JP2002107527A - Photosensitive colored resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive colored resin composition which has good dispersion stability and high sensitivity for exposure to UV rays, which can be developed with an alkali aqueous solution, which can form a hardened film having high electric resistance, high barrier property against light and excellent chemical resistance, heat resistance and adhesion property with a substrate, and which can form a black matrix with high film strength and low reflectance. SOLUTION: The photosensitive colored resin composition contains the following titanium black dispersed liquid, photopolymerizable monomers, photopolymerization initiator, and solvent. The titanium black dispersed liquid is prepared by charging a stirring device having a rotary stirrer and a plurality of granular media in a vessel with the liquid to be treated containing at least a solvent, polymer component having solubility with the solvent or having self dispersion property and titanium black, and rotating the stirrer of the stirring device to disperse the titanium black in the liquid, and by passing the liquid through the stirring device within 10 seconds.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive colored resin composition for forming a black matrix used for a display material such as a liquid crystal display device and an electronic display device.

[0002]

2. Description of the Related Art A color filter used for a display material of a liquid crystal display device, an electronic display device or the like is usually a filter in which red, green and blue color pixels are arranged in a mosaic or stripe shape. In order to obtain an image with better contrast, a black pixel called a black matrix is formed around the above-mentioned color pixel. Further, in the active display device, unnecessary light can be removed by using the black matrix, and the effect of reducing malfunction of the switching element can be exhibited.

[0003] The black matrix as described above is
Conventionally, a metal thin film provided on a glass substrate by a vapor deposition method, a sputtering method, or the like is formed into a fine pattern by a photolithography method.

[0004] Specifically, for example, a photoresist is coated on a chromium thin film, dried, irradiated with ultraviolet rays through a photomask and developed to form a resist pattern. After that, a black matrix is formed.

However, the formation of a black matrix by such a method is time-consuming due to the complicated steps, and is expensive. In addition, since a chromium film is used for the black matrix serving as a light shielding film, the reflectance is high. In recent years, environmental safety has been further considered, and the formation of a black matrix is being replaced by a method using a thin film containing carbon black.

According to this method, carbon black is blended in a photosensitive resin composition, and the resin composition is applied on a substrate.
It is dried to form a black film, which is formed into a fine pattern by photolithography.

[0007] However, although carbon black has a higher light-shielding property than other organic pigments, it has conductivity, and if a large amount of carbon black is added to a photosensitive resin in order to improve the light-shielding property, a black matrix formed is formed. The material itself has conductivity. Therefore, when a color filter is manufactured using these materials, problems such as conduction with a liquid crystal drive electrode or operation of an electric field through a black matrix occur. Therefore, a thicker insulating film or an electric field blocking film is formed. The drawback is that it is necessary to do so.

In order to solve such problems, Japanese Patent Application Laid-Open No. 1-141963 proposes a coating composition using titanium oxide or oxynitride. Although this composition is said to have a volume resistivity of 10 ⁶ Ω · cm or more, a composition containing an oxide or oxynitride of titanium does not exhibit ohmic behavior, and the higher the applied voltage, the higher the applied voltage. Volume resistivity tends to be low. The voltage applied to the measuring instrument is extremely low, and the voltage applied to a device such as a liquid crystal display device, that is, the volume resistivity at 3 to 30 V is lower than this, and in the worst case, there is a possibility that dielectric breakdown may occur. There is a problem that there is. In addition, the dispersion stability of titanium oxide or oxynitride in the composition is poor, and in particular, when an alkali binder is blended to enable alkali development, there has been a problem that strong cohesiveness is exhibited. .

[0009]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems in the prior art, and it is an object of the present invention to provide a method which has a good dispersion stability and an ultraviolet light exposure. It is highly sensitive to water, can be developed with an alkaline aqueous solution, and the cured film has high electrical resistance and high light-shielding properties, and has excellent chemical resistance, heat resistance, and adhesion to substrates. An object of the present invention is to provide a photosensitive colored resin composition capable of forming a black matrix having high strength and low reflectance.

[0010]

Means for Solving the Problems In order to achieve the above object, the present inventors have conducted intensive studies to solve the above problems, and as a result, have reached the following invention.

(1) A stirrer in which a rotary stirrer and a plurality of granular media are arranged inside a vessel has at least a solvent, a polymer component soluble or self-dispersible in the solvent, and titanium black. A titanium black dispersion obtained by loading a liquid to be treated and dispersing titanium black in the liquid to be treated by rotating the stirrer of the stirring device, and the liquid to be treated is stirred within the stirring device within 10 seconds. A photosensitive colored resin composition characterized by comprising a titanium black dispersion obtained by passing through, a photopolymerization monomer, a photopolymerization initiator, and a solvent as components.

(2) A stirrer having a rotary stirrer and a plurality of granular media disposed inside a vessel has at least a solvent, a polymer component soluble or self-dispersible in the solvent, and titanium black. A titanium black dispersion obtained by loading a liquid to be treated and dispersing titanium black in the liquid to be treated by rotating the stirrer of the stirring device, and the liquid to be treated is stirred within the stirring device within 10 seconds. A photosensitive colored resin composition characterized by comprising a titanium black dispersion obtained by passing through, a photoacid generator, a crosslinking agent, and a solvent as components.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail based on embodiments.

As the coloring material according to the present invention, titanium black can be used. This is because it has a high light-shielding property and is suitable for application to a black matrix of a color filter. The titanium black used in the present invention means low-order titanium oxide, titanium oxynitride, or the like.

Further, the titanium black used in the present invention includes those subjected to a surface treatment with an insulating substance. This can be done using known techniques,
A case where silica is used as an insulating material will be described as a specific example. First, as an initial step, titanium black is dispersed in water for 1.5 hours using a bead mill to obtain an aqueous slurry. Next, as a second step, a sodium silicate solution is added to the aqueous slurry of titanium black. As a third step, the above solution is thoroughly stirred using a homogenizer to pulverize the titanium black. In the fourth step, the solution is heated.
In the fifth step, a sodium silicate solution and sulfuric acid are added, and the mixture is stirred well using a homogenizer. This results in a silica coating. The titanium black coated with silica in the final step is filtered out and dried.

The titanium black dispersion used for preparing the photosensitive colored resin composition according to the present invention is prepared by disposing a solvent and a solvent in a stirrer having a rotary stirrer and a plurality of granular media disposed inside a vessel. In a solvent-soluble or self-dispersible polymer component in a solvent, and a liquid to be treated comprising at least titanium black are charged, and the titanium black is dispersed in the liquid to be treated by rotating a stirrer of a stirring device. It is obtained by passing the liquid to be treated within the stirring device within 10 seconds.

That is, the passage time of the liquid to be treated, which contains at least the solvent in the stirring device, the polymer component soluble or self-dispersible in the solvent, and titanium black, is 1 hour.
If the time exceeds 0 second, an excessive shearing force is applied to the liquid to be treated by the granular media while the liquid to be treated passes once in the apparatus, and the liquid to be treated is thickened during the treatment, and the dispersion is increased. There is a risk that processing must be interrupted.

In general, the passage time of the liquid to be treated in the stirring device is substantially uniform in a dispersion processing apparatus or a wet pulverization processing apparatus having a granular medium such as beads as a dispersion medium, which is known as a wet bead mill. And is not significantly affected by factors such as the type, the shape of the stirrer, and the details of its structure.

Therefore, the production method of the present invention can be carried out using any of these wet dispersion processing apparatuses having a spherical medium as a dispersion medium. However, in order to obtain a dispersion with better production efficiency and workability and good characteristics, the dispersion medium has a discharge portion that cannot pass through the granular media but can pass through the liquid to be treated, and the stirrer is located inside or on the wall surface. It is preferable to use a basket mill type in which the granular media is arranged in a basket constituting a part of the basket media.

Examples of the wet dispersion apparatus that can be used in the method for dispersing titanium black fine particles according to the present invention include the following, for example.
Of course, it is not limited to these. Further, for example, regarding the material and shape of the vessel, the material and shape or arrangement position of the stirrer, the material, shape and particle size of the granular media, etc. Properties and specific gravity,
Depending on the physical properties such as the particle size and the like, an optimum one can be selected as appropriate.

Examples of the vessel include various ceramics such as alumina, zirconia, steatite, silicon nitride, silicon carbide, and tungsten carbide; various metals; various metals such as steel, chromium steel, nickel-based alloys such as Hastelloy, and the like. Horizontal or vertical, for example, cylindrical, conical, semi-cylindrical, such as those disclosed in Japanese Patent Publication No. 2-27018 or Diamond Fine Mill (manufactured by Mitsubishi Heavy Industries, Ltd.) ) Etc., and those of the preferred basket mill type as described above (for example, JP-B-6-73620, JP-B-62-16687).
, JP-A-1-20020), SC mill type, vertical bead mill type, horizontal bead mill type and the like.

As the stirrer, similarly to the vessel, various ceramics such as alumina, zirconia, steatite, silicon nitride, silicon carbide, and tungsten carbide, various glasses, steel, chromium steel, nickel alloys such as Hastelloy, etc. Various metals and the like are appropriately selected. In addition, even if this material is different from the material of the vessel, there is no problem. As the shape, for example, in addition to the above-mentioned disk shape (disk type) and pin type, disk turbine type, fan turbine type, propeller type, spiral shaft blade type, spiral band blade type,
Gates, anchors, cylinders, paddles, and various shapes, as well as those with improvements such as the formation of liquid-permeable holes, can be arranged singly or in multiple stages. It is possible. Further, it is possible to provide a baffle or a stator having an appropriate shape according to the shape of the stirrer. Furthermore, the rotating shaft forming such a stirrer is not limited to the one arranged coaxially with the vessel,
It is also possible to displace from the central axis of the vessel, or to arrange it biaxially or multiaxially.

Further, the granular media can be appropriately changed according to the type of titanium black or polymer solution to be treated, the form of the vessel or the stirrer, and the like.
Spherical, cylindrical, composed of various ceramics such as alumina, zirconia, steatite, silicon nitride, silicon carbide, and tungsten carbide, and various metals such as glass, steel, chromium steel, nickel alloys such as Hastelloy,
Spheroidal or other shapes may be used, and among these, spherical beads composed of materials such as alumina, zirconia, steel, and chromium steel, usually having a diameter of 0.
It is desirable that the thickness is about 05 to 20 mm, more preferably 0.1 to 5 mm.

The photosensitive colored resin composition according to the present invention comprises a titanium black dispersion obtained by such a dispersion treatment.

As described above, in the present invention, titanium black is used as a coloring agent or a light-shielding agent of the photosensitive colored resin composition. When this titanium black is mixed into the photosensitive resin composition, Under a specific condition, a solvent, a polymer component soluble or self-dispersible in the solvent, and a titanium black dispersion obtained by subjecting a liquid to be treated having at least titanium black to a dispersion treatment, as described below. In the photosensitive resin composition, compared to the case where titanium black is used as it is, dispersion stability, prevention of sedimentation due to aggregation, viscosity reduction of the dispersion, reduction of structural viscosity, prevention of color separation, etc. Significant improvements are seen in the properties such as adhesion of the film when applied, electrical high resistance of the film, high light-shielding properties, and film strength.

On the other hand, the polymer component in the liquid to be treated used in the dispersion treatment of titanium black is not particularly limited as long as it has solubility or self-dispersibility in the solvent used. However, a (meth) acrylic resin, particularly a (meth) acrylate polymer is preferred.

The acrylic monomer which is a component of the (meth) acrylic resin includes:

[0028]

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R ¹ is H or CH ₃ , R ² is alkyl, branched alkyl, phenyl, cyclohexyl, tetrahydrofurfuryl methacrylate, etc. Specific examples of the resin mainly used in the present invention include: ,

[0030]

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And the like. However, it is needless to say that the resin is not limited to these, and is a resin synthesized from several kinds of monomers selected as necessary from these. In addition to the above acrylic monomers, the following ones can be appropriately selected and used. They are dimethylaminoethyl methacrylate, benzyl acrylate, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate and the like.

The average molecular weight of such a polymer is not particularly limited.
In the case of an acrylate polymer, the number average molecular weight is about 500 to 50,000, more preferably 1,000 to 50,000.
About 30,000 is appropriate.

The solvent is not particularly limited, as long as it can function as a solvent for dispersing the composition in the final photosensitive colored resin composition, depending on the type of the polymer used. , Water-soluble or water-insoluble ones, for example, water;
Alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, allyl alcohol; ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol,
Glycols and derivatives thereof such as polypropylene glycol, diethylene glycol monoethyl ether, polypropylene glycol monoethyl ether, polyethylene glycol monoallyl ether and polypropylene glycol monoallyl ether; glycerol and derivatives thereof such as glycerol, glycerol monoethyl ether and glycerol monoallyl ether Ethers such as tetrahydrofuran and dioxane; ketones such as methyl ethyl ketone and methyl isobutyl ketone; liquid paraffin, decane, decene, methylnaphthalene, decalin, kerosene, diphenylmethane, toluene, dimethylbenzene, ethylbenzene, diethylbenzene, propylbenzene, cyclohexane, Partially hydrogenated hydrocarbons such as triphenyl Silicone oils such as polydimethylsiloxane, partially octyl-substituted polydimethylsiloxane, partially phenyl-substituted polydimethylsiloxane, fluorosilicone oil, halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, bromobenzene, chlorodiphenyl, chlorodiphenylmethane, dilrol ( Fluorides such as Daikin Industries, Ltd.), Demnum (Daikin Industries, Ltd.), ethyl benzoate, octyl benzoate, dioctyl phthalate, trioctyl trimellitate, dibutyl sebacate, ethyl (meth) acrylate And ester compounds such as butyl (meth) acrylate and dodecyl (meth) acrylate are appropriately selected and used alone or in combination.

In preparing the titanium black dispersion according to the present invention, 100 parts by mass of titanium black is used.
5 to 50 parts by weight, more preferably 10 to 3 parts by weight of the polymer component
It is preferable to add 0 parts by mass. That is, if the amount of the polymer is less than 5 parts by mass, it may be difficult to sufficiently modify the surface properties of titanium black.
If the amount exceeds 0 parts by mass, the amount of the polymer dispersed and blended together with the titanium black increases, which may impair the inherently required properties of the titanium black, such as light-shielding properties and coloring properties.

The amount of the solvent varies depending on the type of the polymer.
-5000 parts by mass, more preferably 1000-4000 parts by mass
It is preferred to be parts by mass. When the amount of the solvent is less than 500 parts by mass, the viscosity of the polymer solution (refers to a solution containing a solvent and a polymer component which is soluble or self-dispersible in the solvent; the same applies hereinafter) becomes high, and it becomes difficult to perform a dispersion treatment by stirring. On the other hand, if the amount of the solvent exceeds 5,000 parts by mass, even if a sufficient stirring force is applied, the surface property of titanium black may not be sufficiently modified by the polymer.

The heating temperature at the time of stirring and mixing also depends on the type of the polymer used, etc., and cannot be unconditionally specified. However, it is 40 to 150 ° C., preferably 50 to 120 ° C., more preferably 60-100 ° C
The degree is appropriate. That is, if the heating temperature is extremely low, the detailed reason is not clear, but the modification of the surface properties of titanium black is not sufficient, and if the heating temperature exceeds 150 ° C., the stirring and dispersion system may not be sufficiently improved. This is because control and maintenance become difficult.

Further, in the dispersion treatment, the shear stress applied to the titanium black is not particularly limited, but is preferably at least 10 ² Pa, more preferably at least 10 ³ Pa, particularly preferably at least 10 ⁴ Pa. It is.

The photosensitive colored resin composition of the present invention is characterized in that the titanium black dispersion obtained by the above-mentioned dispersion treatment is used as a main light-shielding or coloring component. Is not particularly limited, for example, an alkaline binder resin,
Radical polymerizable monomer having an ethylenically unsaturated double bond (in the present specification, “radical polymerizable monomer having an ethylenically unsaturated double bond” is also simply referred to as “photopolymerizable monomer”), and photopolymerization is started. Agents, photoacid generators, cross-linking agents, solvents and the like can be appropriately combined and contained.
Specific combinations of the photosensitive colored resin composition according to the present invention include (1) a composition containing a titanium black dispersion, a photopolymerization monomer, a photopolymerization initiator, and a solvent as components; ) A titanium black dispersion, a photoacid generator,
Examples include, but are not limited to, compositions containing a crosslinking agent and a solvent as components.

The amount of the titanium black dispersion in the photosensitive colored resin composition is such that titanium black contained in the titanium black dispersion is 30 to 70% by mass of the total solid content of the photosensitive colored resin composition. More preferably 40
It is preferable to mix so as to be 〜60% by mass. 3
If the amount is less than 0% by mass, sufficient light-shielding properties or coloring properties may not be exhibited. On the other hand, if the amount exceeds 70% by mass, the coating strength may decrease, the dispersion stability, and the patterning property during development may decrease. This is because this occurs.

As the alkaline binder resin in the photosensitive colored resin composition, known polymer compounds can be used. For example, homo- or copolymers of alkyl (meth) acrylates (eg, methyl ester, ethyl ester, butyl ester, etc.), unsaturated dibasic anhydrides such as poly (meth) acrylic acid, styrene and maleic anhydride And the like. In addition, there are high molecular compounds having a carboxyl group, a hydroxyl group, an amino group, a carboxamide group, a sulfonamide group, or the like in the molecule, but the invention is not limited thereto.

The addition amount of these binder resins is preferably from 10 to 43% by mass of the total solid content. If the amount is less than 10% by mass, the pattern strength with the substrate decreases, while if it exceeds 43% by mass, the adhesiveness of the resin layer becomes strong, which causes a decrease in developability.

The radical polymerizable monomer having an ethylenically unsaturated double bond in the photosensitive colored resin composition includes, for example, 2-ethyl-2-propanediol diacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate. Acrylate, dipentaerythritol pentaacrylate, polyoxyethylated trimethylolpropane triacrylate, tris (2-acryloyloxyethyl) isocyanate, 1,4-diisopropenylbenzene, 1,4-dihydroxybenzene methacrylate, decamethylene glycol diacrylate Acrylate, ethylene glycol diacrylate, triethylene glycol acrylate, trimethylolpropane triacrylate, or diallyl fumarate Particularly preferred are 2-butylpropanediol diacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and polyoxyethylated trimethylolpropane triacrylate.

The amount of addition of these radically polymerizable monomers is not particularly limited, but may be 1 to 1 of the total solid content.
10% by mass is preferred. If the amount is less than 1% by mass, sufficient sensitivity cannot be obtained, and a large amount of exposure must be applied. On the other hand, if it exceeds 10% by mass, problems such as a decrease in stability over time and a defective pattern shape occur.

As the photopolymerization initiator in the photosensitive colored resin composition, all known compounds can be used. For example, α-diketones such as benzyl and acetyl, acyloins such as benzoin, acyloin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, thioxanthone, 2,4-diethylxanthone, thioxanthone-4-sulfone Benzophenones such as benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, acetophenone, p-dimethylacetophenone, α, α′-dimethoxyacetoxyacetophenone; Acetophenones such as 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone And quinones such as anthraquinone and 1,4-naphthoquinone, tribromomethylphenylsulfone, phenanthyl chloride, tris (trichloromethyl) -s-triazine, p
-Methoxyphenyl-2,4-bis (trichloromethyl) -s-triazine, 2- (p-butoxystyryl)
-5-trichloromethyl-1,3,4-oxadiazole, 9,10-dimethylbenzphenazine, 9-phenylacridine, thioxanthone / amine, benzophenone / Michler's ketone, benzyldimethylketal, hexaarylbiimidazole / mercaptobenzimidazole, etc. Is mentioned. Particularly preferred are tris (trichloromethyl) -s-triazine, p-methoxyphenyl-2,4-bis (trichloromethyl) -s-triazine and α, α′-dimethoxyacetoxyacetophenone. These photopolymerization initiators may be used alone or in combination.
More than one species can be added and used.

The addition amount of these photopolymerization initiators is not particularly limited because it varies depending on the combination of the compositions. For example, when (1) the photopolymerization monomer is used in combination with the photopolymerization monomer, 5 to 150% by mass, preferably 50 to 60% by mass of the reactive monomer. (2)
When used in combination with a binder resin, the photopolymerization initiator is preferably used in an amount such that the total amount of the photopolymerization initiator is 0.5 to 40% by mass based on the binder resin. That is, when the content is less than 5% by mass with respect to the photopolymerizable monomer or less than 0.5% by mass with respect to the binder resin, it is difficult to obtain sensitivity. On the other hand, if it exceeds 150% by mass with respect to the photopolymerizable monomer or exceeds 40% by mass with respect to the binder resin, it causes insufficient curing due to precipitation of crystals.

The solvent in the photosensitive colored resin composition includes cellosolves such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and acetates thereof. Acetates such as ethyl acetate, n-propyl acetate, isopropyl acetate and n-butyl acetate, benzene, toluene,
Aromatic hydrocarbons such as xylene, methyl ethyl ketone,
Examples include ketones such as acetone, methyl isobutyl ketone, and cyclohexanone, and alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, and glycerin.

The amount of such a solvent used is not particularly limited because it varies depending on the combination of the compositions, but is used together with the solvent component in the above-mentioned titanium black dispersion to determine the total solid content. 50 to 500% by mass,
Preferably, it is used in a range of 100 to 300% by mass. If the amount is less than 50% by mass, the solid content is large and the viscosity of the photosensitive colored resin composition is high, so that it is difficult to obtain a desired flat thin film and the thickness tends to be large. On the other hand, if it exceeds 500% by mass, the solid content is small and the viscosity of the photosensitive colored resin composition is low, so that it is difficult to obtain a desired film thickness, and therefore, sufficient light-shielding properties cannot be obtained.

The photoacid generator in the photosensitive colored resin composition includes a triazine compound and an onium salt compound.

Among them, triazine compounds include
The triazine compounds exemplified in the above photopolymerization initiator can be used.

Examples of the onium salt compounds include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroholonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluene. Sulfonate, 4-methoxyphenyl-phenyliodonium tetrafluoroborate, 4-methoxyphenyl-phenyliodonium hexafluorophosphonate and the like can be mentioned.

The amount of the photoacid generator to be added is not particularly limited since it varies depending on the combination of the compositions.
0 mass%, preferably in the range of 5 to 15 mass%. 1
If the amount is less than mass%, the amount of generated acid is insufficient, and the cross-linking reaction does not sufficiently proceed, and a pattern cannot be formed. On the other hand, if it exceeds 20% by mass, the amount of acid generated is too large, and the acid diffuses into the unexposed area due to heating after pattern exposure, causing a cross-linking reaction and causing deterioration in image quality.

As the crosslinking agent in the photosensitive colored resin composition, those having an N-methylol structure are used. For example, methylolated urea, urea resin, methylolated melamine, butyrolated melamine, methylolated guanamine, or a mixture thereof Alkyl ethers of compounds can be used, and alkyl ether compounds are more preferable in that they have high thermal stability. The alkyl group of the alkyl ether is preferably an alkyl group having 1 to 5 carbon atoms. Particularly, as the alkyl ether compound, an alkyl ether compound of hexamethylolmelamine is more preferable from the viewpoint of sensitivity. The cross-linking agent causes a cross-linking reaction with a polymer component or an alkali binder resin that is soluble or self-dispersible in the solvent as the dispersing resin by heating due to the presence of oxygen generated after exposure, and forms a pattern.

The amount of such a cross-linking agent added is not particularly limited since it varies depending on the combination of the compositions, but the amount is preferably 0.1 to 2 with respect to the photosensitive colored resin composition.
0 mass%, preferably in the range of 0.4 to 15 mass%. If the amount is less than 0.1% by mass, the photosensitive characteristics are disturbed and sufficient curing is not performed. On the other hand, when the content exceeds 20% by mass, the concentration of the coloring material (pigment) in the photosensitive colored resin composition decreases, and sufficient light-shielding properties cannot be obtained.

The method for preparing the photosensitive colored resin composition according to the present invention is not particularly limited. For example, the above-mentioned materials are mixed with a dissolver type stirrer,
The mixing is performed by using a stirrer such as a turbo-type stirrer or a twin-screw stirrer, or by kneading using a disperser such as a two-roll mill, a three-roll mill, a sand mill, or a paint shaker.

Next, the preferred composition of each composition in the present invention will be described. The solid content of the photosensitive colored resin composition is 5
To 45% by mass, preferably 10 to 35% by mass, more preferably 25 to 30% by mass. 5% by mass or less,
Alternatively, when the content is 40% by mass or more, it becomes difficult to obtain a desired film thickness by a coating device such as spin coating or roll coating, and the coating property is reduced.

The proportion of titanium black obtained by surface-treating titanium black with an insulating substance is 50 to 2 with respect to the polymer component which is a dispersing resin and is soluble or self-dispersible in a solvent.
It is 50% by mass, preferably 100 to 200% by mass. If the content is less than 50% by mass, the light-shielding property of the black matrix is reduced, so that a large film thickness is required. As a result, the formation of the liquid crystal alignment film is hindered, and the liquid crystal display performance may be impaired. When the content is 250% by mass or more, it is difficult to uniformly disperse, and even if a light shielding film is formed, mechanical strength such as adhesion may be reduced.

The coating amount of the insulating substance for surface-treating titanium black is not particularly limited. However, in order to make the effect more remarkable, base particles (titanium black) coated on the surface are required.
Is desirably 10% by mass or more and 35% by mass or less. That is, if the content is less than 10% by mass, no apparent effect of addition to the volume resistance value is observed, and if it exceeds 35% by mass, problems such as a decrease in light-shielding properties, poor adhesion to a transparent substrate, and impact resistance occur. In some cases, 15% by mass or more,
The content is more preferably 25% by mass or less.

Next, the step of forming a black matrix using the photosensitive colored resin composition according to the present invention will be described with reference to the drawings.

As shown in FIG. 1, a photosensitive colored resin composition 2 is uniformly coated on a substrate 1 by using a bar coating method, a roll coating method, a spinner method, a curtain coating method, or the like to form a black resin layer. Form. When drying is required, heating may be performed at a temperature of about 70 to 100 ° C.

Next, only the portions to be black matrixes are irradiated with ultraviolet rays by using the mask pattern 3 to perform exposure and radical polymerization for curing. The light source used for exposure is a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, or the like.

Next, a black matrix is formed by removing the unexposed portion of the black resin layer using an aqueous alkali solution as a developing solution.

Examples of the above developer include inorganic alkali solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate and calcium carbonate, alkylamines such as triethylamine, alcoholamines such as triethanolamine, and tetraethylammonium hydroxide. And the like can be used. Further, alcoholic polar solvents such as methanol, ethanol, and isopropyl alcohol can also be used.

Further, other additives such as a surfactant, a wetting agent, and an organic solvent may be added to the developer as needed.

[0064]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples. Note that “parts” in the following Examples and Comparative Examples
Are all by mass.

Example 1 30 parts of silica black-treated titanium black, 67 parts of cyclohexanone as a solvent, and Disperbyk- as a polymer component soluble or self-dispersible in the solvent.
A liquid to be treated consisting of 3.0 parts of 180 (manufactured by Big Chemie) was charged into a vessel, and 1 mm zirconia beads were added to the vessel.
The dispersion treatment was performed at a peripheral speed of 7 m / s using a basket mill SS20Z (manufactured by Asada Iron Works) filled with 3 kg. At this time, the stirring blade attached below the basket was adjusted so that the liquid to be treated passed through the basket within 2 seconds.
After the dispersion treatment for 10 hours, the zirconia beads and the liquid to be treated were separated to obtain a titanium black dispersion liquid (1).

Comparative Example 1 In Example 1, the stirring blade at the bottom of the basket was adjusted.
A comparative titanium black dispersion (C1) was obtained by performing the same operation as in Example 1 except that the liquid to be treated passed through the basket over a time longer than 10 seconds.

Example 2 The titanium black dispersion liquid (1) 35 obtained in Example 1
Parts, 10 parts of a BMA / MMA / HEMA / MAA copolymer (weight average molecular weight; Mw = 50,000), 2.5 parts of pentaerythritol tetraacrylate, p-methoxyphenyl-2,4-bis (trichloromethyl) -s- 1.5 parts of triazine and 51 parts of cyclohexanone were put in a glass bottle and stirred for 1 hour to prepare a photosensitive black resin composition (1).

The photosensitive black resin composition (1) was applied to a glass substrate by a spinner at 1000 rpm for 5 seconds, and dried to form a black resin layer.

This glass substrate was exposed through a mask pattern at an exposure of 150 mJ / cm ² using a 3 KW ultra-high pressure mercury lamp from the resin film side.

Next, development was performed for 50 seconds by a spin development method using a 1% aqueous solution of sodium carbonate to remove the unexposed portion of the black resin layer, followed by baking at 230 ° C. for 1 hour to form a black matrix. Formed.

The performance of the black matrix formed from the photosensitive black resin composition (1) was evaluated as follows.

[0091] 1000 on one side of a substrate on which both sides of Cr were deposited.
Spin coating was performed at 5 rpm for 5 seconds to obtain a coating film of 1.15 μm. A 1.0 μm black resin coating film was formed on this coating film through the above-described steps of exposure, development and baking. Further, the substrate was short-circuited with Cr on both sides using silver paste to obtain a substrate for measuring volume resistance. This substrate is compliant with JIS (C2103)
-1991) was 1010 Ωcm or more when the resistance was measured by a method according to the volume resistivity test.

Further, the transparent substrate is subjected to 1.0
When a black resin coating film having a thickness of μm was prepared and the optical density was measured, a good value of 3.1 was obtained. In addition, the exposure sensitivity was 150 mJ and the resolution was 6 μm (L / S), and the surface smoothness and the linearity of the pattern were good.

The photosensitive black resin composition (1) itself had good stability over time, and the same performance as that at the time of preparation of the composition (1) could be maintained for 3 months at 10 ° C.

Comparative Example 2 The comparative titanium black dispersion (C) obtained in Comparative Example 1
1) 35 parts, 10 parts of BMA / MMA / HEMA / MAA copolymer (weight average molecular weight; Mw = 50,000), 2.5 parts of pentaerythritol tetraacrylate, p-methoxyphenyl-2,4-bis (trichloromethyl) −
One part of s-triazine was placed in a glass bottle and stirred for 1 hour to prepare a photosensitive black resin composition (2).

The photosensitive black resin composition (2) was applied to a glass substrate by a spinner at 1000 rpm for 5 seconds, and dried to form a black resin layer.

The glass substrate was exposed through a mask pattern at an exposure amount of 150 mJ / cm ² using a 3 KW ultra-high pressure mercury lamp from the resin film side.

Next, development was performed for 50 seconds by a spin development method using a 1% aqueous solution of sodium carbonate to remove the unexposed portion of the black resin layer, followed by baking at 230 ° C. for 1 hour to form a black matrix. Formed.

The performance of the black matrix formed from the photosensitive black resin composition (2) was evaluated as follows.

[0094] 1000 on one side of a substrate on which both sides of Cr were deposited.
Spin coating was performed at 5 rpm for 5 seconds to obtain a coating film of 1.15 μm. A 1.0 μm black resin coating film was formed on this coating film through the above-described steps of exposure, development and baking. Further, the substrate was short-circuited with Cr on both sides using silver paste to obtain a substrate for measuring volume resistance. This board is JIS standard (C2103-
1991), it was 1010 Ωcm or more when the resistance was measured by a method according to the volume resistivity test.

Further, a transparent substrate is also subjected to the above-mentioned process in the same manner as above.
When a black resin coating film having a thickness of μm was prepared and the optical density was measured, an extremely low value of 2.3 was obtained. In addition, the exposure sensitivity is 150 mJ, and the resolution is 30 μm (L / S).
Only the resolution was good, and the surface smoothness and the linearity of the pattern were very poor.

The stability over time of the photosensitive black resin composition (2) itself is unstable, and after storage at 10 ° C. for 10 days, 1010 Ω
cm), the resistivity decreased to 107 Ωcm, and the viscosity increased by 3 cP.

[0083]

As described above, according to the present invention, a liquid to be treated comprising at least a solvent, a polymer component soluble or self-dispersible in the solvent, and titanium black is mixed in a stirring apparatus as described above. And a component containing a titanium black dispersion obtained by processing by a dispersion method characterized by passing the liquid to be treated within 10 seconds, a photopolymerization monomer, a photopolymerization initiator, and a solvent. A photosensitive colored resin composition, or a photosensitive colored resin composition comprising the titanium black dispersion, a photoacid generator, a crosslinking agent, and a solvent as components. is there. A photosensitive colored resin composition using such a titanium black dispersion has good dispersion stability, is highly sensitive to ultraviolet light exposure, can be developed with an alkaline aqueous solution, and has a high electrical conductivity. Formed using this photosensitive colored resin composition because it has resistance, high light-shielding properties, excellent chemical resistance, heat resistance, and excellent adhesion to substrates, and has high film strength and low reflectance. The obtained black matrix can exhibit extremely excellent characteristics.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view schematically showing a step of forming a black matrix using a photosensitive colored resin composition according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... board | substrate, 2 ... photosensitive coloring resin composition, 3 ... photomask, 4 ... hot plate, 5 ... photosensitive coloring resin formed product, 6 ... exposure hardening part.

Continuation of the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (reference) G02B 5/00 G02B 5/00 B 4J011 G03F 7/004 505 G03F 7/004 505 4J026 7/027 7/027 7/038 7/038 7/38 501 7/38 501 // C08L 101: 00 C08L 101: 00 (72) Inventor Hayato Ikeda 5-8 Nisomibashi-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd. (72) Inventor Anan Kazuhiro 5-8 Nishiomibashi-cho, Suita-shi, Osaka Inside Nippon Shokubai Co., Ltd. 4-2-2, Takanodai, Minami, Sugito-machi, Kita-Katsushika-gun, Saitama Prefecture Inside the Toppan Printing Co., Ltd. (72) Inventor Shinji Ito 4-2-2, Takano-daiminami, Sugito-machi, Sugito-machi, Saitama Prefecture Mizuhito Tani 4-2-2, Takanodaiminami, Sugito-cho, Kitakatsushika-gun, Saitama Prefecture F-term (reference) 2H025 AA10 AA14 AA20 AB13 AC01 AD01 BC12 BC31 BD06 BE00 BE07 CA00 CB00 CC03 CC12 EA01 FA17 2H042 AA09 AA15 AA26 2H048 BA11 BA48 BB42 2H096 AA27 BA05 BA06 CA20 GA08 4F070 AA32AE02 FC04 FA03 FA04 QA12 QA13 QA23 SA01 SA21 SA41 SA51 SA63 UA06 VA01 WA01 4J026 AA45 AC35 BA28 DB02 DB30 DB36 FA05 GA07

Claims (2)

[Claims] 1. A stirrer having a rotary stirrer and a plurality of granular media disposed inside a vessel, comprising at least a solvent, a polymer component soluble or self-dispersible in the solvent, and titanium black. This is a titanium black dispersion obtained by loading the liquid to be treated and dispersing titanium black in the liquid to be treated by rotating the stirrer of the stirring device. The liquid to be treated is stirred within the stirring device within 10 seconds. A photosensitive colored resin composition comprising, as components, a titanium black dispersion obtained by passing the same, a photopolymerization monomer, a photopolymerization initiator, and a solvent. 2. A stirrer having a rotary stirrer and a plurality of granular media disposed inside a vessel, comprising at least a solvent, a polymer component soluble or self-dispersible in the solvent, and titanium black. This is a titanium black dispersion obtained by loading the liquid to be treated and dispersing titanium black in the liquid to be treated by rotating the stirrer of the stirring device. The liquid to be treated is stirred within the stirring device within 10 seconds. A photosensitive colored resin composition comprising, as components, a titanium black dispersion obtained by passing through, a photoacid generator, a crosslinking agent, and a solvent.