JPH11142639A - Production of black matrix and color filter and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain high optical density and good resolution without using chromium by exposing a film containing a resin, a black pigment, monomers having photopolymerizable unsatd. bonds and a photopolymn. initiator to active rays from a metal halide lamp according to an image to harden the exposed part with light and then removing the unexposed part by developing. SOLUTION: A film comprising a photosensitive material for the formation of a color image is formed, and this film contains a resin, a black pigment, monomers having one or more photopolymerizable unsatd. bonds in the molecule, and a photopolymn. initiator. The film is irradiated with active rays from a metal halide lamp according to an image to harden the exposed part, and then the unexposed part is removed by developing to form a black matrix. As the metal halide lamp, a lamp especially enhanced in 300 to 450 nm wavelength region is used. The light quantity of for exposure is usually 10 to 1000 mJ/cm<2> , preferably 50 to 500 mJ/cm<2> .

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a black matrix of a color filter used in a liquid crystal display device, a sensor, a color separation device, etc., a method for producing a color filter, and a color filter obtained by the method. .

[0002]

2. Description of the Related Art In recent years, color filters have been frequently used in liquid crystal display devices, sensors, color separation devices, and the like. Conventionally, as a method for producing this color filter, a dyeable resin, for example, a material obtained by imparting photosensitivity to natural gelatin or casein is subjected to pattern exposure and development.
A method of forming a colored pixel by mainly dyeing with a dye has been adopted. However, the pixel obtained by this method has a problem that heat resistance and light resistance are low due to restrictions on materials. Therefore, recently, for the purpose of improving heat resistance and light resistance, a method of forming a colored image by pattern exposure and development using a colored photosensitive resin material in which a pigment is dispersed has attracted attention, and many studies have been made. Began to take place. According to this method, it is known that the method for producing a color filter is also simplified, and the obtained color filter is stable and has a long life.

[0003] In addition, metal chromium has conventionally been used as a black matrix used for a color filter.
Recently, two-layer chromium having low reflection has been used. However, in the case of a chromium-based black matrix, treatment of chromium becomes a major problem when the color filter is discarded. Therefore, a resin black matrix is being studied in place of the chromium black matrix. However, when the resin black matrix is formed by photolithography, the optical density (OD
Value cannot be increased, while the black matrix formed by the etching method or the lift-off method has a problem that the number of steps increases.

[0004]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art by using a metal Hide lamp light source for pattern exposure of a black matrix. It is an object of the present invention to provide a method for producing a black matrix and a color filter capable of obtaining high and good resolution and a color filter obtained by the method.

[0005]

Means for Solving the Problems As a result of repeated studies to solve the above problems, the present inventors have found that the use of a specific colored image forming photosensitive material and the use of a metal Hide lamp light source for exposure has resulted in an OD. It has been found that the resolution and pattern adhesion of a black matrix having an optical density of 2 to 5 can be improved, and the present invention has been completed.

That is, the present invention comprises (a) a resin, (b) a black pigment, (c) a monomer containing at least one photopolymerizable unsaturated bond in a molecule, and (d) a photopolymerization initiator. A black matrix is formed by irradiating actinic rays of a metal halide lamp imagewise onto the film made of a photosensitive material for forming a colored image, thereby exposing the film to light and curing the exposed portions, and removing the unexposed portions by development. And a process for producing a black matrix.

Further, the present invention provides a method for irradiating actinic rays of a metal halide lamp onto a film made of the photosensitive material for forming a colored image described above in an image-like manner to cure the exposed portion and develop the unexposed portion. Forming a black matrix by removing the film, and forming a film on the substrate one by one using a plurality of colored image forming photosensitive materials of different colors, and then irradiating the film with an actinic ray imagewise. And subjecting the exposed portions to photo-curing, and removing the unexposed portions by development to repeatedly form pixels of different colors, thereby providing a method for producing a color filter.

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

[0009]

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

[Exposure of Pattern] In the method for producing a black matrix and a color filter of the present invention, it is essential to expose a photosensitive material for black image formation with a metal halide lamp light source. 300 ~ for metal halide lamps
A metal halide exposure apparatus having a 450 nm wavelength region particularly enhanced is used as a metal halide exposure apparatus having a metal halide lamp light source. MHM-5000 manufactured by Oak Manufacturing Co., Ltd.
H, SMX-7000H, SMX-12KSH and the like. Exposure light amount is usually 10 to 1,000 mJ / cm
² , preferably 50 to 500 mJ / cm ² .

The photosensitive material for forming a red image, the photosensitive material for forming a blue image and the photosensitive material for forming a green image may be exposed using a metal halide lamp light source, or may be a carbon arc lamp, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a xenon. lamp,
The exposure may be performed using a fluorescent lamp, a tungsten lamp, or a visible light laser. 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.

[Photosensitive Material for Forming a Colored Image] The resin as the component (a) of the photosensitive material for forming a colored image of the present invention preferably has an acid value of 20 to 300 and a weight average molecular weight of 1,500.
~ 200,000 resins are used. Such a resin is not particularly limited, but a carboxyl group-containing resin,
For example, acrylic acid, methacrylic acid, carboxyl group-containing polymerizable monomers such as itaconic acid, methyl acrylate, ethyl acrylate, acrylates such as n-butyl acrylate, methyl methacrylate, methacrylates such as ethyl methacrylate, styrene and the like A typical example is a copolymer with a polymerizable monomer.

Further, from the viewpoint of improving the photosensitivity of the photosensitive material, a carboxyl group-containing resin having a photopolymerizable unsaturated bond is also a preferred example of the resin (a).

Examples of the carboxyl group-containing resin having a photopolymerizable unsaturated bond include a resin obtained by reacting a carboxyl group-containing resin having a hydroxyl group with an unsaturated compound having a free isocyanate group, and a resin obtained by reacting an epoxy resin with an unsaturated carboxylic acid. A resin obtained by reacting a polybasic acid anhydride with an addition reaction product, a resin obtained by reacting a hydroxyl group-containing polymerizable monomer with an addition reaction product of a conjugated diene polymer or a conjugated diene copolymer and an unsaturated dicarboxylic acid anhydride, Group-containing resins, for example,
Glycidyl group-containing unsaturated compounds such as glycidyl methacrylate and allyl glycidyl ether, and resins obtained by reacting the above-mentioned carboxyl group-containing resin with unsaturated alcohols such as allyl alcohol, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate. ,
A repeating unit represented by the following general formula (I), a repeating unit represented by the following general formula (II), and a repeating unit represented by the following general formula (II)
It consists of the repeating unit (III) represented by I), and the repeating unit (I) and the repeating units (II) and (III)
(I) / {(II) + (III)}
Is a resin of 1 to 5, and among them, from the viewpoint of improving the heat resistance of the pixel and the dispersibility of the pigment, a resin including the above repeating units (I), (II) and (III) is preferable.

[0015]

Embedded image (In the above general formula, R ¹ represents a hydrogen atom or a methyl group,
R ² represents a hydrogen atom, a hydroxyl group or an alkyl group or an alkoxy group having 1 to 12 carbon atoms, and R ³ , R ⁴ and R ⁵ each independently represent an alkyl group having 1 to 12 carbon atoms or a photopolymerizable unsaturated bond. Wherein at least one of R ³ , R ⁴ and R ⁵ is a group having a photopolymerizable unsaturated bond. The method for producing a resin comprising the above repeating units (I), (II) and (III) includes, for example, the repeating (I)
And a precursor resin comprising (II), an unsaturated alcohol such as allyl alcohol, 2-buten-4-ol, furfuryl alcohol, oleyl alcohol, cinnamyl alcohol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, A method of producing by subjecting N-methylol acrylamide or the like to an esterification reaction, a compound having one oxirane ring and one ethylenically unsaturated bond in the precursor resin, for example, glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, α-ethyl A method in which glycidyl acrylate, crotonyl glycidyl ether, monoalkyl monoglycidyl itaconate, or the like is subjected to an addition reaction at a ratio of less than equimolar, and the like, may be mentioned.

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

As the styrene derivative, for example, α-methylstyrene, m or p-methylstyrene, m or p-methylstyrene
Methoxystyrene, p-hydroxystyrene, 2-methoxy-4-hydroxystyrene, 2-hydroxy-4-
Methylstyrene and the like can be mentioned.

Examples of the monoalkyl maleate include, for example, mono-C _1-12 alkyl maleate such as monomethyl maleate, monoethyl maleate, mono-n-propyl maleate, monoisopropyl maleate, and mono-maleate. n-butyl, mono-n-hexyl maleate, mono-n-octyl maleate,
Mono-2-ethylhexyl maleate, mono-n-nonyl maleate, mono-n-dodecyl maleate and the like can be mentioned.

The unsaturated equivalent of the resin comprising the above repeating units (I), (II) and (III) is 400 to 3,
000, and more preferably 500 to 2,000. When the unsaturated equivalent is less than 400,
When it is dispersed with a pigment, it tends to partially cure,
If it exceeds 300, the effect of improving photosensitivity tends to decrease. Here, the unsaturated equivalent means the molecular weight of the resin per one unsaturated bond. A molar ratio of the repeating unit (I) to the total of the repeating units (II) and (III);
(I) / {(II) + (III)} is preferably from 1 to 5, more preferably from 1 to 3. When the molar ratio is less than 1, the heat resistance of the pixel tends to decrease, and when it exceeds 5, the solubility of the coating film tends to decrease.

The acid value of the resin (a) is preferably 20 to 300, more preferably 40 to 200, and more preferably 60 to 1
More preferably, it is 50. If the acid value is less than 20, the alkali developability tends to decrease.
If it exceeds 0, the shape of the image pattern tends to be unclear.

The weight average molecular weight of the resin (a) (measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve) is preferably from 1,500 to 200,000, , 0
It is more preferably set to 100 to 100,000, and 1
More preferably, it is set to be in the range of 0000 to 50,000. When the weight average molecular weight is less than 1,500, the dispersion stability of the black pigment tends to decrease, and 200,0
If it exceeds 00, the viscosity of the photosensitive material becomes high,
There is a tendency that the coatability at the time of coating on a substrate is reduced and a uniform coating film is hardly obtained.

The above various resins exemplified as the resin (a) may be used alone or in combination of two or more. For the purpose of improving the heat resistance of the pixel and the dispersibility of the black pigment, the above repeating units (I), (II) and (I)
When a resin having a photopolymerizable unsaturated group consisting of II) is used, the proportion of the resin having a photopolymerizable unsaturated group is 10 to 100% by weight based on the total amount of the resin (a). Is preferably, and more preferably, 30 to 100% by weight.

The amount of the resin (a) used in the present invention is 10 to 85% by weight based on the total amount of the resin (a), the black pigment (b), the monomer (c) and the photopolymerization initiator (d). Is preferably 20 to 60% by weight, more preferably 25 to 50% by weight. If the amount is less than 10% by weight, the dispersion stability of the black pigment tends to decrease. If the amount exceeds 85% by weight, the viscosity when used as a photosensitive material increases, and the coatability decreases, resulting in a uniform coating. A film tends to be difficult to obtain.

As the black pigment (b) used in the present invention, any of inorganic pigments and organic pigments can be used. Usually, a mixture of inorganic pigments such as black carbon black, graphite, iron black, titanium carbon, manganese dioxide, copper chromium manganese oxide, and organic pigments can be used.However, from the viewpoint of coloring power, carbon black or carbon black and phthalocyanine can be used. Preferred are combinations of blue pigments. Further, carbon black having a resin-coated surface or carbon black having been subjected to graft polymerization may be used. The amount of the black pigment used is such that the optical density of the black matrix becomes 2 to 5. Preferably, the amount is such that the optical density is 3 to 4 from the viewpoint of light shielding properties. If the optical density is less than 2, the light-shielding property tends to decrease, and if the optical density exceeds 5, the adhesion tends to decrease and the pattern tends to flow during development. When a black pigment is used so that the optical density becomes 2 or more when exposure is performed using a high-pressure mercury lamp or the like without using a metal halide lamp, a pattern flow occurs.

The amount of the black pigment (b) used in the method for producing a black matrix of the present invention is 5% of the total amount of the resin (a), the black pigment (b), the monomer (c) and the photopolymerization initiator (d). To 70% by weight, preferably 10 to 5% by weight.
More preferably 0% by weight, 15 to 40% by weight
It is particularly preferred that If the amount is less than 5% by weight, the optical density tends to decrease, and if it exceeds 70% by weight, the light sensitivity tends to decrease.

Examples of the organic pigment include azo-based, phthalocyanine-based, indigo-based, anthraquinone-based, perylene-based, quinacridone-based, methine-azomethine-based organic pigments similar to the organic pigments used in the photosensitive material for forming a colored image of a color filter. Isoindolinones and the like can be mentioned.

In the photosensitive material for forming a colored image of a color filter, each pigment system suitable for a colored image such as red, green and blue is preferably used in place of the above-mentioned black pigment (b). The photosensitive material for forming a colored image of the color filter is preferably a photosensitive material for forming a colored image containing the components (a), (c) and (d) used for the photosensitive material for forming a colored image of a black matrix. Used for

For a red colored image, a single red pigment system may be used, or a yellow pigment system may be mixed with a red pigment system for toning.

The red pigments include, for example, C.I. I. Pingment Red 9, 12
3, 155, 168, 177, 180, 217, 22
0, 224 and the like.

The yellow pigments include, for example, C.I. I. Pigment Yellow 20, 2
4, 83, 93, 109, 110, 117, 125, 1
39, 147, 154 and the like.

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

For a green colored image, a single green pigment system may be used, or the above-mentioned yellow pigment system may be mixed with a green pigment system to perform toning.

The green pigments include, for example, C.I. I. Pigment Green 7, 36,
37 and the like.

These green pigments and yellow pigments can be used as a mixture of two or more kinds. In addition,
When using a mixture of a green pigment system and a yellow pigment system, it is preferable to use 50 parts by weight or less of the yellow pigment system based on 100 parts by weight of the total amount of the green pigment system and the yellow pigment system.

For a blue colored image, a single blue pigment system may be used, or a violet pigment system may be mixed with a blue pigment system for toning.

The blue pigments include, for example, C.I. I. Pigment Blue 15, 15:
3, 15: 4, 15: 6, 22, 60 and the like.

The purple pigments include, for example, C.I. I. Pigment Violet 19,
23, 29, 37, 50 and the like.

These blue pigments and 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 amount of the blue pigment and the violet pigment.

The monomer (c) having one or more photopolymerizable unsaturated bonds in the molecule used in the present invention includes, for example, methyl methacrylate, lauryl methacrylate,
Benzyl methacrylate, butoxyethyl methacrylate, butoxyethyl acrylate, butoxytriethylene glycol acrylate, ECH-modified butyl acrylate (here, ECH means epichlorohydrin; the same applies hereinafter), dicyclopentyl acrylate,
Dicyclopentenyloxyethyl methacrylate, N,
N-dimethylaminoethyl methacrylate, ethyl diethylene glycol acrylate, 2-ethylhexyl acrylate, glycerol methacrylate, heptadecafluorodecyl acrylate, 2-hydroxyethyl methacrylate, caprolactone-modified 2-hydroxyethyl acrylate, isobornyl acrylate, methoxydipropylene glycol acrylate Methoxylated cyclodecatriene acrylate, phenoxyhexaethylene glycol acrylate, EO-modified phosphate acrylate (here, EO means ethylene oxide; the same applies hereinafter), caprolactone-modified tetrahydrofurfuryl acrylate, EO-modified bisphenol A diacrylate, ECH-modified bisphenol A diacrylate, bisphenol di Methacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, diethylene glycol dimethacrylate,
Glycerol dimethacrylate, neopentyl glycol diacrylate, stearyl methylene diacrylate, myristyl methylene diacrylate, EO-modified phosphate diacrylate, ECH-modified phthalic acid diacrylate, polyethylene glycol 400 diacrylate, polypropylene glycol 400 dimethacrylate, tetraethylene glycol diacrylate Acrylate, ECH modified 1,
6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, EO-modified phosphate triacrylate, EO
Modified trimethylolpropane triacrylate, PO-modified trimethylolpropane triacrylate (where
PO means propylene oxide. The same applies to the following. ), Tris (methacryloxyethyl) isocyanurate, acrylates such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and the like, and methacrylates corresponding thereto. Can be
These monomers are used alone or in combination of two or more.

The amount of the monomer (c) used in the present invention is 2 to 50% by weight based on the total amount of the resin (a), the black pigment (b), the monomer (c) and the photopolymerization initiator (d). Is preferably 5 to 40% by weight, and particularly preferably 10 to 30% by weight. When the proportion of the monomer is less than 2% by weight, the light sensitivity tends to be low. If it exceeds 50% by weight, the dispersion stability of the black pigment tends to decrease.

In the present invention, the weight ratio (a) / (c) of the compounding amount of the resin (a) and the monomer (c) is 0.5 to 5.0.
It is preferably 0, more preferably 0.7 to 3.5, and particularly preferably 1.0 to 2.5. If this ratio is less than 0.5, the surface tackiness of the dried coating film tends to deteriorate, and if it exceeds 5.0, the light sensitivity tends to decrease.

The amount of the photopolymerization initiator (d) used in the photosensitive material for forming a colored image in the present invention is as follows: the resin (a), the black pigment (b), the monomer (c) and the photopolymerization initiator (d). Is preferably 0.01 to 20% by weight of the total amount of
It is more preferably set to 15 to 15% by weight, and particularly preferably set to 3 to 12% by weight. When the blending amount is 0.01
If it is less than 20% by weight, the light sensitivity tends to be low,
If the content is more than 10% by weight, the adhesion to the substrate tends to decrease.

In addition, as the photopolymerization initiator of the component (d) in the present invention, a general photopolymerization initiator can be used. Examples of these photopolymerization initiators include benzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, benzyl, 2,2-diethoxyacetophenone, and 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-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-
(Morpholinophenyl) butan-1-one, 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 , 2,2'-bis (2
-Chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole or 2,2'-bis (2-chlorophenyl) -4,5,4', 5'-tetra (3 , 4-Methylenedioxyphenyl) -1,1'-bi-1H-imidazole, 2- (p-methoxystyryl)
-4,6-bis (trichloromethyl) -s-triazine and the like.

When the photosensitive material for forming a colored image of the present invention containing the above resin (a), black pigment (b), monomer (c) and photopolymerization initiator (d) as essential components is used for coating. ,
Usually, the essential components (a), (b), (c) and (d) are dissolved and decomposed in an organic solvent to be used as a coating solution (hereinafter sometimes referred to as a colored image forming photosensitive solution). Examples of the organic solvent that can be used for the colored image forming photosensitive material of the present invention include:
For example, ketone type, cellosolve type, alcohol type, aromatic type and the like can be mentioned. Specifically, acetone, methyl ethyl ketone, cyclohexanone, methyl cellosolve (ethylene glycol monomethyl ether), ethyl cellosolve (ethylene glycol monoethyl ether), butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, ethylene glycol monopropyl ether, ethylene glycol Glycol monohexyl ether, ethylene glycol dimethyl ether, diethylene glycol ethyl ether,
Triethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monoethyl ether, propylene glycol diethyl ether, propylene glycol monopropyl ether, propylene glycol diisopropyl 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,
Organic solvents such as tetrahydrofuran, dioxane, benzene, toluene, xylene, and ethyl acetate are exemplified.
These organic solvents are used alone or in combination of two or more.

When the photosensitive material for forming a colored image of the present invention is dissolved and decomposed in an organic solvent, the amount of the organic solvent is such that the proportion of the organic solvent in the photosensitive material for forming a colored image is 60 to 95% by weight. It is preferred to be an amount. 95 of organic solvent
When the amount is more than 10% by weight, it takes a long time to dry the coating film of the colored image forming photosensitive solution containing the organic solvent.
If the amount is less than 0% by weight, the viscosity of the photosensitive solution tends to be too high, and the coatability tends to decrease.

The photosensitive material for forming a colored image of the present invention suppresses a dark reaction in addition to the essential components (a) resin, (b) black pigment, (c) monomer, and (d) photopolymerization initiator. Hydroquinone, hydroquinone monomethyl ether, pyrogallol, thermal polymerization inhibitors such as t-butyl catechol, a vinyl group for improving the adhesion to the substrate, an epoxy group, an amino group, a silane coupling agent having a mercapto group and the like , Titanate coupling agents such as isopropyltrimethacryloyl titanate, diisopropylisostearoyl-4-aminobenzoyl titanate,
Fluorine-based, silicon-based to improve the smoothness of the film,
Various additives such as a hydrocarbon-based surfactant and other additives such as an ultraviolet absorber and an antioxidant can be used as needed. The total amount of these additives is usually
The amount is preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight based on 100 parts by weight of the total solid content comprising the components (a), (b), (c) and (d). Is more preferred.

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

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

First, in order to disperse the black pigment of the component (b), the resin of the component (a) and the black pigment of the component (b) are mixed with an organic solvent. The dispersion is performed using a dispersion / kneading apparatus such as a ball mill, a sand mill, a bead mill, a homogenizer, and a kneader.

In this dispersion step, 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. Pigment dispersants, anthraquinone-based, perylene-based, phthalocyanine-based, and quinacridone-based organic pigments are introduced with a substituent such as a carboxyl group, a sulfonic acid group, a sulfonate group, a carboxamide group, a sulfonamide group, or a hydroxyl group. Addition of a derivative of an organic pigment or the like is preferable because the dispersibility and dispersion stability of the pigment are improved.

These pigment dispersants and organic pigment derivatives are:
It is preferable to use 50 parts by weight or less based on 100 parts by weight of the black pigment.

Further, the monomer of component (c) and the photopolymerization initiator of component (d) may be added at the time of dispersion of the black pigment, and after the black pigment is dispersed, the monomer of component (c) and the photopolymerization of component (d) can be started. Agents may be added.

The resin of component (a) may be used in its entirety together with the black pigment at the time of dispersion, or a part of the resin may be added after the dispersion. However, it is preferable to use at least 20 parts by weight of the resin at the time of dispersion with respect to 100 parts by weight of the black pigment. If the amount of the resin used is less than 20 parts by weight at the time of dispersion, the dispersion stability of the black pigment tends to decrease.

Similarly, the organic solvent may be used in its entirety when the black pigment is dispersed, or a part of the organic solvent may be added after the dispersion. However, the organic solvent is at least 100 parts by weight based on 100 parts by weight of the total amount of the black pigment and the resin at the time of dispersion.
It is preferable to use at least part by weight. When the amount of the organic solvent used is less than 100 parts by weight at the time of dispersion, the viscosity at the time of dispersion is too high, and dispersion may be difficult particularly when the dispersion is carried out by a ball mill, a sand mill, a bead mill or the like.

The method of applying the photosensitive liquid for forming a colored image containing the photosensitive material for forming a colored image of the present invention and the other photosensitive liquid containing the photosensitive material for forming a colored image to a substrate is as follows.
For example, the coating is performed by roll coater coating, spin coater coating, spray coating, whey coater coating, dip coater coating, curtain flow coater coating, wire 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 plate glass, a blue plate glass, a silica-coated blue plate glass, a polyester resin, a polycarbonate resin, an acrylic resin, a vinyl chloride resin, etc. Examples include a synthetic resin sheet, film or substrate, a metal substrate such as an aluminum plate, a copper plate, a nickel plate, and a stainless steel plate, other ceramic substrates, and a semiconductor substrate having a photoelectric conversion element.

After the coating, the coating is preferably dried by blowing heated air (dry air) on the coating or by placing the substrate on a heated hot plate. . The heating temperature of the drying air or the hot plate is usually preferably from 30 to 200 ° C, particularly preferably from 50 to 130 ° C, and the film can be formed by heating for 1 to 30 minutes. The heating temperature may be kept constant during drying, but may be increased stepwise.

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 photosensitive material (the thickness of the layer is usually 0.1 to 300 μm,
Preferably 0.2 to 30 μm, more preferably 0.2 to 30 μm
5 μm) to form a photosensitive element, which may be laminated on a substrate or the like to form a film on the substrate surface. 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 in this case,
For example, a film such as a polyester film, a polyamideimide film, a polypropylene film, and a polystyrene film may be used. 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, and a surface-treated paper. 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 colored image forming material formed on the substrate surface in this way is appropriately determined depending on the application, but usually,
It is used 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 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.
It may be formed with a thickness of μm and exposed from above.

As a light source of the actinic ray, a metal halide lamp is used when a black matrix is formed. However, when a color pixel is formed, other than a metal halide lamp, for example, a carbon arc lamp, an ultra-high pressure mercury lamp, a high pressure A mercury lamp, a xenon lamp, a fluorescent lamp, a tungsten lamp, a visible light laser or the like is preferably used. Using these light sources, an active light beam is irradiated in an image form by pattern exposure through a photomask, direct drawing by scanning, or the like. Exposure light amount is usually 10 to 1,0
00 mJ / cm ² , preferably 50 to 500 mJ / cm ²
It is.

Subsequently, a colored image pattern of the cured film corresponding to the image can be obtained by a developing step of removing the unexposed portions.

As the developing method, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate and sodium metasilicate, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, triethylamine, n-
Examples thereof include a method of spraying an aqueous solution containing an organic base such as butylamine and a salt, and a method of dipping in an aqueous solution.

After development, the colored image pattern is further
0.5 to 5 J / cm using silver lamp etc. ^TwoIrradiate the amount of light
Post-exposure or after 1-60 minutes at 60-200 ° C
Preferably, heating is performed. After this exposure and post-heating
Therefore, the image pattern becomes stronger.

By repeating the above steps using a plurality of colored image forming photosensitive materials of a plurality of different colors, a color filter having pixels of a plurality of different colors can be manufactured.

As a specific example, a method of manufacturing a color filter used in a liquid crystal display element is illustrated. For example, by repeating the above-described method three times using a photosensitive material for forming a colored image on a glass substrate, red and green are obtained. After forming a colored pixel of blue or the like, 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 with a black colored image or the like in the same manner as above, The formation of colored pixels such as red, green, and blue
There is a method in which a color filter is manufactured by repeating the process twice.

[0069]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples of the present invention and Comparative Examples thereof, but the present invention is not limited to these Examples.

Example 1 As the resin (a), the repeating units (I) and (I) shown in Table 1 were used.
Resin having I) and (III) (25 g) and carbon black (40 g) as pigment (b) were mixed with propylene glycol dimethyl ether (200) as an organic solvent.
In addition to g), this was dissolved and dispersed using a bead mill for 2 hours. To this dispersion, pentaerythritol tetraacrylate (20 g) as a monomer (c) and 2-benzyl-2-dimethylamino- as a photopolymerization initiator (d) were added.
1- (4-morpholinophenyl) -butan-1-one (13 g) and ethylene glycol monoethyl ether (200 g) as an organic solvent were added and mixed to obtain a black colored image forming photosensitive liquid.

The obtained photosensitive solution was applied on a glass substrate (Corning Co., trade name: 7059) by spin coating, and then dried on a hot plate at 100 ° C. for 10 minutes to form a film having a thickness of 1.3 μm. A dried coating film was formed.

Then, a metal halide lamp (manufactured by Oak Manufacturing Co., Ltd., MHM-
5,000 H), imagewise exposure of 200 mJ / cm ² , development with an aqueous solution containing 3% by weight of tetramethylammonium hydroxide,
Post-baking was performed at 0 ° C. for 30 minutes to obtain a black matrix pattern. The obtained black matrix had a thickness of 1.2 μm and an optical density of 3.6. Table 2 shows the results.

Example 2 As the resin (a), the repeating units (I) and (I) shown in Table 1 were used.
Resin having (I) and (III) (35 g) and C.I. I. Pigment Red 177 (21 g) and C.I. I. Pigment Yellow 139 (4 g) was added to propylene glycol diethyl ether (250 g) as an organic solvent, and this was dissolved and dispersed using a bead mill for 2 hours. This dispersion was mixed with the above resin (5 g), trimethylolpropane triacrylate (32 g) as monomer (c), and 2- (p-methoxystyryl)-as photopolymerization initiator (d).
4,6-bis (trichloromethyl) -s-triazine (8 g), and propylene glycol diisopropyl ether (50 g) and ethylene glycol monomethyl ether acetate (100 g) as organic solvents were added and mixed, and the mixture was mixed with a red color image forming photosensitive solution. A liquid was obtained.

Using the obtained photosensitive liquid, a dried coating film having a thickness of 2.0 μm was formed in the same manner as in Example 1, and then the dried coating film was image-formed with a metal halide lamp through a negative mask at 200 mJ / cm ^2. And then developed with an aqueous solution containing 3% by weight of tetramethylammonium hydroxide, and post-baked at 200 ° C. for 30 minutes to obtain a red image pattern.

Example 3 As the resin (a), repeating units (I) and (I) shown in Table 1 were used.
Resin having (I) and (III) (40 g) and C.I. I. Pigment Green 36 (15 g) and C.I. I. Pigment Yellow 83 (6 g) was added to propylene glycol monomethyl ether (200 g) as an organic solvent, and this was dissolved and dispersed using a bead mill for 2 hours. To this dispersion, pentaerythritol tetraacrylate (31 g) as a monomer (c) and 2 as a photopolymerization initiator (d) were added.
-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (5 g) and 2-
(P-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine (5 g) and propylene glycol monomethyl ether (200 g) as an organic solvent
g) was added and mixed to obtain a green colored image forming photosensitive liquid. Using the obtained photosensitive liquid, a dried coating film having a thickness of 2.0 μm was formed in the same manner as in Example 1, and the dried coating film was image-formed by a metal halide lamp through a negative mask.
Exposure was performed at 0 mJ / cm ² , development was performed with an aqueous solution containing 3% by weight of tetramethylammonium hydroxide, and post-baking was performed at 200 ° C. for 30 minutes to obtain a green image pattern.

Example 4 As the resin (a), the repeating units (I) and (I) shown in Table 1 were used.
Resin having (I) and (III) (40 g) and C.I. I. Pigment Blue 15: 6 (17 g) and C.I. I. Pigment Violet 23 (1 g) was added to propylene glycol monomethyl ether (260 g) as an organic solvent, and this was dissolved and dispersed using a bead mill for 2 hours. In this dispersion, trimethylolpropane triacrylate (36 g) was used as the monomer (c), and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1- was used as the photopolymerization initiator (d). ON (5g) and 2
-(P-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine (5 g), and ethylene glycol monomethyl ether (140
g) was added and mixed to obtain a blue colored photosensitive liquid for image formation. Using the obtained photosensitive solution, a dried coating film having a thickness of 2.0 μm was formed in the same manner as in Example 1. A blue image pattern was obtained in the same manner as in Example 1, except that development was performed using an aqueous solution containing 0.5% by weight of sodium carbonate.

Example 5 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 1.5 μm-thick film.
m, a layer containing a colored photosensitive material for forming an image was formed, and a 40 μm-thick polyethylene film was coated thereon to obtain a photosensitive element.

After the polyethylene film was peeled off from the obtained photosensitive element, it was laminated on the same glass substrate as 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, through a negative mask, an image of 80 mJ / cm ² was exposed imagewise from above the polyethylene terephthalate film with a metal halide lamp (MHM-5000H, manufactured by Oak Manufacturing Co., Ltd.), and the polyethylene terephthalate film was peeled off. Example 1
The development was carried out in the same manner and conditions as in
A minute post-bake was performed to obtain a black matrix pattern.

Example 6 Acrylic resin B (38 g) shown in Table 1 as resin (a)
A black colored image forming photosensitive liquid was obtained in the same manner as in Example 1 except that was used.

Using the obtained photosensitive liquid, a dried coating film having a thickness of 1.5 μm was formed in the same manner as in Example 1, and then developed with an aqueous solution containing 3% by weight of tetramethylammonium hydroxide. Table 2 shows the results.

Comparative Example 1 A dried coating film was formed in the same manner as in Example 1, and exposure was performed in the same manner as in Example 1 except that the metal halide lamp was changed to an ultra-high pressure mercury lamp as a light source for the exposure. Was. Table 2 shows the results.

Comparative Example 2 The same phenomenon as in Example 1 was carried out except that the metal halide lamp was changed to a high-pressure mercury lamp as a light source for exposure, and the phenomenon was carried out. Table 2 shows the results.

[0084]

[Table 1]

[0085]

[Table 2] Light sensitivity: The optical density of 0.00 is the first step, and 41 steps of step tablets are prepared in which the optical density increases by 0.05 for each step, and the step tablets are placed on the dried coating film. Exposure was performed at 200 mJ / cm ² using the light source used in each of Examples and Comparative Examples, and then development was performed using an aqueous solution containing 3% by weight of triethanolamine. Observed. Table 2 shows the maximum number of steps that did not hinder the curing of the dried coating film during exposure and did not cause dissolution or flow due to the development processing of the portion under the tablet. The greater the value of the number of steps, the better the light sensitivity.

Resolution: A plurality of striped negative masks having the same line and space width (μm) (line and space width: 1 μm, 3 μm, 5 μm, 1 μm)
(0 μm, 20 μm, 30 μm), exposure was performed at 200 mJ / cm ² using the light source used in each of Examples and Comparative Examples, and then development was performed using an aqueous solution containing 3% by weight of triethanolamine. The evaluation of the resolution is shown in Table 2 with the minimum line and space width (μm) that could be completely developed. The smaller the value, the better the resolution.

OD value: Densitometer P manufactured by Konica Corporation
It was measured with DA-65.

From the results of Example 1, Example 5 and Comparative Example in Table 2, the black matrix production method of the present invention can be used to obtain a black matrix even at an optical density of 3 or more where a black matrix pattern could not be formed until now. It can be seen that a matrix pattern is obtained.

Example 7 After a black matrix was formed on a glass substrate in the same manner as in Example 1, a red image pattern was formed in the same manner as in Example. Then, on a hot plate 180
After heating at 10 ° C. for 10 minutes.

Next, using the substrate, a green image pattern was formed next to the red image pattern in the same manner as in Example 3, and then post-heating was performed at 180 ° C. for 10 minutes in the same manner as described above. .

Next, using the substrate, a blue image pattern is formed between the green image pattern and the red image pattern in the same manner as in Example 4, and then at 200 ° C. for 10 minutes in the same manner as described above. Post heating was performed.

By the above operation, the pattern of the black matrix and each of the red and the 30 μm × 100 μm in size were obtained.
A high-quality color filter in which green and blue pixels were arranged in a mosaic pattern was produced.

The depolarizing property of the color filter obtained in Example 5 was measured at 0 ° with the color filter sandwiched between two polarizing plates.
And the light quantity ratio of 90 ° were measured with an illuminometer. All of the obtained color filters were excellent in optical characteristics with depolarization of 1000 or more, and were confirmed to be excellent as an image display device.

[0094]

According to the method for producing a black matrix of the present invention, the optical density (high OD value) which has been extremely difficult to produce a resin black matrix by the conventional photolithographic method.
To obtain a black matrix pattern.

The color filter of the present invention using the black matrix has excellent optical characteristics such as contrast, high quality, and is excellent as an image display device.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G02F 1/1335 505 G02F 1/1335 505 G03F 7/004 505 G03F 7/004 505 7/038 501 7/038 501 // G03F 7 / 20 501 7/20 501 (72) Inventor Hiroyuki Sonobe 4-13-1, Higashicho, Hitachi City, Ibaraki Prefecture Inside the Ibaraki Research Laboratory, Hitachi Chemical Co., Ltd. 1 Ibaraki Research Laboratory, Hitachi Chemical Co., Ltd. (72) Inventor Yoichi Kimura 14 Goi South Coast, Ichihara-shi, Chiba Prefecture Inside Goi Plant, Hitachi Chemical Co., Ltd. (72) Inventor Koji Yamazaki 14 Goi-minami Coast, Ichihara-shi, Chiba Prefecture Address Hitachi Chemical Industry Co., Ltd.

Claims (6)

[Claims] 1. A colored image forming composition comprising (a) a resin, (b) a black pigment, (c) a monomer containing at least one photopolymerizable unsaturated bond in a molecule, and (d) a photopolymerization initiator. It is characterized in that a black matrix is formed by irradiating actinic rays of a metal halide lamp onto a film made of a photosensitive material in an image-like manner to light-harden exposed portions and removing unexposed portions by development. Manufacturing method of black matrix. 2. The black film according to claim 1, wherein the film made of the colored image forming photosensitive material is a film containing a black pigment (b) such that the optical density (OD value) of the black matrix is 2 to 5. Matrix manufacturing method. (A) a resin having an acid value of 20 to 300, a weight average molecular weight of 1,500 to 200,000, a repeating unit (I) represented by the following general formula (I), and a resin represented by the following general formula: It consists of a repeating unit (II) represented by (II) and a repeating unit (III) represented by the following general formula (III), and is composed of the repeating unit (I) and the total of the repeating units (II) and (III). Molar ratio, (I) / ｛(II) +
(III) A resin wherein｝ is from 1 to 5.
A method for producing the black matrix as described above. Embedded image (In the above formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom, a hydroxyl group or an alkyl group or an alkoxy group having 1 to 12 carbon atoms, and R ³ , R ⁴ and R ⁵ each independently represent Represents an alkyl group having 1 to 12 carbon atoms or a group having a photopolymerizable unsaturated bond, provided that at least one of R ³ , R ⁴ and R ⁵ is a group having a photopolymerizable unsaturated bond.) 4. A film comprising the photosensitive material for forming a colored image according to claim 1, wherein the film is irradiated with actinic rays of a metal halide lamp in an image-like manner, and the exposed portion is light-cured, and the unexposed portion is formed. Forming a black matrix by developing, and forming a film on the substrate one color at a time using a plurality of colored image forming photosensitive materials of different colors, and then applying actinic rays to the film in an imagewise manner. Irradiating the exposed portion with light to cure the exposed portion, and removing the unexposed portion by development, thereby repeatedly forming pixels of different colors, thereby producing a color filter. 5. The method for producing a color filter according to claim 4, wherein a black matrix, a green pixel, a blue pixel, and a red pixel are formed using black, green, blue, and red colored image forming photosensitive materials, respectively. 6. A color filter produced by the production method according to claim 4.