TWI659070B - A red coloring agent composition for a color filter - Google Patents

Abstract

An object of the present invention is to provide a display device which can be used in a television display or the like. The red colorant composition for a color filter with high brightness of the installed color filter and small change in brightness even after post-baking treatment. Specifically, the following is a red colorant composition for a color filter, which includes 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, The dye is at least one selected from CI Acid Red 52, CI Acid Red 87, CI Acid Red 92, CI Acid Red 289, and CI Acid Red 388.

Description

Red colorant composition for color filter

The present invention relates to a red colorant composition for a color filter that can be used for forming a color filter for a color display device.

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

A color liquid crystal display device transmits white light from a backlight through the above-mentioned color filter to color it, and displays a color image on a screen. Therefore, as the basic performance of a color filter, high transparency is required. Therefore, conventionally, it is manufactured by using a so-called dyeing method in which a dye excellent in color characteristics is dispersed in a resin in a molecular state and dyed. However, in recent years, with the diversification of applications, when it is necessary to improve the reliability such as heat resistance and light resistance, organic pigments can be used instead of the dyes with limited performance. In addition, a method for manufacturing a color filter has also been proposed. Various methods such as printing method, inkjet method, and lithographic etching method have been described.

In particular, in applications such as television displays, a color filter having pixels that can achieve high brightness and high definition and high contrast can be achieved with an overall image.

The above-mentioned brightness and contrast performance largely depend on the type of pigment dispersed in each color pixel of the color filter. 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 as the main red pigment.

Patent Document 2 proposes a system using Pigment Red 176 to compensate for the contrast ratio of Pigment Red 254 and the brightness of Pigment Red 177.

However, in recent years, the quality pursued by the pixels of television displays has been increasing, and it is difficult to achieve desired performance as a colorant with a colorant composition for a color filter having only a pigment. In particular, in order to achieve high brightness, it has been proposed to use a pigment and a dye in a colorant composition for a color filter.

Patent Document 3 proposes a system using pigment red 254, pigment red 177 as a pigment, and a modified product such as acid red 289, acid red 87, etc. as a dye. However, the modification steps of the dye are complicated, requiring labor and cost. , So it lacks practicality.

In addition, when a pigment and a dye are used in combination in a colorant composition for a color filter, the temporal stability of the colorant composition for a color filter tends to be insufficient, and in addition, in the production of a color filter Before and after the post-bake step, there is brightness Declining trend.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2010-223987

[Patent Document 2] Japanese Patent Laid-Open No. 2009-237462

[Patent Document 3] Japanese Patent Laid-Open No. 2012-194521

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

The present inventors conducted intensive research in order to solve the above-mentioned problems, and as a result, found that a red colorant composition for a color filter including a pigment, a pigment dispersing aid having an acidic group, a dye, a pigment dispersing agent, a resin, A compound of a phosphoric acid group or a salt thereof, and an organic solvent have high brightness that can be used for a color filter, and have a small change 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, comprising a pigment, a pigment dispersing aid having an acidic group, a dye, a pigment dispersing agent, a resin, a compound having a phosphoric acid group or a salt thereof, and an organic solvent. The pigment has a pyrrolopyrrole dione skeleton, and the dye is selected from CI Acid Red 52 and CI Acid Red. 87. At least one of C.I. Acid Red 92, C.I. Acid Red 289, and C.I. 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 of the dye 10 ~ 1000 parts by mass.

(4) The red colorant composition for a color filter according to any one of (1) to (3), wherein the pigment is a micronized pigment.

(5) The red colorant composition for a color filter according to any one of (1) to (4), wherein the pigment dispersion aid having an acidic group is a Pigment dispersion aid.

In addition, in this specification, "acid value" means dissolving or dispersing a sample with propylene glycol monomethyl ether, titrating an ethanol solution of potassium hydroxide with phenolphthalein as an indicator at 25 ° C, and measuring the solution as The value calculated by the following formula is the end point of light pink.

Acid value (mgKOH / g) = 56.1 × V × C / m

V: titration (ml), C: concentration of the titration solution (mol / l), m: weight (g) of the non-volatile component of the sample.

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

As described above, when a pigment and a dye are combined in the red colorant composition for a color filter, the temporal stability of the colorant composition for a color filter tends to be insufficient. In addition, in a color filter, Before and after the post-baking step of the sheet production, the brightness tends to decrease.

This trend is examined by the following mechanism. That is, among the components forming the coating film of the color filter, the dye molecules have a relatively low molecular weight, so the dye molecules that have been warmed in the post-baking process are liable to thermal movement. In addition, since dye molecules have highly polar groups such as sulfonate salts, thermally moving dye molecules become easily aggregated by the interaction of the highly polar groups. As a result, in the color filter coating film after the post-baking process, a region containing aggregates 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 brightness is observed by the light transmitted through the area where the dye in the color filter coating film is relatively small.

According to the present invention, it is considered that the change in brightness can be suppressed by the following mechanism even after the post-baking treatment. That is, by introducing a substance containing a phosphate group or a salt thereof into the colorant composition for a color filter, even if the dye molecules are thermally moved, the highly polar groups of the dye molecules are caused by the phosphate group or a salt thereof. Interaction is blocked, so even after the post-bake process, the dye molecules are all in the color filter coating film Evenly distributed, the change in brightness before and after the post-baking process becomes small.

Hereinafter, each component of the red colorant 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 for 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 that can be used for a display device of a television display or the like as the effect of the present invention, It is possible to provide a red colorant composition for a color filter having high brightness and a small change in brightness even after post-baking treatment.

(pigment)

As the pigment, the red colorant composition for a color filter of the present invention uses a pigment having a pyrrolopyrrole dione 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 And other pigments, but are not limited to these.

The pigment having a pyrrolopyrrole dione skeleton is preferably C.I. Pigment Red 254 or a bromide thereof. In particular, when C.I. Pigment Red 254 is used, the thickness of the film in order to obtain the necessary brightness is thin, and the color characteristics (x, y, Y) become good. The amount of the pigment having a pyrrolopyrrole dione skeleton in the present invention is preferably 5 to 80% by mass, and more preferably 20 to the total solid content of the red colorant composition of the present invention in terms of mass fraction. 50% by mass.

In order to impart high brightness and contrast to the red colorant composition for a color filter of the present invention, it is preferred to use a coloring pigment that has undergone micronization. By performing the micronization treatment, the primary particle diameter of the colored pigment can be made finer and more uniform.

As the above-mentioned micronization treatment, for example, it is preferable to perform the micronization treatment as follows: an untreated colored pigment, a water-soluble inorganic salt (preferably among sodium chloride, barium chloride, potassium chloride, etc.) It is sodium chloride, and the average particle diameter of the water-soluble inorganic salt used is preferably 50 μm or less), and a water-soluble dispersion medium (alkoxy alcohol, Diols, ethers, etc.), as a planetary mixer described in a kneader, a roll mill, a ball mill, an attritor, a sand mill, and Japanese Patent Laid-Open No. 2006-192385. ) Manufactured by Inoue Manufacturing Co., Ltd. (TRI-MIX (trade name)), a continuous single-shaft kneader, Miracle KCK, etc. by Asada Iron Works Co., Ltd. Salt milling of inorganic salts and the above-mentioned water-soluble dispersion medium.

(Pigment dispersion aid with acidic group)

As the pigment dispersion aid having an acidic group used in the red colorant composition for a color filter of the present invention, it is preferred to introduce an organic solvent into a basic skeleton having the same or similar molecular structure as the pigment to improve the organic solvent. A pigment dispersing aid with an affinity for acidic groups. In such a pigment dispersing aid, during the steps of micronizing and dispersing the pigment, a part of the basic skeleton is adsorbed on the surface of the pigment, and the acidic group improves the affinity with the organic solvent and the pigment dispersant, thereby improving the miniaturization during pigment dispersion And dispersion stability over time. In addition, the pigment dispersion aid is more preferably dissolved in an organic solvent by itself or in a state of being dispersed in a particulate form, because the pigment dispersion aid can be adsorbed on a wider range of the pigment surface.

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 0.5 to 30 parts by mass based on 100 parts by mass of the pigment. When the content of the pigment dispersing assistant having an acidic group is less than 0.5 parts by mass, the pigment dispersing effect is reduced. On the other hand, when it exceeds 30 parts by mass, the pigment dispersing effect is not continuously improved.

The pigment dispersing aid having the above acid group: (1) When using a pigment that has been micronized without the presence of a pigment dispersing aid having an acidic group, when dispersing the micronized pigment, use 100% by mass of the colored pigment with an acidic group The pigment dispersion aid of the pellet is 0.5 to 30 parts by mass, and preferably 3 to 15 parts by mass.

(2) When using a pigment that has been micronized in the presence of a pigment dispersing aid having an acidic group, use 0.5 to 30 parts by mass of the pigment dispersing aid with respect to 100 parts by mass of the pigment during the micronization of the pigment, It is preferably 3 to 15 parts by mass; when dispersing the micronized pigment, use 0 to 29.5 parts by mass of the pigment dispersing aid having an acidic group with respect to 100 parts by mass of the pigment, and preferably 0 to 12 parts by mass .

In addition, the total amount of the pigment dispersing auxiliary agent having an acidic group used in the micronization treatment and the amount of the pigment dispersing auxiliary agent having an acidic group used in dispersing the micronized pigment, The pigment dispersion aid having an acidic group is used in an amount of 0.5 to 30 parts by mass, and preferably 3 to 15 parts by mass, with respect to 100 parts by mass of the pigment.

More specifically, a case where a pigment dispersion auxiliary having a sulfonic acid group is used as a pigment dispersion auxiliary having an acidic group will be described.

As a pigment, when CI Pigment Red 254, which is a red pigment, is dispersed, as a pigment dispersion aid having a sulfonic acid group, a pigment selected from a pyrrolopyrrole diketone skeleton having the same skeleton as CI Pigment Red 254 and / Or pigment sulfonate (sulfide of CI Pigment Red 254, sulfide of brominated CI Pigment Red 254, sulfide of CI Pigment Red 255, sulfide of CI Pigment Red 264, sulfide of CI Pigment Red 272, At least one of a sulfonate of CI Pigment Orange 71, a sulfonate of CI Pigment Orange 73, a sulfonate of CI Pigment Orange 81, and a sulfonate of CI Pigment Red 2 having a sulfonic acid group, among which The sulfide of CI Pigment Red 2 is preferably used.

(dye)

As the dye used for the red colorant composition for a color filter of the present invention, an xanthracene-based acid dye can be used. As the xanthracene-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 rhodium are preferably used. Ming G, CI Acid Violet 9, CI Acid Violet 30. Among them, 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 are preferably used.

(Compounds 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 (manufactured by BYK Chemical Co., Ltd.), PLYSURF A212C can be used. , PLYSURF A215C, PLYSURF A208F, PLYSURF A 208N, PLYSURF A 208B, PLYSURF A 219B, PLYSURF A 210D, PLYSURF AL, PLYSURF AL12H (manufactured by Daiichi Pharmaceutical Co., Ltd.) and the like.

In addition, a polymerizable compound having a phosphate group or a salt thereof and a polymer that copolymerizes another polymerizable compound can also be used. Examples of the polymerizable compound having a phosphate group or a salt thereof include Light Ester P-1M, Light Ester P-2M (manufactured by Kyoeisha Chemical Co., Ltd.), and the like.

In the red colorant composition for a color filter of the present invention, the amount of the compound having a phosphate group or a salt thereof is preferably 10 to 1,000 parts by mass, more preferably 50 to 100 parts by mass of the dye. ~ 500 parts by mass. Relative to the dye 100 When the amount of the compound having a phosphate group or a salt thereof is less than 10 parts by mass or more than 1,000 parts by mass, the temporal stability of the colorant composition for a color filter may be insufficient, and Before and after the post-baking step in color filter production, the brightness may decrease.

In the red colorant composition for a color filter of the present invention, the acid value of the compound having a phosphate group or a salt thereof is preferably 10 to 300 mgKOH / g, more preferably 30 to 250 mgKOH / g, and even more preferably 50 to 200 mgKOH / g. When the acid value of the compound having a phosphate group or a salt thereof is less than 10 mgKOH / g or more than 300 mgKOH / g, the temporal stability of the colorant composition for a color filter may be insufficient. The brightness may decrease before and after the post-baking step in the production of light sheets.

(Pigment Dispersant)

As the pigment dispersant used in 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 1 to 100 parts by mass, and more preferably 1 to 60 parts by mass relative to 100 parts by mass of the color pigment. When the content of the pigment dispersant is less than 1 part by mass, the pigment dispersing effect may be reduced. On the other hand, when the content of the pigment dispersant is more than 100 parts by mass, the developability may be reduced.

Examples of the pigment dispersant include the following.

(1) An amine group and / or an imine group of a polyamine compound (e.g., a poly (lower) alkyleneamine, such as polyarylamine, polyvinylamine, polyethylene polyimide, and the like), and A reaction product of at least one of polyester, polyamidine, and polyesteramido that is free from carboxyl groups.

(2) A carbodiimide compound having at least one side chain each selected from 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-weight amine compound such as poly (lower) alkyleneimine, methyliminobispropylamine, and a polyester having a free carboxyl group.

(4) Alcohols such as methoxypolyethylene glycol, polyesters having one hydroxyl group such as caprolactone polyester, compounds having two to three isocyanate group reactive functional groups, and isocyanate group reactivity A reaction product obtained by sequentially reacting an aliphatic or heterocyclic hydrocarbon compound having a functional group and a tertiary amine group with an isocyanate group of a polyisocyanate compound.

(5) A reaction product of a polyisocyanate compound and 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-weight amine compound.

(7) A reaction product obtained by reacting a compound having an amine group with a compound having an isocyanate group.

(8) In a polyepoxide compound, a reaction product obtained by reacting a linear polymer having a free carboxyl group and an organic amine compound having a secondary amine group.

(9) A reaction product of a polycarbonate compound having a functional group capable of reacting with an amine group at one end and a polyamine compound.

(10) selected from methyl methacrylate, methyl ethacrylate, propyl acrylic acid Methyl ester, methyl butyl acrylate, methyl stearyl acrylate, methyl benzyl acrylate, methylacrylate, ethyl acrylate, propyl acrylate, butyl acrylate, stearyl acrylate And at least one of methacrylic acid esters, methacrylic acid esters, or benzyl acrylates, and acrylamide, methacrylamide, N-methylolamine, vinylimidazole, vinylpyridine At least one of polymerizable monomers containing a basic group, such as a monomer having an amine group and a polycaprolactone skeleton, and at least one of styrene, a styrene derivative, and other polymerizable monomers Copolymer.

(11) An acrylic block copolymer or the like composed of a block having a basic group such as a tertiary amine group and 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 each.

(14) A carbodiimide compound having at least one side chain each having a sulfonylamine group and a basic nitrogen-containing group in the molecule.

(15) A polyurethane compound having a structural unit containing an ethylene oxide chain and a propylene oxide chain and having an amine group quaternized by a quaternary ammonium 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 oxazole ring and / or an azobenzene skeleton. Relative to the molecule in the compound The total amount of isocyanate groups from the isocyanate compound having an isocyanurate ring and the urethane bond and urea bond generated by the reaction of the isocyanate group with the active hydrogen group, the oxazole ring and the azobenzene skeleton The number of compounds is 15-85%.

At present, as a method of manufacturing a color filter using a red colorant composition for a color filter, a resist method is mainly used, and it is divided into color filters used in methods other than the resist method to be colored in red. The agent composition and the red colorant composition for a color filter used in the resist method, and the components and the like contained in each of them will be described below.

[A. Red colorant composition for color filters used other than 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 has no active energy ray curability, and includes a pigment, a pigment dispersing aid having an acidic group, a dye, a pigment dispersant, a resin, A compound having a phosphate group or a salt thereof, and an organic solvent.

As the color pigment, the pigment dispersing aid having an acidic group, and the pigment dispersing agent, the above-mentioned colored pigment, the pigment dispersing aid having an acidic group, and a pigment dispersant are used.

(Resin)

Tree used as red colorant composition for color filter of the present invention As the resin, a resin having a transmittance of 80% or more and preferably 95% or more in a full wavelength region of 400 to 700 nm in the visible light region can be used. Examples of these resins include thermosetting resins, thermoplastic resins, and alkali-soluble resins. These can be used individually or in mixture of 2 or more types.

This resin is preferably 5 to 94% by mass, and more preferably 20 to 50% by mass, based on the total solid content of the red colorant composition for color filters. % Range.

Examples of the thermosetting resin and the thermoplastic resin include a butyral resin, a styrene-maleic acid copolymer, a chlorinated polyethylene, a chlorinated polypropylene, a polyvinyl chloride, a vinyl chloride-vinyl acetate copolymer, and a polymer. Vinyl acetate, polyurethane resin, phenol 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, etc.

The alkali-soluble resin is described in detail in a red colorant resist composition for a color filter described later.

(Organic solvents)

Specific examples of the organic solvent used in the red colorant composition for a color filter of the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol monoisopropyl 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, diethylene glycol di Ethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, etc. Ether organic solvents; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Ether ester organic solvents such as ethyl ether acetate; ketone organic solvents such as methyl isobutyl ketone, cyclohexanone, 2-heptanone, δ-butyrolactone; methyl 2-hydroxypropionate, Ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 3-methyl-3-methoxybutylpropionate, methyl 3-methoxypropionate, 3-methyl Ester organic solvents such as ethyl oxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, n-pentyl formate, etc .; Alcohol solvents such as methanol, ethanol, isopropyl alcohol, butanol; nitrogen-containing organic compounds such as N-methylpyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide Solvents, etc. 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 includes a pigment, a pigment dispersing aid having an acidic group, a dye, a pigment dispersing agent, a resin, a compound having a phosphoric acid group or a salt thereof, and an organic solvent. The red colorant composition for a filter accounts for 90 to 100% by mass.

(Additives that can be added as needed)

Various additives, such as a thermal polymerization inhibitor, an ultraviolet absorber, and an antioxidant, can be used suitably according to the manufacturing method of the coloring agent composition for color filters.

(Method for producing red colorant composition for color filter of the present invention)

A method for producing a red colorant composition for a color filter that is not used in the resist method will be described using the above materials.

CI Pigment Red 254, which has been micronized in the presence or absence of a pigment dispersing aid having an acidic group (preferably a sulfonate of CI Pigment Red 2 or the like), and a pigment dispersing aid having an acidic group is obtained. A mixture of an agent (preferably a sulfonate of CI Pigment Red 2), a pigment dispersant, a resin, a compound having a phosphate group or a salt thereof, an organic solvent, and other additives as necessary. The obtained mixture is kneaded and dispersed using various dispersers 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. A red colorant composition for a light sheet.

In the above-mentioned manufacturing method, when a micronized pigment which is micronized in the presence of a pigment dispersing auxiliary having an acidic group is used, the pigment dispersing auxiliary having an acidic group is not contained even when the micronized pigment is dispersed. Manufacturing is also possible.

In addition, in the above-mentioned manufacturing method, the resin and the compound having a phosphate group or a salt thereof may be added before the kneading and dispersion process and / or after the kneading and dispersion process.

[B. Red colorant composition for color filter used in resist method]

Next, a case where the red colorant composition for a color filter of the present invention is used as a colorant-dispersed resist composition for a color filter will be described.

In the case where 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, including pigments, dyes, and acid groups. Pigment dispersion aids, pigment dispersants, resins, compounds having a phosphate group or a salt thereof, and organic solvents, and the resins are resins containing an alkali-soluble resin and a photopolymerizable compound.

As a pigment, a pigment dispersing adjuvant having an acidic group, and a pigment dispersant, it is used as described above.

(Alkali soluble resin as resin)

The alkali-soluble resin, which is a resin used as the red colorant resist composition for a color filter of the present invention, only has to function as a binder with respect to a red pigment. The developing solution used in the image processing step is particularly preferably an alkali-soluble resin in which the alkali developing solution is soluble, and it is not particularly limited, and conventional alkali-soluble resins can be used. Among these, an alkali-soluble resin having a carboxyl group is preferred, and a copolymer of an ethylenically unsaturated monomer having one or more carboxyl groups and another copolymerizable ethylenically unsaturated monomer is more preferred.

Specific examples include ethylenically unsaturated monomers having a carboxyl group such as acrylic acid and methacrylic acid, and styrene, 2-hydroxyethyl acrylate, 2 which is copolymerizable with ethylenically unsaturated monomers having a carboxyl group, and 2 -Methyl hydroxyethyl acrylate, aryl acrylate, aryl methyl acrylate, benzyl acrylate, methyl benzyl acrylate, cyclohexyl acrylate, methyl cyclohexyl acrylate, glyceryl monoacrylate, glyceryl acrylic acid Monomers and oligomers of methyl ester, N-phenylmaleimide, polystyrene macromonomer, polymethylmethacrylate macromonomer, phenolphthalein epoxy diacrylate, etc. 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 developing characteristics.

In addition, the weight-average molecular weight of the alkali-soluble resin in the present invention is usually from In view of the development characteristics and solubility in an organic solvent, 1,000 to 100,000 is preferred. In the present invention, the weight-average molecular weight of the alkali-soluble resin is a weight-average molecular weight in terms of polystyrene obtained based on gel permeation chromatography (Gel Permeation Chromatography). In the present invention, Water 2690 (manufactured by Waters Corporation) is used as a device, and PLGel 5 μMIXED-D (manufactured by Polymer Laboratories) is used as a column.

The usage-amount of the alkali-soluble resin in this invention is 1-300 mass parts with respect to 100 mass parts of pigments used, Preferably it is 10-200 mass parts. In this case, when the amount of the alkali-soluble resin used is less than 1 part by mass, there is a possibility that the developing characteristics are reduced. On the other hand, when it exceeds 300 parts by mass, the concentration of the colorant is relatively reduced, so that there is a possibility that it is difficult to achieve the target color density as a thin film.

(Photopolymerizable compound forming resin)

As the photopolymerizable compound that can form the resin used in the red colorant resist composition for a color filter of the present invention, a monomer, oligomer, etc. having one or more photopolymerizable unsaturated bonds in the molecule is used. The same photopolymerizable compound as described in the red colorant composition for a color filter. The photopolymerizable unsaturated bond refers to an unsaturated bond that can be polymerized by the following action: a photopolymerization initiator described later generates free radicals and cations upon decomposition by active energy rays such as ultraviolet rays and electron rays.

The photopolymerizable compounds capable of forming these resins can be used alone or in combination of two or more. In the present invention, the used amount of the photopolymerizable compound is preferably 3 by mass fraction with respect to the total solid content in the red colorant resist composition for a color filter. Range of ~ 50% by mass.

(Photopolymerization initiator)

The photopolymerization initiator used as the red colorant resist composition for a color filter of a display device of the present invention is any light capable of generating radicals and cations by irradiating active energy rays such as ultraviolet rays and electron rays. The polymerization initiator is not particularly limited, and examples thereof include benzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone, and 4-methoxy-4'-di Methylaminobenzophenone, benzophenone, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyldimethylketal, α-hydroxyiso Butyl benzophenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenone, third butyl anthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro- 2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-benzoanthraquinone, 2-methyl -1 [4- (methylthio) phenyl] -2-morpholinylpropane-1-one, a triazine-based photopolymerization initiator, and the like. These photoinitiators can be used individually or in combination of 2 or more types.

In the present invention, the content of the photopolymerization initiator is preferably in a range of 1 to 20% by mass based on the total solid content in the red colorant resist composition for the color filter.

(Organic solvents)

As the organic solvent used for the red colorant resist composition for a color filter color filter of the present invention, an organic solvent conventionally used in the field of liquid crystal color filter resists can be suitably used. Specifically, there is a normal pressure (1.013 × 102kPa) The boiling point below is 100 ~ 220 ℃, such as ester organic solvents, ether organic solvents, ether ester organic solvents, ketone organic solvents, aromatic hydrocarbon organic solvents, nitrogen-containing organic solvents, and the like. When a large amount of an organic solvent having a boiling point exceeding 220 ° C is included, when the coating film formed by the coating is pre-baked, there is a possibility that the organic solvent cannot be sufficiently evaporated and remains in the dried coating film, thereby reducing the heat resistance of the dried coating film. In addition, when a large amount of an organic solvent having a boiling point of less than 100 ° C. is used, it is difficult to apply uniformly without mottle, and a coating film having excellent surface smoothness may not be obtained.

Specific examples of the preferable solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, and diethylene glycol monoethyl ether. 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, diethylene glycol Ether organic solvents such as ethylene glycol methyl ethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol mono Ether ester organic solvents such as methyl ether acetate and propylene glycol monoethyl ether acetate; ketone organic solvents such as methyl isobutyl ketone, cyclohexanone, 2-heptanone, and δ-butyrolactone ; Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 3-methyl-3-methoxybutylpropionate, 3-methoxy Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, n-formate Ester organic solvents such as amyl ester; N-methylpyrrolidone, N, N-dimethyl A Amides, N, N- dimethylacetamide and the like of the nitrogen-containing organic solvent. These can be used individually or in mixture of 2 or more types.

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

From the viewpoints of the solubility of the alkali-soluble resin, the dispersibility of the colored pigment, and the coatability, these organic solvents are preferably contained in the red colorant resist composition for a color filter of the present invention at 50 mass. % Or more, more preferably 70% by mass or more.

The red colorant resist composition for a color filter of the present invention includes a color pigment, a pigment dispersing aid having an acidic group, a polymer pigment dispersant having a basic group, an alkali-soluble resin, and a photopolymerizable compound. , Photopolymerization initiator, barium sulfate, and organic solvent, these components account for 90 to 100% by mass of the red colorant resist composition for color filters.

(Additives that can be added as needed)

The red colorant resist composition for a color filter of the present invention can suitably use various additives such as a thermal polymerization inhibitor, an ultraviolet absorber, and an antioxidant, as necessary.

(Method for producing red colorant resist composition for color filter of the present invention)

A method for producing a red colorant resist composition for a color filter using the above materials will be described. A red colorant resist composition for a color filter may It was obtained by the following manufacturing method.

CI Pigment Red 254, which has been micronized in the presence or absence of a pigment dispersing aid having an acidic group (preferably a sulfonate of CI Pigment Red 2 or the like), and a pigment dispersing aid having an acidic group is obtained. A mixture of an agent (preferably a sulfonate of CI Pigment Red 2), a pigment dispersant, a resin, a compound having a phosphate group or a salt thereof, an organic solvent, and other additives as necessary. The obtained mixture is kneaded and dispersed using various dispersers 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. A red colorant composition for a light sheet. A photopolymerizable compound, a photopolymerization initiator, an alkali-soluble resin, an organic solvent, and other additives as necessary are further added to obtain a red colorant resist composition for a color filter of the present invention.

In the above-mentioned manufacturing method, when a micronized pigment which is micronized in the presence of a pigment dispersing auxiliary having an acidic group is used, the pigment dispersing auxiliary having an acidic group is not contained even when the micronized pigment is dispersed. Manufacturing is also possible.

In the above-mentioned production method, a resin, a dye, or a compound having a phosphate group or a salt thereof may be added at the time of production of the colorant composition and / or after production of the colorant composition.

In addition, the method for producing a color filter using the red colorant composition for a color filter of the present invention is as follows. The necessary device can be included. As a configuration other than the colorant composition, a known method can be used. Manufacturing.

In the red colorant composition for a color filter having a specific composition according to the present invention, among the color characteristics (x, y, Y), the chromaticity x is preferably 0.6550. y is preferably 0.322 to 0.330, and more preferably 0.322 to 0.324. Further, the Y value as the brightness is 12.2 or more, particularly preferably 13.0 or more. Within this range, tinting power and / or brightness can be further improved.

Examples

Examples are given below to further explain the present invention, but the present invention is not limited to these examples. And unless otherwise stated, "%" means "mass%".

<Pigment Dispersion Aid>

(Pigment Dispersion Aid C: I. Sulfide of Pigment Red 2)

30 ml of concentrated sulfuric acid was added to a 100 ml Erlenmeyer flask, and 10 parts by mass of C.I. Pigment Red 2 was added while stirring with a magnetic stirrer, and the mixture was stirred at room temperature for 30 minutes. A 1 L beaker was charged with a mixture of 50 parts by mass of water and 50 parts by mass of ice, and the above reactant was poured into the ice water, and stirred with a magnetic stirrer for 30 minutes. This was filtered under reduced pressure and washed with water, and the obtained solid was dried to obtain 12 parts by mass of a pigment dispersion aid A.

<Micronized Pigment>

(Micronized Pigment A: TRI-MIX-treated C.I. Pigment Red 254)

800 in TRI-MIX TX-15 (trade name, manufactured by Inoue Seisakusho) C.I. Pigment Red 254 parts by mass, 8000 parts by mass of sodium chloride having a particle diameter of 20 μm, and 1920 parts by mass of diethylene glycol. Within a range of 70% of the rated current value of 9.3A, kneading was performed at 45 ° C for 3 hours, and salt milling was performed. Next, 1,300 parts by mass of the obtained kneaded product was poured into 3 liters of warm water, and the mixture was stirred for 1 hour while being heated at 70 ° C. to obtain a slurry. After repeated filtration, washing with water to remove sodium chloride and diethylene glycol, and drying at 40 ° C for one day and night, 95 parts by mass of micronized pigment A was obtained.

(Pigment Dispersant)

BYK-LPN 21116 (made by BYK Chemical Co., acrylic polymer, amine number 29)

(Compounds having a phosphate group or a salt thereof)

BYK-111 (manufactured by BYK Chemical Co., Ltd., copolymer containing phosphate group, acid value 136, non-volatile content 95%)

BYK-102 (manufactured by BYK Chemical Co., Ltd., copolymer containing phosphate group, acid value 102, non-volatile content 99%)

BYK-106 (salt of phosphate-containing copolymer manufactured by BYK Chemical Co., acid value 145, non-volatile content 91%)

Phosphate group-containing resin A (2-methacryloyloxyethyl acidulated phosphate copolymer, acid value 50mgKOH / g, mass average molecular weight: 10,000)

Phosphate group-containing resin B (benzyl methyl acrylate / acidified 2-methacryloxyethyl phosphate copolymer, acid value 200 mgKOH / g, mass average molecular weight: 10,000)

Phosphate group-containing resin C (benzyl methyl acrylate / acidified 2-methacrylic acid ethoxyethyl ester copolymer, acid value 20 mgKOH / g, mass average molecular weight: 10,000)

Phosphate group-containing resin D (benzyl methyl acrylate / acidified 2-methacryloxyethyl phosphate copolymer, acid value 300 mgKOH / g, mass average molecular weight: 10,000)

(Resin)

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

(Organic solvents)

PGME: propylene glycol monomethyl ether

PGMEA: propylene glycol monomethyl ether acetate

DAA: Diacetone alcohol

(Photopolymerizable compound)

DPEHA: Dipentaerythritol hexaacrylate

(Photopolymerization initiator)

Yanjiagu 369: 2-benzyl- (dimethylamino) -1- (4-morpholinyl) -1-butanone

<Red colorant composition for color filters>

The micronized pigment, the pigment dispersing auxiliary agent having an acidic group, the pigment dispersing agent, an alkali-soluble resin, a dye, a compound having a phosphate group or a salt thereof, and an organic solvent were used in accordance with the composition of Table 1, using an oxidation of 0.2 mm Φ. Zirconium beads were kneaded with a paint conditioner for 6 hours to obtain a color filter colored in red 剂 组合 物 1 ~ 15。 Composition 1 ~ 15.

<Red colorant composition for color filters used in the resist methods of Examples 1 to 10 and Comparative Examples 1 to 5>

The colorants used in the resist method of Examples 1 to 10 and Comparative Examples 1 to 5 were obtained by uniformly mixing the red colorant resist raw materials for the color filters so as to have the pigment ratio shown in Table 2. Composition with red colorant.

(Evaluation)

<Dispersion stability>

Color filters used in the resist methods of Examples 1 to 10 and Comparative Examples 1 to 5 The red colorant composition for a light sheet was collected into a glass bottle, sealed and stored at room temperature for 7 days, and the state was evaluated in accordance with the following evaluation criteria. The results are shown in Table 2.

○: No thickening or sediment was found.

(Triangle | delta): Thickness and deposit which recovered to the original degree when it was lightly shaken were found.

×: Strong oscillation was not found, and thickening and sediments of the original level were not recovered.

<Evaluation of the color characteristics and brightness maintenance ratio of the red colorant composition for a color filter used in the resist method>

The red colorant composition for color filters used in the resist methods of Examples 1 to 10 and Comparative Examples 1 to 5 was applied on a glass substrate using a spin coater.

Next, after pre-baking at 100 ° C for 3 minutes, exposure was performed with a high-pressure mercury lamp, and further baking was performed 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 with a spectrophotometer (manufactured by Shimadzu Corporation, UV-2500PC, C light source 2 ° field of view) Perform the measurement. In Examples 1 to 10 and Comparative Examples 1 to 3, the film thickness and the luminance Y value when the chromaticity x = 0.6550 and y = 0.3230 were obtained.

The brightness maintenance ratio is defined as follows.

Brightness maintenance rate (%) = (Brightness after pre-baking / Brightness after bake) × 100

According to the results shown in Table 2 above, according to the color filter of the present invention Examples 1 to 10 of the red colorant composition for sheets are excellent in the brightness and the brightness maintenance rate of the red colorant composition for a color filter of the present invention, that is, the brightness can be obtained even after post-baking treatment. The red colorant composition for color filters is also small.

In addition, according to Examples 1 to 10 as the red colorant composition for a color filter of the present invention, a red colorant composition for a color filter having an excellent brightness maintenance ratio can be obtained.

However, according to Comparative Example 1 in which the compound having a phosphate group or a salt thereof has an insufficient acid value, Comparative Example 2 in which a compound having a phosphate group or a salt thereof has an excessive acid value 2, and Comparative Example not containing a compound having a phosphate group or a salt thereof 3 and Comparative Example 4 in which the content of the compound having a phosphate group or a salt thereof was excessive were the results of poor dispersion stability and brightness maintenance ratio.

Comparative Example 5 in which the dye is not contained in the red colorant composition for a color filter according to the present invention has a good dispersion stability but a poor brightness maintenance ratio.

From these results, it is understood that the present invention achieves the effects of excellent dispersion stability and brightness by making the red colorant composition for color filters of a specific composition, and a small change in brightness even after post-baking treatment.

Claims (4)

A red colorant composition for a color filter includes a pigment, a pigment dispersing auxiliary having a sulfonic acid group, a dye, a pigment dispersing agent, a resin, a compound having a phosphoric acid group or a salt thereof, and an organic solvent. The pigment has a pyrrolopyrrole dione skeleton, and the dye is at least one selected from 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 item 1 of the scope of the patent application, 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 item 1 or item 2 of the scope of patent application, wherein the content of the compound having a phosphate group or a salt thereof is 10 to 1000 with respect to 100 parts by mass of the dye. Parts by mass. The red colorant composition for a color filter according to item 1 or item 2 of the scope of patent application, wherein the pigment is a micronized pigment.