WO2004067644A1

WO2004067644A1 - Pigment dispersion, color filter composition and color filter

Info

Publication number: WO2004067644A1
Application number: PCT/JP2004/000827
Authority: WO
Inventors: Tetsuya Yanagimoto; Hiroaki Yamada; Masahiro Tsuchiya; Hironobu Kawasato
Original assignee: Nippon Steel Chemical Co., Ltd.
Priority date: 2003-01-30
Filing date: 2004-01-29
Publication date: 2004-08-12
Also published as: JPWO2004067644A1; CN1742058A; KR20050103910A; CN1325575C; JP4522948B2; KR101057248B1

Abstract

There are provided, for realizing a high level of bright chroma saturation when used in a liquid crystal display, etc., a pigment dispersion, color filter composition, hardening product thereof and color filter. This pigment dispersion comprises colorants and a dispersant both dispersed in a solvent, the colorants containing a pigment of subphthalocyanine compound of the following general formula (1) in an amount of 0.5 wt.% or more based on the total weight of colorants. Further, the pigment dispersion may contain a photosensitive resin and/or a monomer and a photopolymerization initiator. In the general formula (1), each of X1 to X12 represents H or halogen provided that six or more thereof represent halogen, and Y represents halogen or hydroxyl. (1)

Description

TECHNICAL FIELD The present invention relates to a pigment dispersion used for a color liquid crystal display device, a composition for a color filter, a cured product formed using the same, and a pigment dispersion, a composition for a color filter and a force filter. The present invention relates to a force filter, and more particularly to a pigment dispersion suitable for forming a blue pigment, a force filter composition and a cured product thereof. Background Technology Color filters are widely used for the purpose of coloring liquid crystal displays etc. Generally, red, green and blue pixels are arranged in a mosaic manner. As a method of producing this color filter, a dyeing method, a printing method, an electrodeposition method, a pigment dispersion method and the like are known. In particular, the pigment dispersion method of forming fine pixels by photolithography using a composition for color filter (hereinafter also referred to as color resist ink) in which a pigment is dispersed together with a photosensitive resin and / or a monomer is used. Because of the use of pigments, they are the mainstream of color filter manufacturing methods because they are excellent in light resistance, heat resistance and solvent resistance.

In principle, many of the known pigments can be used in the pigment dispersion method. For example, in Japanese Patent Laid-Open No. 5-281414, red, green and blue as coloring materials for color resist ink are available. Several dozens of yellow and purple pigments are disclosed. In addition, the pigment of each pixel is generally selected so that the transmission characteristic of the pixel matches the light emission characteristic of the back light. For example, a red pigment, a yellow pigment, an orange pigment, and a green pixel In addition to the green pigment, the yellow pigment is added to the blue pixel, and the blue pigment is mixed with the violet pigment in a fixed proportion to give the desired transmission characteristics.

However, there are high demands for high definition, high brightness and high color reproducibility for liquid crystal display devices in recent years, and further increase in brightness and color saturation of color filters are desired. Those which are used for display devices etc. and show high levels of light and chroma are very limited. For example, a purple pigment is often used together with pigeon blue 15: 6, which is a copper phthalocyanine-based blue pigment, for the force to form a blue pixel. For example, as disclosed in Japanese Patent No. 2 540 250 2, it is preferable to use Piggment 'Biolate 23 which is a purple pigment composed of carbazole dioxazine. It is almost the only thing you can do.

This Big '' 'Violet 23 has a blue transmission range on the short wavelength side of the copper phthalocyanine blue pigment, so the blue purity of the copper lid cyanine blue pigment transmitting a slight amount of green light is to be increased. Often mixed with However, in the method of mixing two pigments with different transmission range, the high brightness and high saturation are in a trade-off relationship, and the transmission area is largely different from that of the copper lid cyanine blue pigment and the transmittance is also low. Bigment ■ In the method of using biometric 2 3, the problem of not being able to simultaneously satisfy high levels of light and saturation is found.

As described above, in the preparation of color filters used in liquid crystal display devices, etc., the color resisto- kin used is a transmission characteristic suitable for the application and purpose. It is essential to adjust the color material having the property, and it is desirable to have a high coloring power resist ink using a pigment replacing the carbazole dioxazine purple pigment.

On the other hand, subphthalocyanine compounds are known as one of the pigments. Japanese Patent Application Laid-Open Nos. 1 1-2 4 2 5 5 5 and Japanese Patent Application Laid-Open No. 2 0 0 1-3 4 8 6 2 disclose photopolymerizable compositions using this sub-tack orifice cyanine compound. However, focusing on the photosensitizing effect of the subphthalocyanine compound in the visible light region, these photopolymerizable compositions are prepared by dissolving the sub-thin-port cyanine compound in the photosensitive resin composition, and then using an argon laser (51 nm Or as a photosensitizer for visible light such as long wavelength laser light such as YAG (second harmonic) laser (53 2 nm), and the subphthalocyanine compound is used as a pigment for coloring There is no suggestion at all that it is dispersed and used in a color filter composition. Disclosure of the Invention The present invention has been made in view of the disadvantages of the prior art, and is used in liquid crystal display devices etc., and is a pigment dispersant for forming a (blue) pixel giving a high level of light saturation. An object of the present invention is to provide a color filter composition, a cured product formed using the same, and a color filter. That is, according to the present invention, in a pigment dispersion in which a coloring material is dispersed in a solvent together with a dispersing agent, a pigment comprising a subphthalocyanin compound represented by the following general formula (1) as a coloring material is contained in all coloring materials. It is a pigment dispersion characterized by containing 5% by weight or more.

(However, at least six of Xi to X ₁₂ are halogen atoms, and the rest are hydrogen atoms. Υ is a halogen atom or a hydroxyl group.)

Furthermore, the present invention provides a colorant (hereinafter, also referred to as component (Α)), a dispersant (hereinafter, also referred to as component (溶剤)), a solvent (hereinafter, also referred to as component (C)), a photosensitive resin And / or a color filter composition comprising a monomer (hereinafter also referred to as component (D)) and a photopolymerization initiator (hereinafter also referred to as component (D)), the coloring of the component (D) Component containing 0.5% by weight or more of a pigment consisting of the sub-titanium cyanine compound represented by the above general formula (1) in all the colorants, and the photopolymerization initiator as the component (Ε) as the component (D) 0.1% to 2 °% by weight with respect to the photosensitive resin and / or the monomer of the above), and the total weight of each component of the coloring material (Α) and the resin solid content (R) in the composition It is characterized in that (A) Z (R) represented by the ratio is in the range of 0.5 to 1.5.

Furthermore, the present invention is a cured product obtained by curing the color filter composition described above. Also, the present invention is a color fountainer in which a cured film forming blue pixels is made of the above cured product. Hereinafter, the pigment dispersion of the present invention will be described. The pigment dispersion of the present invention contains a colorant (component (A)), a dispersant (component (B)) and a solvent (component (C)) as essential components, and has a predetermined pigment particle size. It is preferable that In addition, the pigment dispersion of the present invention is useful as a composition for a color filter. When the pigment dispersion of the present invention is used as a force filter composition, a photosensitive resin and Z or a monomer (component (D)) and (E) a photopolymerization initiator (component (E) It is preferable to include) as an essential component. In addition, various additives such as other resins and other surface conditioners and antifoaming agents can be blended, if necessary. The coloring material of the component (A) is required to contain a pigment comprising the subphthalocyanine compound represented by the general formula (1) in an amount of 0.5% by weight or more based on the total coloring material. In General Formula (1), at least 6 of X i X are a halogen atom and the rest are a hydrogen atom. The halogen atom may be any of fluorine, chlorine, bromine, iodine and the like, but chlorine or bromine is preferable in terms of hue. More preferably, those in which all of X i X in the general formula (1) are chlorine or bromine are used. Note that plural kinds of halogen atoms may be bound in one molecule. Y in the general formula (1) is a halogen atom or a hydroxyl group, but chlorine or bromine is preferable from the viewpoint of excellent handling.

The component (A) is not less than 0.5% by weight, preferably 5% by weight or more, more preferably 40% by weight or more, and still more preferably 70% by weight or more of the above subphthalocyanine based pigment in the entire coloring material. Any pigment may be used, and other pigments and dyes may be used in combination. Preferably, the weight of the above subphthalocyanine pigment is 40 to 100. / ₀ , using other pigments in the range of 0 to 60% by weight. Other colorings suitable for preparing blue color resist inks As the material, blue and purple pigments are preferable in terms of hue, for example, Big Blue-15, Blue 15: 1, Blue 15: 2, Blue 15: 3, Blue 15: 4 , Same 15: 6, same 16:60, same 80, pig- ment.

Examples thereof include 23 and 37. However, usable pigments are not limited to these.

In the present invention, the reason for using a subphthalocyanine pigment as a coloring material is attributable to the unique spectral characteristics of the pigment. In other words, backlights such as liquid crystal display devices have high color rendering with sharp emission at wavelengths corresponding to the three primary colors of red, green and blue (generally, 6 1 O nm, 5 4 5 nm and 4 3 5 nm) These three-wavelength fluorescent lamps are widely used, and it is necessary to effectively transmit the three-wavelength emission and block the other two-wavelength emission, respectively, to achieve high light saturation of red, green and blue. It is necessary to show. A color filter manufactured using a composition for a color filter which contains the colorant of the subphthalocyanine of the present invention as a main coloring material has a wavelength of about 3700 to 5100 nm and from 6300 nm. In order to exhibit excellent spectral characteristics with transmission in the long wavelength range and absorption in the vicinity of 5 20 to 6 20 nm, the blue emission of the three-wavelength fluorescent lamp is effectively transmitted, and green and red Light emission can be effectively blocked. Therefore, the color filter of the present invention has a high level of light saturation, and can provide a high level of light saturation to a liquid crystal display or the like using it.

Generally, the preparation of the sublid opening cyanine based pigment is carried out by synthesizing the sublid opening cyanine compound and pigmenting it. The synthesis method of the sublid mouth cyanine compound is known, and examples thereof include A. Meller and A. Ossko, Monatshefte fur Chemie 103, 150-155 (1972), and the like. Specifically, 1 mole of boron trihalide and, if necessary, a hydrogen atom of the benzene ring It can be synthesized by reacting 3 moles of orally substituted phthalonitrile. Although the sub-port opening cyanine compound thus obtained often contains impurities generated by side reactions and the like, the impurities can be removed by, for example, filtration washing and Soxhlet extraction. Here, as an impurity, a hydrolysis product of boron trihalide as a raw material, unreacted phthalonitrile, etc. can be mentioned. There are no particular restrictions on the solvent used for filter washing and Soxhlet extraction. For example, alcohol solvents such as methanol and ethanol, ketone solvents such as acetone and methyl ketone, and aromatic solvents such as toluene and xylene can be used. In addition, if necessary, phthalocyanyl or a substituted phthalonitrile other than halogen may be used as a starting material to synthesize an unsubstituted or substituted subphthalocyanine, and then halogenation may be performed by a known method. However, the synthesis method and purification method are not limited to the above methods.

As a method of pigmenting, known methods can be used. For example, after dissolving a subphthalene compound in strong acid such as concentrated sulfuric acid and the like, it is poured into a large amount of water to produce fine paste. Similarly, there may be mentioned an aqueous slurry method which is dispersed in a strong acid and poured into a large amount of water to form a fine pigment. Moreover, in order to obtain a color filter having a high level of light saturation, it is preferable to use a pigment further finely divided as a coloring material, but a known method can be used for the method of finely dividing, for example, salt The sol-milling method and the solv- ent salt milling method, etc., which break the mill in the presence of In the present invention, the methods of pigmentation and atomization are not limited to the methods described above. The pigment used in the present invention preferably has an average particle size of primary particles in the range of 10 to 500 nm, and in the range of 3 to 300 nm. It is more preferable, and most preferably in the range of 50 to 200 nm. The type of the dispersant for the component (B) is not particularly limited, but is selected from (a) poly (lower alkyleneimine) and (b) polyallylamine from the viewpoint of excellent dispersion stability. One or more carboxyl group-containing compounds selected from (i) polyesters, (ii) polyamides and (iii) polyester amides having free carboxyl groups in one or more nitrogen-containing compounds It is preferable to use a graft polymer which is reacted to form an amide or a salt.

(a) Poly (lower alkylene) includes a primary (-NH ₂ ), a secondary (-NH-) and a tertiary (_N) amino group as a lower alkylene chain (-R-, eg -CH It is a polymer having a branched structure linked by ₂ CH _2- ). (B) Polyallylamine is a polymer having a structure of [—CH ₂ _CH (C 3⁄4 NH ₂ ) —] _n . In addition, the carboxyl group-containing compound of (i), (ii) and (iii) has at least one carboxyl group at the terminal or side chain etc., and this is an amino group of (a) or (b) At least a part of them react with part to form graft polymer-NHC0-or thigh ₃ ⁺ -0C0-etc.

The graft polymer is a basic moiety (a) or (b) that adsorbs to the pigment and acts as an anchor, and a polymer chain moiety (i), (ii) that imparts dispersibility by the steric repulsion effect. Or a dispersant having both (iii). Methods for producing such graft polymers are known, and are disclosed, for example, in JP-B-63-3057 and JP-A-9-16982-1. Also, in order to enhance the adsorption of the basic part of the graft polymer to the sub-port opening cyanine-based pigment, a pigment derivative type dispersing aid in which an acidic functional group is introduced to the pigment 'skeleton is used in combination with a dispersant. You can also. The dispersion aid is preferably blue or purple in view of the color phase, for example, a sulfonic acid derivative of copper phthalocyanine, a sulfonic acid derivative of subphthalocyanine, a sulfonic acid derivative of quinataridone, carbazole dio Examples thereof include sulfonic acid derivatives of oxazine and the like.

The powder of the component (B) is not limited to the graphitized polymer as described above, and may be one having a dispersing ability, which is commercially available as a dispersing agent, dispersion accelerator, etc. Including the equivalent. Some resins have a function to be adsorbed to the surface of the pigment to disperse the pigment. Such resins are included in the dispersant because they have dispersing ability. Therefore, when the photosensitive resin and Z or the monomer of the component (D) have a dispersing ability, it may be used as a dispersing agent. However, resins that are high viscosity substances generally have the effect of stabilizing dispersion (dispersion stabilizing ability) but do not have dispersing ability, and thus those that do not have dispersing ability are not treated as dispersing agents. . In the present invention, the dispersant may be one component of the resin component. As the solvent of the component (C), esters, ketones, glycol ethers, nitrogen-containing solvents and the like are preferable from the viewpoint of being excellent in the pigment dispersibility and the solubility of the dispersant. Can be used preferably. For example, esters such as ethyl acetate, butyl acetate, lactate cetyl, γ_butyrorataton etc., ketones such as methinoleic sobutynoleketone, organic acid hexone etc, and glyconee tennores such as ethy / resero sonorev, fethiñero solose And piring gris As the nitrogen-containing solvents, there can be mentioned dimethylformamide, dimethylacetoamide and the like as corneol mono methyle nore tene acetate, diethyleneglycone monomethyl ether and the like. These solvents may be selected appropriately according to the composition of the resin and other additives to be compounded, the solvent resistance of the pigment, and the coatability, and may be used alone or in combination of two or more. Also good. Here, the pigment dispersion contains, as essential components, the colorant of the component (A), the dispersant of the component (B) and the solvent of the component (C). The total solid content is 1 to 40% by weight. It is preferably 5 to 35% by weight. The blending ratio of the component (A) in the pigment dispersion is preferably 1 to 25% by weight, and more preferably 5 to 20% by weight. The content of component (B) is preferably 10 to 60% by weight, and more preferably 20 to 50% by weight, based on the pigment. If the content of the component (B) is less than 10% by weight to the pigment, the dispersion stability of the pigment dispersion becomes insufficient, and if it exceeds 60% by weight, it is effective in one photolithographic process. Pixel formation ability may not be realized. However, when the component (D) has a dispersing ability, it may be contained at more than 60% by weight. The total solid content is the component remaining after drying, curing or polymerization. Usually, the total solid content is obtained by removing components other than volatile components such as solvents. Further, the amount of the pigment which is the basis of the content ratio of the component (B) means the total of the pigments in the colorant. The pigment dispersion is obtained by dispersing the pigment together with the dispersant in a solvent. When the component (D) and the component (E) are contained, they may be simultaneously added and dispersed, or may be obtained in advance without the components (D) and (E). One pigment dispersion may be prepared, and then component (D) and component (E) may be blended to form a second pigment dispersion, which may be used as a color filter composition. The manufacturing method is not particularly limited, and known methods can be used. For example, dispersion treatment using a paint shaker, sand mill, bead mill, etc. can be mentioned. The pigment in the pigment dispersion or composition used in the present invention is desirably dispersed to its primary particle size. That is, the average particle size of the pigment in the pigment dispersion or composition is preferably in the range of 10 to 500 nm, and more preferably in the range of 30 to 3 OO nm. Most preferably, it is in the range of 50 to 200 nm. When the average particle size of the pigment exceeds 500 nm, the light transmittance decreases and polarization tends to occur, so the light filter becomes poor and the contrast is low. On the other hand, when it is less than 10 nm The dispersion stability of the pigment dispersion becomes insufficient.

Although the ratio of the coloring material in the composition for color filter is appropriately selected according to the coloring concentration etc., the ratio of the coloring material of the component (A) in the composition and the resin solid content (R) to (A) / The weight ratio of (R) needs to be in the range of 0.5 to 1.5, and preferably in the range of 0.1 to 1. If this ratio is less than 0.55, the coloring performance can not be sufficiently exhibited, and a good force filter can not be formed, and if it exceeds 1.5, a pixel forming ability effective in one photolithographic process can be formed. Will not be able to The resin solid content (R) is a total of resin components (including monomers) other than the component (D) and the component (D). The photosensitive resin and / or monomer of component (D) is selected from at least one or more of a photopolymerizable resin, a photopolymerizable monomer and a photopolymerizable oligomer, and has an ethylenically unsaturated bond. It is a thing. Cured in the force filter composition It is sufficient to include those that become resin in the condition above, including the case where only components that are not resinified in the uncured state are included. In the resin solid content in the present invention, monomers and oligomers before resinification are also treated as solid content. Component (D) may be selected appropriately in consideration of the color filter production process. Examples of the photopolymerizable resin, the photopolymerizable monomer and the photopolymerizable oligomer include 2—hydroxyl (meth) acrylate, 2—hydroxypropyl (meta) acrylate, 2 —Ethyl Hexyl (Meta) Atlate, Diethylene Glycol (Meta) Atlate, Diethylene Glycol Nose (Meta) Atlate, Tri Ethylene Dale Coal (Meta) Atlate , Poly ethylene glycol (meta) atlate rate, Penta erythritol

(Meta) Atrelate, Dipentaellis Recovery (Meta) Atlet, Dipentaerythritol Hexa (Meta) Atlate, Bisphenol A-type Epoxy Resin (Meta) (A) Acrylic esters such as phthalates, bis-phenol F-type epoxy di (meth) phthalate, bis-phenol fluorene type epoxy di (meth) atlate, etc. may be mentioned. Also, acrylic acid (co) polymer, (meth) acrylic acid (co) polymer, maleic acid

(Co) Bulle resin such as polymer, Poly ethylene oxide, Poly (ethylene oxide), Polyamide, Polyamide, Polyurethane, Polyether, Polyether, Polyester, etc. Resins having an ethylenic double bond in the side chain Can also be mentioned. These may be used alone or in combination of two or more. Further, in order to improve developability, it is preferable that these resins have an alkali-soluble substituent such as a carboxyl group or a phenolic hydroxyl group in the side chain.

The compounding ratio of the photosensitive resin and / or the monomer of the component (D) is preferably 40 to 95% by weight based on the total solid content in the composition for a color filter of the present invention, More preferably, it is 50 to 90% by weight. In the composition, other resins and the like can be blended, if necessary, but in this case, it is desirable that the total amount of the other resins combined is within the above range. The total solid content is the component remaining as a solid content after drying and curing, does not contain a solvent, and contains a monomer. Examples of the photopolymerization initiator of the component (E) include acetophenones such as acetophenone, p-tert-butynoacetophenone, benzophenone, ρ, '' -bis (Ν, Ν-dimethylamino) ) Benzophenones such as benzophenone, benzoin ethenoene, benzoin tert-butynore monotenole such as benzoin ethenoles, 2-methinole 1 1 [4 1 (methylthio) phenyl] 2 2-monorefo rinopropane 1 1-one, 2_benzyl- 2-(N, N- dimethylamino) 1-(4-morpholino-phenyl) butane 1-one-one α-amino alkylphenones such as 2, 4, 6-tris (trichloromethyl)-1, 3, 5-triazine, 2-(4-met (oxyphenyl)) 1 4, 6-bis (trichloromethyl) 1, 3, 3, 5 — Triazines such as triazine, benzene peroxide, organic peroxides such as 3,3 ', 4,4'-tetra (ter't-peptinolepaneoxycarbonyl) benzophenone And sulfur compounds such as thioxanthone and 2,4-jetylthioxanthone. These may be used alone or in combination of two or more.

Although the compounding ratio of a photoinitiator is suitably selected according to exposure sensitivity etc., it is preferable that it is 0.1 to 20 weight% with respect to (D) component, and also 0.5 to 15 It is preferred to be in weight percent. Content is 0. In less than 1% by weight, sensitive light resistance becomes insufficient, and when it exceeds 2 0 weight ^_0/0 Conversely, lack in storage stability as a Regis Toinki. The composition for a color filter of the present invention is not limited in its production method as long as it contains the above-mentioned essential components. And (E), it is advantageous to mix with the resins and other components added as needed.

In addition to the above components, the composition for color filter of the present invention may be added with a resin having alkali solubility as a binder resin component for the purpose of improving developability and film formation ability. For example, polyethylene oxide, polyvinyl pyrrolidone, polyamide, polyurethane, polyester, polyether, etc. containing a carboxyl group in the main chain or side chain and having excellent releasability. I like it. Such materials include, for example, vinyl resins such as acrylic acid (co) polymers, (meth) acrylic acid (co) polymers, and maleic acid (co) polymers. Besides these, resins obtained by adding an acid anhydride to a resin having a hydroxyl group are also useful. These may be used alone or in combination of two or more.

The composition for a color filter of the present invention contains the components (A), (B), (C), (D) and (E) as essential components, but the total solid content is 1 It is preferably -40% by weight, more preferably 5- 30% by weight. As a method of producing a composition for a color filter, a pigment dispersion is prepared by dispersing the above-mentioned sub-thin liquid cyanine pigment alone or in combination with other pigments in a solvent, and this and the resin component. Methods of incorporating a photopolymerization initiator, etc., and methods of directly dispersing a subphthalocyanine pigment in a resin composition, etc. may be mentioned, but from the viewpoint of the stability of the composition for color filters The method of the person is preferred. There is also a method of using a high solubility solvent capable of dissolving a subphthalocyanine pigment and dissolving it in a composition containing a sublid opening cyanine compound and a photosensitive resin to make a color resist ink, but the light resistance, heat resistance and Due to the difficulty in solvent resistance, the method of pigmenting and dispersing it is most preferred.

The cured product obtained by curing the color filter composition of the present invention is obtained by applying the composition to a substrate or the like and curing the composition by light irradiation, heating or the like. As a method of applying the composition, known methods can be used, and examples include application using a coating apparatus such as a spin coater, bar coater, or die coater. After application, drying may be performed using a hot plate, an IR oven or the like.

The composition can be irradiated with light by a known method, and the applicable exposure light source is not particularly limited. For example, xenon lamp, halogen lamp, tungsten lamp, extra-high pressure mercury lamp, high-pressure mercury lamp, medium pressure Lamp light sources such as mercury lamps and low pressure mercury lamps are used. However, the method of application and light irradiation is not limited to the above method. After image exposure with this light source, if it is developed, an image can be formed on the substrate. Any developer may be used as the developer as long as it dissolves the unexposed area and does not dissolve the exposed area. Specifically, it is an alkaline solution containing various additives, and as additives, organic solvents, buffers, surfactants, etc. can be contained. The development method is not particularly limited, but methods such as immersion development, spray development, brush development and ultrasonic development may be used. Further, as a method of increasing the strength of the coating, heat curing may be performed by a hot air oven. The curing conditions of the composition are not particularly limited, but in order to prevent discoloration and discoloration of the cured film obtained by curing the composition, heating is preferably performed at 250 ° C. or less for 1 hour or less. A known method can be used as a method of producing a color filter using the cured film of the above composition for a color filter. BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1 and 2 are dalaffs showing the spectral transmittance of a model force filter. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples. In the following, “parts” refers to parts by weight.

Synthesis example 1

Tetra black mouth phthalo no linole 1 5 0 parts. Add 1 portion of benzene 58 and stir at room temperature for 30 minutes under nitrogen atmosphere, and then 1 portion of boron tribromide is dropped. Thereafter, the mixture is slowly heated to 100 ° C., and when the reaction becomes mild, heating and stirring are further carried out at 150 to 180 ° C. for 10 to 60 minutes. After allowing to cool, the precipitate is collected by filtration, washed with an acetone, an aqueous solution of sodium hydrogen carbonate, water and methanol in this order, and dried. Lid opening Six parts of cyanine boron complex (yield 41%) were obtained. Next, this compound was dissolved in 10 times the amount of concentrated sulfuric acid, this solution was poured into ice water, and the precipitated solid was collected by filtration, washed with water and dried to obtain pigment A.

Synthesis example 2

After adding 30 parts of 1_ chloro naphthalene to 1 part 50 parts of tetra-chloro phthaloyl trizole and stirring for 30 minutes at room temperature under nitrogen atmosphere, dissolve boron trichloride in 1 mo 1 ZL in advance. Add 1 7 parts of the stored heptane solution 4 1. Thereafter, the mixture is slowly heated to 180 ° C., and further heated and stirred at 200 ° C. to 240 ° C. for 10 to 60 minutes. After standing to cool, the precipitate is collected by filtration, washed with acetone, an aqueous solution of sodium hydrogen carbonate, water and methanol in this order and dried, and the C 1 1 dodecachrome-containing sublida cyanine represented by the formula (3) Six 4 parts (yield 40%) of boron complex were obtained. Next, this compound was dissolved in 10 times the amount of concentrated sulfuric acid, this solution was poured into ice water, and the precipitated solid was collected by filtration, washed with water and dried to obtain pigment B. Example 1

100 parts of the pigment A obtained in Synthesis Example 1 were mixed with 40 parts of the dispersant and 80 parts of propylene dale monomethinole ether acetate, and dispersion treatment was carried out for 6 hours using a paint sinter. The solution was filtered to remove beads, and a dispersion of 1000 parts was made. Here, as the dispersing agent, a polyhydroxyl polymer was used to react with a polyester having a free carboxyl group to form an amide. Also, in the media of the paint shaker, ^ :, 0.4 mmφ glass beads were used at a filling rate of 40% or 0.4 mmφ zirconia beads at a filling rate of 15%. The solid content concentration of the dispersion obtained in this manner is 14% by weight, and the proportion of the coloring material in the total solid content is 71.4% by weight, and exhibits low viscosity and low thixotropy. Met. In addition, the average particle diameter of the pigment in the dispersion (diluted to 1% by weight of pigment) measured using a particle size distribution analyzer (trade name: manufactured by Otsuka Electronics Co., Ltd .: particle diameter analyzer FPAR-1 200) was 9 It was 8 nm. Example 2

A dispersion was produced in the same manner as in Example 1 except that the pigment was changed to pigment B obtained in Synthesis Example 2. The solid content concentration of the dispersion B thus obtained is 14% by weight, and the proportion of the coloring material in the total solid content is 71.4% by weight. It showed low thixotropy. Also, the average particle size of the pigment in the dispersion was 10 2 nm. Example 3

5 of epoxy acrylate resin with bisphenol fluorene skeleton

4 - 2 wt ^_0/0 Pro Pirenguri glycol monomethyl ether § cetearyl Ichito solution (Shin鐡化Science Corporation, trade name: V- 2 5 9 ME) 1 3 0 parts Kisaata Li rate 4 to Jipentaeri scan Li toe Le 7 parts, an epoxy resin having a biphenyl skeleton (product name of EPAP Epoxy Resins Co., Ltd .: trade name: Epi coat YX 400 HK) 1 7 parts, 2-methinole 1-[4 one (methylthio) number one]- 2—Monolef olenopropan 1 1 7 7 parts p, p '1 bis (N, N-jetylamino) benzophenone 1 part, dimethylene glycol dimethyl ether 1 6 6 parts, propylene glycol mono methyl ether 5 parts of set ₇ , 1 part of surfactant and 1 part of silane coupling agent are blended and thoroughly stirred to make 5 parts of a composition containing photosensitive resin soluble in weak alkaline solution did.

The dispersion A obtained in Example 1 was added to 4 parts of a composition 4 containing this photosensitive resin.

Five hundred and five parts were mixed and thoroughly stirred until a uniform solution was obtained, to prepare 1000 parts for force filter single use composition. The solid content concentration of the composition thus obtained is 21.6% by weight, and the proportion of the pigment part in the total solid content is 24.3% by weight, and exhibits low viscosity and low thixotropy. there were. The composition for a color filter thus obtained was applied using a spin coater on a blue sheet glass substrate having a 5 inch angle and a thickness of 1 mm. At this time, the number of rotations of the spin coater was changed to manufacture a test piece. This test piece After drying, it was covered with a photo mask and exposed to ultraviolet light at ²⁰ O mj Z cm ² to cure the color resist ink in the exposed area. Next, the test piece was subjected to alkaline development with a 0.4% aqueous solution of sodium carbonate for 60 seconds to remove an unexposed area, and then dried. Finally, the test pieces were heat-cured to produce a cured film of color resist ink as a model color filter. The spectral transmittance, chromaticity (X value, y value) and lightness (Y value) of the model color filter manufactured are the color meter (trade name: made by Tokyo Denshoku Co., Ltd .: Color Analyzer 1 TC-180 MK 2 The light for color measurement at this time was the standard light C. The spectral transmittances of the model filter obtained in this example are shown in FIG. 1, and the chromaticity and lightness are shown in Table 1. Example 4

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 B obtained in Example 2. The solid content concentration of this composition was 21.6% by weight, and the proportion of the pigment part in the total solid content was 24. 3% by weight, showing low viscosity and low thixotropy. Further, the spectral transmittance, the chromaticity, and the lightness of the model color filter were measured in the same manner as in Example 3 for this composition. The results are shown in Figure 1 and Table 1. Reference Example 1

100 parts of pigment 'blue 15: 6 blended with 40 parts of dispersant and 80 parts of propylene glycol monomethyl ether acetate, and dispersed for 6 hours using a paper acre Treatment was performed and filtration was performed to remove beads, to prepare a dispersion C 1000 part. Here, the dispersant is polyallylamine. A polyester having a free carboxyl group was reacted to form an amide. In addition, for the media of Paint Toshiaker, a 5.4 mm zircon air bead was used at a filling rate of 15%. The solid content concentration of the dispersion C thus obtained is 14% by weight, and the proportion of the coloring material in the total solid content is 71.4% by weight, exhibiting low viscosity and low thixotropy. The In addition, the average particle size of the pigment in the dispersion was 15011 m. Example 5

Propylene glycol mono methyl ether acetate solution of 54.2% by weight of epoxylate resin having bisphenol fluorene skeleton (Nippon Chemical Co., Ltd. trade name: V-2 5 9 ME) 1 3 0 part, 7 parts of dipentaerythritol trihydrate, 4 parts of epoxy resin having biphenyl skeleton (trade name: Apico Epoxy Resins Co., Ltd .: YP 4 0 0 0 HK) 1 7 parts, 2—Methinole 1 _ [4- (Methylthio) phenyl] — 2 — 7 parts of morpholinopropanone 1-one, p, p 'bis (N, N-jetylamino) benzophenone 1 part, dimethylene glycol dimethyl ether 1 9 Mix 6 parts, 5 parts of propylene glycol monomethyl ether acetate, 1 part of surfactant and 1 part of silane coupling agent, stir thoroughly to make a weak alkaline solution. It was manufactured composition 4 7 5 parts containing soluble photosensitive resin.

The photosensitive resin-containing composition 4 is blended with 2.5 parts of dispersion B 2 6 5 obtained in Example 2 and 2 5 parts of dispersion C 2 6 obtained in Reference Example 1. The mixture was thoroughly stirred until it became a uniform solution to prepare 1000 parts of a composition for a color filter. The solid concentration of the composition thus obtained is 21.6% by weight, and the proportion of the pigment part in the total solid content is 24.3% by weight, so that it has a low viscosity and a low thixotrope. It showed a pi. The spectral transmittance of the model color filter was also measured in the same manner as in Example 3 for this composition. The result is shown in Fig.2. Example 6

Example 6 was repeated except that the pigment dispersion was changed to 25 parts of dispersion B 47.5 obtained in Example 2 and 2.5 parts of dispersion C 5 obtained in Reference Example 1 The color filter composition was prepared. The solid content concentration of the composition was 21.6% by weight, and the proportion of the pigment part in the total solid content was 24.3% by weight, exhibiting low viscosity and low thixotropy. Further, the spectral transmittance of the model color filter was measured in the same manner as in Example 3 for the composition. The results are shown in Figure 2. Comparative example 1

A pigment dispersion was obtained in the same manner as in Example 1 except that the pigment was changed to pigment-biolet 23 and a composition for a color filter was prepared in the same manner as in Example 3. With respect to this composition, the spectral transmittance, the chromaticity, and the lightness 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 2

A pigment dispersion is formed in the same manner as in Example 1 except that the pigment is changed to a C 1 -subphthalocyanine boron complex pigment represented by the following formula (4), and a color filter is prepared in the same manner as in Example 3. The composition for this was produced. About this composition The spectral transmittance, the chromaticity, and the lightness of the model 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. With respect to this composition, the spectral transmittance of the model filter was measured in the same manner as in Example 3. The results are shown in Figure 2. In FIG. 1 and FIG. 2, E3, E4, E5 and E6 respectively mean Example 3, Example 4, Example 5 and Example 6, and C1, C2 and C3 are Comparative Example 1 and Comparative Example 2, respectively. And Comparative Example 3 is meant. As shown in FIG. 1, the spectral characteristics of the model color filter obtained in the present example effectively transmit the blue emission of the three-wavelength fluorescent lamp as compared with the model color filter of the comparative example. It had a high level of light and saturation that could effectively block red and green emissions. In addition, the cured film had a uniform film thickness and good coatability without aggregation precipitates and the like.

In the case of the model color filter of the comparative example, as is apparent from Table 1, the model color filter comprising the composition for a color filter of the present invention It can be seen that the Y value is significantly increased as compared to the above, and the present invention provides a color filter having a high level of light saturation. table 1

As shown in FIG. 2, even when used in combination with other blue pigments, the spectral characteristics of the model force filter obtained in this example are shorter than those of the model force filter of the comparative example. High-level light saturation that can improve transmission in the wavelength range (around 3800 to 4600 nm) and effectively transmit blue emission (around 435 nm) of a three-wavelength fluorescent lamp The Moreover, the cured film had a uniform film thickness and good coatability without aggregation precipitates and the like. Industrial Applicability The color filter composition of the present invention is extremely useful in that it enables the production of a high quality liquid crystal display and the like because it has a high level of light saturation.

Claims

The scope of the claims

(1) In a pigment dispersion in which a coloring material is dispersed in a solvent together with a dispersing agent, a pigment comprising a subphthalocyanine compound represented by the following general formula (1) as a coloring material is contained in an amount of 0.5 weight to the whole coloring material. The pigment dispersion characterized by containing more than%. +

(However, at least 6 of XL to X ₁₂ are halogen-rich and the rest are hydrogen atoms. Y represents a halogen atom or a hydroxyl group.)

(2) - in the pigment consisting of sub-phthalocyanine compound represented by the general formula (1), pigment component Chikarada of claim 1, wherein all Xi～X ₁₂ is a halogen atom.

(3) at least one nitrogen-containing compound selected from the group consisting of (a) poly (lower alkylene) and (b) polyallylamine; The naphtha polymer according to claim 1 or 2, which is obtained by reacting a compound having at least one kind of free carboxyl group selected from the group consisting of (ii) polyamide and (iii) polyester. Pigment dispersion.

(4) The pigment dispersion according to any one of claims 1 to 3, wherein the average particle diameter of the pigment is in the range of 10 to 500 nm.

(5) The pigment dispersion according to any one of claims 1 to 4, further comprising a photosensitive resin and / or a monomer, and a photopolymerization initiator.

(6) A composition for a color filter, wherein the pigment dispersion according to claim 5 is a composition used for forming a pixel for a color filter.

(7) A composition for a color filter comprising a colorant, a dispersant, a solvent, a photosensitive resin, Z or a monomer, and a photopolymerization initiator. Containing 0.5% by weight or more of a pigment consisting of a sublid opening cyanine compound shown in the above), and 0.1 to 20% by weight of a photopolymerization initiator based on the photosensitive resin and / or the monomer. % (A) Z (R) represented by the weight ratio of the coloring material amount (A) in the composition to the resin solid content (R) is 0.5 to 5

1. A composition for a color filter characterized by being in the range of 5.

(However, at least 6 of X i to X ₁₂ are halogen atoms, and the remainder is a hydrogen atom. Y represents a halogen atom or a hydroxyl group.)

(8) A cured product obtained by curing the force filter composition according to claim 6 or 7.

(9) A color funnel made of the cured product according to claim 8 wherein the cured film forming blue pixels.