JPH0915844A - Colored image forming photosensitive solution, manufacture of color filter using it, and color filter - Google Patents

Abstract

PURPOSE: To provide a colored image forming photosensitive solution in which the dispersibility and dispersion stability of a pigment are improved, and the uniformity of a coating film is remarkably enhanced, a manufacturing method of color filter using it, and a color filter obtained thereby. CONSTITUTION: In a colored image forming photosensitive solution 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 having one or more photo polymerizing unsaturated bonds within the molecule, (d) a photo initiator, and (e) an organic solvent, dipropyleneglycol monoalkylether is contained in the organic solvent. A manufacturing method of color filter using it and a color filter obtained thereby are also provided.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive liquid for forming a colored image, a method for producing a color filter using the same 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.
Conventionally, as a method of manufacturing 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 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. According to this method, it is known that the manufacture 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 an organic solvent that affects the dispersibility of the pigment. Further, when the dispersibility of the pigment is low, there is a problem that when applied on a substrate, uneven coating occurs and a color filter having a uniform color cannot be obtained.

[0003]

SUMMARY OF THE INVENTION The present invention solves the problems of the conventional techniques described above, improves the dispersibility and dispersion stability of the pigment, and significantly enhances the uniformity of the coating film. A liquid, a method for producing a color filter using the liquid, and a color filter are provided.

[0004]

According to the present invention, (a) an acid value of 20 to 300 and a weight average molecular weight of 1,500 to 200,
000 resin, (b) pigment, (c) monomer having one or more photopolymerizable unsaturated bonds in the molecule, (d) photoinitiator and (e) organic solvent for forming a colored image. The liquid relates to a photosensitive liquid for forming a colored image, which contains dipropylene glycol monoalkyl ether in an organic solvent. Further, the present invention comprises applying the colored image forming photosensitive solution onto a substrate, drying the solution to form a film, irradiating an actinic ray imagewise, photocuring the exposed area, and developing the unexposed area. Repeat the removal process for different colors.
The present invention relates to a color filter manufacturing method characterized by forming pixels and a color filter manufactured by this color filter manufacturing method.

The colored image forming photosensitive solution of the present invention comprises (a)
Acid value is 20-300, weight average molecular weight is 1,500-2
An organic solvent, which contains 100,000 resin, (b) pigment, (c) a monomer having at least one photopolymerizable unsaturated bond in the molecule, (d) a photoinitiator, and (e) an organic solvent. It is essential to include dipropylene glycol monoalkyl ether in the solvent.

The acid value (a) in the present invention is 20 to 30.
The resin having a weight average molecular weight of 0, 1,500 to 200,000 is not particularly limited as long as the acid value and the weight average molecular weight are within this range, and examples thereof include carboxyl such as acrylic acid, methacrylic acid and itaconic acid. A typical example thereof is a copolymer of a group-containing polymerizable monomer and a polymerizable monomer such as acrylic acid ester, methacrylic acid ester and styrene. Further, a carboxyl group-containing resin having a photopolymerizable unsaturated bond is also preferable as a resin from the viewpoint of photosensitivity.

The carboxyl group-containing resin having a photopolymerizable unsaturated bond is, for example, 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 obtained by reacting a polybasic acid anhydride with an addition reaction product, resin obtained by reacting a hydroxyl group-containing polymerizable monomer with an addition reaction product of a conjugated diene polymer or a conjugated diene copolymer and an unsaturated dicarboxylic acid anhydride, carboxyl Glycidyl group-containing unsaturated compounds (glycidyl methacrylate, allyl glycidyl ether, etc.) and unsaturated alcohols (allyl alcohol, 2-hydroxyethyl acrylate, 2
-Hydroxyethylmethacrylate, etc.), the following general formula (I)

Embedded image (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, m and n are integers of 1 or more, and 1 ≦ m / n ≦ 5 Selected), and the like. Among them, heat resistance,
From the viewpoint of dispersibility and the like, the resin represented by the general formula (I) is preferable.

As a method for producing the resin represented by the above general formula (I), for example, a precursor of the resin represented by the general formula (I) is mixed with an unsaturated alcohol (allyl alcohol, 2-butene-4-). Oar, furfuryl alcohol, oleyl alcohol, cinnamyl alcohol, 2-hydroxyacrylate, 2-hydroxymethacrylate, N-methylolacrylamide, etc.) to produce an esterification reaction of the resin represented by the general formula (I). As a precursor, a compound having one oxirane ring and one ethylenically unsaturated bond (glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, α-ethyl glycidyl acrylate, crotonyl glycidyl ether, itaconic acid monoalkyl monoglycidyl ester, etc.) Manufactured by an addition reaction The method and the like.

The precursor of the resin represented by the general formula (I) can be obtained by copolymerizing styrene or a derivative thereof with a maleic acid monoalkyl ester (maleic acid half ester). Examples of the styrene derivative include α-methylstyrene, m- or p-methoxystyrene, p-hydroxystyrene, 2-methoxy-4-hydroxystyrene, 2-hydroxy-4-methylstyrene and the like. Examples of maleic acid monoalkyl esters include monomethyl maleate, monoethyl maleate, mono-n-propyl maleate, mono-isopropyl maleate, mono-n-butyl maleate, mono-n-hexyl maleate, and maleic acid. Mono-n-octyl, mono-2-ethylhexyl maleate, mono-n-nonyl maleate, mono-n maleate
-Dodecyl and the like.

The above-mentioned general formula (I) thus obtained
The unsaturated equivalent of the resin represented by is preferably 600 to 3000, and more preferably 800 to 2000. If the unsaturated equivalent is less than 600, there is a tendency for the resin to partially cure during dispersion with the pigment, and if it exceeds 3000,
The effect of improving the photosensitivity tends to decrease. Here, the unsaturated equivalent means the molecular weight of the resin per unsaturated bond.

The acid value of the component (a) in the present invention is 20.
To 300, preferably 40 to 200,
It is more preferable to set it to 60 to 150. Acid value is 20
If it is less than 300, the alkali developability is deteriorated, and if it exceeds 300, the shape of the image pattern becomes unclear. The weight average molecular weight of the component (a) in the present invention (measured by gel permeation chromatography (GPC) and converted using a calibration curve using standard polystyrene) is
1,500 to 200,000 and 5,000 to 10
It is preferably set to 10,000, and 10,000 to 5
More preferably, it is set to 0000. When the weight average 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 is deteriorated. The above-mentioned resin as the component (a) is used alone or in combination of two or more kinds.

As the pigment (b) in the present invention, there are inorganic pigments and organic pigments. Usually, except for black carbon black, graphite and the like, organic pigments are used because of their rich color tone. As the organic pigment, for example, azo-based,
Phthalocyanine type, indigo type, anthraquinone type, perylene type, quinacridone type, methine / azomethine type, isoindolinone type and the like can be mentioned.

When the colored image forming photosensitive liquid 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.

As a red colored image, a single red pigment system may be used, or a yellow pigment system may be mixed with a red pigment system to perform toning. As red pigments, for example, CI Pigment Red 9, 12 by color index name
3, 155, 168, 177, 180, 217, 22
0, 224 and the like. As a yellow pigment, for example, CI Pigment Yellow 20, 24, 83, 93, 109, 110, 117, 1
25, 139, 147, 154 and the like. Two or more kinds of each of these red pigment type and yellow pigment type may be mixed and used. When a mixture of a red pigment system and a yellow pigment system is used, the yellow pigment system is used.
For a total amount of 100 parts by weight of the red pigment system and the yellow pigment system,
Preferably, it is used in an amount of 50 parts by weight or less.

As 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 the green pigment type include CI Pigment Green 7, 36, and 37, which are color index names. These green pigment system and yellow pigment system can be used as a mixture of two or more kinds. In addition, when using a mixture of a green pigment system and a yellow pigment system, 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 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 to perform toning. As blue pigments, for example, CI Pigment Blue 15, 1
5: 3, 15: 4, 15: 6, 22, 60 and the like. Examples of purple pigments include CI Pigment Violet 19, 23, 29,
37, 50 and the like. These blue pigments and violet pigments can be used as a mixture of two or more kinds. 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, black pigments such as carbon black, graphite, titanium carbon, black iron, and manganese dioxide are used.

Examples of the monomer (c) having one or more photopolymerizable unsaturated bond in the molecule thereof in the present invention include, for example, methyl methacrylate, benzyl methacrylate, butoxyethyl methacrylate, butoxyethyl acrylate, butoxytriethylene glycol acrylate, E.
CH (epichlorohydrin) modified butyl acrylate,
Dicyclopentanyl acrylate, EO (ethylene oxide) modified dicyclopentenyl acrylate, N, N-
Dimethylaminoethyl methacrylate, ethyldiethylene glycol acrylate, 2-ethylhexyl acrylate, glycerol methacrylate, heptadecafluorodecyl acrylate, 2-hydroxyethyl methacrylate, caprolactone-modified-2-hydroxyethyl acrylate, isobornyl acrylate, methoxydipropylene glycol acrylate, methoxy Cyclodecatriene acrylate, phenoxyhexaethylene glycol acrylate, EO-modified phosphate acrylate,
Caprolactone modified tetrahydrofurfuryl acrylate, EO modified bisphenol A diacrylate, ECH
Modified bisphenol A diacrylate, bisphenol A dimethacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate,
Diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol diacrylate, EO modified phosphoric acid 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, EO-modified phosphate triacrylate, EO-modified trimethylolpropane triacrylate, PO (propylene oxide) -modified trimethylolpropane triacrylate, tris (methacryloxyethyl) ) Isocyanurate, pentaerythritol tetraacrylate Dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, acrylate such as dipentaerythritol pentaacrylate, etc. methacrylates corresponding to these. These monomers are used alone or in combination of two or more.

As the photoinitiator (d) in the present invention,
For example, 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) -4,5-
Examples thereof include diphenylimidazole dimer. These photoinitiators are used alone or in combination of two or more.

It is essential that the organic solvent (e) in the present invention contains dipropylene glycol monoalkyl ether. Examples of the dipropylene glycol monoalkyl ether include dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol monoisobutyl ether,
Dipropylene glycol mono tert-butyl ether, dipropylene glycol mono isopentyl ether, etc. are mentioned. Among these, dipropylene glycol monomethyl ether and dipropylene glycol monoethyl ether are preferred. These are used alone or in combination of two or more.

The blending amount of the component (a) in the present invention is
The total amount of the components (a), (b), (c) and (d) is preferably 10 to 85% by weight, more preferably 20 to 60% by weight, and 25
It is particularly preferable to set the content to ˜50% by weight. If the content is less than 10% by weight, the dispersion stability of the pigment tends to be lowered, and if 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.

The blending amount of the component (b) in the present invention is
It is preferably 5 to 70% by weight based on the total amount of the components (a), (b), (c) and (d),
It is more preferably 10 to 40% by weight, and preferably 15 to 3
It is particularly preferable to set it to 0% by weight. This blended amount is 5
If it is less than wt%, the color density of the image tends to be too low,
If it exceeds 70% by weight, the photosensitivity tends to decrease.

The amount of component (c) used in the present invention is
It is preferably 2 to 50% by weight based on the total amount of the components (a), (b), (c) and (d),
It is more preferably 5 to 40% by weight, and 10 to 30% by weight.
It is particularly preferable to set it as the weight%. If the content is less than 2% by weight, the photosensitivity tends to be too low, and if it exceeds 50% by weight, the dispersion stability of the pigment tends to decrease.

The blending amount of the component (d) in the present invention is
It 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) and (d). -10
It is particularly preferable to set it as the weight%. This blending amount is 0.
If it is less than 01% by weight, the photosensitivity tends to be too low.
If it exceeds 0% by weight, the adhesion tends to decrease.

The amount of component (e) used in the present invention is
It is preferable that the total solid content including the component (a), the component (b), the component (c) and the component (d) is 5 to 40% by weight. If the total solid content of this blending amount is less than 5% by weight, it tends to take time to dry the coating film, and if it exceeds 40% by weight, the viscosity of the photosensitive solution is too high and the coating property tends to deteriorate. is there.

The photosensitive solution for forming a colored image of the present invention contains a thermal polymerization inhibitor (hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-
Butyl catechol, etc.), titanate coupling agents for improving adhesion to a substrate (a silane coupling agent having a vinyl group, an epoxy group, an amino group, a mercapto group, etc., isopropyl trimethacryloyl titanate,
Diisopropylisostearoyl-4-aminobenzoyl titanate, etc.), surfactants (fluorine-based, silicon-based, hydrocarbon-based, etc.) to improve the smoothness of the film, and various additions of ultraviolet absorbers, antioxidants, etc. The agent can be appropriately used if necessary.

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

Further, in the photosensitive liquid for forming a colored image of the present invention, a general organic solvent other than the organic solvent as the component (e) can be used. The amount used is preferably 90% by weight or less, and more preferably 50% by weight or less, based on the total amount of the component (e). If the amount used exceeds 90% by weight, the pigment dispersion becomes poor, and the effect of using the organic solvent as the component (e) tends to be weakened. Examples of these organic solvents include cyclohexanone, toluene, methyl ethyl ketone, xylene, ethylene glycol monoethyl ether, and ethylene glycol monomethyl ether acetate.

An example of producing the photosensitive liquid for forming a colored image of the present invention will be described below. First, in order to disperse the pigment of the component (b), the resin of the component (a) and the pigment of the component (b) are added (e).
Mix with the organic solvent of the components, this mixture with an ultrasonic disperser,
It is carried out by using various dispersing and kneading devices such as a triple roll, a ball mill, a sand mill, a bead mill, a homogenizer and a kneader. During this dispersion step, anionic pigment dispersants (polycarboxylic acid type polymer activators, polysulfonic acid type polymer activators, etc.), nonionic pigment dispersants (polyoxyethylene / polyoxypropylene block polymers, etc.) Substituents (carboxyl group, sulfonic acid group, sulfonic acid group, carboxylic acid amide group, sulfonic acid amide group, hydroxyl group, etc.) are added to pigment dispersants and organic pigments (anthraquinone type, perylene type, phthalocyanine type, quinacridone type, etc.). It is preferable to add a derivative of the introduced organic pigment, because the dispersibility and dispersion stability of the pigment are good. These pigment dispersants and organic pigment derivatives are based on 100 parts by weight of pigment.
Preferably, it is used in an amount of 50 parts by weight or less. Further, the component (c) and the component (d) can be added at the time of dispersing the pigment, and the component (c) and the component (d) can be added after the dispersion of the pigment.

The resin as the component (a) can be used together with the pigment in the whole amount, or a part of the resin can be used after being dispersed. However, it is preferable to use at least 20 parts by weight or more of the resin when dispersed, with respect to 100 parts by weight of the pigment. If the amount of the resin used is less than 20 parts by weight during dispersion, the dispersion stability of the pigment tends to decrease. Similarly, the entire amount of the organic solvent as the component (e) can be used when the pigment is dispersed, or a part of the organic solvent can be used after the dispersion. However, the organic solvent should be at least 1 part at the time of dispersion with respect to 100 parts by weight of the total amount of pigment and resin at the time of dispersion.
It is preferable to use more than 00 parts by weight. When the amount of the organic solvent used is less than 100 parts by weight at the time of dispersion, the viscosity at the time of dispersion is too high, and dispersion tends to be difficult particularly when the dispersion is carried out by a ball mill, a sand mill, a bead mill or the like.

In the method for producing a color filter of the present invention, the above-mentioned photosensitive liquid for forming a colored image of the present invention is applied onto a substrate and dried to form a film, and an actinic ray is imagewise irradiated to expose the exposed portion. This is a method of forming a pixel by repeating the step of photo-curing and removing the unexposed portion by development for a plurality of different colors.

Examples of the method of applying the above-mentioned colored image forming photosensitive solution of the present invention onto a substrate include roll coater coating, spin coater coating, spray coating, whaler coating, dip coater coating, curtain flow coater coating and wire bar. Examples include coater coating, gravure coater coating, air knife coater coating and the like. The substrate used at this time 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. Sheet, film or substrate, aluminum plate, copper plate,
Examples include metal substrates such as nickel plates and stainless plates, ceramic substrates, semiconductor substrates having photoelectric conversion elements, and the like. After application, usually at a temperature of 50 to 150 ° C. for 1 to 3
A film can be formed by drying for 0 minutes.

Next, 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, an oxygen shielding film such as polyvinyl alcohol having a thickness of 0.5 to 30 μm may be formed on the surface of the obtained film, and then the film may be exposed from above. Examples of the light source of actinic rays include carbon arc lamps, ultrahigh pressure mercury lamps, high pressure mercury lamps, xenon lamps, metal halide lamps, fluorescent lamps, tungsten lamps, and visible light lasers. By using these light sources, pattern exposure through a photomask or direct drawing by scanning,
The actinic ray is irradiated imagewise.

Then, a colored image pattern of the cured film corresponding to the image can be obtained by a developing process for removing the unexposed portion. As a developing method, an inorganic alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium metasilicate, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, triethylamine, n-
Examples thereof include a method of spraying an aqueous solution containing an organic base such as butylamine and a salt, a method of immersing in an aqueous solution, and the like. 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 ²
Post-heating at a temperature of 00 ° C. for 1 to 60 minutes is preferable because the image pattern becomes stronger.

The above steps are repeated for a plurality of different colors to form pixels to obtain a color filter. As a method for producing a color filter used in a liquid crystal display device, for example, by using the photosensitive solution for forming a colored image of the present invention on a glass substrate and repeating the above method, red, green and blue colored pixels are obtained. After forming the above, in the gap between the colored pixels, a method of forming a black colored pixel as a black matrix by the above-described method using the photosensitive liquid for colored image formation (black) of the present invention, chromium vapor deposition or Using the photosensitive liquid for forming an image (black) of the present invention, black colored pixels are formed as a black matrix by the above method, and then red, green and blue colored pixels are formed by the same method as described above. Methods and the like.

[0036]

The present invention will be described below with reference to examples. Example 1 10 g of the resin represented by the general formula (I) shown in Table 1 as the component (a), and carbon black 40 as the component (b).
g was added to 150 g of dipropylene glycol monomethyl ether as the component (e), and this was dispersed for 2 hours using a bead mill. In this dispersion, as the component (c),
30 g of pentaerythritol tetraacrylate,
As component (d), 12 g of benzophenone, 4 g of N, N'-tetraethyl-4,4'-diaminobenzophenone and 100 g of ethylene glycol monoethyl ether, which is an organic solvent other than component (e), were added and mixed to give a black colored image. A photosensitive liquid for formation was obtained. The obtained photosensitive solution is heated to 25 ° C.
The dispersion stability was defined as the number of days until the secondary aggregation started when the sample was allowed to stand still. Further, the obtained photosensitive liquid was used for a glass substrate (manufactured by Corning, trade name 705)
9) After being applied by spin coating on the surface, it is dried at 120 ° C. for 10 minutes to form a film having a thickness of 1.0 μm.
The appearance of the coating film when applied was visually evaluated, and the results are shown in Table 2.
It was shown to.

The obtained film was imagewise exposed to 600 mJ / cm ² through a negative mask with an ultra-high pressure mercury lamp, and then developed with an aqueous solution containing 3% by weight of triethanolamine to form a black image pattern. Obtained. The optical density of the obtained black image pattern was 2.5. The photosensitivity, resolution, and pattern shape of the obtained black image pattern were evaluated by the following methods, and the results are shown in Table 2. Photosensitivity: An optical density of 0.05 was set as the first step, and evaluation was performed using a 21-step step tablet in which the optical density increased by 0.15 for each step. The larger the value, the better the light sensitivity. Resolution: Evaluation was performed using a negative mask having a pattern having equal line and space widths (μm). It is indicated by the width (μm) of the smallest line and space that can be completely developed. The smaller this value, the better the resolution. Pattern shape: The surface condition and cross-sectional shape of the image pattern were evaluated. The more uniform the surface and the shorter the cross-sectional shape, the better the pattern shape.

Example 2 30 g of the resin represented by the general formula (II) shown in Table 1 as the component (a), and 21 g of CI Pigment Red 177 and CI Pigment Yellow 139 4 g as color index names as the component (b). Was added to a mixed solvent of 100 g of dipropylene glycol monoethyl ether as component (e) and 100 g of toluene, and this was dispersed for 2 hours using a bead mill. This dispersion is mixed with the above resin 5
g, 32 g of trimethylolpropane triacrylate as the component (c), and benzophenone 6 as the component (d).
g, N, N'-tetraethyl-4,4'-diaminobenzophenone (2 g) and dipropylene glycol monomethyl ether (200 g) as the component (e) were added and mixed to obtain a red colored image forming photosensitive solution. The obtained photosensitive solution is
The dispersion stability was evaluated in the same manner as in Example 1, and the results are shown in Table 2.
It was shown to. Further, a film having a thickness of 2.0 μm was formed on the obtained photosensitive solution in the same manner as in Example 1, and the appearance of the coating film when applied was visually evaluated, and the results are shown in Table 2. . The resulting film was imagewise exposed to 100 mJ / cm ² through a negative mask with an ultrahigh pressure mercury lamp, and then developed with an aqueous solution containing 3% by weight of triethanolamine to obtain a red image pattern. The photosensitivity, resolution, and pattern shape of the obtained red image pattern were evaluated in the same manner as in Example 1, and the results are shown in Table 2.

Example 3 40 g of the resin represented by the general formula (II) shown in Table 1 as the component (a), and CI Pigment Green 36 15 g and CI Pigment Yellow 835 5 g by the color index name as the component (b). Was added to a mixed solvent of 100 g of dipropylene glycol monoisopropyl ether as component (e) and 200 g of methyl ethyl ketone, and this was dispersed for 2 hours using a bead mill. In this dispersion,
As the component (c), 1,4-butanediacrylate 32
g, (d) component as benzophenone 6g, N, N '
-Tetraethyl-4,4'-diaminobenzophenone 2
g and 100 g of component (e), dipropylene glycol monomethyl ether, were added and mixed to obtain a green colored photosensitive solution for image formation. The resulting photosensitive solution was evaluated for dispersion stability in the same manner as in Example 1, and the results are shown in Table 2. Further, the obtained photosensitive solution was subjected to the same procedure as in Example 2 to form a film, and the appearance of the applied film was visually evaluated, and the results are shown in Table 2. The obtained film was exposed and developed in the same manner as in Example 2 to obtain a green image pattern.
The photosensitivity, resolution, and pattern shape of the obtained green image pattern were evaluated in the same manner as in Example 1, and the results are shown in Table 2.

Example 4 As component (a), 38 g of the acrylic resin shown in Table 1,
As a component (b), CI Pigment Blue 15-6 17 g and CI Pigment Violet 23 1 g with a color index name were added to a solvent of dipropylene glycol monoethyl 250 g as a component (e), and this was added using a bead mill. Time dispersed. In this dispersion,
36 g of trimethylolpropane triacrylate as the component (c), 6 g of benzophenone as the component (d),
2 g of N, N'-tetraethyl-4,4'-diaminobenzophenone and 100 g of ethylene glycol monoethyl ether, which is an organic solvent other than the component (e), and 50 g of toluene were added and mixed to give a blue colored image forming photosensitive solution. Obtained. The resulting photosensitive solution was evaluated for dispersion stability in the same manner as in Example 1, and the results are shown in Table 2. Further, the obtained photosensitive solution was subjected to the same procedure as in Example 2 to form a film, and the appearance of the applied film was visually evaluated, and the results are shown in Table 2. The obtained film was exposed in the same manner as in Example 2 and then developed with an aqueous solution containing 1% by weight of sodium carbonate,
A blue image pattern was obtained. The photosensitivity, resolution, and pattern shape of the obtained blue image pattern were evaluated in the same manner as in Example 1, and the results are shown in Table 2.

Comparative Example 1 A black colored image forming photosensitive solution was obtained in the same manner as in Example 1 except that ethylene glycol monoethyl ether was used instead of the component (e). The resulting photosensitive solution was evaluated for dispersion stability in the same manner as in Example 1, and the results are shown in Table 2. Further, the obtained photosensitive solution was treated in the same manner as in Example 1,
The appearance of the coating film when the film was formed and applied was visually evaluated, and the results are shown in Table 2. The obtained film was exposed and developed in the same manner as in Example 1 to obtain a green image pattern. The light sensitivity, resolution of the obtained green image pattern,
The pattern shape was evaluated in the same manner as in Example 1, and the results are shown in Table 2.

Comparative Example 2 A blue colored image forming photosensitive solution was obtained in the same manner as in Example 4 except that ethylene glycol monomethyl ether acetate was used as the component (e). The resulting photosensitive solution was evaluated for dispersion stability in the same manner as in Example 1, and the results are shown in Table 2. Further, the obtained photosensitive solution was subjected to the same procedure as in Example 4 to form a film, and the appearance of the applied film was visually evaluated, and the results are shown in Table 2. The obtained film was exposed and developed in the same manner as in Example 4 to obtain a blue image pattern. The photosensitivity, resolution, and pattern shape of the obtained blue image pattern were evaluated in the same manner as in Example 1, and the results are shown in Table 2.

[0043]

[Table 1]

[0044]

[Table 2]

It can be seen from Table 2 that the colored image-forming photosensitive liquids (Comparative Examples 1 and 2) prepared using organic solvents outside the range of (e) the organic solvent in the present invention have low pigment dispersion stability.
Secondary aggregation started within 10 days after preparation of the solution. In addition, the appearance of the coating film when these liquids were applied was poor due to uneven coating occurring everywhere. Similarly, the photosensitivity of the coating film was poor, the sensitivity and resolution were low, and there was a problem with the obtained pattern shape. On the other hand, the colored image-forming photosensitive liquids (Examples 1, 2, 3 and 4) produced by using the organic solvent of the component (e) in the present invention have high dispersion stability of the pigment, and after the liquid adjustment, 45 Secondary aggregation did not occur even if left for more than one day. The appearance of the coating film when these liquids were applied was extremely uniform and good. Similarly, the photosensitivity of the coating film is also good,
Both sensitivity and resolution were high, and the obtained pattern shape was rectangular and good.

Example 5 After forming a black matrix with chromium on the glass substrate used in Example 1, a red image pattern was formed in the same manner as in Example 2 and post-heating at 180 ° C. for 10 minutes. I went. Then, using the substrate, in the same manner as in Example 3, a green image pattern was formed next to the red image pattern, and post-heating was performed at 180 ° C. for 10 minutes. Next, using the substrate, a blue image pattern is formed next to the green image pattern in the same manner as in Example 4.
Post-heating was performed at 00 ° C. for 10 minutes. Thus, a high-quality color filter in which one pixel is composed of three colors of red, green, and blue of 30 μm × 100 μm and in which the pixels are arranged in a mosaic shape was manufactured.

Example 6 After forming a black image pattern (black matrix) on the glass substrate used in Example 1 in the same manner as in Example 1, post-heating was performed at 205 ° C. for 20 minutes. Next, in the same manner as in Example 5, pixels are formed in the order of red, green, and blue, and one pixel is 30 μm × 100 μm red,
A high-quality color filter having pixels arranged in a mosaic of three colors of green and blue was produced.

As in Examples 5 and 6, the color filters produced by using a photosensitive solution having a good dispersion stability, which has not been used in the past, have a depolarization of 500 or more, which is excellent in optical characteristics and image display. It was confirmed that the device was excellent.

[0049]

EFFECT OF THE INVENTION The photosensitive liquid for forming a colored image according to claim 1 has a high dispersibility and dispersion stability of the pigment, and a film having an excellent coating film appearance can be obtained. The colored image forming photosensitive solution according to claim 2 exhibits the effect of the colored image forming photosensitive solution according to claim 1, has higher dispersibility and dispersion stability, and further has excellent heat resistance of the obtained film. The method for producing a color filter according to claim 3 can produce a high-quality color filter having excellent optical characteristics. The color filter according to claim 4 has excellent optical characteristics, high quality, and is excellent as an image display device.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical indication location G03F 7/027 G03F 7/027 7/028 7/028 (72) Inventor Satoshi Akahori Hitachi City, Ibaraki Prefecture 4-13-1 Higashimachi Hitachi Chemical Co., Ltd. Ibaraki Research Institute (72) Inventor Koji Yamazaki 4-13-1 Higashimachi Hitachi City, Ibaraki Hitachi Chemical Co., Ltd. Ibaraki Research Institute (72) Inventor Yoichi Kimura 14 Goi Minami Coast, Ichihara City, Chiba Prefecture Goi Plant, Hitachi Chemical Co., Ltd.

Claims (4)

[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, and (c) one or more photopolymerizable unsaturated bonds in the molecule. A photosensitive liquid for forming a colored image, which comprises a monomer, (d) a photoinitiator, and (e) an organic solvent, wherein the organic solvent contains dipropylene glycol monoalkyl ether. 2. A resin having (a) an acid value of 20 to 300 and a weight average molecular weight of 1,500 to 200,000 has the 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 photoreactive unsaturated bond, m and n are integers of 1 or more, and 1 ≦ m / n ≦ 5 2. The photosensitive liquid for forming a colored image according to claim 1, which is a resin represented by the following formula. 3. The photosensitive liquid for forming a colored image according to claim 1 or 2 is applied onto a substrate and dried to form a film, which is irradiated with actinic rays in an imagewise manner, and the exposed portion is photocured. A method of manufacturing a color filter, wherein the step of removing the exposed portion by development is repeated for a plurality of different colors to form pixels. 4. A color filter manufactured by the method for manufacturing a color filter according to claim 3.