JPH10133365A - Composition for nonconductive light shielding layer, nonconductive light shielding layer and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a nonconductive light-shielding compsn. which is stable for a long time, excellent in light-shielding ability and blackness and suitable for the production of a nonconductive light-shielding layer by incorporating specified metal oxide fine particles and/or metal sulfide fine particles into a pigment. SOLUTION: This compsn. for a nonconductive light-shielding layer essentially consists of an alkali-soluble binder, photopolymerizable monomers, a photopolymerizable initiator, pigments and solvents, and the surface of the pigments contains at least one kind of particles selected from metal oxide fine particles and/or metal sulfide fine particles having 0.1 to 30μmol/g hydroxyl groups. By optimizing the amt. of hydroxyl groups which are present on the surface of pigment particles and cause problems, strong adsorption of the binder or other components by the pigment particles and aggregation of the pigment particles themselves are hardly caused. By decreasing aggregation of pigment particles themselves and interaction with the binder in the compsn., storage stability of the liquid compsn. can be improved and intrinsic characteristics of the compsn. can be obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention has a high light shielding ability,
The present invention also relates to a composition for a light-shielding layer that is useful in applications requiring non-conductivity. More specifically, the present invention relates to a composition for a non-conductive light-shielding layer, a non-conductive light-shielding layer, and a color filter useful for forming a light-shielding layer (black matrix) in a color filter used in a liquid crystal display device or the like.

[0002]

2. Description of the Related Art Conventionally, in a color filter used in a liquid crystal display device, a light-shielding layer made of a thin metal such as chromium, nickel, or aluminum, or a carbon black or a titanium black is formed in a non-pixel region in order to enhance the contrast of a displayed image. There is known a method of providing a light-shielding layer obtained by dispersing a pigment such as the above in a binder resin.

[0003]

However, in the conventional method as described above, since the light-shielding layer has conductivity, when the light-shielding layer is used between the transparent electrodes, an additional insulating layer must be provided. In some cases, short-circuiting between the electrodes is likely to occur depending on the light-shielding layer, and crosstalk between adjacent electrode layers increases through the conductive light-shielding layer.

In order to solve the above problems, the present inventors have proposed CuMn ₂ O ₄ which is a black pigment excellent in light-shielding ability and blackness and suitable for producing a non-conductive light-shielding layer.
And a part of the CuMn ₂ O ₄ is Fe, Co and / or Ni
(JP-A-8-95884) has proposed a composition for a non-conductive light-shielding layer using composite oxide fine particles substituted by the above.

However, the pigment composed of the above-mentioned oxide fine particles has a large number of hydroxyl groups on the surface and has a large surface area, so that the pigment itself easily aggregates and, at the same time, swells once in an alkali developing solution with a high molecular weight. To strongly adsorb and aggregate alkali-soluble binders and the like that dissolve from
In the development after the formation of the layer, insolubilization of a region which should be originally dissolved occurs, causing deterioration in resolution and smoothness of the light shielding layer. In addition, the aggregated pigment particles cause a problem that storage stability of the liquid composition is reduced and substrate adhesion during the development process is reduced because the inherent properties of the composition are not exhibited. These problems are also strongly controlled by the molecular weight of the other composition components, especially the alkali-soluble binder, and it has also been found that the higher the molecular weight, the more the above-mentioned problems appear more remarkably.

Accordingly, an object of the present invention is to optimize the amount of hydroxyl groups present on the surface of pigment particles and causing the above-mentioned problems, whereby strong adsorption of other composition components such as binders by the pigment particles, It is hard for self-aggregation to occur,
Non-conductive light-blocking layer composition suitable for producing a non-conductive light-blocking layer, which is stable for a long time, has excellent light-blocking ability and blackness, and is suitable for producing a non-conductive light-blocking layer, and a non-conductive light-blocking layer prepared using the composition It is to provide a color filter.

[0007]

The above object is achieved by the present invention described below. That is, the present invention relates to a composition for a non-conductive light-shielding layer containing an alkali-soluble binder, a photopolymerizable monomer, a photopolymerizable initiator, a pigment and a solvent as main components, wherein the pigment has a surface of 0.1 to 30 μmol / g
A non-conductive light-shielding layer composition comprising at least one selected from metal oxide fine particles having a hydroxyl group and / or metal sulfide fine particles.

In the present invention, by optimizing the amount of hydroxyl groups present on the surface of the pigment particles and causing the above problem, strong adsorption of other composition components such as a binder by the pigment particles, Agglomeration hardly occurs, and the aggregation of the pigment particles in the composition and the interaction with the binder are reduced, so that the storage stability of the liquid composition is improved and the inherent properties of the composition are exhibited.

[0009] Further, at the same time as lowering the molecular weight of the alkali-soluble binder than in the conventional composition, at least a part thereof is exposed to a substrate even in a pattern forming step including exposure and development, particularly when exposed to an alkali developing solution for a long time. A resin having a skeleton structure that does not impair the adhesion, for example, an epoxy resin, and at least a part of the photopolymerizable monomer is a polyfunctional acrylate or a polyfunctional methacrylate, particularly dipentaerythritol penta (meth) acrylate, and the like. The use of the derivative improves the resolution of the non-conductive light-shielding layer, and at the same time provides a composition suitable for producing a non-conductive light-shielding layer having a strength that can withstand practical use.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. The black pigment used in the composition for a non-conductive light-shielding layer of the present invention is black and electrically insulating metal oxide fine particles and / or metal sulfide fine particles, such as iron oxide, chromium oxide, and vanadin trioxide. , Vanadium dioxide, antimony trisulfide, bismuth trisulfide, chromium sulfide, molybdenum trisulfide, molybdenum disulfide, tungsten disulfide, manganese dioxide, rhenium dioxide, rhenium trioxide, rhenium disulfide, iron sulfide, ferric sulfide, oxide Cobalt, cobaltic oxide, cobalt tetroxide, cobalt sulfide, nickel sulfide, Cu-Mn-F
e, at least one selected from composite oxide fine particles made of Cu-Fe-Zn and the like.

A preferred black pigment in the present invention is Cu
Mn ₂ O ₄ and part of Mn of the CuMn ₂ O ₄ are Fe,
Co- and / or Ni-substituted composite oxide fine particles, wherein the pigment is a non-conductive, excellent blackness, and fine-grained pigment, and is a spinel-type compound, and has weather resistance and heat resistance. And a pigment having excellent electrical insulation properties. According to JP-A-4-50119, C
An alkali is added to a water-soluble metal salt of u, Mn, Fe, Co and Ni to neutralize and precipitate, and an oxidizing agent such as hydrogen peroxide is added to the precipitated slurry to perform oxidation in a liquid phase. After washing, drying, baking and crushing, the inorganic pigment is obtained.

According to this production method, a fine pigment having a high specific surface area can be obtained at low production cost. Further, a part of Mn of the composite oxide of CuMn ₂ O ₄ is
Substitution by e, Co or Ni gives a finer pigment with a larger specific surface area. Preferred compositions of the pigment used in the present invention include, for example, CuO, Fe ₂ O
₃ and Mn ₂ O ₃ . The composition ratio of CuO is 25 to 40% by weight, Fe ₂
O ₃ is 5-30 wt%, and _Mn 2 _{O 3} is particularly preferably in the range of 40 to 60 wt%.

The particle size of these pigments is from 0.01 μm to
It is preferably 0.5 μm. Particle size is 0.01μ
When the particle size is less than 0.5 μm, the smoothness of the formed light-shielding layer surface is impaired, It is not preferable because the precision of pattern formation is greatly reduced. A large number of hydroxyl groups (OH groups) are present on the surface of the insulating pigment fine particles.
Is present, causing the above problems, but by adjusting the amount of these hydroxyl groups, since other components such as aggregation of the pigment particles and the binder are prevented from being adsorbed on the pigment surface,
The composition is useful as a composition for forming a light-shielding layer and further for forming a color filter including the light-shielding layer without impairing the inherent properties of the composition.

The amount of hydroxyl groups on the pigment surface is 0.1 to 30 μm
It is preferably in the range of ol / g. 30 hydroxyl groups
When the amount exceeds μmol / g, the above-described problem due to aggregation of the pigment particles is caused.
When the amount is less than ol / g, the hydrophilicity of the pigment is significantly reduced, so that a stable dispersion state in the composition is not formed, and as a result, aggregation of the pigment particles occurs, which is not preferable.

The amount of the hydroxyl groups on the surface of the pigment is determined as follows. That is, 30 ml of a 0.01 N tetrabutylammonium hydroxide-ethanol solution per 2.0 g of the pigment.
Was added and stirred for 1 hour, 10 ml of the supernatant was taken, 30 ml of ethanol was added, and 0.01N perchloric acid-
The value obtained by subtracting the amount of residual tetrabutylammonium hydroxide determined in the ethanol solution from the amount of tetrabutylammonium hydroxide contained in 30 ml of the above 0.01N tetrabutylammonium hydroxide-ethanol solution was defined as the amount of hydroxyl groups on the pigment surface. .

The amount of hydroxyl groups on the pigment surface is 0.1 to 30 μm
The amount of hydroxyl groups on the pigment surface is measured by the above measurement. If the amount of hydroxyl groups is too large, the pigment is heated at 200 ° C. or more for 1 hour or more to adjust the amount of hydroxyl groups. A method of adding a coupling agent having an alkyl group, a phenyl group, or the like, and reacting the coupling agent with a hydroxyl group to reduce the hydroxyl group. Further, a method of reducing the hydroxyl group (such as ethylene glycol mono-n-butyl ether, etc.) ), Carboxyl group (phthalic anhydride, etc.)
And the like, a method of adding an organic compound having both a functional group and a hydrophobic part to the pigment, and heating and stirring in an organic solvent to reduce the number of hydroxyl groups. On the other hand, when the amount of hydroxyl groups of the pigment is too small, a method of coating at least a part of the surface of the pigment with ultrafine metal oxide particles, or dispersing the pigment in water, followed by acid or base, etc. And boiling at 90 ° C. or more. The amount of hydroxyl groups on the surface of the pigment can be adjusted in the range of 0.1 to 30 μmol / g by such a method, but the present invention is not limited to the above method.

The alkali-soluble binder used in the composition for a nonconductive light-shielding layer of the present invention contributes to the dispersibility of the pigment, has good compatibility with the photopolymerizable monomer and the photopolymerizable initiator, and has an alkali developing solution. Solubility in organic solvents, excellent adhesion to substrates during pattern formation processes including exposure and development, especially when exposed to alkaline developers and cleaning solutions for long periods of time, and strength as a light-shielding layer and color filter member Those having an appropriate softening temperature and the like are preferable. These preferred binders can be selected from the wide variety of polymeric substances listed below.

Specifically, side chains such as methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc. And a cellulose derivative having a carboxylic acid group. In addition, a carboxyl-modified polymer obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group is also useful. In addition, water-soluble polymers such as polyvinylpyrrolidone, polyethylene oxide, and polyvinyl alcohol can be used. Further, a copolymer containing an unsaturated organic acid and an unsaturated organic acid ester such as methyl acrylate, ethyl methacrylate, benzyl methacrylate, or glycidyl methacrylate as a monomer may be mentioned. Other unsaturated organic acid esters may be added to the copolymer. Those obtained by quantitative addition polymerization can also be used.

Specifically, side chains such as methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, and the like. And a cellulose derivative having a carboxylic acid group. In addition, a carboxyl-modified polymer obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group is also useful. In addition, water-soluble polymers such as polyvinylpyrrolidone, polyethylene oxide, and polyvinyl alcohol can be used. Further, a copolymer containing an unsaturated organic acid and an unsaturated organic acid ester such as methyl acrylate, ethyl methacrylate, benzyl methacrylate, or glycidyl methacrylate as a monomer may be mentioned. Other unsaturated organic acid esters may be added to the copolymer. Those obtained by quantitative addition polymerization can also be used.

As an example of a preferable alkali-soluble binder, at least a part of the binder is an epoxy resin, and glycidyl methacrylate or the like is added to two or more epoxy groups contained in the molecule of the epoxy resin. A resin having a reactive double bond group or a modified epoxy resin obtained by adding a cyclic acid anhydride to the epoxy resin to introduce a carboxyl group and imparting a polymerization initiation ability or an alkali phenomenon to the epoxy resin. Can be As these epoxy resins, a bisphenol A type vinyl ester whose basic skeleton is a condensation reaction product of bisphenol A and epichlorohydrin is particularly preferable, and these epoxy resin modified products are resistant to alkalis and adherence to substrates,
Furthermore, it is suitable as satisfying the above-mentioned characteristics in realizing the film strength of the formed light shielding layer.

Further, by introducing a reactive double bond group into at least a part of the alkali-soluble binder to form a polymerizable binder as described above, the strength of the light-shielding layer formed can be improved. Can be. The number of reactive double bond groups to be introduced is preferably in the range of 0.1 to 20 on average per one molecule of the binder. Further, in order to impart a suitable alkali developing solution resistance, the acid value is about 70 to 250 mg KOH.
/ G is preferable. When the acid value exceeds this range, the pattern is resolved after exposure and development of the light-shielding layer, but there is no resistance to an alkali developing solution, and small cracks are generated on the developed pattern surface. The rapid penetration of the liquid eventually causes the resist to peel (peel) from the substrate surface. On the other hand, when the acid value is less than the above range, solubility in alkali is lost, and even in the unexposed portion of the light-shielding film, no dissolution occurs in the developing solution, so that an appropriate pattern cannot be formed.

The molecular weight of these alkali-soluble binders is preferably in the range of 2,000 to 20,000.
When it is less than 2,000, it does not function sufficiently as a binder. On the other hand, when it exceeds 20,000, aggregates of a plurality of pigment particles are easily formed, and the storage stability of the composition caused by the aggregation of the pigment particles and This is not preferable because it causes a decrease in adhesion to the substrate, pattern forming property, and smoothness of the coating film. The content of the alkali-soluble binder is preferably in the range of 5 to 80% by weight of the total solids in the liquid composition. Further, the epoxy resin used as at least a part of the alkali-soluble binder also has the effect of stabilizing the dispersion of the pigment in the liquid.

Preferred examples of the alkali-soluble binder as described above include bisphenol A type epoxy acrylate (trade names: VR-60, V-60, manufactured by Showa Polymer Co., Ltd.).
R-90), a bisphenol A type epoxy acrylate (trade name: EB60) manufactured by Daicel UCB Co., Ltd.
0, EB3701), dimethacrylate (trade name: NK ester, BPE-100, manufactured by Shin-Nakamura Chemical Co., Ltd.)
BPE-200), cresol novolak type epoxy acrylate, phenol novolak type epoxy acrylate and the like.

As the photopolymerizable monomer used in the composition of the present invention, a polyfunctional acrylate or a polyfunctional methacrylate having three or more double bond functional groups in one molecule is preferably used. It is preferable that at least a part of the hydrophilic monomer is dipentaerythritol penta (meth) acrylate having five double bond groups.
The reason that dipentaerythritol penta (meth) acrylate is particularly preferable is that when the number of functional groups is 6 or more, the formed light-shielding layer itself becomes hard, but becomes brittle, so that sufficient film strength cannot be exhibited. On the other hand, when the ratio is 4 or less, the curing of the film is insufficient, and in this case, it is considered that the strength is also insufficient.

Other photopolymerizable monomers used in the present invention include, for example, polyethylene glycol di (meth)
Acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, neopentyl glycol di (meth) acrylate,
Pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri ((meth) Polyacrylic alcohols such as acryloyloxypropyl) ether, tri ((meth) acryloyloxyethyl) isocyanurate, tri ((meth) acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate, trimethylolpropane, glycerin and ethylene oxide and propylene (Meth) acrylates after addition reaction of oxides, and polyester (meth) acrylates. Rimmer, i.e. a dimer or trimer is also effective. The content of the monomer is preferably in the range of 5 to 50% by weight of the total solids in the composition for the non-conductive light-shielding layer.

In practicing the present invention, a suitable non-conductive light-shielding layer can be formed by combining the alkali-soluble binder with the photopolymerizable monomer. The modified epoxy resin obtained has a preferred molecular weight range of 2,000 for the alkali-soluble binder in the present invention.
In the range of ２０20,000, the adhesive compound is a sticky compound, and the non-conductive light-shielding layer itself formed therefor has tackiness. When a light-shielding layer or a color filter is manufactured using such a composition for a non-conductive light-shielding layer, dust or the like easily adheres to the surface of the light-shielding layer during manufacturing, and defects in the light-shielding layer or the color filter easily occur. Therefore, in the present invention, when the modified epoxy resin is used as the alkali-soluble binder, it is preferable to further add a high molecular weight additive to the composition to remove the tackiness of the formed light-shielding layer.

As the high molecular weight additive for eliminating the tackiness of the light-shielding layer, those having a property capable of removing only the tackiness while maintaining the properties of the non-conductive light-shielding layer such as developability and resolution are preferable. In the present invention, non-conductive light-shielding is achieved by using a graft copolymer and / or a block copolymer having both a compatible part (hydrophilic part) and an incompatible part (hydrophobic part) with an alkali-soluble binder. It is possible to uniformly distribute the heterogeneous portion (hydrophobic portion) in the layer, and it is possible to remove only the tackiness while maintaining the characteristics of the non-conductive light-shielding layer.

The compatible part (hydrophilic part) of the high molecular weight additive in the present invention is a high molecular weight having a hydrophilic functional group such as -OH group or -COOH group, for example, polyacrylic acid, polyvinylpyrrolidone, Polyvinyl alcohol, poly (2-hydroxyethyl methacrylate), hydroxypropyl methylcellulose and the like, and high molecular weight compounds having an -O- bond in the main chain, for example, polyethylene glycol, polypropylene glycol and the like, Examples of the incompatible portion (hydrophobic portion) of the high molecular weight additive include polymethyl methacrylate, polystyrene, polybutene, and the like having no hydrophilic group in the skeleton, and these are particularly preferable in the present invention.

When the molecular weight of the high molecular weight additive is a graft copolymer, the molecular weight of the hydrophobic part is 5,000 to 3
000, and the molecular weight of the hydrophilic portion is 1,0.
It is preferably in the range of from 00 to 10,000, while in the case of a block copolymer, it is from 5,000 to 50,000.
000 is preferable. When the respective molecular weights are less than the above ranges, there is almost no effect of removing the tackiness of the light-shielding layer. On the other hand, when the respective molecular weights exceed the above ranges, it is not preferable because aggregation of the pigment particles occurs in the composition.

In the present invention, the high molecular weight additive may have a reactive double bond group or an alkali-soluble acid value. . The reactive double bond group to be introduced is in the range of 0.1 to 20 on average per one molecule of the high molecular weight additive, and the acid value of alkali solubility is 10 to 250 mgKOH / g.
Is preferably within the range. At least a part of these high molecular weight additives are adsorbed on the surface of the pigment particles, and also have an effect as a so-called dispersion stabilizer for preventing aggregation of the pigment particles in the liquid composition. The high molecular weight additive as described above can be synthesized by various known methods,
It can be easily obtained from the market and used, and as an example, for example, comb polymer (trade name: L-20) manufactured by Soken Chemical Co., Ltd. can be mentioned.

Examples of the photopolymerizable initiator used in the composition for a non-conductive light-shielding layer of the present invention include thioxanthone, acetophenone, benzophenone, benzoin ether and peroxide compounds. It is also effective to use an amine-based or quinone-based photopolymerization accelerator in accordance with the necessity such as improvement of sensitivity. The content of the photopolymerization initiator and the photopolymerization accelerator is preferably in the range of 0.5 to 40% by weight of the total solids in the composition for the non-conductive light-shielding layer.

The solvent used in the composition for a non-conductive light-shielding layer of the present invention is selected from the group consisting of a coating suitability of the composition, a solubility of a polymer, a monomer and a photopolymerization initiator, and a dispersibility of a pigment. One or more solvents can be selected and used, and the solvent preferably contains at least one polyhydric alcohol or a derivative thereof. In particular, considering the dispersibility of the pigment, among the polyhydric alcohols and derivatives thereof, those having a solubility of 20 parts by weight or more with respect to 100 parts by weight of water are particularly effective in the present invention.

Specific examples of the solvent include, for example, ethylene glycol, ethylene glycol monomethyl ether,
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, glycol monoethyl ether acetate, ethylene glycol diethyl ether, ethylene glycol monobutyl ether,
Ethylene glycol isoamyl ether, methoxymethoxy ether, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,
Diethylene glycol monomethyl ether acetate,
Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, 1-butoxyethoxypropanol, dipropylene glycol monomethyl ether, butanediol and the like. .

The composition for a non-conductive light-shielding layer of the present invention may further comprise, in addition to the above components, a silane coupling agent in order to impart adhesion to a substrate to which the composition is applied. And a titanate coupling agent, an aluminum coupling agent and the like can also be added. In addition, if necessary,
Known additives, for example, dispersants, plasticizers, surfactants and the like can also be added. By coating and drying the composition for a non-conductive light-shielding layer of the present invention on a substrate by a known method, a non-conductive light-shielding layer can be formed on the substrate. Specific examples of the coating method include, for example, a spinner,
Examples include a wheeler, a roller coater, a curtain coater, a knife coater, a bar coater, and an extruder. The non-conductive light-shielding layer of the present invention can be provided on a substrate by drying a coating layer.

When a pattern is exposed on the substrate on which the non-conductive light-shielding layer of the present invention is formed as described above, the light source is selected according to the photosensitivity of the non-conductive light-shielding layer. Known ones such as a xenon lamp, a carbon arc lamp, and an argon laser can be used. Further, as a developing solution for developing the non-conductive light-shielding layer subjected to pattern exposure,
For example, an alkaline aqueous developer is suitable. The alkaline aqueous developer mentioned in the present invention, in order to perform development with an aqueous, OH at the time of development in a narrow sense ^- a developer releasing. The pH of the alkaline aqueous developer is optimally 7.5.
The alkali component to be used is, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, and further an organic ammonium compound, for example, tetraethylammonium hydroxide, other, sulfide, oxide or weak acid. Those hydrolyzed by an anion (eg, F ⁻ , CN ^−, etc.) and the like can be mentioned. Further, a buffer solution in the above pH range may be adjusted and used as an alkaline aqueous developer.

Further, according to the present invention, according to a known method, red, green and blue pixels and a black matrix are provided on a transparent substrate, and the black matrix is used in a color filter provided with a transparent electrode layer on the surface. And a color filter formed from the composition for a non-conductive light-shielding layer of the present invention.

[0037]

Next, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to these examples. Example 1 (1) Preparation of Black Pigment Dispersion Non-conductive black pigment: TM Black # 9550 (hydroxyl amount: 4.23 μmol / g) 23 parts by weight (Mn of CuMn ₂ O ₄ was partly replaced with Fe) Composite oxide fine particles; Dainichi Seika Kogyo Co., Ltd.) Dispersion: Disperbyk 111 2 parts by weight (polymer dispersant; BYK Japan Japan Ltd.) Ethylene glycol monobutyl ether 75 parts by weight Well dispersed.

(2) Preparation of composition for non-conductive light-shielding layer 61 parts by weight of black pigment dispersion prepared in (1) Alkali-soluble binder: VR-60 2.8 parts by weight (bisphenol A type epoxy acrylate; Showa Koto Photopolymerizable monomer: 3.5 parts by weight of dipentaerythritol pentaacrylate High molecular weight additive: 0.7 parts by weight of L-20 (comb-shaped polymer; manufactured by Soken Chemical Co., Ltd.) Agent: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 1.6 parts by weight 4,4-diethylthioxanthone 0.3 part by weight 2,4-diethylthioxanthone 0.1 part by weight Parts ethylene glycol monobutyl ether 30 parts by weight The above components were mixed well to obtain a composition for a non-conductive light-shielding layer of the present invention.

(3) Preparation of a light-shielding layer The composition for a non-conductive light-shielding layer prepared in (2) was applied on a glass substrate by a roll coater and dried at 100 ° C. for 3 minutes to form a light-shielding layer having a thickness of about 1 μm. Was formed. (4) Exposure and Development The light-shielding layer was exposed to a light-shielding layer pattern with an ultrahigh-pressure mercury lamp under a nitrogen stream, and then developed with a 1% by weight aqueous solution of sodium carbonate.

Example 2 (1) Preparation of Black Pigment Dispersion SICOCER F Black 2912 as a non-conductive black pigment
A black pigment dispersion was obtained in the same manner as in Example 1 except that (Cu—Fe—Zn-based composite oxide fine particles; manufactured by BASF; hydroxyl group content: 5.04 μmol / g) was used. (2) Preparation of composition for non-conductive light-shielding layer A composition for non-conductive light-shielding layer was obtained under the same preparation conditions as in Example 1.

(3) Preparation of a light-shielding layer The composition for a non-conductive light-shielding layer prepared in (2) is applied on a glass substrate by a roll coater, and dried at 100 ° C. for 3 minutes. Was formed. (4) Exposure and Development The light-shielding layer was exposed to a light-shielding layer pattern with an ultrahigh-pressure mercury lamp under a nitrogen stream, and then developed with a 1% by weight aqueous solution of sodium carbonate.

Example 3 (1) Preparation of Non-conductive Black Pigment Dispersion PA-8646M (iron oxide-based fine particles; manufactured by Sakai Chemical Co., Ltd .; hydroxyl group content: 3.33 μmol /
A non-conductive black pigment dispersion was obtained in the same manner as in Example 1 except that g) was used. (2) Preparation of composition for non-conductive light-shielding layer A composition for non-conductive light-shielding layer was obtained under the same preparation conditions as in Example 1.

(3) Preparation of a light-shielding layer The composition for a non-conductive light-shielding layer prepared in (2) was applied on a glass substrate by a roll coater and dried at 100 ° C. for 3 minutes to form a light-shielding layer having a thickness of about 1 μm. Was formed. (4) Exposure and Development The light-shielding layer was exposed to a light-shielding layer pattern with an ultrahigh-pressure mercury lamp under a nitrogen stream, and then developed with a 1% by weight aqueous solution of sodium carbonate.

Comparative Example Non-conductive black pigment TM Black # 3550 (hydroxyl content:
Using 32 μmol / g), a black pigment dispersion and a composition for a non-conductive light-shielding layer were prepared in the same manner as in Example 1, a light-shielding layer was formed, and exposure and development were performed. The results of comparing the characteristics of the above composition for a non-conductive light-shielding layer are shown below.

Change with time of the composition solution for the non-conductive light-shielding layer The composition solutions of Examples 1 to 3 showed no change in viscosity or particle size distribution for more than one month, but the composition solution of Comparative Example 3 A precipitate was observed after day and the entire solution lost fluidity after 7 days. Smoothness of light-shielding layer The light-shielding layer from the composition solutions of Examples 1 to 3 was completely smooth, but the light-shielding layer from the comparative example confirmed aggregates of several μm in the film.

Substrate adhesion during development and cleaning Most of the light-shielding layer of the comparative example was peeled off during development and cleaning, but the light-shielding layers of Examples 1 to 3 were peeled or missing during development and cleaning. Was not found.

[0047]

According to the present invention, stable over a long period of time,
In addition, a non-conductive light-shielding layer having high light-shielding ability and excellent in substrate adhesion and excellent in pattern formation even when exposed to an alkali developing solution for a long time can be obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G02B 5/20 101 G02B 5/20 101 G02F 1/1335 500 G02F 1/1335 500 505 505 G03F 7/027 502 G03F 7/027 502 // C08F 2/48 C08F 2/48 C09D 4/00 C09D 4/00

Claims (17)

[Claims] 1. A composition for a non-conductive light-shielding layer comprising an alkali-soluble binder, a photopolymerizable monomer, a photopolymerizable initiator, a pigment and a solvent as main components, wherein the pigment has 0.1 to 30 μmol on its surface. A composition for a non-conductive light-shielding layer, comprising at least one selected from metal oxide fine particles and / or metal sulfide fine particles having a hydroxyl group of / g. 2. The composition for a non-conductive light-shielding layer according to claim 1, wherein the pigment has a particle size of 0.01 to 0.5 μm. 3. An alkali-soluble binder, wherein at least a part of the binder contains an average of 0.1 to 20 reactive double bond groups per molecule of the binder, and has an acid value of 70 to 250 mg.
The composition for a non-conductive light-shielding layer according to claim 1, which is an epoxy resin having a KOH / g. 4. The composition for a non-conductive light-shielding layer according to claim 3, wherein the epoxy resin is a bisphenol A type vinyl ester. 5. The molecular weight of the alkali-soluble binder is:
The composition for a non-conductive light-shielding layer according to claim 1, wherein the composition is 2,000 to 20,000. 6. A photopolymerizable monomer having at least a part of 3
The composition for a non-conductive light-shielding layer according to claim 1, which is a polyfunctional acrylate and / or a polyfunctional methacrylate having two or more double bond functional groups. 7. At least a part of the photopolymerizable monomer is
The composition for a non-conductive light-shielding layer according to claim 1, which is dipentaerythritol penta (meth) acrylate or a derivative thereof. 8. The composition for a non-conductive light-shielding layer according to claim 1, further comprising a high molecular weight additive. 9. At least a part of the high molecular weight additive is:
The composition for a non-conductive light-shielding layer according to claim 8, which is a graft copolymer comprising a hydrophobic main chain and a hydrophilic side chain. 10. The composition for a nonconductive light-shielding layer according to claim 8, wherein at least a part of the high molecular weight additive is a graft copolymer comprising a hydrophilic main chain and a hydrophobic side chain. . 11. The graft copolymer according to claim 9, wherein the hydrophobic portion has a molecular weight of 5,000 to 30,000, and the hydrophilic portion has a molecular weight of 1,000 to 10,000. The composition for a non-conductive light-shielding layer of the above. 12. The composition for a non-conductive light-shielding layer according to claim 8, wherein at least a part of the high molecular weight additive is a block copolymer having both a hydrophobic part and a hydrophilic part. 13. The molecular weight of the block copolymer is 5,0.
13. The composition for a non-conductive light-shielding layer according to claim 12, wherein the number is from 00 to 50,000. 14. The high molecular weight additive has an average of 0.1 to 20 reactive double bond groups per molecule of the high molecular weight additive.
9. The composition for a non-conductive light-shielding layer according to claim 8, wherein 15. The high molecular weight additive having an acid value of 10 to 2
The composition for a non-conductive light-shielding layer according to claim 8, wherein the composition is 50 mgKOH / g. 16. A non-conductive light-shielding layer according to claim 1, which is formed by applying a composition for a non-conductive light-shielding layer onto a substrate and drying the composition, and then performing a pattern forming step including at least exposure and development. Conductive light shielding layer. 17. Red, green and blue pixels on a transparent substrate;
And a color filter provided with a black matrix and further provided with a transparent electrode layer on the surface, wherein the black matrix is formed from the composition for a non-conductive light-shielding layer according to claim 1. Color filter.