JP2017173566A - Colored composition for color filter, and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored composition for a color filter to be used in a developing step using a potassium hydroxide developing solution, which shows good linearity of a pattern and leaves little residue, and a color filter excellent in resolution formed by using the above colored composition for a color filter.SOLUTION: The colored composition for a color filter is a colored composition for a color filter to be subjected to potassium hydroxide development, and the composition comprises a colorant (A), a resin type dispersant (B), a binder resin (C), a photopolymerizable monomer (D) and a photopolymerization initiator (E). The photopolymerizable monomer (D) contains a (meth)acryl compound (D1) having 1 to 3 unsaturated bond groups in one molecule and having a weight average molecular weight of 250 to 1000, by 10 mass% to 90 mass% in 100 mass% of the photopolymerizable monomer (D). The resin type dispersant (B) comprises a resin type dispersant having a glass transition temperature (Tg) of 30 to 100°C and an amine value of 50 to 150 mgKOH/g.SELECTED DRAWING: None

Description

  The present invention relates to a color liquid crystal display device, a color composition for color filter used in the production of a color filter used in a color imaging device, and the like, and a color filter including a filter segment formed using the same. is there.

In the liquid crystal display device, a liquid crystal material and a pixel are interposed between two polarizing plates, a voltage is applied to each pixel to change the alignment state of the liquid crystal material, and the degree of polarization of light passing through the first polarizing plate is changed. It is a display device that changes and controls the transmitted light passing through the second polarizing plate to display the screen.
By providing a color filter between the two polarizing plates, color display becomes possible, and it has come to be used for televisions, personal computers, monitors and the like.

  As a method of forming a color filter, a color resist is formed by mixing and preparing a photosensitive agent or an additive in a resin in which pigment particles as a colorant are dispersed in a resin, and this color resist is formed on a substrate by a spin coater or the like. A method of forming a coating film with a coating apparatus is generally used. Then, a method of obtaining pixels of each color by performing selective exposure through a photomask with an aligner, a stepper, etc., developing with an alkali developer to dissolve and remove the unexposed portions, and performing thermosetting (for example, (See Patent Documents 1 and 2). This is a method for producing a color filter by repeating this operation.

  In general, a sodium carbonate developer or a potassium hydroxide developer is used as an alkaline developer used for forming a color filter.

  In recent years, as the color purity of color liquid crystal display devices has increased, the concentration of pigments contained in colorants has increased, and the solubility of coating films in alkaline developers has decreased significantly. Residue on the (unexposed portion) substrate is generated. Further, in order to obtain a clear color liquid crystal display device, the miniaturization of pixels progresses and the generation of residue becomes remarkable, and the display defect of the color liquid crystal display device becomes a problem. In addition, with the increase in contrast of color liquid crystal display devices, the use of a basic resin type dispersant is an effective means to stably disperse fine pigments. In some cases, the solubility was extremely low, which caused the residue to deteriorate. For this reason, it is becoming clear that the reduction of the glass transition temperature of the basic resin type dispersant is effective in reducing the residue, but the film hardness decreases with the decrease of the glass transition temperature. It is difficult to put it to practical use.

  For the residue on the substrate of the light-shielding part during development, it is effective to use a polyfunctional monomer containing a carboxyl group, as disclosed in Patent Document 3 and Patent Document 4, for example. Are known. However, when a potassium hydroxide developer is used, the coating film is not sufficiently soluble in the developer and curing is not sufficient.

JP-A-2-144502 JP-A-3-53201 Japanese Patent Laid-Open No. 10-332929 JP2012-168545A

  An object of the present invention is a coloring composition for a color filter used in a development process using a potassium hydroxide developer, wherein the linearity and residue of the pattern are good, and the coloring composition for a color filter is used. It is to provide a formed color filter having excellent resolution.

  As a result of intensive studies to solve the above problems, the present inventors have identified a specific photopolymerizable monomer and a specific color composition for forming a color filter using a potassium hydroxide developer. It was found that it was possible to obtain an excellent color filter having not only linearity of the pattern but also no residue by using the resin type dispersant of the present invention, and the present invention was made based on this knowledge. is there.

  That is, the present invention provides a color for a color filter containing a colorant (A), a resin-type dispersant (B), a binder resin (C), a photopolymerizable monomer (D), and a photopolymerization initiator (E). In the composition, the photopolymerizable monomer (D) is a photopolymerizable monomer having a weight average molecular weight of 250 to 1000 (meth) acrylic compound (D1) having 1 to 3 unsaturated bond groups in one molecule. 10% to 90% by mass in 100% by mass of the monomer (D), the resin-type dispersant (B) has a glass transition temperature (Tg) of 30 to 100 ° C., and an amine value of 50 to 150 mgKOH / g. It is related with the coloring composition for color filters for potassium hydroxide development characterized by containing the resin type dispersing agent which is.

  The coloring composition for a color filter of the present invention has good pattern linearity and residue in the development process using a potassium hydroxide developer. By using the coloring composition for a color filter, the linearity of the pattern is obtained. It is possible to provide a color filter with good residue.

  First, the coloring composition for a color filter of the present invention will be described. The coloring composition for a color filter of the present invention is for potassium hydroxide development, and includes a colorant (A), a resin-type dispersant (B), a binder resin (C), a photopolymerizable monomer (D), And a colored composition for a color filter containing a photopolymerization initiator (E), the photopolymerizable monomer (D) has a weight average molecular weight of 250 to 1000 having 1 to 3 unsaturated bond groups in one molecule. (Meth) acrylic compound (D1) is contained in 10% by mass to 90% by mass in 100% by mass of the photopolymerizable monomer (D), and the resin-type dispersant (B) has a glass transition temperature (Tg). However, the amine value is 30 to 100 ° C. and the amine value is 50 to 150 mgKOH / g.

<Colorant (A)>
The coloring composition for a color filter of the present invention can arbitrarily use various conventionally known pigments / dyes as a colorant, and these pigments / dyes can be used alone or in any ratio as necessary. Two or more kinds can be mixed and used.

(dye)
Examples of the dye include compounds classified in the color index (published by The Society of Dyers and Colorists), and dyes and known dyes described in dyeing notes (color dyeing company). Acid dyes, metal complex dyes, basic dyes, direct dyes, disperse dyes, mordant dyes, and the like. Of these, oil-soluble dyes, acid dyes, metal complex dyes, and basic dyes are preferred.
Also, according to chemical structure, azo dye, cyanine dye, triphenylmethane dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, acridine dye, styryl dye, coumarin dye, quinoline And dyes and nitro dyes.

(Pigment)
As a means for reducing the primary particle size of the pigment, a method of mechanically pulverizing the pigment (referred to as a grinding method), a solution dissolved in a good solvent is introduced into a poor solvent, and a pigment having a desired primary particle size is precipitated. And a method of producing a pigment having a desired primary particle size at the time of synthesis (referred to as a synthetic precipitation method). Depending on the synthesis method and chemical properties of the pigment used, an appropriate method can be selected for each pigment. Each method will be described below.

In the grinding method, the pigment is mechanically kneaded with a grinding agent such as water-soluble inorganic salt such as salt and a water-soluble organic solvent that does not dissolve it using a ball mill, sand mill, or kneader (hereinafter, this process is salted). In this method, the inorganic salt and the organic solvent are washed away with water and dried to obtain a pigment having a desired specific surface area. However, since the pigment may crystallize due to the salt milling treatment, a method of preventing crystal growth by adding a solid resin that is at least partially dissolved in the water-soluble organic solvent or a dispersion aid described later during the treatment is effective. It is.
As for the ratio of the pigment to the inorganic salt, if the ratio of the inorganic salt is increased, the efficiency of refining the pigment is improved. Generally, the inorganic salt is used in an amount of 100 to 3000 parts by weight, preferably 200 to 20000 parts by weight, based on 100 parts by weight of the pigment.

Further, the water-soluble organic solvent is added so that the pigment and the inorganic salt are uniformly solidified, and depending on the blending ratio of the pigment and the inorganic salt, it is usually 50 to 300 mass with respect to 100 mass parts of the pigment. The quantity of parts is used.
The grinding method will be explained in more detail. A small amount of a water-soluble organic solvent is added as a wetting agent to a mixture of a pigment and a water-soluble inorganic salt, and after kneading with a kneader or the like, the mixture is put into water and high-speed. Agitate with a mixer to make a slurry. Next, a pigment having a desired primary particle size can be obtained by filtering, washing, and drying the slurry.

  The precipitation method is a method in which a pigment is dissolved in an appropriate good solvent and then mixed with a poor solvent to precipitate a pigment having a desired primary particle size. The primary method depends on the type and amount of the solvent, the precipitation temperature, the precipitation rate, etc. The particle size can be controlled. In general, pigments are difficult to dissolve in a solvent, so the solvents that can be used are limited. For example, strongly acidic solvents such as concentrated sulfuric acid, polyphosphoric acid, and chlorosulfonic acid, or bases such as dimethylformamide solution of liquid ammonia and sodium methylate Solvents and the like are known.

  As a typical example of the precipitation method, there is an acid pasting method in which a solution in which a pigment is dissolved in an acidic solvent is poured into another solvent and reprecipitated to obtain fine particles. Industrially, a method of injecting a sulfuric acid solution into water is generally used from the viewpoint of cost. The sulfuric acid concentration is not particularly limited, but is preferably 95 to 100% by mass. The amount of sulfuric acid used with respect to the pigment is not particularly limited. However, if the amount is small, the solution viscosity is high and handling becomes bad. Conversely, if the amount is too large, the pigment processing efficiency decreases, so 300 to 1000 parts by mass with respect to 100 parts by mass of pigment. It is preferable to use sulfuric acid. The pigment need not be completely dissolved. The temperature at the time of dissolution is preferably from 0 to 50 ° C. Below this temperature, sulfuric acid may freeze and the solubility will be low. If the temperature is too high, side reactions tend to occur. The temperature of the water to be injected is preferably 1 to 60 ° C., and if the injection is started at a temperature higher than this temperature, it boils with the heat of dissolution of sulfuric acid, and the operation is dangerous. It will freeze at temperatures below this. The injection time is preferably 0.1 to 30 minutes with respect to 1 part of the pigment.

The primary particle size of the pigment can be controlled while taking into consideration the degree of sizing of the pigment by selecting a method that combines a precipitation method such as the acid pasting method and a grinding method such as the salt milling method. Is more preferable because the fluidity as a dispersion can be secured at this time.
At the time of salt milling or acid pasting, a dispersion aid such as a pigment derivative, a resin-type dispersant, or a surfactant described later can be used in combination in order to prevent pigment aggregation associated with primary particle size control. In addition, by controlling the primary particle size in the form of coexistence of two or more pigments, even a pigment that is difficult to disperse alone can be finished as a stable dispersion.

The synthetic precipitation method is a method of synthesizing a pigment and simultaneously depositing a pigment having a desired primary particle size. However, when the produced fine pigment is taken out from the solvent, if the pigment particles are not aggregated into large secondary particles, filtration, which is a general separation method, becomes difficult. It is applied to azo pigments that are easily synthesized in water.
Furthermore, as a means for controlling the primary particle diameter of the pigment, the primary particle diameter of the pigment is reduced and dispersed simultaneously by dispersing the pigment for a long time with a high-speed sand mill or the like (so-called dry milling method in which the pigment is dry-pulverized). It is also possible.

<Resin type dispersant (B)>
The resin-type dispersant (B) has a colorant affinity part having a property of adsorbing to the added colorant and a compatible part in the colorant carrier, and adsorbs to the added colorant to cause the colorant It serves to stabilize dispersion in the carrier. The colorant carrier refers to a component excluding a colorant such as a binder resin and a photopolymerizable monomer. Specific examples of the resin type dispersant (B) include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, and polycarboxylic acid. Alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters and their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups And oil-based dispersants such as salts thereof, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone, etc. Water-soluble resins, water-soluble polymer compounds, polyesters, Polyacrylate, ethylene oxide / propylene oxide adduct, phosphoric ester or the like is used, they may be used alone or in combination, it is not necessarily limited thereto.

  A polymer dispersant having a basic functional group is preferred because the viscosity of the dispersion is lowered and a high contrast is exhibited with a small addition amount of the resin type dispersant (B), and a nitrogen atom-containing graft copolymer is preferred. In addition, a nitrogen atom-containing acrylic block copolymer and a urethane polymer dispersant having a functional group containing a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocyclic ring, or the like in the side chain are preferable.

  Commercially available resin-type dispersants include Dsperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- P104, P104S, 220S, 6919, or SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000 manufactured by Nihon Lubrizol Corporation, such as Lactimon, Lactimon-WS or Bykumen. 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., Ciba Japan EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320 , 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 755 , 1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

Among these, the coloring composition for color filters in the present invention is a resin mold in which the resin-type dispersant (B) has a glass transition temperature (Tg) of 30 to 100 ° C. and an amine value of 50 to 150 mgKOH / g. It contains a dispersant.
As a result, it is possible to achieve a high contrast ratio and excellent pattern linearity and residue. When the amine value is lower than 50 mgKOH / g or higher than 150 mgKOH / g, the viscosity stability and the residue are remarkably deteriorated. Moreover, when Tg is less than 30 ° C., the pattern linearity is deteriorated, and when it exceeds 100 ° C., the residue becomes a problem.

The amine value is more preferably 70 to 110 mg KOH / g.
Tg is more preferably 50 to 70 ° C.
Thereby, viscosity stability, pattern linearity, and a residue become a better thing.

  The blending amount of the resin-type dispersant having a glass transition temperature (Tg) of 30 to 100 ° C. and an amine value of 50 to 150 mgKOH / g is preferably 0.1 to 55 with respect to 100 parts by mass of the colorant (A). Part by mass, more preferably 0.1 to 45 parts by mass. When the blending amount of the resin type dispersant having a glass transition temperature (Tg) of 30 to 100 ° C. and an amine value of 50 to 150 mgKOH / g is less than 0.1 parts by mass, the added effect is hardly obtained. If the amount is more than 55 parts by mass, excessive dispersion may adversely affect the dispersion. Other dispersants may be used in combination.

<Other dispersants>
When dispersing the colorant in the colorant carrier, other dispersants other than the resin-type dispersant (B) such as a pigment derivative and a surfactant may be appropriately contained. Since these dispersants have a great effect of preventing re-aggregation of the colorant after dispersion, a color composition obtained by dispersing the colorant in the colorant carrier has good spectral characteristics and viscosity stability.

(Dye derivative)
Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone, or triazine. 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, etc. can be used. These can be used alone or in combination of two or more.

  The blending amount of the pigment derivative is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, most preferably 3 with respect to 100 parts by mass of the colorant (A) from the viewpoint of improving the dispersibility of the additive colorant. More than part by mass. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by mass or less, and more preferably 35 parts by mass or less with respect to 100 parts by mass of the colorant (A).

(Surfactant)
Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

  The compounding amount of the surfactant is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass with respect to 100 parts by mass of the colorant (A). When the blending amount of the surfactant is less than 0.1 parts by mass, it is difficult to obtain the added effect, and when it is more than 55 parts by mass, the dispersion may be adversely affected by an excessive dispersant.

<Binder resin (C)>
The binder resin (C) is preferably a resin having a spectral 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 weight average molecular weight (Mw) of the binder resin (C) is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000 in order to disperse the colorant preferably. . The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  When the binder resin (C) is used as a photosensitive coloring composition for a color filter, a carboxyl group that functions as a colorant adsorption group and an alkali-soluble group during development, a fat that functions as an affinity group for the colorant carrier and the solvent The balance between the group and the aromatic group is important for the dispersibility, penetrability, developability, and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, no fine pattern remains.

  The binder resin (C) is preferably used in an amount of 20 parts by mass or more with respect to 100 parts by mass of the total mass of the colorant (A) because the film formability and various resistances are good. It is preferably used in an amount of 1000 parts by mass or less because the concentration is high and good color characteristics can be expressed.

(Thermoplastic resin)
Examples of the thermoplastic resin used for the binder resin (C) include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, Polyvinyl acetate, polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resin, etc. Is mentioned. Among them, it is preferable to use an acrylic resin.

Examples of the vinyl-based alkali-soluble resin copolymerized with an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfone group.
Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins having an unsaturated ethylenic double bond introduced by the following methods (i) and (ii).

[Method (i)]
As the method (i), for example, the side chain epoxy group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group and one or more other monomers is used. Then, the carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenic double bond is subjected to an addition reaction, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to convert the unsaturated ethylenic double bond and the carboxyl group into There is a way to introduce.

  Examples of the unsaturated ethylenic monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4 epoxybutyl (meth) acrylate, And 3,4 epoxy cyclohexyl (meth) acrylates, and these may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can also be hydrolyzed. Moreover, when an etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be increased.

  As a method similar to the method (i), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group and one or more other monomers. There is a method in which an unsaturated ethylenic monomer having an epoxy group is added to a part of a carboxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.

[Method (ii)]
As the method (ii), an unsaturated ethylenic monomer having a hydroxyl group is used, and a monomer of an unsaturated monobasic acid having another carboxyl group or another monomer is copolymerized. There is a method of reacting an isocyanate group of an unsaturated ethylenic monomer having an isocyanate group with a side chain hydroxyl group of the obtained copolymer.

  Examples of unsaturated ethylenic monomers having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) 12-hydroxystearic acid added (poly) ester mono (meth) acrylate can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable.

  Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. In addition, two or more types can be used in combination.

(Thermosetting compound)
In the present invention, a thermosetting compound may be further contained in combination with the thermoplastic resin which is a binder resin.

  Examples of the thermosetting compound include epoxy compounds and / or resins, benzoguanamine compounds and / or resins, rosin-modified maleic acid compounds and / or resins, rosin-modified fumaric acid compounds and / or resins, melamine compounds and / or resins, Examples include urea compounds and / or resins, phenol compounds and / or resins, but the present invention is not limited thereto.

<Organic solvent>
In the coloring composition of the present invention, the coloring agent is sufficiently dispersed and permeated in the coloring agent carrier, and is applied onto a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. In order to make it easy to form, it is preferable to contain an organic solvent. The organic solvent is selected in consideration of good applicability of the coloring composition, solubility of each component of the coloring composition, and safety.

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl- 1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, N, N-dimethyl Acetamide, N, N-dimethylformamide, n-butyl alcohol, n-butyl Benzene, n-propyl acetate, o-xylene, o-diethylbenzene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol Monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl Ether, ethylene glycol Dimonomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene Glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl Chill ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol Monopropyl ether, propylene glycol monomethyl ether, methoxypropyl acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate , Dibasic acid Le, and the like.
These solvents can be used alone or in admixture of two or more at any ratio as required.

  Among them, the dispersibility of the colorant, the penetrability, and the coating property of the coloring composition are good, so that ethyl lactate, methoxypropyl acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate It is preferable to use glycol acetates such as alcohol, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

  Moreover, since an organic solvent can adjust a coloring composition to appropriate viscosity and can form the colored film of the target uniform film thickness, it is 500-4000 parts mass part with respect to 100 mass parts of colorants (A). It is preferable to use in.

<Photopolymerizable monomer (D)>
The color filter coloring composition according to the present embodiment is a photopolymerizable monomer (D) having, as a photopolymerizable monomer (D), a (meth) acrylic compound (D1) having 1 to 3 unsaturated bond groups in one molecule. It is contained in an amount of 10% by mass to 90% by mass or less based on the total amount of monomers. Thereby, it can be excellent in pattern linearity and residue.
As the unsaturated bond group, an ethylenically unsaturated double bond is preferable.

((Meth) acrylic compound (D1))
The (meth) acrylic compound (D1) is a (meth) acrylic compound having 1 to 3 unsaturated bonding groups in one molecule, and having 1 to 3 unsaturated bonding groups in one molecule. Examples include (meth) acrylic acid esters of functional acrylates and / or polyfunctional methacrylates.

  Specifically, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, EO-modified phthalic acid (meth) acrylate, PO-modified phthalic acid (meth) acrylate, acrylated isocyanurate, bis (acrylate) Roxyneopentyl glycol) adipate, polyethylene glycol 200 di (meth) acrylate, polyethylene glycol 400 di (meth) acrylate, tetraethylene glycol di (meth) acrylate, EO modified trimethylolpropane triacrylate, PO modified trimethylolpropane tri (meta) ) Acrylate, tripropylene glycol di (meth) acrylate, tris (acryloxyethyl) isocyanurate, caprolactone modified tris (acrylo) Siethyl) isocyanurate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dicyclopentanyl di (meth) acrylate, EO modified bisphenol A di (meth) acrylate, PO modified bisphenol A di Examples include (meth) acrylate.

As these commercially available products, KAYARAD R526, KAYARAD PEG400DA, KAYARAD MAND, KAYARD NPGDA, KAYARAD R-167, KAYARAD HX-220, KAYARAD R-551, KAYARAD R712, KAYARAD R-60, KAYARAD R-60, manufactured by Nippon Kayaku Co., Ltd. -684, KAYARAD GPO-303, KAYARAD TMPTA, Toa Gosei M305, M306, M309, M310, M321, M325, M350 Osaka Organic Chemicals V # 310HP, V # 335HP, V # 700, V # 295, V # 330, V # 360, V # GPT, etc. can be suitably used.

  These (meth) acrylic compounds (D1) can be used singly or as a mixture of two or more at any ratio as required.

  Moreover, it is preferable that the molecular weights of the (meth) acrylic compound (D1) which has 1-3 unsaturated bond groups in 1 molecule are the range of 250-1000. A more preferable range is that the molecular weight of the (meth) acrylic compound is 300 to 600, and the pattern linearity and the residue are good. If the molecular weight is less than 250, pattern linearity is not preferred, and if the molecular weight is greater than 1000, residues are not preferred.

  The molecular weight and average molecular weight of the monomer specified in the present specification are expressed by theoretical values converted from atomic weights. The first decimal place was calculated as a significant figure, and the calculated value was rounded off to exclude the minority.

  The content of the (meth) acrylic compound (D1) having 1 to 3 unsaturated bonding groups in one molecule is 10% by mass to 90% by mass in 100% by mass of the total amount of the photopolymerizable monomer (D). is there. A more preferable range is that the content of the (meth) acrylic compound (D1) is 30 to 60% by mass in 100% by mass of the total amount of the photopolymerizable monomer (D), and the pattern linearity and the residue are good. When it is more than 90% by mass, pattern linearity is not preferable. Residues less than 10% by weight are not preferred.

  In addition, a residue is unpreferable when the (meth) acryl compound which has more than three unsaturated bond groups in 1 molecule is 100 mass%.

((Meth) acrylic compound (D2))
Moreover, the coloring composition which concerns on this embodiment contains the (meth) acrylic compound (D2) which has four or more unsaturated bond groups in 1 molecule as a photopolymerizable monomer (D). It is preferable to have 5 or 6 unsaturated bonding groups in one molecule, and it is also preferable to use 5 and 6 in combination.

  By including the (meth) acrylic compound (D2), a color filter with good pattern linearity can be produced.

  As the (meth) acrylic compound (D2) having 4 or more unsaturated bond groups in one molecule, polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Epoxy (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, 1,4-butanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol Di (meth) acrylate, polyester (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, tris (methacryloxyethyl) isocyanurate, dipen Various acrylic esters such as erythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexaacrylate, ditrimethylolpropane tetra (meth) acrylate, epoxy acrylate, pentaerythritol tetra (meth) acrylate, and the like Examples include methacrylic acid esters and (meth) acrylic acid.

  As these commercially available products, KAYARAD DPHA, KAYARAD DPEA-12, KAYARAD DPHA-2C, KAYARAD D-310, KAYARAD D-330, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-60, KAYARAD DPCA-120, Toa Gosei Co., Ltd. M-402, Osaka Organic V # 400, etc. can be used suitably.

  These (meth) acrylic compounds (D2) can be used alone or in admixture of two or more at any ratio as required.

  The content of the (meth) acrylic compound (D2) having 4 or more unsaturated bonding groups in one molecule is 10% by mass to 90% by mass in 100% by mass of the total amount of the photopolymerizable monomer (D). . A more preferable range is that the content of the (meth) acrylic compound (D2) is 40 to 70% by mass in 100% by mass of the total amount of the photopolymerizable monomer (D), and the pattern linearity and the residue are good. If it is more than 90% by mass, the residue is not preferred. When the amount is less than 10% by mass, pattern loss is observed and pattern linearity is not preferable.

(Other photopolymerizable monomers)
In addition, the colored composition of the present invention may be used in combination with other photopolymerizable monomers in addition to the (meth) acrylic compound (D1) as long as the effects of the present invention are not impaired.

  Specifically, polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, 1,4- Butanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyester (meth) acrylate, trimethylolpropane tri (meth) acrylate , Tris (acryloxyethyl) isocyanurate, tris (methacryloxyethyl) isocyanurate, dipentaerythritol penta (meth) acrylate, dipentaerythritol (Meth) acrylic compounds (D1) and (meth) acrylic compounds such as sa (meth) acrylate, caprolactone-modified dipentaerythritol hexaacrylate, ditrimethylolpropane tetra (meth) acrylate, epoxy acrylate, pentaerythritol tetra (meth) acrylate ( Acrylic esters and methacrylic esters deviating from D2), (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) Examples include acrylamide, N-vinylformamide, acrylonitrile and the like.

  As these commercially available products, KAYARAD R-128H, KAYARAD NPGDA manufactured by Nippon Kayaku Co., Ltd., M-321, M-211B, M-101A manufactured by Toa Gosei Co., Ltd., Biscoat # 405, Biscoat V-2500P, manufactured by Osaka Organic Chemicals 2- (2-vinyloxyethoxy) ethyl acrylate, 2- (2-vinyloxyethoxy) ethyl methacrylate, BDVE, TEGDVE, Nippon Carbide, Light Ester 041MA, Light Ester 14EG, UF-8001G, etc. Is mentioned.

  These other photopolymerizable monomers can be used singly or as a mixture of two or more at any ratio as required.

<Photopolymerization initiator (E)>
The photopolymerization initiator used in the present invention is a compound that generates active species capable of initiating polymerization of the photopolymerizable monomer by exposure to radiation such as ultraviolet rays, visible rays, far ultraviolet rays, electron beams, and X-rays. is there.

Examples of such a photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1 -One, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) Acetophenone series such as methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one Compound: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin iso Benzoin compounds such as propyl ether or benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 Benzophenone compounds such as', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4- Thioxanthone compounds such as diethyl thioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, -(P-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4, 6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl)- s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2, Triazine compounds such as 4-trichloromethyl- (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-ben) Oxime)], or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6 Phosphine compounds such as trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; A carbazole compound; an imidazole compound; or a titanocene compound is used.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

  The content of the photopolymerization initiator is preferably 5 to 200 parts by mass with respect to 100 parts by mass of the colorant (A), and more preferably 10 to 150 parts by mass from the viewpoint of photocurability and developability. preferable.

(Sensitizer)
Furthermore, the coloring composition of the present invention can contain a sensitizer.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', or 4,4'-tetra (t-butylperoxycarbonyl) benzopheno And 4,4′-diethylaminobenzophenone.
These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

  More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

  The content of the sensitizer is preferably 3 to 60 parts by mass with respect to 100 parts by mass of the photopolymerization initiator (E) contained in the colored composition, and 5 to 5 from the viewpoint of photocurability and developability. More preferably, it is 50 mass parts.

(Antioxidant)
The coloring composition for a color filter of the present invention can contain an antioxidant. Antioxidants are used to prevent the photopolymerization initiators and thermosetting compounds contained in the color filter coloring composition from oxidizing and yellowing due to thermal processes during thermal curing and ITO annealing. Can be high. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high coating film transmittance can be obtained.

  The “antioxidant” in the present invention may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type are used. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used. In addition, the antioxidant used in the present invention preferably does not contain a halogen atom.

  Among these antioxidants, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, or a sulfur antioxidant is preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Agents. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants.

  As the hindered phenol-based antioxidant, 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di- -T-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4- Nonylphenol, 2,2′-isobutylidene-bis- (4,6-dimethyl-phenol), 4,4′-butylidene-bis- (2-tert-butyl-5-methylphenol), 2,2′-thio -Bis- (6-tert-butyl-4-methylphenol), 2,5-di-tert-amyl-hydroquinone, 2,2'thiodiethylbis- (3,5-di-tert-butyl-4-hydroxy Phenyl) -propionate, 1,1,3-tris- (2′-methyl-4′-hydroxy-5′-t-butylphenyl) -butane, 2,2′-methylene-bis- (6- (1- Methyl-cyclohexyl) -p-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol, N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-) Hydrocinnamamide) and the like. In addition, oligomer-type and polymer-type compounds having a hindered phenol structure can also be used.

  Examples of hindered amine-based antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4 -Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3, 4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6 -Tetramethyl-4-piperidi ) Imino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) {(2, 2,6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl)- Polycondensate with 4-hydroxy-2,2,6,6-tetramethylpiperidine, N, N′-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2 , 6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, etc. Other oligomer type having a hindered amine structure as well as Rimmer type of compounds and the like can also be used.

  Phosphorous antioxidants include tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl Phosphite, diphenyltridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, 4,4 ′ isopropylidenediphenol phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di ( , 4-di-t-butylphenyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4′-butylidenebis (3-methyl-) 6-t-butylphenol) diphosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite, 3,5-di-t-butyl -4-hydroxybenzyl phosphite diethyl ester, sodium bis (4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3 -Bis (diphenoxyphosphonoxy)- Benzene, phosphorous acid ethyl bis (2,4-di-tert- butyl-6-methylphenyl), and the like. In addition, oligomer type and polymer type compounds having a phosphite structure can also be used.

  As sulfur-based antioxidants, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl]- o-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol and the like. In addition, oligomer type and polymer type compounds having a thioether structure can also be used.

  As the benzotriazole-based antioxidant, oligomer-type and polymer-type compounds having a benzotriazole structure can be used.

  Specific examples of the benzophenone antioxidant include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2- Hydroxy-4-octadecyloxybenzophenone, 2,2′dihydroxy-4-methoxybenzophenone, 2,2′dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2- Hydroxy-4-methoxy-5sulfobenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone and the like can be mentioned. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

  Examples of the triazine antioxidant include 2,4-bis (allyl) -6- (2-hydroxyphenyl) 1,3,5-triazine. In addition, oligomer-type and polymer-type compounds having a triazine structure can also be used.

  Examples of the salicylate ester antioxidant include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate, and the like. In addition, oligomer-type and polymer-type compounds having a salicylate structure can also be used.

  These antioxidants can be used singly or in combination of two or more at any ratio as required.

  Further, the content of the antioxidant is more preferably 0.5 to 5.0% by mass in 100% by mass of the solid content of the coloring composition because the spectral characteristics and sensitivity are good.

(Amine compound)
Moreover, the coloring composition of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen.

  Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

(Leveling agent)
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the coloring composition for a color filter of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the content of the leveling agent is preferably 0.003 to 0.5% by mass in 100% by mass of the total mass of the coloring composition.

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

(Curing agent, curing accelerator)
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivatives bicyclic amidine compounds and salts thereof (eg imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl) -4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc.), phosphorus compounds (for example tri Phenylphosphine ), Guanamine compounds (for example, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (for example, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino) -S-triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) Can do. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01-15 mass parts is preferable with respect to 100 mass parts of thermosetting resins.

(Other additive components)
The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity with time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

(Storage stabilizer)
Examples of the storage stabilizer include organic acids such as lactic acid and oxalic acid and methyl ether thereof, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine, and phosphites. The storage stabilizer can be used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the colorant (A).

(Adhesion improver)
Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the colorant (A) in the coloring composition.

(Multifunctional thiol)
The coloring composition of the present invention may contain a compound having two or more thiol (SH) groups as the polyfunctional thiol.
By using a polyfunctional thiol together with a photopolymerization initiator, a thiyl radical that acts as a chain transfer agent and is less susceptible to polymerization inhibition by oxygen is generated in the radical polymerization process after light irradiation, so the resulting colored composition is highly sensitive. It becomes. In particular, a polyfunctional aliphatic thiol in which an SH group is bonded to an aliphatic group such as methylene or ethylene group is preferable. Examples of the polyfunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropioate. , Trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid Tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibu Arylamino) -4,6-dimercapto--s- triazine and the like, preferably ethylene glycol bisthiopropionate, trimethylolpropane tris thiopropionate, pentaerythritol tetrakis thiopropionate.

These polyfunctional thiols can be used individually by 1 type or in mixture of 2 or more types.
The content of the polyfunctional thiol is preferably 0.05 to 100 parts by mass, and more preferably 1.0 to 50.0 parts by mass with respect to 100 parts by mass of the colorant (A). When the polyfunctional thiol content is less than 0.05 parts by mass, the effect of the chain transfer agent is small, and even when the content is more than 100 parts by mass, the polymerization initiation function is not improved, and developability, adhesion, and the like become insufficient. .

(Method for producing colored composition)
The coloring composition of the present invention comprises a colorant (A) in a colorant carrier such as a binder resin (C) and / or a solvent, preferably together with a dispersion aid, a kneader, a two-roll mill, a three-roll mill. And finely dispersed using various dispersing means such as a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor (colorant dispersion). At this time, two or more kinds of colorants or the like may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed.
When the solubility of the colorant such as a dye is high, specifically, it is highly soluble in the solvent to be used, and if it is dissolved and no foreign matter is confirmed by stirring, it is finely dispersed as described above. There is no need.

  Moreover, when using as a photosensitive coloring composition (resist material) for color filters, it can prepare as a solvent developing type or an alkali developing type coloring composition. The solvent development type or alkali development type coloring composition includes the colorant dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, other pigment dispersants, and additives. Etc. can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the colored composition, or may be added later to the prepared colored composition.

(Removal of coarse particles)
The colored composition of the present invention is prepared by means of centrifugal separation, filtration with a sintered filter or a membrane filter, and the like. Coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more It is preferable to remove the mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.

(Color filter)
The color filter of the present invention is a color filter comprising at least one filter segment formed from the coloring composition for a color filter of the present invention.
The color filter comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment, and the at least one filter segment comprises the coloring composition for a color filter of the present invention. It is preferable to form by using.

(Color filter manufacturing method)
The color filter of the present invention can be produced by a photolithography method using a colored composition.
Specifically, for example, a method for producing a color filter according to the following steps (i), (ii), (iii) and (iv), wherein the following color filter coloring composition comprises a colorant (A), a resin A mold dispersant (B), a binder resin (C), a photopolymerizable monomer (D), and a photopolymerization initiator (E),
The photopolymerizable monomer (D) is a photopolymerizable monomer (D1) having a weight average molecular weight of 250 to 1000 (meth) acrylic compound (D1) having 1 to 3 unsaturated bond groups in one molecule. ) 10% to 90% by mass in 100% by mass,
The resin-type dispersant (B) can be produced by a method for producing a color filter, which has a glass transition temperature (Tg) of 30 to 100 ° C. and an amine value of 50 to 150 mgKOH / g.
<Process>
(I): Step of obtaining a coating film by applying a coloring composition for a color filter on a substrate (ii): Step (iii) After step (i), exposing the coating film with ultraviolet rays through a mask (iii): After the step (ii), a pattern is obtained by developing the exposed coating film with a potassium hydroxide developer (iv): a step of post-baking the pattern after the step (iii)

  The coloring composition of the present invention is applied on a transparent substrate by a coating method such as spray coating, spin coating, slit coating, or roll coating so that the dry film thickness is 0.2 to 5 μm. 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 dipping in a potassium hydroxide developer or spraying the developer by spraying 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.

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, a water-soluble or alkaline water-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 colored composition of the present invention is excellent in resolution with no residue or pattern missing after development.

If the black matrix is formed in advance before forming the filter segment on the transparent substrate or the reflective substrate, the contrast of the display panel can be further increased. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. Further, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then a filter segment may be formed. By forming the filter segment on the TFT substrate, the aperture ratio of the panel can be increased and the luminance can be improved.
On the color filter of the present invention, an overcoat film or a transparent conductive film is formed as necessary.

  The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as the above.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “parts” and “%” represent “parts by mass” and “mass%”, respectively.

  Moreover, the measuring method of the average primary particle diameter of a pigment, the weight average molecular weight (Mw) of resin, and the measuring method of the acid value of resin are as follows.

(Average primary particle diameter of pigment)
The average primary particle diameter of the pigment was measured by a method of directly measuring the size of primary particles from an electron micrograph using a transmission electron microscope (TEM). Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the primary pigment particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was obtained by approximating the obtained particle size cube, and the volume average particle size was defined as the average primary particle size.

(Weight average molecular weight of resin (Mw))
The weight average molecular weight (Mw) of the resin was measured in terms of polystyrene measured using TSKgel column (manufactured by Tosoh Corporation) and GPC equipped with RI detector (manufactured by Tosoh Corporation, HLC-8120GPC) using THF as a developing solvent. It is a weight average molecular weight (Mw).

(Resin acid value)
To 0.5 to 1.0 part of the resin solution, 80 ml of acetone and 10 ml of water are added and stirred to dissolve uniformly, and a 0.1 mol / L KOH aqueous solution is used as a titrant and an automatic titrator (“COM-555”). Titration using Hiranuma Sangyo) and the acid value of the resin solution was measured. Then, the acid value per solid content of the resin was calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

<Method for producing binder resin solution>
(Production of binder resin solution (B-1))
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device was charged with 196 parts of cyclohexanone, heated to 80 ° C., and purged with nitrogen in the reaction vessel. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) 20.7 A mixture of 1.1 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction was further continued for 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes, and the nonvolatile content was measured. The methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass. Was added to prepare a binder resin solution (B-1). The weight average molecular weight (Mw) was 26000.

(Production of binder resin solution (B-2))
207 parts of cyclohexanone was charged into a reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2′-azobis A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin solution. Next, after the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK). MOI) A mixture of 6.5 parts, 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropwise addition, the reaction was further continued for 1 hour to obtain an acrylic resin solution. After cooling to room temperature, sample 2 parts of the resin solution, heat dry at 180 ° C. for 20 minutes, measure the nonvolatile content, and add cyclohexanone to the previously synthesized resin solution so that the nonvolatile content is 20% by mass. Thus, a binder resin solution (B-2) was prepared. The weight average molecular weight (Mw) was 18000.

<Production of resin-type dispersant solution>
(Production of resin-type dispersant solution (C-1))
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 133 parts of methoxypropyl acetate and heated to 110 ° C. while purging with nitrogen. The reaction vessel was charged with 38 parts of dimethylaminoethyl methacrylate, 162 parts of methyl methacrylate, and 6 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) and stirred until uniform. Thereafter, the reaction was carried out at the same temperature for 3 hours. In this way, a resin type dispersant solution having an amine value per solid content of 67.8 mg KOH / g and a weight average molecular weight of 9000 (Mw) was obtained.
After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Then, methoxypropyl acetate was added so that the non-volatile content was 20% by mass, and the resin-type dispersant was added. A solution (C-1) was obtained.

(Production of resin-type dispersant (C-2 to 7))
Resin-type dispersant solutions (C-2 to 7) were synthesized in the same manner as the resin-type dispersant solution (C-1) except that the composition and the amount (parts by mass) shown in Table 1 were changed.

<Manufacture of refined pigments>
(Red refined pigment (PR254-1))
Red pigment C.I. I. Pigment Red 254 (PR254) ("Irga Fore Red B-CF" manufactured by BASF) 152 parts, 8 parts of a pigment derivative of the chemical formula (1), 1600 parts of sodium chloride, and 190 parts of diethylene glycol 1 gallon kneader (Inoue Seisakusho) And kneaded at 60 ° C. for 10 hours. Next, the mixture is poured into 3 liters of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and solvent, and then 80 It was dried for 1 day at 0 ° C. to obtain a red refined pigment (PR254-1).

Chemical formula (1)

(Red refined pigment (PR177-1))
Red pigment C.I. I. 500 parts of Pigment Red 177 (PR177) (“chromophthaled red A2B” manufactured by BASF), 3500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. . Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a red-refined pigment (PR177-1) was obtained.

(Red refined pigment (PR242-1))
Red pigment C.I. I. 200 parts of Pigment Red 242 (“NOVOPERM SCARLET 4RF” manufactured by Clariant), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. As a result, a red refined pigment (PR242-1) was obtained.

(Green refined pigment (PG58-1))
Phthalocyanine green pigment C.I. I. 200 parts of Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine green pigment (PG58-1) was obtained.

(Yellow refined pigment (PY150-1))
Nickel complex yellow pigment C.I. I. 200 parts of Pigment Yellow 150 (“E-4GN” manufactured by LANXESS), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine yellow pigment (PY150-1) was obtained.

(Blue refined pigment (PB15: 6-1))
Blue pigment C.I. I. Pigment Blue 15: 6 (PB15: 6) (“Lionol Blue ES” manufactured by Toyocolor Co., Ltd.) 500 parts, 2500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho). The mixture was kneaded at 120 ° C. for 12 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a blue refined pigment (PB15: 6-1) was obtained.

(Purple refinement treatment pigment (PV23-1))
Dioxazine-based purple pigment C.I. I. 500 parts of Pigment Violet 23 (PV23) (“Fast Violet RL” manufactured by Clariant), 2500 parts of sodium chloride, and 250 parts of polyethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho). The mixture was kneaded at 120 ° C. for 12 hours. Next, this mixture is poured into about 5 liters of warm water, heated to about 70 ° C. and stirred with a high speed mixer for about 1 hour to form a slurry, then filtered and washed to remove sodium chloride and diethylene glycol, It dried at 80 degreeC all day and night, and obtained the purple refinement | purification processed pigment (PV23-1).

<Method for producing pigment dispersion>
(Red pigment dispersion (PR-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. And a red pigment dispersion (PR-1) was produced.

Red refined pigment (PR254-1): 15.0 parts resin type dispersant (C-1) solution: 25.0 parts binder resin solution (B-1): 25.0 parts solvent
PGMAC: 35.0 parts (methoxypropyl acetate)

(Red pigment dispersion (PR-2 to 3), yellow pigment dispersion (PY-1), green pigment dispersion (PG-1), blue pigment dispersion (PB-1 to 2), purple pigment dispersion ( PV-1))
The red pigment dispersion is the same as the red pigment dispersion (PR-1) except that the colorant, the resin-type dispersant, the acrylic resin solution, and the solvent are changed to the compositions and blending amounts (parts by mass) shown in Table 2. Body (PR-2 to 3), yellow pigment dispersion (PY-1), green pigment dispersion (PG-1), blue pigment dispersion (PB-1 to 2), purple pigment dispersion (PV-1) Was made.

(Blue pigment dispersion (PB-3-8))
Disperse the blue pigment in the same manner as the red pigment dispersion (PR-1), except that the colorant, resin-type dispersant, acrylic resin solution, and solvent were changed to the compositions and blending amounts (parts by mass) shown in Table 2. A body (PB-3 to 8) was prepared.

<Number of unsaturated functional groups and molecular weight of photopolymerizable monomer (D)>
The number of unsaturated functional groups and molecular weight of the photopolymerizable monomer used are shown.

[Example 1]
(Coloring composition ((R-R1))
A mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1.0 μm filter to prepare a colored composition (R-R1).

6. Pigment dispersion (PR-1): 20.0 parts Pigment dispersion (PR-2): 20.0 parts Binder resin solution (B-1): 10.0 parts (meth) acrylic compound (D1): Part 5 “Aronix M-350” manufactured by Toagosei Co., Ltd.
(Meth) acrylic compound (D2): 7.5 parts “Aronix M-403” manufactured by Toagosei Co., Ltd.
Photopolymerization initiator: 2.0 parts "Irgacure 907" manufactured by BASF
Solvent: 33.0 parts methoxypropyl acetate (PGMAC)

[Examples 2 to 21, Comparative Examples 1 to 9]
(Coloring composition (R-R2), (R-G1), (R-B1-27))
After stirring and mixing the mixture shown in Tables 5 and 6 and the blending amount (parts by mass) uniformly, the mixture was filtered through a 1 μm filter, and the same as in the colored composition (R-R1) of Example 1. Thus, colored compositions (R-R2), (R-G1), and (R-B1-27) of Examples 2 to 21 and Comparative Examples 1 to 9 were obtained.

IRG907; BASF "Irgacure 907"
PGMAC; methoxypropyl acetate

<Evaluation of coloring composition>
The coating compositions of the resulting colored composition (R-R1-2), (R-G1), (R-B1-27) were tested by the following method. The test results are shown in Table 7.

(Residue evaluation)
About the obtained coloring composition (R-R1-2), (R-G1), (R-B1-27), a film thickness is 2.5 micrometers on a 100 mm x 100 mm and 0.7 mm glass substrate. Then, UV exposure was performed under a condition of 100 mJ / cm ² through a mask having a predetermined pattern. Thereafter, a potassium hydroxide developer was sprayed by spraying to remove uncured portions and form a desired pattern. About the obtained coating film, it heat-processed for 40 minutes in 230 degreeC oven (post-baking), and the presence or absence of the residue was confirmed with the microscope (OLYMPUS Optical Co., Ltd. "BX-51"). In the evaluation, the remaining area of the residue in the square pixel having a hollow of 50 μm × 50 μm was calculated and evaluated as follows. The film thickness of the coating film was measured using Dektak 8 (manufactured by Nippon Vacuum Technology Co., Ltd.).

○: No residual Δ: 100 μm ² or more and less than 500 μm ²
×: 500 μm ² or more

(Pattern linearity evaluation)
About the obtained coloring composition (R-R1-2), (R-G1), (R-B1-27), a film thickness is 2.5 micrometers on a 100 mm x 100 mm and 0.7 mm glass substrate. Then, UV exposure was performed under a condition of 100 mJ / cm ² through a mask having a predetermined pattern. Thereafter, a potassium hydroxide developer was sprayed by spraying to remove uncured portions and form a desired pattern. The obtained coating film was subjected to a heat treatment (post-bake) for 40 minutes in an oven at 230 ° C., and the presence or absence of a pixel pattern was confirmed with a microscope (“BX-51” manufactured by Olympus Optical Co., Ltd.). In the evaluation, the number of missing rectangular pixel patterns of 1000 μm × 100 μm was calculated and evaluated as follows. The film thickness of the coating film was measured using Dektak 8 (manufactured by Nippon Vacuum Technology Co., Ltd.).

○: No missing pattern Δ: 1-20 pieces / 10 ⁵ μm ²
×: 21 or more / 10 ⁵ μm ²

  As shown in Table 7, the (meth) acrylic compound (D1) having a weight average molecular weight of 250 to 1000 having 1 to 3 unsaturated bond groups of the present invention in one molecule is used as a photopolymerizable monomer (D). 10% to 90% by mass in 100% by mass, the resin-type dispersant (B) has a glass transition temperature (Tg) of 30 to 100 ° C., and an amine value of 50 to 150 mgKOH / g. By using the colored composition containing the resin-type dispersant (B1), there was little residue and no pattern was lost.

  Among them, (meth) acrylic compound having 1 to 3 unsaturated bond groups in a molecule and having a weight average molecular weight of 300 to 700 is 30% to 60% by weight of the total amount of the photopolymerizable monomer, and the unsaturated bond. 40% to 70% by weight of (meth) acrylic compound (D2) having 4 or more groups in one molecule, and Tg of resin-type dispersant (B) is 50 to 70 ° C. and amine value In the coloring composition characterized in that the composition was 50 to 150 mgKOH / g, no residue was observed, the pattern linearity was excellent, and no pattern loss was observed.

  On the other hand, a (meth) acrylic compound acrylic resin having 1 to 3 unsaturated bond groups in one molecule and a weight average molecular weight of 1000 or more, or a weight average molecular weight 250 having 1 to 3 unsaturated bond groups in one molecule. When less than 10% by mass of the total amount of the photopolymerizable monomer of (meth) acrylic compound (D1) of ~ 1000, or when the Tg of the resin-type dispersant (B) is higher than 100 ° C, a residue is seen, When a (meth) acrylic compound having 1 to 3 unsaturated bond groups in a molecule and having a weight average molecular weight of less than 250 is used, the weight average molecular weight having 1 to 3 unsaturated bond groups in a molecule is 250 to 1000. When the amount of the (meth) acrylic compound is more than 90% by mass of the total amount of the photopolymerizable monomer, or when the Tg of the resin-type dispersant (B) is lower than 30 ° C., the coloring composition has poor pattern linearity. Missing of over emissions was seen many.

Therefore, according to the present invention, it was possible to produce a high-quality coloring composition for developing potassium hydroxide with no residue and no pattern loss and good linearity.
Thereby, it was confirmed that a color filter excellent in resolution and a liquid crystal display device were obtained.

Claims (6)

In the color filter coloring composition containing the colorant (A), the resin-type dispersant (B), the binder resin (C), the photopolymerizable monomer (D), and the photopolymerization initiator (E),
The photopolymerizable monomer (D) is a photopolymerizable monomer (D1) having a weight average molecular weight of 250 to 1000 (meth) acrylic compound (D1) having 1 to 3 unsaturated bond groups in one molecule. ) 10% to 90% by mass in 100% by mass,
Resin-type dispersant (B) contains a resin-type dispersant having a glass transition temperature (Tg) of 30 to 100 ° C. and an amine value of 50 to 150 mgKOH / g. Coloring composition for filters.   The colored composition for a color filter for potassium hydroxide development according to claim 1, wherein the (meth) acrylic compound (D1) has a weight average molecular weight of 300 to 700.   The coloring composition for a color filter for potassium hydroxide development according to claim 1 or 2, wherein the (meth) acrylic compound (D1) has an alkyleneoxy chain.   A color filter comprising a filter segment formed using the colored composition for color filter for potassium hydroxide development according to any one of claims 1 to 3.   A liquid crystal display device comprising the color filter according to claim 4. A method for producing a color filter according to the following steps (i), (ii), (iii) and (iv), wherein the following color filter coloring composition comprises a colorant (A), a resin-type dispersant (B), Containing a binder resin (C), a photopolymerizable monomer (D), and a photopolymerization initiator (E);
The photopolymerizable monomer (D) is a photopolymerizable monomer (D1) having a weight average molecular weight of 250 to 1000 (meth) acrylic compound (D1) having 1 to 3 unsaturated bond groups in one molecule. ) 10% to 90% by mass in 100% by mass,
The resin type dispersant (B) has a glass transition temperature (Tg) of 30 to 100 ° C. and an amine value of 50 to 150 mgKOH / g.

<Process>
(I): Step of obtaining a coating film by applying a coloring composition for a color filter on a substrate (ii): Step (iii) After step (i), exposing the coating film with ultraviolet rays through a mask (iii): After the step (ii), a pattern is obtained by developing the exposed coating film with a potassium hydroxide developer (iv): a step of post-baking the pattern after the step (iii)