TW200524979A - Pigment dispersion, composition for color filter and color filter - Google Patents

Abstract

The present invention is related to pigment dispersion that can provide high brightness and full color when used in color liquid crystal display device, as well as composition for color filter, its cured article and color filter. Said pigment dispersion is formed by dispersing both coloring material and a dispersing agent in a solvent, wherein said coloring material contains, based on the total weight of the coloring material, 0.05 wt% of subphthalocyanine of general formula (I), (wherein X1 to X12 represent hydrogen or halogen atoms, and Y represents a halogen atom or a hydroxy group; provided that at least 6 of X1 to X12 are halogen atoms). Said pigment dispersion may further contains photosensitive resin and /or monomer, and a photopolymerization initiator.

Description

200524979 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a pigment body, a color filter, a light filter component used in a color liquid crystal display device, and the like and a color filter formed therefrom; More specifically, the present invention relates to a pigment dispersion suitable for forming a blue pixel, a composition for a color filter, and a cured product thereof. > 7 [Prior art] Color calenders are widely used for the purpose of colorization of liquid crystal display devices and the like. Generally, red, green, and blue pixels are arranged in a mosaic pattern. Methods for producing this color filter m are known, for example, a color method, a printing method, an electroplating method, and a pigment dispersion method. In particular, a composition for a color calender (hereinafter also referred to as "color photoresist ink") is used in which a photosensitive resin and / or a monomer and / or a pigment is used, and a photolithography process is used. The pigment dispersion method for forming fine pixels is superior in light resistance, education resistance, and solvent resistance due to the use of materials, and has become the mainstay of the color filter manufacturing method.

In principle, most of the well-known pigments may be used for pigment dispersion2. For example, in Japanese Patent Application Laid-Open No. 5-2 81414, color photoresists of up to dozens of red, green, blue, yellow, and purple pigments are disclosed. Ink colorant. In addition, '-generally the pigment of each pixel is selected to match the light-emitting characteristics of the background light: transmissive 2'. For example, in addition to the red pigment in red pixels, yellow pigments and orange pigments with a fixed ratio are used. In addition to the green color pigments, the green pixels are mixed with a fixed ratio of yellow pigments and M color H. In addition to the blue pigments in the blue M pixels, a certain ratio of purple pigments are also mixed to give the required Its penetration characteristics. 315616 5 200524979 Shang Renhuan, in recent years, the requirements for high-definition, high-brightness, and color reproducibility of liquid crystal display devices have been increasing. It is expected that color phosphors will be brighter and brighter. Among these pigments, In liquid crystal displays, such as Pei Chi, etc., pigments that do not show horse-like brightness are extremely limited. For example, in the color photoresist inks of color pixels, most of them use blue pigment 15: 6 which is Ejing ^ blue ^ 2 and purple pigment, but this purple pigment is as disclosed in Japanese Patent Publication No. 25,52. There is almost only one type of purple pigment 23 (a purple pigment composed of carbazole dioxin). This purple pigment 23, compared with ketocyanine-based blue pigments, has blue penetration, and the domain is on a shorter wavelength side. Therefore, #To improve the penetration of copper that only transmits green light, blue Pureness is often mixed in. However, in the two methods that are difficult to mix in different areas, there is a contradiction between high brightness and high brightness. In the use of the penetrating region, it is very different from the copper blue green pigment, and the transmittance In the method of pigment Violet 23, which is also relatively low, there is a problem that it cannot simultaneously satisfy high-level bright chroma. Therefore, the color photoresist ink made by the color calender used in the production of liquid sa display devices and the like must be a color material that has tooth penetration characteristics suitable for the material and purpose, and a color photoresist ink using a pigment that is preferably a purple pigment. Highly anticipated. Furthermore, it is known to use a phthalocyanine compound as one of the pigments. Japanese Patent Application Laid-Open No. 2425255 and Japanese Patent Application Laid-Open No. 2G㈣_2 disclose photopolymerizable compositions using this subphthalocyanine compound. However, these photopolymerizable compositions have a light sensitizing effect in the visible light region compared to the sub-cyanine compound, and the osmium compound is dissolved in the photosensitive resin composition. 俾 315616 6 200524979 is used for argon laser ( 514nm), or quasi-quadratic wave) laser ⑸2nm) and other visible light sensitizers, but it is used as a color filter to disperse the phthalocyanine pigment to form a coloring material and disperse it. There is no teaching about the composition of optical devices. [Summary of the Invention] In view of the above-mentioned technical disadvantages, a hairy month provides a pigment dispersion, a color filter, a (blue) pixel that can be used in liquid crystal display devices and the like and imparts a high level of brilliance. Optical device ribs, hardened products formed using the same, and color filters. That is, the pigment dispersion system of the present invention is a pigment dispersion made by dispersing a coloring material and a dispersant in a solvent; in #, the coloring material 3 is shown as below 05% by weight of the total coloring material—shown below Phthalocyanine compound: n 11

At least 6 of X1 to Xi2 are halogen atoms, and the rest are hydrogen atoms; Y is a _ prime atom or a hydroxyl group ^ The present invention includes: a coloring material (hereinafter referred to as "component 2 agent (hereinafter referred to as" component ⑻ ") Solvent (hereinafter referred to as "photosensitive resin and / or monomer (hereinafter referred to as" ingredient (D) ") and photopolymer 315616 7 200524979 agent (hereinafter referred to as" ingredient (E) ") for a color filter composition; Among them, the coloring material component of the component (A) contains 0.5% by weight or more of the total coloring material as the above-mentioned general phthalocyanine compound (1); the content of the photopolymerization initiator of the component (E) is Component (D) 0.1 to 20% by weight of the photosensitive resin and / or monomer; the coloring material (a) and the solid content of the resin in the composition are each made to a total weight of 1 '(A) / (R ) Means "from time to time" in the range of 0.05 to 1.5. In addition, the present invention is obtained by curing the above-mentioned composition for a color filter. In addition, the present invention is a cured film forming a blue pixel. A color filter made of the cured product. The pigment dispersion of the present invention will be described below.疋 Pigment particle size. In addition, the composition for filters and optical devices. When the composition for optical devices is used, the pigment dispersion system of the present invention contains a coloring material (ingredient (A)) and a dispersant (ingredient (B) ), And a solvent (component (C)) are essential components, and are preferably formed, and the pigment dispersion system of the present invention is effective in color

315616 8 200524979 A plurality of halo atoms. -The Y-based halide atom or hydroxyl group in the general formula ⑴ is preferably chlorine or hydrogen from the viewpoint of handling superiority. «If the component (A) contains more than 0.05% by weight of the coloring material (especially 5% by weight or more, more preferably 40% by weight or more, and particularly preferably 6% by weight or more) The cyanine pigment may be used, and other pigments or dyes may be used in combination. Preferably, the above phthalocyanine-based pigment is used in the range of 40 to 100% by weight of f, and other pigments are used in the range of 0 to 60% by weight. Other coloring materials suitable for the modulation of blue-shaped photoresist inks are, from a hue point of view, preferably blue and purple pigments, for example: blue pigments 15, 15: Bu 15: 2, 15 · 3, 15 · 4, 15: 6, 16, 60, and 80; purple pigments 19, 23, and 37, but the pigments that can be used in combination are not limited to these. The reason for using a subphthalocyanine pigment as the coloring material in the present invention is that the pigment has specific spectral characteristics. ~, For liquid crystal display devices, etc., as light sources, tri-color fluorescent lamps with sharp light emission at wavelengths corresponding to the three primary colors of red, green, and blue (typically 610nm, 545nm, and 435nm) are commonly used. In order to show high-level red, green, and blue chrominance, it is necessary to effectively penetrate the three wavelengths of light and shield the other two wavelengths of light. The composition for a color filter using a coloring material containing a pigment mainly composed of a phthalocyanine of the present invention has superior transmission properties in the vicinity of 370 to 510 nm and a longer wavelength range than 630 nm, and is in the range of 520 to 620 nm Nearby, it has excellent knife light characteristics of absorption, so it can effectively penetrate the blue light of a two-wavelength fluorescent lamp, and can effectively block green and red light. Therefore, the color filter of the present invention will have a high level of brilliance, and can impart a high level of brilliance to a liquid crystal display 315616 9 200524979 display device using the same. The production of arylene blue pigments is generally formed by synthesizing a phthalocyanine compound and then pigmentizing it. Synthetic methods of phthalocyanine pigments are well known, for example: A · MellerandA. Ossko, Monatsheftefur

Chemie 103'150-155 (1972) and others. Specifically, it is synthesized by reacting 1 mol of boron trihalide and 3 mol of phthalocyanine substituted with a benzene ring hydrogen atom as a casein. Most of the phthalocyanine compounds thus obtained contain impurities due to side reactions, but the impurities can be removed by performing, for example, filtration and washing or Soxhlet extraction. Among them, the impurities are, for example, hydrolyzed products of boron tridentate, unreacted phthalocyanine, and the like. There are no particular restrictions on the solvents used for filtration, washing, or Soxhlet extraction. Alcohol solvents such as methanol, ethanol, etc .; rhenium solvents such as acetone, methyl ethyl, etc .; or aromatic elixirs such as toluene and xylene. In addition, according to the needs, cyanine or substituted cyanine other than _ can be presented as the starting material to synthesize unsubstituted (or substituted) sulfonium, and then halogenated by well-known methods. However, the synthesis method and the purification method are not limited to the above methods. The pigmentation method can be a well-known method. For example, after dissolving the lysine compound in strong acid towels such as thick Wei, and then putting them into a large number of water towels, the method, or the same dispersion in the strong 7 main into large water, Acid sug method to produce fine pigments4. In addition, in order to obtain a color filter with a high level of brilliance, the coloring material should preferably be fine-grained: = well-known methods can also be used, for example, in the presence of alkali, the solvent grinding method, Solute solvent grinding method. In the present invention, the method of 315616 10 200524979 is not limited to the above method. In the pigment used in the present invention, the average particle diameter of the primary particles is preferably in the range of 10 to 5000 nm, more preferably in the range of 30 to 300 nm, and more preferably 50 to 2000 nm. Within range is best. The type of the dispersant of the component (B) is not particularly limited, but from the viewpoint of superior dispersion stability, it is preferable to use i selected from the group consisting of fluorene (low carbon carbodiimide) and fluorene polyallylamine. One or two or more nitrogen-containing compounds are reacted with one or two or more silk-containing compounds selected from fluorene polyesters having free carboxyl groups, (ii) polyfluorene and (iii) polyester fluoramines to form fluoramines or salts. Graft polymers. (a) Poly (lower alkyl alkylimine) has a primary (_guan 2), secondary (-NH-), and tertiary (-N <) amine group to extend the lower carbon alkyl chain ( _r_, such as: -CH2CH2-) bonded polymer with branched structure. ⑻Polypropylamine system A polymer having a [-CH2CH (CH2NH2)-] n structure. In addition, the carboxyl-containing compounds of fluorene, (10, and (ill) have at least one m group at the terminal or side chain, etc., and they react with at least one part of (a) or the amine group of fluorene, etc. , To form -NHCO- or ΝΗ3 + · -〇c〇_, etc., 俾 to form a graft polymer. The above-mentioned graft polymer has an I part (a) or ⑻ 'which is adsorbed on a pigment and exerts an indefinite function, and borrows A dispersant for both the polymer chain part ⑴, ⑴) or (iii) which imparts dispersibility due to the three-dimensional rebound effect. The method for producing such a graft polymer is well known, and is disclosed in, for example, Japanese Patent Application Publication No. 63_30057 and Japanese Patent Application Publication No. 9_169821. This is to increase the adsorption of Yagan Yima pigment by the basic part of the graft polymer. It can also introduce acidic functional groups on the sincere skeleton = 315616 11 200524979 pigment derivative type dispersing aid and dispersant. Combined. From the point of view of the above-mentioned dispersing aids, 'preferable is blue or purple, which can be similar to: luteolinic acid derivative of copper cyanine, sulfonic acid derivative of phthalocyanine, and quinacridine 酉cHdone) sulfonic acid derivatives, carbazole disulfonic acid sulfonic acid derivatives, and the like. Moreover, the dispersant of the component (B) is not limited to the above-mentioned graft polymer, as long as it has a dispersing ability, it covers the market Dispersing agent, separating accelerator, or equivalent. Among the resins, there are resins which have the effect of adsorbing on the surface of the pigment and dispersing the pigment. Because such resins have a dispersing power, they are contained in a dispersant. Therefore, when the photosensitive resin and / or precursor of component VII has a dispersing ability, it can also be used as a dispersant. The ancient viscosity substance ⑽ lipids-generally have the ability to disperse prostitutes, but do not have the ability to disperse. This type of method that does not have the ability to disperse is used as a dispersant. In the present invention, the dispersant may be a component of the resin component. From the viewpoint of superior dispersibility and solubility of the pigment, the solvent of the component VII is preferably prepared as a gardenia ether, a nitrogen-containing solvent, and the like. Examples of chain vinegar, butyl acetate, and lactic acid are: ethyl methyl acetate-ributinone rp — butyrolactone, etc .; _ classes can be exemplified: ::, butylamine, hexane, etc .;-ethers of alcohols For example: ethylene glycol: diether methyl ethyl: alcohol ether acetate, propylene glycol monomethyl ether acetate, and diethyl nitrogen-containing solvents. For example: dimethylformamide and two agents, as long as the composition is formulated The solvent resistance and coating properties of 枓 are appropriately selected. 315616 12 200524979 can be used alone or in combination of two or more. Among them, the pigment dispersion contains the above-mentioned material-forming two-component (B) dispersant and component (c) solvent as essential components, and the total solid content is preferably from i to 4 and 0 is preferred; and from 5 to 35% by weight is more preferred. good. Blending of ingredients ⑴. The ratio is preferably 1 to 25% by weight in the pigment dispersion, and more preferably 5 to 20% by weight. In addition, the formulation ratio of the ingredient ⑻ is preferably 10 to ^ of the pigment. Especially preferably, it is 20 to 50% by weight. If the content of -t pigment contains less than 1 {% by weight of pigment, the dispersion of pigment dispersion 2 will be insufficient; otherwise, if it exceeds 60% by weight, in the lithography process, two or more methods may play a role, and the pigment is formed. ability. However, # component⑻ has a dispersing ability II 'even if the content exceeds 60% by weight. In addition, the "total solid form:" refers to components remaining after drying, hardening, or polymerization. Generally, components other than volatile components such as :: 丨 belong to total solids. The amount of pigment, which is the basis of the ratio in the component ⑻ s, refers to the total amount of pigment in the coloring material. 'Pigment dispersion system is obtained by dispersing a pigment in a solvent together with a dispersant. When the component (D) and the component 含有 are contained, these components can also be added and dispersed at the same time, or it can also be made without the component ⑼ and the component (the first pigment dispersion of Ej ', and then the component and the component ( E) The second pigment knife body is produced as a composition for color filters. There are no particular restrictions on the production method, and well-known methods can be used. For example, such as paint mixers, sanders, etc. Machine, bead mill (Beads Min), etc. are divided into 1 under treatment. The pigment in the pigment dispersion or composition used in the present invention is 2 knives to-secondary particle size. In other words, the pigment dispersion or composition The average particle diameter of the pigment is preferably in the range of 10 to 500 nm, more preferably in the range of 30 315616 13 200524979 to 300mn, and even more preferably in the range of 50 to 2000 nm. Above 500 nm, because the light transmittance will be lower and it is easier to produce polarized light, the brightness will be worse, and a shape filter with a lower contrast will be formed. On the contrary, if it is less than 10 nm, the pigment will be dispersed The dispersion stability of the body will be inadequate. Although the color material ratio can be appropriately selected in accordance with the coloring degree, etc., the weight ratio of the component (A) / (R) to the resin solid content (R) in the composition, the coloring material, and the resin solid content (R) must be from 0.05 to In the range of 15, the best range is from 0.1 to 1. If the ratio is lower than 0.05, the coloring performance cannot be fully exerted, and a good color filter cannot be formed; otherwise, if it exceeds 1.5, the lithography In the manufacturing process, the effective pixel formation ability cannot be exhibited. In addition, the resin solid content (R) is composed of the above-mentioned component (D) and the total amount of resin components (including monomers) other than the component (D). The photosensitive resin and / or monomer of the component (D) is at least one selected from the group consisting of a photopolymerizable resin, a photopolymerizable monomer, and a photopolymerizable oligomer, and has an ethylenically unsaturated bond. The composition for an optical device may include a resin that is in a cured state, and also includes a case where it contains only components that are not resinized in an uncured state. The resin solid content of the present invention is a monomer or a copolymer before resinization. It is also regarded as solid content. The component (D) should be considered in the color filter system The photopolymerizable resin, the photopolymerizable monomer, and the photopolymerizable oligomer may be, for example, 2-hydroxyhexyl (meth) acrylate, hydroxypropyl acrylate, and the like. (F-based) 2-ethylethyl acrylate, di (fluorenyl) ethylene glycol 酉, mono (f-based) diethylene glycol acrylate, di (p-based) triethylene diacrylate 315616 14 200524979 alcohol vinegar , Polyethylene glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol tetra (fluorenyl) acrylate, pentaerythritol hexa (meth) acrylate, di (meth) acrylic acid Bisphenol A epoxy esters, bis (metha) acrylic acid F-type epoxy resins, bis (meth) propanoic acid bis-pan epoxy epoxy ^ and other (fluorenyl) acrylic vinegars, etc. In addition, vinyl resins such as acetic acid (co) polymer, (meth) acrylic acid (co) polymer, maleic acid (co) polymer, etc .; or, for example, polyethylene oxide , Polyvinyl crocodile ravioli, amidine, polyurethane, amidine, polyacetate and other resins with ethyl-female double bonds in the side bonds. These can be used alone or in combination of two or more. In addition, for the purpose of improving the developability of these resins, it is preferable to have a base-soluble substituent such as a carboxyl group or a phenolic hydroxyl group on the side chain. The addition ratio of the photosensitive resin and / or monomer of the component (D) is preferably 4 (), which is the total solid content in the composition for a color calender of the present invention, and more preferably 50 to 90% by weight. good. In the composition, 1 needs to be added = other resins are added, but in this case, the total amount with other resins should preferably be within the above range. In addition, the "total solid content" refers to a component remaining as a solid content after the wire is dried and hardened. It does not include a solvent, but includes monomers. The photopolymerization initiator of the component (E) may include, for example, acetophenones such as acetophenone and p-tert-butylacetophenone; or benzophenone, p, p, -bis (N, N (Dimethylamino) benzophenones, such as benzophenone; or such as: benzoin ether, benzoin, benzoin, etc .; or such as: 2-methyl-bu [4- (Methylthio) Benzoyl] -2-morpholin-4-ylpropanone, 2-benzyl—take dimethylaminophenyl 1- (4-morpholine + ylphenyl, etc.) Base class; or 315616 15 200524979 w'3'5 ,, ... oxybenzoic benzyl, two 44 (i. Tributyl carbonyl) benzophenone proprietary organic peroxides; or sulfides such as __hioxanthone), 24_ monoethylthioxanthone, and use more than two kinds. 14 #. Yuansi can be used alone early, It is also possible to appropriately select the addition rate of the initiator in accordance with the sensitivity of the exposure, etc. = 0.1 to 20% by weight of the ⑻ component is preferred, and 0.5% to 15% by weight is more preferable. If the ratio of the right 3 is less than 0.1% by weight, the sensitivity will be too small. If it exceeds 2. The% by weight is used as a photoresist ink. Upgrade this = color painting ^ ^ fat for sticky_ " purpose == such as also ketones, polyurethanes, polyurethanes, polyurethanes, poly trips, etc., the most "2" or the side chain contains the county And the alkali developability is good = polymers, polymers, etc. Ethylene is a tree species. Others such as in _ Jihong, addition of acid field is also effective. ^ Combined use of 2 types The above can be used for flat collars. In addition, the ocher calender of the present invention contains two: the above components 上述, ⑻, ⑹, ⑻, and ⑻, and the total solid content is 40% by weight. The best is 5 to 30% by weight. The method for making a composition for a color calender can be, for example, pre-315616 16 200524979 The above K-cyanine pigment alone or in combination with other pigments-dissolved with a dispersant and dissolved A method of dispersing in a solvent to make a pigment dispersion, and then adding a wax component and a first polymerization initiator; or a method of incorporating an adenocyanate-based lipid composition, etc .; among them, from a color ferrule: = stability From the viewpoint of sex, the former method is better. In addition, it can also be a high-solubility solvent that dissolves sub-cyan pigments. A method of forming a colored photoresist ink by using a composition yarn of a phthalocyanine compound and a photosensitive resin, but this method is difficult to obtain sufficient light resistance, heat resistance, and solvent resistance. Therefore, it is a method of dispersing pigments and dispersing them. The hardened product obtained by hardening the composition for a color calender of the present invention is obtained by coating the composition on a substrate or the like and hardening by light irradiation, heating, etc. The method of coating the composition can be adopted Well-known methods include, for example, a coating method using a coating device such as a spin coater, a bar coater, a metal-type coater, etc. After coating, drying can also be performed using a hot plate, an IR oven, or the like. A well-known method can also be used for irradiating the composition with light. The applicable exposure light is not particularly limited, and can be used, such as: 氤 lamp, _ prime lamp, crane lamp, ultra high pressure mercury lamp, high pressure mercury lamp, medium pressure mercury lamp, Light source such as low-pressure mercury lamp. However, the method of coating and light irradiation is not limited to the above. If image exposure is performed with the relevant light source and then development is performed, an image can be formed on the substrate. As long as the developing solution can dissolve the unexposed portion but cannot dissolve the exposed portion, any substance can be used. Specifically, the alkaline solution contains various additives, and the additives may include an organic solvent, a buffering agent, a surfactant, and the like. Relevant development processing methods are not particularly limited, and methods such as immersion development, spray image development, airbrush development, and ultrasonic development can be used 315616 17 200524979. In addition, the method of improving the strength of the coating film can also be heated and hardened using a hot air oven. There are no particular restrictions on the hardening conditions of the relevant composition. In order to prevent discoloration and discoloration of the cured film obtained after the composition is hardened, it is best to set the heating conditions to 25 (rc or less and less than i hours. In addition, the above-mentioned% color A well-known method can be used for the method of forming a cured film of the composition for a filter using a well-known method. [Embodiment] Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples. In addition, "part" in the following means "part by weight." Synthesis Example 1 To 150 parts of tetragas phthalocyanine, 588 parts of o-dichlorobenzene was added, and the mixture was stirred at room temperature for 30 minutes under a nitrogen atmosphere. 71 drops of boron tribromide were added.; ,,;, and later, slowly heated to 100C, after the reaction was stable, and then heated and stirred at 150 to 180C for 10 to 60 minutes. After leaving to cool The precipitate was filtered, washed with acetone, sodium bicarbonate aqueous solution, water, and methanol in order and dried to obtain the fraction of twelve-gas arsenine boron complex (produced in formula (2)). Rate 41%). Second, this compound was dissolved in 10 times the amount of concentrated sulfuric acid After 'then this solution was poured into ice water, and the precipitated solid was collected by filtration, washed with water and dried to obtain Pigment A. 315616 200524979 after

In 150 parts of tetragas phthalocyanine, 300 parts of 1-naphthalene was added, and after stirring at room temperature for 30 minutes under a nitrogen atmosphere, 417 parts of a heptane solution in which boron tribromide had been dissolved in 1 mol / L was dropped. . Then, slowly heat to i0 (rc, after the reaction is stable, and then heat and stir at 200 to 240 ° C for 10 to 60 minutes. After leaving to cool, the precipitate is filtered off, and acetone and sodium carbonate are sequentially used. The aqueous solution, water, and methanol are washed and dried to obtain 64 parts (yield 40%) of the € 1,12 gas boron phthalocyanine complex shown in formula (3). Next, this compound is dissolved in 10 After double the amount of concentrated sulfuric acid, this solution was poured into ice water, and the precipitated solid was filtered, washed with water, and dried to obtain Pigment B.

Example 1 To 100 parts of Pigment A obtained in Synthesis Example 1, a dispersant part and 860 parts of propylene glycol monomethyl ether acetate were added, a dispersion treatment was performed for 6 hours using a paint shaker, and particles were removed after filtration to prepare a dispersion 1 〇〇〇 copies. 315616 19 200524979 Among them, the dispersant is a graft polymer obtained by reacting polyallylamine with a polyester having a free carboxyl group to form amidine. In addition, the media of the paint agitator uses 0.4 mm p glass beads with a filling rate of 40%, or 0.4-ρ zirconia beads with a filling rate of 15%. The solid content concentration of the dispersion A thus obtained was 14% by weight, and the ratio of the coloring material in the total solid content was 7 ·· *% by weight, which showed low viscosity and low thixotropy. In addition, a particle size distribution meter (manufactured by Dakuso Electronics Co., Ltd., trade name and particle control analyzer FPar-1000) was used for measurement. As a result, the average particle diameter of the pigment in the dispersion (diluted to a pigment concentration of 1% by weight) was 98nm. Example 2 A dispersion was prepared in the same manner as in Example 1 except that the pigment was changed to the pigment b obtained in Synthesis Example 2. The solid content concentration of the dispersion B thus obtained was 14% by weight, and the ratio of the coloring material in the total solid content was 71.4% by weight, showing low viscosity and low thixotropy. The average particle diameter of the pigment in the dispersion was 102 nm. Example 3 130 parts of propylene glycol monofluorenyl acetate solution (produced by Nippon Steel Chemical Co., Ltd., trade name: V-259ME) was added as a 42 · 42% by weight acrylic acid epoxy ester resin with a bisphenol fluorene skeleton, and dipentaerythritol hexaacrylate was added. 47 parts of esters, epoxy resin with a double-g skeleton (produced by Japan Epoxy Co., Ltd., trade name: Epik〇te YX4000HKM, 7 parts, 2-methyl-bu [4- (methylthio) phenyl] -2 -7 parts of morpholin-4-ylpropan-1-one, 1 part of p, p '-bis (N, N-diethylamino) benzophenone, 196 parts of diethylene glycol dimethyl ether, and propylene glycol mono 75 parts of methyl ether acetate, 1 part of a surfactant, and 1 part of a silane coupling agent were thoroughly stirred to prepare 475 parts of a composition containing a soluble photosensitive resin in a weak 20 315616 200524979 test solution. To 475 parts of the composition of the basic resin, the dispersion A (525 parts) obtained in Example 1 was added, and after stirring sufficiently to form a homogeneous solution, 1000 parts of the composition for a color filter were prepared. The thus obtained dispersion The solid content concentration of B was 21.6 wt%, and the pigment ratio in the total solids was 24.3 wt%, showing low viscosity. Low thixotropy. The thus obtained composition for a color filter was coated on a 5 inch square, 1 mm thick blue plate glass substrate with a spin coater. At this time, the number of rotations of the spin coater was changed to produce a test piece. After the test piece was dried, it was covered with a mask and subjected to ultraviolet exposure at 200 mJ / cm2 to harden the color photoresist ink in the exposed portion. Next, the test piece was subjected to alkali development with a 0.4% sodium carbonate aqueous solution for 2 seconds to remove unexposed light. The color photoresist ink is dried and dried. Finally, the test piece is heat cured to obtain a color photoresist ink cured film for a model color filter. The spectral transmittance and color of the model color filter obtained Degree (X value, y value), and brightness (γ value) are measured using a colorimeter (manufactured by Tokyo Denshoku Co., Ltd., trade name: color analyzer TC_1800MK2). The color measurement light at this time is set as the standard $ C. The spectral transmittance of the model color ferrule obtained according to this example is shown in Figure 丨, and the chromaticity and brightness are shown in Table 丨. Example 4 In addition to changing the pigment dispersion into an example Points scored in 2 The body B 'and the rest were made in the same manner as in Example 3. A composition for a color filter was prepared. The solid content concentration of this composition was 21.6% by weight, and the pigment content ratio in the solid content was 24.3% by weight, showing Low viscosity and thixotropy 315616 200524979. In addition, the composition was measured for the spectral transmittance, chromaticity and brightness of the model color filter according to the same method as in Example 3. The results are shown in Figure 1 and Table. Refer to 1. Reference Example 1 Prepared by adding 40 parts of dispersant and 860 parts of propylene glycol monomethyl ether acetate to 100 parts of blue pigment 15: 6, and using a paint agitator to perform a dispersion treatment for 6 hours. The particles were removed by filtration Into a dispersion (^ "⑽ 份. Among them, the dispersant is a graft polymer obtained by reacting polypropylamine with a polyester having a free carboxyl group to form amidine. In addition, the media of the paint agitator uses 0.4 mmp oxide beads and the filling rate is 15%. The solid content concentration of the dispersion thus obtained was 14% by weight, and the coloring material ratio in the total solid content was 71.4% by weight, showing low viscosity and low thixotropy. In addition, the average particle diameter of the pigment in the dispersion was 150 nm. Example 5 130 parts of propylene glycol monofluorenyl acetate solution (produced by Nippon Steel Chemical Co., Ltd., trade name: V-259ME) and hexapropanoic acid were added in an amount of 5.42% by weight of an acrylic epoxy resin having a bisphenol fluorene skeleton. 47 parts of dipentaerythritol ester, epoxy resin with double hope framework (manufactured by Japan Epoxy Resin Company, trade name:

EpikoteYX4000HK (transliteration)) 17 parts, 2-fluorenyl-1- [4- (methylthio) benzyl] -2-morpholin-4-ylpropan-1_one 7 parts, ρ, ρ'-bis ( N, N-diethylamino) 1 part of benzophenone, 196 parts of diethylene glycol dimethyl ether, 75 parts of propylene glycol monomethyl-acetate, 1 part of surfactant, and 1 part of silane coupling agent. 475 parts of a composition containing a soluble photosensitive resin in a weak test solution. 315616 22 200524979 To 475 parts of the composition containing this photosensitive resin, the dispersion B (262 · 5 parts) obtained in Example 2 was added, and after stirring sufficiently to form a homogeneous solution, it was made into a color filter The composition was 10,000 parts. The solid content concentration of the thus obtained composition was 21.6 wt%, and the pigment content ratio in the total solids was 24.3 wt%, showing low viscosity and low thixotropy. In addition, the composition was measured for the spectral transmittance, chromaticity, and brightness of the model color filter according to the same method as in Example 3. The results are shown in Figure 2. Example 6 Except changing the pigment dispersion to the dispersion B obtained in Example 2 (472 · 5 parts) and a reference example! Except for the dispersion c (52.5 parts) obtained in, the rest were the same as in the method of Example 5 to prepare a composition for a color calender. The solid content concentration of this composition was 216% by weight, and the pigment content ratio in the total solid content was 24.3% by weight, showing low viscosity and low thixotropy. In addition, the spectral transmittance of the model color filter was measured for this composition in the same manner as in Example 3. The results are shown in Figure 2. Comparative Example 1 Except that the pigment was changed to purple pigment 23, the rest were the same as in Example i: a pigment dispersion was prepared in the same manner as in Example 3, and a composition for a color it photocatalyst was prepared in the same manner as in Example 3. For this composition, the spectral transmittance, chromaticity, and immunity of the model color filter were measured in the same manner as in Example 2. The results are shown in Figure 1 and Table 1. Comparative Example 2 A pigment was dispersed in the same manner as in Example 1 except that the pigment was changed to a Π-phthalocyanine boron complex pigment shown in the following formula (4). In the same manner as in Example 3, a composition for a color filter was produced. For this composition, the spectral transmittance, chromaticity, and brightness of the model color filter were measured in the same manner as in Example 3. The results are shown in Figure 1 and Table 1.

Comparative Example 3 A composition for a color filter was produced in the same manner as in Example 3 except that the pigment dispersion was changed to the dispersion c obtained in Reference Example 1. For this composition, the spectral transmittance of the model color filter was measured in the same manner as in Example 3. The results are shown in Figure 2. In Figures 1 and 2, E3, E4, E5, and E6 refer to Example 3, Example 4, Example 5, and Example 6, respectively; C1, C2, and C3 refer to Comparative Example 1, respectively Example 2 and Comparative Example 3. As shown in FIG. J, the spectral characteristics of the model color filter obtained in this embodiment are compared with the model color filter of the comparative example, which can effectively pass through the blue light of the three-wavelength fluorescent lamp. , And effectively shield red and green light, is a high-level bright chroma. In addition, the cured film has a uniform film thickness and is free of agglomerated precipitates, and thus belongs to those with good coatability. As can be seen from Table 1, the model color filter composed of the composition for a color filter of the present invention has a significantly higher y value than the model color filter of the comparative example, and thus it can be determined that the present invention can be obtained by the present invention. High level bright 315616 24 200524979 Chroma color filter. Table 1 Test piece X y Y Example 3 0. 176 0. 051 4. 2 Example 4 0. 162 0. 052 4. 6 Comparative Example 1 0. 183 0. 052 3. 3 Comparative Example 2 0. 202 0 052 3 · 4 As shown in Figure 2, even when other blue pigments are used in combination, the spectral characteristics of the model color filter obtained by the present invention can be improved compared with the model color filter of the comparative example. The transmittance in the short wavelength region (near 380 to 46nm) allows the blue light emission (near 435nm) of the three-wavelength fluorescent lamp to be effectively penetrated, which belongs to those with a high level of brilliance. In addition, the cured film has a uniform film thickness and no phenomenon of agglomerated precipitates, and thus belongs to the group with good coatability. (Industrial Applicability) Since the color filter composition of the present invention has a high level of brilliance, it is extremely effective in terms of manufacturing a high-quality liquid crystal display device and the like. [Brief description of the drawings] Figures 1 and 2 are spectral transmittance diagrams of the color filter model. 315616 25

Claims (1)

200524979 Scope of patent application: A pigment dispersion, which is a pigment dispersion in which a coloring material and a dispersant are dispersed together in a solvent; among them, 0.5% by weight or more of the total coloring material is shown in the following general formula: Pigments made of Subphthalocyanine: x6: at least 6 of the two of X1 to X2 in the middle are halogen atoms, and the rest are hydrogen atoms; γ refers to a halogen atom or a radical). 2. For example, the pigment dispersion of item i in the patent application range, wherein all pigments composed of a phthalocyanine compound not included in the formula (1) are i element atoms. 11 3. If the pigment dispersion basin of item No. 2 or item 2 of the patent application is divided into at least one part, it is at least one selected from the group consisting of poly (epicarbonamide) and poly (polyamine). Nitrogen-containing compounds in the group are reacted with up to a species of compounds derived from free carboxyl groups formed from amyl esters, ammonium polyamines, and ammonium amines, and the grafts obtained are obtained. The pigment dispersion of any one of the three items, eighth, the average particle size of the pigment is in the range of 0 to the brother. 5 · If the scope of patent application is the first! Pigment dispersions of any one of four items, 315616 26 200524979 additionally contain a photosensitive resin and / or monomer, and a photopolymerization initiator. 6. A kind of color it light n Laisi, which is a composition for forming a pixel for a color calender using the pigment dispersion of the above-mentioned patent claim No. 5. 7. A composition for a color calender, containing a coloring material and a dispersant ^ Rongqi! , A photosensitive resin and / or a monomer, and a composition for a color filter of a polymerization initiator; wherein 0.5% by weight or more of the coloring material as a whole of the coloring material component is not shown in the following general indication Pigment composed of a cyanine compound; the content of the photopolymerization initiator is from 0.01 to 20% by weight of the photosensitive resin and / or the monomer; the coloring material (A) and the resin solid content (R) in the composition are each composed of When the total weight ratio (A) / (R) is expressed, it is in the range of 0.05 to 15; (Wherein '乂 1 to 乂 12, at least 6 are halogen atoms, and the remainder are hydrogen atoms; fluorene is a halogen atom or a radical). 8. A hardened material obtained by hardening the composition for a color filter in the scope of patent application No. 6 or 7. 9 · A color filter in which a hardened film forming a blue pixel is formed of a hardened product according to item 8 of the patent application. 27 315616