TW201609990A - A red coloring agent composition for a color filter - Google Patents

Abstract

An object of the present invention is to provide a red coloring agent composition for a color filter, which can be used for a color filter for a display device such as TV monitors, and which have high brightness and have small changes of brightness even with a post baking treatment. The red coloring agent composition for a color filter includes a pigment, an pigment dispersant aid containing an acid group, a colorant, a pigment dispersant, a resin, a compound containing phosphate groups and salt thereof, and an organic solvent, wherein the colorant comprises at least one selected from the C.I. acid red 52, C.I. acid red 87, C.I. acid red 92, C.I. acid red 289, and C.I. acid red 388.

Description

Color filter with red colorant composition

The present invention relates to a red colorant composition for a color filter which can be used for the formation of a color filter for a color display device.

The color filter used in a color liquid crystal display device or the like is configured by arranging two or more fine bands (strips) of different hue in parallel on the surface of a transparent substrate such as glass, or fixing fine pixels in a vertical and horizontal direction. The sequence is configured. The pixel size is a fine size of 10 to several 100 μm, and each hue is neatly arranged in a predetermined order.

In the color liquid crystal display device, white light from the backlight is transmitted through the color filter to be colored, and a color image is displayed on the screen. Therefore, as a basic property of a color filter, high transparency is required. Therefore, conventionally, it is produced by using a so-called dyeing method in which a dye excellent in color characteristics is dispersed in a molecular state in a resin to perform dyeing. However, in recent years, as the use is diversified, when it is required to improve the reliability of heat resistance, light resistance, and the like, an organic pigment can be used instead of the above-described dye having limited performance. Further, various methods such as a printing method, an inkjet method, and a lithography method have been proposed for the method of producing a color filter. In particular, in the use of a television display or the like, a color filter having the following pixels is required: high brightness can be achieved, and high contrast of the overall image can be achieved.

The above-mentioned brightness and contrast performance largely depend on the kind of the pigment dispersed in each color pixel of the color filter, and in particular, Pigment Red 254, Pigment Red 177, and the like can be frequently used. For example, Patent Document 1 proposes a system in which an orange pigment is used in combination with Pigment Red 254 and Pigment Red 177 of a main red pigment. Patent Document 2 proposes a system in which the pigment red 176 is used to compensate for the contrast ratio of the pigment red 254 and the brightness of the pigment red 177. However, in recent years, the quality sought by the pixels of television displays has increased, and it has been difficult to achieve desired performance as a colorant by a colorant composition for color filters having only pigments. In particular, it has been proposed to use a pigment and a dye in a colorant composition for a color filter in order to achieve high brightness. Patent Document 3 proposes a system in which pigment red 254 and pigment red 177 are used as a pigment, and a modified product such as acid red 289 or acid red 87 is used as a dye. However, since the modification step of the dye is complicated, labor and cost are required. Therefore, it lacks practicality. Further, when a pigment and a dye are used in combination with a colorant composition for a color filter, the stability of the colorant composition for a color filter tends to be insufficient, and the color filter is produced. Before and after the post-baking step, there is a tendency for the brightness to decrease. [Prior Art Document] [Patent Literature]

[Patent Document 1] JP-A-2009-237462 (Patent Document 3) JP-A-2009-237521 (Patent Document 3) JP-A-2012-194521

An object of the present invention is to provide a red colorant composition for a color filter having a high brightness of a color filter which can be used for a display device such as a television display and which is small in brightness even after post-baking treatment.

The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found that a red colorant composition for a color filter which mainly consists of a pigment, a pigment dispersing aid having an acidic group, a dye, a pigment dispersing agent, and a resin can be obtained. The composition is a compound having a phosphate group or a salt thereof and an organic solvent, and has high luminance which can be used for a color filter, and is small in brightness even after post-baking treatment, thereby completing the present invention.

That is, the present invention is as follows, (1) a red colorant composition for a color filter mainly composed of a pigment, a pigment dispersing aid having an acidic group, a dye, a pigment dispersing agent, a resin, or a phosphate group or a salt compound and an organic solvent composition, characterized in that the pigment has a pyrrolopyrroledione skeleton selected from the group consisting of CI Acid Red 52, CI Acid Red 87, CI Acid Red 92, CI Acid Red 289, and CI. At least one of acid red 388. (2) The red colorant composition for a color filter according to (1), wherein the compound having a phosphate group or a salt thereof has an acid value of 10 to 300 mgKOH/g. (3) The red colorant composition for a color filter according to (1) or (2), wherein the content of the compound having a phosphate group or a salt thereof is 100 parts by mass based on 100 parts by mass of the dye 10 to 1000 parts by mass. The red coloring agent composition for a color filter according to any one of (1) to (3), wherein the pigment is a microparticulated pigment. (5) The red colorant composition for a color filter according to any one of (1) to (4) wherein the pigment dispersing aid having an acidic group is a sulfonic acid group. Pigment dispersing aid. In the present specification, the "acid value" is obtained by dissolving or dispersing a sample with propylene glycol monomethyl ether, and titrating the phenolphthalein as an indicator with an aqueous solution of potassium hydroxide at 25 ° C, and measuring the solution. The light pink point is used as the end point to calculate the value by the following formula. Acid value (mgKOH/g) = 56.1 × V × C / m V: titration (ml), C: concentration of the titration solution (mol / l), m: weight of the nonvolatile component (g) of the sample.

According to the present invention, it is possible to obtain a red colorant composition for a color filter which is excellent in brightness and which is small in brightness change by post-baking treatment.

As described above, when a pigment and a dye are used in combination with a red colorant composition for a color filter, the temporal stability of the colorant composition for a color filter tends to be insufficient, and in addition, color filtering is performed. There is a tendency for the brightness to decrease before and after the post-baking step of the sheet. This trend is examined by the following mechanism. That is, in the components of the coating film forming the color filter, the dye molecules have a relatively low molecular weight, so that the dye molecules heated in the post-baking treatment become easy to perform thermal motion. Further, since the dye molecules have a highly polar group such as a sulfonate, the thermally moving dye molecules become easily aggregated by the interaction of the highly polar groups with each other. As a result, in the color filter coating film after the post-baking treatment, a region containing an aggregate of dye molecules and a region containing relatively few dye molecules are generated. When the light of the backlight is irradiated on the color filter after the post-baking treatment, the low luminance is observed by the light transmitted through the relatively small area of the dye in the color filter coating film. According to the present invention, the change in brightness can be suppressed even after the post-baking treatment by the following mechanism. That is, by introducing a substance containing a phosphate group or a salt thereof into a colorant composition for a color filter, even if the dye molecules undergo thermal motion, the dye molecules have high polar groups by the phosphate group or a salt thereof. The interaction is hindered, so that even after the post-baking treatment, the dye molecules are uniformly present in the color filter coating film, and therefore, the change in brightness before and after the post-baking treatment becomes small.

Hereinafter, each component of the red coloring agent composition for a color filter of the present invention will be specifically described.

The present invention relates to a red colorant composition for a color filter of a display device such as a television display. The red colorant composition for the color filter may be a composition other than a resist, or may be Resist composition. In short, the red colorant composition for a color filter of a display device such as a television display of the present invention is a composition of a color filter which can be used for a display device such as a television display, and the effect of the present invention thus produced is A red colorant composition for a color filter having high brightness and having a small change in brightness even after post-baking treatment can be provided.

(Pigment) As the pigment, the red colorant composition for a color filter of the present invention uses a pigment having a pyrrolopyrroledione skeleton. Specific examples include CI Pigment Red 254, Brominated CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, CI Pigment Red 272, CI Pigment Orange 71, CI Pigment Orange 73, or CI Pigment Orange 81. Pigments such as, but not limited to these. As the pigment having a pyrrolopyrroledione skeleton, C.I. Pigment Red 254 or a bromide thereof is preferred. In particular, when C.I. Pigment Red 254 is used, the thickness of the film to obtain the necessary brightness is small, and the color characteristics (x, y, Y) become good. The amount of the pigment having a pyrrolopyrroledione skeleton in the present invention is preferably from 5 to 80% by mass, more preferably from 20 to 80% by mass based on the total solid content of the red colorant composition of the present invention. 50% by mass. In order to impart high definition and contrast to the red colorant composition for a color filter of the present invention, it is preferred to use a micronized coloring pigment. By performing the microparticulation treatment, the primary particle diameter of the colored pigment can be further fine and uniform. As the above-described microparticulation treatment, for example, it is preferred to carry out the microparticulation treatment as follows: an inorganic salt containing an untreated colored pigment and water-soluble (preferably in sodium chloride, cesium chloride, potassium chloride, etc.) The sodium chloride is a water-soluble inorganic salt having an average particle diameter of 50 μm or less as the water-soluble inorganic salt to be used, and a water-soluble dispersion medium (alkoxy alcohol, which does not substantially dissolve the water-soluble inorganic salt). A mixture of a glycol, an ether, and the like is used as a planetary mixer by a kneader, a roll mill, a ball mill, an attritor, a sand mill, and the Japanese Patent Publication No. 2006-192385. TRI-MIX (trade name) manufactured by Inoue Co., Ltd., and a kneading device such as Miracle KCK manufactured by Asada Iron Works Co., Ltd., which is a continuous uniaxial kneader, are kneaded, and the water-soluble one is removed. Salt milling treatment of inorganic salts and the above water-soluble dispersion medium.

(Pigment Dispersing Aid with Acid Group) The pigment dispersing aid having an acidic group used as the red coloring agent composition for a color filter of the present invention preferably has the same or similar molecule as the pigment. A pigment dispersing aid that introduces an acidic group having an affinity for an organic solvent is introduced into the basic skeleton of the structure. In the step of atomizing and dispersing the pigment, such a pigment dispersing aid adsorbs a part of the basic skeleton on the surface of the pigment, and the acidic group increases the affinity with the organic solvent or the pigment dispersing agent, thereby improving the fineness of the pigment dispersion. The effect of dispersion stability over time after dispersion. Further, since the pigment dispersing aid itself is dissolved in an organic solvent or a pigment dispersing aid in a state of being dispersed in a particulate form, it can be adsorbed on a wider surface of the pigment, which is more preferable. Among them, when a pigment dispersing aid having a sulfonic acid group or the like is used as the acidic group, good results can be obtained. In the red colorant composition for a color filter of the present invention, the amount of the pigment dispersing aid having an acidic group is from 0.5 to 30 parts by mass based on 100 parts by mass of the pigment. When the content of the above-mentioned pigment dispersing aid having an acidic group is less than 0.5 part by mass, the pigment dispersing effect is lowered. On the other hand, when it exceeds 30 parts by mass, the pigment dispersing effect is not continuously improved.

The above-mentioned pigment dispersing aid having an acidic group: (1) When a microparticulated pigment is used in the absence of a pigment dispersing aid having an acidic group, when the microparticulated pigment is dispersed, the relative The pigment dispersing aid having an acidic group is used in an amount of 0.5 to 30 parts by mass, preferably 3 to 15 parts by mass, per 100 parts by mass of the coloring pigment. (2) When a pigment which is microparticulated in the presence of a pigment dispersing aid having an acidic group is used, 0.5 to 30 parts by mass of the pigment dispersing aid is used per 100 parts by mass of the pigment during the microparticulation treatment of the pigment. It is preferably 3 to 15 parts by mass; and when the finely divided pigment is dispersed, 0 to 29.5 parts by mass, preferably 0 to 12 parts by mass, based on 100 parts by mass of the pigment, of the pigment dispersing aid having an acidic group. . Moreover, the sum of the amount of the pigment dispersing aid having an acidic group used in the microparticulation treatment and the amount of the pigment dispersing aid having an acidic group used in dispersing the microparticulated pigment, The pigment dispersing aid having an acidic group is used in an amount of 0.5 to 30 parts by mass, preferably 3 to 15 parts by mass, based on 100 parts by mass of the pigment. More specifically, as a pigment dispersing aid having an acidic group, a case of using a pigment dispersing aid having a sulfonic acid group will be described. When the CI Pigment Red 254 as a red pigment is dispersed as a pigment, a pigment selected from a pyrrolopyrroledione skeleton having the same skeleton as CI Pigment Red 254 and/or a pigment dispersion aid having a sulfonic acid group can be used. Or a sulfonate of a pigment (sulfonate of CI Pigment Red 254, sulfonated compound of brominated CI Pigment Red 254, sulfonate of CI Pigment Red 255, sulfonate of CI Pigment Red 264, sulfonate of CI Pigment Red 272, a pigment dispersing aid having at least one of a sulfonate group of a sulfonate of CI Pigment Orange 71, a sulfonate of CI Pigment Orange 73, a sulfonate of CI Pigment Orange 81, and the like, and a sulfonate of CI Pigment Red 2, wherein It is preferred to use a sulfonate of CI Pigment Red 2.

(Dye) As the dye used for the red colorant composition for a color filter of the present invention, a xanthene-based acid dye can be used. As the xanthene-based acid dye, CI Acid Red 50, CI Acid Red 51, CI Acid Red 52, CI Acid Red 87, CI Acid Red 92, CI Acid Red 289, CI Acid Red 388, and Acid Rudan are preferably used. Ming G, CI Acid Violet 9, CI Acid Violet 30. Among them, it is preferred to use C.I. Acid Red 52, C.I. Acid Red 87, C.I. Acid Red 92, C.I. Acid Red 289 or C.I. Acid Red 388.

(Compound having a phosphate group or a salt thereof) As the compound having a phosphate group or a salt thereof used in the red colorant composition for a color filter of the present invention, for example, DISPERBYK-111, DISPERBYK-102, DISPERBYK-106 can be used. (manufactured by BYK Chemical Co., Ltd.), PLYSURF A212C, PLYSURF A215C, PLYSURF A208F, PLYSURF A 208N, PLYSURF A 208B, PLYSURF A 219B, PLYSURF A 210D, PLYSURF AL, PLYSURF AL12H (manufactured by First Industrial Pharmaceutical Co., Ltd.), and the like. Further, a polymerizable compound having a phosphate group or a salt thereof and a polymer copolymerized with another polymerizable compound may also be used. As the polymerizable compound having a phosphate group or a salt thereof, Light Ester P-1M, Light Ester P-2M (manufactured by Kyoeisha Chemical Co., Ltd.), or the like can be used. In the red colorant composition for a color filter of the present invention, the compound having a phosphate group or a salt thereof is preferably used in an amount of 10 to 1000 parts by mass, more preferably 50% by mass based on 100 parts by mass of the dye. ~500 parts by mass. When the amount of the compound having a phosphate group or a salt thereof is less than 10 parts by mass or more than 1000 parts by mass based on 100 parts by mass of the dye, the stability of the colorant composition for a color filter may be changed over time. Insufficient, in addition, the brightness may be lowered before and after the post-baking step in the production of the color filter. In the red colorant composition for a color filter of the present invention, the acid value of the compound having a phosphoric acid group or a salt thereof is preferably from 10 to 300 mgKOH/g, more preferably from 30 to 250 mgKOH/g, further preferably 50 to 200 mgKOH/g. When the acid value of the compound having a phosphoric acid group or a salt thereof is less than 10 mgKOH/g or more than 300 mgKOH/g, the stability of the colorant composition for color filters may be insufficient over time. The brightness is sometimes lowered before and after the post-baking step in the color filter production.

(Pigment Dispersant) As the pigment dispersant used for the red colorant composition for a color filter of the present invention, a pigment dispersant conventionally used in the field of color filters can be used. In the red colorant composition for a color filter of the present invention, the amount of the pigment dispersant used is preferably from 1 to 100 parts by mass, more preferably from 1 to 60 parts by mass, per 100 parts by mass of the coloring pigment. When the content of the pigment dispersant is less than 1 part by mass, the pigment dispersing effect may be lowered. On the other hand, when it exceeds 100 parts by mass, the developing property may be lowered.

As a pigment dispersing agent, the following are mentioned, for example. (1) Amine and/or an imine group of a polyamine compound (for example, a poly(lower) alkyleneamine such as a polyarylamine, a polyvinylamine or a polyethyleneimine) and a group selected from the group consisting of having a free carboxyl group A reaction product of at least one of polyester, polyamide, and polyester decylamine. (2) A carbodiimide compound having at least one side chain selected from the group consisting of a polyester side chain, a polyether side chain, and a polypropylene side chain, and a basic nitrogen-containing group in the molecule. (3) A reaction product of a low molecular amine compound such as a poly(lower) alkyleneimine or a methylimidopropylamine and a polyester having a free carboxyl group. (4) A polyester having one hydroxyl group such as an alcohol such as methoxypolyethylene glycol or a caprolactone polyester, or a compound having two to three isocyanate-reactive functional groups, and having isocyanate group reactivity A reaction product obtained by sequentially reacting a functional group and a tertiary amino group-containing aliphatic or heterocyclic hydrocarbon compound with an isocyanate group of a polyisocyanate compound. (5) A reaction product of reacting a polyisocyanate compound with a hydrocarbon compound having an amine group in a polymer of an acrylate having an alcoholic hydroxyl group. (6) A reaction product obtained by adding a polyether chain to a low molecular amine compound. (7) A reaction product obtained by reacting a compound having an amine group in a compound having an isocyanate group. (8) A reaction product obtained by reacting a linear polymer having a free carboxyl group and an organic amine compound having one secondary amine group in the polyepoxy compound. (9) A reaction product of a polycarbonate compound having a functional group reactive with an amine group at one end and a polyamine compound. (10) selected from the group consisting of methyl methacrylate, methyl methacrylate, methyl propyl acrylate, methyl butyl acrylate, methyl stearyl acrylate, methyl benzyl acrylate, methyl acrylate, At least one of methacrylic acid ester or acrylate such as ethacrylate, propyl acrylate, butyl acrylate, stearyl acrylate, benzyl acrylate, and acrylamide, A At least one of a basic group-containing polymerizable monomer such as acrylamide, N-hydroxymethyl decylamine, vinyl imidazole, vinyl pyridine, a monomer having an amine group and a polycaprolactone skeleton A copolymer of at least one of styrene, a styrene derivative, and another polymerizable monomer. (11) An acrylic block copolymer composed of a block having a basic group such as a tertiary amino group or a quaternary ammonium base and a block having no basic functional group. (12) A pigment dispersant obtained by subjecting a polycarbonate compound to a Michael addition reaction in a polyarylamine. (13) A carbodiimide compound having at least one polybutadiene chain and a basic nitrogen-containing group. (14) A carbodiimide compound having at least one side chain having a guanamine group and a basic nitrogen-containing group in the molecule. (15) A polyurethane compound having an amine group containing an ethylene oxide chain and an propylene oxide chain and having an amine group quaternized by a quaternary ammonating agent. (16) A compound obtained by reacting an isocyanate group of an isocyanate compound having an isocyanurate ring in the molecule with an active hydrogen group of a compound having an active hydrogen group in the molecule and having an indazole ring and/or an azobenzene skeleton The total amount of the urethane bond and the urea bond formed by the reaction of the isocyanate group derived from the isocyanurate ring having an isocyanurate ring and the reaction between the isocyanate group and the active hydrogen group, in the molecule of the compound, The number of the carbazole ring and the azobenzene skeleton is 15 to 85% of the compound.

Now, a method of manufacturing a color filter using a red colorant composition using a color filter is mainly a resist method, and later, a color filter used by a method other than the resist method is colored with red. The composition of the agent and the red colorant composition for the color filter used in the resist method, and the components and the like contained in each of them are described below.

[A. Red colorant composition for color filter used in addition to the resist method] A case where the red colorant composition for a color filter of the present invention is not a resist composition will be described. When the present invention is not a red colorant resist composition for a color filter, the composition does not have active energy ray curability, and is mainly composed of a pigment, a pigment dispersing aid having an acidic group, a dye, a pigment dispersing agent, and a resin. A compound having a phosphate group or a salt thereof and an organic solvent. As the coloring pigment, the pigment dispersing aid having an acidic group, and the pigment dispersing agent, the above-described coloring pigment, a pigment dispersing aid having an acidic group, and a pigment dispersing agent are used.

(Resin) The resin used for the red colorant composition for a color filter of the present invention can be used in a total wavelength range of 400 to 700 nm in the visible light region, and the transmittance is 80% or more, preferably 95% or more. Resin. Examples of such resins include thermosetting resins, thermoplastic resins, and alkali-soluble resins. These can be used individually or in mixture of 2 or more types. The total solid content of the resin with respect to the red colorant composition for the color filter is preferably 5 to 94% by mass, more preferably 20 to 50% by mass based on the total mass of the resin to be used. The range of %. Examples of the thermosetting resin and the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, and polycondensation. Vinyl acetate, polyurethane resin, phenolic resin, polyester resin, acrylic resin, alkyd resin, styrene resin, polyamide resin, rubber resin, cyclized rubber, epoxy resin, cellulose, polybutylene Diene, polyimide resin, benzoguanamine resin, melamine resin, urea resin, and the like. The alkali-soluble resin is described in detail in a red colorant resist composition for a color filter to be described later.

(Organic solvent) The organic solvent used as the red colorant composition for a color filter of the present invention may, for example, be ethylene glycol monomethyl ether, ethylene glycol monoethyl ether or ethylene glycol. Isopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, two An ether organic solvent such as ethylene glycol diethyl ether, diethylene glycol dimethyl ether or diethylene glycol methyl ethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl Ether ester organic solvent such as ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; methyl isobutyl ketone, cyclohexyl a ketone organic solvent such as ketone, 2-heptanone or δ-butyrolactone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 3- Methyl-3-methoxybutylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropane Ethyl acetate, ethyl ethoxyacetate, ethyl hydroxyacetate, An ester organic solvent such as n-amyl formate; an alcohol solvent such as methanol, ethanol, isopropyl alcohol or butanol; N-methylpyrrolidone, N,N-dimethylformamide, N,N-di A nitrogen-containing organic solvent such as methyl acetamide or the like. These can be used individually or in mixture of 2 or more types. The red colorant composition for a color filter of the present invention is mainly composed of a pigment, a pigment dispersing aid having an acidic group, a dye, a pigment dispersing agent, a resin, a compound having a phosphate group or a salt thereof, and an organic solvent, and these components are composed of these components. The color filter is 90 to 100% by mass in the red colorant composition.

(Additives to be added as needed) Various additives such as a thermal polymerization inhibitor, an ultraviolet absorber, and an antioxidant can be suitably used depending on the method for producing the colorant composition for a color filter.

(Method for Producing Red Colorant Composition for Color Filter of the Present Invention) A method of producing a red colorant composition for a color filter which is not used for the resist method using the above materials will be described.

Obtaining CI Pigment Red 254, which is micronized in the presence or absence of a pigment dispersing aid having an acidic group (preferably a sulfonate of CI Pigment Red 2, etc.), dispersing a pigment having an acidic group A mixture of a solvent (preferably a sulfonate of CI Pigment Red 2, etc.), a pigment dispersant, a resin, a compound having a phosphate group or a salt thereof, an organic solvent, and other additives as needed. The obtained mixture is kneaded and dispersed by various dispersing machines such as a roll mill, a kneader, a high-speed stirring device, a bead mill, a ball mill, a sand mill, an ultrasonic disperser, and a high-pressure disperser to obtain a color filter. The light sheet is composed of a red colorant.

In the above production method, when the microparticulated microparticles are micronized in the presence of a pigment dispersing aid having an acidic group, even if the dispersing of the micronized pigment does not contain a pigment dispersing aid having an acidic group It can also be manufactured. Further, in the above production method, the resin, the compound having a phosphate group or a salt thereof may be added before the kneading/dispersion treatment and/or after the kneading/dispersion treatment.

[B. Red colorant composition for color filter used in the resist method] Next, the red colorant composition for a color filter of the present invention is used as a colorant dispersion resist for color filters The case of the composition will be described. When the present invention is a red colorant resist composition for a color filter, the composition has active energy ray curability, and is an alkali-developable resist composition mainly composed of a pigment, a dye, and an acid. A pigment dispersing aid of a group, a pigment dispersing agent, a resin, a compound having a phosphate group or a salt thereof, and an organic solvent, and the resin is a resin containing an alkali-soluble resin and a photopolymerizable compound. As the pigment, a pigment dispersing aid having an acidic group, and a pigment dispersing agent, it is used as described above.

(Alkyl Soluble Resin as a Resin) The alkali-soluble resin of the resin used as the red colorant resist composition for a color filter of the present invention functions as a binder with respect to a red pigment, and is manufactured in color. In the filter, the alkali-soluble resin which is soluble in the developing solution used in the development processing step, particularly preferably an alkali developing solution, is not particularly limited, and a conventional alkali-soluble resin can be used. Among them, an alkali-soluble resin having a carboxyl group is preferable, and a copolymer of an ethylenically unsaturated monomer having one or more carboxyl groups and another copolymerizable ethylenically unsaturated monomer is more preferable. Specific examples thereof include an ethylenically unsaturated monomer having a carboxyl group such as acrylic acid or methacrylic acid, and styrene or 2-hydroxyethyl acrylate which is copolymerizable with an ethylenically unsaturated monomer having a carboxyl group. -hydroxyethyl methacrylate, aryl acrylate, methyl aryl acrylate, benzyl acrylate, methyl benzyl acrylate, cyclohexyl acrylate, methyl cyclohexyl acrylate, glyceryl monoacrylate, glyceryl acrylate In the monomers, oligomers, such as methyl ester, N-phenyl maleimide, polystyrene macromonomer, polymethyl methacrylate macromonomer, phenolphthalein epoxy diacrylate A copolymer of at least one ethylenically unsaturated monomer. The acid value of the alkali-soluble resin in the present invention is preferably from 50 to 300 mgKOH/g from the viewpoint of development characteristics. Further, the weight average molecular weight of the alkali-soluble resin in the present invention is usually from 1,000 to 100,000 in terms of development characteristics and solubility in an organic solvent. Further, in the present invention, the weight average molecular weight of the alkali-soluble resin is a polystyrene-equivalent weight average molecular weight obtained by gel permeation chromatography (Gel Permeation Chromatography). In the present invention, Water 2690 (manufactured by Waters Corporation) was used as a device, and PLGel 5 μ MIXED-D (manufactured by Polymer Laboratories Co., Ltd.) was used as a column. The amount of the alkali-soluble resin used in the present invention is from 1 to 300 parts by mass, preferably from 10 to 200 parts by mass, per 100 parts by mass of the pigment to be used. In this case, when the amount of the alkali-soluble resin used is less than 1 part by mass, the development characteristics may be lowered. On the other hand, when it exceeds 300 parts by mass, since the concentration of the colorant is relatively lowered, it is difficult to achieve the target color density as a film.

(Photopolymerizable Compound Forming Resin) The photopolymerizable compound which is a resin which can be used for forming the red colorant resist composition for a color filter of the present invention has one or more photopolymerizable unsaturated groups in the molecule. The same photopolymerizable compound as that described in the red colorant composition of the color filter described above, such as a monomer or an oligomer of a bond. The photopolymerizable unsaturated bond is an unsaturated bond which can be polymerized by the following action: The photopolymerization initiator to be described later generates radicals and cations upon decomposition by an active energy ray such as ultraviolet rays or electron beams. The photopolymerizable compound which can form these resins can be used individually or in combination of 2 or more types. In the present invention, the amount of the photopolymerizable compound to be used is preferably in the range of 3 to 50% by mass based on the total solid content of the red colorant resist composition in the color filter.

(Photopolymerization Initiator) The photopolymerization initiator used as the red colorant resist composition for a color filter of the display device of the present invention can be produced by irradiating an active energy ray such as ultraviolet rays or electron beams. The photopolymerization initiator of the radical or cation is not particularly limited, and examples thereof include benzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, and 4-methoxyl. -4'-dimethylaminobenzophenone, benzoin, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl condensate Ketone, α-hydroxyisobutyl benzophenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl benzophenone, tert-butyl hydrazine, 1-chloroindole, 2,3-dichloropurine Bismuth, 3-chloro-2-methylindole, 2-ethylhydrazine, 1,4-naphthoquinone, 1,2-benzopyrene, 1,4-dimethylhydrazine, 2-benzoquinone Anthracene, 2-methyl-1[4-(methylthio)phenyl]-2-morpholinylpropan-1-one, a triazine-based photopolymerization initiator, and the like. These photopolymerization initiators may be used alone or in combination of two or more. In the present invention, the content of the photopolymerization initiator is preferably in the range of 1 to 20% by mass based on the total solid content of the red colorant resist composition in the color filter.

(Organic solvent) The organic solvent used as the red colorant resist composition for the color filter color filter of the present invention can be suitably used organically used in the field of liquid crystal color filter resists. Solvent. Specifically, there are an ester organic solvent having a boiling point of 100 to 220 ° C at normal pressure (1.013 × 102 kPa), an ether organic solvent, an ether ester organic solvent, a ketone organic solvent, an aromatic hydrocarbon organic solvent, A nitrogen-containing organic solvent or the like. When a large amount of the organic solvent having a boiling point of more than 220 ° C is contained, when the coating film formed by coating is pre-baked, the organic solvent may not be sufficiently evaporated and remain in the dried coating film, whereby the heat resistance of the dried coating film may be lowered. Further, when a large amount of an organic solvent having a boiling point of less than 100 ° C is contained, it is difficult to apply it without being mottled and uniformly, and a coating film having excellent surface smoothness cannot be obtained. Specific examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, and diethylene glycol alone. Methyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, two An ether organic solvent such as ethylene glycol methyl ethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol single An ether ester organic solvent such as methyl ether acetate or propylene glycol monoethyl ether acetate; a ketone organic solvent such as methyl isobutyl ketone, cyclohexanone, 2-heptanone or δ-butyrolactone ; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 3-methyl-3-methoxybutylpropionate, 3-methoxy Methyl propyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, formic acid Ester organic solvent such as amyl ester; N-methylpyrrolidone, N, N-dimethyl A Amides, N, N- dimethylacetamide and the like of the nitrogen-containing organic solvent. These may be used alone or in combination of two or more.

Among these organic solvents, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, ethylene glycol monomethyl ether acetate are preferable in terms of solubility, dispersibility, coatability and the like. , propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, ethyl 2-hydroxypropionate, 3-methyl-3-methoxybutylpropionic acid Ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, n-amyl formate, etc., more preferably propylene glycol monomethyl ether acetate.

The organic solvent preferably contains 50 masses in the red colorant resist composition for a color filter of the present invention from the viewpoints of solubility of the alkali-soluble resin, dispersibility of a coloring pigment, coating properties, and the like. More than %, more preferably 70% by mass or more.

The red colorant resist composition for a color filter of the present invention mainly comprises a color pigment, a pigment dispersing aid having an acidic group, a polymer pigment dispersing agent having a basic group, an alkali-soluble resin, and photopolymerizability. A compound, a photopolymerization initiator, barium sulfate, and an organic solvent are contained, and these components account for 90 to 100% by mass of the red colorant resist composition for a color filter.

(Additives to be added as needed) The red colorant resist composition for a color filter of the present invention may suitably use various additives such as a thermal polymerization inhibitor, an ultraviolet absorber, and an antioxidant as needed.

(Method for Producing Red Colorant Resist Composition for Color Filter of the Present Invention) A method of producing a red colorant resist composition for a color filter using the above materials will be described. The red colorant resist composition for a color filter can be obtained by the following production method.

Obtaining CI Pigment Red 254, which is micronized in the presence or absence of a pigment dispersing aid having an acidic group (preferably a sulfonate of CI Pigment Red 2, etc.), dispersing a pigment having an acidic group A mixture of a solvent (preferably a sulfonate of CI Pigment Red 2, etc.), a pigment dispersant, a resin, a compound having a phosphate group or a salt thereof, an organic solvent, and other additives as needed. The obtained mixture is kneaded and dispersed by various dispersing machines such as a roll mill, a kneader, a high-speed stirring device, a bead mill, a ball mill, a sand mill, an ultrasonic disperser, and a high-pressure disperser to obtain a color filter. The light sheet is composed of a red colorant. Further, a photopolymerizable compound, a photopolymerization initiator, an alkali-soluble resin, an organic solvent, and other additives as needed are further added to obtain a red colorant resist composition for a color filter of the present invention.

In the above production method, when the microparticulated microparticles are micronized in the presence of a pigment dispersing aid having an acidic group, even if the dispersing of the micronized pigment does not contain a pigment dispersing aid having an acidic group It can also be manufactured. Further, in the above production method, a resin, a dye, a compound having a phosphoric acid group or a salt thereof may be added after the preparation of the colorant composition and/or after the preparation of the colorant composition. Further, the method of producing a color filter using the red colorant composition for a color filter of the present invention is as follows, and may include a device necessary for the color filter, and a configuration other than the colorant composition may be carried out by a known method. Manufacturing. For the red colorant composition for a color filter having a specific composition of the present invention, as its color characteristic (x, y, Y), the chromaticity x is preferably 0.6550. y is preferably from 0.322 to 0.330, more preferably from 0.322 to 0.324. Further, the Y value as the brightness is 12.2 or more, and particularly preferably 13.0 or more. In this range, the coloring power and/or brightness can be further improved. Example

The invention is further illustrated by the following examples, but the invention is not limited to the examples. And if there is no special statement, "%" means "% by mass".

<Pigment dispersing aid> (Pigment dispersing aid A: sulfonate of CI Pigment Red 2) 30 ml of concentrated sulfuric acid was added to a 100 ml Erlenmeyer flask, and 10 parts by mass of CI Pigment Red 2 was added while stirring with a magnetic stirrer at room temperature. Stir for 30 minutes. A mixture of 50 parts by mass of water and 50 parts by mass of ice was placed in a 1 L beaker, and the above reaction was poured into the ice water, and stirred with a magnetic stirrer for 30 minutes. This was filtered and washed with water under reduced pressure, and the obtained solid was dried to obtain 12 parts by mass of a pigment dispersing aid A.

<Micronized Pigment> (Micronized Pigment A: TRI-MIX-treated CI Pigment Red 254) 800 parts by mass of CI Pigment Red was placed in a kettle of TRI-MIX TX-15 (trade name, manufactured by Inoue Seisakusho Co., Ltd.) 254, 8000 parts by mass of sodium chloride having a particle diameter of 20 μm and 1920 parts by mass of diethylene glycol. The mixture was kneaded at 45 ° C for 3 hours in a range of 70% of the rated current value of 9.3 A, and subjected to a salt milling treatment. Next, the obtained 1300 parts by mass of the kneaded product was placed in 3 liters of warm water, and stirred while heating at 70 ° C for 1 hour to obtain a slurry. After repeatedly filtering and washing with water to remove sodium chloride and diethylene glycol, it was dried at 40 ° C for a day and night to obtain 95 parts by mass of the finely divided pigment A.

(Pigment Dispersant) BYK-LPN 21116 (made by BYK Chemical Co., Ltd., acrylic polymer, amine value 29)

(Compound having a phosphate group or a salt thereof) BYK-111 (a copolymer containing a phosphate group, an acid value of 136, and a nonvolatile content of 95%) BYK-102 (manufactured by BYK Chemical Co., Ltd., containing a phosphate group) Copolymer, acid value 102, non-volatile content 99%) BYK-106 (manufactured by BYK Chemical Co., Ltd., salt of copolymer containing phosphate group, acid value 145, nonvolatile matter 91%) Phosphate-based resin A (benzyl Methyl methacrylate/acidified 2-methacryloyloxyethyl acidulated phosphate copolymer, acid value 50 mgKOH/g, mass average molecular weight: 10,000) Phosphate-based resin B (benzyl acrylate) Methyl ester/acidified 2-methylpropenyloxyethyl ester copolymer, acid value 200 mgKOH/g, mass average molecular weight: 10,000) Phosphate-based resin C (methyl benzyl acrylate/acidified 2-methyl group) Propylene oxiranyl ethyl ester copolymer, acid value 20 mgKOH/g, mass average molecular weight: 10,000) Phosphate-based resin D (methyl methacrylate/acidified 2-methylpropenyloxyethyl ester copolymer) , acid value 300 mgKOH / g, mass average molecular weight 10,000)

(Resin) Alkali-soluble resin A (methyl methacrylate/methacrylic acid copolymer, acid value 120 mgKOH/g, mass average molecular weight: 25,000)

(Organic solvent) PGME: Propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate DAA: Diacetone alcohol

(Photopolymerizable compound) DPEHA: dipentaerythritol hexaacrylate (photopolymerization initiator) Yan Jiagu 369: 2-benzyl-(dimethylamino)-1-(4-morpholinylphenyl)-1- Butanone

<Red coloring agent composition for color filter> The above micronized pigment, a pigment dispersing aid having an acidic group, a pigment dispersing agent, an alkali-soluble resin, a dye, a compound having a phosphate group or a salt thereof, and an organic solvent According to the composition of Table 1, 0.2 mm Φ zirconia beads were kneaded with a paint conditioner for 6 hours to obtain red colorant compositions 1 to 15 for color filters.

[Table 1-1] [Table 1-2]

<Red colorant composition for color filters used in the resist methods of Examples 1 to 10 and Comparative Examples 1 to 5> The color filters are uniformly mixed and colored with red so as to have a pigment ratio of Table 2 The resist raw materials were used to obtain red colorant compositions for color filters used in the resist methods of Examples 1 to 10 and Comparative Examples 1 to 5.

[table 2-1] [Table 2-2]

(Evaluation) <Dispersion Stability> The red colorant compositions for color filters used in the resist methods of Examples 1 to 10 and Comparative Examples 1 to 5 were collected in glass bottles and sealed in a chamber. After 7 days of warm storage, the state was evaluated in accordance with the following evaluation criteria. The results are shown in Table 2. ○: No adhesion or sediment was found. △: It was found that there was an increase in viscosity and sediment at the original level when it was gently shaken. ×: It was found that there was a strong oscillation and the original viscosity and precipitate were not restored.

<Evaluation of Color Characteristics and Brightness Maintenance Ratio of Red Colorant Composition for Color Filter Used in Resist Method> Color Filters Used in Resist Method of Examples 1 to 10 and Comparative Examples 1 to 5 The light sheet was coated on the glass substrate with a red colorant composition using a spin coater. Next, after prebaking at 100 ° C for 3 minutes, exposure was carried out with a high pressure mercury lamp, and further baked at 230 ° C for 2 hours. Next, the color characteristics (x, y, Y) of the respective resists of Examples 1 to 10 and Comparative Examples 1 to 5 were measured by a spectrophotometer (UV-2500PC, C-2 source, 2° field of view, manufactured by Shimadzu Corporation). The measurement was carried out. In Examples 1 to 10 and Comparative Examples 1 to 3, the film thickness and the luminance Y value at the chromaticity x = 0.6550 and y = 0.3230 were obtained. In addition, the brightness maintenance rate is defined as follows. Brightness maintenance rate (%) = (brightness after pre-bake / brightness after post-baking) × 100

According to the results of the above-mentioned Table 2, according to Examples 1 to 10 which are red colorant compositions for color filters of the present invention, the red colorant composition for color filters of the present invention is excellent in brightness. The brightness maintenance ratio is also excellent, that is, a red colorant composition for a color filter which is small even if the change in brightness after the post-baking treatment is obtained. Further, according to Examples 1 to 10 which are red colorant compositions for color filters of the present invention, a red colorant composition for a color filter excellent in brightness retention can be obtained. However, Comparative Example 2 in which the acid value of the compound having a phosphate group or a salt thereof is insufficient, Comparative Example 2 in which the acid value of the compound having a phosphate group or a salt thereof is excessive, and Comparative Example 2 in which the compound having a phosphate group or a salt thereof is not contained In Comparative Example 4 in which the content of the compound having a phosphate group or a salt thereof was excessive, the dispersion stability and the brightness retention ratio were inferior. Comparative Example 5, which does not contain a dye in the red colorant composition for a color filter according to the present invention, has a good dispersion stability but a poor brightness retention ratio. According to the results of the present invention, it is understood that the red colorant composition for a color filter having a specific composition can achieve excellent dispersion stability and brightness, and the effect of the change in brightness after post-baking treatment is small.

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Claims (5)

A red colorant composition for a color filter, which is mainly composed of a pigment, a pigment dispersing aid having an acidic group, a dye, a pigment dispersing agent, a resin, a compound having a phosphate group or a salt thereof, and an organic solvent, and is characterized by The pigment has a pyrrolopyrroledione skeleton which is at least one selected from the group consisting of CI Acid Red 52, CI Acid Red 87, CI Acid Red 92, CI Acid Red 289, and CI Acid Red 388. The red colorant composition for a color filter according to claim 1, wherein the compound having a phosphate group or a salt thereof has an acid value of 10 to 300 mgKOH/g. The red colorant composition for a color filter according to the first or second aspect of the invention, wherein the content of the compound having a phosphate group or a salt thereof is from 10 to 1,000 based on 100 parts by mass of the dye. Parts by mass. The red colorant composition for a color filter according to any one of claims 1 to 3, wherein the pigment is a micronized pigment. The red colorant composition for a color filter according to any one of claims 1 to 4, wherein the pigment dispersing aid having an acidic group is a pigment dispersion aid having a sulfonic acid group. Agent.