JP2008158124A - Coloring composition for color filter and color filter - Google Patents

Abstract

An object of the present invention is to provide a coloring composition for a color filter excellent in fluidity and heat resistance after formation of a coating film, and a color filter excellent in heat resistance.
An acidic group-containing urethane (meth) acrylate system obtained by reacting polyisocyanate (a1) having three or more isocyanate groups, a hydroxyl group-containing (meth) acrylate (a2) and an acidic group-containing polyol (a3) as raw materials. Resin [A], at least one basic group-containing derivative selected from the group consisting of a pigment derivative having a specific basic group, a triazine derivative, an anthraquinone derivative and an acridone derivative, a pigment and a monomer A color filter comprising: a coloring composition for a color filter comprising: and a filter segment formed from the coloring composition.
[Selection figure] None

Description

  The present invention relates to a colored composition for a color filter used for producing a color filter used for a color liquid crystal display device, a color image pickup tube element, and the like, and a color filter formed using the same.

  A color filter has two or more kinds of fine band (striped) filter segments arranged in parallel or intersecting with each other on the surface of a transparent substrate such as glass, or the fine filter segments are arranged vertically and horizontally. It is made up of those arranged in The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue. Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Yes. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to form them generally at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher.

  Therefore, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used. The color filter is mainly produced by the following two methods. Is manufactured. In the first method, a dispersion of a pigment in a photosensitive transparent resin solution (pigment resist) is applied to a transparent substrate such as glass, and after removing the solvent by drying, pattern exposure of one filter color is performed. Next, the unexposed area is removed in the development process to form a first color pattern, and after processing such as heating as necessary, a color filter can be manufactured by sequentially repeating the same operation for all filter colors. it can.

  In the second method, a dispersion of a pigment in a transparent resin solution is applied to a transparent substrate such as glass, the solvent is removed by drying, and then a resist such as a positive resist is applied on the coating film. Two filter color patterns are exposed and developed to form a resist pattern. Using this as an etching resist, the pigment-dispersed coating film without the resist pattern is removed with an etching solution, and the resist coating film is peeled off. A color filter can be manufactured by forming a color pattern and, if necessary, applying a treatment such as heating, and then repeating the same operation for all filter colors. Note that the development of the resist and the etching of the pigment-dispersed coating film can be performed simultaneously.

  In general, it is difficult to obtain a stable dispersion by dispersing fine pigment particles in a colorant carrier such as a varnish, and the dispersion often has a high viscosity due to aggregation of pigment particles over time, resulting in thixotropic properties. Will come to show. Such an increase in viscosity and poor fluidity of the composition cause various problems in manufacturing operations and product value. For example, the filter segment of a color filter is generally formed by spin-coating a colored composition in which a pigment is dispersed in a carrier containing a monomer and a resin on a glass substrate, but it has a high viscosity and poor fluidity. When the colored composition is used, it is not preferable because a coating film having a uniform film thickness cannot be obtained due to poor spin coatability or poor leveling.

  Specifically, since the viscosity of the pigment dispersion depends on the shear rate and the film thickness when spin-coated is proportional to the viscosity, the viscosity of the pigment resist at the time of application is the same at the center and the outer periphery of the transparent substrate. There is a need. The apparent viscosity of the pigment resist when the pigment resist is dispensed on the substrate and rotated is close to the viscosity when the shear rate is low because the peripheral speed is slow at the center. Therefore, in the case of a thixotropic pigment resist, the apparent viscosity is high at the central portion where the shear rate is small, and conversely, the apparent viscosity is low at the outer peripheral portion. Since the color filter requires a uniform film thickness within the substrate, the pigment resist needs to have a fluidity with a constant viscosity, that is, a Newtonian flow regardless of the displacement speed. In order to solve the above-described problems, an organic pigment is used as a base skeleton, and a pigment derivative having an acidic or basic substituent in the side chain is mixed as a dispersant, and the pigment derivative and the resin component in the varnish are mixed with each other. Methods for stabilizing pigment dispersion by action are known (for example, see Patent Documents 1 to 5).

However, since various resins are used in the color composition for color filters, the pigment derivative and the resin in the color composition do not always work effectively. In the above method, some resin systems are used. The fact is that a satisfactory effect has not been obtained. In addition, some pigment derivatives tend to be inferior in heat resistance as compared with pigments, and it is problematic to use a coloring composition containing a pigment derivative inferior in heat resistance when producing a color filter. There was a case. That is, with the conventional technology, it has been difficult to achieve both of ensuring the fluidity of the colored composition and maintaining heat resistance after forming the coating film.
Japanese Patent Publication No.41-2466 U.S. Pat. No. 2,855,403 JP-A-63-305173 JP-A-1-247468 JP-A-3-26767

  Then, an object of this invention is to provide the coloring composition for color filters which is excellent in fluidity | liquidity and maintains heat resistance after coating-film formation.

  As a result of intensive studies to solve the above problems, the present inventors have made fine pigment particles into an acidic group-containing urethane (meth) acrylate resin [A] and a pigment derivative having a specific basic group, anthraquinone. For color filters that can form a coating film with low viscosity, high fluidity, and excellent heat resistance after coating on a glass substrate by dispersing it in a pigment carrier containing monomers together with a derivative, acridone derivative or triazine derivative The inventors have found that a colored composition can be obtained, and have reached the present invention.

That is, the present invention has a double bond equivalent of 150 to 400 obtained by reacting a polyisocyanate (a1) having three or more isocyanate groups, a hydroxyl group-containing (meth) acrylate (a2) and an acidic group-containing polyol (a3). And an acidic group-containing urethane (meth) acrylate resin [A] having a weight average molecular weight of 3,000 to 100,000;
Pigments,
And at least one basic group-containing derivative selected from the group consisting of a pigment derivative having a basic group, an anthraquinone derivative having a basic group, an acridone derivative having a basic group, and a triazine derivative having a basic group. A basic group-containing derivative having at least one basic group selected from the group represented by the following general formulas (1), (2), (3) and (4):
The present invention relates to a coloring composition for a color filter comprising a pigment carrier containing a monomer.

  Formula (1)

式（２）

Formula (2)

式（３）

Formula (3)

式（４）

Formula (4)

式（５）

Formula (5)

式（６）

Formula (6)

(In the formula, X, X ¹ and X ^{2 each} represent —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond.
m represents an integer of 1 to 10.
R ¹ , R ² Each independently represents an optionally substituted alkyl group, alkenyl group, phenyl group, or a heterocyclic ring formed by integrating R ¹ and R ² . However, the heterocycle may contain further nitrogen, oxygen or sulfur atoms.
R ³ Represents an alkyl group, an alkenyl group or a phenyl group which may be substituted.
R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom, an optionally substituted alkyl group, an alkenyl group or a phenyl group.
Y represents —NR ⁸ —Z—NR ⁹ — or a direct bond.
R ⁸ and R ⁹ each independently represents a hydrogen atom, an optionally substituted alkyl group, an alkenyl group or a phenyl group.
Z represents an alkylene group, an alkenylene group, or a phenylene group, which may be substituted.
P represents a substituent represented by the formula (5) or a substituent represented by the formula (6).
Q represents a hydroxyl group, an alkoxyl group, a substituent represented by the formula (5) or a substituent represented by the formula (6). )
Furthermore, the present invention relates to the color filter coloring composition, wherein the polyisocyanate (a1) is a diisocyanate trimer.

  Furthermore, this invention relates to the said coloring composition for color filters characterized by the polyisocyanate (a1) being a trimer of isophorone diisocyanate.

  Furthermore, in the present invention, the color derived from the polyisocyanate (a1) in the nonvolatile component of the acidic group-containing urethane (meth) acrylate resin [A] is 25% by weight to 60% by weight. It is related with the coloring composition for filters.

  Furthermore, the present invention relates to the above color filter coloring composition, wherein the hydroxyl group-containing (meth) acrylate (a2) is pentaerythritol tri (meth) acrylate and / or dipentaerythritol penta (meth) acrylate.

  Furthermore, this invention relates to the said coloring composition for color filters characterized by the acidic group containing polyol (a3) being dimethylol butanoic acid or dimethylol propionic acid.

  Further, in the present invention, the acidic group-containing urethane (meth) acrylate resin [A] reacts the acidic group-containing polyol (a3) with the reaction product of the polyisocyanate (a1) and the hydroxyl group-containing (meth) acrylate (a2). The present invention relates to a coloring composition for a color filter.

  Furthermore, the present invention relates to the coloring composition for a color filter, wherein the pigment carrier further contains a resin.

  Furthermore, this invention relates to the color filter characterized by including the filter segment formed from the said coloring composition for color filters.

  The colored composition of the present invention is excellent in fluidity, has excellent workability during production and coating film formation, and can form a uniform coating film on a coated substrate. Moreover, since the coloring composition of this invention is excellent in heat resistance, the color filter excellent in heat resistance can be obtained by forming a filter segment using this.

  First, the urethane (meth) acrylate resin contained in the color filter coloring composition of the present invention will be described. The colored composition of the present invention includes an acidic group-containing urethane (meth) acrylate resin [A]. The acidic group-containing urethane (meth) acrylate resin [A] reacts with a polyisocyanate (a1) having three or more isocyanate groups, a hydroxyl group-containing (meth) acrylate (a2), and an acidic group-containing polyol (a3). Obtainable.

  The polyisocyanate (a1) having three or more isocyanate groups as a raw material for the acidic group-containing urethane (meth) acrylate resin [A] is particularly limited as long as it is a compound having three or more isocyanate groups in the molecule. For example, aromatic polyisocyanate, aliphatic polyisocyanate, araliphatic polyisocyanate, alicyclic polyisocyanate and the like can be mentioned.

  The polyisocyanate (a1) is preferably a trimethylolpropane adduct of diisocyanate shown below, a burette reacted with water, and a trimer having an isocyanurate ring.

  Examples of the diisocyanate include aromatic diisocyanates, aliphatic diisocyanates, araliphatic diisocyanates, alicyclic diisocyanates, and the like.

  Examples of the aromatic diisocyanate include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, and 4,4′-diphenylmethane diester. Isocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1 , 3,5-triisocyanatobenzene, dianisidine diisocyanate, 4,4′-diphenyl ether diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, etc. Can do.

  Examples of the aliphatic diisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, and 1,2-propylene diisocyanate. 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, etc. Can do.

  Examples of the araliphatic diisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate. -1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.

  Examples of the alicyclic diisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, and 1,3-cyclohexane diisocyanate. 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate) G), 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane and the like.

  Of the above, taking into account the viscosity after pigment dispersion, aliphatic polyisocyanates, araliphatic polyisocyanates, and alicyclic polyisocyanates are preferred, and alicyclic polyisocyanates, particularly isophorone diisocyanate trimers. Is preferred.

  In this invention, it is preferable that the ratio derived from polyisocyanate (a1) in the non-volatile component of acidic group containing urethane (meth) acrylate type resin [A] is 25 to 60 weight%. If the amount is less than 25% by weight, the pigment dispersibility may be deteriorated due to insufficient pigment adsorbing ability. If the amount exceeds 60% by weight, the pigment adsorbing ability is too high, so that a sufficient steric repulsion effect cannot be obtained. Sexuality may decline.

  The hydroxyl group-containing (meth) acrylate (a2) that is a raw material of the acidic group-containing urethane (meth) acrylate resin [A] contained in the colored composition of the present invention will be described. The hydroxyl group-containing (meth) acrylate (a2) is not particularly limited as long as it is a (meth) acrylate compound having one or more hydroxyl groups in the molecule. For example, pentaerythritol tri (meth) acrylate, dipenta Erythritol penta (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethylacryloyl phosphate, 4-hydroxybutyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, glycerin di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, caprolactone-modified 2-hydroxyethyl (Meth) acrylate, cyclohexanedimethanol mono (meth) acrylate. Among these, pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate are preferable.

  The acidic group-containing urethane (meth) acrylate resin [A] of the present invention preferably has a double bond equivalent of 150 to 400. If the resin is less than 150, it may be difficult to synthesize. If it exceeds 400, the amount of double bonds introduced may be reduced, and curing may not be sufficient.

  The acidic group containing polyol (a3) used as the raw material of acidic group containing urethane (meth) acrylate resin [A] contained in the coloring composition of this invention is demonstrated. The acidic group-containing polyol (a3) is not particularly limited as long as it is a compound having one or more carboxyl groups and two or more hydroxyl groups in the molecule. Specifically, 2,2-bis ( Hydroxymethyl) butyric acid [dimethylolbutanoic acid], 2,2-bis (hydroxymethyl) propionic acid [dimethylolpropionic acid], 2,2-bis (hydroxyethyl) propionic acid, 2,2-bis (hydroxypropyl) Propionic acid, tartaric acid, dihydroxymethylacetic acid, bis (4-hydroxyphenyl) acetic acid, 4,4-bis (p-hydroxyphenyl) pentanoic acid, 2,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, homogentisic acid Etc. Preferably, 2,2-bis (hydroxymethyl) butyric acid [dimethylolbutanoic acid], 2,2-bis (hydroxymethyl) propionic acid [dimethylolpropionic acid], 2,2-bis (hydroxyethyl) propionic acid 2,2-bis (hydroxypropyl) propionic acid is used. Of these, dimethylolbutanoic acid and dimethylolpropionic acid are preferred.

  Moreover, you may use the acidic group containing polyol obtained by organic synthesis. For example, an acidic group-containing polyol obtained from a reaction between an acid anhydride and a polyfunctional alcohol. As the acid anhydride, a compound having one acid anhydride group in the molecule and a compound having two or more acid anhydride groups in the molecule can be used. These may be used alone or in combination.

  Examples of the compound having one acid anhydride group in the molecule include succinic anhydride, itaconic anhydride, maleic anhydride, glutaric anhydride, hexahydrophthalic anhydride, and aliphatic cyclic acid anhydrides such as tetrahydrophthalic anhydride, Aromatic cyclic acid anhydrides such as phthalic anhydride, isatoic anhydride, diphenic anhydride, and derivatives in which a saturated or unsaturated aliphatic hydrocarbon group, aryl group, halogen group, heterocyclic group, etc. are bonded. Can be used.

  Examples of the compound having two or more acid anhydride groups in the molecule include polycarboxylic acids such as tetracarboxylic dianhydride, hexacarboxylic dianhydride, hexacarboxylic dianhydride, and maleic anhydride copolymer resin. Anhydrides can be used. More specifically, as tetracarboxylic dianhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, oxydiphthalic dianhydride, diphenyl sulfone tetracarboxylic dianhydride, Diphenyl sulfide tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, perylene tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, "Ricacid TMTA-C", "Ricacid MTA-" manufactured by Shin Nippon Chemical Co., Ltd. 10 "," Licacid MTA-15 "," Licacid TMEG series "," Licacid TDA ", etc. can be used.

  Examples of the polyfunctional alcohol include aliphatic glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylene glycol, propylene glycol, butanediol, pentanediol, neopentyl glycol, hexamethylene glycol, and dodecamethylene glycol. Alicyclic glycols such as cyclohexanedimethanol, 1,3-bis (2-hydroxyethoxy) benzene, 1,2-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, etc. Aromatic diols such as glycols, bisphenols, hydroquinone and 2,2-bis (4-β-hydroxyethoxyphenyl) propane containing the above aromatic group can be used. Furthermore, the polyfunctional alcohol may contain a unit derived from a polyfunctional alcohol having 3 or more hydroxy groups. For example, glycerin, 1,1,1-trimethylolethane, 1,1,1- Trimethylolpropane, 1,1,1-trimethylolmethane, pentaerythritol and the like can be used. Two or more of these polyfunctional alcohols can be used in combination.

  In this invention, said acidic group containing polyol can be used individually or in combination.

  In producing the acidic group-containing urethane (meth) acrylate resin [A] contained in the colored composition of the present invention, if necessary, in addition to the essential components (a1), (a2) and (a3) above, Other compounds containing a plurality of active hydrogens, such as polyols, may be reacted. Specifically, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, 1,3-butanediol, 1,4-butanediol, polybutylene Glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,9-nonanediol, cyclohexanedimethanol, hydrogenated bisphenol A, polycaprolactone diol, trimethylolethane, polytril Methylolethane, trimethylolpropane, polytrimethylolpropane, pentaerythritol, polypentaerythritol, sorbitol, mannitol, alla Polyhydric alcohols such as tall, xylitol, galactitol, glycerin, polyglycerin, polytetramethylene glycol; polyether polyols such as polyethylene oxide, polypropylene oxide, block copolymer or random copolymer of ethylene oxide / propylene oxide Polyester polyols that are condensates of polyhydric alcohols or polyether polyols with polybasic acids such as maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid, and isophthalic acid; caprolactone-modified poly; Examples include polyols such as caprolactone-modified polyols such as tetramethylene polyol, polyolefin-based polyols, and polybutadiene-based polyols such as hydrogenated polybutadiene polyol.

  In addition, when producing the acidic group-containing urethane (meth) acrylate resin [A] contained in the colored composition of the present invention, if necessary, other than the essential components (a1), (a2) and (a3) above In addition, a diisocyanate may be reacted. Specifically, the aromatic diisocyanate, aliphatic diisocyanate, araliphatic diisocyanate, alicyclic diisocyanate, etc. mentioned above are mentioned.

  The acid value of the acidic group-containing urethane (meth) acrylate resin [A] contained in the colored composition of the present invention is preferably 10 to 100, more preferably 20 to 90, and more preferably 30 to 80. It is particularly preferred. If the acid value is less than 10, the pigment dispersibility may be deteriorated due to insufficient pigment adsorbing ability. If the acid value exceeds 100, the pigment adsorbing ability is too high, so that sufficient steric repulsion effect cannot be obtained. Dispersibility may decrease on the contrary.

  Moreover, it is preferable that the weight average molecular weights (polystyrene conversion value by GPC measurement) of acidic group containing urethane (meth) acrylate type resin [A] contained in the coloring composition of this invention are 3000-100000, 3000-50000. It is more preferable that it is 3,000-30000. When the weight average molecular weight is less than 3000, sufficient steric repulsion effect cannot be maintained, and thus the pigment dispersibility is poor. When the weight average molecular weight exceeds 100,000, the pigment dispersibility is lowered due to cross-linking of pigment particles.

  As the catalyst used for the production of the acidic group-containing urethane (meth) acrylate resin [A] contained in the colored composition of the present invention, a known catalyst can be used. Examples thereof include tertiary amine compounds and organometallic compounds. Examples of tertiary amine compounds include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo. -[4.3.0] -5-Nonene etc. are mentioned.

  Examples of organometallic compounds include tin compounds and non-tin compounds. Examples of the tin compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyl Examples thereof include tin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, and tin 2-ethylhexanoate. Examples of non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride, and lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate. Iron, such as iron 2-ethylhexanoate and iron acetylacetonate, cobalt-based such as cobalt benzoate and cobalt 2-ethylhexanoate, zinc-based such as zinc naphthenate and zinc 2-ethylhexanoate, naphthene Examples thereof include zirconium acid. These can be used alone or in combination.

  The acidic group-containing urethane (meth) acrylate resin [A] contained in the colored composition of the present invention can be produced using only the raw materials listed so far, but the viscosity becomes high and the reaction becomes non-uniform. From the above problem, it is preferable to use a solvent. As the solvent to be used, known solvents can be used. For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, toluene, xylene, acetonitrile and the like can be mentioned. The reaction temperature for obtaining the acidic group-containing urethane (meth) acrylate resin [A] contained in the colored composition of the present invention is preferably 40 to 120 ° C. More preferably, it is 50-100 degreeC.

  As a manufacturing method of acidic group containing urethane (meth) acrylate type resin [A] contained in the coloring composition of the present invention, polyisocyanate (a1), hydroxyl group containing (meth) acrylate (a2), acidic group containing polyol (a3 ) And a polymer diol or diisocyanate added as necessary, and is not particularly limited, and can be produced by a known method. For example, a method in which all raw materials are mixed and reacted, a reaction product of polyisocyanate (a1) and hydroxyl group-containing (meth) acrylate (a2), an acidic group-containing polyol (a3), and optionally a polyol and And / or a method of reacting diisocyanate. The latter synthesis method is particularly preferable.

  As the pigment contained in the coloring composition of the present invention, organic or inorganic pigments can be used alone or in admixture of two or more. The pigment is preferably a pigment having high color developability and high heat resistance, particularly a pigment having high heat decomposition resistance, and an organic pigment is usually used. Below, the specific example of the organic pigment which can be used for the coloring composition of this invention is shown with a color index number.

  Examples of the red coloring composition for forming the red filter segment include C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 246, 254, 255, 264, Red pigments such as 272 can be used. A yellow pigment and an orange pigment can be used in combination with the red composition.

  Examples of the yellow coloring composition for forming the yellow filter segment include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 1 Yellow pigments such as 75, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199 can be used.

  Examples of the orange coloring composition for forming the orange filter segment include C.I. I. Orange pigments such as Pigment Orange 36, 43, 51, 55, 59, 61 can be used.

  Examples of the green coloring composition for forming the green filter segment include C.I. I. Green pigments such as Pigment Green 7, 10, 36, and 37 can be used. A yellow pigment can be used in combination with the green composition.

  Examples of the blue coloring composition for forming the blue filter segment include C.I. I. Blue pigments such as Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, and 64 can be used. Blue compositions include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, and other purple pigments can be used in combination.

  Examples of the cyan coloring composition for forming the cyan filter segment include C.I. I. Blue pigments such as Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, and 81 can be used.

  Examples of magenta colored compositions for forming magenta color filter segments include C.I. I. Pigment Violet 1, 19, C.I. I. Purple pigments such as Pigment Red 144, 146, 177, 169, 81, and red pigments can be used. A yellow pigment can be used in combination with the magenta composition.

  In addition, inorganic pigments include titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean [red iron oxide (III)], cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt green, amber , Titanium black, synthetic iron black, carbon black and the like. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability and the like while maintaining a balance between saturation and lightness. The coloring composition of the present invention can contain a dye within a range that does not decrease heat resistance for color matching.

  A pigment derivative having a basic group, an anthraquinone derivative having a basic group, an acridone derivative having a basic group or a triazine derivative having a basic group included in the present invention are represented by the following general formulas (1), (2), ( It has at least one substituent selected from the group represented by 3) and (4).

  Formula (1)

式（２）

Formula (2)

式（３）

Formula (3)

式（４）

Formula (4)

X, X ¹ and X ² represent —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond.

  m represents an integer of 1 to 10.

R ¹ , R ² Each independently represents an optionally substituted alkyl group, alkenyl group, phenyl group, or a heterocyclic ring formed by integrating R ¹ and R ² . However, the heterocycle may contain further nitrogen, oxygen or sulfur atoms. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.

R ³ Represents an alkyl group, an alkenyl group or a phenyl group which may be substituted. As for carbon number of an alkyl group and an alkenyl group, 1-10 are preferable.
R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom, an optionally substituted alkyl group, an alkenyl group or a phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferable.

Y represents —NR ⁸ —Z—NR ⁹ — or a direct bond.

R ⁸ and R ⁹ each independently represents a hydrogen atom, an optionally substituted alkyl group, an alkenyl group or a phenyl group. As for carbon number of an alkyl group and an alkenyl group, 1-5 are preferable.

  Z represents an alkylene group, an alkenylene group, or a phenylene group, which may be substituted. As for carbon number of an alkyl group and an alkenyl group, 1-8 are preferable.

  P represents a substituent represented by the formula (5) or a substituent represented by the formula (6).

  Q represents a hydroxyl group, an alkoxyl group, a substituent represented by the formula (5) or a substituent represented by the formula (6).

  Formula (5)

式（６）

Formula (6)

Examples of the alkyl group in R ^{1 to} R ⁹ in the above general formula include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Examples of the alkenyl group include a vinyl group and a propenyl group.

  Examples of the alkylene group in Z in the general formula include a methylene group, an ethylene group, a propylene group, and a butylene group. Examples of the alkenylene group include a vinylene group and a propenylene group.

  Examples of the alkoxyl group for Q in the above general formula include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

  Examples of the functional group that may be substituted include a halogen group, a cyano group, an alkoxyl group, an amino group, a hydroxyl group, a nitro group, and an epoxy group.

  Examples of the amine component used for forming the substituents represented by the formulas (1) to (6) include dimethylamine, diethylamine, N, N-ethylisopropylamine, N, N-ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine, dibutylamine , Di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N-methyloctadecylamine, Didecylamine, diallylamine, N, -Ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminoamyl Amine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N, N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N-methyl-laurylaminopro Ruamine, N, N-ethyl-hexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecholine, 3-pipecholine, 4 -Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-Piperidinmethanol, Pipecolic acid, Isonipecotic acid, Methyl isnicopetinate, Ethyl isonicopetic acid, 2-Piperidinethanol, Pyrrolidine, 3-hydroxy Pyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, N-aminopropyl-4-pipecholine, N-aminopropyl Examples include propylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine and the like.

  Organic dyes contained in pigment derivatives having basic groups include, for example, diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine, flavantrons, anthanthrones , Indanthrone, pyranthrone, violanthrone, anthraquinone dyes, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindoline dyes, isoindolinone dyes, quinophthalone dyes, selenium dyes It is a dye such as a dye or a metal complex dye. In addition, anthraquinone derivatives having a basic group and acridone derivatives having a basic group include alkyl groups such as methyl and ethyl groups, amino groups, nitro groups, hydroxyl groups or methoxy groups, alkoxy groups such as ethoxy groups, chlorine, etc. It may have a substituent such as halogen.

  The triazine contained in the triazine derivative having a basic group includes an alkyl group such as a methyl group and an ethyl group, an amino group, or an alkylamino group such as a dimethylamino group, a diethylamino group, and a dibutylamino group, a nitro group, a hydroxyl group, Alternatively, an alkoxy group such as a methoxy group, an ethoxy group, or a butoxy group, a halogen such as chlorine, or a phenyl group that may be substituted with a methyl group, a methoxy group, an amino group, a dimethylamino group, a hydroxyl group, or the like, a methyl group, or an ethyl group Group, methoxy group, ethoxy group, amino group, dimethylamino group, diethylamino group, nitro group, optionally substituted with phenylamino group etc. Triazine.

  The pigment derivative, anthraquinone derivative and acridone derivative having a basic group included in the present invention can be synthesized by various synthetic routes. For example, after introducing a substituent represented by formula (7) to formula (10) into an organic dye, anthraquinone or acridone, the substituent represented by formula (1) to formula (4) is reacted with the above substituent. Amine component to be formed, for example, N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] -1,3,5-triazine It can be obtained by reacting 2-ylamino] aniline or the like.

Formula (7) —SO ₂ Cl
Formula (8) -COCl
Formula (9) —CH ₂ NHCOCH ₂ Cl
Equation (10) -CH ₂ Cl

  Further, when the organic dye is an azo dye, the substituent represented by the formula (1) to the formula (4) is previously introduced into the diazo component or the coupling component, and then the coupling reaction is performed, thereby performing the azo pigment. Derivatives can also be produced.

  The triazine derivative having a basic group included in the present invention can be synthesized by various synthetic routes. For example, an amine component starting from cyanuric chloride and forming a substituent represented by formula (1) to formula (4) on at least one chlorine of cyanuric chloride, such as N, N-dimethylaminopropylamine or N- It can be obtained by reacting methylpiperazine or the like and then reacting the remaining chlorine of cyanuric chloride with various amines or alcohols.

  Specific examples of the derivative having a specific basic group are shown below, but are not limited thereto. These derivatives can be used alone or in admixture of two or more.

  The compounding amount of the acidic group-containing urethane (meth) acrylate resin [A] contained in the colored composition of the present invention is preferably 0.01 to 40% by weight based on the pigment. The content is preferably 0.001 to 40% by weight based on the pigment. Moreover, you may mix various solvents, resin, an additive, a dispersing agent, etc. if needed.

  The pigment carrier contained in the coloring composition of the present invention is composed of a monomer and, if necessary, a resin. As monomers, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene Glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri ( (Meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentylglyco Various acrylic esters such as rubidiglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, melamine (meth) acrylate, epoxy (meth) acrylate, urethane acrylate And methacrylic acid ester, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile These may be used alone or in combination of two or more.

  The resin is a transparent resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. The transparent resin includes a thermoplastic resin, a thermosetting resin, and a photosensitive resin, and these can be used alone or in combination of two or more. Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and phenol resin. , Polyester resins, acrylic resins, alkyd resins, styrene resins, polyamide resins, rubber resins, cyclized rubbers, celluloses, polybutadiene, polyimide resins, and the like. Moreover, as a thermosetting resin, an epoxy resin, a benzoguanamine resin, a rosin modified maleic acid resin, a rosin modified fumaric acid resin, a melamine resin, a urea resin etc. are mentioned, for example.

  As the photosensitive resin, a (meth) acrylic compound having a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amino group, A resin obtained by reacting cinnamic acid and introducing a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the linear polymer is used. Also, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin maleic anhydride copolymer is half-treated with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. An esterified product is also used.

  When the composition is cured by ultraviolet irradiation, a photoinitiator or the like is added to the colored composition of the present invention. As photoinitiators, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxy Acetophenone photoinitiators such as cyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Benzoin photoinitiators such as benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4 Benzophenone photoinitiators such as methyldiphenyl sulfide, thioxanthone photoinitiators such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2, 4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-pienyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl)- -Triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4- Triazine photoinitiators such as trichloromethyl (4′-methoxystyryl) -6-triazine, borate photoinitiators, carbazole photoinitiators, imidazole photoinitiators and the like are used.

  These photoinitiators are used alone or in combination of two or more. As sensitizers, α-acyloxime ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrene. Compounds such as quinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone Can also be used together.

  The colored composition of the present invention can be adjusted in the form of a solvent development type or alkali development type colored resist material. The colored resist material is obtained by dispersing a pigment in a pigment carrier containing a thermoplastic resin, a thermosetting resin or a photosensitive resin and a monomer, and a pigment composition composed of a pigment or two or more pigments is necessary. Accordingly, together with the photoinitiator, it can be produced by finely dispersing in a pigment carrier using various dispersing means such as a three roll mill, a two roll mill, a sand mill, a kneader, and an attritor. The colored composition of the present invention can also be produced by mixing several types of pigments separately dispersed on a pigment carrier.

  The coloring composition of the present invention is mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove dust. When dispersing the pigment in the pigment carrier, a dispersion aid such as a resin-type pigment dispersant and a surfactant can be appropriately used. The dispersion aid is excellent in dispersing the pigment and has a great effect of preventing re-aggregation of the pigment after dispersion. Therefore, when a coloring composition obtained by dispersing the pigment in the pigment carrier using the dispersion aid is used. Provides a color filter excellent in transparency.

  The resin-type pigment dispersant has a pigment affinity part having a property of adsorbing to the pigment and a part compatible with the pigment carrier, and adsorbs to the pigment to stabilize the dispersion of the pigment on the pigment carrier. It works. Specific examples of resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and the like Salt or the like is used. In addition, water-soluble resins such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, and polyvinylpyrrolidone, and water-soluble Polymer compounds, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and the like are used. These can be used alone or in admixture of two or more.

  Examples of the surfactant include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid. Anionic surfactants such as sodium, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sol Nonionic surfactants such as tan monostearate and polyethylene glycol monolaurate; Chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; Alkyl betaines such as alkyldimethylaminoacetic acid betaines; Alkyl imidazolines These amphoteric surfactants can be used, and these can be used alone or in admixture of two or more.

  In the colored composition of the present invention, a pigment is sufficiently dispersed in a pigment carrier and applied on a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm to form a filter segment. In order to facilitate the process, a solvent can be contained. Examples of the solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n amyl ketone, propylene glycol monomethyl ether toluene, methyl ethyl ketone. , Ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent and the like, and these are used alone or in combination.

  In addition, the colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time of the composition. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Examples thereof include phosphine and phosphite. The pigment is preferably contained in the coloring composition at a ratio of 1.5 to 7% by weight. Further, the pigment is preferably contained in the final filter segment in a proportion of 10 to 40% by weight, more preferably 20 to 40% by weight, and the remainder substantially consists of a resinous binder provided by the pigment carrier. .

  The color filter of the present invention comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment, or at least one magenta filter segment, at least one cyan filter segment, and at least It comprises one yellow filter segment, wherein at least one filter segment is formed using the colored composition of the present invention.

  The color filter of this invention can be manufactured by forming the filter segment of each color on a transparent substrate using the coloring composition of this invention by the photolithographic method. As the transparent substrate, a glass plate or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is used.

  Each color filter segment is formed by the photolithography method by the following method. That is, the colored film composition prepared as the solvent developing type or alkali developing type colored resist material has a dry film thickness of 0.2 on a transparent substrate by a coating method such as spray coating, spin coating, slit coating or roll coating. It applies so that it may become ~ 5micrometer. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or an alkaline developer, or spraying the developer with a spray or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the printing method can be manufactured.

  In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution. In order to increase the UV exposure sensitivity, after coating and drying the colored resist material, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method or the like in addition to the photolithography method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a transparent substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. is there. The transfer method is a method in which a color filter layer is formed in advance on the surface of a peelable transfer base sheet, and this color filter layer is transferred to a desired transparent substrate.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In Examples and Comparative Examples, “parts” means “parts by weight” and “%” means “% by weight”. First, adjustment of the acrylic resin solution and the acidic group-containing urethane (meth) acrylate resin solution used in Examples and Comparative Examples will be described. The molecular weight of the resin is a weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).

[Production Example 1]
(Preparation of acidic group-containing urethane (meth) acrylate resin solution 1)
In a four-necked flask equipped with a stirrer, reflux condenser, gas inlet tube, thermometer, and dropping funnel, 173.7 parts of trade name biscoat # 300 (pentaerythritol triacrylate, Osaka Organic Chemical Co., Ltd.), dimethylolbutane Acid (DMBA, Nippon Kasei Co., Ltd.) 48.2 parts, Spiroglycol (Nippon Hydrazine Industry Co., Ltd.) 30.2 parts, DM Z 4470BA (Isophorone diisocyanate 70% isocyanurate product, Sumitomo Bayer Urethane Co., Ltd.) 197 4 parts, 50.5 parts of isophorone diisocyanate (IPDI, manufactured by Degussa Japan Co., Ltd.) and 500.0 parts of cyclohexanone were gradually heated, reacted at 90 ° C., and 2270 cm ⁻ based on isocyanate group by IR. after confirming the ^first disappearance of the peak, then cooled to 40 ° C., poly Urethane was obtained solution (U-1).

[Production Examples 2, 4, 5]
(Preparation of acidic group-containing urethane (meth) acrylate resin solutions 2, 4 and 5)
In the same manner as in Production Example 1, the polyurethane solution (U) described in Table 1 was synthesized to obtain (U-2), (U-4) and (U-5).

[Production Example 3]
(Preparation of acidic group-containing urethane (meth) acrylate resin solution 3)
In a four-necked flask equipped with a stirrer, reflux condenser, gas inlet tube, thermometer, and dropping funnel, trade name Biscote # 300 173.7 parts, DM Z 4470 BA 197.4 parts, cyclohexane 350.0 g was added at 80 ° C. Then, IPDI 50.5 parts, DMBA 48.2 parts, spiroglycol 30.2 parts, cyclohexanone 150.0 parts were further charged, and the temperature was gradually raised and reacted at 90 ° C. After confirming the disappearance of the peak at 2270 cm ⁻¹ based on the isocyanate group by IR, it was cooled to 40 ° C. to obtain a polyurethane solution (U-3).

[Production Example 6]
(Preparation of acrylic resin solution, pigment carrier resin)
450 parts of cyclohexanone was placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomer and thermal polymerization initiator was added dropwise at the same temperature over 1 hour to carry out a polymerization reaction.

  20.0 parts of methacrylic acid, 10.0 parts of methyl methacrylate, 55.0 parts of n-butyl methacrylate, 15.0 parts of 2-hydroxyethyl methacrylate, 4.0 parts of 2,2′-azobisisobutyronitrile are added dropwise. did. After completion of dropping, the reaction was allowed to proceed at 80 ° C. for 3 hours. Further, 1.0 part of 2,2′-azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was continued at 80 ° C. for 1 hour to obtain an acrylic resin solution. The weight average molecular weight of the acrylic resin was 40000. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20%. An acrylic resin solution was prepared.

Biscoat # 300: Pentaerythritol triacrylate (Osaka Organic Chemical Co., Ltd.)
Benzyl alcohol: Wako Pure Chemical Industries, Ltd. DMBA: Dimethylol butanoic acid (Nippon Kasei Co., Ltd.)
Spiroglycol: (Nippon Hydrazine Industry Co., Ltd.)
C-1015N: Bifunctional polycarbonate polyol, trade name Kuraray polyol C-1015N (manufactured by Kuraray Co., Ltd.)
IPDI: Isophorone diisocyanate (Degussa Japan Co., Ltd.)
DMZ 4470 BA: 70% isocyanurate product of isophorone diisocyanate (butyl acetate solution, manufactured by Sumitomo Bayer Urethane Co., Ltd.)
Anone: cyclohexanone

[Example 1]
10.0 parts of ε-type copper phthalocyanine pigment (CI Pigment Blue 15: 6) (“Heliogen Blue L-6700F” manufactured by BASF), 1.0 part of phthalocyanine pigment derivative (derivative 48), urethane resin solution [ A] A mixture of 1.0 part of (U-1), 40.0 parts of an acrylic resin solution, and 48.0 parts of cyclohexanone was stirred and mixed uniformly, and then dispersed in a sand mill for 5 hours using glass beads having a diameter of 1 mm. Thereafter, the mixture was filtered with a 5 μm filter to prepare a copper phthalocyanine dispersion.

  Subsequently, 45.0 parts of the above copper phthalocyanine dispersion, 15.0 parts of an acrylic resin solution, 5.6 parts of trimethylolpropane triacrylate (“NK Ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.), a photoinitiator (“Ciba Geigy” Irgacure 907 ") 2.0 parts, sensitizer (" EAB-F "manufactured by Hodogaya Chemical Co., Ltd.) 0.2 parts, and cyclohexanone 32.2 parts were stirred and mixed uniformly to obtain a 1 [mu] m filter To obtain a blue colored composition (resist material).

[Examples 2 to 5 and Comparative Examples 1 to 6]
First, a pigment dispersion was prepared in the same manner as in Example 1, and then each colored composition (resist material) was obtained.

Blue pigment: ε-type copper phthalocyanine pigment (CI Pigment Blue 15: 6) (“Heliogen Blue L-6700F” manufactured by BASF)
Blue derivative: phthalocyanine pigment derivative (derivative 48)
Purple pigment: Dioxazine violet pigment (CI Pigment Violet 23) (“Lionogen Violet RL” manufactured by Toyo Ink Co., Ltd.)
Purple Derivative: Dioxazine Pigment Derivative (Derivative 49)
Pigment for red: 8.33 parts of diketopyrrolopyrrole pigment (CI Pigment Red 254) ("Irga Four Red B-CF" manufactured by Ciba Geigy), anthraquinone pigment (CI Pigment Red 177) 1 .33 parts (“Chromophthal Red A2B” manufactured by Ciba Geigy), 0.34 parts of anthraquinone pigment (CI Pigment Yellow 199) (“Chromophthal Yellow GT-AD” manufactured by Ciba Geigy)
Red derivative: Anthraquinone derivative (derivative 4)
Yellow pigment: Isoindoline pigment (CI Pigment Yellow 139) ("Paliotor Yellow D1819" manufactured by BASF)
Yellow derivative: Triazine derivative (derivative 44)
Monomer: Trimethylolpropane triacrylate (Shin Nakamura Chemical "NK Ester ATMPT")
Photoinitiator: “Irgacure 907” manufactured by Ciba Geigy
Sensitizer: “EAB-F” manufactured by Hodogaya Chemical Co., Ltd.
Solvent: cyclohexanone

  In order to evaluate the performance of the resist agent of the present invention, the viscosity of the obtained paint was measured with an E-type viscometer (at 10 rpm, 25 ° C.). The lower the viscosity, the better. The viscosity at 100 rpm was also determined, and the TI value (= viscosity at 10 rpm / viscosity at 100 rpm, 25 ° C.) was determined. A TI value closer to 1 indicates a Newtonian fluid and is better.

  Moreover, the obtained resist material was apply | coated on the glass substrate of 100 mm x 100 mm and 1.1 mm thickness using the spin coater, and the application board | substrate was obtained. Next, after drying at 70 ° C. for 20 minutes, ultraviolet exposure was performed with an integrated light amount of 150 mJ using an ultrahigh pressure mercury lamp. A coated substrate prepared at 230 ° C. for 20 minutes and further heated at 260 ° C. for 1 hour was prepared, and chromaticity was measured by a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.) using a C light source. The color difference (ΔE) was calculated and the heat resistance was evaluated. The results are shown in Table 3.

  As shown in Table 3, Examples 1 to 5, which are colored compositions for color filters of the present invention, had good viscosity characteristics and excellent heat resistance, whereas Comparative Examples 1 to 3 Comparative Examples 1 to 5 using the urethane resin [A] having a high double bond equivalent or a high weight average molecular weight were poor in viscosity or heat resistance.

Claims (9)

Double bond equivalent formed by reacting polyisocyanate (a1) having three or more isocyanate groups, hydroxyl group-containing (meth) acrylate (a2) and acidic group-containing polyol (a3) is 150 to 400, and weight An acidic group-containing urethane (meth) acrylate resin [A] having an average molecular weight of 3,000 to 100,000;
Pigments,
And at least one basic group-containing derivative selected from the group consisting of a pigment derivative having a basic group, an anthraquinone derivative having a basic group, an acridone derivative having a basic group, and a triazine derivative having a basic group. A basic group-containing derivative having at least one basic group selected from the group represented by the following general formulas (1), (2), (3) and (4):
A coloring composition for a color filter comprising a pigment carrier containing a monomer.
Formula (1)

Formula (2)

Formula (3)

Formula (4)

Formula (5)

Formula (6)

(In the formula, X, X ¹ and X ^{2 each} represent —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond.
m represents an integer of 1 to 10.
R ¹ , R ² Each independently represents an optionally substituted alkyl group, alkenyl group, phenyl group, or a heterocyclic ring formed by integrating R ¹ and R ² . However, the heterocycle may contain further nitrogen, oxygen or sulfur atoms.
R ³ Represents an alkyl group, an alkenyl group or a phenyl group which may be substituted.
R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom, an optionally substituted alkyl group, an alkenyl group or a phenyl group.
Y represents —NR ⁸ —Z—NR ⁹ — or a direct bond.
R ⁸ and R ⁹ each independently represents a hydrogen atom, an optionally substituted alkyl group, an alkenyl group or a phenyl group.
Z represents an alkylene group, an alkenylene group, or a phenylene group, which may be substituted.
P represents a substituent represented by the formula (5) or a substituent represented by the formula (6).
Q represents a hydroxyl group, an alkoxyl group, a substituent represented by the formula (5) or a substituent represented by the formula (6). )   The color composition for color filter according to claim 1, wherein the polyisocyanate (a1) is a trimer of diisocyanate.   The colored composition for a color filter according to claim 1 or 2, wherein the polyisocyanate (a1) is a trimer of isophorone diisocyanate.   The proportion derived from the polyisocyanate (a1) in the nonvolatile component of the acidic group-containing urethane (meth) acrylate resin [A] is 25 wt% to 60 wt%. The coloring composition for color filters as described.   The coloring composition for a color filter according to any one of claims 1 to 4, wherein the hydroxyl group-containing (meth) acrylate (a2) is pentaerythritol tri (meth) acrylate and / or dipentaerythritol penta (meth) acrylate. object.   The coloring composition for a color filter according to any one of claims 1 to 5, wherein the acidic group-containing polyol (a3) is dimethylolbutanoic acid or dimethylolpropionic acid.   The acidic group-containing urethane (meth) acrylate resin [A] is obtained by reacting the acidic group-containing polyol (a3) with the reaction product of the polyisocyanate (a1) and the hydroxyl group-containing (meth) acrylate (a2). The colored composition for a color filter according to any one of claims 1 to 6.   The coloring composition for a color filter according to any one of claims 1 to 7, wherein the pigment carrier further contains a resin.   A color filter comprising a filter segment formed from the colored composition for a color filter according to claim 1.