-forming material was formed thereon, and the layer was covered with a polyethylene film having a thickness of 40 μm to obtain a photosensitive element.

After the polyethylene film was peeled off from the obtained photosensitive element, it was laminated on a glass substrate similar to that used in Example 1. Lamination conditions were as follows: glass substrate temperature 40 ° C., laminating roll temperature 11
The lamination was performed at 0 ° C., a lamination pressure of 3.5 kgf / cm ² , and a lamination speed of 1.5 m / min.

Next, the polyethylene terephthalate film was exposed imagewise at 60 mJ / cm ^{2 with} a super-high pressure mercury lamp through a negative mask, and then the polyethylene terephthalate film was peeled off. Development was performed. The obtained red image pattern was evaluated.

Example 5 A red image pattern was formed on the glass substrate used in Example 1 in which a black matrix was formed by chromium vapor deposition in the same manner and under the same conditions as in Example 1, and then a color image was formed at 150 ° C. for 10 minutes. Post heating was performed. Next, using the substrate, a green image pattern was formed next to the red image pattern under the same method and conditions as in Example 2. Then 15
Post-heating was performed at 0 ° C. for 10 minutes. Next, using the substrate, a blue image pattern was formed next to the green image pattern under the same method and conditions as in Example 3. afterwards,
Post-heating was performed at 150 ° C. for 10 minutes. From the above, 1
A color filter was prepared in which three pixels were arranged in a mosaic of 30 μm × 100 μm consisting of three colors of red, green and blue.

Example 6 A red image pattern was formed on the glass substrate used in Example 1 on which a black matrix was formed by chromium vapor deposition in the same manner and under the same conditions as in Example 4, and then a color image was formed at 150 ° C. for 10 minutes. Post heating was performed. Next, using the photosensitive liquid obtained in Example 2, a photosensitive element was produced in the same manner and under the same conditions as in Example 4. After laminating this photosensitive element on the above-described substrate in the same manner and under the same conditions as in Example 4, further exposing the film, and peeling off the polyethylene terephthalate film, developing was performed under the same manner and under the same conditions as in Example 1. A green image pattern was formed next to the red image pattern. Thereafter, post-heating was performed at 150 ° C. for 10 minutes. Next, using the photosensitive liquid obtained in Example 3, a photosensitive element was produced in the same manner and under the same conditions as in Example 4. After laminating this photosensitive element on the above-described substrate in the same manner and under the same conditions as in Example 4, further exposing the film, and peeling off the polyethylene terephthalate film, developing was performed under the same manner and under the same conditions as in Example 1. A blue image pattern was formed next to the green image pattern. Thereafter, post-heating was performed at 150 ° C. for 10 minutes.
As described above, a color filter in which one pixel is arranged in a mosaic shape of three colors of red, green, and blue of 30 μm × 100 μm was produced.

Comparative Example 1 Example 1 was repeated except that the component (e) was not used.
A photosensitive solution was obtained under the same composition, method and conditions as in the above.

Using this photosensitive solution, a film having a thickness of 2.0 μm was formed in the same manner and under the same conditions as in Example 1, and was further exposed and developed. Table 1 shows the results.

Comparative Example 2 Instead of using the specific silane coupling agent as the component (e) in Example 1, γ-methacryloxypropyltrimethoxysilane (trade name K, manufactured by Shin-Etsu Silicone Co., Ltd.)
A photosensitive solution was obtained under the same composition, method, and conditions as in Example 1, except that 3 g of BM-503) was used alone.

Using this photosensitive liquid, a film having a thickness of 2.0 μm was formed in the same manner and under the same conditions as in Example 1, and further, exposure and development were carried out. Table 1 shows the results.

[0088]

[Table 1] 1) 100 squares of 1 mm square are formed with a cutter, and a peeling test is performed using a cellophane tape. The adhesion is evaluated by the number of squares remaining without peeling. 2) The optical density of 0.05 is set as the first stage. Evaluation using a 21-stage ST (step tablet) in which the optical density increases by 0.15 for each stage From Table 1, it is understood that the silane coupling agent which is a substance that improves the adhesion of the component (e) in the present invention Is not added at all (Comparative Example 1), the adhesion of the film is extremely poor.
It can be seen that the image pattern peeled off during development, and no image was obtained.

When the silane coupling agent is added alone (Comparative Example 2), the adhesion of the film is improved as compared with Comparative Example 1, but is not perfect. For this reason, in the image pattern obtained by the development, fine lines were peeled off, and only an image pattern having a wide width remained, resulting in a low resolution. In addition, when exposure was performed under high humidity, it was found that all of the image patterns were peeled off and no image was obtained.

On the other hand, within the scope of the present invention, in the case of Examples 1, 2 and 3 in which the specific silane coupling agent (e) was used in combination, the adhesion of the film was significantly improved. And a high-sensitivity, high-resolution image pattern can be obtained. Also, unlike the case of 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 was used, the light sensitivity was further improved, and the sensitivity was 60 mJ / c.
Even at an exposure amount of m ^2, the same light sensitivity and resolution as in Example 1 were exhibited.

As described above, a color filter (Example 5) produced using a colored image forming material having better characteristics than ever before.
And 6) all confirmed that the depolarizing property was 500 or more, which was excellent in optical properties, and was effective as an image display device.

[0093]

The method for producing the color filter of the present invention is as follows.
It is possible to manufacture an excellent color filter which can significantly improve the adhesion to a substrate, and can maintain good photosensitivity without being affected by the environment at the time of exposure.

The color filter produced by the method for producing a color filter of the present invention can be used as an image display device having excellent optical characteristics.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Yoichi Kimura 14 Goi South Coast, Ichihara City, Chiba Prefecture Within the Goi Works of Hitachi Chemical Co., Ltd. Within the Goi Works Co., Ltd. (72) Inventor Tetsuya Okazaki 14 Goi Minami Coast, Ichihara-shi, Chiba Hitachi Chemical Co., Ltd. Goi Works F-term (reference) 2H025 AB13 BC14 BC34 BC43 BC82 CA00 CB43 CC03 CC06 CC12 2H048 AA06 AA12 BA02 BA45 BA48 BB42

Claims (7)

[Claims] (1) a resin having an acid value of 20 to 300 and a weight average molecular weight of 1,500 to 200,000;
Pigment, (c) a monomer containing two or more photopolymerizable unsaturated bonds in a molecule, (d) a photoinitiator, and (e) at least one methacryloxypropyl group bonded to a silicon atom in the molecule, and a silicon atom. A colored image-forming material comprising a silane coupling agent having at least three methoxy groups bonded to a silane coupling agent and a silane coupling agent containing dimethyldimethoxysilane or trimethylmethoxysilane. 2. A photosensitive liquid containing the colored image forming material according to claim 1 and an organic solvent. 3. A photosensitive element comprising a layer containing the colored image forming material according to claim 1 and a support film. 4. The photosensitive element according to claim 3, further comprising a peelable cover film laminated on the layer containing the colored image forming material. 5. The step of forming a film of the colored image forming material according to claim 1 on a substrate, irradiating the film with an actinic ray in an image form, light-curing an exposed portion, and removing an unexposed portion by development. A method for producing a color filter, wherein pixels are formed by repeating the process for colored image forming materials of a plurality of different colors. 6. The method according to claim 5, wherein the plurality of different colors are red, green and blue. 7. A color filter produced by the production method according to claim 5. Description: