JP2009149779A - Colored fine coloring material, transparent coloring composition for color filter containing the same, and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coloring material that has a fine primary particle diameter, is excellent in dispersibility to a vehicle colored highly and with high pigment density, and is superior in light fastness and heat resistance, as well as to provide a transparent coloring composition for a color filter excellent in light fastness, heat resistance and transparency, and having high coloring power, and a color filter using it. <P>SOLUTION: This colored fine coloring material includes a colored fine composite pigment of the primary particle diameter of ≤50 nm, wherein the colored fine composite pigment is absorbed on the surface of a dispersant in an amount of 1.0 to 5.0 mg/m<SP>2</SP>, and the amount of silica contained in the colored fine coloring material is 0 to 9 wt.%, in terms of Si, relative to the colored fine coloring material. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention has a colorant and light resistance that have a fine primary particle size, have excellent dispersibility even in a vehicle with high coloring power and high pigment concentration, and are excellent in light resistance and heat resistance. The present invention provides a transparent coloring composition for a color filter and a color filter that are excellent in heat resistance and excellent in transparency.

  Color filters are widely used for monitors such as TVs, personal computers, mobile phones, and CCDs or CMOSs used in digital cameras. Pigment-dispersed types are the mainstream due to problems of light resistance and heat resistance. . Currently, there is a demand for higher pixel count and higher contrast for color filters. For this purpose, even in organic pigments used, fine particles that can be stably dispersed at the nano level in vehicles with high pigment concentrations. Is required.

  However, organic pigments form fine primary particles of about 20 nm to 100 nm from a pigment in a molecular state by a chemical reaction or the like. However, in this state, the surface energy of the particles is very high, and thus aggregation tends to occur. In particular, it is known to form secondary particles having a large particle size and a strong cohesive force, and a technique for refining the pigment is required.

  At present, as a method for refining organic pigments, wet pulverization represented by the solvent salt milling method, in which the pigment particles are mechanically pulverized together with the highly viscous water-soluble organic solvent using grinding such as salt, is used. A dry pulverization method using a pulverizer such as a ball mill, an attritor, or a vibration mill, a method of further solubilizing a pigment into a solution, and precipitating it under specific conditions to obtain a fine pigment, etc. Is widely used.

  However, in any of these methods, the agglomeration force between the pigment particles becomes stronger as the pigment becomes finer, and the dry agglomeration becomes remarkable especially in the water-based wet method, so that it is extremely difficult to maintain the shape of the primary particles. As a result, since the pigment particles are present as secondary aggregates in the state of an aggregate having a very strong cohesive force, the dispersion treatment in the solvent becomes more difficult.

  In addition, the color filter is required to have light resistance because it does not fade when exposed to backlight. Furthermore, heat resistance is required to perform heat treatment at about 250 ° C. during patterning curing and ITO film deposition. Is done. However, it is known that light resistance and heat resistance generally decrease when the pigment is finely divided. Thus, there is a strong demand for the development of colorants for color filters that are nano-level, can be stably dispersed in a vehicle, and have excellent light resistance and heat resistance.

To date, as a technology for making organic pigments into fine particles, a pigment composition for a color filter blue pixel portion in which a fine organic pigment ε-type copper phthalocyanine pigment and a dioxazine violet pigment having an aspect ratio of 10 to 25 are both subjected to solvent salt milling treatment. The organic pigment is produced by circulating a solution of an organic pigment dissolved in an alkaline or acidic aqueous medium as a laminar flow in the flow path and changing the pH of the solution in the laminar flow process. Has been proposed (Patent Document 2).

  In addition, a color composition for a color filter including an organic-inorganic composite pigment having an average particle diameter of 1 to 100 nm in which an organic pigment is attached to the surface of white inorganic fine particles, and a color filter including the color filter colorant (Patent Document 3) are proposed. Has been.

  In addition, as a fine colorant having excellent transparency, the entire amount of white inorganic particles as core particles can be dissolved in composite particles in which organic pigments are attached to the surface of white inorganic particles via a paste material such as alkoxysilane. Colored fine particle powder (Patent Document 4) in which core particles are completely dissolved and removed using an acid or alkali equal to or greater than the theoretical value, or a color filter in which a part of the core particles is removed by adjusting the amount of acid or alkali A coloring material (Patent Document 5) has been proposed.

JP 2006-091649 A JP 2005-307154 A JP 2004-307853 A JP 2003-246941 A International Publication No. 2007-029694 Pamphlet

  Color filter colorants that have a small primary particle size, high coloring power, excellent light resistance and heat resistance, and can stably maintain a finely dispersed state even in vehicles with high pigment concentrations are currently the most That is where it is required. However, in order to obtain high transparency, it is necessary to make the pigment finer. However, in a vehicle having a high pigment concentration, when the particle size of the pigment becomes smaller, the cohesive force becomes stronger, and as a result, the pigment particles are in an aggregated state. Therefore, it is difficult to obtain high transparency, and light resistance and heat resistance tend to be reduced, so that a coloring material satisfying these contradicting characteristics has not yet been obtained. It is not done.

  That is, Patent Document 1 discloses a method for producing a pigment composition for a color filter blue pixel portion in which a fine organic pigment ε-type copper phthalocyanine pigment and a dioxazine violet pigment having an aspect ratio of 10 to 25 are both subjected to solvent salt milling. Further, Patent Document 2 discloses that an organic pigment solution dissolved in an alkaline or acidic aqueous medium is circulated in a flow path as a laminar flow, and the pH of the solution is changed in the laminar flow process, whereby fine particles of the organic pigment. However, in either production method, a wet treatment in an aqueous system is essential, and it is necessary to dry after that, resulting in dry agglomeration, resulting in good dispersibility in the vehicle and It becomes difficult to obtain dispersion stability.

Further, in Patent Document 3, an organic-inorganic composite pigment having an average particle diameter of 1 to 100 nm of primary particles in which an organic pigment is attached to the surface of white inorganic particles directly or via a surface modifier is dispersed in a solvent. Although there is a description of the transparent coloring composition, etc., as shown in the comparative example below, a colored composition having a small primary particle size and high transparency can be obtained, but in a vehicle with a high pigment concentration, the primary particle size is Therefore, it was difficult to obtain a sufficient dispersion effect and to obtain excellent dispersibility and long-term storage stability. Moreover, since white inorganic particles are used as the core particles, it is difficult to obtain high coloring power.

  Further, Patent Document 4 discloses a theoretical equivalent amount or more that can dissolve all of the white inorganic particles as the core particles with respect to the composite particles in which the organic pigment is attached to the surface of the white inorganic particles through a paste material such as alkoxysilane. The method of completely dissolving and removing the core particles using an acid or alkali to leave the organic pigment is described. However, as shown in the comparative example, the organic pigment is used because the acid or alkali is used in an amount equal to or more than the theoretical value. It is difficult to obtain a colorant with good light resistance and heat resistance. Further, in a high concentration vehicle, since the primary particle size is small, a sufficient dispersion effect cannot be obtained, and it has been difficult to obtain excellent dispersibility and long-term storage stability.

Patent Document 5 discloses a color filter colorant in which silica is included in an organic pigment, and the silica contained in the color filter colorant is 0.001 in terms of Si with respect to the color filter colorant. Although it is described as a color filter colorant characterized in that it is ˜9% by weight, since the primary particle size is small in a high concentration vehicle due to the fine particles, a sufficient dispersion effect can be obtained. Therefore, it was difficult to obtain excellent dispersibility and long-term storage stability.

  Therefore, the present invention is a colored micro-coloring that has a small primary particle size, a high coloring power, an excellent dispersibility even in a vehicle having a high pigment concentration, and a high light resistance and heat resistance. It is an object of the present invention to provide a material, a transparent coloring composition for a color filter using the colored fine coloring material, and a color filter.

  The technical problem can be achieved by the present invention as follows.

That is, the present invention is a colored fine colorant having a primary particle diameter of 50 nm or less, and the colored fine colorant has a surface adsorption amount of 1.0 to 5.0 mg / m ² , and the colored fine colorant. The silica contained in the material is 0 to 9% by weight in terms of Si with respect to the colored fine colorant (colored microcolorant (Invention 1)).

  In addition, the present invention is a colored micro colorant, wherein the colored micro colorant of the present invention 1 is obtained by surface-treating a colored fine particle powder with a dispersant. (Invention 2).

  Moreover, this invention is a transparent coloring composition characterized by disperse | distributing the colored fine coloring material of this invention 1 thru | or this invention 2 to a solvent (this invention 3).

  Further, the present invention provides the transparent coloring composition for color filters, wherein the transparent coloring composition according to the present invention 3 is dispersed in a transparent resin solution having at least one acidic group and / or latent acidic group. It is a composition (Invention 4).

  Moreover, the present invention is characterized in that the transparent coloring composition for a color filter described in the present invention 4 contains a photo radical polymerization initiator and a polyfunctional monomer having two or more ethylenically unsaturated double bonds. This is a transparent coloring composition for a color filter to which photosensitivity is imparted (Invention 5).

  Moreover, this invention is a transparent coloring composition for color filters characterized by the transparent coloring composition for color filters as described in this invention 4 containing a photo-acid generator (this invention 6).

  In addition, the present invention is a color filter obtained from the coating film formed of the transparent coloring composition for a color filter according to any of the fourth to sixth aspects (Invention 7).

  The colored fine coloring material according to the present invention has high coloring power, is excellent in dispersibility in a vehicle having a high pigment concentration, and has high light resistance and heat resistance. It is suitable as a coloring material for various uses.

  Since the transparent coloring composition for a color filter according to the present invention uses a colorant having the above characteristics, it has excellent dispersibility, dispersion stability, light resistance, and heat resistance in a vehicle having a high pigment concentration. It is suitable as a transparent coloring composition for filters.

  Since the color filter according to the present invention uses a transparent coloring composition for a color filter made of a transparent colorant for a color filter having the above characteristics, it is suitable as a color filter because it is excellent in spectral characteristics, light resistance and heat resistance. is there.

  The colored micro colorant according to the present invention will be described below.

  The colored micro colorant according to the present invention is a composite particle in which the surface of a silica particle as a core particle is coated with a surface modifier, and an organic pigment is attached to the surface modifier coating, After producing colored fine particles in which the total amount and / or part of the silica and the surface modifier is dissolved by subjecting the composite particles to an alkali treatment, the primary particle diameter of the colored fine particle surface treated with a dispersant is as follows. It consists of a colored fine coloring material of 50 nm or less.

  The amount of silica contained in the colored fine colorant according to the present invention is 0 to 9.0% by weight with respect to the colored fine colorant in terms of Si. The present invention contains no silica and 9.0% by weight or less of silica. By containing silica, a colored fine colorant having excellent light resistance and heat resistance can be obtained. When the amount of silica exceeds 9.0% by weight in terms of Si, it is difficult to obtain sufficient coloring power because the amount of silica contained in the colored fine coloring material is too large. More preferably, it is 0.005-7.0 weight%, More preferably, it is 0.01-5.0 weight%.

  The average primary particle diameter of the colored fine colorant according to the present invention is 50 nm or less, more preferably 1 to 40 nm, and most preferably 1 to 30 nm. When the average primary particle diameter exceeds 50 nm, the particle size is too large, and the optical characteristics are deteriorated, which is not preferable.

  The number converted average particle diameter of the colored fine colorant according to the present invention is preferably 100 nm or less, more preferably 1 to 75 nm, and most preferably 1 to 50 nm. When the number-average particle diameter in terms of the number of colored micro-coloring materials exceeds 100 nm, the particle size is too large, so that the optical characteristics deteriorate, which is not preferable.

  The average particle diameter in terms of volume of the colored fine colorant according to the present invention is preferably 150 nm or less, more preferably 1 to 125 nm, and most preferably 1 to 100 nm. If the average particle diameter in terms of volume of the colored fine colorant exceeds 150 nm, the particle size is too large, and the optical properties are lowered, which is not preferable.

BET specific surface area of the colored fine colorant according to the present invention is preferably from 20 to 500 m ² / g, more preferably 25~400m ² / g, still more preferably 30~300m ² / g. When the BET specific surface area value is less than 20 m ² / g, the particles are coarse and the coloring power is reduced.

  The coloring power of the colored micro colorant according to the present invention is preferably 102% or more, more preferably 103% or more, and still more preferably 104% or more, according to the evaluation method described later.

The dispersant adsorption amount of the colored fine colorant according to the present invention is 1.0 to 5.0 mg / m ² . More preferably, it is 1.5-4.5 mg / m < ² >, Most preferably, it is 2.0-4.0 mg / m < ² >. When the amount of adsorbing dispersant is less than 1.0 mg / m ² , dispersion becomes difficult with a high-concentration vehicle, and the optical characteristics deteriorate. In this composition system, it is difficult for industrial production to have a dispersant adsorption amount exceeding 5.0 mg / m ² .

The light resistance of the colored micro-coloring material according to the present invention is 5.0 or less in ΔE ^* value when Si is contained in the colored micro-coloring material in an evaluation method to be described later. It is more preferable that the light resistance is 5.0 or less because deterioration of optical characteristics due to backlight irradiation or the like can be suppressed.

The heat resistance of the colored microcoloring material according to the present invention is 5.0 or less in ΔE ^* value when Si is contained in the colored microcoloring material in an evaluation method described later in an amount of 0.001% by weight or more. When the heat resistance is 5.0 or less, the discoloration is small even in the baking process and the like, and the deterioration of the optical characteristics can be suppressed.

  Next, the transparent coloring composition containing the colored fine coloring material according to the present invention will be described.

  The transparent coloring composition which concerns on this invention 3 is comprised from the colored micro coloring material which concerns on this invention, and a solvent. Moreover, you may add additives, such as a dispersing agent, a pigment derivative, an antifoamer, and surfactant, as needed.

  The transparent coloring composition according to the present invention 3 contains the colored fine coloring material according to the present invention in an amount of 3 to 1000 parts by weight, more preferably 4 to 500 parts by weight, based on 100 parts by weight of the colored composition-constituting substrate. More preferably, it contains 5 to 300 parts by weight.

  As the solvent in the present invention, the colored fine colorant and the transparent resin according to the present invention, and further the polyfunctional monomer having two or more ethylenically unsaturated double bonds, the photopolymerization initiator and the photoacid generator are dissolved. Or if it can disperse | distribute and can be volatilized and removed after application | coating, it can use suitably. For example, water; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone and cyclohexanone; amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; ethylene glycol monomethyl ether; Ether alcohols such as ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl Ether acetates such as ether acetate; ethyl acetate, butyl acetate, isoacetic acid Acetic esters such as chill; methyl lactate ester, ethyl lactate esters, lactate esters such as lactic acid propyl ester, ethylene carbonate, propylene carbonate, and cyclic esters such as γ- butyrolactone. These solvents can be used alone or in combination of two or more.

  Examples of the dispersant in the present invention include single-type polyester-based, random-type polyester-based, comb-type polyester-based, acrylic block copolymer, urethane block copolymer, and other polymer-type dispersants, ammonium lauryl sulfate, polyoxyethylene Anionic surfactants such as alkyl ether sulfates, cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride, amphoteric surfactants such as lauryldimethylamine oxide and laurylcarboxymethylhydroxyethylimidazolium betaine, poly One kind or two or more kinds of nonionic surfactants such as oxyethylene lauryl ether, polyoxyethylene stearyl ether, sorbitan monostearate can be used.

  The number-average dispersion average particle diameter of the transparent coloring composition according to the present invention 3 is preferably 1 to 100 nm, more preferably 1 to 75 nm, and still more preferably 1 to 50 nm. When the number-converted dispersed particle diameter exceeds 100 nm, the particle size is too large, and the optical properties are deteriorated.

  As for the volume conversion dispersion | distribution average particle diameter of the transparent coloring composition which concerns on this invention 3, 1-150 nm is preferable, More preferably, it is 1-125 nm, More preferably, it is 1-100 nm. When the volume-converted dispersed particle diameter exceeds 150 nm, the particle size is too large, and the optical characteristics are deteriorated.

  The dispersion stability of the transparent coloring composition according to the present invention 3 is an evaluation method described later, and the rate of change in viscosity is preferably 20% or less, more preferably 10% or less, and still more preferably 8% or less. It is. When the rate of change in viscosity is greater than 20%, it becomes difficult to maintain dispersibility over a long period of time in a stable dispersion state.

  The transmittance of the transparent coloring composition according to the third aspect of the present invention is such that the transmittance at 530 nm is 70% or more, preferably 75% or more, more preferably, when a green color transparent composition for color filters is used. Is 80% or more. The specific extinction coefficient (weight basis) at 650 nm is 1.05 to 5.00, preferably 1.10 to 5.00, and more preferably 1.20 to 5.00 in the evaluation method described later. .

  When a blue color transparent composition for color filters is used, the transmittance at 460 nm is 70% or more, preferably 75% or more, more preferably 80% or more. The specific extinction coefficient (weight basis) at 610 nm is 1.05 to 5.00, preferably 1.10 to 5.00, more preferably 1.20 to 5.00 in the evaluation method described later. .

  When a red color transparent composition for color filters is used, the transmittance at 620 nm is 70% or more, preferably 75% or more, more preferably 80% or more. Moreover, the specific extinction coefficient (weight basis) in 550 nm is 1.05-5.00 in the evaluation method mentioned later, Preferably it is 1.10-5.00, More preferably, it is 1.20-5.00. .

  When a yellow colored transparent composition for color filters is used, the transmittance at 550 nm is 70% or more, preferably 75% or more, more preferably 80% or more. The specific extinction coefficient (weight basis) at 400 nm is 1.05 to 5.00, preferably 1.10 to 5.00, more preferably 1.20 to 5.00 in the evaluation method described later. .

  The transparent coloring composition for color filters according to the present invention 4 is composed of the transparent coloring composition according to the present invention 3 and a transparent resin.

  The transparent resin in the present invention may be any resin as long as it satisfies the conditions that it is soluble in an alkali developer, does not have an absorption band in the visible wavelength region, and has film-forming ability. Examples of the transparent resin for this purpose include a polymer substituted with one or more acidic groups, or a polymer having one or more latent acidic groups that are converted into acidic groups by a deprotection reaction due to the action of an acid. The acidic group in the present invention is a phenolic hydroxyl group and a carboxyl group, and the amount introduced thereof may be appropriately adjusted depending on the solubility in an alkaline aqueous solution.

  Examples of the polymer having a phenolic hydroxyl group include novolak resins and 4-hydroxystyrene homopolymers and copolymers.

  The transparent resin having a carboxyl group is preferably a vinyl copolymer of an ethylenically unsaturated monomer and another copolymerizable unsaturated monomer. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, 2-acryloyloxyethyl phthalate, 2-acryloyloxypropyl phthalate, maleic acid, maleic anhydride, itaconic acid, and itaconic anhydride. . Other monomers that copolymerize with these carboxyl group-containing monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic acid. Cyclohexyl, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, 2- (meth) acrylate 2- Ethoxyethyl, 2-phenoxyethyl (meth) acrylate, 2- (N, N-dimethylamino) ethyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylamide, (meth) Acryloyl morpholide, N-methylmaleimide, N-phenylmale Bromide, N- cyclohexyl maleimide, styrene, 4-vinyl toluene, vinyl acetate, may be may be mentioned vinyl methyl ether, is not limited thereto.

  The molar ratio of the carboxyl group-containing monomer in the transparent resin is 0.005 to 0.5, preferably 0.05 to 0.4. When the copolymer has a molar ratio of less than 0.05, the solubility in an alkaline aqueous solution is lowered, and background staining is likely to occur during patterning. On the other hand, at a molar ratio of 0.5 or more, when alkali development is performed after the coating film made of the resulting photosensitive composition is exposed, the insolubilized exposed portion swells, resulting in a decrease in resolution or coating. The smoothness of the film surface is impaired. The weight average molecular weight of the transparent resin is 2000 to 500000, preferably 3000 to 300000.

  As a transparent resin containing a carboxyl group, a polyamic acid obtained by a polyaddition reaction of tetracarboxylic dianhydride and diamine can be used. Examples of tetracarboxylic dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4 -Cyclopentanetetracarboxylic dianhydride, 1,2,4,5-bicyclehexene tetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, pyromellitic acid 2 Anhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and the like are exemplified, but are not limited thereto. It is not a thing. Moreover, 1 type (s) or 2 or more types can be used for these dianhydrides. Examples of diamines to be reacted with these dianhydrides include ethylenediamine, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, and 4,4′-diamino. Diphenylmethane, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diamino Although toluene etc. can be mentioned, it is not limited to these.

  The synthesis of the polyamic acid is performed by a known method of tetracarboxylic dianhydride and diamine in a polar organic solvent, and the degree of polymerization of the polyamic acid can be adjusted by the mixing molar ratio.

  A transparent resin having a latent acidic group is a polymer having a substituent that generates a carboxyl group or a phenolic hydroxyl group by the catalytic action of an acid generated from a photoacid generator, and is used in an alkali developable chemically amplified photoresist. Base polymer can be utilized. For example, cyclohexyl (meth) acrylate, tert-butyl (meth) acrylate, tert-amyl (meth) acrylate, 1,1-dimethylbenzyl (meth) acrylate, 1-ethoxyethyl (meth) acrylate, and (meth) acrylic acid Copolymers with other acrylate monomers containing, homopolymers such as 4- (tert-butoxycarbonyloxy) styrene, 4- (1-methoxyethoxy) styrene, 4- (1-ethoxyethoxy) styrene, or 4-hydroxy Mention may be made of copolymers with styrene.

  The mixing ratio of the transparent resin substituted with these acidic groups and / or latent acidic groups with respect to the colored fine colorant is usually 5 to 500 parts by weight, preferably 100 parts by weight of the colored fine composite colorant, preferably 7 to 300 parts by weight. When the mixing ratio of the transparent resin is less than 5 parts by weight, the film forming property and alkali developability are deteriorated. In the case of 500 parts by weight or more, since the pigment concentration is relatively lowered, it is difficult to obtain a uniform film thickness by increasing the film thickness in order to ensure the color density as a color filter, and optical characteristics. Also decreases.

  The number conversion dispersion average particle size of the transparent coloring composition for a color filter according to the present invention 4 is preferably 1 to 100 nm, more preferably 1 to 75 nm, and still more preferably 1 to 50 nm. When the number-converted dispersed particle diameter exceeds 100 nm, the particle size is too large, and the optical properties are deteriorated.

  As for the volume conversion dispersion | distribution average particle diameter of the transparent coloring composition for color filters which concerns on this invention 4, 1-150 nm is preferable, More preferably, it is 1-125 nm, More preferably, it is 1-100 nm. When the volume-converted dispersed particle diameter exceeds 150 nm, the particle size is too large, and the optical characteristics are deteriorated.

  The viscosity of the transparent coloring composition for a color filter according to the present invention 4 is preferably 0.5 to 1000 mPa · s, more preferably 0.5 to 200 mPa · s, and still more preferably 0.5 to 100 mPa · s. s. If the viscosity exceeds 1000 mPa · s, uniform coating becomes difficult. When it is less than 0.5 mPa · s, the coating film becomes too thin, which is not preferable.

  The dispersion stability of the transparent coloring composition for a color filter according to the present invention 4 is an evaluation method described later, and the rate of change in viscosity is preferably 20% or less, more preferably 10% or less, and even more preferably 8% or less. is there. When the rate of change in viscosity is greater than 20%, it becomes difficult to maintain dispersibility over a long period of time in a stable dispersion state.

  The specific absorption coefficient (weight basis) of the transparent colored composition for a color filter according to the present invention 4 is 1.05 at a wavelength of 650 nm when a green color coloring material is used in an evaluation method described later. Preferably, it is 1.10 to 5.00, more preferably 1.20 to 5.00, and a wavelength of 610 nm is used when a blue-based color coloring material is used. In this case, it is preferably 1.05 or more, more preferably 1.10 to 5.00, still more preferably 1.20 to 5.00, and when a red color coloring material is used, At a wavelength of 550 nm, 1.05 or more is preferable, more preferably 1.10 to 5.00, and still more preferably 1.20 to 5.00. When using, at a wavelength of 400 nm, preferably at least 1.05, more preferably from 1.10 to 5.00, still more preferably from 1.20 to 5.00.

The light resistance of the colored permeable membrane produced using the transparent colored composition for a color filter according to the present invention 4 is, in the evaluation method described later, when the colored micro colorant contains 0.001% by weight or more of Si, The ΔE ^* value is 5.0 or less. It is preferable that the light resistance is 5.0 or less because deterioration of the optical characteristics of the color filter can be suppressed by backlight irradiation or the like.

The heat resistance of the transparent coloring composition for a color filter according to the fourth aspect of the present invention is 5.0 or less in ΔE ^* value when Si is contained in the colored fine coloring material in an evaluation method described later in an amount of 0.001 wt% or more. It is. When the heat resistance is 5.0 or less, it is preferable because the optical characteristics can be prevented from being deteriorated by the heat treatment when forming the color filter or depositing the ITO film.

  The transmittance of the colored permeable membrane for a color filter produced using the transparent colored composition for a color filter according to the present invention 4 is such that the transmittance at 530 nm is 85% or more when a green color coloring material is used. Preferably, it is 87% or more, more preferably 90% or more, and when a blue color material is used as the colored micro colorant, the transmittance at 460 nm is 85% or more, preferably 87% or more. Preferably, it is 90% or more, and when a red color material is used as the colored fine coloring material, the transmittance at 620 nm is 85% or more, preferably 87% or more, more preferably 90% or more. When a yellow material is used as the colorant, the transmittance at 550 nm is 85% or more, preferably 87% or more, more preferably 90% or more.

  The specific absorption coefficient (weight basis) of the colored permeable membrane for a color filter produced using the transparent colored composition for a color filter according to the present invention 4 is an evaluation method to be described later. When used, it is preferably 1.05 or more at a wavelength of 650 nm, more preferably 1.10 to 5.00, and still more preferably 1.20 to 5.00. When a blue type is used, it is preferably 1.05 or more at a wavelength of 610 nm, more preferably 1.10 to 5.00, and still more preferably 1.20 to 5.00. When a red colorant is used as the colorant, 1.05 or more is preferable at a wavelength of 550 nm, more preferably 1.10 to 5.00, and still more preferably 1.20. In the case of using a yellowish color fine composite colorant, it is preferably 1.05 or more at a wavelength of 400 nm, more preferably 1.10 to 5.00. Preferably it is 1.20-5.00.

  The transparent colored composition for a color filter according to the present invention 5 is a polyfunctional monomer having two or more photoradical polymerization initiators and ethylenically unsaturated double bonds in the transparent colored composition for a color filter according to the present invention 4. It consists of what added.

  Moreover, the transparent coloring composition for color filters which concerns on this invention 6 consists of what added the photo-acid generator to the transparent coloring composition for color filters which concerns on the said invention 4. FIG.

<Polyfunctional monomer having two or more ethylenically unsaturated double bonds>
In order to produce a pigment-dispersed color filter, a photosensitive film containing no pigment is provided on a coating film containing pigment and exposed to light, and a pattern is formed on the photosensitive layer during the development process, and at the same time, the pigment coating layer is removed. An etching method and a coloring material method in which a pigment is dispersed in the photosensitive layer itself have been proposed. The transparent coloring composition for a color filter comprising the colored fine coloring material and the transparent resin having an acidic group according to the present invention 4 can correspond to the former etching method. In order to apply to the latter coloring photosensitive material method, it is necessary to give photosensitivity to this transparent coloring composition for color filters. The polyfunctional monomer having two or more ethylenically unsaturated double bonds is a substance added to the transparent resin for this purpose. In the exposed part, polymerization is performed by radical species generated from the photopolymerization initiator. Starts and plays a role in causing insolubilization by inducing a crosslinking reaction.

  As the polyfunctional monomer having two or more ethylenically unsaturated double bonds in the present invention, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethyleneethylene glycol di (meth) acrylate, tetramethylene glycol di (Meth) acrylate, pentamethylene glycol di (meth) acrylate, hexamethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, stearic acid Modified pentaerythritol meta (a) acrylate, trimethylolpropane tri (meth) acrylate, tris (acryloyloxyethyl) isocyanurate, dipen Hexaacrylate, polyfunctional monomers such as dipentaerythritol pentaacrylate, and the like. Furthermore, the acrylate oligomer etc. which are obtained from a polyester resin, an epoxy resin, a urethane resin, a silicon resin etc. are mentioned.

  A monofunctional monomer can be mixed with these polyfunctional monomers. Monofunctional monomers include methoxytriethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-acryloyloxyethyl succinate, 2-acryloyloxyethyl phthalate, 2-acryloyloxypropyl phthalate Etc. These monofunctional monomers are 0 to 80% by weight, preferably 0 to 40% by weight, based on 100 parts by weight of the polyfunctional monomer. When the monofunctional monomer is mixed beyond this range, when the exposed film is subjected to an alkali development treatment, the film is partially peeled or the resolution is lowered.

  The polyfunctional monomer in the present invention is particularly preferably mixed with the vinyl copolymer having a carboxyl group among the above-described transparent resins. The usage ratio of the polyfunctional monomer is 5 to 300 parts by weight, more preferably 10 to 200 parts by weight, based on 100 parts by weight of the transparent resin. When the mixing ratio of the polyfunctional monomer is less than 5 parts by weight, a part of the coating film after alkali development is peeled off or the resolution is lowered. When the mixing ratio is 300 parts by weight or more, the alkali developability deteriorates, resulting in problems such as background contamination and film residue in unexposed areas.

<Photopolymerization initiator>
The photopolymerization initiator in the present invention is a substance that efficiently generates radical species by light irradiation, and this initiates polymerization of the above-described polyfunctional monomer to form a crosslinked structure, and is a transparent resin having an acidic group. A negative image is provided by a decrease in alkali solubility. Examples of the photopolymerization initiator include ketone compounds, triazine compounds having a trichloromethyl group, electron transfer initiators, and the like. Polymerization initiators that generate radical species by ultraviolet rays in the range of 200 to 450 nm include Selected.

  Examples of ketone photopolymerization initiators include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxy-1-benzoylcyclohexane, 2-morpholino-2-methyl-1-phenylpropane-1- ON, 2-morpholino-2-methyl-1- (4-methoxyphenyl) propan-1-one, 2-morpholino-2-methyl-1- (4-methylthiophenyl) propan-1-one, 2-benzyl- 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-phenyl-2,2-dimethoxy-1- (4-methylthiophenyl) ethane-1-one, diphenylmesitylenephosphine oxide, phenacyltetra Examples include methylenesulfonium hexafluorophosphate.

  Examples of triazine derivatives having a trichloromethyl group include 2- (4-methoxy-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 1-phenyl-3,5-bis (trichloromethyl)- s-triazine, 1- (4-chlorophenyl) -3,5-bis (trichloromethyl) -s-triazine, 1- (4-methoxyphenyl) -3,5-bis (trichloromethyl) -s-triazine, 1 -(4-butoxyphenyl) -3,5-bis (trichloromethyl) -s-triazine, 1- (3,4-methylenedioxyphenyl) -3,5-bis (trichloromethyl) -s-triazine, 1 -(3,4-dimethoxyphenyl) -3,5-bis (trichloromethyl) -s-triazine, 1- (4-methoxynaphthyl-1) -3,5-bis ( Lichloromethyl) -s-triazine, 1- {2- (4-methoxyphenyl) ethenyl} -3,5-bis (trichloromethyl) -s-triazine, 1- {2- (2-methoxyphenyl) ethenyl} -3 , 5-bis (trichloromethyl) -s-triazine, 1- {2- (3,4-dimethoxyphenyl) ethenyl} -3,5-bis (trichloromethyl) -s-triazine, 1- {2- (3 -Chloro-4-methoxyphenyl) ethenyl} -3,5-bis (trichloromethyl) -s-triazine, 1- (biphenyl-1) -3,5-bis (trichloromethyl) -s-triazine and the like. .

  The electron transfer type initiator comprises a radical generator and a sensitizer as an electron accepting compound or an electron donating compound. Examples of the electron-accepting compound include the trichloromethyl-substituted triazine derivatives, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′phenylbiimidazole, and 2,2′-bis (2,4 -Dichlorophenyl) -4,4 ′, 5,5′phenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′tetrakis (4-ethoxycarbonylphenyl) biimidazole, etc. Examples include iodonium salts such as biimidazole compounds, diphenyliodonium hexafluorophosphate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, (4-methoxyphenyl) (4-octyloxyphenyl) iodonium hexafluorophosphate, and the like. . As the sensitizer, 9,10-dimethylanthracene, 9,10-diphenylanthracene, 9,10-bis (phenylethynyl) anthracene, 1,8-dimethyl-9,10-bis (phenylethynyl) anthracene, 9, Examples include 10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, thioxanthone, isopropylthioxanthone, 4,4′-bis (diethylamino) benzophenone. Furthermore, a photopolymerization initiator composed of an electron donating compound and a sensitizer can be used. Examples of the electron donor include p-dimethylaminobenzoate and diethanolamine, and a thioxanthone derivative is preferably used as the sensitizer. One or more of the above sensitizers can be used in combination with the electron accepting compound or electron donating compound.

<Photo acid generator>
As the photoacid generator in the present invention, a compound having absorption in the range of 200 to 430 nm is used among chemical amplification type photoresists and compounds used for photocationic polymerization, and onium cation compounds and hydrohalic acids are used. And halogenated compounds that generate sulfonic acid and sulfonated compounds that generate sulfonic acid. Examples of onium salts include p-phenylthiophenyldiphenylsulfonium, phenacyltetramethylenesulfonium, phenacyldimethylsulfonium, (2-naphthylcarbonylmethyl) tetramethylenesulfonium, phenyl (4-methoxyphenyl) iodonium, phenyl {4- (tert - butyl) phenyl} iodonium, (4- bis {4- (tert-butyl) phenyl} iodonium, bis (4-dodecylphenyl) _BF of iodonium ^{_{4 -, PF 6 -, AsF}} 6 -, SbF 6 -, CH ₃ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , perfluorobutane sulfonate, benzene sulfonate, p-toluene sulfonate, and (C ₆ F ₅ ) ₄ B ^- salt. -(3 4-dimethoxyphenyl) -3,5-bis (trichloromethyl) -s-triazine, 1- (4-methoxynaphthyl-1) -3,5-bis (trichloromethyl) -s-triazine, 1- {2- (4-methoxyphenyl) ethenyl} -3,5-bis (trichloromethyl) -s-triazine, 1- {2- (2-methoxyphenyl) ethenyl} -3,5-bis (trichloromethyl) -s-triazine 1- {2- (3,4-dimethoxyphenyl) ethenyl} -3,5-bis (trichloromethyl) -s-triazine, 1- {2- (3-chloro-4-methoxyphenyl) ethenyl} -3 , 5-bis (trichloromethyl) -s-triazine, 1- (biphenyl-1) -3,5-bis (trichloromethyl) -s-triazine, 1- (4-hydroxybiphenyl) -1) -3,5-bis (trichloromethyl) -s-triazine, 1- (4-methoxybiphenyl-1) -3,5-bis (trichloromethyl) -s-triazine, and the like. Examples of the acid generator to be generated include N-trifluoromethanesulfonyloxydiphenylmaleimide, Np-toluenesulfonyloxysuccinimide, N-camphorsulfonyloxysuccinimide, N-trifluoromethanesulfonyloxysuccinimide, N-perfluorobutane Sulfonyloxyphthalimide, Np-toluenesulfonyloxy-1,8-naphthalenecarboximide, N-camphorsulfonyloxy-1,8-naphthalenecarboximide, N-trifluoromethanesulfonyloxy-1,8-naphthalenecarboxyimi , N- perfluorobutane sulfonyloxy-1,8-naphthalene dicarboximide and the like.

  These photoacid generators can be used alone or in the presence of a sensitizer shown below. Sensitizers include 9-methylanthracene, 9,10-dimethylanthracene, 9,10-diphenylanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9, Examples include 10-dibutoxyanthracene, 1-methylpyrene, thioxanthone derivatives, and the like.

  The number conversion dispersion average particle size of the transparent coloring composition for color filters according to the present invention 5 and 6 is preferably 1 to 100 nm, more preferably 1 to 75 nm, and still more preferably 1 to 50 nm. When the number-converted dispersed particle diameter exceeds 100 nm, the particle size is too large, and the optical properties are deteriorated.

  1-150 nm is preferable, as for the volume conversion dispersion | distribution average particle diameter of the transparent coloring composition for color filters which concerns on this invention 5 and 6, More preferably, it is 1-125 nm, More preferably, it is 1-100 nm. When the volume-converted dispersed particle diameter exceeds 150 nm, the particle size is too large, so that the optical characteristics deteriorate, which is not preferable.

  The viscosity of the transparent colored composition for a color filter according to the present invention 5 and 6 is preferably 0.5 to 1000 mPa · s, more preferably 0.5 to 200 mPa · s, still more preferably 0.5 to 100 mPa · s. If the viscosity exceeds 1000 mPa · s, uniform coating becomes difficult. When it is less than 0.5 mPa · s, the coating film becomes too thin, which is not preferable.

  The dispersion stability of the transparent coloring composition for color filters according to the present invention 5 and 6 is an evaluation method described later, and the rate of change in viscosity is preferably 20% or less, more preferably 10% or less, and still more preferably 8%. It is as follows. If the rate of change in viscosity is greater than 20%, it will be difficult to maintain a stable dispersibility over a long period of time.

  The specific extinction coefficient (weight basis) of the transparent colored composition for color filters according to the present invention 5 and 6 is 1 in a wavelength of 650 nm when a green color coloring material is used in the evaluation method described later. .05 or more, more preferably 1.10 to 5.00, still more preferably 1.20 to 5.00, and 610 nm when a blue color coloring material is used. The wavelength is preferably 1.05 or more, more preferably 1.10 to 5.00, and still more preferably 1.20 to 5.00, and a red color coloring material is used. In this case, at a wavelength of 550 nm, 1.05 or more is preferable, more preferably 1.10 to 5.00, still more preferably 1.20 to 5.00, and yellow as a colored fine colorant. When using those, at a wavelength of 400 nm, preferably at least 1.05, more preferably from 1.10 to 5.00, still more preferably from 1.20 to 5.00.

The light resistance of the colored transmission film produced using the transparent coloring composition for color filters according to the present invention 5 and 6 is that, in the evaluation method described later, the colored micro-coloring material contains 0.001% by weight or more of Si. In this case, the ΔE ^* value is 5.0 or less. It is preferable that the light resistance is 5.0 or less because deterioration of the optical characteristics of the color filter can be suppressed by backlight irradiation or the like.

The heat resistance of the transparent coloring composition for a color filter according to the fifth and sixth aspects of the invention is such that, in the evaluation method described later, when the colored fine coloring material contains 0.001% by weight or more of Si, the ΔE ^* value is 5. 0 or less. When the heat resistance is 5.0 or less, it is preferable because the optical characteristics can be prevented from being deteriorated by the heat treatment when forming the color filter or depositing the ITO film.

  The transmittance of the colored permeable membrane for a color filter produced using the transparent colored composition for a color filter according to the present invention 5 and 6 is such that the transmittance at 530 nm is 85 when a green color coloring material is used. % Or more, preferably 87% or more, more preferably 90% or more. When a blue color material is used as the colored micro colorant, the transmittance at 460 nm is 85% or more, preferably 87% or more. More preferably, it is 90% or more, and when a red color coloring material is used, the transmittance at 620 nm is 85% or more, preferably 87% or more, more preferably 90% or more, When a yellow color material is used as the colored fine colorant, the transmittance at 550 nm is 85% or more, preferably 87% or more, more preferably 90% or more.

  The specific absorption coefficient (weight basis) of the colored permeable membrane produced using the transparent coloring composition for color filters according to the present invention 5 and 6 was an evaluation method described later, and a green color coloring material was used as the colored micro-coloring material. In this case, it is preferably 1.05 or more at a wavelength of 650 nm, more preferably 1.10 to 5.00, still more preferably 1.20 to 5.00, and blue as a colored micro colorant. Is preferably 1.05 or more at a wavelength of 610 nm, more preferably 1.10 to 5.00, and still more preferably 1.20 to 5.00. When a red type is used, 1.05 or more is preferable at a wavelength of 550 nm, more preferably 1.10 to 5.00, still more preferably 1.20 to 5.00. When a yellow colorant is used as the colored micro colorant, it is preferably 1.05 or more, more preferably 1.10 to 5.00, and still more preferably 1.20 to 5 at a wavelength of 400 nm. .00.

  The color filter according to the present invention has a light transmittance of 85% or more, preferably 87% or more, more preferably 90% or more, in each color transmission region. Further, the contrast is preferably 1000 or more, more preferably 1200 or more, and still more preferably 1400 or more.

  Next, a method for producing a colored fine coloring material according to the present invention will be described.

  The colored micro colorant according to the present invention is prepared by mixing and stirring silica particles as a core particle and a surface modifier to coat the surface modifier on the surface of the silica particles, adding an organic pigment, and mixing and stirring. Composite particles in which an organic pigment is attached to the surface of the silica particles coated with the surface modifier, and using an alkaline solution, the total amount of silica particles and the surface modifier in the composite particles and / or It can be obtained by preparing colored fine particles by dissolving a part thereof and then treating the colored fine particles with a dispersant.

  The average primary particle diameter of the silica particles in the present invention is preferably 1 to 50 nm, more preferably 1 to 40 nm, and most preferably 1 to 20 nm.

BET specific surface area value of the silica particles in the invention is preferably from 10 to 1000 m ² / g, more preferably 15~500m ² / g.

  As the surface modifier in the present invention, anything may be used as long as an organic pigment can be attached to the surface of the silica particles, and an organosilicon compound such as alkoxysilane, silane coupling agent and organopolysiloxane, Coupling agents such as titanate-based, aluminate-based and zirconate-based, low-molecular or high-molecular surfactants and the like are preferably used. More preferred are organosilane compounds such as alkoxysilanes, silane coupling agents and organopolysiloxanes.

  Examples of organosilicon compounds include methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, ethyltriethoxysilane, propyl Alkoxysilanes such as triethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane and decyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltriethoxysilane , Γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacryloyloxypropyltrime Silane coupling agents such as xylsilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-chloropropyltrimethoxysilane, polysiloxane, methylhydrogen And organopolysiloxanes such as polysiloxane and modified polysiloxane.

  Titanate coupling agents include isopropyl tristearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethylaminoethyl) titanate, tetraoctyl bis (ditridecyl phosphate titanate, tetra (2,2 diallyl) Examples include oxymethyl-1-butyl) bis (ditridecyl) phosphate titanate, bis (dioctylpyrophosphate) oxyacetate titanate, and bis (dioctylpyrophosphate) ethylene titanate.

  Examples of the aluminate coupling agent include acetoalkoxy aluminum diisopropylate, aluminum diisopropoxy monoethyl acetoacetate, aluminum trisethyl acetoacetate, aluminum trisacetylacetonate and the like.

  Examples of the zirconate coupling agent include zirconium tetrakisacetylacetonate, zirconium dibutoxybisacetylacetonate, zirconium tetrakisethylacetoacetate, zirconium tribotoxymonoethylacetoacetate, zirconium tributoxyacetylacetonate and the like.

  Examples of the low molecular surfactant include alkylbenzene sulfonate, dioctyl sulfone succinate, alkylamine acetate, and alkyl fatty acid salt. Examples of the polymeric surfactant include polyvinyl alcohol, polyacrylate, carboxymethylcellulose, acrylic acid-maleate copolymer, and olefin-maleate copolymer.

  The coating amount of the surface modifier is preferably 0.05 to 15.0% by weight, more preferably 0.1 to 12.0% by weight, and still more preferably, in terms of C with respect to the silica particles as the core particles. 0.15 to 10.0% by weight. By setting it as 0.05-15 weight%, 10-500 weight part of organic pigments can be made to adhere with respect to 100 weight part of silica particles.

  As the organic pigment in the present invention, a red organic pigment, a blue organic pigment, a yellow organic pigment, a green organic pigment, an orange organic pigment, a brown organic pigment, and a purple color that are generally used as a color filter coloring material. Various organic pigment particle powders such as organic organic pigments can be used.

  Among various organic pigments, red organic pigments include azo pigments such as brilliant carmine, permanent red, and condensed azo red, and diaminoanthraquinonyl red, quinacridone red, thioindigo red, perylene red, perinone red, and diketopyrrolopyrrole. A condensed polycyclic pigment such as red can be used. As the blue organic pigment, phthalocyanine pigments such as metal-free phthalocyanine blue, phthalocyanine blue and fast sky blue, and condensed polycyclic pigments such as indanthrone blue and indigo blue can be used. As the yellow organic pigment, azo pigments such as Hansa Yellow, Benzidine Yellow, Permanent Yellow, and condensed azo yellow, and condensed polycyclic pigments such as anthrapyrimidine yellow and quinophthalone yellow can be used. As the green organic pigment, a phthalocyanine pigment such as phthalocyanine green can be used. As the orange organic pigment, azo pigments such as permanent orange, resol fast orange, pyrazolone orange, and vulcan orange, and condensed polycyclic pigments such as quinacridone, perinone orange, and diketopyrrolopyrrole orange can be used. As the brown organic pigment, azo pigments such as permanent brown, para brown and benzimidazolone brown and condensed polycyclic pigments such as thioindigo brown can be used. As the purple organic pigment, azo pigments such as fast violet and condensed polycyclic pigments such as unsubstituted quinacridone, dioxazine violet and perylene violet can be used. The organic pigment used in the present invention is not limited to the pigments exemplified above.

  The addition amount of the organic pigment is 10 to 500 parts by weight, preferably 30 to 400 parts by weight, and more preferably 50 to 300 parts by weight with respect to 100 parts by weight of the silica particles as the core particles.

  In the composite particles in the present invention, silica particles and a surface modifier are mixed, the surface of the silica particles is coated with the surface modifier, and then the silica coated with the surface modifier and the organic pigment are mixed. Can be obtained. Almost all of the added surface modifier is coated on the silica surface.

  As a device for mixing and stirring silica particles and a surface modifier, and mixing and stirring organic pigments and silica particles whose surface is coated with a surface modifier, a shear force can be applied to the powder layer. An apparatus is preferable, and in particular, an apparatus capable of simultaneously performing shearing, spatula and compression, for example, a wheel-type kneading machine, a ball-type kneading machine, a blade-type kneading machine, a roll-type kneading can be used, and a wheel The mold kneader can be used more effectively.

  Examples of the wheel type kneader include edge runners (synonymous with “mix muller”, “simpson mill”, “sand mill”), multi-mal, stotz mill, wet pan mill, conner mill, ring muller, etc. Are edge runners, multi-mals, stocks mills, wet pan mills, ring mullers, more preferably edge runners. Examples of the ball kneader include a vibration mill. Examples of the blade-type kneader include a Henschel mixer, a planetary mixer, and a nauter mixer. Examples of the roll-type kneader include an extruder.

  After the surface of the silica particles is coated with a surface modifier, an organic pigment is added, mixed and stirred to adhere the organic pigment to the surface of the surface modifier-coated silica particles. The organic pigment is added little by little while taking a time of about 5 minutes to 24 hours, preferably about 5 minutes to 20 hours, or 5 to 25 parts by weight of the organic pigment with respect to 100 parts by weight of silica particles, It is preferable to divide and add until a desired addition amount is obtained.

  After the organic pigment is adhered to the surface modifier-coated inorganic particle surfaces, drying or heat treatment may be further performed as necessary. In the case of performing drying or heat treatment, the heating temperature is usually preferably 40 to 150 ° C, more preferably 60 to 120 ° C, and the heating time is preferably 10 minutes to 12 hours, more preferably 30 minutes to 3 hours. preferable.

  The average primary particle diameter of the obtained composite particles is 1 to 100 nm, more preferably 1 to 50 nm, and still more preferably 1 to 30 nm.

  The average particle diameter in terms of volume of the composite particles in the present invention is preferably 150 nm or less, more preferably 1 to 125 nm, and most preferably 1 to 100 nm.

BET specific surface area value of the composite particles is preferably from 10 to 500 m ² / g, more preferably 15~400m ² / g, still more preferably 20 to 300 m ² / g.

  The degree of detachment of the organic pigment from the composite particles is preferably 4 or 3 and more preferably 4 in visual observation in the later evaluation method. When the degree of desorption of the organic pigment is 2 or less, since the desorbed organic pigment is coarsened by causing recrystallization or agglomeration, etc., it is mixed in the colored micro colorant that is the final product. It is not preferable.

  The colored fine particles in the present invention can be obtained by treating the composite particles with an alkali and dissolving silica or silica and a surface modifier so that the total amount and / or part of the Si component remains.

  As the alkali used for dissolution, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, ammonia, or the like can be used.

  The composite particle concentration in the solution at the time of the dissolution treatment is preferably 1.0 to 30.0 parts by weight, more preferably 2.5 to 25.0 parts by weight, still more preferably 5. 0 to 20.0 parts by weight.

When the silica particles in the composite particles or the silica particles and the surface modifier are dissolved, the alkali amount of the solution is when the silica particles or the silica particles and the surface modifier are completely dissolved, the alkali concentration ( mol / l) may be more than the theoretical amount capable of dissolving the inorganic compound particles, and is preferably about 1 to 2 times.
When a part of the silica is left, it may be dissolved at less than 1 time, preferably 0.01 to 0.95 times, more preferably 0.02 to 0.90 times, and still more preferably 0.00. It is 05 to 0.85 times. When the alkali concentration is less than 0.01 times, the silica particles or the silica particles and the surface modifier are industrially used because it takes a very long time to dissolve the colored fine particles to 9% by weight or less. It is not preferable. Moreover, in order to dissolve the silica particles or the silica particles and the surface modifier in an entire amount, an alkali concentration exceeding 2.0 times is not necessary.

  The pH when the silica particles in the composite particles or the silica particles and the surface modifier are dissolved is preferably 10.0 to 14.0, more preferably 11.0 to 13.7, and even more preferably 11. .5 to 13.4. When the pH exceeds 14.0, damage to the organic pigment due to alkali increases, and the light resistance of the colored fine particles deteriorates, which is not preferable. When the pH is less than 10.0, it is industrial because it has a very long time to dissolve the silica particles or the silica particles and the surface modifier in the composite particles to 9% by weight or less with respect to the colored fine particles. It is not preferable.

  40-100 degreeC is preferable, as for the process temperature at the time of performing a melt | dissolution process, More preferably, it is 45-90 degreeC, More preferably, it is 50-80 degreeC. When the temperature is lower than 40 ° C., it takes a long time exceeding 50 hours to dissolve the silica, which is industrially disadvantageous. When the temperature exceeds 100 ° C., it is difficult to obtain colored fine particles having good light resistance due to damage to the organic pigment, and an apparatus such as an autoclave is required, which is not industrially preferable.

  The treatment time for performing the dissolution treatment is preferably 5 minutes to 50 hours, more preferably 10 minutes to 30 hours, and even more preferably 20 minutes to 10 hours. When the treatment time is longer than 50 hours, it is industrially unfavorable because it takes a long time for the dissolution treatment.

  After the dissolution treatment, the solid content and the solution can be separated by filtration, washed, and then taken out using a normal drying or freeze-drying method.

  The amount of silica contained in the obtained colored fine particles is 0 to 9.0% by weight, more preferably 0.005 to 7.0% by weight, and most preferably, in terms of Si, based on the colored fine particles. 0.01 to 5.0% by weight. When the amount of silica exceeds 9.0% by weight in terms of Si, it is difficult to obtain sufficient coloring power because the amount of silica contained in the colored fine particles is too large.

  The average primary particle diameter of the colored fine particles in the present invention is 1 to 100 nm, more preferably 1 to 50 nm, and still more preferably 1 to 30 nm.

  The average particle diameter in terms of volume of the colored fine particles in the present invention is preferably 150 nm or less, more preferably 1 to 125 nm, and most preferably 1 to 100 nm.

BET specific surface area of the colored fine particles is preferably from 10 to 500 m ² / g, more preferably 15~400m ² / g, still more preferably 20 to 300 m ² / g.

  The colored fine colorant according to the present invention can be obtained by treating the colored fine particles with a dispersant.

  As the dispersant to be treated, a dispersant that is a constituent material of the transparent resin composition described above may be used.

  As a method of treating with the dispersant, any method can be used as long as it can adsorb only the dispersant to the pigment while solving the secondary agglomerated colored fine particles. Examples thereof include a wet method such as an ultrasonic treatment method and a dry method using a wheel-type kneader, a ball-type kneader, a blade-type kneader, or the like. In addition, as a dispersing agent processing method, it is not restricted to the method illustrated above.

  Next, the manufacturing method of the transparent coloring composition which concerns on this invention, and the transparent coloring composition for color filters is described.

  In order to adjust the transparent coloring composition of the present invention 3, the colored fine coloring material of the present invention 1 or the present invention 2 is redispersed in an organic solvent or an oil vehicle, or after treatment with a dispersant, It can be obtained by dispersing in an oil vehicle. For mixing / dispersing, a ball mill, a bead mill, a sand mill, an edge runner, a two or three roll mill, an extruder, a high-speed impact mill, or the like can be used. As the grinding media used in the grinding mill, steel beads, glass beads, ceramic beads, etc. can be used depending on the material of the mill, and the size is preferably in the range of 0.01 to 10 mm, 0.03 A range of ˜3 mm is more preferable. The grinding temperature is not particularly limited and may be in the range from room temperature to the boiling point of the solvent. If necessary, additives such as a dispersant, a pigment derivative, an antifoaming agent, and a surfactant may be added as an additive.

  In order to prepare the transparent colored composition for a color filter of the present invention 4, a transparent resin having an acidic group or a transparent resin having a latent acidic group may be dissolved in the transparent colored composition of the present invention 3. Alternatively, the colored fine colorant can be mixed and dispersed using a solvent in which a transparent resin having an acidic group or a transparent resin having a latent acidic group is dissolved in advance.

  In order to prepare the transparent colored composition for a color filter to which the photosensitivity of the present invention 5 is imparted, the photopolymerization initiator and the ethylenic non-polymerizing composition are added to the transparent colored composition containing the transparent resin having an acidic group of the present invention 4. A polyfunctional monomer having two or more saturated double bonds may be added and mixed. In this case, if necessary, a solvent can be added to adjust the pigment concentration, viscosity, and the like. Furthermore, if necessary, a polymerization inhibitor, a curing accelerator such as 2-mercaptobienimidazole, and the like can be used.

  In order to prepare the transparent coloring composition for color filters to which the photosensitivity of the present invention 6 was imparted, photoacid generation was performed on the transparent coloring composition for color filters containing the transparent resin having a latent acidic group of the present invention 4. What is necessary is just to add and mix an agent.

  Next, the manufacturing method of the color filter using the transparent coloring composition for color filters of this invention is demonstrated.

  That is, after applying the transparent coloring composition for a color filter of the present invention on a transparent substrate on which a black matrix pattern is formed, a solvent is sufficiently removed by pre-baking to obtain a colored coating film. In the case of a colored coating film not imparted with photosensitivity, a positive photoresist layer capable of alkali development is provided on the film to obtain a coating film having a two-layer structure. As the alkali developable positive photoresist, a quinonediazide-based photoresist is preferably used. The colored coating film is irradiated with light through a photomask and then developed with an alkaline aqueous solution. Since the exposed portion of the coating film coated with the positive photoresist layer becomes alkali-soluble, the exposed colored layer is also etched with an alkaline solution to form a colored positive image. Next, the photoresist layer is selectively removed with a solvent to obtain a colored pattern. On the other hand, in the case of a transparent coloring composition for a photosensitive color filter to which a photopolymerization initiator and a polyfunctional monomer are added, a coating film prepared therefrom is used as it is as a colored photosensitive layer. Similarly, if alkali development is performed after exposure through a photomask, the exposed portion is insolubilized and a negative colored pattern can be obtained. For the development treatment, an immersion method, a spray method, a paddle method, a shower method, or the like is used. After alkali development, the substrate is washed with water and dried.

  As a transparent substrate for producing a color filter, polycarbonate, polyester, polyamide, polyimide, polyamideimide, or the like can be used in addition to silica glass. A silicon substrate can also be used for manufacturing a solid-state imaging device. In order to apply the transparent coloring composition for a color filter onto these transparent substrates, methods such as spin coating, cast coating, roll coating, screen printing, and inkjet method can be appropriately used. Although the thickness of a coating film is dependent also on the density | concentration of a colored micro coloring material, it is 0.1-10 micrometers, Preferably it is 0.2-5.0 micrometers.

As the alkaline developer, an aqueous solution of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide or the like is preferable. Methanol, ethanol, isopropyl alcohol, a surfactant and the like can also be added to the alkaline aqueous solution.

  Hereinafter, the present invention will be described in detail with reference to examples.

  The average primary particle size of each particle powder was measured by measuring the particle size of 350 particles shown in the transmission electron micrograph, and the average primary particle size was indicated by the average value.

  The number-average particle size and the volume-average particle size of each particle powder are determined by dispersing an aqueous solution obtained by mixing the particle powder to be measured and water for 1 minute using an ultrasonic disperser, It was measured using a system particle size analyzer FPAR-1000 "(Otsuka Electronics Co., Ltd.).

  The specific surface area value was indicated by a value measured by the BET method.

  The coating amount of the surface modifier coated on the particle surface of the silica particles and the coating amount of the organic pigment adhering to the composite particle powder are “Horiba Metal Carbon / Sulfur Analyzer EMIA-2200 Model” (Horiba Co., Ltd.). It was determined by measuring the amount of carbon using a manufacturer).

  The amount of silica encapsulated in the colored fine coloring material was measured using a “fluorescence X-ray analyzer 3063M type” (manufactured by Rigaku Denki Kogyo Co., Ltd.) according to “General X-ray fluorescence analysis rules” of JIS K 0119.

The dispersant adsorption amount indicates the dispersant adsorption amount per unit surface area of the particle. The larger the dispersant adsorption amount determined by the following method, the easier the dispersant is adsorbed on the particle surface, and the dispersion in the vehicle. The property is good.

  10 g of measured particle powder, 0.5 g of polyester dispersant Solsperse 24000SC (manufactured by LUBRIZOL Co., Ltd.) and 49.5 g of propylene glycol monomethyl ether acetate (PGMEA) are placed in a 100 ml plastic bottle together with 120 g of 3 mmφ steel beads and mixed for 60 minutes with a paint shaker. scatter.

Next, 50 g of this coating composition is taken out, put into a 100 ml settling tube, and centrifuged at 8000 rpm for 15 minutes to separate the solid portion and the solvent portion. Thereafter, the unsettled coating composition is put in a 50 ml settling tube, and centrifuged at 20000 rpm for 30 minutes to separate the solid portion and the solvent portion. Then, the solid content concentration of the dispersant contained in the solvent portion is quantified by a gravimetric method, and the amount of the dispersant present in the solid portion is obtained by subtraction from the amount of the prepared dispersant, and then divided by the BET specific surface area value. The amount of the dispersant adsorbed per unit area of the measured particle Da (mg / m ² ).

The hue of each particle powder is 0.5 g of a sample and 0.5 ml of castor oil, kneaded with a Hoover-type Mahler to form a paste. To this paste, 4.5 g of clear lacquer is added, kneaded and coated to form 150 μm on cast coated paper. An application piece (coating thickness: about 30 μm) applied using a (6 mil) applicator is prepared and measured using a “spectral colorimeter CM-3610d” (manufactured by Minolta Co., Ltd.). The color index is shown according to the definition. The C ^* value represents saturation and can be obtained according to the following formula 1.

<Equation 1>
C ^* value = ((a ^* value) ² + (b ^* value) ² ) ^1/2

The coloring power of each particle powder is as follows. First, each of the primary color enamel and the color development enamel prepared according to the method described below is applied onto a cast coated paper using a 150 μm (6 mil) applicator to prepare a coated piece. The L ^* value was measured using a colorimeter CM-3610d (manufactured by Minolta Co., Ltd.), and the difference was taken as the ΔL ^* value.

Next, using the organic pigment used when the colored micro colorant is prepared as a standard sample of the color filter colorant, the primary color enamel and color-enameled application pieces are prepared in the same manner as described above. The L ^* value was measured and the difference was taken as the ΔLs ^* value.

The value calculated according to the following equation 2 using DerutaLs ^* value of [Delta] L ^* value and the standard sample of the resulting colored fine colorant shown as tinting strength (%).

<Equation 2>
Coloring power (%) = 100 + {( ΔLs * values -Delta L ^* value) × 10}

Production of primary color enamel:
10g of the above sample powder, 16g of amino alkyd resin and 6g of thinner were mixed and added to a 140ml glass bottle together with 90g of 3mmφ glass beads. After mixing and dispersing for 45 minutes with a paint shaker, 50g of amino alkyd resin was added. Further, the primary color enamel was prepared by dispersing with a paint shaker for 5 minutes.

Production of color-enamel:
The primary color enamel (12 g) and amylac white (titanium dioxide-dispersed aminoalkyd resin) (80 g) were blended and mixed and dispersed for 15 minutes with a paint shaker to produce a color-enamel.

The light resistance of each particle powder is that the primary color enamel prepared for measuring the above-mentioned coloring power is applied to a glass plate (0.8 mm × 70 mm × 150 mm) at a thickness of 150 μm and dried to form a coating film. Half of the obtained coating piece for measurement was covered with a metal foil, and using “I Super UV Tester SUV-W13” (manufactured by Iwasaki Electric Co., Ltd.), ultraviolet rays were continuously irradiated for 6 hours at an irradiation intensity of 100 mW / cm ² . Thereafter, the hue (L ^* value, a ^* value, b ^* value) of the portion not irradiated with ultraviolet rays and the portion irradiated with ultraviolet rays was measured by covering with a metal foil, and ΔE ^* calculated according to the following Equation 3 Indicated by value.

<Equation 3>
ΔE ^* value = ((ΔL ^* value) ² + (Δa ^* value) ² + (Δb ^* value) ² ) ^1/2
ΔL ^* value: difference in L ^* value of sample to be compared with UV irradiation Δa ^* value: difference in a ^* value of sample to be compared with UV irradiation Δb ^* value: b ^* value of sample to be compared with UV irradiation difference

For the heat resistance of each particle powder, the primary color enamel prepared for measuring the coloring power described above was applied to a glass plate (0.8 mm × 70 mm × 150 mm) at a thickness of 150 μm and dried to form a coating film. After holding at 240 ° C. for 1 hour using a gear oven, the hue (L ^* value, a ^* value, b ^* value) before and after the heat treatment test was measured, and indicated by the ΔE ^* value calculated according to the following Equation 4. .

<Equation 4>
ΔE ^* value = ((ΔL ^* value) ² + (Δa ^* value) ² + (Δb ^* value) ² ) ^1/2
ΔL ^* value: difference in L ^* value before and after the heat treatment test of the sample to be compared Δa ^* value: difference in a ^* value before and after the heat treatment test of the sample to be compared Δb ^* value: b ^* value before and after the heat treatment test of the sample to be compared difference

The viscosity of each transparent coloring composition was determined by measuring the viscosity of the obtained composition at 25 ° C. using an “E-type viscometer EMD-R” (manufactured by Tokyo Keiki Co., Ltd.), and a shear rate D = 383 sec ^−1. It was shown by the value in.

The viscosity change rate of each transparent coloring composition was determined by measuring the viscosity value at a shear rate D = 383 sec ⁻¹ at 25 ° C. after allowing the obtained transparent coloring composition to stand at 60 ° C. for 1 week, and before and after standing. The value obtained by dividing the amount of change in viscosity by the value before standing was shown as a percentage of change.

  The number conversion dispersion average particle diameter and volume conversion dispersion average particle diameter of each transparent coloring composition were measured using a dynamic light scattering method “Dense System Particle Size Analyzer FPAR-1000” (manufactured by Otsuka Electronics Co., Ltd.).

The coloring power of each transparent coloring composition is as follows. The PGMEA solution in which the concentration of the colored micro-coloring material is adjusted to 0.08% by weight is put in a quartz cell, and the extinction coefficient at the wavelength with the largest light absorption is expressed as “Self-recording photoelectric spectrophotometry. Each was measured using “total UV-2100” (manufactured by Shimadzu Corporation), and indicated by a specific extinction coefficient ε _w calculated according to the following formula 5. It shows that the coloring power of a transparent coloring composition is so high that the value of a specific extinction coefficient is large.

<Equation 5>
ε _w = ε _h / ε ₀
ε _w : specific extinction coefficient ε _h : extinction coefficient per unit weight of each colored micro colorant ε ₀ : extinction coefficient per unit weight of the organic pigment used as a raw material for each colored micro colorant

  The light transmittance of the transparent coloring composition for a color filter is such that the transparent coloring composition for a color filter diluted so that the organic pigment concentration is 0.008% by weight is placed in a quartz cell, and the transparent coloring composition for a green color filter In the case of a transparent coloring composition for a blue color filter, a transmittance of a wavelength of 460 nm, and in the case of a transparent coloring composition for a red color filter, a transmittance of a wavelength of 620 nm. In the case of the transparent coloring composition for yellow color filters, the transmittance at a wavelength of 550 nm was measured using “Self-recorded photoelectric spectrophotometer UV-2100” (manufactured by Shimadzu Corporation).

  The chromaticity of the transparent colored permeable membrane for a color filter obtained using the transparent colored composition for a color filter is obtained by applying a transparent colored composition for a color filter prepared according to a formulation described later to a clear film with a thickness of 150 μm and drying. The measurement coating pieces obtained were measured using a “spectral colorimeter CM-3610d” (manufactured by Minolta Co., Ltd.) and shown in accordance with an XY chromaticity diagram defined by CIE (International Commission on Illumination).

The light resistance of the colored permeable membrane for color filters obtained using the transparent colored composition for color filters is such that the transparent colored composition for color filters is applied to a glass plate (0.8 mm × 70 mm × 150 mm) with a thickness of 150 μm. Then, a part of the measurement coating piece obtained by drying was covered with a metal foil, and using “I Super UV Tester” (SUV-W13 (manufactured by Iwasaki Electric Co., Ltd.)), the irradiation intensity of ultraviolet rays was 100 mW / cm. After 6 hours of continuous irradiation at ² , the hue (L ^* value, a ^* value, b ^* value) of the portion not irradiated with ultraviolet rays and the portion irradiated with ultraviolet rays by covering with a metal foil was determined by “spectral colorimetry”. with a total of CM-3610d "(manufactured by Minolta Co., Ltd.) was measured, based on the measurement value of the portion ultraviolet is not irradiated, shown by the calculated Delta] E ^* value according to the number 3 It was.

The heat resistance of the colored permeable membrane for a color filter obtained using the transparent colored composition for a color filter is obtained by applying the colored composition for a color filter to a glass plate (0.8 mm × 70 mm × 150 mm) with a thickness of 150 μm, After drying and holding the coating piece for measurement at 240 ° C. for 1 hour using a gear oven, the hues (L ^* value, a ^* value, b ^* value) before and after the heat treatment test were measured, respectively, It was shown by the ΔE ^* value calculated according to

  The light transmittance of the colored transmission film for color filter obtained using the transparent coloring composition for color filter is obtained by using a measurement coating piece prepared for measuring the chromaticity of the colored transmission film for color filter. In the case of a colored transmission film for a green color filter, the transmittance at a wavelength of 530 nm, in the case of a colored transmission film for a blue color filter, the transmittance at a wavelength of 460 nm, and in the case of a colored transmission film for a red color filter, 620 nm. The transmittance at a wavelength of 550 nm in the case of a colored transmission film for a yellow color filter was measured using “Self-recorded photoelectric spectrophotometer UV-2100” (manufactured by Shimadzu Corporation).

The coloring power of the colored transmission film for color filter obtained using the transparent coloring composition for color filter is the absorption coefficient of the colored transmission film for color filter at the wavelength with the largest light absorption. -2100 "(manufactured by Shimadzu Corporation), and indicated by the specific extinction coefficient ε _w calculated according to Equation 5 above. It shows that the coloring power of the colored permeable membrane for color filters is so high that the value of a specific extinction coefficient is large.

  As for the transmittance of the color filter, the transmittance of each wavelength of 530 nm, 460 nm and 620 nm was measured using a color filter produced by the method described later, and “Self-recorded photoelectric spectrophotometer UV-2100” (manufactured by Shimadzu Corporation) was used. And measured.

  The contrast of the color filter is the brightness when the color filter produced by the method described later is sandwiched between two polarizing plates on the backlight and the direction of the polarizing plate is parallel (A) and crossed. (B) was measured and indicated as (A) / (B).

<Composite Particle 1: Production of Composite Particle Powder (G)>
3.5 kg of silica 1 (average primary particle size: 16 nm, BET specific surface area value: 204.3 m ² / g, light resistance ΔE ^* value: 5.36, heat resistance ΔE ^* value: 3.46) 70 g of polysiloxane (trade name: TSF484: manufactured by GE Toshiba Silicone Co., Ltd.) was added while operating the edge runner, and the mixture was stirred for 30 minutes at a linear load of 588 N / cm (60 Kg / cm). The stirring speed at this time was 22 rpm.

Next, organic pigment G (type: phthalocyanine pigment, average primary particle size: 100 nm, number-converted average particle size: 319 nm, volume-converted average particle size: 813 nm, BET specific surface area value: 67.3 m ² / g, L ^* Value: 29.77, a ^* value: -15.30, b ^* value: -1.12, C ^* value: 15.34, dispersant adsorption amount: 0.26 mg / m ² , light resistance E ^* value: 8.06, heat resistance ΔE ^* value: 7.46) 7.0 kg was added over 30 minutes while running the edge runner, and further mixed and stirred for 150 minutes at a line load of 392 N / cm (40 Kg / cm). The organic pigment G was adhered to the methyl hydrogen polysiloxane coating to obtain composite particles 1. The stirring speed at this time was 22 rpm.

The obtained composite particle 1 has an average primary particle diameter of 19 nm, a number-converted average particle diameter of 27 nm, a volume-converted average particle diameter of 55 nm, a BET specific surface area value of 74.8 m ² / g, and an L ^* value of 30. .38, a ^* value was -14.74, b ^* value was -1.16, C ^* value was 14.79, and the degree of desorption of the organic pigment was 4. The dispersant adsorption amount was 0.71 mg / m ² , the coloring power was 97%, the light resistance ΔE ^* value was 2.31, and the heat resistance ΔE ^* value was 2.51. The coating amount of methyl hydrogen polysiloxane was 0.53% by weight in terms of C. The adhering organic pigment G was 24.06% by weight in terms of C (corresponding to 200 parts by weight with respect to 100 parts by weight of the silica particle powder).

  From the observation result of the transmission electron micrograph of the obtained composite particle 1, since almost no particles of the added organic pigment G are observed, almost the whole amount of the organic pigment G is adhered to the methylhydrogenpolysiloxane coating. It was recognized that

<Composite Particle 2: Production of Composite Particle Powder (B)>
To 13.5 kg of the silica, 140 g of methyltriethoxysilane (trade name: TSL8123: manufactured by GE Toshiba Silicone Co., Ltd.) was added while operating the edge runner, and a linear load of 441 N / cm (45 Kg / cm) for 20 minutes. Mixing and stirring were performed. The stirring speed at this time was 22 rpm.

Next, organic pigment B (type: phthalocyanine pigment, average primary particle size: 80 nm, number conversion average particle size: 246 nm, volume conversion average particle size: 724 nm, BET specific surface area value: 87.9 m ² / g, L ^* value: 23.04, ^{a *} value: 5.99, ^{b *} value: -13.16, ^{C *} value: 14.46, dispersing agent adsorption amount: 0.14 mg / ^{m 2,} light resistance Delta] E ^* value: 8 .83, heat resistance ΔE ^* value: 9.04) 7.0 kg is added over 30 minutes while the edge runner is running, and further mixed and stirred for 120 minutes with a linear load of 588 N / cm (60 Kg / cm). The organic pigment B was attached to the methyltriethoxysilane coating to obtain composite particles 2. The stirring speed at this time was 22 rpm.

The obtained composite particle 2 has an average primary particle diameter of 20 nm, a number-converted average particle diameter of 31 nm, a volume-converted average particle diameter of 59 nm, a BET specific surface area value of 93.6 m ² / g, and an L ^* value of 26. .21, a ^* value was 5.96, b ^* value was −12.88, C ^* value was 14.19, and the degree of desorption of the organic pigment was 4. The dispersant adsorption amount was 0.60 mg / m ² , the coloring power was 96%, the light resistance ΔE ^* value was 2.62, and the heat resistance ΔE ^* value was 2.73. The coating amount of methyltriethoxysilane was 0.27% by weight in terms of C. The adhering organic pigment B was 44.65% by weight in terms of C (corresponding to 200 parts by weight with respect to 100 parts by weight of the silica particle powder).

  From the observation result of the transmission electron micrograph of the obtained composite particle 2, since almost no particles of the added organic pigment B are observed, almost all of the organic pigment B is attached to the methyltriethoxysilane coating. Was recognized.

<Composite Particle 3: Production of Composite Particle Powder (R)>
Silica 2 (average primary particle size: 21 nm, BET specific surface area value: 189.2 m ² / g, light resistance ΔE ^* value: 5.41, heat resistance ΔE ^* value: 3.52) 3.5 kg, phenyltriethoxy 210 g of silane (trade name: TSL8178: manufactured by GE Toshiba Silicone Co., Ltd.) was added while operating the edge runner, and the mixture was stirred for 20 minutes with a linear load of 735 N / cm (75 Kg / cm). The stirring speed at this time was 22 rpm.

Next, organic pigment R (type: diketopyrrolopyrrole pigment, average primary particle size: 130 nm, number-converted average particle size: 398 nm, volume-converted average particle size: 948 nm, BET specific surface area value: 82.4 m ² / g , L ^* value: 38.42, a ^* value: 43.20, b ^* value: 23.36, C ^* value: 49.11, dispersant adsorption amount: 0.33 mg / m ² , light resistance ΔE ^* value : 7.92, heat resistance ΔE ^* value: 7.28) 7.0 kg was added over 30 minutes while running the edge runner, and further mixed and stirred for 90 minutes at a linear load of 735 N / cm (75 Kg / cm). The organic pigment R was attached to the phenyltriethoxysilane coating to obtain composite particles 3. The stirring speed at this time was 22 rpm.

The obtained composite particle 3 has an average primary particle diameter of 29 nm, a number-converted average particle diameter of 36 nm, a volume-converted average particle diameter of 64 nm, a BET specific surface area value of 86.3 m ² / g, and an L ^* value of 47. .49, a ^* value was 48.17, b ^* value was 22.49, C ^* value was 53.16, and the degree of desorption of the organic pigment was 4. The dispersant adsorption amount was 0.96 mg / m ² , the coloring power was 96%, the light resistance ΔE ^* value was 2.54, and the heat resistance ΔE ^* value was 2.28. Moreover, the coating amount of phenyltriethoxysilane was 2.02% by weight in terms of C. The adhering organic pigment R was 40.40% by weight in terms of C (corresponding to 200 parts by weight with respect to 100 parts by weight of the silica particle powder).

  From the observation result of the transmission electron micrograph of the composite particle 3 obtained, almost no particles of the added organic pigment R are observed, so that almost all of the organic pigment R is adhered to the phenyltriethoxysilane coating. Was recognized.

<Composite Particle 4: Production of Composite Particle Powder (Y)>
To 3.5 kg of silica 3 (average primary particle size: 40 nm, BET specific surface area value: 96.6 m ² / g, light resistance ΔE ^* value: 5.04, heat resistance ΔE ^* value: 3.28), γ-amino 420 g of propyltriethoxysilane (trade name: TSL8331: manufactured by GE Toshiba Silicone Co., Ltd.) was added while operating the edge runner, and mixed and stirred for 60 minutes at a linear load of 588 N / cm (60 Kg / cm). The stirring speed at this time was 22 rpm.

Next, organic pigment Y (type: quinophthalone pigment, average primary particle size: 252 nm, number conversion average particle size: 744 nm, volume conversion average particle size: 1746 nm, BET specific surface area value: 27.9 m ² / g, L ^* Value: 84.21, a ^* value: 3.00, b ^* value: 91.31, C ^* value: 91.36, dispersant adsorption amount: 0.11 mg / m ² , light resistance ΔE ^* value: 7. 22. Heat resistance ΔE ^* value: 8.84) 10.5 kg was added over 30 minutes while running the edge runner, and further mixed and stirred for 180 minutes with a linear load of 441 N / cm (45 Kg / cm), The organic pigment R was attached to the γ-aminopropyltriethoxysilane coating to obtain composite particles 4. The stirring speed at this time was 22 rpm.

The obtained composite particles 4 have an average primary particle diameter of 46 nm, a number-converted average particle diameter of 59 nm, a volume-converted average particle diameter of 84 nm, a BET specific surface area value of 49.7 m ² / g, and an L ^* value of 86. .34, a ^* value was 3.46, b ^* value was 89.62, C ^* value was 89.69, and the degree of desorption of the organic pigment was 4. The dispersant adsorption amount was 0.48 mg / m ² , the coloring power was 99%, the light resistance ΔE ^* value was 2.06, and the heat resistance ΔE ^* value was 2.48. The coating amount of γ-aminopropyltriethoxysilane was 1.72% by weight in terms of C. The adhering organic pigment Y was 33.57% by weight in terms of C (corresponding to 300 parts by weight with respect to 100 parts by weight of the silica particle powder).

  From the observation result of the transmission electron micrograph of the obtained composite particle 4, since almost no particles of the added organic pigment Y are observed, almost the whole amount of the organic pigment Y adheres to the γ-aminopropyltriethoxysilane coating. It was recognized that

<Colored fine particles 1: Production of colored fine particles (G)>
In a 3 l beaker, 300 g of the composite particle 1 powder obtained above and 2 l of a 0.44 mol / l sodium hydroxide aqueous solution (0.2 times the theoretical amount capable of dissolving the silica particles and the surface modifier as core particles) The pH was 13.2 and the mixture was stirred at 60 ° C. for 30 minutes. This was filtered, washed with water, and dried to obtain colored fine particles (G).

The obtained colored fine particles (G) had an average primary particle diameter of 16 nm, a number-converted average particle diameter of 23 nm, a volume-converted average particle diameter of 74 nm, and a BET specific surface area value of 84.7 m ² / g. The amount of silica contained in the colored fine particles (G) is 1.02% by weight in terms of Si. Among the hues, the L ^* value is 31.38, the a ^* value is −14.29, and the b ^* value is −1.11. The C ^* value was 14.33, the coloring power was 106%, the dispersant adsorption amount was 0.66 mg / m ² , the light resistance ΔE ^* value was 3.50, and the heat resistance ΔE ^* value was 3.69.

<Colored fine particles 2: Production of colored fine particles (B)>
Colored fine particles (B) were obtained in the same manner as the colored fine particles (G) except that the composite particles 2 were used as the composite particles.

The obtained colored fine particles (B) had an average primary particle diameter of 20 nm, a number-converted average particle diameter of 27 nm, a volume-converted average particle diameter of 78 nm, and a BET specific surface area value of 95.2 m ² / g. The amount of silica contained in the colored fine particles (B) is 0.26% by weight in terms of Si. Among the hues, the L ^* value is 26.49, the a ^* value is 5.83, and the b ^* value is −12.88. The C ^* value was 14.14, the coloring power was 106%, the dispersant adsorption amount was 0.54 mg / m ² , the light resistance ΔE ^* value was 3.62, and the heat resistance ΔE ^* value was 3.94.

<Colored fine particles 3: Production of colored fine particles (R)>
Colored fine particles (R) were obtained in the same manner as the colored fine particles (G) except that the composite particles 3 were used as the composite particles.

The obtained colored fine particles (R) had an average primary particle diameter of 17 nm, a number-converted average particle diameter of 28 nm, a volume-converted average particle diameter of 84 nm, and a BET specific surface area value of 88.6 m ² / g. The amount of silica contained in the colored fine particles (R) is 1.94% by weight in terms of Si. Among the hues, the L ^* value is 40.19, the a ^* value is 43.26, the b ^* value is 23.51, C ^* Value was 49.24, coloring power was 105%, dispersant adsorption amount was 0.92 mg / m ² , light resistance ΔE ^* value was 3.24, and heat resistance ΔE ^* value was 3.42.

<Colored fine particles 4: Production of colored fine particles (Y)>
Colored fine particles (Y) were obtained in the same manner as the colored fine particles (G) except that the composite particles 4 were used as the composite particles.

The obtained colored fine particles (Y) had an average primary particle diameter of 18 nm, a number-converted average particle diameter of 56 nm, a volume-converted average particle diameter of 98 nm, and a BET specific surface area value of 60.4 m ² / g. The amount of silica contained in the colored fine particles (Y) is 0.00% by weight in terms of Si. Among the hues, the L ^* value is 83.74, the a ^* value is 2.85, the b ^* value is 87.38, C ^{* The} value was 87.43, the coloring power was 107%, the dispersant adsorption amount was 0.44 mg / m ² , the light resistance ΔE ^* value was 5.44, and the heat resistance ΔE ^* value was 5.73.

<Example 1-1: Production of colored fine coloring material (G)>
As the colored fine coloring material (G), 100 parts by weight of the colored fine particles (G), 5 parts by weight of the comb-shaped polyester dispersant Solsperse 24000SC and 10 parts by weight of PGMEA are mixed, and an automatic mortar NM-200 (manufactured by Nippon Ceramic Science Co., Ltd.) is used. The mixture was kneaded for 30 minutes and then dried at 140 degrees for 60 minutes to completely evaporate the solvent.

The obtained colored micro colorant (G) had an average primary particle diameter of 18 nm, a number-converted average particle diameter of 23 nm, a volume-converted average particle diameter of 54 nm, and a BET specific surface area value of 81.6 m ² / g. The amount of silica contained in the colored fine coloring material (G) is 0.96% by weight in terms of Si. Among the hues, the L ^* value is 31.62, the a ^* value is -14.90, and the b ^* value is -1. 16, C ^* value was 14.95, coloring power was 107%, dispersant adsorption amount was 2.39 mg / m ² , light resistance ΔE ^* value was 3.44, and heat resistance ΔE ^* value was 3.68. .

<Example 1-2: Production of colored fine coloring material (B)>
A colored fine colorant (B) was obtained in the same manner as the colored fine colorant (G) except that the colored fine particles (B) were used as the colored fine particles.

The obtained colored micro colorant (B) had an average primary particle diameter of 19 nm, a number-converted average particle diameter of 27 nm, a volume-converted average particle diameter of 56 nm, and a BET specific surface area value of 92.4 m ² / g. The amount of silica contained in the colored fine coloring material (G) is 0.24% by weight in terms of Si. Among the hues, the L ^* value is 26.59, the a ^* value is 5.91, and the b ^* value is -12.94. The C ^* value was 14.23, the coloring power was 106%, the dispersant adsorption amount was 2.16 mg / m ² , the light resistance ΔE ^* value was 3.55, and the heat resistance ΔE ^* value was 3.88.

<Example 1-3: Production of colored fine coloring material (R)>
A colored micro-coloring material (R) was obtained in the same manner as the colored micro-coloring material (G) except that the colored micro-particles 3 were used as the colored micro-particles and an acrylic block copolymer was used as the dispersant. .

The obtained colored micro colorant (R) had an average primary particle size of 26 nm, a number-converted average particle size of 28 nm, a volume-converted average particle size of 59 nm, and a BET specific surface area value of 85.4 m ² / g. The amount of silica contained in the colored fine coloring material (R) is 1.88% by weight in terms of Si. Among the hues, the L ^* value is 46.42, the a ^* value is 49.15, the b ^* value is 22.51, The C ^* value was 54.06, the coloring power was 106%, the dispersant adsorption amount was 2.29 mg / m ² , the light resistance ΔE ^* value was 3.21, and the heat resistance ΔE ^* value was 3.37.

<Example 1-4: Production of colored fine coloring material (Y)>
The colored fine colorant (Y) was obtained in the same manner as the colored fine colorant (G) except that the colored fine particles 4 were used as the colored fine particles and the urethane block copolymer was used as the dispersant. .

The obtained colored micro colorant (Y) had an average primary particle diameter of 39 nm, a number-converted average particle diameter of 48 nm, a volume-converted average particle diameter of 72 nm, and a BET specific surface area value of 55.9 m ² / g. The amount of silica contained in the colored fine coloring material (Y) is 0.00% by weight in terms of Si. Among the hues, the L ^* value is 84.94, the a ^* value is 3.56, and the b ^* value is 88.16. The C ^* value was 88.23, the coloring power was 108%, the dispersant adsorption amount was 2.25 mg / m ² , the light resistance ΔE ^* value was 5.39, and the heat resistance ΔE ^* value was 5.66.

<Example 2-1: Production of transparent colored composition (G)>
Using a bead mill, 105.0 parts by weight of the colored micro composite colorant (G), 5.0 parts by weight of a dispersant (polyester dispersant) (trade name: Solsperse 24000SC: manufactured by LUBRIZOL) and 290.0 parts by weight of PGMEA are used. By mixing and dispersing for a time, a transparent colored composition (G) was obtained.

The obtained transparent coloring composition (G) has a number-converted dispersed particle size of 22 nm, a volume-converted dispersed particle size of 35 nm, a viscosity change rate of 4.2%, and a transmittance at a wavelength of 530 nm of 84.8%, The specific extinction coefficient ε _w (weight basis) at a wavelength of 650 nm was 2.42.

<Example 2-2: Production of transparent colored composition (B)>
A transparent colored composition (B) was obtained in the same manner as in Example 2-1, except that the colored fine composite colorant (B) was used as the colorant.

The obtained transparent coloring composition (B) has a number-converted dispersed particle diameter of 23 nm, a volume-converted dispersed particle diameter of 38 nm, a viscosity change rate of 4.6%, and a transmittance at a wavelength of 460 nm of 83.1%, The specific extinction coefficient ε _w (weight basis) at a wavelength of 610 nm was 2.37.

<Example 2-3: Production of transparent colored composition (R)>
A transparent colored composition (R) was obtained in the same manner as in Example 2-1, except that the colored fine composite colorant (R) was used as the colorant.

The obtained transparent coloring composition (R) has a number-converted dispersed particle diameter of 31 nm, a volume-converted dispersed particle diameter of 41 nm, a viscosity change rate of 4.9%, and a transmittance at a wavelength of 620 nm of 88.5%, The specific extinction coefficient ε _w (weight basis) at a wavelength of 550 nm was 2.10.

<Example 2-4: Production of transparent colored composition (Y)>
A transparent colored composition (Y) was obtained in the same manner as in Example 2-1, except that the colored fine composite colorant (Y) was used as the colorant.

The obtained transparent coloring composition (Y) has a number-converted dispersed particle size of 48 nm, a volume-converted dispersed particle size of 79 nm, a viscosity change rate of 5.4%, and a transmittance at a wavelength of 550 nm of 87.4%, The specific extinction coefficient ε _w (weight basis) at a wavelength of 400 nm was 2.24.

<Example 3-1: Production of transparent colored composition (IG) for color filter>
400.0 parts by weight of the transparent coloring composition (G) and 100.0 parts by weight of a methyl methacrylate / methacrylic acid copolymer were mixed and dispersed using a bead mill for 2 hours, and the resulting kneaded product was filtered with a 5 μm glass filter. Filtration yielded a transparent colored composition (IG) for color filters.

The obtained transparent colored composition for color filter (IG) has a number-converted dispersed particle size of 22 nm, a volume-converted dispersed particle size of 33 nm, a viscosity of 15.9 mPa · s, and a viscosity change rate of 4.2. %, Ε _{w of} 650 nm (weight basis) was 2.45.

The transparent colored composition for color filter (IG) was applied to a clear base film with a thickness of 150 μm (6 mil) and dried to obtain a colored permeable membrane for color filter (IG). As for the chromaticity of the obtained colored permeable membrane for color filter (IG), the x value is 0.2769, the y value is 0.3892, the Y value is 70.86, and the light resistance is ΔE ^* value is 3.42. The heat resistance ΔE ^* value was 3.65. The transmittance at a wavelength of 530 nm was 91.9%, and the specific extinction coefficient ε _w (weight basis) at 650 nm was 2.46.

<Example 3-2: Production of transparent colored composition (IB) for color filter>
The transparent colored composition for color filter (IB) is the same as the transparent colored composition for color filter (IG) except that the transparent colored composition (B) is used as the transparent colored composition. Got.

The obtained colored composition for color filter (IB) has a number-converted dispersed particle diameter of 23 nm, a volume-converted dispersed particle diameter of 35 nm, a viscosity of 15.6 mPa · s, and a viscosity change rate of 4.6%. , 610 _{w of} 610 nm (weight basis) was 2.37.

The transparent colored composition for color filter (IB) was applied to a clear base film with a thickness of 150 μm (6 mil) and dried to obtain a colored permeable membrane for color filter (IB). As for the chromaticity of the obtained colored permeable membrane for color filter (IB), the x value is 0.1474, the y value is 0.2183, the Y value is 29.49, and the light resistance is ΔE ^* value is 3.52. The heat resistance ΔE ^* value was 3.85. The transmittance at a wavelength of 460 nm was 91.2%, and the specific extinction coefficient ε _w (weight basis) at 610 nm was 2.38.

<Example 3-3: Production of transparent colored composition (IR) for color filter>
The transparent colored composition for color filter (IR) is the same as the transparent colored composition for color filter (IG) except that the transparent colored composition (R) is used as the transparent colored composition. Got.

The obtained transparent colored composition for color filter (IR) has a number-converted dispersed particle size of 31 nm, a volume-converted dispersed particle size of 40 nm, a viscosity of 16.3 mPa · s, and a viscosity change rate of 4.9. %, 550 nm ε _w (weight basis) was 2.14.

The transparent colored composition for color filter (IR) was applied to a clear base film with a thickness of 150 μm (6 mil) and dried to obtain a colored permeable membrane for color filter (IR). As for the chromaticity of the obtained colored permeable membrane for color filter (IR), the x value is 0.5845, the y value is 0.3404, the Y value is 23, and the 38 light resistance is ΔE ^* value 3.19. The heat resistance ΔE ^* value was 3.35. The transmittance at a wavelength of 620 nm was 96.8%, and the specific extinction coefficient ε _w (weight basis) at 550 nm was 2.16.

<Example 3-3: Production of transparent colored composition (I-Y) for color filter>
The transparent colored composition for color filter (I-Y) is the same as the transparent colored composition for color filter (IG) except that the transparent colored composition (Y) is used as the transparent colored composition. Got.

The obtained transparent coloring composition for color filter (I-Y) has a number-converted dispersed particle diameter of 48 nm, a volume-converted dispersed particle diameter of 72 nm, a viscosity of 17.1 mPa · s, and a viscosity change rate of 5.4. %, 400 nm ε _w (weight basis) was 2.19.

The transparent colored composition for color filter (I-Y) was applied to a clear base film with a thickness of 150 μm (6 mil) and dried to obtain a colored permeable membrane for color filter (IR). As for the chromaticity of the obtained colored transmission film for color filter (I-Y), the x value is 0.3460, the y value is 0.4954, the Y value is 74.82, the light resistance is ΔE ^* value is 5.36, The heat resistance ΔE ^* value was 5.59. The transmittance at a wavelength of 550 nm was 96.5%, and the specific extinction coefficient ε _w (on a weight basis) at 400 nm was 2.20.

<Example 4-1: Production of transparent coloring composition (II-G) for color filter>
500.0 parts by weight of the transparent coloring composition (IG) for color filter, 100.0 parts by weight of dipentaerythritol pentaacrylate, 2- (4-methoxy-β-styryl) -bis (4,6-trichloromethyl) ) -S-triazine (5.0 parts by weight) was mixed and dispersed using a bead mill for 2 hours, and the resulting kneaded product was filtered through a 1 μm glass filter to obtain a transparent colored composition (II-G) for a color filter. It was.

The obtained colored composition for color filter (II-G) has a number-converted dispersed particle size of 22 nm, a volume-converted dispersed particle size of 32 nm, a viscosity of 16.0 mPa · s, and a viscosity change rate of 4.1%. The specific extinction coefficient ε _w (weight basis) at 650 nm was 2.44.

The transparent colored composition for color filter (II-G) was applied to a clear base film with a thickness of 150 μm (6 mil) and dried to obtain a colored permeable membrane for color filter (II-G). As for the chromaticity of the obtained colored permeable membrane for color filters (II-G), the x value is 0.2770, the y value is 0.3891, the Y value is 70.87, and the light resistance is ΔE ^* value 3.40. The heat resistance ΔE ^* value was 3.59. The transmittance at a wavelength of 530 nm was 92.0%, and the specific extinction coefficient ε _w (weight basis) at 650 nm was 2.47.

<Example 4-2: Production of transparent colored composition (II-B) for color filter>
The transparent coloring composition for color filters was the same as the transparent coloring composition for color filters (II-G) except that the transparent coloring composition for color filters (IB) was used as the transparent coloring composition for color filters. A composition (II-B) was obtained.

The obtained transparent coloring composition for color filter (II-B) has a number-converted dispersed particle diameter of 23 nm, a volume-converted dispersed particle diameter of 35 nm, a viscosity of 15.8 mPa · s, and a viscosity change rate of 4.5. %, The specific extinction coefficient ε _w (weight basis) of 610 nm was 2.36.

The transparent colored composition for color filter (II-B) was applied to a clear base film with a thickness of 150 μm (6 mil) and dried to obtain a colored permeable membrane for color filter (II-B). As for the chromaticity of the obtained colored permeable membrane for color filter (II-B), the x value is 0.1472, the y value is 0.2180, the Y value is 29.51, and the light resistance is ΔE ^* value is 3.49. The heat resistance ΔE ^* value was 3.78. The transmittance at a wavelength of 460 nm was 91.4%, and the specific absorption coefficient ε _w (weight basis) at 610 nm was 2.39.

<Example 4-3: Production of transparent colored composition (II-R) for color filter>
The transparent coloring composition for color filters is the same as the transparent coloring composition for color filters (II-G) except that the transparent coloring composition for color filters (IR) is used as the transparent coloring composition for color filters. A composition (II-R) was obtained.

The obtained transparent coloring composition for color filter (II-R) has a number-converted dispersed particle diameter of 31 nm, a volume-converted dispersed particle diameter of 39 nm, a viscosity of 16.5 mPa · s, and a viscosity change rate of 4.7. %, 550 nm specific extinction coefficient ε _w (weight basis) was 2.15.

The transparent colored composition for color filter (II-R) was applied to a clear base film with a thickness of 150 μm (6 mil) and dried to obtain a colored permeable membrane for color filter (II-R). As for the chromaticity of the obtained colored permeable membrane for color filter (II-R), the x value is 0.5841, the y value is 0.3401, the Y value is 23.39, and the light resistance is ΔE ^* value is 3.15. The heat resistance ΔE ^* value was 3.30. The transmittance at a wavelength of 620 nm was 97.0%, and the specific extinction coefficient ε _w (weight basis) at 550 nm was 2.17.

<Example 4-4: Production of transparent colored composition (II-Y) for color filter>
The transparent coloring composition for color filters was the same as the transparent coloring composition for color filters (II-G) except that the transparent coloring composition for color filters (I-Y) was used as the transparent coloring composition for color filters. A composition (II-Y) was obtained.

The obtained transparent coloring composition for color filter (II-Y) has a number-converted dispersed particle size of 47 nm, a volume-converted dispersed particle size of 69 nm, a viscosity of 17.4 mPa · s, and a viscosity change rate of 5.2. %, The specific extinction coefficient ε _w (weight basis) of 400 nm was 2.19.

The transparent colored composition for color filter (II-Y) was applied to a clear base film at a thickness of 150 μm (6 mil) and dried to obtain a colored permeable membrane for color filter (II-Y). As for the chromaticity of the obtained colored permeable membrane for color filters (II-Y), the x value is 0.3462, the y value is 0.4951, the Y value is 74.85, and the light resistance is ΔE ^* value is 5.33. The heat resistance ΔE ^* value was 5.51. The transmittance at a wavelength of 550 nm was 96.8%, and the specific extinction coefficient ε _w (weight basis) at 400 nm was 2.21.

<Example 5-1: Production of transparent coloring composition (III-G) for color filter>
500.0 parts by weight of the transparent coloring composition for color filter (IG) and 5.0 parts by weight of p-phenylthiophenyldiphenylsulfonium trifluoroacetate are dispersed using a sand grinder, and the obtained kneaded product is 1 μm. The glass fiber filter was used to obtain a transparent colored composition (III-G) for a color filter.

The obtained transparent coloring composition for color filters (III-G) has a number-converted dispersed particle diameter of 22 nm, a volume-converted dispersed particle diameter of 33 nm, a viscosity of 15.8 mPa · s, and a viscosity change rate of 3.9. %, The specific extinction coefficient ε _w (weight basis) at 650 nm was 2.45.

The transparent colored composition for color filter (III-G) was applied to a clear base film with a thickness of 150 μm (6 mil) and dried to obtain a colored permeable membrane for color filter (III-G). As for the chromaticity of the obtained colored permeable membrane for color filters (III-G), the x value is 0.2769, the y value is 0.3888, the Y value is 70.85, and the light resistance is ΔE ^* value is 3.41. The heat resistance ΔE ^* value was 3.61. The transmittance at a wavelength of 530 nm was 91.9%, and the specific extinction coefficient ε _w (weight basis) at 650 nm was 2.46.

<Example 5-2: Production of transparent coloring composition (III-B) for color filter>
A transparent color filter composition is the same as the transparent colored composition for color filter (III-G) except that the transparent colored composition for color filter (IB) is used as the transparent colored composition for color filter. A colored composition (III-B) was obtained.

The obtained transparent coloring composition for color filter (III-B) has a number-converted dispersed particle diameter of 23 nm, a volume-converted dispersed particle diameter of 36 nm, a viscosity of 15.7 mPa · s, and a viscosity change rate of 4.3. %, The specific extinction coefficient ε _w (weight basis) of 610 nm was 2.37.

The transparent colored composition for color filter (III-B) was applied to a clear base film with a thickness of 150 μm (6 mil) and dried to obtain a colored permeable membrane for color filter (III-B). As for the chromaticity of the obtained colored permeable membrane for color filters (III-B), the x value is 0.1474, the y value is 0.2183, the Y value is 29.49, the light resistance is ΔE ^* is 3.50. The heat resistance ΔE ^* was 3.80. The transmittance at a wavelength of 460 nm was 91.2, and the specific extinction coefficient ε _w (weight basis) at 610 nm was 2.39.

<Example 5-3: Production of transparent coloring composition (III-R) for color filter>
The color filter transparent color composition is the same as the color filter transparent color composition (III-G) except that the color filter transparent color composition (IR) is used as the color filter transparent color composition. A colored composition (III-R) was obtained.

The obtained transparent coloring composition for color filter (III-R) has a number-converted dispersed particle diameter of 31 nm, a volume-converted dispersed particle diameter of 39 nm, a viscosity of 16.3 mPa · s, and a viscosity change rate of 4.6. %, 550 nm specific extinction coefficient ε _w (weight basis) was 2.17.

The transparent colored composition for color filter (III-R) was applied to a clear base film with a thickness of 150 μm (6 mil) and dried to obtain a colored permeable membrane for color filter (III-R). As for the chromaticity of the obtained colored permeable membrane for color filters (III-R), the x value is 0.5839, the y value is 0.3405, the Y value is 23.35, and the light resistance is ΔE ^* value is 3.17. The heat resistance ΔE ^* value was 3.34. The transmittance at a wavelength of 620 nm was 96.5%, and the specific extinction coefficient ε _w (weight basis) at 550 nm was 2.17.

<Example 5-3: Production of transparent coloring composition for color filter (III-Y)>
A transparent color filter composition is the same as the transparent colored composition for color filters (III-G) except that the transparent colored composition for color filters (I-Y) is used as the transparent colored composition for color filters. A colored composition (III-Y) was obtained.

The obtained transparent colored composition for color filter (III-Y) has a number-converted dispersed particle size of 48 nm, a volume-converted dispersed particle size of 71 nm, a viscosity of 17.1 mPa · s, and a viscosity change rate of 5.1. %, The specific extinction coefficient ε _w (weight basis) of 400 nm was 2.20.

The transparent colored composition for color filter (III-Y) was applied to a clear base film with a thickness of 150 μm (6 mil) and dried to obtain a colored permeable membrane for color filter (III-Y). As for the chromaticity of the obtained colored permeable membrane for color filters (III-Y), the x value is 0.3465, the y value is 0.4949, the Y value is 74.82, and the light resistance is ΔE ^* value is 5.35. The heat resistance ΔE ^* value was 5.57. The transmittance at a wavelength of 550 nm was 95.6, and the specific extinction coefficient ε _w (weight basis) at 400 nm was 2.20.

<Example 6-1: Production of color filter (I)>
The transparent coloring composition for color filter (IG) was spin-coated on a non-alkali glass substrate (thickness 0.7 mm) on which a resin black matrix pattern with a thickness of 1.0 μm was formed, and the coating was performed at 90 ° C. for 4 minutes. After pre-baking using a hot plate, a positive photoresist was applied on this film and dried by heating at 80 ° C. for 20 minutes to obtain a resist film. Using an ultrahigh pressure mercury lamp 2.50 kW, exposure was performed with a light amount of 400 mJ / cm ² . Subsequently, after developing with sodium carbonate aqueous solution, the unnecessary photoresist layer was peeled off with methyl cellosolve acetate. Furthermore, the obtained colored film was heat-treated at 250 ° C. for 30 minutes in a nitrogen atmosphere to obtain a green colored film pattern.

  Then, similarly, the pattern of each colored film was formed using the transparent coloring composition for color filters (IB) and the transparent coloring composition for color filters (IR).

  The transmittance of the obtained color filter (I) was 91.9% at a wavelength of 530 nm, 91.2% at a wavelength of 460 nm, 96.8% at a wavelength of 620 nm, and the contrast was 1750.

<Preparation of color filter (II)>
As the transparent coloring composition for color filters, the transparent coloring composition for color filters (II-G), the transparent coloring composition for color filters (II-B), and the transparent coloring composition for color filters (II-R) were used. Except for the above, color filter (II) was obtained in the same manner as color filter (I).

  The transmittance of the obtained color filter (II) was 92.0% at a wavelength of 530 nm, 91.4% at a wavelength of 460 nm, 97.0% at a wavelength of 620 nm, and the contrast was 1790.

<Preparation of color filter (III)>
As the transparent coloring composition for color filters, the transparent coloring composition for color filters (III-G), the transparent coloring composition for color filters (III-B), and the transparent coloring composition for color filters (III-R) were used. Except for the above, color filter (III) was obtained in the same manner as color filter (II).

  The transmittance of the obtained color filter (III) was 91.9% at a wavelength of 530 nm, 91.2% at a wavelength of 460 nm, 96.5% at a wavelength of 620 nm, and the contrast was 1730.

  According to the composite particle 1 and Examples 1-1 to 6-1, composite particle powder, colored fine particles, colored fine colorant, transparent coloring composition, transparent coloring composition for color filter, and color filter were prepared. Various characteristics of each production condition and the obtained composite particle powder, colored fine composite coloring material, transparent coloring composition, transparent coloring composition for color filter and color filter are shown.

Silica 1-4:
As the core particles, silica particle powders 1 to 3 having the characteristics shown in Table 1 were prepared.

Organic pigments G, B, R, Y:
An organic pigment having the characteristics shown in Table 2 was prepared as the organic pigment.

<Manufacture of composite particle powder>
Composite particles 2-4:
Type of core particles, type and addition amount of surface modifier, line load and time for edge runner treatment in coating process of surface modifier, type of organic pigment in addition process of organic pigment, addition amount, edge runner treatment A composite particle powder was obtained in the same manner as the composite particle 1 except that the line load and time were variously changed.

  The production conditions at this time are shown in Table 3, and various characteristics of the obtained composite particle powder are shown in Table 4.

<Manufacture of colored fine particles>
Colored fine particles 2-4:
Colored fine particles were obtained in the same manner as the colored fine particles 1 except that the type of composite particles, the pH of the solution at the time of alkali dissolution, the theoretical amount of alkali to be added, and the treatment temperature were variously changed. The concentration (g / 100 ml) of the composite particle powder is the weight (g) of the composite particle powder with respect to 100 ml of the solution.

  Table 5 shows the manufacturing conditions at this time, and Table 6 shows the characteristics of the colored fine particles obtained.

<Manufacture of colored micro colorants>
Examples 1-2 to 1-4:
A colored micro colorant was obtained in the same manner as in Example 1-1 except that the type of colored fine particles and the type of dispersant were variously changed.

  Table 7 shows the manufacturing conditions at this time, and Table 8 shows the characteristics of the obtained colored micro colorant.

Comparative Example 1-1 (Japanese Patent Laid-Open No. 2006-091649 Example 1 Additional Test):
4 parts of acicular dioxazine violet pigment prepared by acid slurry treatment, organic pigment B (type: phthalocyanine pigment, average primary particle size: 80 nm, number conversion average particle size: 246 nm, volume conversion average particle size: 724 nm, BET specific surface area value: 87.9 m ² / g, L ^* value: 23.04, a ^* value: 5.99, b ^* value: −13.16, C ^* value: 14.46, dispersant adsorption amount: 0.14 mg / m ² , light resistance ΔE ^* value: 8.83, heat resistance ΔE ^* value: 9.04) 36 parts, 400 parts of crushed sodium chloride, 80 parts of diethylene glycol were charged into a double-arm kneader, After kneading at 110 ° C. for 8 hours, the mixture is taken out in 100 parts of 1% aqueous hydrochloric acid solution at 80 ° C., stirred for 1 hour, filtered, washed with hot water, dried, crushed, and phthalocyanine blue face It was obtained.

Comparative Example 1-2:
Organic pigment G (type: phthalocyanine pigment, average primary particle size: 100 nm, number-converted average particle size: 319 nm, volume-converted average particle size: 813 nm, BET specific surface area value: 67.3 m ² / g, L ^* value: 29 .77, a ^* value: -15.30, b ^* value: -1.12, C ^* value: 15.34, dispersant adsorption amount: 0.26 mg / m ² , light resistance E ^* value: 8.06 , Heat resistance ΔE ^* value: 7.46) 36 parts, 400 parts of crushed sodium chloride, 80 parts of diethylene glycol were charged into a double arm kneader, kneaded at 100-110 ° C. for 8 hours, and then 1% hydrochloric acid at 80 ° C. The mixture was taken out in 100 parts of an aqueous solution, stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a phthalocyanine green pigment.

Comparative Example 1-3:
Organic pigment R (type: diketopyrrolopyrrole pigment, average primary particle size: 130 nm, number-converted average particle size: 398 nm, volume-converted average particle size: 948 nm, BET specific surface area value: 82.4 m ² / g, L ^* Value: 38.42, a ^* value: 43.20, b ^* value: 23.36, C ^* value: 49.11, dispersant adsorption amount: 0.33 mg / m ² , light resistance ΔE ^* value: 7. 92, heat resistance ΔE ^* value: 7.28) 36 parts, 400 parts of crushed sodium chloride, 80 parts of diethylene glycol were charged into a double arm kneader, kneaded at 100-110 ° C. for 8 hours, and then 1% of 80 ° C. The mixture was taken out in 100 parts of an aqueous hydrochloric acid solution, stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a diketopyrrolopyrrole pigment.

Comparative Example 1-4:
Organic pigment Y (type: quinophthalone pigment, average primary particle size: 252 nm, number-converted average particle size: 744 nm, volume-converted average particle size: 1746 nm, BET specific surface area value: 27.9 m ² / g, L ^* value: 84 .21, a ^* value: 3.00, b ^* value: 91.31, C ^* value: 91.36, dispersant adsorption amount: 0.11 mg / m ² , light resistance ΔE ^* value: 7.22, heat resistance Property ΔE ^* value: 8.84) 36 parts, 400 parts of crushed sodium chloride and 80 parts of diethylene glycol were charged into a double-arm kneader, kneaded at 100 to 110 ° C. for 8 hours, and then 1% aqueous hydrochloric acid solution at 80 ° C. 100 The mixture was taken out into the part, stirred for 1 hour, filtered, washed with hot water, dried and pulverized to obtain a quinophthalone pigment.

  Table 8 shows properties of the obtained phthalocyanine blue pigment, phthalocyanine green pigment, diketopyrrolopyrrole pigment, and quinophthalone pigment.

<Transparent coloring composition>
Examples 2-2 to 2-4, comparative examples 2-1 to 2-16:
A transparent colored composition was obtained in the same manner as in Example 2-1, except that the type of the color pigment was changed.

  The production conditions at this time are shown in Table 9, and the properties of the transparent colored composition obtained are shown in Table 10.

<Transparent coloring composition for color filter (I)>
Examples 3-2 to 3-4, Comparative examples 3-1 to 3-16:
A transparent colored composition (I) for a color filter was obtained in the same manner as in Example 3-1, except that the type of the transparent colored composition was changed.

  The production conditions at this time are shown in Table 11, the properties of the transparent colored composition for color filter (I) obtained are shown in Table 12, and the color filter obtained by applying the transparent colored composition for color filter (I) Table 13 shows the physical properties of the colored permeable membrane (I).

<Transparent coloring composition for color filter (II)>
Examples 4-2 to 4-4, Comparative Examples 4-1 to 4-16:
A transparent colored composition for color filter (II) was obtained in the same manner as in Example 4-1, except that the type of the transparent colored composition for color filter (I) was changed.

  The production conditions at this time are shown in Table 14, the properties of the transparent colored composition (II) for color filter obtained are shown in Table 15, and the color filter obtained by applying the transparent colored composition (II) for color filter. Table 16 shows the physical properties of the colored permeable membrane (II).

<Transparent coloring composition for color filter (III)>
Examples 5-2 to 5-4, comparative examples 5-1 to 5-16:
A transparent colored composition for color filter (III) was obtained in the same manner as in Example 5-1, except that the type of transparent colored composition for color filter (I) was variously changed.

  The production conditions at this time are shown in Table 17, the characteristics of the obtained transparent colored composition for color filter (III) are shown in Table 18, and the color filter obtained by applying the transparent colored composition for color filter (III) Table 19 shows the physical properties of the colored permeable membrane (III) for use.

<Color filter>
Comparative Examples 6-1, 6-4, 6-7, 6-10:
A color filter (I) was obtained in the same manner as in Example 6-1 except that the type of the transparent coloring composition for color filter was changed.

  Table 20 shows the manufacturing conditions and various characteristics of the obtained color filter.

Comparative Examples 6-2, 6-5, 6-8, 6-11:
A color filter (II) was obtained in the same manner as in Example 6-2 except that the transparent coloring composition for color filter was changed.

  Table 20 shows the manufacturing conditions and various characteristics of the obtained color filter.

Comparative Examples 6-3, 6-6, 6-9, 6-12:
A color filter (III) was obtained in the same manner as in Example 6-3 except that the transparent coloring composition for color filter was used.

  Table 20 shows the manufacturing conditions and various characteristics of the obtained color filter.

The primary particle size is very small, it has excellent dispersibility even in vehicles with high coloring power and high pigment concentration, and it has excellent light resistance and heat resistance, as well as excellent light resistance and heat resistance. Therefore, it is suitable as a transparent coloring composition for a color filter having high coloring power and excellent transparency.

Claims (7)

A colored fine colorant having a primary particle size of 50 nm or less, and the amount of the dispersant adsorbed on the colored fine colorant is 1.0 to 5.0 mg / m ² , and the silica contained in the colored fine colorant The colored micro colorant is characterized by being 0 to 9% by weight in terms of Si with respect to the color micro colorant. A colored fine colorant obtained by surface-treating a colored fine particle powder with a dispersant. The transparent coloring composition formed by disperse | distributing the colored micro coloring material of Claim 1 or Claim 2 to the solvent. A transparent coloring composition for a color filter, wherein the transparent coloring composition according to claim 3 is dispersed in a transparent resin solution having at least one acidic group and / or latent acidic group. The transparent coloring composition for a color filter according to claim 4, wherein the transparent coloring composition for a color filter is provided with photosensitivity containing a photo-radical polymerization initiator and a polyfunctional monomer having two or more ethylenically unsaturated double bonds. Composition. The transparent colored composition for a color filter, wherein the transparent colored composition for a color filter according to claim 4 contains a photoacid generator. The color filter obtained from the coating-film formation thing of the transparent coloring composition for color filters in any one of Claims 4 thru | or 6.