JP2002107922A - Color resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color photosensitive resin composition for the formation of a black matrix, which has good dispersion stability and high sensitivity for exposure to UV rays, which can be developed with an alkali aqueous solution and which can form a hardened film having a high electric resistance, high light shielding property, excellent chemical resistance, heat resistance and adhesion property with a substrate, a high film strength and low reflectance. SOLUTION: The photosensitive color resin composition is prepared by using a titanium black dispersion liquid obtained by the following method. A stirring device equipped with a rotary stirrer 3 and granular media 4 in a vessel 1 is charged with a liquid 5 to be treated containing a solvent, a polymer component soluble with the solvent or having self dispersibility, and titanium black. The liquid 5 is treated by using a mill composed of a basket body 2 filled with the granular media under such conditions that the liquid to be treated in a mixed state with air bubbles is sucked by the sucking part in the upper side of the mill into the basket body. The basket body 2 has an inlet part 6 and discharge part 7 where the granular media can not pass but the liquid to be treated can pass and has the stirrer constituting the inner part or a part of the wall.

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.

(A) (1) A solvent, a polymer component soluble or self-dispersible in the solvent, and titanium black are placed in a stirrer having a rotary stirrer and a plurality of granular media disposed inside a vessel. A titanium black dispersion obtained by loading a liquid to be treated having the same and dispersing titanium black in the liquid to be treated, wherein the stirring device does not allow the passage of granular media but the passage of the liquid to be treated. Part and a discharge part, using a mill in which the granular media is arranged in a basket in which the stirrer is located inside or a part of a wall surface, and located on the upper side of the mill In the inflow part, the air is sucked together with the liquid to be treated by the negative pressure generated by the rotation of the stirrer, and the stirring treatment is performed under the condition that the liquid to be treated is sucked into the basket with air bubbles entrained. A titanium black dispersion obtained, (2) a photopolymerization monomer, and (3) a photopolymerization initiator,
(4) A photosensitive colored resin composition, comprising: a solvent;

(B) (1) At least a solvent, a polymer component soluble or self-dispersible in the solvent and titanium black are placed in a stirrer in which a rotary stirrer and a plurality of granular media are arranged inside a vessel. A titanium black dispersion obtained by loading a liquid to be treated having the same and dispersing titanium black in the liquid to be treated, wherein the stirring device does not allow the passage of granular media but the passage of the liquid to be treated. Part and a discharge part, using a mill in which the granular media is arranged in a basket in which the stirrer is located inside or a part of a wall surface, and located on the upper side of the mill In the inflow part, the air is sucked together with the liquid to be treated by the negative pressure generated by the rotation of the stirrer, and the stirring treatment is performed under the condition that the liquid to be treated is sucked into the basket with air bubbles entrained. A photosensitive colored resin composition comprising: a titanium black dispersion obtained as described above; (2) a photoacid generator; (3) a crosslinking agent; and (4) a solvent.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described 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, as the titanium black used in the present invention, those having been subjected to a surface treatment with an insulating material are also included. This can be carried out by using a known technique, and a specific example using silica will be described.
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 has an inlet and an outlet which cannot pass through the granular media but can pass through the liquid to be treated, and has a rotary stirrer. Place the granular media in a cage that is located inside or that forms part of the wall,
Further, the basket is manufactured using a mill-type stirring device in which the basket is disposed in a vessel. And in the stirring device,
A titanium black dispersion obtained by loading a solvent, a liquid to be treated having at least a polymer component soluble or self-dispersible in the solvent, and titanium black, and subjecting the titanium black to a dispersion treatment in the liquid to be treated. In the inflow section located on the upper side of the mill, air is sucked together with the liquid to be treated by a negative pressure generated by rotation of the stirrer,
This is obtained by performing a stirring process under a condition in which the liquid to be treated is sucked into the basket in a state where air bubbles are entrained.

Various types of wet dispersion apparatuses that can be used for the dispersion treatment of titanium black in a liquid are known. In the present invention, as a wet dispersion apparatus having a spherical medium as a dispersion medium, As described above, as the mill type, a basket mill type, an SC mill type, a vertical bead mill type, a horizontal bead mill type, or the like can be used.

According to the present invention, when the stirring process is performed by such a mill, the condition is such that the liquid to be treated flows into the basket with air bubbles entrained. That is, although the detailed reason is not clear, in the stirring process using a mill, when the liquid to be treated flows into the basket in a state where air bubbles are entrapped in the inflow portion, the liquid to be treated is Appropriate shearing force by the granular media is given to the titanium black inside, and good fine dispersion of titanium black can be achieved. On the other hand, if the liquid to be treated flows into the basket in a state where air bubbles are not substantially entrained in the inflow portion, it is likely that the liquid to be treated is not sufficiently circulated inside the vessel, There is a possibility that the treatment liquid thickens and the dispersion treatment must be interrupted.

The state of the flow of the liquid to be processed into the inflow portion of the mill depends on the relationship between the size of the vessel in the stirring device and the size of the basket disposed inside the vessel, and the state of the liquid held in the vessel. It is affected by the arrangement position (depth etc.) of the basket with respect to the treatment liquid, the shape and number of the stirrer blades and pins, the rotation speed of the stirrer, the viscosity of the liquid to be treated, etc. By doing so, the desired inflow condition can be formed.

FIG. 1 is a schematic view showing the structure of a basket mill type wet dispersion apparatus which can be used in the titanium black dispersion method according to the present invention as an example.
Examples of the wet dispersion processing device used in the present invention include:
As described above, the inside of the vessel 1 has the inflow portion 6 and the discharge portion 7 through which the granular media 4 cannot pass but the liquid to be treated 5 can pass, and the stirrer 3 is located inside or constitutes a part of the wall surface. The detailed structure is not particularly limited as long as it has a structure in which the granular media 4 is arranged in the basket 2 to be formed. Various modes generally known as a basket mill type (for example, Fairness 6
-73620, JP-B-62-16687, JP-A-1-20020, etc.) can be used. Also, for example, materials such as vessels, baskets, stirrers,
The shape or arrangement position, the material, the shape and the particle size of the granular media are appropriately optimized according to the chemical properties and specific properties of the dispersion or titanium black to be treated and the physical properties such as the particle size. Can be selected. In addition, the inflow part 6 in the basket 2 needs to exist on the upper side of the basket 2 from the definition in the present invention,
The position of the discharge portion 7 may be on any of the side surface side, the bottom surface side, or both, of the basket body 2.

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 nickel-based alloys such as steel, chromium steel, and Hastelloy; Such as those composed of two or more
It can be of various forms.

As the material constituting the basket and the stirrer, various ceramics such as alumina, zirconia, steatite, silicon nitride, silicon carbide, tungsten carbide, various glasses, steel, chromium steel, and Hastelloy, as in the vessel. Various metals such as nickel-based alloys are appropriately selected. In addition, even if this material is different from the material of the vessel, there is no problem.

The shape of the stirrer depends on the shape of the basket, etc., but, for example, besides the disk shape (disk type) and the pin type, a disk turbine type, a fan turbine type, a propeller type, a spiral shaft blade Type, spiral band wing type, gate type, anchor type, cylindrical type, paddle type, etc., as well as those with improvements such as forming liquid-permeable holes in Alternatively, they can be arranged in multiple stages. Further, it is possible to provide a baffle or a stator having an appropriate shape according to the shape of the stirrer.
Further, the rotating shaft forming such a stirrer can be arranged not only coaxially with the vessel but also displaced from the central axis of the vessel, or arranged biaxially or multiaxially.

Examples of the granular media include the type of titanium black or a polymer solution (including a solvent and a polymer component soluble or self-dispersible in the solvent; hereinafter the same), the form of a vessel or a stirrer, and the like. It can be changed as appropriate according to the requirements, and is composed of various ceramics such as alumina, zirconia, steatite, silicon nitride, silicon carbide, and tungsten carbide, and various metals such as various glasses, steel, chromium steel, and nickel alloys such as Hastelloy. Spherical, cylindrical, spheroidal and other shapes can be used. Among them, spherical beads composed of materials such as alumina, zirconia, steel and chromium steel, and usually having a diameter of 0 It is preferably about 0.05 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 blending the titanium black in the photosensitive resin composition, When using a titanium black dispersion obtained by performing a dispersion treatment with a polymer solution under specific conditions, in a photosensitive resin composition as described below, compared to the case where titanium black is used as it is, dispersion stability, due to aggregation Characteristic aspects such as sedimentation prevention, dispersion viscosity reduction, structural viscosity reduction, color separation prevention, film adhesion when applied to the substrate surface, electrical high resistance of the film,
Significant improvements are seen in characteristics such as high light-shielding properties and film strength.

On the other hand, the polymer component of the polymer solution 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, especially a (meth) acrylate polymer is preferred.

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

[0029]

Embedded image

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: ,

[0031]

Embedded image

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 of the polymer solution is not particularly limited, and functions as a solvent for dispersing the composition in the final photosensitive colored resin composition according to the type of the polymer used. Various water-soluble or water-insoluble substances can be used as long as they can be obtained. For example, water; alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, allyl alcohol; ethylene glycol;
Glycol or derivatives thereof such as propylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, diethylene glycol monoethyl ether, polypropylene glycol monoethyl ether, polyethylene glycol monoallyl ether, and polypropylene glycol monoallyl ether; glycerol, glycerol monoethyl ether, glycerol mono Glycerol or derivatives thereof such as allyl ether; ethers such as tetrahydrofuran and dioxane; ketones such as methyl ethyl ketone and methyl isobutyl ketone; liquid paraffin, decane, decene, methyl naphthalene, decalin, kerosene, diphenylmethane, toluene, dimethylbenzene and ethylbenzene , Diethylbenzene, propylene Benzene, cyclohexane, hydrocarbons triphenyl or the like which is partially hydrogenated, polydimethylsiloxane, partially octyl-substituted polydimethylsiloxane,
Silicone oils such as partially phenyl-substituted polydimethylsiloxane and fluorosilicone oil; halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, bromobenzene, chlorodiphenyl, and chlorodiphenylmethane; Dairol (Daikin Industries, Ltd.); (Manufactured by Kogyo Co., Ltd.), ethyl benzoate, octyl benzoate, dioctyl phthalate, trioctyl trimellitate, dibutyl sebacate, (meth)
Ester compounds such as ethyl acrylate, butyl (meth) acrylate, and dodecyl (meth) acrylate,
They 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 becomes high, and the dispersion treatment by stirring becomes difficult. On the other hand, when the amount of the solvent exceeds 5,000 parts by mass, even if a sufficient stirring force is applied, the surface of the titanium black by the polymer is obtained. This is because property modification may not be sufficient.

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, the heating temperature is 40 to 150 ° C., preferably 50 to 120 ° C., and more preferably 50 to 120 ° C. 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, 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 the above titanium black dispersion, a photopolymerization monomer, a photopolymerization initiator, and a solvent, 2) Examples include, but are not limited to, compositions containing the above-described titanium black dispersion, a photoacid generator, 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 film 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, a known polymer compound 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 radically 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.
0% 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. One
If it exceeds 0% 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 amount of addition of these photopolymerization initiators is not particularly limited since it varies depending on the combination of the compositions. For example, when (1) a photopolymerizable monomer is used in combination, 5 to 150% by mass, preferably 50 to 60% by mass of the reactive monomer. (2)
When used in combination with a binder resin, it is preferable to use the photopolymerization initiator 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, 150% by mass based on the photopolymerizable monomer
If the amount exceeds 40% by mass or exceeds 40% by mass with respect to the binder resin, it causes insufficient curing due to precipitation of crystals.

Examples of the solvent in the photosensitive colored resin composition include 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 since it varies depending on the combination of the compositions, but the amount of the solvent used in combination with the solvent component in the above-mentioned coagulable fine particle dispersion is reduced to the total solid content. It is preferably used in a range of 50 to 500% by mass, preferably 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,
When the amount 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 onium salt compounds include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroholonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, and diphenyliodonium-p-toluenesulfonate. Nate, 4-methoxyphenyl-phenyliodonium tetrafluoroborate,
4-methoxyphenyl-phenyliodonium hexafluorophosphonate and the like.

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, one having an N-methylol structure is used. For example, methylolated urea, urea resin, methylolated melamine, butyrolated melamine, methylolated guanamine,
Alternatively, alkyl ethers of these compounds can be used, and alkyl ether compounds are more preferable from the viewpoint of 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 crosslinking agent to be added is not particularly limited because it varies depending on the combination of the compositions.
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 may be 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 coloring composition is 5 to 4
5 mass%, preferably 10 to 35 mass%, more preferably 25 to 30 mass%. When the content is 5% by mass or less, or 40% by mass or more, it becomes difficult to obtain a desired film thickness with a coating device such as spin coating or roll coating, and the coating property is also reduced.

The ratio of the surface-treated titanium black is as follows:
It is from 50 to 250% by mass, preferably from 100 to 200% by mass, based on the polymer component soluble or self-dispersible in the solvent, which is a dispersion resin. 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. 25
If it is 0% 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 the surface treatment of titanium black is not particularly limited, but 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. 2, a photosensitive colored resin composition 22 is coated on a substrate 21 by a bar coating method, a roll coating method, a spinner method, a curtain coating method or the like.
Apply uniformly to form a black resin layer. 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 23, exposure is performed, radical polymerization is performed, and curing is performed. 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 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, if necessary.

[0065]

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 As a stirring device having a rotary stirrer and a plurality of granular media disposed inside a vessel, an inlet portion and an outlet portion through which the granular media cannot pass but the liquid to be treated can pass are provided. In the basket in which the rotary stirrer is located, a granular medium is arranged, and further, using a basket mill in which the basket is arranged in a vessel, the dispersion treatment of titanium black in the liquid to be treated is performed. (See FIG. 1).

More specifically, 30 parts of silica black-treated titanium black and 68.5% of cyclohexanone as a solvent were used.
And Disperbyk-180 (by Big Chemie) as a polymer component soluble or self-dispersible in the solvent.
The liquid to be treated consisting of 3.0 parts was charged into a vessel, and a dispersion treatment was carried out at a peripheral speed of 10 m / s using a basket mill SS20Z (manufactured by Asada Iron Works) filled with 23 kg of 1 mm zirconia beads as granular media in a basket. went. At this time, the depth from the liquid surface of the liquid to be treated in the vessel to the inflow portion of the upper surface of the cage is set to 5 cm, and air is sucked into the cage together with the liquid to be treated by the negative pressure generated by the rotation of the rotary stirrer in the cage. I was doing it. Thus, the stirring process is performed under the condition that the liquid to be treated is sucked into the basket with the air bubbles involved. After performing the dispersion treatment for 7 hours, the zirconia beads and the liquid to be treated were separated to obtain a titanium black dispersion liquid (1).

Comparative Example 1 The procedure of Example 1 was repeated except that the depth from the liquid surface of the liquid to be treated in the vessel to the inflow portion of the upper surface of the basket was set to 30 cm to prevent air from being sucked into the basket. By performing the same operation as in Example 1, a comparative titanium black dispersion (C1) was obtained.

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.

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

Next, development was performed for 50 seconds by a spin development method using a 1% aqueous solution of sodium carbonate to remove the black resin layer in the unexposed area, and further baked 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.

[0074] 1000 on one side of a substrate on both sides of which Cr is deposited.
Spin coating was performed at 5 rpm for 5 seconds to obtain a coating film of 1.13 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, 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 3.2 was obtained. The exposure sensitivity was 130 mJ, the resolution was 6 μm (L / S), and the surface smoothness and pattern linearity 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 obtained in Comparative Example 1 (C
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 a light exposure of 250 mJ / cm ² using a 3 KW ultra-high pressure mercury lamp from the resin film surface side.

Next, development was carried out for 50 seconds by a spin developing 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.

One side of a substrate on which both sides of Cr were deposited, 1000
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 2.5 was obtained. The exposure sensitivity is 150 mJ, and the resolution is 20 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 10 days at 10 ° C. storage, 1010 Ω
cm or lower, and the resistivity decreased to 108 Ωcm, and the viscosity increased by 3.5 cP.

[0085]

As described above, according to the present invention, a solvent and a polymer soluble or self-dispersible in the solvent are provided in a stirrer in which a rotary stirrer and a plurality of granular media are arranged inside a vessel. A titanium black dispersion obtained by loading a liquid to be treated having at least a component and titanium black, and dispersing titanium black in the liquid to be treated. The treatment liquid has an inflow portion and an outflow portion through which the stirrer is located, or a basket in which the stirrer is located or forms a part of a wall surface, using a mill in which the granular media is arranged, and In the inflow portion located on the upper side, air is sucked together with the liquid to be treated by the negative pressure generated by the rotation of the stirrer, and the liquid to be treated is sucked into the basket with air bubbles entrained. Titanium black formed by stirring treatment in matters under dispersion having a photosensitive colored resin composition obtained by using.
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. Has resistance, high light-shielding properties,
Black matrix formed using this photosensitive colored resin composition has extremely excellent properties because it has excellent chemical resistance, heat resistance, adhesion to the substrate, and high film strength and low reflectance. Can be demonstrated.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a schematic configuration of a basket mill type stirring device used in a method for producing a titanium black dispersion used for preparing a photosensitive colored resin composition according to the present invention.

FIG. 2 is a cross-sectional view schematically showing a forming process when a black matrix is formed using the photosensitive colored resin composition according to the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Vessel, 2 ... basket, 3 ... Stirrer, 4 ... Granular media, 5 ... Liquid to be processed, 6 ... Inflow part, 7 ... Discharge part
Reference numeral 21 denotes a substrate, 22 denotes a photosensitive colored resin composition, 23 denotes a photomask, 24 denotes a hot plate, 25 denotes a photosensitive colored resin formed product, and 26 denotes an exposed and cured portion.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G02B 5/20 101 G02B 5/20 101 G03F 7/027 G03F 7/027 7/028 7/028 // C08L 101: 00 C08L 101: 00 (72) Inventor Hayato Ikeda 5-8 Nishiburi-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd. (72) Kazuhiro Anan 5-8 Nishi-Mabori-cho, Suita-shi, Osaka Within Nippon Shokubai (72) Inventor Ken Itoi 4-2-2, Takanodaiminami, Sugito-machi, Kitakatsushika-gun, Saitama Prefecture Inside Toppan Printing Co., Ltd. Inside Toppan Printing Co., Ltd. (72) Inventor Shinji Ito 4-2-2, Takanodai Minami, Sugito-cho, Kita-Katsushika-gun, Saitama Prefecture Inside Toppan Printing Co., Ltd. (72) Inventor Mizuhito Tani Saitama F-term (reference) 2H025 AA01 AA04 AA06 AA10 AA13 AA14 AA20 AB20 BC00 BJ10 CA00 CB42 CC03 CC11 CC17 DA40 FA17 2H048 BA02 BA45 BA47 BA48 BB01 BB02 BB02 BB01 BB02 BB01 BB02 4 AA32 AC15 AE04 AE08 FA04 FA14 FB06 FC03 4J011 PA69 PB25 PC02 QA12 QA13 QA23 SA01 SA21 SA41 SA51 SA63 UA06 VA01 WA01 4J026 AA45 AC35 BA28 DB02 DB36 FA05 GA07

Claims (2)

[Claims] (1) A solvent, a polymer component soluble or self-dispersible in the solvent, and titanium black are provided in a stirring device having a rotary stirrer and a plurality of granular media disposed inside a vessel. A titanium black dispersion obtained by loading the liquid to be treated and dispersing titanium black in the liquid to be treated, wherein, as the stirring device, an inflow portion through which the granular medium cannot pass but the liquid to be treated can pass And having a discharge portion, using a mill in which the granular media is arranged in a basket in which the stirrer is located inside or constituting a part of a wall surface, and wherein the mill is located on the upper side of the mill. At the inlet,
Air is sucked together with the liquid to be treated by the negative pressure generated by the rotation of the stirrer, and a titanium black dispersion obtained by stirring under the condition that the liquid to be treated is sucked into the cage in a state where air bubbles are involved. And (2) a photopolymerizable monomer; (3) a photopolymerization initiator; and (4) a solvent. 2. A solvent, a polymer component soluble or self-dispersible in the solvent, and titanium black are provided in a stirring device having a rotary stirrer and a plurality of granular media disposed inside a vessel. A titanium black dispersion obtained by loading the liquid to be treated and dispersing titanium black in the liquid to be treated, wherein, as the stirring device, an inflow portion through which the granular medium cannot pass but the liquid to be treated can pass And a discharge section, using a mill in which the granular media is arranged in a basket in which the stirrer is located inside or a part of a wall surface, and wherein the mill is located on the upper side of the mill. In the inflow section, air is sucked together with the liquid to be treated by the negative pressure generated by the rotation of the stirrer, and the liquid to be treated is stirred under the condition that the liquid to be treated is sucked into the basket with air bubbles entrained. That the titanium black dispersion, (2) a photoacid generator, (3) a crosslinking agent, (4) a photosensitive colored resin composition, which comprises a solvent, and the ingredients.