JP2010180386A - Method for producing organic pigment nanoparticle, organic pigment nanoparticle obtained thereby, pigment dispersion, colored photosensitive resin composition, inkjet ink for color filter, and photosensitive resin transfer material containing the same, and color filter and liquid crystal display obtained using them - Google Patents

Abstract

The present invention provides a method capable of producing organic pigment fine particles refined to a nanometer size extremely efficiently and in large quantities.
A step of preparing a dispersion A in which an organic pigment is precipitated as fine particles, a step of preparing a dispersion B in which a low molecular weight organic material is precipitated as fine particles, and the dispersion A and the dispersion B are provided. And a step of passing through a state in which the solubility of the low molecular weight organic material in the mixed solution becomes higher than the solubility of the organic pigment.
[Selection figure] None

Description

  The present invention relates to a method for producing organic pigment nanoparticles, organic pigment nanoparticles obtained thereby, pigment dispersion containing the same, colored photosensitive resin composition, inkjet ink for color filter, and photosensitive resin transfer material, and The present invention relates to a color filter and a liquid crystal display device using them.

  In recent years, the quality of image-related precision equipment such as a color image sensor and a color liquid crystal display device has been rapidly improved and its application has been rapidly expanded. Reflecting this, there has been a strong demand for high-quality display performance for color filters. As for the color material of the color filter, an organic pigment has been used instead of a dye, and recently, pigment nanoparticles having a nanometer size level and being monodispersed and stable have been demanded. And the manufacturing method of the novel color filter using an inkjet technique is examined. As a result, a significant improvement in design freedom and a significant reduction in cost are expected, but there is still no dispersion of pigment nanoparticles suitable for this and capable of exhibiting sufficient performance.

Here, regarding the method for producing organic pigment particles, breakdown methods such as a bead mill method and a salt milling method are common. In the milling method, it takes a lot of time and energy to sufficiently refine the organic pigment and disperse it in the composition. Also, the types of pigment that can be used are limited. As the pigment becomes finer, the dispersion composition may exhibit high viscosity, and in some cases, the dispersion composition may gel during storage and become unusable.
On the other hand, recently, a method for producing a pigment dispersion composition having high dispersion safety by a liquid phase method has been developed. The liquid phase method is suitable for obtaining fine pigment particles. Specifically, a method is disclosed in which a pigment solution and a poor solvent are mixed to precipitate nanoparticles, and a predetermined polymer compound is added. (See Patent Documents 1 to 3). However, the dispersion stability of the pigment dispersion obtained by these methods is still not sufficient when considering application to the above-mentioned image-related precision equipment and other high-performance precision equipment.

International Publication No. WO2006 / 121016 Pamphlet JP 2004-43776 A JP 2007-119586 A

  An object of the present invention is to provide a method capable of producing organic pigment fine particles refined to a nanometer size extremely efficiently and in large quantities, and further, the obtained organic pigment nanoparticles are dispersed over a long period of time in a dispersion. An object is to provide a method for producing organic pigment nanoparticles capable of imparting dispersion stability, organic pigment nanoparticles obtained thereby, and a pigment dispersion containing the same. In addition, an inkjet ink using the organic pigment nanoparticles or a pigment dispersion containing the organic pigment nanoparticles, a colored photosensitive resin composition, a photosensitive resin transfer material, and a color filter having a high contrast and produced using the same. An object of the present invention is to provide a liquid crystal display device including the same.

The above problems have been achieved by the following means.
(1) Mixing an organic pigment solution obtained by dissolving an organic pigment in a first good solvent and a first poor solvent that is compatible with the first good solvent and that is a poor solvent for the organic pigment. And preparing a dispersion A in which the organic pigment is precipitated as fine particles, an organic material solution in which a low molecular organic material is dissolved in a second good solvent and containing a polymer compound, and the second good A step of preparing a dispersion B in which a low-molecular-weight organic material is mixed with a second poor solvent that is a poor solvent for the low-molecular-weight organic material and the low-molecular-weight organic material is precipitated as fine particles; After mixing the dispersion liquid A and the dispersion liquid B, the organic pigment nanoparticles have a step of passing through a state in which the solubility of the low molecular weight organic material in the mixture liquid is higher than the solubility of the organic pigment Manufacturing method.
(2) In the step of mixing the dispersion A and the dispersion B, maintaining the mixed state of the mixture, adjusting the temperature, adjusting the pressure, adjusting the amount of solvent, adjusting the pH, or a combination thereof (1) The method for producing organic pigment nanoparticles according to (1).
(3) The organic pigment nano described in (1) or (2), wherein the low molecular organic material is selected from the group consisting of organic pigments, organic dyes, aromatic hydrocarbons, and aliphatic hydrocarbons. Particle production method.
(4) The method for producing organic pigment nanoparticles according to any one of (1) to (3), wherein the polymer compound has a mass average molecular weight of 1,000 to 500,000.
(5) The polymer compound is at least one selected from the group consisting of a vinyl monomer polymer, a vinyl monomer copolymer, an ester polymer, an ether polymer, a modified product thereof, and a copolymer thereof. It is a high molecular compound, The manufacturing method of the organic pigment nanoparticle of any one of (1)-(4) characterized by the above-mentioned.
(6) Organic pigment nanoparticles characterized by removing the solvent from the dispersion containing the organic pigment nanoparticles prepared by the method according to any one of (1) to (5) and pulverizing .
(7) A pigment dispersion comprising organic pigment nanoparticles prepared by the method according to any one of (1) to (5).
(8) A colored photosensitive resin composition comprising the pigment dispersion described in (7), a binder, a monomer or an oligomer, and a photopolymerization initiator or a photopolymerization initiator system.
(9) An ink-jet ink for a color filter comprising the pigment dispersion described in (7), a binder, and a monomer or oligomer.
(10) A photosensitive resin transfer material, wherein a photosensitive resin layer containing at least the colored photosensitive resin composition according to (8) is provided on a temporary support.
(11) A colored photosensitive resin composition described in (8), an inkjet ink for a color filter described in (9), and / or a photosensitive resin transfer material described in (10). Color filter.
(12) A liquid crystal display device comprising the color filter according to (11).

  According to the production method of the present invention, organic pigment fine particles refined to a nanometer size can be produced extremely efficiently and in large quantities, and further, the obtained organic pigment nanoparticles can be dispersed in a dispersion for a long period of time. It can give a high dispersion stability. Further, the organic pigment nanoparticles obtained by the above production method or the pigment dispersion containing the organic pigment nanoparticles are preferably used as a color material for an ink-jet ink for a color filter, a colored photosensitive resin composition, and a photosensitive resin transfer material. As a result, a color filter having high contrast and high display quality can be produced, and a high-performance liquid crystal display device including the same can be provided.

Hereinafter, the present invention will be described in detail.
The kind of the organic pigment used in the production method of the present invention is not limited in terms of hue. For example, perylene compound pigment, perinone compound pigment, quinacridone compound pigment, quinacridone quinone compound pigment, anthraquinone compound pigment, anthanthrone compound Pigment, benzimidazolone compound pigment, disazo condensation compound pigment, disazo compound pigment, azo compound pigment, indanthrone compound pigment, phthalocyanine compound pigment, triarylcarbonium compound pigment, dioxazine compound pigment, aminoanthraquinone compound pigment, diketopyrrolopyrrole Compound pigments, thioindigo compound pigments, isoindoline compound pigments, isoindolinone compound pigments, pyranthrone compound pigments, isoviolanthrone compound pigments, and mixtures thereof.

  Among these, a perylene compound pigment, a quinacridone compound pigment, an anthraquinone compound pigment, a diketopyrrolopyrrole compound pigment, an aminoanthraquinone compound pigment, a dioxazine compound pigment, a phthalocyanine compound pigment, or an azo compound pigment is preferable, and a diketopyrrolopyrrole compound More preferred are pigments, aminoanthraquinone compound pigments, phthalocyanine compound pigments, dioxazine compound pigments, or azo compound pigments.

  In the production method of the present invention, two or more kinds of organic pigments or solid solutions of organic pigments may be used in combination, or may be used in combination with organic dyes.

  The low molecular weight organic material used in the method for producing organic nanoparticles of the present invention is not particularly limited as long as particles can be formed by a reprecipitation method. For example, organic pigments, organic dyes, aromatic hydrocarbons or aliphatic carbonizations are used. And particles composed of hydrogen (for example, oriented aromatic hydrocarbons or aliphatic hydrocarbons, or sublimable aromatic hydrocarbons or aliphatic hydrocarbons), organic pigments, organic dyes are preferred, Pigments are particularly preferred. The molecular weight of the low molecular weight organic material is preferably 1000 or less, and particularly preferably 100 or more and 700 or less.

  The amount of the low molecular weight organic material used is not particularly limited, but when the dispersion A and the dispersion B are mixed, it is preferably in the range of 0.1 to 500% by mass with respect to the organic pigment. The range of 1 to 100% by mass is more preferable, and the range of 0.1 to 20% by mass is particularly preferable. When the amount is less than the above range, sufficient fine dispersibility cannot be imparted to the produced organic pigment nanoparticle dispersion. On the other hand, when the amount is more than the above range, the produced organic pigment nanoparticle dispersion may be gelled or a desired color tone may not be obtained.

  The polymer compound used in the present invention is contained in a solution in which a low-molecular organic material is dissolved in a second good solvent. At this time, even if the polymer compound is dissolved, it is in a dispersed state. Or other mixed state. However, it is preferable that the polymer compound is in a state dissolved in the second good solvent, so that the low molecular organic material and the polymer compound are mixed together with the second poor solvent as described later. It can be precipitated and can be made into uniform fine particles. From this point of view, the polymer compound is preferably soluble in the second good solvent, and is insoluble in the second poor solvent (that is, the second solvent becomes the poor solvent). ) Is preferable. Among them, when the low molecular organic material is precipitated by mixing the low molecular organic material solution and the second poor solvent, the high molecular compound quickly adsorbs to the deposited low molecular organic material. It is preferable. Here, in the present invention, when the solubility of the compound in the solvent is less than 2.0% by mass, the compound is defined as insoluble in the solvent, and is preferably 0.02% by mass or less. More preferably, it is 0.01 mass% or less.

  Although the mass mean molecular weight of the said high molecular compound is not specifically limited, It is preferable that it is 1000-500000, It is more preferable that it is 2000-300000, It is especially preferable that it is 3000-200000. The shape of the polymer compound may be linear or branched (for example, graft, star shape, etc.). Moreover, when a polymer is a copolymer, any of a random copolymer, an alternating copolymer, and a block copolymer may be sufficient. In the present invention, the molecular weight means a mass average molecular weight unless otherwise specified, and the mass average molecular weight (Mw) is a polystyrene equivalent mass average molecular weight measured by gel permeation chromatography (carrier: tetrahydrofuran).

  The polymer compound is not particularly limited, but a vinyl monomer polymer or copolymer (for example, an alkyl methacrylate homopolymer, a styrene homopolymer, an alkyl methacrylate / styrene copolymer), Polyvinyl butyral, etc.), ester polymers (eg, polycaprolactone), ether polymers (eg, polytetramethylene oxide), urethane polymers (eg, polyurethane made of tetramethylene glycol and hexamethylene diisocyanate), amides Polymer (for example, polyamide 6, polyamide 66, etc.), silicone-based polymer (for example, polydimethylsiloxane), carbonate-based polymer (for example, polycarbonate synthesized from bisphenol A and phosgene) And the like.

  Among these, the polymer compound is selected from the group consisting of a vinyl monomer polymer, a vinyl monomer copolymer, an ester polymer, an ether polymer, a modified product thereof, and a copolymer thereof. High molecular compounds are preferred. From the viewpoints of adjusting solubility in a solvent, cost, ease of synthesis, and the like, the polymer compound is particularly preferably a vinyl monomer polymer or copolymer.

  Although it does not restrict | limit especially as said vinyl monomer, For example, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides Styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile and the like are preferable examples.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (Meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid t-octyl, (meth) acrylic acid dodecyl, (meth) acrylic acid octadecyl, (meth) acrylic acid acetoxyethyl, (meth) acrylic acid phenyl, (meth) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, (meth 3-hydroxypropyl acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) (meth) acrylate Ethyl, 3-methoxy-2-hydroxypropyl (meth) acrylate, 2-chloroethyl (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, (meth) acrylic acid Vinyl, 2-phenylvinyl (meth) acrylate, 1-propenyl (meth) acrylate, allyl (meth) acrylate, 2-allyloxyethyl (meth) acrylate, propargyl (meth) acrylate, (meth) acrylic Benzyl acid, (meth) acrylic acid diethylene glycol monomethyl ether (Meth) acrylic acid diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol Monoethyl ether, β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, (meth) acrylic acid Trifluoroethyl, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, (meth) acrylic Tribromophenyl, (meth) tribromophenyl oxyethyl acrylate, and (meth) acrylic acid γ- butyrolactone.

  Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.

  Examples of vinyl esters include vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.

  Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

  Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

  Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. (Meth) acrylamide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N- Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, N-methylo Acrylamide, N- hydroxyethyl acrylamide, vinyl (meth) acrylamide, N, N- diallyl (meth) acrylamide, such as N- allyl (meth) acrylamide.

  Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.

  Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether, and phenyl vinyl ether.

  Examples of vinyl ketones include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.

  Examples of olefins include ethylene, propylene, isobutylene, butadiene, isoprene and the like.

  Examples of maleimides include maleimide, butyl maleimide, cyclohexyl maleimide, and phenyl maleimide.

  (Meth) acrylonitrile, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, vinylcaprolactone and the like can also be used.

  In addition to the above, preferred examples of the vinyl monomer include a vinyl monomer having an acidic group, a vinyl monomer having a basic group, and a monomer having an organic dye structure or a heterocyclic structure.

  Examples of the vinyl monomer having an acidic group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, and cinnamic acid. And acrylic acid dimer. Further, an addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, (meth) acrylic acid ω- Carboxy-polycaprolactone can also be used. Examples of the carboxyl group precursor include anhydride-containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride. Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid, and examples of the vinyl monomer having a phosphoric acid group include phosphoric acid mono (2-acryloyloxyethyl ester) and phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester) and the like.

  As a monomer having a basic nitrogen atom, (meth) acrylic acid ester, (meth) acrylic acid N, N-dimethylaminoethyl, (meth) acrylic acid N, N-dimethylaminopropyl, (meth) acrylic acid 1- (N, N-dimethylamino) -1,1-dimethylmethyl, (meth) acrylic acid N, N-dimethylaminohexyl, (meth) acrylic acid N, N-diethylaminoethyl, (meth) acrylic acid N, N- Diisopropylaminoethyl, N, N-di-n-butylaminoethyl (meth) acrylate, N, N-di-i-butylaminoethyl (meth) acrylate, morpholinoethyl (meth) acrylate, (meth) acryl Piperidinoethyl acid, 1-pyrrolidinoethyl (meth) acrylate, N, N-methyl-2-pyrrolidyl (meth) acrylate And (meth) acrylamides include N- (N ′, N′-dimethylaminoethyl) acrylamide, N- (N ′, N ′), and the like. -Dimethylaminoethyl) methacrylamide, N- (N ', N'-diethylaminoethyl) acrylamide, N- (N', N'-diethylaminoethyl) methacrylamide, N- (N ', N'-dimethylaminopropyl) Acrylamide, N- (N ′, N′-dimethylaminopropyl) methacrylamide, N- (N ′, N′-diethylaminopropyl) acrylamide, N- (N ′, N′-diethylaminopropyl) methacrylamide, 2- ( N, N-dimethylamino) ethyl (meth) acrylamide, 2- (N, N-diethylamino) Ethyl (meth) acrylamide, 3- (N, N-diethylamino) propyl (meth) acrylamide, 3- (N, N-dimethylamino) propyl (meth) acrylamide, 1- (N, N-dimethylamino) -1, Examples thereof include 1-dimethylmethyl (meth) acrylamide and 6- (N, N-diethylamino) hexyl (meth) acrylamide, morpholino (meth) acrylamide, piperidino (meth) acrylamide, N-methyl-2-pyrrolidyl (meth) acrylamide and the like. Examples of styrenes include N, N-dimethylaminostyrene and N, N-dimethylaminomethylstyrene.

  Examples of the monomer having an organic dye structure or a heterocyclic structure include, for example, phthalocyanine series, insoluble azo series, azo lake series, anthraquinone series, quinacridone series, dioxazine series, diketopyrrolopyrrole series, anthrapyridine series, ansanthrone series, Ron, flavanthrone, perinone, perylene, and thioindigo dye structures such as thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadi Azole, triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolino , Mention may be made of benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, a monomer having a heterocyclic structure anthraquinone.

  Further, a polymerizable oligomer having an ethylenically unsaturated bond at the terminal (hereinafter sometimes referred to as a macromonomer) may be used. Here, the polymerizable oligomer is composed of a polymer chain portion and a polymerizable functional group portion having an ethylenically unsaturated double bond at its terminal. The polymer chain portion is a homopolymer or copolymer formed from at least one monomer selected from the group consisting of alkyl (meth) acrylate, styrene and derivatives thereof, acrylonitrile, vinyl acetate and butadiene, or polyethylene oxide. Polypropylene oxide and polycaprolactone are generally used. The group having an ethylenically unsaturated double bond is preferably a (meth) acryloyl group.

Moreover, it is preferable that this macromonomer has the number average molecular weight (Mn) of polystyrene conversion in the range of 1000-10000, and the range of 2000-9000 is especially preferable.
Preferable examples of the macromonomer include polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and poly-i-butyl (meth) acrylate, and a (meth) acryloyl group bonded to one molecular terminal of polystyrene. Mention may be made of polymers. As such polymerizable oligomers available on the market, one-end methacryloylated polystyrene oligomer (Mn = 6000, trade name: AS-6, manufactured by Toagosei Chemical Co., Ltd.), one-end methacryloylated polymethyl methacrylate oligomer ( Mn = 6000, trade name: AA-6, manufactured by Toa Gosei Chemical Co., Ltd.) and one-terminal methacryloylated poly-n-butyl acrylate oligomer (Mn = 6000, trade name: AB-6, Toa Gosei Chemical Co., Ltd.) ) Made).

  For the production of a polymer or copolymer of vinyl monomers, for example, a radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing a vinyl monomer polymer or copolymer by radical polymerization can be easily set by those skilled in the art. The conditions can also be determined experimentally.

  The polymer or copolymer of the vinyl monomer may be a polymer compound having a functional group at the terminal. The functional group is preferably a functional group excellent in adsorbability to the deposited pigment.

  The polymer compound having a functional group at the terminal can be polymerized using, for example, a method of performing radical polymerization using a chain transfer agent containing a functional group, or a polymerization initiator containing a functional group (eg, radical polymerization, cationic polymerization). , Anionic polymerization, etc.).

  Examples of the chain transfer agent capable of introducing a functional group at the terminal of the polymer compound include mercapto compounds (for example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mecaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto- 2-propanol, 3-mercapto-2- (Tanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol, benzenethiol, toluenethiol, mercaptoacetophenone, naphthalenethiol, naphthalenemethanethiol, etc.) or oxidized products of these mercapto compounds Examples thereof include disulfide compounds and halogen compounds (for example, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.).

  Examples of the polymerization initiator capable of introducing a functional group at the terminal of the polymer compound include 2,2′-azobis (2-cyanopropanol), 2,2′-azobis (2-cyanopentanol), 4, 4'-azobis (4-cyanovaleric acid), 4,4'-azobis (4-cyanovaleric acid chloride), 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane ], 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] 2,2′-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane}, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -Propionamide] etc. And derivatives thereof.

  The amount of the polymer compound used is not particularly limited, but when the dispersion A and the dispersion B are mixed, it is preferably in the range of 0.1 to 1000% by mass with respect to the organic pigment, A range of 500% by mass is more preferable, and a range of 0.1 to 100% by mass is particularly preferable. When the amount is less than the above range, sufficient fine dispersibility cannot be imparted to the produced organic pigment nanoparticle dispersion. On the other hand, when the amount is more than the above range, the produced organic pigment nanoparticle dispersion may be gelled.

  The polymer compound may coexist with an organic compound having a basic group or an acidic group in the above-mentioned low molecular organic material solution, but a nitrogen-containing polymer compound and a polymer compound having an acidic group are used in combination. Therefore, it is preferable not to coexist. If the two types of compounds are used in combination, the organic pigment fine particles may easily aggregate due to the interaction between the nitrogen atom of the nitrogen-containing polymer compound and the acidic group of the polymer compound having an acidic group. In some cases, the contrast may decrease when a color filter is used. Further, when the polymer compound contains a nitrogen-containing polymer compound, it is preferable not to allow a compound having a basic nitrogen atom to coexist in the pigment solution. If this is coexisted, the color filter may be colored by baking.

In the present invention, first, a solution in which an organic pigment and a low molecular weight organic material are dissolved in respective good solvents (first good solvent, second good solvent) and compatibility with the good solvent, the organic pigment And an organic pigment obtained by mixing a low-molecular organic material with a solvent that is a poor solvent (a first poor solvent and a second poor solvent) to produce an organic pigment and a low-molecular organic material as nano-sized fine particles Nanoparticle dispersions (Dispersion A, Dispersion B) are prepared.
Here, the combination of the good solvent and the poor solvent needs to have a sufficient difference in the solubility of the organic pigment, and it is necessary to select a preferable one according to the organic pigment, but enables the process in the present invention. Any combination is possible.

  The good solvent is not particularly limited as long as it can dissolve the organic pigment or the low molecular weight organic material to be used, and is compatible with or uniformly mixed with the poor solvent. The solubility of the organic pigment or low molecular organic material in a good solvent is preferably such that the solubility of the organic pigment is 0.2% by mass or more, and more preferably 0.5% by mass or more. There is no particular upper limit to the solubility of the organic pigment or low molecular organic material in a good solvent, but it is practical that it is 50% by mass or less in consideration of a commonly used organic pigment or low molecular organic material. This solubility may be the solubility when dissolved in the presence of an acid or alkali.

  Examples of the good solvent include an aqueous solvent (for example, water or hydrochloric acid, an aqueous sodium hydroxide solution), an alcohol compound solvent, an amide compound solvent, a ketone compound solvent, an ether compound solvent, an aromatic compound solvent, a carbon disulfide solvent, and a fat. Group compound solvents, nitrile compound solvents, sulfoxide compound solvents, halogen compound solvents, ester compound solvents, ionic liquids, mixed solvents thereof, and the like, aqueous solvents, alcohol compound solvents, ketone compound solvents, ether compound solvents, sulfoxide compounds Solvents, ester compound solvents, amide compound solvents, or mixtures thereof are preferred, aqueous solvents, alcohol compound solvents, ester compound solvents, sulfoxide compound solvents or amide compound solvents are preferred, aqueous solvents, sulfoxide compound solvents or amide compounds. More preferably medium, sulfoxide compound solvent or the amide compound solvent is particularly preferred.

  Examples of the sulfoxide compound solvent include dimethyl sulfoxide, diethyl sulfoxide, hexamethylene sulfoxide, sulfolane and the like. Examples of the amide compound solvent include N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ε-caprolactam, formamide, N -Methylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide and the like.

The concentration of the solution in which the organic pigment or the low molecular weight organic material is dissolved in the good solvent is preferably a saturation concentration of the organic pigment or the low molecular weight organic material in the good solvent or a range of about 1/100 of this. .
There are no particular limitations on the conditions for preparing the organic pigment solution or the low molecular weight organic material, and a range from normal pressure to subcritical and supercritical conditions can be selected. The temperature at normal pressure is preferably −10 to 150 ° C., more preferably −5 to 130 ° C., and particularly preferably 0 to 100 ° C.

  Although there are things common between those listed as specific examples of good solvents and those listed as poor solvents, the same thing as a good solvent and a poor solvent is not combined, and each organic pigment or low molecular organic material to be adopted Therefore, the solubility in the good solvent should be sufficiently higher than the solubility in the poor solvent. For example, the solubility difference is preferably 0.2% by mass or more, more preferably 0.5% by mass or more. Although there is no particular upper limit on the difference in solubility between the good solvent and the poor solvent, it is practical that it is 50% by mass or less in consideration of a commonly used organic pigment or low molecular organic material.

  When the organic pigment or the low molecular weight organic material is uniformly dissolved in a good solvent, a dissolution accelerator such as acid or alkali may be added and dissolved. Generally, in the case of pigments or low molecular weight organic materials having an alkaline dissociable group in the molecule, the addition of alkali does not have an alkaline dissociable group, and the molecule has many nitrogen atoms and the like that are prone to add protons. Sometimes addition of an acid is preferred. For example, quinacridone, diketopyrrolopyrrole and disazo condensation compound pigments are alkaline and dissolved. Phthalocyanine compound pigments are dissolved in an acidic manner, but some of them are dissolved in an alkaline manner, and the mechanism of dissolving in an alkaline manner is not clear.

  Examples of the alkali include inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and barium hydroxide, or organic bases such as trialkylamine, diazabicycloundecene (DBU), and metal alkoxide. Of these, trialkylamines and metal alkoxides are preferable, and metal alkoxides are more preferable. The amount of alkali added is not particularly limited, but in the case of an inorganic base, it is preferably 1.0 to 30 molar equivalents, more preferably 1.0 to 25 molar equivalents, and 1.0 Particularly preferred is ˜20 molar equivalents. In the case of an organic base, it is preferably 1.0 to 100 molar equivalents, more preferably 5.0 to 100 molar equivalents, and particularly preferably 20 to 100 molar equivalents with respect to the organic pigment.

  Examples of the acid include inorganic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid, or organic acids such as acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid, and trifluoromethanesulfonic acid. Among them, inorganic acids are preferable. More preferably, it is sulfuric acid. The amount of acid to be added is not particularly limited, but it is often used in excess compared to the base. Regardless of inorganic acid and organic acid, it is preferably 3 to 500 molar equivalents, more preferably 10 to 500 molar equivalents, and more preferably 30 to 200 molar equivalents with respect to the organic pigment or low molecular organic material. It is particularly preferred.

  When alkali or acid is mixed with an organic solvent and used as a good solvent for organic pigments or low molecular weight organic materials, the alkali or acid is completely dissolved. A solvent with high solubility can be added to the organic solvent. The amount of water or lower alcohol is preferably 50% by mass or less, and more preferably 30% by mass or less, based on the total amount of the organic pigment solution or the low molecular organic material solution. Although there is no restriction | limiting in particular in the lower limit of this quantity, Usually, it is 0.01 mass% or more. Specifically, water, methanol, ethanol, n-propanol, isopropanol, butyl alcohol, or the like can be used.

  The viscosity of the organic pigment solution or the low molecular weight organic material solution is preferably 0.5 to 80.0 mPa · s, and more preferably 1.0 to 50.0 mPa · s.

  Although a poor solvent is not specifically limited, It is preferable that the solubility of an organic pigment or a low molecular weight organic material is 0.02 mass% or less, and it is more preferable that it is 0.01 mass% or less. Although there is no particular lower limit to the solubility of the organic pigment or low molecular weight organic material in the poor solvent, 0.000001% by mass or more is practical in consideration of a commonly used organic pigment or low molecular weight organic material. This solubility may be the solubility when dissolved in the presence of an acid or alkali. In addition, the compatibility or uniform mixing property of the good solvent and the poor solvent is preferably 30% by mass or more, more preferably 50% by mass or more, with respect to the poor solvent. There is no particular upper limit to the amount of good solvent dissolved in the poor solvent, but it is practical to mix them in an arbitrary ratio.

  Examples of the poor solvent include an aqueous solvent (for example, water or hydrochloric acid, an aqueous sodium hydroxide solution), an alcohol compound solvent, a ketone compound solvent, an ether compound solvent, an aromatic compound solvent, a carbon disulfide solvent, an aliphatic compound solvent, Examples thereof include nitrile compound solvents, halogen compound solvents, ester compound solvents, ionic liquids, and mixed solvents thereof, and aqueous solvents, alcohol compound solvents, ketone compound solvents, ether compound solvents, ester compound solvents, or mixtures thereof are preferable. An aqueous solvent, an alcohol compound solvent or an ester compound solvent is more preferable.

Examples of the alcohol compound solvent include methanol, ethanol, isopropyl alcohol, n-propyl alcohol, 1-methoxy-2-propanol and the like. Examples of the ketone compound solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of the ether compound solvent include dimethyl ether, diethyl ether, tetrahydrofuran, and the like. Examples of the aromatic compound solvent include benzene and toluene. Examples of the aliphatic compound solvent include hexane. Examples of the nitrile compound solvent include acetonitrile. Examples of the halogen compound solvent include dichloromethane and trichloroethylene. Examples of the ester compound solvent include ethyl acetate, ethyl lactate, 2- (1-methoxy) propyl acetate and the like. The ionic liquids, for example, 1-butyl-3-methylimidazolium and PF ₆ ^-, etc. and salts thereof.

  The first good solvent and the second good solvent may be the same or different, but it is preferable to use the same type or the same type in combination. The first poor solvent and the second poor solvent may be the same or different, but it is preferable to use the same type or the same type in combination.

  There is no particular limitation on the conditions of the poor solvent when the pigment fine particles or the low molecular organic material fine particles are precipitated and produced, and a range from normal pressure to subcritical and supercritical conditions can be selected. The temperature at normal pressure is preferably −30 to 100 ° C., more preferably −10 to 60 ° C., and particularly preferably 0 to 30 ° C.

  When mixing the organic pigment solution or the low molecular organic material solution and the poor solvent, either of them may be added and mixed, but the organic pigment solution or the low molecular organic material solution is jetted into the poor solvent and mixed. It is preferable that the poor solvent is in a stirred state. The stirring speed is preferably 100 to 10,000 rpm, more preferably 150 to 8000 rpm, and particularly preferably 200 to 6000 rpm. A pump or the like may be used for the addition, or it may not be used. Moreover, although addition in a liquid or addition outside a liquid may be sufficient, addition in a liquid is more preferable. Further, it is preferable to continuously supply the liquid into the liquid through a supply pipe. The inner diameter of the supply pipe is preferably 0.1 to 200 mm, more preferably 0.2 to 100 mm. As a speed | rate supplied into a liquid from a supply pipe | tube, 1-1000 ml / min is preferable and 5-5000 ml / min is more preferable.

By adjusting the Reynolds number in mixing the organic pigment solution or the low molecular organic material solution and the poor solvent, the particle diameter of the pigment fine particles or low molecular organic material fine particles to be formed can be controlled. Here, the Reynolds number is a dimensionless number representing the state of fluid flow and is represented by the following equation.
Re = ρUL / μ Equation (1)
In Equation (1), Re represents the Reynolds number, ρ represents the density [kg / m ³ ] of the organic pigment solution or the low molecular organic material solution, U represents the organic pigment solution or the low molecular organic material solution, the poor solvent, Represents the relative velocity [m / s] when L meets, L represents the equivalent diameter [m] of the flow path or supply port of the portion where the organic pigment solution or low molecular organic material solution and the poor solvent meet, and μ represents the organic It represents the viscosity coefficient [Pa · s] of the pigment solution or the low molecular organic material solution.

The equivalent diameter L is the diameter of an equivalent circular pipe when assuming an opening diameter of a pipe having an arbitrary cross-sectional shape or a circular pipe equivalent to a flow path. The equivalent diameter L is expressed by the following equation (2), where A is the cross-sectional area of the pipe, p is the wetted length (circumferential length) of the pipe, or p is the outer periphery of the flow path.
L = 4 A / p Equation (2)
It is preferable to form particles by injecting an organic pigment solution or a low molecular weight organic material solution into a poor solvent through a pipe. When a circular pipe is used for the pipe, the equivalent diameter matches the diameter of the circular pipe. For example, the equivalent diameter can be adjusted by changing the opening diameter of the liquid supply port. Although the value of the equivalent diameter L is not specifically limited, For example, it is synonymous with the preferable internal diameter of the supply port mentioned above.

  The relative speed U when the organic pigment solution or the low molecular weight organic material solution meets the poor solvent is defined as the relative speed in the direction perpendicular to the surface of the portion where both meet. That is, for example, when an organic pigment solution or a low molecular weight organic material solution is injected and mixed in a stationary poor solvent, the injection speed from the supply port becomes equal to the relative speed U. Although the value of the relative speed U is not specifically limited, For example, it is preferable to set it as 0.5-100 m / s, and it is more preferable to set it as 1.0-50 m / s.

The density ρ of the organic pigment solution or the low molecular weight organic material solution is a value determined by the type of the material selected, but in the range of materials preferably used in the production method of the present invention, for example, 0.8-2. It is practical to be 0 kg / m ³ . Further, the viscosity coefficient μ of the organic pigment solution or the low molecular organic material solution is also a value determined by the material used, the ambient temperature, etc., but the preferred range is the preferred organic pigment solution or low molecular organic material solution described above. Synonymous with viscosity.

  The smaller the Reynolds number (Re) value, the easier it is to form a laminar flow, and the larger the value, the easier it is to form a turbulent flow. For example, it can be obtained by adjusting the Reynolds number to 60 or more to control the particle diameter of the pigment fine particles or low molecular organic material fine particles, preferably 100 or more, and more preferably 150 or more. Although there is no particular upper limit to the number of lay nozzles, for example, favorable pigment fine particles or low molecular organic material fine particles can be obtained by controlling and controlling in the range of 100,000 or less, which is preferable. Or it is good also as conditions which raised Reynolds number so that the average particle diameter of the microparticles | fine-particles obtained might be 60 nm or less. At this time, within the above range, it is possible to control and obtain pigment fine particles or low molecular organic material fine particles having a smaller particle size by increasing the Reynolds number.

The mixing ratio of the organic pigment solution or low molecular weight organic material solution to the poor solvent is preferably 1/50 to 2/3, more preferably 1/40 to 1/2, and particularly preferably 1/20 to 3/8. preferable.
When pigment fine particles or low-molecular-weight organic material fine particles are deposited, the particle concentration in the liquid is not particularly limited, but the pigment fine-particle or low-molecular-weight organic material fine particles are preferably in the range of 10 to 40,000 mg with respect to 1000 ml of the solvent. Preferably it is the range of 20-30000 mg, Most preferably, it is the range of 50-25000 mg.
Moreover, the preparation scale when producing pigment fine particles or low-molecular-weight organic material fine particles is not particularly limited, but the mixing amount of the poor solvent is preferably a preparation scale of 10 to 2000 L, and a preparation scale of 50 to 1000 L. It is more preferable.

  In the production method of the present invention, the dispersion A of the organic pigment prepared as described above and the dispersion B of the low molecular weight organic material are mixed, and the solubility of the low molecular weight organic material in the mixed liquid is the solubility of the organic pigment. The target organic pigment nanoparticles are obtained by a process (aging process) that goes through a higher state. As a preferred embodiment of the method for adjusting the solubility of the organic pigment and the low molecular weight organic material in the mixed solution, the mixed solution is maintained in the mixed state, the stirring condition is adjusted, the temperature is adjusted, the pressure is adjusted, and the amount of the solvent is adjusted. Adjustment of pH of a liquid mixture or combining these is mentioned. Specifically, maintaining the mixed state includes maintaining the organic pigment and the low molecular weight organic material for a predetermined time if the desired solubility of the organic pigment and the low molecular weight organic material is obtained by mixing the two dispersions A and B. Examples of the adjustment of the amount of the good solvent include addition of a good solvent, and examples of the pH adjustment include addition of an acid or an alkali. In the ripening step, these adjustment items are appropriately selected according to the type of organic pigment and low molecular weight organic material, and it is preferable to adjust at least the temperature, the amount of the good solvent, and the pH. More preferably, the pH is adjusted.

  In the ripening step, the amount of the organic pigment dispersion A and the low molecular weight organic material dispersion B to be mixed is not particularly limited, but is mixed in an amount that is a preferable range of the amount of the low molecular weight organic material to the organic pigment. It is preferable to do. The content ratio of the organic pigment and the low molecular weight organic material in the mixed solution is not particularly limited, but it is preferable that the organic pigment content is 0.001 to 4% by mass, and the content is 0.001 to 2% by mass. It is more preferable that

  When adjusting the temperature of the mixed solution in the aging step, it is preferable to raise the temperature by 5 to 80 ° C. from the temperature before mixing. As temperature after adjustment, it is preferable to set it as 10-80 degreeC, and it is more preferable to set it as 20-60 degreeC. When adjusting the pressure, it is preferable that the pressure is 0.01 to 2 MPa from the pressure before mixing. The adjusted pressure is preferably 0.11 to 2.1 MPa, more preferably 0.15 to 1.1 MPa. When adjusting the amount of the first or second good solvent, it is preferably 1.05 to 5 times, more preferably 1.1 to 2 times the amount of the good solvent before mixing. . When adjusting the pH of the mixed solution, it is preferable to change the pH of the dispersion B before mixing by one or more. In the case of alkaline, the pH after adjustment is preferably 8 to 12, more preferably 9 to 11, and in the case of acidity, 1 to 6 is preferable, and 2 to 5 is more preferable. preferable.

  The aging time of the mixed solution in the aging step is not particularly limited, but is preferably 0.1 to 5 hours, and more preferably 0.2 to 2 hours.

The difference between the solubility of the low molecular weight organic material and the solubility of the organic pigment in the mixed solution in the aging step is evaluated by a solubility test described below.
[Aging solubility test]
Separately from this, the organic pigment, the low molecular organic material, and the polymer compound are mixed with the organic pigment dispersion A and the low molecular weight organic material dispersion B (test object) for evaluating the solubility. A solution (test solution) having a component composition excluding the components is prepared. To this test solution, an appropriate amount of the same organic pigment or low molecular weight organic material as that in the mixed solution (test object) is added, shaken for 24 hours, and allowed to stand for 24 hours. Then, the amount added gradually increases, and the amount added before and after the mixed state in the test solution changes from a uniform and transparent state to an incompletely dissolved state with a granular appearance and obvious turbidity. The intermediate value is converted to the number of moles as the solubility (mol / liter). The conditions at this time are the same as the conditions (temperature, pressure, amount of solvent, amount of acid or alkali added, etc.) applied in the aging step. When the solubility measured in this way is distinguished from normal solubility, it is particularly called “ripening solubility”. In the above procedure, the solubility may seem to be equal depending on the combination of the organic pigment and the low molecular weight organic material and how to increase the amount of addition gradually increased during the solubility test. In such a case, the increase in the amount of addition is further subdivided and the above solubility test is performed so that the order of solubility of the organic pigment and the low molecular weight organic material is obtained.
It is presumed that the organic pigment fine particles formed through the aging step described above have a structure in which a low molecular compound is coated and a part of the high molecular compound is embedded in the low molecular compound layer.

  Regarding the particle diameter of pigment nanoparticles, there is a method of expressing the average size of the population by quantifying by a measurement method, but as a common method, the mode diameter indicating the maximum value of the distribution, the center of the integral distribution curve There are median diameters corresponding to the values, various average diameters (number average, length average, area average, mass average, volume average, etc.), etc. In the present invention, unless otherwise specified, the average particle diameter is a number. Mean diameter. The average particle diameter of the pigment nanoparticles (primary particles) is nanometer size, the average particle diameter is preferably 1 nm to 0.5 μm, more preferably 1 to 200 nm, and more preferably 2 to 100 nm. Further preferred is 5 to 80 nm. The particles formed by the production method of the present invention may be crystalline particles, amorphous particles, or a mixture thereof.

Further, in the present invention, the ratio (Mv / Mn) of the volume average particle diameter (Mv) and the number average particle diameter (Mn) is used as an index representing the monodispersity of the particles unless otherwise specified. The monodispersity of the pigment nanoparticles (primary particles), that is, Mv / Mn, is preferably 1.0 to 2.0, more preferably 1.0 to 1.8, and 1.0 to 1 .5 is particularly preferred.
Examples of the method for measuring the particle size of pigment nanoparticles include a microscopy method, a mass method, a light scattering method, a light blocking method, an electrical resistance method, an acoustic method, and a dynamic light scattering method. Is particularly preferred. Examples of the microscope used for the microscopy include a scanning electron microscope and a transmission electron microscope. Examples of the particle measuring apparatus based on the dynamic light scattering method include Nikkiso's Nanotrac UPA-EX150, Otsuka Electronics' dynamic light scattering photometer DLS-7000 series (both are trade names), and the like.

  In preparing the dispersion liquid by precipitating the pigment fine particles, at least the first poor solvent is a good solvent (solubility in the second solvent is 4.0% by mass or more) in at least one of the pigment solution and the first poor solvent. Such a compound (hereinafter sometimes referred to as a particle size adjusting agent) may be contained.

Examples of the polymer particle size adjusting agent include polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene glycol, polypropylene glycol, polyacrylamide, vinyl alcohol-vinyl acetate copolymer, polyvinyl alcohol-partial formalized product, polyvinyl alcohol-part. Butyralized product, vinylpyrrolidone-vinyl acetate copolymer, polyethylene oxide / propylene oxide block copolymer, polyacrylic acid, sodium polyacrylate, polyvinyl sulfate, poly (4-vinylpyridine) salt, polyallylamine, polyallylamine hydrochloride, polyvinylamine hydrochloride, allylamine hydrochloride / diallylamine hydrochloride copolymer, a diallylamine monomer / SO ₂ copolymers, diallylamine hydrochloride / Ma Examples thereof include oleic acid copolymer, polydiallylmethylamine hydrochloride, polydiallyldimethylammonium chloride, diallyldimethylammonium chloride / acrylamide copolymer, condensed naphthalene sulfonate, cellulose derivative, starch derivative and the like. In addition, natural polymers such as alginate, gelatin, albumin, casein, gum arabic, tonganto gum and lignin sulfonate can also be used. Of these, polyvinylpyrrolidone, polyacrylic acid, polyallylamine, polyallylamine hydrochloride, polyvinylamine hydrochloride, allylamine hydrochloride / diallylamine hydrochloride copolymer, diallylamine monomer / SO ₂ copolymer, and the like are preferable. These particle size adjusting agents can be used singly or in combination of two or more.
The mass average molecular weight is preferably 1,000 to 500,000, more preferably 10,000 to 500,000, and particularly preferably 10,000 to 100,000.

  As an anionic particle size adjusting agent (anionic surfactant), N-acyl-N-alkyl taurine salt, fatty acid salt, alkyl sulfate ester salt, alkylbenzene sulfonate, alkyl naphthalene sulfonate, dialkyl sulfosuccinate, alkyl Examples thereof include phosphoric acid ester salts, naphthalenesulfonic acid formalin condensate, polyoxyethylene alkyl sulfate ester salts and the like. Of these, N-acyl-N-alkyltaurine salts are preferred. As the N-acyl-N-alkyltaurine salt, those described in JP-A-3-273067 are preferable. These anionic particle size regulators can be used alone or in combination of two or more.

  Cationic particle size modifiers (cationic surfactants) include quaternary ammonium salts, alkoxylated polyamines, aliphatic amine polyglycol ethers, aliphatic amines, diamines derived from aliphatic amines and fatty alcohols, and Examples include salts of cationic substances of imidazoline derived from polyamines and fatty acids. These cationic particle size regulators can be used alone or in combination of two or more.

  The amphoteric particle size regulator is a particle size in which the anionic particle size regulator has both an anion group moiety in the molecule and a cationic group moiety in the molecule of the cationic particle size modifier. It is a regulator.

  Nonionic particle size adjusting agents (nonionic surfactants) include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene Examples thereof include alkylamines and glycerin fatty acid esters. Of these, polyoxyethylene alkylaryl ether is preferable. These nonionic particle size regulators may be used alone or in combination of two or more.

  When a nitrogen-containing polymer compound is used as the polymer compound, as the particle size adjusting agent, a particle size adjusting agent composed of a polymer compound having an acidic group and a particle size adjusting agent composed of a compound having a basic nitrogen atom are used in combination. Preferably not. Moreover, when using the high molecular compound which has an acidic group as the said high molecular compound, it is preferable not to use together the particle size adjusting agent which consists of a nitrogen-containing high molecular compound as a particle size adjusting agent.

  The content of the particle size adjusting agent is preferably in the range of 0.1 to 1000% by mass, more preferably 1 to 500% by mass with respect to the pigment in order to further improve the particle size control of the pigment fine particles. More preferably, it is the range of 5-200 mass%. In addition, the particle size adjusting agents may be used alone or in combination.

  In the production method of the present invention, after the pigment nanoparticles are precipitated, it is preferable to reduce or remove the solvent content of the dispersion containing the precipitated particles (hereinafter, this operation may be simply referred to as concentration). is there.). Thereby, it is possible to obtain a nanoparticle concentrate or pigment nanoparticle powder suitable for a color filter coating liquid or an inkjet ink.

In the present invention, a normal apparatus can be used alone or in combination for the concentration of the solvent. For example, as dryers using hot air, shelf dryers, band dryers, stirring dryers, fluidized bed dryers, spray dryers, air dryers, etc., dryers using heat conduction are drum dryers, multiple dryers, etc. A tube dryer, a cylindrical dryer or the like is preferably used. Depending on the solvent composition, a freeze dryer or an infrared dryer can be used.
Among these means, a spray dryer (for example, COC-12 [trade name] manufactured by Okawara Kako Co., Ltd.), fluidized from the viewpoint that it is suitable for obtaining pigment nanoparticle powder dried directly from the dispersion. A layer dryer (for example, MSD-100 [trade name] manufactured by Nara Machinery Co., Ltd.) is particularly preferably used. Also, a plurality of drying means may be used in combination in order to obtain pigment nanoparticle powder with a small amount of residual solvent. For example, a pigment dispersion pre-concentrated with a cylindrical dryer is completely dried with a drum dryer. Processes such as obtaining pigment nanoparticle powders can be used.
The drying conditions are not particularly limited as long as the solvent can be evaporated and materials such as pigments and dispersants are not denatured. Of course, when other dispersants are denatured at a lower temperature, it is necessary to lower the temperature. However, depending on the type of solvent used, the drying speed may be reduced within the allowable temperature range. In this case, for the purpose of increasing the drying speed, depending on the type of dryer, means such as decompression, stirring and mixing, multiple stages, etc. Can be combined.

The amount to reduce or remove the solvent content is not particularly limited, but in an embodiment in which the solvent content is reduced, it is preferable to remove 50% by mass or more of the total solvent content, and more preferably 75% by mass or more. In an embodiment in which the solvent content is removed to obtain pigment nanoparticle powder, it is preferable to remove 80% by mass or more, and more preferably 90% by mass or more of the total solvent content.
When the solvent content is reduced by reducing or removing the solvent content, the water content in the remaining dispersion is not particularly limited, but is preferably 0.01 to 3% by mass, preferably 0.01 to 1%. It is more preferable to set it as the mass%. At this time, for example, it is preferable to remove the solvent by the above-described drying method or the like to obtain a pigment nanoparticle powder. At this time, the solid content is preferably 50 to 100% by mass, and 70 to 100% by mass. More preferably.
The concentration step may be performed a plurality of times, for example, preferably before and / or after the addition of the third solvent described later.

  The pigment nanoparticles can be used, for example, in a dispersed state in a vehicle. The vehicle refers to a portion of a medium in which a pigment is dispersed when it is in a liquid state, a portion that is liquid and binds to the pigment to harden a coating film (binder). And a component (organic solvent) to be dissolved and diluted. In the present invention, the binder used for forming the pigment nanoparticles and the binder used for redispersion may be the same or different.

The pigment nanoparticle concentration of the pigment dispersion of the present invention is appropriately determined according to the purpose, but it is preferably 2 to 30% by mass of the pigment nanoparticles with respect to the total amount of the dispersion, and preferably 4 to 20% by mass. More preferably, it is particularly preferably 5 to 15% by mass.
In the case of dispersing in the vehicle as described above, the amount of the binder and dissolved dilution component is appropriately determined depending on the type of the organic pigment and the like, but the binder is 1 to 30% by mass with respect to the total amount of the dispersion composition. Preferably, it is 3-20 mass%, More preferably, it is 5-15 mass%. It is preferable that a dissolution dilution component is 5-80 mass%, and it is more preferable that it is 10-70 mass%.

In the concentrated pigment nanoparticle liquid in which the solvent content is reduced, the nanoparticles may aggregate as described above. As a method of redispersing such aggregated pigment nanoparticles, for example, a dispersion method using ultrasonic waves or a method of applying physical energy can be used. The ultrasonic irradiation device used preferably has a function capable of applying an ultrasonic wave of 10 kHz or higher, and examples thereof include an ultrasonic homogenizer and an ultrasonic cleaner. When the liquid temperature rises during ultrasonic irradiation, thermal aggregation of the nanoparticles occurs (see Non-Patent Document 1). Therefore, the liquid temperature is preferably 1 to 100 ° C, more preferably 5 to 60 ° C. The temperature control method can be performed by controlling the dispersion temperature, controlling the temperature of the temperature adjusting layer that controls the temperature of the dispersion, and the like.
There are no particular restrictions on the dispersing machine used to disperse the concentrated pigment nanoparticles by applying physical energy, for example, kneader, roll mill, atrider, super mill, dissolver, homomixer, sand mill, etc. Machine. In addition, a high-pressure dispersion method and a dispersion method using fine particle beads are also preferable.

  The colored photosensitive resin composition of the present invention includes a dispersion of the organic pigment nanoparticles, a binder, a monomer or an oligomer, and a photopolymerization initiator or a photopolymerization initiator system. Hereinafter, each component of the colored photosensitive resin composition will be described.

  The method for producing nanometer-sized organic pigment nanoparticles and dispersions thereof has already been described in detail. The content of the pigment nanoparticles is 3 to 90% by mass with respect to the total solid content in the colored photosensitive resin composition (in the present invention, the total solid content refers to the total composition excluding the organic solvent). Preferably, 20-80 mass% is more preferable, and 25-60 mass% is further more preferable. If this amount is too large, the viscosity of the dispersion increases, which may cause problems in production suitability. If the amount is too small, coloring power is not sufficient. Moreover, you may use it in combination with a normal pigment for toning. As the pigment, those described above can be used.

The monomer or oligomer is preferably a polyfunctional monomer that has two or more ethylenically unsaturated double bonds and undergoes addition polymerization upon irradiation with light. Examples of such monomers and oligomers include compounds having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure.
Monomers or oligomers may be used alone or in admixture of two or more. The content of the colored photosensitive resin composition with respect to the total solid content is generally 5 to 50% by mass, and 10 to 40% by mass. Is preferred. If this amount is too large, it becomes difficult to control the developability, which causes a problem in production suitability. If the amount is too small, the curing power at the time of exposure is insufficient.

  As the binder, a binder having an acidic group is preferable, and it can be added at the time of preparing the inkjet ink or the colored photosensitive resin composition, but it is added at the time of producing the pigment nanoparticle dispersion composition or forming the pigment nanoparticle. It is also preferable to do. It is also possible to add a binder to both or one of the poor solvent for adding the organic pigment solution and the organic pigment solution to form pigment nanoparticles. Alternatively, it is also preferable to add the binder solution in a separate system when forming the pigment nanoparticles. The binder is preferably an alkali-soluble polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain. The binder may be used singly or may be used in the state of a composition used in combination with a normal film-forming polymer, and the addition amount relative to 100 parts by mass of pigment nanoparticles is generally 10 to 200 parts by mass. And 25-100 mass parts is preferable.

As a photopolymerization initiator or a photopolymerization initiator system (in the present invention, a photopolymerization initiator system refers to a mixture that exhibits a photopolymerization initiation function by a combination of a plurality of compounds), U.S. Pat. No. 2,367,660 Vicinal polyketaldonyl compounds disclosed in US Pat. No. 2,448,828, acyloin ether compounds described in US Pat. No. 2,448,828, α-hydrocarbon-substituted fragrances described in US Pat. No. 2,722,512 Group acyloin compounds, polynuclear quinone compounds described in US Pat. Nos. 3,046,127 and 2,951,758, combinations of triarylimidazole dimers described in US Pat. No. 3,549,367 and p-amino ketones, Benzothiazole compounds and trihalomethyl-s-triazines described in Japanese Patent No. 51-48516 Compound, trihalomethyl are described in U.S. Patent No. 4239850 - triazine compounds include U.S. Patent trihalomethyl oxadiazole compounds described in No. 4,212,976 specification or the like. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole, and triarylimidazole dimer are preferable.
In addition, “polymerization initiator C” described in JP-A-11-133600, oxime-based compounds such as 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O— Benzoyl-4 '-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenylcarbonyl-diphenyl phosphonyl oxide, hexafluorophospho-trialkylphenyl phosphonium salt and the like may be mentioned as suitable ones. it can.
The photopolymerization initiator or the photopolymerization initiator system may be used alone or in combination of two or more, but it is particularly preferable to use two or more. When at least two kinds of photopolymerization initiators are used, display characteristics, particularly display unevenness, can be reduced.
The content of the photopolymerization initiator or the photopolymerization initiator system with respect to the total solid content of the colored photosensitive resin composition is generally 0.5 to 20% by mass, and preferably 1 to 15% by mass. If this amount is too large, the sensitivity becomes too high and control becomes difficult. If the amount is too small, the exposure sensitivity becomes too low. The radiation that can be used for exposure is particularly preferably ultraviolet rays such as g-line and i-line. Irradiation dose is preferably 5~1500mJ / cm ^2, more preferably ^{10~1000mJ / cm 2, 10~500mJ / cm} 2 is particularly preferred.

  In the colored photosensitive resin composition, in addition to the above components, an organic solvent for preparing a resin composition (fourth solvent) may be further used. Examples of the fourth solvent include, but are not limited to, esters, ethers, and ketones. Among these solvents, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol Acetate, propylene glycol methyl ether acetate and the like are preferably used as the solvent. These solvents may be used alone or in combination of two or more. The high-boiling organic solvent can be used as the fourth solvent. For example, a solvent having a boiling point of 180 ° C. to 250 ° C. can be used if necessary. As for content of a 4th solvent, 10-95 mass% is preferable with respect to the resin composition whole quantity.

  The colored photosensitive resin composition can contain a surfactant, a thermal polymerization inhibitor, a colorant (dye, pigment), an ultraviolet absorber, an adhesion aid, other additives, and the like.

In addition to the color filter, the inkjet ink of the present invention may be a normal inkjet ink for image formation or the like. In particular, the inkjet ink for a color filter is preferable. The ink jet ink is not particularly limited as an embodiment in the present invention, but for example, a method described in JP-A-2002-201387 can be preferably used.
The inkjet ink of the present invention may be any ink using the organic pigment nanoparticles (a), and preferably further contains a binder (b) and a monomer or oligomer (c). Here, as a binder (b) monomer or oligomer (c), what was previously demonstrated in the colored photosensitive resin composition can be used. The inkjet ink of the present invention may further contain a photopolymerization initiator or a photopolymerization initiator system (d) and other additives. The content of each component ((a) to (d), other additives) may be the same as that described above for the colored photosensitive composition. However, when the inkjet ink of the present invention is used as an ink for preparing a color filter, an embodiment that is not a photosensitive ink is preferable, and it is preferable not to use a photopolymerization initiator or a photopolymerization initiator system.

In the ink-jet ink of the present invention, it is preferable to control the ink temperature so that the fluctuation range of the viscosity is within ± 5%. The viscosity at the time of injection is preferably 5 to 25 mPa · s, more preferably 8 to 22 mPa · s, and particularly preferably 10 to 20 mPa · s (in the present invention, unless otherwise specified) It is a value at 25 ° C.). In addition to the setting of the injection temperature, the viscosity can be adjusted by adjusting the type and amount of components contained in the ink. The viscosity can be measured, for example, by a normal apparatus such as a conical plate type rotational viscometer or an E type viscometer.
The surface tension of the ink upon ejection is preferably 15 to 40 mN / m from the viewpoint of improving the flatness of the pixel (in the present invention, the surface tension is a value at 23 ° C. unless otherwise specified). ). More preferably, it is 20-35 mN / m, Most preferably, it is 25-30 mN / m. The surface tension can be adjusted by adding a surfactant or the type of solvent. For example, the surface tension is platinum by using a measuring instrument such as a surface tension measuring device (CBVP-Z, manufactured by Kyowa Interface Science Co., Ltd.) or a fully automatic balanced electro surface tension meter ESB-V (manufactured by Kyowa Scientific Co., Ltd.). It can be measured by the plate method.

Ink jet ink for color filters can be sprayed by continuously ejecting charged ink and controlled by an electric field, intermittently ejecting ink using piezoelectric elements, or intermittently using ink by heating and foaming. Various methods such as a method of spraying can be employed.
In addition, regarding the ink jet method used for forming each pixel, a normal method such as a method of thermally curing ink, a method of photocuring, or a method of ejecting droplets after forming a transparent image receiving layer on a substrate in advance. Can be used.

  In the present invention, it is preferable that a partition wall is prepared in advance and ink is applied to a portion surrounded by the partition wall before forming a pixel using the color filter inkjet ink. Any partition may be used, but in the case of manufacturing a color filter, it is preferably a light-blocking partition having a black matrix function (hereinafter also simply referred to as “partition”). The partition wall can be produced by the same material and method as those of a normal color filter black matrix.

  Said colored photosensitive resin composition can be apply | coated by the normal apply | coating method, and a coating film can be formed by drying it. Examples of the coating method include coating with a slit nozzle, spin coating, and the like.

  The photosensitive transfer material of the present invention has a photosensitive resin layer containing the above-described colored photosensitive resin composition, and the specific configuration is not particularly limited. For example, an integrated film is used. It is preferable that it is formed. As an example of the structure of the integral film, a structure in which a temporary support / thermoplastic resin layer / intermediate layer / photosensitive resin layer / protective film is laminated in this order can be given.

  In the photosensitive transfer material, it is necessary that the temporary support has flexibility and does not cause significant deformation, contraction or elongation even under pressure, or under pressure and heat. Examples of such a temporary support include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, a polycarbonate film, etc. Among them, a biaxially stretched polyethylene terephthalate film is particularly preferable.

  As the component used for the thermoplastic resin layer, organic polymer substances described in JP-A-5-72724 are preferable, and the polymer softening point according to the Viker Vicat method (specifically, the American Material Testing Method ASTM D1 ASTM D1235). It is particularly preferable that the softening point by the measurement method is selected from organic polymer substances having a temperature of about 80 ° C. or less. Specifically, polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and vinyl acetate or saponified products thereof, ethylene and acrylic acid esters or saponified products thereof, polyvinyl chloride, vinyl chloride and vinyl acetate and saponified products thereof. Vinyl chloride copolymer such as fluoride, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer such as styrene and (meth) acrylic acid ester or saponified product thereof, polyvinyl toluene, vinyl toluene and (meta ) Vinyl toluene copolymer such as acrylic ester or saponified product thereof, poly (meth) acrylic ester, (meth) acrylic ester copolymer such as butyl (meth) acrylate and vinyl acetate, vinyl acetate copolymer Combined nylon, copolymer nylon, N-alkoxyme Le nylon, and organic polymeric polyamide resins such as N- dimethylamino nylon.

In the photosensitive transfer material, it is preferable to provide an intermediate layer for the purpose of preventing mixing of components during application of a plurality of application layers and during storage after application. As the intermediate layer, it is preferable to use an oxygen-blocking film having an oxygen-blocking function, which is described as “separation layer” in JP-A-5-72724. This reduces the time load and improves productivity.
The oxygen barrier film is preferably one that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution, and can be appropriately selected from ordinary ones. Of these, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable.

  It is preferable to provide a thin protective film on the photosensitive resin layer in order to protect it from contamination and damage during storage. The protective film may be made of the same or similar material as the temporary support, but it must be easily separated from the photosensitive resin layer. For example, silicone paper, polyolefin or polytetrafluoroethylene sheet is suitable as the protective film material.

The photosensitive transfer material is provided with a thermoplastic resin layer by applying a coating solution (thermoplastic resin coating solution) in which a thermoplastic resin layer additive is dissolved on a temporary support, followed by drying. An intermediate layer material solution composed of a solvent that does not dissolve the thermoplastic resin layer is applied and dried on the resin layer, and then the photosensitive resin layer is prepared by applying and drying with a solvent that does not dissolve the intermediate layer. Can do.
Also, a sheet provided with the thermoplastic resin layer and the intermediate layer on the temporary support and a sheet provided with the photosensitive resin layer on the protective film are prepared, and the intermediate layer and the photosensitive resin layer are in contact with each other. In addition, a sheet provided with a thermoplastic resin layer on the temporary support and a sheet provided with a photosensitive resin layer and an intermediate layer on a protective film are prepared, and a thermoplastic resin layer is prepared. Can also be produced by bonding them so that the intermediate layer is in contact with each other.

  In the photosensitive transfer material, the thickness of the photosensitive resin layer is preferably 1.0 to 5.0 μm, more preferably 1.0 to 4.0 μm, and particularly preferably 1.0 to 3.0 μm. Further, although not particularly limited, preferred film thicknesses of other layers are 15 to 100 μm for the temporary support, 2 to 30 μm for the thermoplastic resin layer, 0.5 to 3.0 μm for the intermediate layer, and protection. The film is generally preferably 4 to 40 μm.

The color filter of the present invention is excellent in contrast. In the present invention, the contrast represents the ratio of the amount of transmitted light between two polarizing plates when the polarization axis is parallel and when it is vertical (“1990 Seventh Color Optical Conference, 512-color display 10.4. "Refer to" Color TFT for TFT-LCD, Ueki, Koseki, Fukunaga, Yamanaka "etc.).
The high contrast of the color filter means that the bright and dark discrimination when combined with the liquid crystal can be increased, and this is a very important performance in order to replace the liquid crystal display with a CRT.

  When the color filter of the present invention is used for a television, the chromaticities of all the single colors of red (R), green (G), and blue (B) by the F10 light source are the values shown in the table below ( Hereinafter, in the present invention, the difference (ΔE) from the “target chromaticity”) is preferably in the range of 5 or less, more preferably 3 or less, and particularly preferably 2 or less.

x y Y
------------------------
R 0.656 0.336 21.4
G 0.293 0.634 52.1
B 0.146 0.088 6.90
------------------------

In the present invention, the chromaticity is measured with a microspectrophotometer (manufactured by Olympus Optical Co., Ltd .; OSP100 or 200), calculated as a result of the F10 light source field of view of 2 degrees, and expressed as an xyY value in the xyz color system. Further, the difference from the target chromaticity is represented by a color difference of the La ^* b ^* color system.

  The liquid crystal display device provided with the color filter of the present invention has a high contrast and excellent descriptive power such as black spots, and the VA system is particularly preferable. It can also be suitably used as a large-screen liquid crystal display device such as a notebook personal computer display or a television monitor. The color filter of the present invention can be used for a CCD device and exhibits excellent performance.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these.

(Example 1 and Comparative Example 1)
<Production of Color Filter A1 (Production by Application Using Slit Nozzle)>
[Preparation of concentrated pigment liquid A]
To 970 ml of dimethyl sulfoxide (manufactured by Wako Pure Chemical Industries, Ltd.), 31.0 ml of 30% methanol solution of sodium methoxide, pigment C.I. I. Pigment Red 254 (Irgaphor Red BT-CF, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) 34 g, and polyvinylpyrrolidone (K-30, trade name, manufactured by Wako Pure Chemical Industries, Ltd.) 10 g are added to a pigment solution Aa. Was prepared. Separately, 1200 ml of water containing 30 ml of 1 mol / l hydrochloric acid aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) was prepared as a poor solvent. Here, the temperature of the solution was controlled at 18 ° C., and the pigment solution Aa was added to 1200 ml of poor solvent water stirred at 600 rpm by a GK-0222-10 type Lamond Stirrer (trade name, manufactured by Fujisawa Pharmaceutical Co., Ltd.). NP-KX-500 A large-capacity non-pulsating pump (trade name, manufactured by Nippon Seimitsu Chemical Co., Ltd.) was used to inject 100 ml (for 1 minute) at a flow rate of 100 ml / min to form organic pigment nanoparticles, thereby preparing a pigment fine particle dispersion Aa.

  To 90 ml of dimethyl sulfoxide (manufactured by Wako Pure Chemical Industries, Ltd.), 5.1 ml of a 30% sodium methoxide methanol solution, pigment C.I. I. Pigment Red 255 (Irgazin DPP SCARLET EK, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.58 g and polymethyl methacrylate (mass average molecular weight 20000) 10.0 g were added to prepare a pigment solution Ab. . Separately, 200 ml of water containing 6 ml of a 1 mol / l hydrochloric acid aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) was prepared as a poor solvent. Here, the temperature of the solution was controlled at 18 ° C., and the pigment solution Ab was added to 200 ml of poor solvent water stirred at 200 rpm by a GK-0222-10 type Lamond Stirrer (trade name, manufactured by Fujisawa Pharmaceutical Co., Ltd.). NP-KX-500 Low molecular organic material fine particles are formed by injecting 20 ml (12 seconds) at a flow rate of 100 ml / min using a large-capacity non-pulsating flow pump (trade name, manufactured by Nippon Seimitsu Chemical Co., Ltd.). Ab was prepared.

  The temperature of the dispersion Ab was controlled at 18 ° C. and stirred at 600 rpm by a GK-0222-10 type Lamond Stirrer (trade name, manufactured by Fujisawa Pharmaceutical Co., Ltd.). A liquid mixture A was prepared by addition.

  Subsequently, the temperature of the mixed solution A was controlled at 18 ° C., and a sodium methoxide 30% methanol solution was added to pH 10 while stirring at 600 rpm with a GK-0222-10 type lamond stirrer (trade name, manufactured by Fujisawa Pharmaceutical Co., Ltd.). After the preparation, an aging solution A was prepared after 1 hour. The particle size and monodispersity of the fine particles in the ripening liquid A were measured using Nanotrack UPA-EX150 [trade name] manufactured by Nikkiso Co., Ltd., and the number average particle size was 28 nm and Mv / Mn was 1.50. there were. Note that the C.I. I. Pigment red 254 and C.I. I. The aging solubilities of CI Pigment Red 255 measured by the procedure shown in the above section [Aging Solubility Test] were 0.00005 mol / liter and 0.001 mol / liter, respectively.

  The matured liquid A prepared by the above method was centrifuged at 3100 rpm (2000 G) for 1 hour using a high-speed centrifugal cooler HIMAC SCR20B (trade name, manufactured by Hitachi Koki Co., Ltd.), and the supernatant was discarded and sedimented. The pigment nanoparticle concentrated paste was recovered. When the pigment content of the paste was measured using an 8453 type spectrophotometer (trade name, manufactured by Agilent), Pigment Red 254 was 22.0% by mass.

  Add 50.0 ml of ethyl lactate to 14.5 g of the above pigment nanoparticle concentrated paste, stir at 3000 rpm for 60 minutes with a dissolver, transfer to an eggplant-shaped flask, and dry under reduced pressure at 70 ° C. for 1.5 hours with an evaporator. Thus, a pigment dry powder A (Pigment Red 254 concentration 52.0% by mass) was obtained.

[Preparation of R Pigment Dispersion A]
Using the dry powder A, an R pigment dispersion A having the following composition was prepared.
Pigment dry powder A 6.0 g
1-methoxy-2-propyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) 18.0 g

  The R pigment dispersion A having the above composition was dispersed with a motor mill M-50 (trade name, manufactured by Eiger Japan) for 1 hour at a peripheral speed of 7 m / s using zirconia beads having a diameter of 0.65 mm.

[Formation of black (K) image]
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state.
After cooling the substrate and adjusting the temperature to 23 ° C., it is described in Table 1-1 below with a glass substrate coater (manufactured by FS Asia Co., Ltd., trade name: MH-1600) having a slit-like nozzle. A colored photosensitive resin composition K1 having the composition: Subsequently, a part of the solvent was dried by VCD (vacuum drying apparatus; manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating layer, and then pre-baked at 120 ° C. for 3 minutes to obtain a film thickness of 2. A 4 μm photosensitive resin layer K1 was obtained.

[Table 1-1]
--------------------------------------
K pigment dispersion 1 (carbon black) 25 parts by mass Propylene glycol monomethyl ether acetate 8.0 parts by mass Methyl ethyl ketone 53 parts by mass Binder 2 9.1 parts by mass Hydroquinone monomethyl ether 0.002 parts by mass DPHA solution 4.2 parts by mass Polymerization start Agent A 0.16 parts by mass Surfactant 1 0.044 parts by mass -------------------------------- ------

In a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra high pressure mercury lamp, with the substrate and mask (quartz exposure mask having an image pattern) standing vertically, the exposure mask surface and the mask The distance between the photosensitive resin layers was set to 200 μm, and pattern exposure was performed at an exposure amount of 300 mJ / cm ² .
Next, after spraying pure water with a shower nozzle to uniformly wet the surface of the photosensitive resin layer K1, a KOH developer (KOH, containing nonionic surfactant, trade name: CDK-1, (Fujifilm Electronics Materials, Inc., 100-fold diluted solution) was subjected to shower development at 23 ° C. for 80 seconds and a flat nozzle pressure of 0.04 MPa to obtain a patterning image. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultrahigh pressure washing nozzle to remove the residue, and a black (K) image K was obtained. Subsequently, heat treatment was performed at 220 ° C. for 30 minutes.

  For the colored photosensitive resin composition K1, first, K pigment dispersion 1 and propylene glycol monomethyl ether acetate are weighed, mixed at a temperature of 24 ° C. (± 2 ° C.), stirred at 150 rpm for 10 minutes, and then methyl ethyl ketone, binder 2 , Hydroquinone monomethyl ether, DPHA solution, polymerization initiator A (2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethyl) amino-3'-bromophenyl] -s- Triazine) and surfactant 1 were weighed out, added in this order at a temperature of 25 ° C. (± 2 ° C.), and stirred at 150 rpm for 30 minutes at a temperature of 40 ° C. (± 2 ° C.).

<K pigment dispersion 1>
・ Carbon black (trade name: Nipex 35, manufactured by Degussa Japan)
13.1 parts by mass / dispersant (compound J1) 0.65 parts by mass / polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio
Random copolymer of, molecular weight 37,000) 6.72 parts by mass / propylene glycol monomethyl ether acetate 79.53 parts by mass

<Binder 2>
・ Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio
Random copolymer of, molecular weight 38,000) 27 parts by mass / propylene glycol monomethyl ether acetate 73 parts by mass <DPHA solution>
Dipentaerythritol hexaacrylate (containing polymerization inhibitor MEHQ 500 ppm, manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) 76 parts by mass Propylene glycol monomethyl ether acetate 24 parts by mass <Surfactant 1>
Megafac F-780-F (Dainippon Ink and Chemicals, Inc.): composition below _{· C 6 F 13 CH 2 CH} 2 OCOCH = CH 2 40 parts by weight and _{H (OCH (CH 3) CH} 2) Copolymer of ₇ OCOCH = CH ₂ 55 parts by mass and H (OCH ₂ CH ₂ ) ₇ OCOCH = CH ₂ 5 parts by mass (molecular weight 30,000)
30 parts by mass, 70 parts by mass of methyl ethyl ketone

[Formation of red (R) pixels]
Using the colored photosensitive resin composition RA1 having the composition shown in Table 1-2 below on the substrate on which the image K has been formed, a heat-treated pixel R is formed in the same process as the formation of the black (K) image. did. The film thickness of the photosensitive resin layer RA1 and the coating amount of the pigment are shown below. In addition, the preparation procedure of the colored photosensitive resin composition was the same as that of the colored photosensitive resin composition K1.
Photosensitive resin film thickness (μm) 1.60
Pigment coating amount (g / m ² ) 1.00
C. I. P. R. 254 coating amount (g / m ² ) 0.90
C. I. P. R. 177 coating amount (g / m ² ) 0.10

[Table 1-2]
--------------------------------------
R pigment dispersion A 40 parts by mass R pigment dispersion 2 (CIPR177) 4.5 parts by mass Propylene glycol monomethyl ether acetate 7.6 parts by mass Methyl ethyl ketone 37 parts by mass Binder 1 0.7 parts by mass DPHA solution 3.8 parts by mass Polymerization Initiator B 0.12 parts by mass Polymerization initiator A 0.05 parts by mass Phenothiazine 0.01 parts by mass Surfactant 1 0.06 parts by mass ----------------- ---------------------

<R pigment dispersion 2>
・ C. I. P. R. 177 (Product name: Chromophthal Red A2B,
Ciba Specialty Chemicals Co., Ltd.) 18 parts by mass Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio)
Random copolymer of, molecular weight 30,000) 12 parts by mass / 70 parts by mass of propylene glycol monomethyl ether acetate <Binder 1>
・ Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio
Random copolymer of, molecular weight 40,000) 27 parts by mass, 73 parts by mass of propylene glycol monomethyl ether acetate <polymerization initiator B>
2-Trichloromethyl- (p-styrylstyryl) 1,3,4-oxadiazole

[Formation of green (G) pixels]
In the same process as the formation of the black (K) image, the heat-treated pixel is formed using the colored photosensitive resin composition G1 having the composition described in Table 1-3 below on the substrate on which the image K and the pixel R are formed. G was formed. The film thickness of the photosensitive resin layer G1 and the coating amount of the pigment are shown below. In addition, the preparation procedure of the colored photosensitive resin composition was the same as that of the colored photosensitive resin composition K1.
Photosensitive resin film thickness (μm) 1.60
Pigment application amount (g / m ² ) 1.92
C. I. P. G. 36 coating amount (g / m ² ) 1.34
C. I. P. Y. 150 coating amount (g / m ² ) 0.58

[Table 1-3]
--------------------------------------
G pigment dispersion 1 (CIPG 36) 28 parts by mass Y pigment dispersion 1 (CIPI 150) 15 parts by mass Propylene glycol monomethyl ether acetate 29 parts by mass Methyl ethyl ketone 26 parts by mass Cyclohexanone 1.3 parts by mass Binder 2 2.5 parts by mass DPHA solution 3 0.5 part by weight Polymerization initiator B 0.12 part by weight Polymerization initiator A 0.05 part by weight Phenothiazine 0.01 part by weight Surfactant 1 0.07 part by weight ------------ -------------------------

<G pigment dispersion 1>
"Product name: GT-2" manufactured by FUJIFILM Electronics Materials Co., Ltd.

<Y pigment dispersion 1>
"Product name: CF Yellow-EX3393" manufactured by Gokoku Color Co., Ltd.

[Formation of blue (B) pixels]
Using the colored photosensitive resin composition B1 having the composition described in Table 1-4 below on the substrate on which the image K, the pixel R, and the pixel G are formed, A heat-treated pixel B was formed to obtain a target color filter A1. The film thickness of the photosensitive resin layer B1 and the coating amount of the pigment are shown below. In addition, the preparation procedure of the colored photosensitive resin composition was the same as that of the colored photosensitive resin composition K1.
Photosensitive resin film thickness (μm) 1.60
Pigment application amount (g / m ² ) 0.75
C. I. P. B. 15: 6 coating amount (g / m ² ) 0.705
C. I. P. V. 23 coating amount (g / m ² ) 0.045

[Table 1-4]
--------------------------------------
B pigment dispersion 1 (CIPB15: 6) 8.6 parts by mass B pigment dispersion 2 (CIPB15: 6 + CIPV23) 15 parts by mass Propylene glycol monomethyl ether acetate 28 parts by mass Methyl ethyl ketone 26 parts by mass Binder 3 17 parts by mass DPHA solution 4.0 Parts by mass polymerization initiator B 0.17 parts by mass phenothiazine 0.02 parts by mass surfactant 1 0.06 parts by mass ---------------------- ---------------

<B pigment dispersion 1>
"Product name: CF Bull-EX3357" manufactured by Gokoku Color Co., Ltd.
<B pigment dispersion 2>
"Product name: CF Bull-EX3383" manufactured by Gokoku Color Co., Ltd.
<Binder 3>
・ Polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate = 36/22/42 molar ratio random copolymer, molecular weight 38,000) 27 parts by mass-propylene glycol monomethyl ether acetate 73 parts by mass

<Preparation of color filter B1>
In preparation of the color filter A1, the pigment nanoparticle concentrated paste obtained by centrifuging the ripening liquid A was dried at 80 ° C. for 12 hours to obtain a pigment dry powder B (pigment red 254 concentration 55.0 mass%).

[Preparation of R Pigment Dispersion B]
Using the dry powder B, an R pigment dispersion B having the following composition was prepared.
5.6 g of the pigment dry powder A
1-methoxy-2-propyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) 18.0 g

The R pigment dispersion B having the above composition was dispersed with a motor mill M-50 (trade name, manufactured by Eiger Japan) for 1 hour at a peripheral speed of 7 m / s using zirconia beads having a diameter of 0.65 mm.
In the same manner as the color filter A1, an R pigment dispersion B and a colored photosensitive resin composition RB1 were prepared, and a color filter B1 was produced.

<Preparation of color filter C1>
In the production of the color filter B1, the R pigment dispersion C and the colored photosensitive resin composition RC1 were similarly prepared except that the mass average molecular weight of polymethyl methacrylate used for the preparation of the dispersion Ab was changed to 600,000. A color filter C1 was produced.

<Preparation of color filter D1>
Centrifugation of unmixed liquid mixture A obtained in the production of color filter A1 was performed at 3100 rpm (2000 G) for 1 hour with high-speed centrifugal cooler HIMAC SCR20B (trade name, manufactured by Hitachi Koki Co., Ltd.) The supernatant was discarded and the pigment nanoparticle concentrated paste that settled down was recovered. The collected paste was dried at 80 ° C. for 12 hours to obtain pigment dry powder D (Pigment Red 254 concentration 53.0% by mass).

[Preparation of R Pigment Dispersion D]
Using the dry powder D, an R pigment dispersion D having the following composition was prepared.
5.9 g of the pigment dry powder D
1-methoxy-2-propyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) 18.0 g

The R pigment dispersion D having the above composition was dispersed with a motor mill M-50 (trade name, manufactured by Eiger Japan) for 1 hour at a peripheral speed of 7 m / s using zirconia beads having a diameter of 0.65 mm.
In the same manner as the color filter A1, an R pigment dispersion D and a colored photosensitive resin composition RD1 were prepared, and a color filter D1 was produced.

<Preparation of color filter E1>
[Preparation of concentrated pigment liquid E]
To 970 ml of dimethyl sulfoxide (manufactured by Wako Pure Chemical Industries, Ltd.), 31.0 ml of 30% methanol solution of sodium methoxide, pigment C.I. I. Pigment Red 254 (Irgaphor Red BT-CF, trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) 34 g, polyvinyl pyrrolidone (K-30, trade name, manufactured by Wako Pure Chemical Industries, Ltd.) 10 g, and polymethyl methacrylate 22 g An added pigment solution Ea was prepared. Separately, 1200 ml of water containing 30 ml of 1 mol / l hydrochloric acid aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) was prepared as a poor solvent. Here, the temperature of the solution was controlled at 18 ° C., and the pigment solution Aa was added to 1200 ml of poor solvent water stirred at 600 rpm by a GK-0222-10 type Lamond Stirrer (trade name, manufactured by Fujisawa Pharmaceutical Co., Ltd.). NP-KX-500 A large-capacity non-pulsating flow pump (trade name, manufactured by Nippon Seimitsu Chemical Co., Ltd.) was used to inject 100 ml (for 1 minute) at a flow rate of 100 ml / min to form organic pigment nanoparticles, thereby preparing pigment fine particle dispersion Ea.
The fine particles in the dispersion Ea were measured for their particle size and monodispersity using a Nitraso Nanotrac UPA-EX150. The number average particle size was 27 nm and Mv / Mn was 1.52, respectively.

  The dispersion Ea prepared by the above method was centrifuged at 3100 rpm (2000 G) for 1 hour with a high-speed centrifugal chiller HIMAC SCR20B (trade name, manufactured by Hitachi Koki Co., Ltd.), and the supernatant was discarded and sedimented. The pigment nanoparticle concentrated paste was recovered. The collected paste was dried at 80 ° C. for 12 hours to obtain pigment dry powder E (Pigment Red 254 concentration 56.0 mass%).

[Preparation of R Pigment Dispersion E]
Using the dry powder E, an R pigment dispersion E having the following composition was prepared.
5.4 g of the pigment dry powder E
1-methoxy-2-propyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) 18.0 g

The R pigment dispersion E having the above composition was dispersed with a motor mill M-50 (trade name, manufactured by Eiger Japan) for 1 hour at a peripheral speed of 7 m / s using zirconia beads having a diameter of 0.65 mm.
In the same manner as the color filter A1, an R pigment dispersion E and a colored photosensitive resin composition RE1 were prepared, and a color filter E1 was produced.

<Preparation of color filter F1>
In the production of the color filter E1, the R pigment dispersion F and the polymethyl methacrylate used in the preparation of the dispersion Ea were changed in the same manner except that the polymethyl methacrylate was changed to polyvinyl pyrrolidone (K-30, trade name, manufactured by Wako Pure Chemical Industries, Ltd.). A colored photosensitive resin composition RF1 was prepared to produce a color filter F1.

  The color filters A1 to F1 produced by coating using a slit-like nozzle as described above are also collectively referred to as the color filter 1.

[Measurement of contrast of color filters A1 to F1]
Using the produced color filter as a backlight unit, a three-wavelength cold cathode tube light source (FWL18EX-N, trade name, manufactured by Toshiba Lighting & Technology Co., Ltd.) with a diffusion plate installed, two polarizing plates (HLC2- 2518, trade name, manufactured by Sanritsu Co., Ltd.), measured the amount of transmitted light when the polarization axis was parallel and vertical, and the ratio was taken as contrast (Ueki, Koseki, Fukunaga, Yamanaka) , "512 color display 10.4" size TFT-LCD color filter ", 7th Color Optical Conference (1990), etc.).
The measurement results of the contrast of the color filters A1 to F1 are shown in Table 1-6.

[Evaluation of process stability]
The viscosity (initial viscosity) at 25 ° C. immediately after the production of the produced colored photosensitive resin compositions RA1 to RF1 was measured. Further, the viscosity (viscosity with time) at 25 ° C. of the colored photosensitive resin compositions RA1 to RG1 stored for 1 month in an environment of 40 ° C. was measured. The results are shown in Table 1-7 together with the increased values when the initial viscosity and the viscosity with time are compared. At this time, the viscosity was measured using a vibration viscometer VM-100A-L [trade name].

[Table 1-6]
--------------------------------------
Color filter Contrast Initial viscosity Viscosity with time Viscosity increase -------------------------------------
A1 9200 13cp 16cp 3cp
B1 9670 11cp 12cp 1cp
C1 9100 14cp 19cp 5cp
D1 6000 15cp 26cp 11cp
E1 8300 12cp 27cp 15cp
F1 4500 13cp 37cp 24cp
--------------------------------------

  As is apparent from the results of Table 1-6, it can be seen that the color filters A1 to C1 of the example of the present invention show a higher contrast than the color filters D1, E1 and F1 of the comparative example and show good display characteristics. It was. In addition, the colored photosensitive resin compositions RA1 to RC1 of the examples of the present invention maintain high dispersion stability over a long period of time as compared with the colored photosensitive resin compositions RD1, RE1 and RF1 of the comparative examples, and are favorable. It was found to show stability over time.

(Example 2 and Comparative Example 2)
<Production of Color Filters A2 to F2 (Production by Laminating Photosensitive Resin Transfer Material)>
[Production of photosensitive resin transfer material]
On a 75 μm thick polyethylene terephthalate film temporary support, a coating solution for a thermoplastic resin layer having the following formulation H1 was applied and dried using a slit nozzle. Next, an intermediate layer coating solution having the following formulation P1 was applied and dried. Further, the colored photosensitive resin composition K1 is applied and dried, and a thermoplastic resin layer having a dry film thickness of 14.6 μm, an intermediate layer having a dry film thickness of 1.6 μm, and a dry layer are dried on the temporary support. A photosensitive resin layer having a film thickness of 2.4 μm was provided, and a protective film (polypropylene film having a thickness of 12 μm) was pressure-bonded.
Thus, a photosensitive resin transfer material K1 in which the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), and the black (K) photosensitive resin layer were integrated was produced.

<Coating liquid for thermoplastic resin layer: Formulation H1>
Methanol 11.1 parts by mass Propylene glycol monomethyl ether acetate 6.36 parts by mass Methyl ethyl ketone 52.4 parts by mass Methyl methacrylate / 2-ethylhexyl acrylate / benzyl
Methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55 / 11.7 / 4.5 / 28.8,
Molecular weight: 90,000, Tg: about 70 ° C.) 5.83 parts by mass. Styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio))
= 63/37, molecular weight: 10,000, Tg: about 100 ° C.) 13.6 parts by mass. Compound obtained by dehydration condensation of 2 equivalents of bisphenol A and pentaethylene glycol monomethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.,
Product name: 2,2-bis [4- (methacryloxypolyethoxy)
Phenyl] propane) 9.1 parts by mass / surfactant 1 0.54 parts by mass

<Interlayer coating solution: Formulation P1>
・ PVA205 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.,
Degree of saponification = 88%, degree of polymerization 550) 32.2 parts by mass / polyvinylpyrrolidone (manufactured by ASP Japan Co., Ltd.)
K-30) 14.9 parts by mass, 524 parts by mass of distilled water, 429 parts by mass of methanol

  Next, the colored photosensitive resin composition RA2 and G101 having the compositions described in Tables 2-1 to 2-3 below are used as the colored photosensitive resin composition K1 used in the production of the photosensitive resin transfer material K1. Photoresin transfer materials RA2, G101, and B101 were prepared in the same manner as described above except that they were changed to B101 and B101. In addition, the preparation method of colored photosensitive resin composition RA2, G101, and B101 is based on the preparation method of the said colored photosensitive resin composition RA1, G1, and B1, respectively.

[Table 2-1] RA2
--------------------------------------
R pigment dispersion A 40 parts by weight R pigment dispersion 2 (CIPR177) 4.5 parts by weight Propylene glycol monomethyl ether acetate 7.1 parts by weight Methyl ethyl ketone 57 parts by weight Binder 1 0.8 parts by weight DPHA solution 4.4 parts by weight Polymerization Initiator B 0.14 parts by weight Polymerization initiator A 0.06 parts by weight Phenothiazine 0.01 parts by weight Additive 1 0.52 parts by weight Surfactant 1 0.06 parts by weight ---------- ----------------------------

[Table 2-2] G101
--------------------------------------
G pigment dispersion 1 (CIPG36) 28 parts by mass Y pigment dispersion 1 (CIPI150) 13 parts by mass Propylene glycol monomethyl ether acetate 39 parts by mass Methyl ethyl ketone 16 parts by mass Cyclohexanone 1.3 parts by mass Binder 2 3.0 parts by mass DPHA solution 4 .3 parts by weight Polymerization initiator B 0.15 parts by weight Polymerization initiator A 0.06 parts by weight Phenothiazine 0.01 parts by weight Surfactant 1 0.07 parts by weight ------------ -------------------------

[Table 2-3] B101
--------------------------------------
B pigment dispersion 1 (CIPB 15: 6) 8.6 parts by mass B pigment dispersion 2 (CIPB 15: 6 + CIPV 23) 15 parts by mass Propylene glycol monomethyl ether acetate 28 parts by mass Methyl ethyl ketone 26 parts by mass Binder 3 18.5 parts by mass DPHA solution 4 .3 parts by mass Polymerization initiator B 0.17 parts by mass Phenothiazine 0.02 parts by mass Surfactant 1 0.06 parts by mass -------------------- -----------------

  In addition, among the compositions described in Table 2-1, as the additive 1, a phosphate ester special activator (manufactured by Enomoto Kasei Co., Ltd., trade name: HIPLAAD ED152) was used.

[Formation of black (K) image]
The alkali-free glass substrate was washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds by showering, and after washing with pure water shower, silane coupling solution (N-β (aminoethyl)) A 0.3% by mass aqueous solution of γ-aminopropyltrimethoxysilane, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower, and washed with pure water. This substrate was heated at 100 ° C. for 2 minutes with a substrate preheating device and sent to the next laminator.
After peeling off the protective film of the photosensitive resin transfer material K1, a substrate heated to 100 ° C. using a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)), rubber roller temperature 130 ° C., linear pressure Lamination was performed at 100 N / cm ² and a conveyance speed of 2.2 m / min.
After peeling the temporary support at the interface with the thermoplastic resin layer, the substrate and mask (quartz exposure mask with image pattern) are used with a proximity-type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp. ) Was set vertically, the distance between the exposure mask surface and the thermoplastic resin layer was set to 200 μm, and pattern exposure was performed at an exposure amount of 70 mJ / cm ² .

Next, a triethanolamine developer (containing 2.5% triethanolamine, trade name: T-PD2, Fuji Photo Film Co., Ltd., 12-fold diluted with pure water (1 part of T-PD2 The mixture was mixed at a ratio of 11 parts of water.))) At 30 ° C. for 50 seconds and a flat nozzle pressure of 0.04 MPa, and the thermoplastic resin layer and the intermediate layer were removed.
Subsequently, sodium carbonate developer (0.38 mol / liter sodium bicarbonate, 0.47 mol / liter sodium carbonate, 5% sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoaming agent, stabilizer included , Trade name: T-CD1, manufactured by Fuji Photo Film Co., Ltd. diluted 5 times with pure water) and developed at 29 ° C. for 30 seconds at a cone type nozzle pressure of 0.15 MPa to develop the photosensitive resin layer. A patterning image was obtained.
Subsequently, using a solution obtained by diluting a cleaning agent (trade name “T-SD1 (manufactured by Fuji Photo Film Co., Ltd.) 10 times with pure water, a shower and nylon hair were removed at 33 ° C. for 20 seconds and a cone type nozzle pressure of 0.02 MPa. Residue removal was performed with a rotating brush, and a black (K) image was obtained, and then post-exposure was performed on the substrate from the resin layer side with a 500 mJ / cm ² light with an ultrahigh pressure mercury lamp. It heat-processed at 15 degreeC for 15 minutes.
The substrate on which this image K was formed was again cleaned with a brush as described above, and after pure water shower cleaning, the silane coupling solution was not used and was sent to a substrate preheating device.

[Formation of red (R) pixels]
Using the photosensitive resin transfer material RA2, heat-treated red (R) pixels R were obtained in the same process as the photosensitive resin transfer material K1. However, the exposure amount was 40 mJ / cm ² , and development with a sodium carbonate developer was 35 ° C. for 35 seconds. The film thickness of the photosensitive resin layer RA2 and the coating amount of the pigment (CIPR 254 and CIPR 177) are shown below.
Photosensitive resin film thickness (μm) 2.00
Pigment coating amount (g / m ² ) 1.00
C. I. P. R. 254 coating amount (g / m ² ) 0.90
C. I. P. R. 177 coating amount (g / m ² ) 0.10
The substrate on which the image K and the pixel R were formed was again cleaned with a brush as described above, and after pure water shower cleaning, the silane coupling liquid was not used and the substrate was sent to a substrate preheating device.

[Formation of green (G) pixels]
Using the photosensitive resin transfer material G101, a heat-treated green (G) pixel G was obtained in the same process as the photosensitive resin transfer material RA2. However, the exposure amount was 40 mJ / cm ² , and development with a sodium carbonate developer was 34 ° C. for 45 seconds. The film thickness of the photosensitive resin layer G101 and the coating amount of the pigment (CIPG36 and CIPY150) are shown below.
Photosensitive resin film thickness (μm) 2.00
Pigment application amount (g / m ² ) 1.92
C. I. P. G. 36 coating amount (g / m ² ) 1.34
C. I. P. Y. 150 coating amount (g / m ² ) 0.58
The substrate on which the image K, the pixel R, and the pixel G were formed was again cleaned with a brush as described above, and after pure water shower cleaning, the silane coupling liquid was not used and the substrate was sent to a substrate preheating device.

[Formation of blue (B) pixels]
Using the photosensitive resin transfer material B101, heat-treated blue (B) pixels B were obtained in the same process as the photosensitive resin transfer material RA2. However, the exposure amount was 30 mJ / cm ² , and development with a sodium carbonate developer was 36 ° C. for 40 seconds. The film thickness of the photosensitive resin layer B101 and the coating amount of the pigment (CIPB15: 6 and CIPVV23) are shown below.
Photosensitive resin film thickness (μm) 2.00
Pigment application amount (g / m ² ) 0.75
C. I. P. B. 15: 6 coating amount (g / m ² ) 0.705
C. I. P. V. 23 coating amount (g / m ² ) 0.045
The substrate on which the pixel R, pixel G, pixel B, and image K were formed was baked at 240 ° C. for 50 minutes to obtain a color filter A2.

  R pigment dispersion A was changed to R pigment dispersions B to F, respectively, to the method for producing color filter A2, and colored photosensitive resin compositions RB2 to RF2 and color filters B2 to F2 were produced.

  The color filters A2 to F2 prepared by laminating the photosensitive resin transfer material as described above are also collectively referred to as the color filter 2.

  The contrast of the obtained color filters A2 to F2 and the temporal stability of the colored photosensitive resin compositions RA2 to RF2 were evaluated in the same manner as in Example 1 and Comparative Example 1. The results are shown in Table 2-4.

[Table 2-4]
--------------------------------------
Color filter Contrast Initial viscosity Viscosity with time Viscosity increase -------------------------------------
A2 10000 17cp 18cp 1cp
B2 11000 15cp 17cp 2cp
C2 9800 13cp 17cp 4cp
D2 7500 16cp 28cp 12cp
E2 8500 19cp 28cp 9cp
F2 5500 13cp 31cp 18cp
--------------------------------------

  As is apparent from the results in Table 2-4, it can be seen that the color filters A2 to C2 of the example of the present invention show higher contrast and better display characteristics than the color filters D2, E2 and F2 of the comparative example. It was. In addition, the colored photosensitive resin compositions RA2 to RC2 of the present invention examples maintain high dispersion stability over a long period of time as compared with the colored photosensitive resin compositions RD2, RE2 and RF2 of the comparative examples, and have good stability over time. It was found to show sex.

(Example 3 and Comparative Example 3)
<Production of Color Filters A3 to F3 (Production by Inkjet)>
Regarding the production procedure of the photosensitive resin transfer material K1, the photosensitive resin transfer material K2 was similarly prepared except that the colored photosensitive resin composition K1 was replaced with the colored photosensitive resin composition K2 described in Table 3-1 below. Produced.

[Table 3-1] Colored photosensitive resin composition K2
--------------------------------------
K pigment dispersion 1 (carbon black) 30 parts by mass Propylene glycol monomethyl ether acetate 7.3 parts by mass Methyl ethyl ketone 34 parts by mass Cyclohexanone 8.6 parts by mass Binder 2 14 parts by mass DPHA solution 5.8 parts by mass Polymerization initiator A 0. 22 parts by mass Phenothiazine 0.006 parts by mass The above surfactant 1 0.058 parts by mass ----------------------------- ---------

  The resin composition K2 having light-shielding properties was first weighed in K pigment dispersion 1 and propylene glycol monomethyl ether acetate, mixed at a temperature of 24 ° C. (± 2 ° C.), stirred at 150 rpm for 10 minutes, and then described in Table 3-1. Of methyl ethyl ketone, cyclohexanone, binder 2, phenothiazine, DPHA solution, polymerization initiator A and surfactant 1 were added in this order at a temperature of 25 ° C. (± 2 ° C.), and a temperature of 40 ° C. (± 2 ° C. ) At 150 rpm for 30 minutes.

[Formation of light-blocking partition walls]
The alkali-free glass substrate was washed with a rotating brush having nylon hair while spraying a glass detergent solution adjusted to 25 ° C. for 20 seconds by showering, and after washing with pure water shower, silane coupling solution (N-β (aminoethyl)) A 0.3% by mass aqueous solution of γ-aminopropyltrimethoxysilane, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower, and washed with pure water. This substrate was heated at 100 ° C. for 2 minutes with a substrate preheating apparatus.

After peeling off the protective film of the photosensitive resin transfer material K2, a substrate heated at 100 ° C. for 2 minutes using a laminator (manufactured by Hitachi Industries, Ltd. (Lamic II type)), a rubber roller temperature of 130 ° C., a wire Lamination was performed at a pressure of 100 N / cm and a conveyance speed of 2.2 m / min.
After peeling off the temporary support, exposure is performed with a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp with the substrate and mask (quartz exposure mask with image pattern) standing vertically. The distance between the mask surface and the thermoplastic resin layer was set to 200 μm, and pattern exposure was performed with an exposure amount of 100 mJ / cm ² . The mask shape is a lattice shape, and the radius of curvature of the corner convex toward the light-shielding partition wall in the portion corresponding to the boundary line between the pixel and the light-shielding partition wall is 0.6 μm.

Next, a triethanolamine developer (containing 30% triethanolamine, trade name: T-PD2, manufactured by Fuji Photo Film Co., Ltd. 12 times with pure water (1 part of T-PD2 and 11 parts of pure water) The resulting mixture was diluted with a mixture) at 30 ° C. for 50 seconds at a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the intermediate layer (oxygen barrier layer).
Subsequently, sodium carbonate developer (0.38 mol / liter sodium bicarbonate, 0.47 mol / liter sodium carbonate, 5% sodium dibutylnaphthalene sulfonate, anionic surfactant, antifoaming agent, stabilizer included , Trade name: T-CD1, manufactured by Fuji Photo Film Co., Ltd. diluted 5 times with pure water) and shower-developed at 29 ° C. for 30 seconds with a cone type nozzle pressure of 0.15 MPa to have a light shielding property Was developed to obtain a patterning separation wall (a partition wall pattern having a light shielding property).

Subsequently, using a cleaning agent (trade name “T-SD3 (manufactured by Fuji Photo Film Co., Ltd.)” diluted 10 times with pure water), a shower and nylon hair at 33 ° C. for 20 seconds and a cone type nozzle pressure of 0.02 MPa. Residue was removed with a rotating brush having a light shielding property to obtain a light-shielding partition. Thereafter, the substrate was further post-exposed with light of 500 mJ / cm ^{2 with} an ultra-high pressure mercury lamp from the resin layer side, and then heat treated at 240 ° C. for 50 minutes.

[Plasma water repellency treatment]
Thereafter, plasma water repellency treatment was performed by the following method.
Plasma water repellency treatment was performed on the substrate on which the light-shielding barrier ribs were formed using a cathode coupling parallel plate type plasma processing apparatus under the following conditions.
Gas used: CF ₄
Gas flow rate: 80sccm
Pressure: 40Pa
RF power: 50W
Processing time: 30 sec

[Preparation of inkjet ink for color filter]
An inkjet ink for a color filter was prepared according to the following formulation.
[Table 3-R]
--------------------------------------
Composition component Content (parts by mass) Ink RA3
--------------------------------------
R pigment dispersion A 63
R pigment dispersion 2 (CIPR177) 7
Polymer dispersant (Solsperse 20000 (trade name) manufactured by AVECIA) 1.0
Polymer 1 2.0 below
Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) 6.0
Alkynoyl-modified dipentaerythritol triacrylate (Nippon Kayaku, KAYARAD D330) 4.0
Phenothiazine 0.005
1,3-butylene glycol diacetate 25
--------------------------------------

[Table 3-G]
--------------------------------------
Composition component Content (parts by mass) Ink G1
--------------------------------------
G pigment dispersion 1 (P.G.36) 35
Y pigment dispersion 1 (P.Y.150) 32
Polymer dispersant (Solsperse 20000 manufactured by AVECIA) 1.0
Polymer 1 2.0 below
Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) 6.0
Alkynoyl-modified dipentaerythritol triacrylate (Nippon Kayaku, KAYARAD D330) 4.0
Phenothiazine 0.005
1,3-butylene glycol diacetate 25
--------------------------------------

[Table 3-B]
--------------------------------------
Composition component Content (parts by mass) Ink B1
--------------------------------------
B pigment dispersion 1 (P.B.15: 6 + P.V.23) 8
B pigment dispersion 2 (P.B.15: 6) 71
Polymer dispersant (Solsperse 20000 (trade name) manufactured by AVECIA) 1.0
Polymer 1 2.0 below
Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA) 6.0
Alkynoyl-modified dipentaerythritol triacrylate (Nippon Kayaku, KAYARAD D330) 4.0
Phenothiazine 0.005
1,3-butylene glycol diacetate 25
--------------------------------------
Polymer 1 Random copolymer of benzyl methacrylate / methacrylic acid = 72/28 molar ratio, molecular weight 37,000

  Regarding the mixing of each of the components in Tables 3-R, 3-G, and 3-B, first, the pigment and the polymer dispersant are charged into a part of the solvent, mixed, and stirred using a three roll and bead mill. Thus, a pigment dispersion was obtained. On the other hand, other compounding components were added to the remainder of the solvent, and were dissolved and dispersed by stirring to obtain a monomer solution. Then, while adding the pigment dispersion or the pigment dispersion composition little by little to the monomer solution, the mixture was sufficiently stirred with a dissolver to prepare an inkjet ink for a color filter.

[Pixel formation]
First, a color filter A3 was produced using the ink RA3, the ink G-1, and the ink B-1 described above as follows.
The inkjet head used was Dimatix SE-128, and the discharge controller used was Dimatix Apollo II. An inkjet head is mounted on an automatic two-dimensional moving stage (KS211-200 manufactured by Suruga Seiki), and the stage is moved from the head by the discharge control device while moving the stage so that a predetermined amount of ink is discharged into the gap of the partition wall produced above. The discharge was synchronized.
Here, the inks of the three colors of ink RA3, ink G-1, and ink B-1 described above are filled in different heads, each head is fixed on the XY stage, and each ink is in a predetermined position. The three heads were independently controlled by the discharge control device so as to land on.
For droplet ejection, the ink composition is discharged until the desired concentration is reached, heated and dried on a hot plate at 100 ° C. for 2 minutes, and then baked in an oven at 230 ° C. for 30 minutes to completely cure both the partition walls and pixels. A color filter A3 was produced.

  R pigment dispersion A was changed to R pigment dispersions B to F, respectively, and inks RB3 to RF3 and color filters B3 to F3 were prepared with respect to the method for producing color filter A3.

  In this specification, the color filters A3 to F3 manufactured by inkjet as described above are collectively referred to as the color filter 3.

  The contrast of the obtained color filters A3 to F3 and the stability over time of the inks RA3 to RF3 were evaluated in the same manner as in Example 1 and Comparative Example 1. The results are shown in Table 3-2.

[Table 3-2]
--------------------------------------
Color filter Contrast Initial viscosity Viscosity with time Viscosity increase ----------------------------------
A3 12100 10cp 12cp 2cp
B3 12500 12cp 12cp 0cp
C3 10700 13cp 16cp 3cp
D3 8600 11cp 22cp 11cp
E3 9500 12cp 22cp 10cp
F3 7300 12cp 20cp 8cp
--------------------------------------
As is clear from the results in Table 3-2, it can be seen that the color filters A3 to C3 of the example of the present invention exhibit higher contrast and better display characteristics than the color filters D3, E3, and F3 of the comparative example. It was. In addition, it was found that the inks RA3 to RC3 of the example of the present invention maintained high dispersion stability over a long period of time as compared with the inks RD3, RE3 and RF3 of the comparative examples, and exhibited good temporal stability.

(Example 4 and Comparative Example 4)
[Production of liquid crystal display elements]
A liquid crystal display device was produced according to the following method.
(1) A patterned 1 cm ² ITO film is formed on one surface of a glass substrate, and a commercially available liquid crystal aligning agent for active matrix is applied onto the ITO film using a spinner, and then 1 at 180 ° C. The coating was dried for a time to form a coating film having a thickness of 600 mm.
(2) After forming a patterned 1 cm ² ITO film on each of the color filters 1 to 3 produced in the above-mentioned examples and comparative examples, on the ITO film, in the same manner as (1), A liquid crystal aligning agent coating was formed.
(3) After forming an ITO film (continuous film) on one surface of the glass substrate, a coating film of a liquid crystal aligning agent was formed on the ITO film in the same manner as (1).
(4) Next, the surface of the coating film on each substrate obtained in (1) to (3) is subjected to a rubbing process using a rubbing machine provided with a roll around which a cloth made of rayon is wound, and a liquid crystal alignment film Formed. The rubbing conditions at that time were a roll rotation speed of 400 rpm, a stage moving speed of 3 cm / second, and a push-in length of the hair foot of 0.4 mm.
(5) Of the substrates on which the liquid crystal alignment film is thus formed, each substrate that has undergone the treatment of (1) or (2) is combined with the substrate that has undergone the treatment of (3) to form a set of two pieces, For each set, an epoxy resin adhesive containing a silica gel columnar spacer with a diameter of 5.5 μm was applied to the outer edge of the two substrates by screen printing, and the rubbing direction of each liquid crystal alignment film crossed 90 degrees. As described above, the two substrates were placed opposite each other with a gap between them, and the adhesive was cured by pressing the substrates so that the outer edges of each substrate were in contact with each other.
(6) Next, for each set, nematic liquid crystal “ZLI-5081” (trade name, made of fluorobiphenyl derivative) in a cell gap defined by the inner surface of the two substrates and the hardened layer of the adhesive. After injection and filling (Merck Japan Co., Ltd.), the injection hole was sealed to prepare a liquid crystal cell. Thereafter, a polarizing plate was bonded to the outer surface of the liquid crystal cell so that the polarization direction thereof coincided with the rubbing direction of the liquid crystal alignment film on each substrate, thereby producing a liquid crystal display element.

  The manufactured liquid crystal display device was visually evaluated for display characteristics (color unevenness, black margin). As a result, in the liquid crystal display elements produced using each of the color filters A1 to C1, A2 to C2 and A3 to C3 of the present invention, all of the color filters D1, E1, F1, D2, E2, It was found that the liquid crystal display element manufactured using F2, D3, E3, or F3 showed better display characteristics.

  From the above results, by using the organic pigment nanoparticles prepared by the production method of the present invention and the pigment dispersion composition thereof, it is possible to obtain a color filter with extremely high contrast, and a liquid crystal using the color filter of the present invention. It can be seen that the display device exhibits good display characteristics.

Claims (12)

Mixing an organic pigment solution in which an organic pigment is dissolved in a first good solvent and a first poor solvent that is compatible with the first good solvent and that is a poor solvent for the organic pigment, A step of preparing a dispersion A in which the organic pigment is precipitated as fine particles, an organic material solution in which a low molecular organic material is dissolved in a second good solvent and containing a polymer compound, and the second good solvent. A step of preparing a dispersion B in which the low molecular weight organic material is mixed with a second poor solvent which is a poor solvent for the low molecular weight organic material, and the low molecular weight organic material is precipitated as fine particles; A method of producing organic pigment nanoparticles, comprising: mixing A and the dispersion B; and passing through a state in which the solubility of the low molecular weight organic material in the mixture is higher than the solubility of the organic pigment. .   In the step of mixing the dispersion A and the dispersion B, the mixed solution is maintained in a mixed state, adjusted in temperature, adjusted in pressure, adjusted in solvent amount, adjusted in pH, or a combination thereof. The method for producing organic pigment nanoparticles according to claim 1.   The method for producing organic pigment nanoparticles according to claim 1 or 2, wherein the low molecular organic material is selected from the group consisting of organic pigments, organic dyes, aromatic hydrocarbons, and aliphatic hydrocarbons.   The method for producing organic pigment nanoparticles according to any one of claims 1 to 3, wherein the polymer compound has a mass average molecular weight of 1,000 to 500,000.   The polymer compound is at least one polymer compound selected from the group consisting of vinyl monomer polymers, vinyl monomer copolymers, ester polymers, ether polymers, modified products thereof, and copolymers thereof. The method for producing organic pigment nanoparticles according to any one of claims 1 to 4, wherein:   Organic pigment nanoparticles, wherein the dispersion containing the organic pigment nanoparticles prepared by the method according to any one of claims 1 to 5 is pulverized by removing the solvent.   A pigment dispersion comprising organic pigment nanoparticles produced by the method according to claim 1.   A colored photosensitive resin composition comprising the pigment dispersion according to claim 7, a binder, a monomer or an oligomer, and a photopolymerization initiator or a photopolymerization initiator system.   An ink-jet ink for a color filter comprising the pigment dispersion according to claim 7, a binder, and a monomer or oligomer.   A photosensitive resin transfer material, wherein a photosensitive resin layer containing at least the colored photosensitive resin composition according to claim 8 is provided on a temporary support.   A color produced using the colored photosensitive resin composition according to claim 8, the inkjet ink for a color filter according to claim 9, and / or the photosensitive resin transfer material according to claim 10. filter.   A liquid crystal display device comprising the color filter according to claim 11.