KR101057248B1 - Pigment dispersions, compositions for color filters and color filters - Google Patents

Abstract

The present invention relates to a pigment dispersion, a color filter composition, a cured product thereof, and a color filter which give a high level of brightness when used in a liquid crystal display. The pigment dispersion disperses the coloring material in a solvent together with a dispersant. It consists of 0.5 wt% or more of the subphthalocyanine compound pigment represented by following General formula (1) as a coloring material, and a coloring material. It is also possible to contain photosensitive resins and / or monomers and photopolymerization initiators. However, in General formula (1), X <_1> -X <_12> represents H or halogen, 6 or more are halogen, and Y represents a halogen or a hydroxyl group.

Liquid crystal display, composition for color filters, pigment dispersion, color filter, subphthalocyanine compound

Description

Pigment dispersion, color filter composition and color filter {PIGMENT DISPERSION, COLOR FILTER COMPOSITION AND COLOR FILTER}

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 and a color filter formed using the same, and in particular, a pigment dispersion suitable for forming a blue pixel, a composition for a color filter; It is about the hardened | cured material.

The color filter is widely used for the purpose of colorization of a liquid crystal display device, etc. Generally, red, green, and blue pixels are arranged in a mosaic shape. As a method of producing this color filter, the dyeing method, the printing method, the electrodeposition method, the pigment dispersion method, etc. are known. In particular, the pigment dispersion method of forming a fine pixel by photolithography using a composition for color filters (hereinafter also referred to as color resist inks) in which a pigment is dispersed together with a photosensitive resin and / or a monomer, has a light resistance, It is becoming the mainstream of the color filter manufacturing method in that it is excellent in heat resistance and solvent resistance.

In principle, most of known pigments can be used in the pigment dispersion method. For example, Japanese Patent Laid-Open No. 5-281414 discloses red, green, blue, yellow and purple (as colorants of color resist inks). Purple pigments have been disclosed over dozens of species. In addition, the pigment of each pixel is generally selected so that the transmission characteristics of the pixel are adapted to the light emission characteristics of the backlight light, for example, in addition to the red pigment in the red pixel, yellow pigment, mars yellow pigment, in addition to the green pigment in the green pixel The yellow pigment is given to the blue pixel by mixing a purple pigment in addition to the blue pigment at a constant ratio, thereby providing desired transmission characteristics.

However, in recent years, high definition, high brightness, and high color reproducibility of liquid crystal display devices are highly demanded, and higher brightness and color saturation of color filters are desired. Therefore, it is extremely limited to show a high level of chromaticity. For example, in the color resist ink for forming a blue pixel, a purple pigment is often used together with pigment blue 15: 6, which is a copper phthalocyanine-based blue pigment, which is a Japanese patent. As disclosed in 2543052, Pigment Violet 23, which is a purple pigment composed of carbazole dioxazine, is almost the only one that can be used well.

This pigment violet 23 is often mixed for the purpose of improving the blue purity of the copper phthalocyanine-based blue pigment which barely transmits green light because the blue transmission region is shorter than the copper phthalocyanine-based blue pigment. However, in the method of mixing two pigments having different permeation ranges, high brightness and high saturation have a relationship of doubled rate, and a method of using pigment violet 23 having a significantly different permeation range and a low permeability with the copper phthalocyanine-based blue pigment There was a problem in that it could not satisfy the high level of brightness at the same time.

As described above, in the preparation of color filters used in liquid crystal display devices and the like, the color resist ink used is required to be adjusted to a color material having a transmission characteristic suitable for a purpose or purpose, and replaces a carbazole dioxazine violet pigment. Highly colorful color resist inks using pigments are desired.

On the other hand, a subphthalocyanine compound is known as one of the pigment | dyes. Japanese Unexamined Patent Application Publication No. 11-24255 and Japanese Unexamined Patent Application Publication No. 2001-318462 disclose a photopolymerizable composition using this subphthalocyanine compound. However, these photopolymerizable compositions focus on the photosensitizing action of the visible light region of the subphthalocyanine compound to dissolve the subphthalocyanine compound in the photosensitive resin composition, such as long wavelength laser light such as argon laser (514 nm) or YAG (second harmonic) laser (532 nm). It is used as a photosensitizer for visible light and the like, and it is not suggested that the subphthalocyanine compound is pigmented and dispersed as a coloring material and used in a color filter composition.

SUMMARY OF THE INVENTION The present invention has been made in view of the drawbacks of the prior art, and is used in liquid crystal display devices and the like, and includes a pigment dispersion for forming a (blue) pixel which gives a high level of brightness, a composition for color filters, and a light filter formed using the same. It is an object to provide cargo and color filters.

That is, this invention is a pigment dispersion which disperse | distributes a coloring material to a solvent with a dispersing agent WHEREIN: It contains 0.5 weight% or more of the pigment which consists of a subphthalocyanine compound represented by following General formula (1) as a coloring material. It is a pigment dispersion characterized by the above-mentioned.

(However, at least six of X ₁ to X ₁₂ represent halogen atoms, and the rest represent hydrogen atoms. Y represents a halogen atom or a hydroxyl group.)

Furthermore, the present invention provides a coloring material (hereinafter referred to as component (A)), a dispersant (hereinafter referred to as component (B)), a solvent (hereinafter referred to as component (C)), a photosensitive resin and / or a monomer (hereinafter, Subphthalocyanine represented by the said General formula (1) as a coloring material component of component (A) in the composition for color filters containing component (D)) and a photoinitiator (henceforth a component (E)). 0.5 weight% or more of the pigment which consists of a compound is contained in all the coloring materials, 0.1-20 weight% of photoinitiators of a component (E) are contained with respect to the photosensitive resin and / or monomer of a component (D), and the coloring material in the said composition (A) / (R) represented by the total weight ratio of each component of (A) and resin solid content (R) is characterized by the range of 0.05-1.5.

Furthermore, this invention is hardened | cured material obtained by hardening | curing the said composition for color filters. Moreover, this invention is a color filter in which the cured film which forms a blue pixel consists of said hardened | cured material.

Hereinafter, the pigment dispersion of this invention is demonstrated.

It is preferable that the pigment dispersion of this invention contains a coloring material (component (A)), a dispersing agent (component (B)), and a solvent (component (C)) as an essential component, and made it the predetermined pigment particle size. . Moreover, the pigment dispersion of this invention is useful as a composition for color filters. When using the pigment dispersion of this invention as a composition for color filters, it is preferable to further contain photosensitive resin and / or monomer (component (D)) and (E) photoinitiator (component (E)) as an essential component. Moreover, as needed, various additives, such as other resin and other surface control agents, an antifoamer, can be mix | blended.

The coloring material of component (A) needs to contain 0.5 weight% or more of the pigment which consists of a subphthalocyanine compound represented by the said General formula (1) in all coloring materials. In General formula (1), in X <_1> -X <_12> , at least 6 is a halogen atom and the remainder is a hydrogen atom. The halogen atom may be any one of fluorine, chlorine, bromine and iodine, and chlorine or bromine is preferable in terms of color. More preferably, all of X ₁ to X ₁₂ in General Formula (1) are chlorine or bromine. In addition, a plurality of halogen atoms may be bonded in one molecule. Y in General formula (1) is a halogen atom or a hydroxyl group, but chlorine or bromine is preferable from the viewpoint of excellent handling.

Component (A) should just contain 0.5 weight% or more, Preferably it is 5 weight% or more, More preferably, it is 40 weight% or more, More preferably, 70 weight% or more of the said subphthalocyanine type pigments in all the coloring materials. You may use together and use another pigment and dye. Preferably it uses 40-100 weight% of said subphthalocyanine pigments, and 0 to 60 weight% of other pigments. As other coloring materials suitable for preparing a blue color resist ink, blue and purple pigments are preferable in terms of color, and are, for example, Pigment Blue 15, Copper 15: 1, Copper 15: 2, and Copper 15: 3. Although, 15: 4, 15: 6, 16, 60, 80, pigment violet 19, 23, 37 etc. are mentioned, the pigment which can be used together is not limited to these.

In the present invention, the reason for using the subphthalocyanine-based pigment as the coloring material is attributable to the specific spectral characteristics of the pigment. That is, a high color rendering three-wavelength fluorescent lamp having a light emission sensitive to wavelengths (typically 610 nm, 545 nm and 435 nm) corresponding to three primary colors of red, green, and blue is widely used for backlights of liquid crystal displays. It is necessary to effectively transmit these three wavelengths of light and to block the emission of the other two wavelengths in order to exhibit high levels of red, green, and blue brightness. The color filter manufactured using the composition for color filters containing the pigment which consists of the subphthalocyanine of this invention as a main coloring material has the outstanding spectral characteristic which has the transmittance in the wavelength range near 370-510 nm and 630 nm, and has absorption in 520-620 nm vicinity. Therefore, the blue light emitted by the three-wavelength fluorescent lamp can be effectively transmitted, and the green and red light can be effectively blocked. Therefore, the color filter of this invention has a high level of brightness, and can give a high level of brightness to the liquid crystal display device etc. which use this.

Production of a subphthalocyanine-based pigment is generally accomplished by synthesizing a subphthalocyanine compound and pigmenting it. The synthesis method of a subphthalocyanine compound is well-known, As an example, A. Meller and A. Ossko, Monatshefte fur Chemie 103, 150-155 (1972), etc. are mentioned. Specifically, it can synthesize | combine by reacting 1 mol of boron trihalide and 3 mol of phthalonitrile which the hydrogen atom of the benzene ring halogen-substituted as needed. The subphthalocyanine compound thus obtained often contains impurities generated by side reactions and the like. For example, the impurities can be removed by filtration washing or soxhlet extraction. Examples of the impurities include hydrolysis products of boron trihalide, which are raw materials, and unreacted phthalonitrile. There is no restriction | limiting in particular about the solvent used for filtration washing and a soxhlet extraction. For example, alcohol solvents, such as methanol and ethanol, ketone solvents, such as acetone and methyl ethyl ketone, aromatic solvents, such as toluene and xylene, etc. can be used. If necessary, after substituted phthalonitrile or substituted phthalonitrile other than halogen as a starting material, unsubstituted or substituted subphthalocyanine may be synthesized and then halogenated according to a known method. However, the synthesis method and the purification method are not limited to the above method.

As a method of pigmentation, a well-known method can be used, For example, after dissolving a subphthalocyanine compound in strong acids, such as concentrated sulfuric acid, it introduce | pours into a large quantity of water and produces | generates a fine pigment. As an acid pasting method, the acid slurry method which disperse | distributes in a strong acid and puts this in a large quantity of water, and produces | generates a fine pigment is mentioned. Further, in order to obtain a color filter having a high level of clarity, it is preferable to use a finely divided pigment as a coloring material. A well-known method can also be used for the atomization method, for example, mill crushed in the presence of a salt. The salt milling method, the solvent salt milling method, etc. are mentioned. In this invention, the method of pigmentation and atomization is not limited to said method, either. It is preferable that the average particle diameter of a primary particle of the pigment used by this invention is the range of 10-500 nm, It is more preferable that it is the range of 30-300 nm, Furthermore, it is most preferable that it is the range of 50-200 nm.

Although the kind in particular as a dispersing agent of component (B) is not restrict | limited, 1 or 2 or more types of nitrogen chosen from (a) poly (lower alkyleneimine) and (b) polyallylamine by the point which is excellent in dispersion stability. One or two or more carboxyl group-containing compounds selected from (i) polyesters, (ii) polyamides, and (iii) polyesteramides having free carboxyl groups are reacted with the compound to form amides or salts. It is preferable to use a graft polymer which is made.

(a) Poly (lower alkyleneimines) include amino groups of primary (-NH ₂ ), secondary (-NH-) and tertiary (-N <) lower alkylene chains (-R-, e.g. A polymer having a branched structure bonded with CH ₂ CH _2- ), and (b) polyallylamine is a polymer having a structure consisting of [-CH ₂ -CH (CH ₂ 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., which reacts with at least a part of the amino group of (a) or (b) or the like to give -NHCO- or NH ₃ ^{+ --} OCO- and the like to form a graft polymer.

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) or (iii) that imparts dispersibility by steric repulsion effect. Dispersant having both sides. The manufacturing method of such a graft polymer is well-known, For example, it is disclosed by Unexamined-Japanese-Patent No. 63-30057 and Unexamined-Japanese-Patent No. 9-169821.

Moreover, in order to improve the adsorption property of the basic part of a graft polymer with respect to the subphthalocyanine type pigment, it is also possible to use together with a dispersing agent the pigment derivative type dispersion adjuvant which introduce | transduced the acidic functional group into the pigment skeleton. The dispersing aid is preferably blue or purple in terms of color, and examples thereof include sulfonic acid derivatives of copper phthalocyanine, sulfonic acid derivatives of subphthalocyanine, sulfonic acid derivatives of quinacridone, and sulfonic acid derivatives of carbazole dioxazine. have.

In addition, the dispersing agent of component (B) is not limited to the above-mentioned graft polymer, What is necessary is just to have a dispersibility, and the thing marketed by a dispersing agent, a dispersing accelerator, etc., or its equivalent is included. Some resins have an action of adsorbing onto the surface of the pigment to disperse the pigment. Such resins are included in the dispersant because they have dispersibility. Therefore, when the photosensitive resin and / or monomer of component (D) have dispersibility, you may use this as a dispersing agent. However, resins, which are highly viscous substances, generally have a function of stabilizing dispersion (dispersion stability), but do not have a dispersibility. Such dispersants are not treated as a dispersant. In the present invention, the dispersant may be one component of the resin component.

As a solvent of component (C), when mix | blending the dispersibility of a pigment and a dispersing agent, since it is excellent in the solubility, ester, ketones, glycol ethers, a containing nitrogen-type solvent, etc. can be used preferably. For example, ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, etc. in esters, methyl isobutyl ketone, cyclohexanone, etc. in ketones, ethyl cellosolv, ethyl cellosolve in glycol ethers, etc. Examples of the nitrogen-containing solvents such as acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, and the like include dimethylformamide and dimethylacetamide. These solvents may be appropriately selected depending on the composition of the resins and other additives to be blended, the solvent resistance of the pigment, and the coating property, and may be used alone or in combination of two or more thereof.

A pigment dispersion contains the coloring material of the said component (A), the dispersing agent of a component (B), and the solvent of a component (C) as an essential component here, It is preferable that the total solid is 1-40 weight%, and 5-35 It is more preferable that it is weight%. It is preferable that it is 1-25 weight% in a pigment dispersion, and, as for the compounding ratio of a component (A), it is more preferable that it is 5-20 weight%. Moreover, it is preferable that it is 10 to 60 weight% with respect to a pigment, and, as for the compounding ratio of a component (B), it is more preferable that it is 20 to 50 weight%. If the content ratio of component (B) is less than 10% by weight with respect to the pigment, the dispersion stability of the pigment dispersion becomes insufficient. On the contrary, if the content of the component (B) exceeds 60% by weight, there is a fear that effective pixel forming ability in the photolithography process cannot be exhibited. have. However, when component (D) has dispersibility, even if it contains more than 60 weight%, it does not interfere. In addition, total solids means the component which remains after drying, hardening, or superposition | polymerization. Usually, what removes components other than volatile matters, such as a solvent, becomes total solid. In addition, the quantity of the pigment used as the reference of the content rate of a component (B) means the sum total of the pigment in a coloring material.

The pigment dispersion is obtained by dispersing a pigment together with a dispersant in a solvent. In the case of containing the component (D) and the component (E), it may be obtained by adding and dispersing them at the same time, or preparing a first pigment dispersion without containing the component (D) and the component (E) in advance, and then A component (D) and a component (E) are mix | blended and a 2nd pigment dispersion can be made and this can be used as a composition for color filters. The production method is not particularly limited, and a known method can be used. For example, dispersion processing by a paint shaker, a sand mill, a bead mill, etc. is mentioned. It is preferable that the pigment in the pigment dispersion or composition used by this invention is disperse | distributed to the primary particle diameter. That is, the average particle diameter of the pigment in the pigment dispersion or the composition is preferably in the range of 10 to 500 nm, more preferably in the range of 30 to 300 nm, and most preferably in the range of 50 to 200 nm. When the average particle diameter of the pigment exceeds 500 nm, the light transmittance is lowered and polarization is liable to occur, resulting in a low brightness and a low contrast color filter. On the contrary, when the average particle diameter is less than 10 nm, the dispersion stability of the pigment dispersion is insufficient.

The ratio of the coloring material in the composition for color filters is appropriately selected depending on the coloring concentration and the like, but the weight ratio of (A) / (R) of the coloring material of the component (A) and the resin solid content (R) in the composition is in the range of 0.05 to 1.5. It is necessary to be, Preferably it is the range of 0.1-1. If this ratio is less than 0.05, the coloring performance is not sufficiently exhibited, so that a good color filter cannot be formed, and if it exceeds 1.5, the effective pixel formation ability in the photolithography step cannot be exhibited. On the other hand, resin solid content (R) consists of the sum total of resin components (including monomer) other than the said component (D) and component (D).

The photosensitive resin and / or monomer of component (D) is chosen from at least 1 sort (s) or more of a photopolymerizable resin, a photopolymerizable monomer, and a photopolymerizable oligomer, and has an ethylenically unsaturated bond. What is necessary is just to include what becomes resin in the hardened state in the composition for color filters, and includes the case where only the component which is not resinized is contained in an uncured state. In the resin solid content of the present invention, monomers and oligomers before resinization are also treated as solid content. The component (D) may be appropriately selected in consideration of the manufacturing process of the color filter.

As a photopolymerizable resin, a photopolymerizable monomer, and a photopolymerizable oligomer, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethylene glycol, for example Di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol tetra ( Meta) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A type epoxy di (meth) acrylate, bisphenol F type epoxy di (meth) acrylate, bisphenol fluorene type epoxy di (meth) acrylate, etc. (Meth) acrylic acid ester etc. are mentioned. In addition, to the side chains of vinyl resins such as acrylic acid (co) polymers, (meth) acrylic acid (co) polymers, maleic acid (co) polymers, polyethylene oxides, polyvinylpyrrolidones, polyamides, polyurethanes, polyethers, polyesters, etc. The resin which has ethylenic double bond is also mentioned. These may be used independently and may use 2 or more types together. Moreover, it is preferable that these resin has alkali-soluble substituents, such as a carboxyl group and a phenolic hydroxyl group, in a side chain for the purpose of improving developability.

It is preferable that it is 40 to 95 weight% in the total solid in the composition for color filters of this invention, and, as for the compounding ratio of the photosensitive resin and / or monomer of a component (D), it is more preferable that it is 50 to 90 weight%. Although it is possible to mix | blend other resins etc. in a composition as needed, in this case, it is preferable that the total amount which combined other resins falls in the said range. In addition, total solids means the component which remains as solid after drying and hardening, and does not contain a solvent and contains a monomer.

As a photoinitiator of component (E), for example, acetphenones, such as acetphenone and p-tert- butylacetphenone, benzophenone, benzo, such as p, p'-bis (N, N-dimethylamino) benzophenone Benzoin ethers such as phenones, benzoin ethyl ether and benzoin tert-butyl ether, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2 Α-aminoalkylphenones such as -benzyl-2- (N, N-dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and 2,4,6-tris (trichloromethyl) Triazines such as -1,3,5-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, benzoyl peroxide, 3,3 Organic peroxides such as', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, sulfur compounds such as thioxanthone and 2,4-diethyl thioxanthone; have. These may be used independently and may use 2 or more types together.

Although the compounding ratio of a photoinitiator is suitably selected according to exposure sensitivity etc., it is preferable that it is 0.1-20 weight% with respect to (D) component, Furthermore, it is preferable that it is 0.5-15 weight%. If the content ratio is less than 0.1% by weight, the photosensitivity is insufficient, whereas if it is more than 20% by weight, the storage stability as a resist ink is insufficient.

Although the manufacturing method is not limited as long as the composition for color filters of this invention contains the said essential component, The pigment dispersion which has a pigment, a dispersing agent, and a solvent as a main component is produced beforehand, and a component (D) and (E) are then produced. It is advantageous to mix with the resins and other components added as needed.

In addition to the said component, the composition for color filters of this invention may add resin which has alkali solubility as a binder resin component for the purpose of improving developability and coating film forming ability. For example, polyethylene oxide, polyvinylpyrrolidone, polyamide, polyurethane, polyester, polyether, etc. are mentioned, It is preferable to contain a carboxyl group in a main chain or a side chain, and to be excellent in alkali developability. As such a thing, vinyl resins, such as an acrylic acid (co) polymer, a (meth) acrylic acid (co) polymer, a maleic acid (co) polymer, are mentioned, for example. In addition, addition of an acid anhydride to a resin having a hydroxyl group is also useful. These may be used independently and may use 2 or more types together.

Moreover, the composition for color filters of this invention contains said component (A), (B), (C), (D) and (E) as an essential component, It is preferable that total solids is 1-40 weight%, It is more preferable that it is 5-30 weight%.

As a method of manufacturing the composition for color filters, the pigment dispersion which previously disperse | distributed the said subphthalocyanine pigment individually or in combination with another pigment using the dispersing agent is produced, The method of mix | blending this with a resin component, a photoinitiator, etc. Although the method of disperse | distributing a subphthalocyanine pigment directly in a resin composition etc. is mentioned, The former method is preferable at the point of stability of the composition for color filters. There is also a method of dissolving in a composition containing a subphthalocyanine compound and a photosensitive resin using a high-solubility solvent capable of dissolving the subphthalocyanine-based pigment to form a color resist ink, but since it is difficult in terms of light resistance, heat resistance and solvent resistance, Most preferred is a method of pigmenting and dispersing it.

The hardened | cured material obtained by hardening the composition for color filters of this invention is obtained by apply | coating this composition to a board | substrate etc., and hardening by light irradiation, heating, etc. A well-known method can be used as a method of apply | coating a composition, For example, application | coating by the coating apparatuses, such as a spin coater, a bar coater, and a die coater, is mentioned. After application, you may dry using a hotplate, an IR oven, etc.

The method of irradiating the composition to light may also use a known method, and the exposure light source that can be applied is not particularly limited. For example, xenon lamps, halogen lamps, tungsten lamps, ultrahigh pressure mercury lamps, etc. Lamp light sources, such as a high pressure mercury lamp, a medium pressure mercury lamp, and a low pressure mercury lamp, are used. However, the method of application | coating and light irradiation is not limited to said method.

After image exposure is performed with such a light source and developed, an image can be formed on the substrate. As the developer, any developer can be used as long as the developer does not dissolve the unexposed part and does not dissolve the exposed part. It is an alkaline solution containing various additives specifically, and can contain an organic solvent, a buffer, surfactant, etc. as an additive. Although there is no restriction | limiting in particular about the developing method, The methods, such as an immersion development, a spray development, a brush development, an ultrasonic development, are used.

Moreover, you may perform heat hardening by a hot air oven as a method for improving the intensity | strength of a coating film. Although there is no restriction | limiting in particular about the hardening conditions of a composition, In order to prevent discoloration and discoloration of the cured film obtained by hardening | curing a composition, it is preferable to carry out within 1 hour at 250 degrees C or less about heating. Moreover, a well-known method can be used as a method of manufacturing a color filter using the cured film of the said composition for color filters.

1 and 2 are graphs showing the spectral transmittances of a model color filter.

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to a following example. In addition, all the "parts" below represent a weight part.

Synthesis Example 1

588 parts of o-dichlorobenzene are added to 150 parts of tetrachloro phthalonitrile, and it stirred for 30 minutes at room temperature in nitrogen atmosphere, and then 71 parts of boron tribromide is dripped. Then, it heats up to 100 degreeC slowly, and when reaction becomes quiet, it heat-stirrs for 10 to 60 minutes at 150-180 degreeC further. After standing to cool, the precipitate was filtered out, washed with acetone, aqueous sodium hydrogen carbonate solution, water and methanol in that order and dried, followed by 68 parts of Br-dodecachloro subphthalocyanine boron complex represented by formula (2) (yield 41). %) Was obtained. Next, this compound was dissolved in 10 times the concentrated sulfuric acid, the solution was poured into ice water, and the precipitated solid was filtered out, washed with water and dried to obtain Pigment A.

Synthesis Example 2

300 parts of 1-chloronaphthalene was added to 150 parts of tetrachloro phthalonitrile, and it stirred for 30 minutes at room temperature in nitrogen atmosphere, and then 417 parts of heptane solution which boron tribromide was melt | dissolved in 1 mol / L previously was dripped. do. Then, it heats slowly to 180 degreeC, and also performs 10-60 minutes of heating and stirring at 200-240 degreeC. After standing to cool, the precipitate was filtered out, washed with acetone, aqueous sodium hydrogen carbonate solution, water and methanol in that order and dried, and 64 parts of C1-dodecachloro subphthalocyanine boron complex represented by formula (3) (yield 40%) ) Next, the compound was dissolved in 10 times the concentrated sulfuric acid, the solution was poured into ice water, and the precipitated solid was extracted by filtration, washed with water and dried to obtain Pigment B.

Example 1

To 100 parts of Pigment A obtained in Synthesis Example 1, 40 parts of a dispersant and 860 parts of propylene glycol monomethyl ether acetate were added, a dispersion treatment was performed for 6 hours using a paint shaker, filtered to remove beads, and the dispersion 1000 parts were produced. As the dispersant, a graft polymer in which an amide was formed by reacting a polyester having a carboxyl group liberated with polyallylamine was used. In addition, as a medium for the paint shaker, 0.4 mmφ glass beads were used at a filling rate of 40% or 0.4mmφ zirconia beads at a filling rate of 15%. Solid content concentration of the dispersion A obtained in this way was 14 weight%, and the ratio of the coloring material in total solid content was 71.4 weight%, and was low viscosity and showed the low thixotropy property. In addition, the average particle diameter of the pigment in the dispersion (diluted to 1 weight% of pigment concentrations) measured using the particle size distribution system (Otsuka Denshi Co., Ltd. brand name: particle size analyzer FPAR-1000) was 98 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. Solid content concentration of the dispersion B obtained in this way was 14 weight%, and the ratio of the coloring material in all solid content was 71.4 weight%, and it showed low viscosity and low thixotropy. In addition, the average particle diameter of the pigment in a dispersion was 102 nm.

Example 3

130 parts of 54.2 weight% propylene glycol monomethyl ether acetate solution (The Shin-Nitetsu Chemical Co., Ltd. brand name: V-259ME) of the epoxy acrylate resin which has a bisphenol fluorene skeleton, 47 parts of dipentaerythritol hexaacrylates, and a biphenyl skeleton Epoxy resin (Japan Epoxy Resins Co., Ltd.Product name: Epicoat YX 4000HK) 17 parts, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one 7 parts , p, p'-bis (N, N-diethylamino) benzophenone 1 part, diethylene glycol dimethyl ether 196 parts, propylene glycol monomethyl ether acetate 75 parts, surfactant 1 part and silane coupling agent 1 part was mix | blended and 475 parts of compositions containing the photosensitive resin which were fully stirred and soluble in the weak alkali solution were produced.

525 parts of the dispersion A obtained in Example 1 were blended with 475 parts of the composition containing the photosensitive resin, and stirred sufficiently until a uniform solution was prepared to prepare 1000 parts of a color filter composition. Solid content concentration of the composition obtained in this way was 21.6 weight%, and the ratio of the pigment content in all solid content was 24.3 weight%, and it showed low viscosity and low thixotropy.

The composition for color filters obtained in this way was apply | coated using the spin coater on the blue plate glass substrate of 5 inches x 5 inches and thickness 1mm. At this time, the test piece was produced by changing the rotation speed of a spin coater. After drying this test piece, the photomask was coat | covered, the ultraviolet-ray exposure of 200mJ / cm <^2> was performed, and the color resist ink of the exposure part was hardened. Then, the test piece was alkali developed for 60 seconds with 0.4% sodium carbonate aqueous solution to remove the color resist ink of the unexposed part, and it was dried. Finally, the test piece was thermosetted, and the cured film of the color resist ink as a model color filter was produced.

Spectral transmittance, chromaticity (x value, y value) and brightness (Y value) of the produced model color filter were measured using a colorimeter (trade name: Color Analyzer TC-1800MK2, manufactured by Tokyo Denshoku Co., Ltd.). It was set as light C. The spectral transmittance of the model color filter obtained in the present example is shown in FIG. 1, and chromaticity and lightness are shown in Table 1. FIG.

Example 4

The composition for color filters was produced by the same method as Example 3 except having changed the pigment dispersion into the dispersion B obtained in Example 2. Solid content concentration of this composition was 21.6 weight%, the ratio of the pigment content in total solids was 24.3 weight%, and it was low viscosity and showed low thixotropy property. In addition, the spectral transmittance, chromaticity and 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.

Reference Example 1

40 parts of dispersant and 860 parts of propylene glycol monomethyl ether acetate were blended with 100 parts of Pigment Blue 15: 6, and a dispersion treatment was performed for 6 hours using a paint shaker, filtered to remove beads to prepare 1000 parts of dispersion C. . As the dispersant, a graft polymer in which an amide was formed by reacting a polyester having a carboxyl group liberated with polyallylamine was used. In addition, 0.4 mmφ zirconia beads were used as a filling rate of 15% as the media of the paint shaker. Solid content concentration of the dispersion C obtained in this way was 14 weight%, and the ratio of the coloring material in all solid content was 71.4 weight%, and was low viscosity and showed low thixotropy. In addition, the average particle diameter of the pigment in a dispersion was 150 nm.

Example 5

54.2% by weight propylene glycol monomethyl ether acetate solution (Shin-Nitetsu Chemical Co., Ltd. product name: V-259ME) of epoxy acrylate resin having bisphenol fluorene skeleton, 130 parts of dipentaerythritol hexaacrylate, having biphenyl skeleton 17 parts of epoxy resins (the Japan epoxy resin company make: Epicoat YX 4000HK), 7 parts of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, p, p 1 part of '-bis (N, N-diethylamino) benzophenone, 196 parts of diethylene glycol dimethyl ether, 75 parts of propylene glycol monomethyl ether acetate, 1 part of surfactant, and 1 part of silane coupling agent are mixed and stirred 475 parts of compositions containing the photosensitive resin soluble in the weak alkali solution were produced.

475 parts of the composition containing this photosensitive resin were mixed with 262.5 parts of the dispersion B obtained in Example 2 and 262.5 parts of the dispersion C obtained in Reference Example 1, and sufficiently stirred until a uniform solution was obtained, thereby obtaining the composition 1000 for color filters. Wealth was produced. Solid content concentration of the composition obtained in this way was 21.6 weight%, and the ratio of the pigment content in all solid content was 24.3 weight%, and it showed low viscosity and low thixotropy. In addition, the spectral transmittance of the model color filter was measured in the same manner as in Example 3. The results are shown in Fig.

Example 6

A composition for color filters was produced in the same manner as in Example 5 except that the pigment dispersion was changed to 472.5 parts of dispersion B obtained in Example 2 and 52.5 parts of dispersion C obtained in Reference Example 1. Solid content concentration of this composition was 21.6 weight%, the ratio of the pigment content in total solids was 24.3 weight%, and was low viscosity and showed low thixotropy. In addition, the spectral transmittance of the model color filter was measured in the same manner as in Example 3. The results are shown in Fig.

Comparative Example 1

Except having changed the pigment into pigment violet 23, pigment dispersion was carried out by the method similar to Example 1, and the composition for color filters was produced like Example 3 further. About this composition, the spectral transmittance, chromaticity, and lightness of the model color filter were measured by the method similar to Example 3. The results are shown in Figure 1 and Table 1.

Comparative Example 2

Pigment dispersion was carried out in the same manner as in Example 1 except that the pigment was changed to a C1-subphthalocyanine boron complex pigment represented by the following formula (4), and a composition for a color filter was prepared in the same manner as in Example 3. About this composition, the spectral transmittance, chromaticity, and lightness of the model color filter were measured by the method similar to Example 3. The results are shown in Figure 1 and Table 1.

Comparative Example 3

The composition for color filters was produced by the same method as Example 3 except having changed the pigment dispersion into the dispersion C obtained by the reference example 1. About this composition, the spectral transmittance of the model color filter was measured by the method similar to Example 3. The results are shown in Fig.

1 and 2, E3, E4, E5 and E6 mean Example 3, Example 4, Example 5 and Example 6, respectively, and C1, C2 and C3 are Comparative Example 1 and Comparative Example 2, respectively. And Comparative Example 3. As shown in Fig. 1, the spectral characteristics of the model color filter obtained in this example effectively transmit blue light of the three-wavelength fluorescent lamp as compared with the model color filter of the comparative example, and effectively block red and green exposures. It had a high level of clarity. Moreover, the cured film had a favorable film | membrane uniformity and the applicability | paintability without aggregation precipitate etc. was favorable.

As is apparent from Table 1, the model color filter composed of the composition for color filters of the present invention has a significantly increased Y value compared to the case of the model color filter of the comparative example, and has a high level of clarity according to the present invention. It can be seen that a color filter is obtained.

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 Fig. 2, even when used in combination with other blue pigments, the spectral characteristics of the model color filter obtained in this embodiment improve the transmittance in the short wavelength region (near 380 to 460 nm) as compared with the model color filter of the comparative example. It was to have a high level of brightness that can effectively transmit blue light emission (around 435 nm) of the three-wavelength fluorescent lamp. Moreover, the cured film was favorable in applicability | paintability without agglomerated precipitates, while being uniform in film thickness.

Since the composition for color filters of this invention has a high level of brightness, it is extremely useful at the point which enables manufacture of a high quality liquid crystal display etc.

Claims (13)

delete delete delete delete delete delete The composition for color filters containing (A) a coloring material, (B) dispersing agent, (C) solvent, (D) photosensitive resin, a monomer, or mixtures thereof, and (E) photoinitiator, As a coloring material component It contains 0.5 weight% or more of the pigment which consists of a subphthalocyanine compound represented by Formula (1), 0.1-20 weight% of photoinitiators with respect to the photosensitive resin and / or monomer, and the amount of the coloring material in the said composition ( (A) / (R) represented by the weight ratio of A) and resin solid content (R) is the range of 0.05-1.5, The composition for color filters characterized by the above-mentioned.

(However, at least 6 of X ₁ to X ₁₂ are halogen atoms, and the rest represent hydrogen atoms. Y represents a halogen atom or a hydroxyl group.) delete delete The method of claim 7, wherein The pigment which consists of a subphthalocyanine compound represented by General formula (1) WHEREIN: All of X <_1> -X <_12> is a halogen atom, The composition for color filters characterized by the above-mentioned. The method of claim 7, wherein (I) polyester, (ii) polyamide and (iii) at least one nitrogen-containing compound selected from the group consisting of at least a portion of A graft polymer obtained by reacting a compound having at least one free carboxyl group selected from the group consisting of polyesteramides. Hardened | cured material obtained by hardening | curing the composition for color filters in any one of Claims 7, 10, and 11. The cured film which forms a blue pixel consists of the hardened | cured material of Claim 12, The color filter characterized by the above-mentioned.

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