JPH11349842A - Photopolymerizable pigment dispersant, photosensitive coloring composition and composition for shading layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a dispersant which has an excellent dispersibility and improves stability of a composition and substrate adhesiveness by blending not less than one compound having a photo-curing ethylenically unsaturated group. SOLUTION: This is a photopolymerizable pigment dispersant containing not less than one compound selected from the compounds of formulas I-III. A coloring liquid is prepared by blending a black pigment whose particle diameter is 0.001-0.5 μm, 2-80 wt.%, against all the solid content of the composition, of the dispersant and a solvent such as a polyhydric alcohol or the like. A coloring composition is prepared by adding and blending, with this coloring liquid, 5-80 wt.% of an alkali-soluble binder such as an epoxy resin or the like, 5-50 wt.% of a photopolymerizable monomer such as a multi-functional (meth)acrylate having not less than 3 double-bonding functional groups or the like, 0.1-40 wt.% of a material-property improving agent for a coated layer and 0.5-40 wt.% of a photopolymerization initiator. In the formulas, R1 , R3 and R6 are each hydrogen or methyl; R2 and R4 are each a 1-10C alkylene; R5 is an alkylene or a phenylene; X1 -X4 are each oxyethylene or the like; i and q are each 0 or 1; p is 1 or 2; and l, m, n, r and s are each 0-100 or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photopolymerizable pigment dispersant, and particularly to a pigment dispersant having excellent pigment dispersion stability in an organic solvent system and having reactivity to UV and EB. It can also be used as a compatibilizer for various resists such as UV / EB curable paints, inks, solder resists, and polymer alloys. In particular, a dispersant for a coloring composition in a pigment dispersion color filter, a photopolymerizable pigment dispersant suitable as a dispersant for a light-shielding layer, a photosensitive coloring composition using the dispersant, and a composition for a light-shielding layer About.

[0002]

2. Description of the Related Art A method of producing a color filter by a photolithography method using a pigment-dispersed resist is stable with respect to light and heat due to the use of a pigment, and is patterned by the photolithography method. It is a suitable method for producing a high-resolution pongee color display. However, in a color filter produced by the pigment dispersion method, if the dispersibility of the pigment is insufficient, problems occur in color purity and dimensional accuracy, and the display contrast ratio is significantly deteriorated due to depolarization. In addition, resist compositions with poor pigment dispersion stability not only adversely affect the film thickness uniformity during application in the color filter manufacturing process, the sensitivity during exposure, and the solubility during development, but also cause aggregation over time. There is also a problem that the viscosity increases and the pot life is extremely short. In general, pigments have poor dispersibility and miscibility in organic media such as organic solvents and polymer compounds. Therefore, as a means for increasing the dispersibility of pigments, dispersants such as surfactants and pigment derivatives are used. .

[0003]

However, since the conventional dispersant does not have a photosensitive group in its molecule, materials having no photocurability such as a binder resin and a dispersant are contained in the resist composition. The presence of a large amount causes a decrease in the sensitivity of the resist. In particular, in the composition for the light-shielding layer,
Due to the light-shielding properties, the amount of exposure was significantly reduced, resulting in insufficient curing,
The effect of non-reactive components is likely to appear. In addition, when the dispersant is soluble in an aqueous alkaline solution, the dispersant present in the exposed portion is eluted from the photocured portion during the alkali development, which adversely affects the adhesion of the coating film to the substrate and the pattern shape. Have a problem. The present invention solves the above-mentioned problems of the prior art, and an object of the present invention is to provide a photopolymerizable pigment dispersant having high dispersion stability, which is effective for improving resist characteristics. Another object of the present invention is to provide a photosensitive colored composition suitable for producing a color filter and a composition for a light shielding layer.

[0004]

As a result of diligent studies to achieve the above object, the following general formulas (I) and (I)
The photopolymerizable pigment dispersant comprising at least one compound represented by (I) or (III) has excellent dispersibility in various pigments, and has excellent stability in the photosensitive coloring composition and the composition for the light-shielding layer. The present inventors have found that sensitivity and substrate adhesion are improved, and have reached the present invention.

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The photosensitive coloring composition of the present invention comprises an alkali-soluble binder, a photopolymerizable monomer, a photopolymerizable initiator,
It is characterized by containing a dispersant, a pigment and a solvent as main components, and the dispersant contains at least one photopolymerizable dispersant represented by the above general formula (I), (II) or (III).
Further, the composition for a light-shielding layer of the present invention, an alkali-soluble binder, a photopolymerizable monomer, a photopolymerizable initiator, a dispersant,
It comprises an inorganic black pigment and a solvent as main components, and the dispersant contains at least one photopolymerizable dispersant represented by the above general formula (I), (II) or (III).
The inorganic black pigment is a composite metal oxide containing at least copper, iron and manganese.

It is characterized in that the photopolymerizable monomer is a polyfunctional acrylate having 3 to 6 reactive double bond groups and / or a polyfunctional methacrylate. The average molecular weight of the above alkali-soluble binder is 2000
20,000, and at least a part thereof is an epoxy resin containing 0.05 to 5 mmol of a reactive double bond group per 1 g and an acid value of 50 to 250 mgKOH / g. The epoxy resin is a bisphenol A type vinyl ester.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The general formulas (I) and (II) of the present invention
Alternatively, since the photopolymerizable dispersant represented by (III) has a photocurable ethylenically unsaturated group, when used in a pigment-dispersed resist, the sensitivity of the resist is improved. In addition, it is possible to improve the disadvantages of a dispersant having no photocurability, such as a decrease in substrate adhesion of a coating film due to alkali development and a deterioration in pattern shape.

Specific examples of the photopolymerizable dispersant represented by the general formula (I) of the present invention are shown below.

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Embedded image In the above Chemical Formulas 7 to 12, all p represents 1 or 2.

The synthesis of these organic phosphoric compounds is carried out using O
It can be produced by reacting a monomer containing an H group with a phosphate esterifying agent such as phosphorus pentoxide, phosphorus pentachloride, phosphorus trichloride, phosphorus oxychloride, and phosphorus pentasulfide. Specifically, JP-A-58-128393, US Pat.
No. 2, etc., can be used. Examples of monomers containing an OH group include Plaxel FM1D, FM2D, F
M3, FM4, FM5, FM6X, Plaxel FA1D
T, FA2D, FA3, FA4, FA5 (manufactured by Daicel Chemical Industries), Blemmer AP-400, AE-350, 7
0PEP-350B, 55PET-800, NKH-5
050 (manufactured by NOF Corporation) and the like.

Specific examples of the photopolymerizable dispersant represented by the general formula (II) of the present invention are shown below.

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These compounds can be produced by reacting a monomer containing an OH group with an acid anhydride such as succinic anhydride, glutaric anhydride, and phthalic anhydride. OH
The monomers containing a group include Plaxel FM1D, F
M2D, FM3, FM4, FM5, FM6X, Praxel FA1DT, FA2D, FA3, FA4, FA5 (manufactured by Daicel Chemical Industries), Blemmer AP-400, AE-
350, 70 PEP-350B, 55 PET-800,
NKH-5050 (manufactured by NOF Corporation) and the like. In addition, as commercial products, Plaxel FM1A, FM4A, F
M10A (manufactured by Daicel Chemical Industries, Ltd.) and the like.

As the surfactant represented by the general formula (III) of the present invention, commercially available Aronix M-53 is used.
00 (manufactured by Toa Gosei). Further, the surfactant can be prepared by the reaction of (meth) acrylic acid or (meth) OH @ - and acrylic acid chloride _{(C 5 H 10 COO) t} -H,.

The photopolymerizable pigment dispersant of the present invention can be applied to various inorganic pigments and organic pigments. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium,
Magnesium, chromium, zinc, antimony, metal oxides such as manganese, and composite oxides of the above metals, barium sulfate, silica, zinc chromate, strontium chromate,
Inorganic compounds such as carbon black, metallic aluminum, metallic lead, metallic zinc, basic lead sulfate, aluminum hydroxide, basic lead carbonate, or organic pigments such as quinacridone, phthalocyanine blue, phthalocyanine green, azo pigments,
Color index such as isoindoline pigment and dioxazine pigment (C.I .; The Society of
And Dyersand Colorists).

The pigment usually forms an aggregate, and it is not easy to make the pigment into fine particles. Therefore, the photosensitive coloring composition of the present invention is a pigment, a photopolymerizable dispersant, a coloring solution comprising a solvent is prepared in advance, and the coloring solution is an alkali-soluble binder, a photopolymerizable monomer, a photopolymerizable initiator, a solvent. Is prepared by mixing. In the preparation of the coloring liquid, the dispersant of the present invention is previously mixed homogeneously with a finely divided pigment or the like, or dissolved in advance in a dispersion medium and used, or added to a dispersion system comprising a pigment or the like and a non-aqueous solvent. It is preferable to use them.

The present dispersant can be used alone or as a mixture with a general low-molecular surfactant, high-molecular surfactant, or pigment derivative. As such a dispersant, commercially available (meth) acrylic acid-based (co) polymer Polyflow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo), Megafac F171, F17
2, F173 (manufactured by Dainippon Ink and Chemicals), Florad Fc430, Fc431 (manufactured by Sumitomo 3M), Solspass 12000, 13240, 20000, 2400
Solsperse dispersants such as 0, 26000 and 28000 (manufactured by Zeneca), Disperse Big 111 and 16
1, 164, 165 (made by Big Chemie), Addispar P
B711, PB411, PB111, PB821 (made by Ajinomoto) and the like can be used.

In the preparation of the coloring liquid, any disperser may be used, for example, a ball mill, a sand mill,
Visco mills, roll mills, kneaders, attritors, high-speed mixers, homomixers and the like can be mentioned. The photopolymerizable pigment dispersant is used in an amount of 2% by weight to 80% by weight, preferably 2% by weight to 4% by weight, based on the total solid content of the liquid photosensitive composition.
0% by weight is added. If the amount is less than 2% by weight, the dispersion stability is insufficient, and the viscosity increases and the pigment sediments over time. However, the optimal amount of the dispersant varies depending on the combination of the pigment, solvent, and resist component used. Also,
As described above, the photopolymerizable pigment dispersant may be used alone or in combination with another non-aqueous dispersant. In this case, the other non-aqueous dispersant can be used in an amount of 0 to 80% by weight of the dispersant of the present invention. If it is used in excess of 80% by weight, the sensitivity which is the object of the present invention is reduced.

Hereinafter, as the photosensitive coloring composition of the present invention,
In particular, the case where the composition is a light shielding layer composition will be described in detail. The photopolymerizable pigment dispersant of the present invention exhibits an excellent effect on a composition for a light shielding layer using an inorganic black pigment. This is because, due to the light-shielding property, the exposure amount in the film is remarkably reduced, the curing is insufficient, and the adverse effect of the non-reactive component is likely to occur. However, the sensitivity is increased by the dispersant of the present invention. Already proposed by the present inventors, at least copper, manganese, for a composition for a light-shielding layer using composite metal oxide fine particles containing a metal of iron, particularly excellent effect in terms of dispersibility. I do.

The pigment in the composition for a light-shielding layer of the present invention comprises:
According to the wet method disclosed in JP-A-9-25126, an alkali is added to three kinds of water-soluble metal salts of copper, manganese, and iron, and the precipitate is neutralized and precipitated. After oxidizing in the liquid phase,
It can be manufactured by washing, drying, baking and pulverizing. In addition, a water-soluble metal salt of zirconium or zinc can be added to make the surface state of the pigment more easily dispersed.

The composite metal oxide composed of copper, manganese, and iron is, for example, CuMn ₂ O ₄ in which a part of Mn is replaced by Fe. The composition ratio of CuO is 25% by weight to 40% by weight. 5 wt% to 30 wt% of Fe ₂ O ₃ ,
And those having Mn ₂ O _{3 in} the range of 40% by weight to 60% by weight. The content of the composite metal oxide of zirconium and zinc is 0.1% by weight to 50% by weight, preferably 0.1% by weight, based on the composite metal oxide of copper, manganese, and iron.
It is 3% by weight to 10% by weight. When the amount is less than 0.1% by weight, a desired light-shielding layer cannot be obtained due to poor affinity with an alkali-soluble binder and the like. When used as a filter, it is not preferable because of poor developability.

The black pigment used in the composition for a light-shielding layer of the present invention has optimum values for the particle diameter, specific surface area and surface hydroxyl group amount. For particle size, 0.01μ
m to 0.5 μm, preferably 0.01 μm to 0.3 μm
Is preferably within the range. If the particle diameter is less than 0.01 μm, the light-shielding property is not sufficient, and if it exceeds 0.5 μm, it is not preferable because the smoothness of the film surface is impaired or the precision of pattern formation is greatly reduced.

The specific surface area is 15 m ² / g to 40 m
² / g, preferably in the range of 18m ² / g~35m ² / g. Here, it is considered that the specific surface area exceeds 40 m ² / g when a pigment having an appropriate particle size or less is contained, and when the pigment has a porous or amorphous structure even within the range of the appropriate particle size. If the particle size is less than the appropriate particle size, light-shielding properties cannot be sufficiently obtained, and even if the pigment has a porous structure or an amorphous structure even within the range of the appropriate particle size,
At the same time, the pigment itself has a strong cohesive force and, at the same time, firmly adsorbs the binder component to form an aggregate, which is not preferable because the dispersibility of the pigment is significantly inhibited. When the specific surface area is less than 15 m ² / g, it is not preferable because a pigment having an appropriate particle size or more is contained. Furthermore, even when the particle diameter and the specific surface area are within the appropriate ranges, the pigment used in the present invention has a surface hydroxyl content of 0.1 μmol / g to 40 μmol / g, preferably 0.5 μmol / g to 25 μmol. / G. When the amount of surface hydroxyl groups is less than 0.1 μmol / g,
Since the affinity of the pigment surface for the solvent or dispersant is extremely reduced, aggregation or precipitation of the pigment occurs, resulting in 40 μmol / g.
When the specific surface area is larger than the specific surface area, the cohesive force of the pigment itself and the adsorbing force of other binder components become too strong, which is not preferable.

The amount of hydroxyl groups on the pigment surface in the present invention is determined by the following quantitative method. (Quantitative method) To 2.0 g of pigment, 30 ml of 0.01N tetrabutylammonium hydroxide-ethanol solution was added, and the mixture was stirred for 1 hour, 10 ml of supernatant was taken, 30 ml of ethanol was added, and 0.01N perchloric acid- The value obtained by subtracting the amount of tetrabutylammonium hydroxide remaining in the ethanol solution from the amount of tetrabutylammonium hydroxide contained in 30 ml of the above 0.01N tetrabutylammonium hydroxide-ethanol solution is defined as the amount of hydroxyl groups on the pigment surface. . Such pigments are commercially available, for example, “Dipiroxide T” manufactured by Dainichi Seika Kogyo Co., Ltd.
M black # 3950 "," Dipiroxide TM Black # 3952 "," Dipiroxide TM Black #
9550 ”,“ Dipiroxide Side Black # 355 ”
0 ”, BASF“ SICOCER F Black ”
2904 ”,“ SICOCER F Black 2 ”
912 "and" SICOPUR SE 1435 ".

Further, the pigment surface may have a particle diameter of 0.005 μm.
m to 0.02 μm of Zr, Zn, Fe, Co, or Ni
And / or the like. Further, the transition metal may be used alone or in combination. As a coating method, a known method such as dispersing a pigment in an aqueous solution of a transition metal salt, dropping an alkaline solution to neutralize and deposit and deposit transition metal hydroxide fine particles and / or transition metal oxide fine particles on the pigment surface is used. It may be coated by a method. The coating amount on the pigment particle surface is 0.01% by weight to 20% by weight. Next, as an alkali-soluble binder, it contributes to the dispersibility of the pigment particles, has good compatibility with the photopolymerizable monomer and the photopolymerizable initiator, and has excellent solubility in an alkali developing solution and organic solvent solubility. Is required. Further, in the pattern forming process including exposure and development, it is required to have excellent adhesion to the substrate even when exposed to an alkali developing solution or a cleaning solution for a long time, and further, the strength and softening as a color filter member are required. Those having an appropriate temperature and the like are preferable.

As such an alkali-soluble binder, an epoxy resin, in particular, a condensation reaction product of a basic skeleton of bisphenol A and epichlorohydrin and a ring-opening reaction of two or more epoxy groups contained in the molecule. Preferably, a reactive double bond group or a cyclic acid anhydride is added using glycidyl methacrylate or the like, and polymerization initiation ability or alkali developability is imparted using a resulting carboxyl group or the like. For example, a bisphenol A type vinyl ester is mentioned, which satisfies the above-mentioned characteristics in realizing alkali resistance, substrate adhesion, and film strength. Further, in the alkali-soluble binder of the present invention, various strengths of a light-shielding layer formed by introducing a polymerizable binder by introducing a reactive double bond group can be further improved. The reactive double bond group introduced is 0.0
5 mmol to 5 mmol, preferably 0.2 mmol to
In the range of 3 mmol. Further, in order to impart a suitable alkali developing solution resistance, the acid value is 50 mgKOH /
g to 250 mg KOH / g, preferably 60 mg KOH
/ G to 150 mgKOH / g.

If the acid value exceeds 250 mg KOH / g, the pattern is resolved after exposure and development, but it has no resistance to an alkali developing solution, and small cracks occur on the developed pattern surface. Is rapidly generated and eventually causes the resist to be peeled (peeled) from the glass substrate surface. In addition, the acid value is 50 mgK
If it is less than OH / g, the solubility to alkali is lost, and no dissolution occurs even in the unexposed area, so that an appropriate pattern cannot be formed. The average molecular weight of the alkali-soluble binder is 2,000 to 20,000, preferably 3,000 to 1,
It is in the range of 5,000. If it is less than 2,000, it does not function sufficiently as a binder, and if it exceeds 20,000, it is easy to form aggregates of pigments, and the composition life due to pigment aggregation, substrate adhesion, pattern formability and smoothness of coating film It is not preferable because it causes a decrease. Further, when the above-mentioned epoxy resin is used as the alkali-soluble binder, it also has an effect of stabilizing the dispersion of the pigment in the composition for a light-shielding layer.

Examples of preferred epoxy resins as the alkali-soluble binder include, for example, "Bisphenol A type epoxy acrylate, VR-60T" manufactured by Showa Polymer Co., Ltd.
H, 0.29 mmol of double bond groups per gram, acid value 7
0 mgKOH / g, average molecular weight 7,000 "," bisphenol A type epoxy acrylate, VR-90TH,
0.57 mmol of double bond groups / g, acid value 125
mgKOH / g, average molecular weight 3500 "," cresol type novolak type epoxy acrylate, 0.6 mmol of double bond group per 1 g, acid value 110 mgKOH / g,
"Average molecular weight 7500", "phenol novolak type epoxy acrylate, 0.6 mmol of double bond group per 1 g, acid value 120 mgKOH / g, average molecular weight 550
0 "and the like. The alkali-soluble binder is in the range of 5% to 80% by weight, preferably 5% to 60% by weight of the total solids in the composition for a light-shielding layer. The alkali-soluble binder of the present invention includes, for example, Japanese Patent Application No. 8-95.
Even those having a high molecular weight described in No. 884 may be used in combination as long as the action of an epoxy resin which is preferable as an alkali-soluble binder is not impaired.

Next, as the photopolymerizable monomer, a polyfunctional acrylate or a polyfunctional methacrylate having three or more double bond functional groups in one molecule (hereinafter, an acrylate compound and a methacrylate compound are referred to simultaneously) (Referred to as (meth) acrylate). In a polyfunctional (meth) acrylate, if the number of functional groups exceeds 6, the film itself becomes hard, but becomes brittle, so that sufficient strength cannot be exhibited, and
If it is less than 3, the effect is insufficient, and in this case, the strength is considered to be insufficient. However, in practical use, it is only necessary to have three or more double bond groups. Particularly, dipentaerythritol penta (meth) acrylate having five double bond groups and a derivative thereof are preferable.

In addition, for example, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate,
Pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexaacrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether Addition reaction of ethylene oxide or propylene oxide to polyfunctional alcohols such as tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate, trimethylolpropane and glycerin, and then (meth) acrylated And polyester acrylates. The acrylate and methacrylates described above may be used alone or as a mixture. In addition to monomers, prepolymers, that is, dimers and trimers are also effective. The content of the above monomer is in the range of 5% by weight to 50% by weight, preferably 5% by weight to 40% by weight of the total solids in the composition for a light-shielding layer.

For realizing the present invention, it is possible to form a suitable non-conductive light-shielding layer by combining the above alkali-soluble binder and a photopolymerizable monomer.
The epoxy resin used as the alkali-soluble binder has a preferred molecular weight range of 2,000 to 20,000.
Is non-sticky, the non-conductive light-shielding layer itself is sticky, dust and the like easily adhere to the surface during manufacturing, and the color filter tends to be defective. Therefore, in the composition for a non-conductive light-shielding layer of the present invention, it is desirable to add a coating property improving agent to remove "stickiness".

The coating film property improver preferably has the property of removing only stickiness while maintaining the properties of the non-conductive light-shielding layer such as developability and resolution. Examples include a graft copolymer and a block copolymer having both a (hydrophilic part) and an incompatible part (hydrophobic part). When such a coating property improving agent is added to the non-conductive light-shielding layer, the heterogeneous portion (hydrophobic portion) can be uniformly distributed in the non-conductive light-shielding layer, and the characteristics of the non-conductive light-shielding layer can be improved. While holding, only stickiness can be removed.

The compatible part (hydrophilic part) of the coating film property improving agent is
High molecular weight compounds having a hydrophilic functional group such as an OH group or a COOH group, such as polyacrylic acid, polyvinylpyrrolidone, polyvinyl alcohol, poly-2-hydroxyethyl methacrylate, hydroxypropylmethylcellulose, and polyethylene glycol. The hydrophobic part is polymethyl methacrylate, polystyrene, polybutene, or the like having no hydrophilic part in the skeleton. The coating film property improver is adsorbed on the pigment surface to prevent aggregation of the pigment in the liquid,
It also has an effect as a so-called dispersion stabilizer.

Examples of such a coating property improving agent include "L-20-3 (graft polymer) manufactured by Soken Chemical Co., Ltd., no double bond group, acid value 0 mgKOH / g, average molecular weight 56,000", "L-403A, no double bond group, acid value 0 mgKOH / g, average molecular weight 30,000
0 "," LH-448, no double bond group, acid value 0 mgK
OH / g, average molecular weight 30,000 "or a graft polymer of main chain poly (2-hydroxyethyl methacrylate) / side-chain polymethyl methacrylate containing an ethylenically unsaturated double bond obtained by a known method. (0.45 mmol / g of double bond group polymer, acid value 7 mg KOH /
g, weight average molecular weight 18,000), main chain poly (methyl methacrylate) containing an ethylenically unsaturated double bond /
Graft polymer of side chain poly (2-hydroxyethyl methacrylate) (0.5 g / g of double bond group polymer)
Mmol, acid value 1 mgKOH / g, weight average molecular weight 4
4,000). The content of the coating film property improver is 0.1% by weight of the total solids of the composition for the non-conductive light-shielding layer.
５０50% by weight, preferably 0.1-30% by weight.

Examples of the photopolymerizable initiator include thioxanthone-based, acetophenone-based, benzophenone-based, benzoin ether-based, peroxide-based, and biimidazole-based compounds. It is effective to add a quinone-based photopolymerization accelerator. The content of the photopolymerization initiator and the photopolymerization accelerator is 0.5% by weight to 40% by weight, preferably 5% by weight of the total solids of the composition for a light-shielding layer.
% To 40% by weight. As the solvent, the coating suitability of the composition for the light-shielding layer, polymers and monomers such as an alkali-soluble binder, a photopolymerizable pigment dispersant, a solubility in a photopolymerization initiator, and considering the dispersibility of the pigment, are shown below. One or two or more solvents can be appropriately selected and used, but it is preferable that one or more polyhydric alcohols or derivatives thereof are contained. In particular, considering the dispersibility of the pigment, a polyhydric alcohol or a derivative thereof having a solubility of 20 parts by weight or more in 100 parts by weight of water at 20 ° C. is effective.

Specific examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, glycol monoethyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monopropyl ether acetate, and ethylene glycol monobutyl ether. , Ethylene glycol monobutyl 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 monoethyl 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, diethylene glycol Propylene glycol monomethyl ether, 3-
Examples thereof include methyl-3-methoxybutanol, 3-methyl-3-methoxybutyl acetate, methyl amyl ketone, methyl lactate, ethyl lactate, methyl-α-hydroxyisobutyrate, and methyl-β-methoxyisobutyrate.

In addition to the above components, the composition for a light-shielding layer according to the present invention may further comprise a silane coupling agent or a titanate coupling in order to impart adhesion to a substrate to which the composition is applied. , An aluminum coupling agent and the like can be added. The composition for a light-shielding layer of the present invention can be applied to a substrate by a known method and dried to form a light-shielding layer on the substrate. Specific examples of the coating method include a spinner, a wheeler roller coater, a curtain coater, a knife coater, a bar coater, an extruder, and the like.
It is applied at a thickness of from 5 μm to 5 μm, preferably from 0.5 μm to 3 μm. When exposing the substrate on which the light-shielding layer is formed, the light source is selected according to the photosensitivity of the light-shielding layer, and a known light source such as an ultra-high pressure mercury lamp, a xenon lamp, a carbon arc lamp, and an argon laser can be used.

An alkali water-based developer is preferably used as a developer for developing the light-shielding layer subjected to pattern exposure. The alkaline aqueous developer, for performing 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.
領域 12. The alkali component used is, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, or an organic ammonium compound such as tetraethylammonium hydroxide, and other anions of sulfide, oxide or weak acid (for example, F ⁻ , CN ^- ) And the like. Further, a buffer solution in this pH range may be prepared and used as an alkaline aqueous developer. The composition for a light-shielding layer of the present invention is used for forming a black matrix for partitioning red, green and blue pixels on a transparent substrate, and thereafter, according to a known method,
Red, green, and blue pixels are formed. A transparent electrode layer is further provided on the surface to form a color filter. However, if necessary, a protective film is formed before providing the transparent conductive layer.

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. “Parts” in the examples means parts by weight.

[Synthesis Example] Synthesis of Photopolymerizable Dispersant Having Phosphoric Acid Group Synthesis Example 1 26.6 parts (0.18 mol) of phosphorus oxychloride was dissolved in 70 parts of tetrahydrofuran, and placed in a reaction vessel.
Cooled to 0 ° C. 100 parts of Praxel FM4 (manufactured by Daicel Chemical Industries) and 16.7 g of triethylamine (0.1
7 mol) and hydroquinone monomethyl ether 0.1
Was dissolved in 150 parts of tetrahydrofuran and placed in a dropping funnel. While blowing dry nitrogen gas, the phosphorus oxychloride solution was stirred, and the above-mentioned Praxel 4A solution was dropped. During the dropwise addition, the temperature was maintained at -45 to -50 ° C, and at the end of the dropwise addition, the temperature was maintained at -45 ° C for 1 hour. Then, the temperature was raised to 0 ° C, and water 15
And a solution of 37.9 parts of triethylamine in 100 parts of tetrahydrofuran were added dropwise. After dropping, 1
The mixture was stirred for 5 hours under ice cooling to complete the hydrolysis of the PC1 bond. Thereafter, the precipitated triethylammonium chloride was filtered off, and tetrahydrofuran was removed under reduced pressure at a temperature of 30 ° C. or lower. The obtained solid was washed with a 0.3N aqueous hydrochloric acid solution. Next, the resultant was washed several times with toluene and dried under reduced pressure at room temperature to obtain a photopolymerizable dispersant represented by the following chemical formula 19.

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The photopolymerizable dispersant having a carboxyl group
Synthesis Example 2 Blenmer 55 PET-800 (manufactured by NOF Corporation) 10 was placed in a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser.
0 parts and 300 parts of tetrahydrofuran were charged and dissolved by stirring. A solution of 11.7 parts of succinic anhydride in tetrahydrofuran was gradually added with stirring. 2 at 70 ° C
Allowed to react for hours. The reaction solution was purified by reprecipitation in cyclohexane to obtain a photopolymerizable dispersant represented by the following chemical formula 20.

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Example 1 Preparation - black pigment black pigment dispersion: The relative TM Black # 3952 (CuMn composite metal oxide part of the ₂ O ₄ of Mn in the vicinity of the composite oxide fine particle surface was substitution of Fe to Zr in terms of ZrO ₂ Pigment with 2.5% by weight and Zn added at 1.0% by weight in terms of ZnO; manufactured by Dainichi Seika Kogyo Co., Ltd. 100 parts by weight Pigment dispersant 7 parts by weight Diethylene glycol dimethyl ether -151 parts by weight The above components were mixed, zirconia beads having a diameter of 0.3 mm were added, and the mixture was dispersed with a paint shaker for 3 hours.

2. Pigment particle size distribution measurement The black pigment dispersion obtained in the above 1 was diluted 100 times, and the particle size of the pigment in the dispersion was measured with a particle size analyzer (manufactured by Nikkiso Co., Ltd., 9340UPA) to determine the initial dispersibility. evaluated.

[0041] 3. Preparation of composition for light-shielding layer-Black pigment dispersion prepared in 1 above-56 parts by weight-Alkali-soluble binder (bisphenol A type epoxy acrylate, manufactured by Showa Polymer Co., Ltd., "VR-60TH", average molecular weight) 7,000, reactive double bond group 20 mol%, acid value 70 mgKOH / g) ... 10 parts by weight-Photopolymerizable monomer (dipentaerythritol pentaacrylate) ... 2.9 parts by weight-Coating properties Improver (comb-shaped polymer, L-20-3 manufactured by Soken Chemical Co., Ltd.) 0.7 parts by weight Photopolymerizable initiator 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone-1 1.6 parts by weight 4,4'-diethylthioxanthone 0.3 parts by weight 2,4-diethylthioxanthone 0.1 parts by weight Biimidazo 0.4 parts by weight ・ Solvent (diethylene glycol dimethyl ether) ・ ・ ・ 25 parts by weight ・ Solvent (methyl lactate) ・ ・ ・ 3 parts by weight A composition for use was obtained.

4. Preparation of light-shielding layer The composition for light-shielding layer prepared in 3 above was applied on a glass substrate by a spin coater and dried at 100 ° C. for 3 minutes to form a light-shielding layer having a thickness of about 1 μm.

5. Exposure and Development The light-shielding layer was exposed to a light-shielding layer pattern with an ultrahigh-pressure mercury lamp at an exposure amount of 300 mJ / cm ² under a nitrogen stream, and then developed with a 1% aqueous solution of potassium hydroxide.

In Examples and Comparative Examples, each pigment dispersion was prepared using a photopolymerizable dispersant under the conditions shown in Table 1 below, and the average particle size of the pigment dispersion and the development characteristics of the resist were compared. The results are shown in Table 2 below.

[Table 1]

[0045]

[Table 2]

As can be seen from the table, the photopolymerizable dispersants of Examples 1 and 4 have the same pigment dispersing ability as the non-photoreactive dispersant of Comparative Example 1, and the resist has a developing property of Comparative Example 1. 1
Better than. It is considered that this excellent development characteristic is due to the fact that the use of a surfactant having an ethylenic double bond increased the sensitivity and further reduced the dissolution of the dispersant from the cured portion.

[0047]

According to the present invention, it is possible to obtain a photosensitive coloring composition and a composition for a light-shielding layer which are excellent in substrate adhesion and pattern formability and are suitable for producing a color filter.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // G03F 7/004 504 G03F 7/004 504 505 505 (72) Inventor Akira Inoue 1-1-1 Kagamachi, Ichigaya-cho, Shinjuku-ku, Tokyo No. 1 Dai Nippon Printing Co., Ltd.

Claims (7)

[Claims] 1. A photopolymerizable pigment dispersant comprising at least one compound represented by the following general formula (I), (II) or (III). Embedded image Embedded image Embedded image 2. An alkali-soluble binder, a photopolymerizable monomer, a photopolymerizable initiator, a dispersant, a pigment and a solvent as main components, wherein the dispersant is represented by the above general formula (I), (II) or (III). A photosensitive colored composition comprising at least one photopolymerizable dispersant represented by the formula: 3. An alkali-soluble binder, a photopolymerizable monomer, a photopolymerizable initiator, a dispersant, an inorganic black pigment and a solvent as main components, wherein the dispersant is represented by the above general formula (I) or (I).
A composition for a light-shielding layer, comprising at least one photopolymerizable dispersant represented by I) or (III). 4. The method according to claim 1, wherein the inorganic black pigment is at least copper,
The composition for a light-shielding layer according to claim 3, wherein the composition is a composite metal oxide containing iron and manganese. 5. The method according to claim 4, wherein the photopolymerizable monomer is a polyfunctional acrylate having 3 to 6 reactive double bond groups and / or a polyfunctional methacrylate.
The composition for a light-shielding layer according to the above. 6. The alkali-soluble binder has an average molecular weight of 2,000 to 20,000, and at least a part thereof has an average molecular weight of 1 to 2.
The composition for a light-shielding layer according to claim 4, wherein the composition is an epoxy resin containing 0.05 to 5 mmol of a reactive double bond group per g and having an acid value of 50 to 250 mgKOH / g. 7. The composition for a light-shielding layer according to claim 4, wherein the epoxy resin is a bisphenol A type vinyl ester.