WO2006011446A1 - Composition for color filter and color filter - Google Patents

Composition for color filter and color filter Download PDF

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Publication number
WO2006011446A1
WO2006011446A1 PCT/JP2005/013569 JP2005013569W WO2006011446A1 WO 2006011446 A1 WO2006011446 A1 WO 2006011446A1 JP 2005013569 W JP2005013569 W JP 2005013569W WO 2006011446 A1 WO2006011446 A1 WO 2006011446A1
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Prior art keywords
color filter
composition
group
pigment
general formula
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PCT/JP2005/013569
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French (fr)
Japanese (ja)
Inventor
Tetsuya Yanagimoto
Naohiro Nishiyama
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Nippon Steel Chemical Co., Ltd.
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Application filed by Nippon Steel Chemical Co., Ltd. filed Critical Nippon Steel Chemical Co., Ltd.
Priority to JP2006529316A priority Critical patent/JP4571138B2/en
Publication of WO2006011446A1 publication Critical patent/WO2006011446A1/en

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays

Definitions

  • the present invention relates to a color filter composition used for a color liquid crystal display device and the like, a cured product formed using the same, and a color filter, and more specifically, a color filter suitable for forming a blue pixel.
  • the present invention relates to a composition and a cured product thereof.
  • a color filter has been widely used for the purpose of colorization of a liquid crystal display device or the like, and generally, red, green, and blue pixels are arranged in a mosaic pattern.
  • Known methods for producing this color filter include dyeing, printing, electrodeposition, and pigment dispersion.
  • a pigment dispersion method in which a fine pixel is formed by photolithography using a composition for a color filter in which a pigment is dispersed together with a photosensitive resin and Z or a monomer (hereinafter also referred to as a color resist ink). Because of the use of pigments, it is excellent in light resistance, heat resistance and solvent resistance, and has become the mainstream of color filter manufacturing methods.
  • the pigment of each pixel is generally selected so as to match the transmission characteristics of the pixel and the light emission characteristics of the backlight.
  • a yellow pigment, an orange pigment, and a green pixel are used for a red pixel.
  • a blue pixel is added to a blue pixel in a certain ratio in addition to a blue pigment to give a desired transmission characteristic.
  • Documents related to the present invention include the following documents.
  • Patent Document 1 JP5-281414 A
  • Patent Document 2 _JP2543052 B
  • Patent Document 3 _JP2004-010838 A
  • This pigment 'violet 23 is often mixed for the purpose of improving the blue purity of a copper phthalocyanine blue pigment that slightly transmits green light because the blue transmission region is closer to the short wavelength side than the copper phthalocyanine blue pigment.
  • This pigment 'violet 23 is often mixed for the purpose of improving the blue purity of a copper phthalocyanine blue pigment that slightly transmits green light because the blue transmission region is closer to the short wavelength side than the copper phthalocyanine blue pigment.
  • This method of mixing two pigments with different transmission regions there is a trade-off between high brightness and high saturation, and there is a pigment that has a large transmission range and low transmittance compared to copper phthalocyanine blue pigments.
  • this method using Violet 23 there was a problem that the high level of lightness and saturation could not be satisfied at the same time.
  • Patent Document 3 discloses a pigment dispersion, a color resist ink, and a color filter using a pigment having a power of a subphthalocyanine compound, and the model color filter using the pigment has high brightness and saturation (blue). However, since the transmittance on the long wavelength side is high and red light is transmitted with little force, color selectivity may be impaired. Disclosure of the invention
  • the present invention has been made in view of the disadvantages of the prior art, and uses a composition for a color filter for forming a pixel that gives high, lightness, and saturation, and is used for a liquid crystal display device and the like.
  • An object of the present invention is to provide a cured product and a color filter formed. Means for solving the problem [0010]
  • the present inventors As a result of intensive investigations to solve the above-mentioned problems, the present inventors, as a result, have high brightness, color, and the like, in particular, with respect to blue color of yarns and composites containing a specific pigment and blended with the specific pigment.
  • the present invention has been completed by finding that it is suitable for use in color filter pixel formation.
  • the present invention provides a color filter comprising (A) a photosensitive resin and Z or monomer, (B) a coloring material, (C) a solvent, and (D) a photopolymerization initiator.
  • the composition further comprises 0.5% by weight or more of a pigment having a subphthalocyanine compound strength represented by the following general formula (1) as a coloring material component of (B) in the total coloring material:
  • Composition for color filter characterized in that (B) / (R), expressed as a weight ratio of the colorant (B) to the solid content of the resin (B) / (R) in the range of 0.05 to L.5 It is a thing.
  • X to X are hydrogen atoms or halogen atoms, preferably at least 6
  • Halogen atoms more preferably all are halogen atoms.
  • Y represents an alkyl group, aryl group, alkoxy group or aryloxy group which may have a substituent.
  • This color filter composition further comprises, as a dispersant, at least one nitrogen-containing compound that is selected from (a) poly (lower alkyleneimine) and (b) polyallylamine, and (i) polyester.
  • a graft polymer obtained by reacting at least one compound having a free carboxyl group, which is selected from the group consisting of (ii) polyamide and (iii) polyesteramide, can also be contained.
  • (A) photosensitive resin and Z or monomer It is preferably made of an epoxy acrylate having a fluorene skeleton.
  • the present invention relates to a cured product obtained by curing the composition for a color filter and a color filter in which a cured film forming a blue pixel is composed of the cured product.
  • the color filter composition (color filter material) of the present invention comprises (A) photosensitive resin and Z or monomer (hereinafter also referred to as component (A)), (B) colorant (hereinafter referred to as component). It contains (B), u), (C) solvent (hereinafter referred to as component (C)) and (D) photopolymerization initiator (hereinafter also referred to as component (D)) as essential components.
  • component (A) photosensitive resin and Z or monomer
  • component hereinafter also referred to as component
  • component contains (B), u), (C) solvent (hereinafter referred to as component (C)) and (D) photopolymerization initiator (hereinafter also referred to as component (D)) as essential components.
  • the photosensitive resin and Z or monomer of component (A) is selected from at least one of photopolymerizable resin, photopolymerizable monomer and photopolymerizable oligomer, and has an ethylenically unsaturated bond. It is what you have. What is necessary is just to include the thing which becomes rosin in the cured state in the composition for color filters. In the solids content of the present invention, monomers and oligomers before the solidification are treated as solids. Component (A) may be appropriately selected in consideration of the color filter manufacturing process.
  • photopolymerizable resin, photopolymerizable monomer and photopolymerizable oligomer examples include 2-hydroxyxetyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethyl hexyl (meth).
  • ethylene glycol di (meth) acrylate diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, di Pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A type epoxy di (meth) acrylate, bisphenol F type epoxy di (meth) acrylate, bisphenol fluorene type epoxy di (meta) ) Atre relay (Meth) acrylic acid esters and the like, and the like.
  • bur resin such as acrylic acid (co) polymers, (meth) acrylic acid (co) polymers, maleic acid (co) polymers, polyethylene oxide, polybutaphthalidone, polyamide, polyurethane, polyether, polyester Examples thereof include coffins having an ethylenic double bond in the side chain. These may be used alone or in combination You may use the above together.
  • these photosensitive resins preferably have an alkali-soluble substituent such as a carboxyl group or a phenolic hydroxyl group in the side chain for the purpose of improving developability.
  • the photosensitive resin and Z or monomer are at least one component because the cured product provides a high level of heat resistance and solvent resistance. It is advantageous to use an epoxy acrylate resin having a fluorene skeleton.
  • the epoxy acrylate resin having a fluorene skeleton preferably includes those obtained by reacting an epoxy (meth) acrylate represented by the following general formula (2) with a polybasic acid or an acid anhydride thereof. .
  • R and R are any one of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenol group, and a halogen atom, and X represents the following formula (3)
  • N 0 to 10
  • R hydrogen
  • an epoxy acrylate resin as used in the present invention is used to include derivatives of epoxy acrylate resin, such as epoxy meta acrylate resin.
  • examples of the polybasic acid or acid anhydride thereof include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, and chlorende.
  • examples include acids, methyltetrahydrophthalic acid, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, and acid anhydrides thereof.
  • (S2) saturated dicarboxylic acids or (S4) saturated tetracarboxylic acids as these polybasic acids or acid anhydrides thereof.
  • the saturation of the saturated dicarboxylic acids and saturated tetracarboxylic rubonic acids does not have an unsaturated bond (bond other than a single bond) other than a carboxylic group (CO) constituting a carboxyl group or an acid anhydride group.
  • saturated carboxylic acids include butanetetracarboxylic acid, hexahydrophthalic acid, succinic acid and acid anhydrides thereof. Tetrahydrophthalic acid is also preferred carboxylic acid As an example.
  • each of (S2) saturated dicarboxylic acids and (S4) saturated tetracarboxylic acids can be used, and the use ratio of the saturated dicarboxylic acids and saturated tetracarboxylic acids is the molar ratio of S2 ZS4.
  • the range is from 0.1 to 10, preferably from 0.2 to 1.
  • the ratio of use can be selected in accordance with the optimal molecular weight, alkali developability, light transmission, heat resistance, solvent resistance, and pattern shape effect.
  • the larger the ratio of saturated tetracarboxylic acids used the greater the alkalinity.
  • the solubility tends to increase and the molecular weight tends to increase.
  • the above molar ratio is preferably satisfied.
  • the blending ratio of photosensitive resin and Z or monomer is preferably 40 to 95% by weight based on the total solid content in the composition for a color filter of the present invention. It is preferable that it is -90weight%.
  • the composition it is desirable that other greaves and the like can be blended as necessary. In this case, it is desirable that the total amount of the other greaves falls within the above range.
  • the total solid content means a component remaining as a solid content after polymerization, curing, and drying, and does not include a solvent but includes a monomer.
  • the colorant of component (B) needs to contain 0.5% by weight or more of the pigment made of the subphthalocyanine compound represented by the general formula (1) in the total colorant.
  • X to X each represents a hydrogen atom or a halogen atom, preferably at least 6
  • Rogen atoms more preferably all are halogen atoms.
  • the halogen atom may be any of fluorine, chlorine, bromine, iodine and the like, but is preferably chlorine or bromine from the viewpoint of hue.
  • all of X to x in the general formula (1) are
  • Y in the general formula (1) represents an alkyl group, an aryl group, an alkoxy group or an aryloxy group.
  • the alkyl group includes a methyl group, an ethyl group, a propyl group, and a butyl group
  • the aryl group includes a phenyl group, a naphthyl group, an anthryl group, a furyl group, a pyridyl group, an indolyl group, and the like.
  • alkoxy group examples include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group
  • examples of the aryloxy group include a phenoxy group and a naphthoxy group. These are also halogen
  • You may have substituents, such as a ruoxy group.
  • it may have a substituent having a subphthalocyanine structure and may be a dimer or multimer such as Sub-Y′-Sub.
  • Sub represents a substituent having a subphthalocyanine structure such as a group generated by removing Y from the general formula (1).
  • Component (B) may contain other pigments or dyes as long as it contains 0.5% by weight or more, preferably 5% by weight or more of the above-mentioned subphthalocyanine pigment in the total colorant. It can also be used. If the content of the subphthalocyanine pigment is less than 0.5% by weight in the colorant, the excellent coloring performance of the pigment cannot be sufficiently exhibited, and a color filter having good transmission characteristics cannot be formed.
  • colorants suitable for preparing a blue color resist ink blue and purple pigments are preferable from the viewpoint of hue, for example, Pigment, Blue 15, 15: 1, 15: 2. , 15: 3, 15: 4, 15: 6, 16, 60, 80, Pigment 'Violet 19, 23, 37, etc. Is not to be done.
  • the reason for using the subphthalocyanine pigment of the present invention as a colorant is due to the special spectral characteristics of the pigment.
  • high-color-rendering three-wavelength fluorescent lamps that have sharp emission at wavelengths corresponding to the three primary colors of red, green, and blue (generally 610 nm, 545 nm, and 435 nm) are widely used for backlights of liquid crystal display devices and the like. It is necessary to effectively transmit these three wavelengths of light and shield the other two wavelengths of light in order to show a high level of lightness and saturation of red, green and blue.
  • a color filter manufactured using a color filter composition containing a pigment made of subphthalocyanine as a main colorant disclosed in Patent Document 3 transmits light at around 370 to 510 nm and absorbs at around 520 to 610 nm.
  • the color filter manufactured using the color filter composition containing the pigment comprising the subphthalocyanine of the present invention as the main coloring material has a transmission in the vicinity of 370 to 510 nm, while absorbing in a wide range of about 530 to 650 nm. Since it has excellent spectral characteristics, red light emission can also be effectively shielded.
  • the color filter of the present invention has high brightness and high saturation, particularly for blue. Also Since the heat resistance of the pigment is increased by changing Y in the general formula (1) to an alkyl group, aryl group, alkoxy group or aryloxy group, it is possible to provide a color filter composition and a color filter with excellent fastness properties. It becomes.
  • the production of the subphthalocyanine pigment is generally performed by synthesizing a subphthalocyanine compound and pigmenting it.
  • Methods for synthesizing subphthalocyanine compounds are known, and examples include A. Meller and A. Ossko, Monatshefte for Chemie 103, 150-155 (1972), and the like.
  • the subphthalocyanine compound obtained by the above method can be converted into the subphthalocyanine compound represented by the general formula (1) used in the present invention by a known method. .
  • the thus obtained subphthalocyanine compound often contains impurities caused by side reactions and the like.
  • the impurities can be removed by Soxhlet extraction after filtration and washing.
  • examples of the impurities include hydrolysis products of raw material trihalogen boron, unreacted lid-tolyl, and the like.
  • solvent used for filtration washing or Soxhlet extraction For example, alcohol solvents such as methanol and ethanol, ketone solvents such as acetone and methyl ethyl ketone, and aromatic solvents such as toluene and xylene can be used.
  • halogenation may be performed by a known method.
  • the synthesis method and purification method are not limited to the above methods.
  • a known method can be used as a method for producing a pigment.
  • a subphthalocyanine compound is dissolved in a strong acid such as concentrated sulfuric acid and then poured into a large amount of water to form a fine pigment.
  • the acid pasting method in which a fine pigment is formed by dispersing in a strong acid and pouring the solution into a large amount of water, can be exemplified.
  • a finer pigment in order to obtain a color filter having a high level of color saturation, it is preferable to use a finer pigment as a coloring material.
  • a known method can be used for the method of fine graining. Examples thereof include a salt milling method in which the mill is crushed in the presence.
  • pigmentation and fine particles The method of conversion is not limited to the above method.
  • the pigment used in the present invention is preferably dispersed in an average particle diameter of 50 to 250 nm in the composition! /.
  • the ratio of the colorant in the color filter composition is appropriately selected depending on the color concentration and the like, but the weight ratio of (B) colorant to rosin solid (R) in the composition ( B) Z (R) must be in the range of 0.05 to L5, and preferably in the range of 0.1 to 1. If this ratio is less than 0.05! /, The coloring performance cannot be sufficiently exhibited, and it becomes impossible to form a good color filter, and if it exceeds 1.5, the pixel forming ability effective in the photolithography process is not achieved. Cannot be used.
  • the solids (R) of the resin is composed of a resin component (including monomers) other than the component (A) and the component (A).
  • the solvent of component (C) is preferably an ester, a ketone, a glycol ether, a nitrogen-containing solvent, or the like from the viewpoint of excellent dispersibility of the pigment and, when a dispersant is blended, the solubility thereof.
  • ketones for ketones, ethyl ether solvate, cetyl solvate sorb acetate, propylene glycol monomethyl for glycol ethers
  • nitrogen-containing solvents such as ether acetate and diethylene glycol dimethyl ether include dimethylformamide and dimethylacetamide. These solvents can be used alone or in combination of two or more, as long as they are appropriately selected according to the composition of the blended resin and other additives, the solvent resistance of the pigment, and the coating properties. Good.
  • Examples of the photopolymerization initiator of component (D) include acetophenones such as acetophenone and p-tert-butylacetophenone, benzophenones such as benzophenone and p, p'-bis (N, N-dimethylamino) benzophenone.
  • Benzoin ethers such as benzoinethyl ether and benzoin-tert-butyl ether, 2-methyl-1- [4- (methylthio) phenol] -2-morpholinopropan-1-one, 2-benzyl- 2-Aminoalkylphenones such as 2- (N, N-dimethylamino) -1- (4-morpholinophenol) butan-1-one, 2, 4, 6-tris (trichloromethyl) -1, 3,5-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine and other triazines, benzoyl peroxide, 3, 3 ', 4, A'-tetra (tert-butylperoxycarbol) benzophenone Peroxides, Chiokisanton And sulfur compounds such as 2,4-jetylthioxanthone. These may be used alone or in combination of two or more.
  • the blending ratio of the photopolymerization initiator is appropriately selected according to the exposure sensitivity and the like, but is preferably 0.1 to 20% by weight with respect to the component (A). It is preferably 5 to 15% by weight. If the content is less than 0.1% by weight, the photosensitivity becomes insufficient. On the other hand, if it exceeds 20% by weight, the storage stability as a resist ink is insufficient.
  • the production method of the color filter composition of the present invention is not limited as long as it contains the above-mentioned essential components, but is a pigment mainly composed of a pigment, a dispersant (hereinafter also referred to as component (E)) and a solvent. It is advantageous to make the dispersion in advance (hereinafter also referred to as pigment dispersion) and then mix with components (A) and (D), optionally added rosins and other components.
  • the pigment dispersion contains the above-mentioned subphthalocyanine pigment, dispersant and solvent, and it is preferable that the total solid content in the pigment dispersion is 1 to 40% by weight. It is preferably 5 to 35% by weight.
  • the blending ratio of the pigment is preferably 1 to 25% by weight in the pigment dispersion, and more preferably 5 to 20% by weight. Further, the blending ratio of the dispersant is preferably 10 to 60% by weight, more preferably 20 to 50% by weight with respect to the pigment.
  • the total solid content means a component remaining after drying and curing.
  • the pigment dispersion can be obtained by dispersing the pigment in a solvent together with a dispersant, but the production method is not particularly limited, and a known method can be used. For example, a dispersion treatment using a paint shaker or a bead mill can be used.
  • the type thereof is not particularly limited, but from the viewpoint of excellent dispersion stability, it can be derived from (a) poly (lower alkyleneimine) and (b) polyallylamin.
  • One or more selected nitrogen-containing compounds are reacted with (i) polyester having a free carboxyl group, (ii) polyamide, and (iii) polyester amideca. It is preferable to use a graft polymer obtained by forming an amide or salt.
  • Poly (lower alkyleneimine) is a primary (—NH 2), secondary (—NH—) and tertiary (—N) alkyl.
  • a polymer having a branched structure in which a mino group is connected by a lower alkylene chain (-R-, for example, -CH CH-).
  • (B) polyallylamine is a polymer having a structure of [—CH—CH (CH NH) —]
  • the carboxyl group-containing compound (i), (ii) and () has at least one carboxyl group at the terminal or side chain, and this is a group such as -NH in (a) and (b). at least
  • the graft polymer comprises a basic part (a) or (b) that acts as an anchor by adsorbing to a pigment, and a polymer chain part (i, ii, or) that imparts dispersibility by a steric repulsion effect. Both are dispersants.
  • a method for producing a graft polymer is known and disclosed in, for example, Japanese Patent Publication No. 63-30057 and Japanese Patent Laid-Open No. 9-169821.
  • a pigment derivative type dispersion aid in which an acidic functional group is introduced into the pigment skeleton is used in combination with the dispersant.
  • the above-mentioned dispersion aids are preferably those having a hue of blue or purple.
  • An acid derivative etc. can be mentioned.
  • the dispersant of component (E) is not limited to the graft polymer as described above, and refers to a dispersant having a dispersibility, which is commercially available as a dispersant, a dispersion accelerator, or the like.
  • a dispersant having a dispersibility which is commercially available as a dispersant, a dispersion accelerator, or the like.
  • Some greaves have the function of adsorbing on the surface of the pigment and dispersing the pigment.
  • Such rosins are included in the dispersant because they have dispersibility. Therefore, when (A) the photosensitive resin and Z or the monomer has a dispersibility, this may be used as a dispersant.
  • coffins which are high viscosity substances, generally have an action to stabilize dispersion (dispersion stability) but do not have dispersibility, and those that do not have such dispersibility are treated as dispersants. Absent.
  • the dispersant is not an essential component, but when it is used, it can be a constituent component of the resin component.
  • the color filter composition of the present invention may contain an alkali-soluble resin as a binder resin component for the purpose of improving developability and coating film-forming ability.
  • an alkali-soluble resin for the purpose of improving developability and coating film-forming ability.
  • polyethylene oxide, polybutylpyrrolidone, polyamide, polyurethane, polyester, polyether, and the like are preferred.
  • Those having a carboxyl group in the main chain or side chain and having excellent alkali developability are preferred.
  • acrylic Examples thereof include vinyl resins such as acid (co) polymers, (meth) acrylic acid (co) polymers, and maleic acid (co) polymers.
  • an acid anhydride to rosin having a hydroxyl group is also useful. These may be used alone or in combination of two or more.
  • composition for a color filter of the present invention contains the above-mentioned components (A) to (D) as essential components, but the total solid content is preferably 1 to 40% by weight. It is preferably ⁇ 30% by weight.
  • a pigment dispersion in which the above-mentioned subphthalocyanine pigment is dispersed in a solvent using a dispersant alone or together with other pigments is prepared, and this is a resin component.
  • a cured product obtained by curing the composition for a color filter of the present invention is obtained by applying the composition to a substrate or the like and curing it by light irradiation, heating or the like.
  • a method for applying the composition a known method can be used, and examples thereof include application by a coating apparatus such as a spin coater, a bar coater, and a die coater. After application, dry using a hot plate, IR oven, etc.!
  • a known method can be used for irradiating the coated composition with light, and the exposure light source is not particularly limited.
  • a xenon lamp, a halogen lamp, a tungsten lamp, an ultra-high pressure mercury lamp, a high-pressure mercury lamp Lamp light sources such as medium-pressure mercury lamps and low-pressure mercury lamps are used.
  • the coating and light irradiation methods are not limited to the above methods.
  • An image can be formed on a substrate by developing after image exposure with such a light source.
  • Any developer can be used as long as it dissolves the unexposed part and does not dissolve the exposed part.
  • it is an alkaline solution containing various additives, and the additives can contain organic solvents, buffers, surfactants, and the like.
  • the development processing method is not particularly limited, but methods such as immersion development, spray development, brush development and ultrasonic development are used.
  • FIG. 1 is a graph showing the spectral transmittance of a model color filter.
  • a graft polymer obtained by reacting polyallylamine with a polyester having a free carboxyl group to form an amide was used as the dispersant.
  • the media of the paint shaker 0.4 mm ⁇ glass beads were used at a filling rate of 40%, or 0.4 mm ⁇ zirco beads were used at a filling rate of 15%.
  • the dispersion thus obtained had a solid content concentration of 14% by weight, and the ratio of the coloring material in the total solid content was 71.4% by weight, indicating low viscosity and low thixotropy.
  • This composition for a color filter was applied on a blue plate glass substrate having a size of 5 inches square and a thickness of 1 mm using a spin coater. At this time, test pieces were manufactured by changing the rotation speed of the spin coater. After drying this test piece, it was covered with a photomask and exposed to UV light of 200 mj / cm 2 to cure the color resist ink in the exposed area. Next, the test piece was alkali-developed with a 0.4% aqueous sodium carbonate solution for 60 seconds to remove the unexposed color resist ink and dried. Finally, the test piece was thermally cured to produce a cured film of color resist ink as a model color filter.
  • the spectral transmittance, chromaticity (X value, y value), and brightness (Y value) of the model color filter produced were measured using a chromaticity meter (trade name: Color Analyzer TC-1800MK2 manufactured by Tokyo Denshoku Co., Ltd.) The light for colorimetry at this time was auxiliary standard illuminant C.
  • the spectral transmittance of the model color filter obtained in this example is shown in FIG. 1, and the chromaticity and brightness are shown in Table 1.
  • a dispersion was obtained in the same manner as in Production Example 3, except that the colorant was changed to the chloroethodese decachlorosubphthalocyanine boron complex obtained in Production Example 4.
  • a color filter composition was prepared in the same manner as in Example 1 except that this dispersion was used. With respect to this composition, a model color filter was produced in the same manner as in Example 1, and the spectral transmittance, chromaticity, and brightness were measured.
  • Propylene glycol monomethyl ether acetate solution of epoxy attalate resin having bisphenol fluorene skeleton is mixed with propylene glycol monomethyl ether acetate solution of methacrylic acid Zbenzyl methacrylate copolymer (methacrylic acid: benzyl methacrylate) (molar ratio)
  • methacrylic acid: benzyl methacrylate methacrylic acid: benzyl methacrylate
  • the brightness was measured.
  • Comparative Example 1 A dispersion was obtained in the same manner as in Production Example 3, except that the colorant was changed to pigment 'violet 23'.
  • a color filter composition was prepared in the same manner as in Example 1 except that this dispersion was used.
  • a model color filter was produced in the same manner as in Example 1, and the spectral transmittance, chromaticity, and brightness were measured.
  • a dispersion was obtained in the same manner as in Production Example 3, except that the colorant was changed to a black mouth-subphthalocyanine boron complex pigment represented by the following formula (7).
  • a color filter composition was prepared in the same manner as in Example 1 except that this dispersion was used. With this composition, a model color filter was produced in the same manner as in Example 1, and the spectral transmittance, chromaticity, and brightness were measured.
  • FIG. 1 and Table 1 show the results of measuring the spectral transmittance, chromaticity, and brightness of the model color filters obtained in the examples and comparative examples.
  • the model color filter comprising the color filter composition of the present invention can effectively transmit the blue light emission of the three-wavelength fluorescent lamp, and can effectively block the red and green light emission. And had high saturation.
  • the color is blue (X value force S is small) and the brightness is greatly improved (Y value is increased).
  • the cured film had a uniform film thickness and good coatability without aggregated precipitates.
  • the color filter composition of the present invention has excellent heat resistance, high brightness, and high saturation, so that it is extremely useful in terms of enabling production of a high-quality liquid crystal display or the like.

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Abstract

Disclosed is a composition for color filters which enables to provide high-level brightness and chromaticness when used in a liquid crystal display or the like. Also disclosed are a cured product of such a composition and a color filter. This composition for color filters contains (A) a photosensitive resin and/or monomer, (b) a coloring agent, (C) a solvent and (D) a photopolymerization initiator. The coloring agent (b) contains, as a component, a pigment composed of a subphthalocyanine compound represented by the general formula (1) below in an amount of 0.5% by weight relative to the total of the coloring agent. The weight ratio (b)/(R) between the coloring agent (b) and the resin solid content (R) in the composition is within the range of 0.05-1.5. In the general formula (1) below, X1-X12 respectively represent a hydrogen atom or a halogen atom, and Y represents an optionally substituted alkyl group, aryl group, alkoxy group or aryloxy group.

Description

明 細 書  Specification
カラーフィルター用組成物及びカラーフィルター  Color filter composition and color filter
技術分野  Technical field
[0001] 本発明は、カラー液晶表示装置等に用いられるカラーフィルター用組成物及びこ れを用いて形成される硬化物並びにカラーフィルターに関するものであり、詳しくは、 青色画素形成に好適なカラーフィルター用組成物とその硬化物に関する。  TECHNICAL FIELD [0001] The present invention relates to a color filter composition used for a color liquid crystal display device and the like, a cured product formed using the same, and a color filter, and more specifically, a color filter suitable for forming a blue pixel. The present invention relates to a composition and a cured product thereof.
背景技術  Background art
[0002] 従来、カラーフィルタ一は液晶表示装置等のカラー化の目的で広く用いられており 、一般に赤、緑、青の画素がモザイク様に配置されている。このカラーフィルターを作 成する方法としては、染色法、印刷法、電着法、顔料分散法などが知られている。特 に、感光性榭脂及び Z又は単量体と共に顔料を分散させたカラーフィルター用組成 物（以下、カラーレジストインキとも称する。）を用いてフォトリソグラフィによって微細画 素を形成させる顔料分散法は、顔料を使用しているために、耐光性、耐熱性及び耐 溶剤性に優れて 、ることからカラーフィルター製造法の主流となって 、る。  Conventionally, a color filter has been widely used for the purpose of colorization of a liquid crystal display device or the like, and generally, red, green, and blue pixels are arranged in a mosaic pattern. Known methods for producing this color filter include dyeing, printing, electrodeposition, and pigment dispersion. In particular, a pigment dispersion method in which a fine pixel is formed by photolithography using a composition for a color filter in which a pigment is dispersed together with a photosensitive resin and Z or a monomer (hereinafter also referred to as a color resist ink). Because of the use of pigments, it is excellent in light resistance, heat resistance and solvent resistance, and has become the mainstream of color filter manufacturing methods.
[0003] 原理的には公知の顔料の多くが顔料分散法に使用可能であり、例えば、下記特許 文献 1にはカラーレジストインキの着色材として赤色、緑色、青色、黄色及び紫色の 顔料が数十種にわたり開示されている。また、各画素の顔料は、一般にその画素の 透過特性力バックライト光の発光特性に合うよう選択され、例えば、赤色画素には赤 色顔料のほかに黄色顔料、橙色顔料を、緑色画素には緑色顔料のほかに黄色顔料 を、青色画素には青色顔料のほかに紫色顔料を一定割合で混合することにより所望 の透過特性を付与して ヽる。  [0003] In principle, many of the known pigments can be used in the pigment dispersion method. For example, in Patent Document 1 below, there are a number of red, green, blue, yellow, and purple pigments as color resist ink colorants. Ten types have been disclosed. In addition, the pigment of each pixel is generally selected so as to match the transmission characteristics of the pixel and the light emission characteristics of the backlight. For example, in addition to the red pigment, a yellow pigment, an orange pigment, and a green pixel are used for a red pixel. In addition to a green pigment, a yellow pigment is added, and a blue pixel is added to a blue pixel in a certain ratio in addition to a blue pigment to give a desired transmission characteristic.
[0004] 本発明に関連する文献としては、下記文献がある。  [0004] Documents related to the present invention include the following documents.
特許文献 1 :JP5- 281414 A  Patent Document 1: JP5-281414 A
特許文献 2 :_JP2543052 B  Patent Document 2: _JP2543052 B
特許文献 3 :_JP2004 - 010838 A  Patent Document 3: _JP2004-010838 A
[0005] 近年の液晶表示装置に対する高精細化、高輝度化、高色再現性の要求は高ぐ力 ラーフィルターの更なる高明度化、高彩度化が望まれている。しかし、これらの顔料 のうち液晶表示装置等に用いて高水準の明彩度性を示すものはきわめて限定され ている。例えば、青色画素を形成するためのカラーレジストインキには銅フタロシア- ン系の青色顔料であるビグメント 'ブルー 15： 6と共に紫色顔料が使用されることが多 いが、この紫色の顔料としては、特許文献 2に開示されているように、カルバゾールジ ォキサジンより成る紫色顔料であるビグメント 'バイオレット 23が良好に用いることので きるほとんど唯一のものである。 [0005] In recent years, demands for high definition, high brightness, and high color reproducibility for liquid crystal display devices have been increasing. It is desired to further increase the brightness and saturation of color filters. But these pigments Among them, those that are used in liquid crystal display devices and the like and exhibit a high level of color saturation are extremely limited. For example, violet pigments are often used together with pigment 'Blue 15: 6, which is a copper phthalocyanine-based blue pigment, in color resist inks for forming blue pixels. As disclosed in Patent Document 2, Pigment 'Violet 23, which is a purple pigment composed of carbazole dioxazine, is almost the only one that can be used successfully.
[0006] このビグメント 'バイオレット 23は、銅フタロシアニン系青色顔料より青色透過域が短 波長側にあるため、僅かに緑色光を透過する銅フタロシアニン系青色顔料の青色純 度を高める目的でしばしば混合される。しかし、透過域の異なる 2つの顔料を混合す る方法においては、高明度化と高彩度化は二律背反の関係にあり、銅フタロシア二 ン系青色顔料と透過域が大きく異なりその透過率も低いビグメント 'バイオレット 23を 用いるこの方法においては、高水準の明度、彩度を同時に満足できないという問題 かあつた。 [0006] This pigment 'violet 23 is often mixed for the purpose of improving the blue purity of a copper phthalocyanine blue pigment that slightly transmits green light because the blue transmission region is closer to the short wavelength side than the copper phthalocyanine blue pigment. The However, in the method of mixing two pigments with different transmission regions, there is a trade-off between high brightness and high saturation, and there is a pigment that has a large transmission range and low transmittance compared to copper phthalocyanine blue pigments. In this method using Violet 23, there was a problem that the high level of lightness and saturation could not be satisfied at the same time.
[0007] このように、液晶表示装置等に使用されるカラーフィルターの作成に当たっては、使 用されるカラーレジストインキは用途や目的に適した透過特性を有する色材の調整 が必須であり、カルバゾールジォキサジン紫色顔料に代わる顔料を使用した高明度 、高彩度のカラーレジストインキが望まれていた。  [0007] As described above, in the production of a color filter used in a liquid crystal display device or the like, it is essential to adjust the color material having transmission characteristics suitable for the purpose and purpose of the color resist ink used. A high brightness and high saturation color resist ink using a pigment in place of dioxazine purple pigment has been desired.
[0008] 一方、色素の 1つとしてサブフタロシアニン化合物が知られている。特許文献 3には 、サブフタロシアニン化合物力 なる顔料を用いた、顔料分散体、カラーレジストイン キ及びカラーフィルターが開示されており、該顔料を用いたモデルカラーフィルター が高い明度、彩度 (青色)を満たしていることが示されているが、長波長側の透過率 が高く赤色光を少な力ゝらず透過してしまうため色選択性を損なう場合があった。 発明の開示  On the other hand, a subphthalocyanine compound is known as one of pigments. Patent Document 3 discloses a pigment dispersion, a color resist ink, and a color filter using a pigment having a power of a subphthalocyanine compound, and the model color filter using the pigment has high brightness and saturation (blue). However, since the transmittance on the long wavelength side is high and red light is transmitted with little force, color selectivity may be impaired. Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0009] 本発明は、力かる従来技術の欠点に鑑みなされたもので、液晶表示装置等に用い られる高 、明度、彩度を与える画素形成のためのカラーフィルター用組成物及びこ れを用いて形成される硬化物並びにカラーフィルターを提供することを目的とする。 課題を解決するための手段 [0010] 本発明者等は、上記課題を解決するために鋭意検討を重ねた結果、特定の顔料を 含み、これを配合した糸且成物やその硬化物が特に青色について、高い明度、彩度を 与え、カラーフィルターの画素形成用途に好適であることを見出し、本発明を完成し た。 [0009] The present invention has been made in view of the disadvantages of the prior art, and uses a composition for a color filter for forming a pixel that gives high, lightness, and saturation, and is used for a liquid crystal display device and the like. An object of the present invention is to provide a cured product and a color filter formed. Means for solving the problem [0010] As a result of intensive investigations to solve the above-mentioned problems, the present inventors, as a result, have high brightness, color, and the like, in particular, with respect to blue color of yarns and composites containing a specific pigment and blended with the specific pigment. The present invention has been completed by finding that it is suitable for use in color filter pixel formation.
[0011] すなわち、本発明は、（A)感光性榭脂及び Z又は単量体、（B)着色材、（C)溶剤及 び (D)光重合開始剤を含有して成るカラーフィルター用組成物にぉ 、て、 (B)の着 色材成分として下記一般式（1)で示されるサブフタロシアニンィ匕合物力 なる顔料を 全着色材中 0. 5重量％以上含有し、前記組成物中の着色材 (B)と榭脂固形分 ( と の重量比で表される（B) / (R)が 0. 05〜： L . 5の範囲であることを特徴とするカラーフ ィルター用組成物である。  That is, the present invention provides a color filter comprising (A) a photosensitive resin and Z or monomer, (B) a coloring material, (C) a solvent, and (D) a photopolymerization initiator. The composition further comprises 0.5% by weight or more of a pigment having a subphthalocyanine compound strength represented by the following general formula (1) as a coloring material component of (B) in the total coloring material: Composition for color filter, characterized in that (B) / (R), expressed as a weight ratio of the colorant (B) to the solid content of the resin (B) / (R) in the range of 0.05 to L.5 It is a thing.
Figure imgf000005_0001
ここで、 X〜X は水素原子又はハロゲン原子を示す力 好ましくは少なくとも 6個が
Figure imgf000005_0001
Where X to X are hydrogen atoms or halogen atoms, preferably at least 6
1 12  1 12
ハロゲン原子であり、更に好ましくはすべてがハロゲン原子である。 Yは置換基を有し てもよいアルキル基、ァリール基、アルコキシ基又はァリールォキシ基を示す。  Halogen atoms, more preferably all are halogen atoms. Y represents an alkyl group, aryl group, alkoxy group or aryloxy group which may have a substituent.
このカラーフィルター用組成物は、更に、分散剤として、（a)ポリ（低級アルキレンイミ ン)及び (b)ポリアリルアミンカもなる群力も選ばれる少なくとも 1種の含窒素化合物に 、（i)ポリエステル、（ii)ポリアミド及び (iii)ポリエステルアミドから成る群力も選ばれる 少なくとも 1種の遊離のカルボキシル基を有する化合物を反応させて得られるグラフト ポリマーを含有することができる。また、（A)感光性榭脂及び Z又は単量体としては、 フルオレン骨格を有するエポキシアタリレートからなることが好ましい。 This color filter composition further comprises, as a dispersant, at least one nitrogen-containing compound that is selected from (a) poly (lower alkyleneimine) and (b) polyallylamine, and (i) polyester. A graft polymer obtained by reacting at least one compound having a free carboxyl group, which is selected from the group consisting of (ii) polyamide and (iii) polyesteramide, can also be contained. In addition, as (A) photosensitive resin and Z or monomer, It is preferably made of an epoxy acrylate having a fluorene skeleton.
[0013] 更に、本発明は、前記のカラーフィルター用組成物を硬化して得られる硬化物及び 青色画素を形成する硬化膜がこの硬化物からなるカラーフィルターに関する。  [0013] Further, the present invention relates to a cured product obtained by curing the composition for a color filter and a color filter in which a cured film forming a blue pixel is composed of the cured product.
[0014] 以下、本発明を更に詳細に説明する。  [0014] Hereinafter, the present invention will be described in more detail.
本発明のカラーフィルター用組成物 (カラーフィルター用材料）は、（A)感光性榭脂 及び Z又は単量体 (以下、成分 (A)とも 、う）、 (B)着色材 (以下、成分 (B)とも 、う）、 (C)溶剤 (以下、成分 (C)とも 、う)及び (D)光重合開始剤 (以下、成分 (D)とも 、う） を必須成分として含有し、必要により他の榭脂類及びその他の表面調整剤、消泡剤 等の各種添加剤を配合することができる。  The color filter composition (color filter material) of the present invention comprises (A) photosensitive resin and Z or monomer (hereinafter also referred to as component (A)), (B) colorant (hereinafter referred to as component). It contains (B), u), (C) solvent (hereinafter referred to as component (C)) and (D) photopolymerization initiator (hereinafter also referred to as component (D)) as essential components. According to the above, other additives such as other rosins and other surface conditioners and antifoaming agents can be blended.
[0015] 成分 (A)の感光性榭脂及び Z又は単量体は、光重合性榭脂、光重合性モノマー 及び光重合性オリゴマーの少なくとも 1種以上力 選ばれ、エチレン性不飽和結合を 有するものである。カラーフィルター用組成物には硬化した状態で榭脂となるものを 含めばよく、未硬化の状態では榭脂化して!/、な!、成分のみが含まれる場合を含む。 本発明における榭脂固形分には、榭脂ィ匕する前のモノマーやオリゴマーも固形分と して扱うものとする。成分 (A)は、カラーフィルターの製造プロセスを考慮して適宜選 択すればよい。  The photosensitive resin and Z or monomer of component (A) is selected from at least one of photopolymerizable resin, photopolymerizable monomer and photopolymerizable oligomer, and has an ethylenically unsaturated bond. It is what you have. What is necessary is just to include the thing which becomes rosin in the cured state in the composition for color filters. In the solids content of the present invention, monomers and oligomers before the solidification are treated as solids. Component (A) may be appropriately selected in consideration of the color filter manufacturing process.
[0016] 光重合性榭脂、光重合性モノマー及び光重合性オリゴマーとしては、例えば 2-ヒド ロキシェチル (メタ）アタリレート、 2-ヒドロキシプロピル (メタ）アタリレート、 2-ェチルへ キシル (メタ）アタリレート、エチレングリコールジ (メタ）アタリレート、ジエチレングリコー ルジ (メタ）アタリレート、トリエチレングリコールジ (メタ）アタリレート、ポリエチレングリコ ールジ（メタ）アタリレート、ペンタエリスリトールジ (メタ）アタリレート、ジペンタエリスリト ールテトラ (メタ）アタリレート、ジペンタエリスリトールへキサ（メタ）アタリレート、ビスフ ェノール A型エポキシジ (メタ）アタリレート、ビスフエノール F型エポキシジ (メタ）アタリ レート、ビスフエノールフルオレン型エポキシジ（メタ）アタリレート等の（メタ）アクリル酸 エステル類等が挙げられる。また、アクリル酸 (共)重合体、（メタ)アクリル酸 (共)重合 体、マレイン酸 (共)重合体等のビュル榭脂や、ポリエチレンオキサイド、ポリビュルピ 口リドン、ポリアミド、ポリウレタン、ポリエーテル、ポリエステル等の側鎖にエチレン性 二重結合を有する榭脂類も挙げることができる。これらは単独で用いてもよいし、 2種 以上を併用してもよい。また、これらの感光性榭脂は、現像性を高める目的で、側鎖 にカルボキシル基、フエノール性水酸基等のアルカリ溶解性置換基を有して ヽること が望ましい。 [0016] Examples of photopolymerizable resin, photopolymerizable monomer and photopolymerizable oligomer include 2-hydroxyxetyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethyl hexyl (meth). Atalylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, di Pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A type epoxy di (meth) acrylate, bisphenol F type epoxy di (meth) acrylate, bisphenol fluorene type epoxy di (meta) ) Atre relay (Meth) acrylic acid esters and the like, and the like. In addition, bur resin such as acrylic acid (co) polymers, (meth) acrylic acid (co) polymers, maleic acid (co) polymers, polyethylene oxide, polybutaphthalidone, polyamide, polyurethane, polyether, polyester Examples thereof include coffins having an ethylenic double bond in the side chain. These may be used alone or in combination You may use the above together. In addition, these photosensitive resins preferably have an alkali-soluble substituent such as a carboxyl group or a phenolic hydroxyl group in the side chain for the purpose of improving developability.
[0017] 本発明のカラーフィルター用組成物において、その硬化物が高水準の耐熱性、耐 溶剤性を与える点から、（A)感光性榭脂及び Z又は単量体としては少なくともその一 成分にフルオレン骨格を有するエポキシアタリレート榭脂を用いることが有利である。 好ま 、フルオレン骨格を有するエポキシアタリレート榭脂としては、下記一般式（2) で表されるエポキシ (メタ）アタリレートと多塩基酸又はその酸無水物とを反応させて 得られるものが挙げられる。  [0017] In the composition for a color filter of the present invention, (A) the photosensitive resin and Z or monomer are at least one component because the cured product provides a high level of heat resistance and solvent resistance. It is advantageous to use an epoxy acrylate resin having a fluorene skeleton. The epoxy acrylate resin having a fluorene skeleton preferably includes those obtained by reacting an epoxy (meth) acrylate represented by the following general formula (2) with a polybasic acid or an acid anhydride thereof. .
[0018]  [0018]
Figure imgf000007_0001
Figure imgf000007_0001
(式中、 R及び Rは水素原子、炭素数 1〜5のアルキル基、フエ-ル基、ハロゲン原 子の何れかであり、 Xは下記式（3) (In the formula, R and R are any one of a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenol group, and a halogen atom, and X represents the following formula (3)
Figure imgf000008_0001
Figure imgf000008_0001
で表される 2価の基を示し、 nは 0〜10であり、 Aは CH =CR'-CO-を示し、 R，は水素 N is 0 to 10, A is CH = CR'-CO-, R is hydrogen
2  2
原子又はメチル基を示す。 )  An atom or a methyl group is shown. )
[0019] 一般式（2)で表されるエポキシアタリレートと多塩基酸又はその酸無水物とを反応さ せて、成分 (A)として優れるフルオレン骨格を有するエポキシアタリレート榭脂を製造 する方法については、特に限定されるものでなぐ公知の方法を採用することができ る。なお、本発明でいうエポキシアタリレート榭脂は、エポキシメタアタリレート榭脂等 のエポキシアタリレート榭脂の誘導体を含む意味で使用される。  [0019] A method for producing an epoxy acrylate resin having an excellent fluorene skeleton as component (A) by reacting an epoxy acrylate represented by the general formula (2) with a polybasic acid or an acid anhydride thereof As for, known methods that are not particularly limited can be employed. The epoxy acrylate resin as used in the present invention is used to include derivatives of epoxy acrylate resin, such as epoxy meta acrylate resin.
[0020] ここで、多塩基酸又はその酸無水物としては、例えば、マレイン酸、コハク酸、イタコ ン酸、フタル酸、テトラヒドロフタル酸、へキサヒドロフタル酸、メチルエンドメチレンテト ラヒドロフタル酸、クロレンド酸、メチルテトラヒドロフタル酸、トリメリット酸、ピロメリット酸 、ベンゾフエノンテトラカルボン酸、ビフエ-ルテトラカルボン酸、ビフエ-ルエーテル テトラカルボン酸及びこれらの酸無水物が挙げられる。本発明においては、これら多 塩基酸又はその酸無水物として、 (S2)飽和ジカルボン酸類又は（S4)飽和テトラカル ボン酸類を用いることが特に好ましい。ここで、飽和ジカルボン酸類及び飽和テトラ力 ルボン酸類の飽和は、カルボキシル基又は酸無水物基を構成するカルボ-ル基（C O)以外の不飽和結合 (単結合以外の結合)を有しな 、ことを意味する。好ま 、飽 和カルボン酸類を例示すると、ブタンテトラカルボン酸、へキサヒドロフタル酸、コハク 酸とこれらの酸無水物が例示される。なお、テトラヒドロフタル酸も好ましいカルボン酸 類として例示される。 [0020] Here, examples of the polybasic acid or acid anhydride thereof include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, and chlorende. Examples include acids, methyltetrahydrophthalic acid, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, and acid anhydrides thereof. In the present invention, it is particularly preferable to use (S2) saturated dicarboxylic acids or (S4) saturated tetracarboxylic acids as these polybasic acids or acid anhydrides thereof. Here, the saturation of the saturated dicarboxylic acids and saturated tetracarboxylic rubonic acids does not have an unsaturated bond (bond other than a single bond) other than a carboxylic group (CO) constituting a carboxyl group or an acid anhydride group. Means that. Preferable examples of saturated carboxylic acids include butanetetracarboxylic acid, hexahydrophthalic acid, succinic acid and acid anhydrides thereof. Tetrahydrophthalic acid is also preferred carboxylic acid As an example.
[0021] (S2)飽和ジカルボン酸類と (S4)飽和テトラカルボン酸類は、それぞれ 1種以上を使 用することができ、飽和ジカルボン酸類と飽和テトラカルボン酸類の使用割合は、 S2 ZS4のモル比として 0. 1〜10となる範囲、好ましくは 0. 2〜1となる範囲である。この 使用割合は、最適分子量、アルカリ現像性、光透過性、耐熱性、対溶剤性、パターン 形状の効果に適した割合を選択することができるが、飽和テトラカルボン酸類の使用 割合が大きいほどアルカリ溶解性が大となり、分子量が大となる傾向がなる。なお、飽 和ジカルボン酸類と飽和テトラカルボン酸類以外の、ジカルボン酸類とテトラカルボン 酸類を使用する場合も、上記モル比を満足させることがよい。  [0021] One or more of each of (S2) saturated dicarboxylic acids and (S4) saturated tetracarboxylic acids can be used, and the use ratio of the saturated dicarboxylic acids and saturated tetracarboxylic acids is the molar ratio of S2 ZS4. The range is from 0.1 to 10, preferably from 0.2 to 1. The ratio of use can be selected in accordance with the optimal molecular weight, alkali developability, light transmission, heat resistance, solvent resistance, and pattern shape effect. However, the larger the ratio of saturated tetracarboxylic acids used, the greater the alkalinity. The solubility tends to increase and the molecular weight tends to increase. In addition, when using dicarboxylic acids and tetracarboxylic acids other than saturated dicarboxylic acids and saturated tetracarboxylic acids, the above molar ratio is preferably satisfied.
[0022] (A)感光性榭脂及び Z又は単量体の配合率は、本発明のカラーフィルター用組成 物中の全固形分中 40〜95重量％であることが好ましぐ更には 50〜90重量％であ ることが好ましい。組成物中には、必要に応じて他の榭脂類等を配合することができ る力 この場合には、他の榭脂類を合わせた合計量が上記範囲に入ることが望まし い。なお、全固形分とは重合又は硬化、乾燥後に固形分として残る成分をいい、溶 剤を含まず、単量体を含む。  [0022] (A) The blending ratio of photosensitive resin and Z or monomer is preferably 40 to 95% by weight based on the total solid content in the composition for a color filter of the present invention. It is preferable that it is -90weight%. In the composition, it is desirable that other greaves and the like can be blended as necessary. In this case, it is desirable that the total amount of the other greaves falls within the above range. The total solid content means a component remaining as a solid content after polymerization, curing, and drying, and does not include a solvent but includes a monomer.
[0023] 成分 (B)の着色材には、前記一般式（1)で示されるサブフタロシアニンィ匕合物から なる顔料を全着色材中 0. 5重量％以上含有することを必要とする。一般式（1)にお いて、 X〜X は水素原子又はハロゲン原子を示す力 好ましくは少なくとも 6個がハ [0023] The colorant of component (B) needs to contain 0.5% by weight or more of the pigment made of the subphthalocyanine compound represented by the general formula (1) in the total colorant. In the general formula (1), X to X each represents a hydrogen atom or a halogen atom, preferably at least 6
1 12 1 12
ロゲン原子であり、更に好ましくはすべてがハロゲン原子である。ハロゲン原子として は、フッ素、塩素、臭素、ヨウ素等のいずれでも良く限定されるものではないが、色相 の点から塩素、臭素が好ましい。特に好ましくは、一般式（1)中の X〜x の全てが  Rogen atoms, more preferably all are halogen atoms. The halogen atom may be any of fluorine, chlorine, bromine, iodine and the like, but is preferably chlorine or bromine from the viewpoint of hue. Particularly preferably, all of X to x in the general formula (1) are
1 12 塩素又は臭素であるものが用いられる。なお、 1つの分子内に複数種のハロゲン原 子が結合していてもよい。また、一般式（1)中の Yはアルキル基、ァリール基、アルコ キシ基又はァリールォキシ基を示す。ここで、例えばアルキル基としては、メチル基、 ェチル基、プロピル基、ブチル基が挙げられ、ァリール基としてはフエニル基、ナフチ ル基、アントリル基、フリル基、ピリジル基、インドリル基等が挙げられ、アルコキシ基と してはメトキシ基、エトキシ基、プロポキシ基、ブトキシ基等が挙げられ、ァリールォキ シ基としてはフエノキシ基、ナフトキシ基等が挙げられる。また、これらはハロゲン、ァ ルコキシ基等の置換基を有してもよい。更に、サブフタロシアニン構造を有する置換 基を有して、 Sub-Y'-Subのような 2量体又は多量体となってもよい。ここで、 Subは一 般式（ 1)から Yを除 、て生ずる基等のサブフタロシアニン構造を有する置換基を示す 1 12 Chlorine or bromine is used. Multiple types of halogen atoms may be bonded in one molecule. Y in the general formula (1) represents an alkyl group, an aryl group, an alkoxy group or an aryloxy group. Here, for example, the alkyl group includes a methyl group, an ethyl group, a propyl group, and a butyl group, and the aryl group includes a phenyl group, a naphthyl group, an anthryl group, a furyl group, a pyridyl group, an indolyl group, and the like. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and examples of the aryloxy group include a phenoxy group and a naphthoxy group. These are also halogen, You may have substituents, such as a ruoxy group. Furthermore, it may have a substituent having a subphthalocyanine structure and may be a dimer or multimer such as Sub-Y′-Sub. Here, Sub represents a substituent having a subphthalocyanine structure such as a group generated by removing Y from the general formula (1).
[0024] 成分 (B)は、上記サブフタロシアニン系顔料を全着色材中 0. 5重量％以上、好まし くは 5重量％以上含有するものであればよぐ他の顔料や染料を併用して用いること もできる。上記サブフタロシアニン系顔料の含有量が着色材中 0. 5重量％に満たな いと、該顔料の優れた着色性能が十分発揮できず、また良好な透過特性のカラーフ ィルターを形成できなくなる。なお、青色のカラーレジストインキを調製するために適 した他の着色材としては、色相の点から青色、紫色の顔料が好ましぐ例えばビグメン ト，ブルー 15、同 15 : 1、同 15 : 2、 15 : 3、同 15 :4、同 15 : 6、同 16、同 60、同 80、ピ グメント 'バイオレット 19、同 23、同 37等を挙げることができる力 併用可能な顔料は これらに限定されるものではない。 Component (B) may contain other pigments or dyes as long as it contains 0.5% by weight or more, preferably 5% by weight or more of the above-mentioned subphthalocyanine pigment in the total colorant. It can also be used. If the content of the subphthalocyanine pigment is less than 0.5% by weight in the colorant, the excellent coloring performance of the pigment cannot be sufficiently exhibited, and a color filter having good transmission characteristics cannot be formed. As other colorants suitable for preparing a blue color resist ink, blue and purple pigments are preferable from the viewpoint of hue, for example, Pigment, Blue 15, 15: 1, 15: 2. , 15: 3, 15: 4, 15: 6, 16, 60, 80, Pigment 'Violet 19, 23, 37, etc. Is not to be done.
[0025] 着色材として本発明のサブフタロシアニン系顔料を用いる理由は、顔料の有する特 異な分光特性に起因する。つまり、液晶表示装置等のバックライトには、赤、緑及び 青の三原色に対応する波長（一般的に 610nm、 545nm及び 435nm)に鋭い発光 を有する高演色性の三波長型蛍光ランプが広く用いられており、この三波長の発光 をそれぞれ効果的に透過し他の二波長の発光を遮光することが高水準の赤、緑及 び青の明度、彩度を示すために必要であり、前記特許文献 3に開示されているサブ フタロシアニンよりなる顔料を主たる着色材として含むカラーフィルター用組成物を用 いて製作されるカラーフィルタ一は、 370〜510nm付近に透過を、 520〜610nm付 近に吸収を持ち、三波長型蛍光ランプの青の発光を効果的に透過し、緑の発光を効 果的に遮光することができる力 620nmより長波長域を透過させてしまうため、赤の 発光の遮光は不十分である。本発明のサブフタロシアニンより成る顔料を主たる着色 材として含むカラーフィルター用組成物を用いて製作されるカラーフィルタ一は、 370 〜510nm付近に透過を持つ一方、 530〜650nm付近の広い範囲に吸収を有する 優れた分光特性を示すため、赤の発光も効果的に遮光することができる。そのため に、本発明のカラーフィルタ一は特に青色について、高明度、高彩度を有する。また 、一般式（1)中の Yをアルキル基、ァリール基、アルコキシ基又はァリールォキシ基と することにより顔料の耐熱性が増すので、堅牢性に優れたカラーフィルター用組成物 及びカラーフィルターの提供が可能となる。 [0025] The reason for using the subphthalocyanine pigment of the present invention as a colorant is due to the special spectral characteristics of the pigment. In other words, high-color-rendering three-wavelength fluorescent lamps that have sharp emission at wavelengths corresponding to the three primary colors of red, green, and blue (generally 610 nm, 545 nm, and 435 nm) are widely used for backlights of liquid crystal display devices and the like. It is necessary to effectively transmit these three wavelengths of light and shield the other two wavelengths of light in order to show a high level of lightness and saturation of red, green and blue. A color filter manufactured using a color filter composition containing a pigment made of subphthalocyanine as a main colorant disclosed in Patent Document 3 transmits light at around 370 to 510 nm and absorbs at around 520 to 610 nm. The ability to effectively transmit the blue light emitted from the three-wavelength fluorescent lamp and effectively shield the green light from being transmitted. Is insufficient. The color filter manufactured using the color filter composition containing the pigment comprising the subphthalocyanine of the present invention as the main coloring material has a transmission in the vicinity of 370 to 510 nm, while absorbing in a wide range of about 530 to 650 nm. Since it has excellent spectral characteristics, red light emission can also be effectively shielded. For this reason, the color filter of the present invention has high brightness and high saturation, particularly for blue. Also Since the heat resistance of the pigment is increased by changing Y in the general formula (1) to an alkyl group, aryl group, alkoxy group or aryloxy group, it is possible to provide a color filter composition and a color filter with excellent fastness properties. It becomes.
[0026] サブフタロシアニン系顔料の製造は、一般的には、サブフタロシア-ンィ匕合物を合 成しそれを顔料ィ匕することで成される。サブフタロシア-ンィ匕合物の合成方法は公知 であり、その例としては、 A. Meller and A. Ossko, Monatshefte for Chemie 103, 150- 155 (1972)などが挙げられ、化学量論的には三ハロゲン化硼素 1モルと必要に応じ てベンゼン骨格形成炭素の水素原子がハロゲン置換されたフタ口-トリル 3モルを反 応させることで合成できる。更に、上記の方法により得られたサブフタロシア-ンィ匕合 物を公知の方法により、本発明で使用する前記一般式（1)で示されるサブフタロシア ニンィ匕合物に変換することができる。こうして得られたサブフタロシア-ンィ匕合物には 副反応等によって生ずる不純物が含まれていることが多いが、例えば濾過洗浄ゃソ ックスレー抽出を行うことにより不純物を取り除くことができる。ここで、不純物としては 、原料の三ハロゲンィ匕硼素の加水分解生成物、未反応のフタ口-トリル等を挙げるこ とができる。濾過洗浄やソックスレー抽出で用いる溶媒については、特に制約はない 。例えば、メタノール、エタノール等のアルコール系溶剤、アセトン、メチルェチルケト ン等のケトン系溶剤、トルエン、キシレン等の芳香族系溶剤等を用いることができる。 また、必要に応じて、フタ口-トリル又はハロゲン以外の置換フタ口-トリルを出発原 料として、無置換又は置換サブフタロシアニンを合成した後、公知の方法によりハロ ゲンィ匕を行なってもよぐ合成法及び精製法は上記の方法に限定されるものではな い。  [0026] The production of the subphthalocyanine pigment is generally performed by synthesizing a subphthalocyanine compound and pigmenting it. Methods for synthesizing subphthalocyanine compounds are known, and examples include A. Meller and A. Ossko, Monatshefte for Chemie 103, 150-155 (1972), and the like. Can be synthesized by reacting 1 mol of boron trihalide with 3 mol of lid-tolyl in which the hydrogen atom of the benzene skeleton-forming carbon is halogen-substituted as necessary. Furthermore, the subphthalocyanine compound obtained by the above method can be converted into the subphthalocyanine compound represented by the general formula (1) used in the present invention by a known method. . The thus obtained subphthalocyanine compound often contains impurities caused by side reactions and the like. For example, the impurities can be removed by Soxhlet extraction after filtration and washing. Here, examples of the impurities include hydrolysis products of raw material trihalogen boron, unreacted lid-tolyl, and the like. There are no particular restrictions on the solvent used for filtration washing or Soxhlet extraction. For example, alcohol solvents such as methanol and ethanol, ketone solvents such as acetone and methyl ethyl ketone, and aromatic solvents such as toluene and xylene can be used. In addition, if necessary, after synthesis of unsubstituted or substituted subphthalocyanine using a substituted lid mouth-tolyl other than a lid mouth-tolyl or a halogen as a starting material, halogenation may be performed by a known method. The synthesis method and purification method are not limited to the above methods.
[0027] 顔料ィ匕する方法としては公知の方法が利用でき、例えばサブフタロシア-ンィ匕合物 を濃硫酸等の強酸に溶解した後、大量の水中に投入して微細顔料を生成させるァシ ッドペースティング法、同様に強酸に分散してこれを大量の水中に注 、で微細顔料 を生成させるアシッドスラリー法等を挙げることができる。また、高水準の明彩度性を 有するカラーフィルターを得るには、着色材として更に微粒ィ匕した顔料を用いることが 好ましいが、微粒ィ匕する方法も公知の方法が利用でき、例えば塩の存在下でミル破 砕するソルトミリング法等を挙げることができる。本発明においては、顔料化及び微粒 化の方法も上記の方法に限定されるものではない。本発明で使用される顔料は、組 成物中で平均粒子径が 50〜250nmの範囲で分散して!/、ることが好まし!/、。 [0027] A known method can be used as a method for producing a pigment. For example, a subphthalocyanine compound is dissolved in a strong acid such as concentrated sulfuric acid and then poured into a large amount of water to form a fine pigment. The acid pasting method, in which a fine pigment is formed by dispersing in a strong acid and pouring the solution into a large amount of water, can be exemplified. Further, in order to obtain a color filter having a high level of color saturation, it is preferable to use a finer pigment as a coloring material. However, a known method can be used for the method of fine graining. Examples thereof include a salt milling method in which the mill is crushed in the presence. In the present invention, pigmentation and fine particles The method of conversion is not limited to the above method. The pigment used in the present invention is preferably dispersed in an average particle diameter of 50 to 250 nm in the composition! /.
[0028] カラーフィルター用組成物中の着色材の割合は、着色濃度等に応じて適宜選定さ れるが、組成物中の (B)着色材と榭脂固形分 (R)との重量比 (B)Z(R)が 0. 05〜： L 5の範囲であることが必要であり、好ましくは、 0. 1〜1の範囲である。この比が 0. 05 に満たな!/、と、着色性能が十分発揮できず良好なカラーフィルターを形成できなくな り、また、 1. 5を超えると、フォトリソグラフィー工程において有効な画素形成能が発揮 できなくなる。なお、榭脂固形分 (R)は、前記成分 (A)及び成分 (A)以外の榭脂成分 (モノマーを含む)からなる。  [0028] The ratio of the colorant in the color filter composition is appropriately selected depending on the color concentration and the like, but the weight ratio of (B) colorant to rosin solid (R) in the composition ( B) Z (R) must be in the range of 0.05 to L5, and preferably in the range of 0.1 to 1. If this ratio is less than 0.05! /, The coloring performance cannot be sufficiently exhibited, and it becomes impossible to form a good color filter, and if it exceeds 1.5, the pixel forming ability effective in the photolithography process is not achieved. Cannot be used. The solids (R) of the resin is composed of a resin component (including monomers) other than the component (A) and the component (A).
[0029] 成分 (C)の溶剤としては、顔料の分散性と分散剤を配合した場合にはその溶解性 に優れる点から、エステル類、ケトン類、グリコールエーテル類、含窒素系溶剤等を 好ましく用いることができる。例えばエステル類では酢酸ェチル、酢酸ブチル、乳酸 ェチル、 y -ブチ口ラタトン等、ケトン類ではメチルイソブチルケトン、シクロへキサノン 等、グリコ-ルエーテル類ではェチルセ口ソルブ、ェチルセ口ソルブアセテート、プロピ レングリコールモノメチルエーテルアセテート、ジエチレングリコールジメチルエーテ ル等、含窒素系溶剤ではジメチルホルムアミド、ジメチルァセトアミド等をそれぞれ挙 げることができる。これらの溶剤は、配合される榭脂類及びその他の添加物の構成、 顔料の耐溶剤性、塗布性に応じて適宜選択すれば良ぐ単独で用いても、 2種以上 を併用してもよい。  [0029] The solvent of component (C) is preferably an ester, a ketone, a glycol ether, a nitrogen-containing solvent, or the like from the viewpoint of excellent dispersibility of the pigment and, when a dispersant is blended, the solubility thereof. Can be used. For example, ethyl acetate, butyl acetate, ethyl lactate, y-butarate rataton, etc. for esters, methyl isobutyl ketone, cyclohexanone, etc. for ketones, ethyl ether solvate, cetyl solvate sorb acetate, propylene glycol monomethyl for glycol ethers Examples of nitrogen-containing solvents such as ether acetate and diethylene glycol dimethyl ether include dimethylformamide and dimethylacetamide. These solvents can be used alone or in combination of two or more, as long as they are appropriately selected according to the composition of the blended resin and other additives, the solvent resistance of the pigment, and the coating properties. Good.
[0030] 成分 (D)の光重合開始剤としては、例えばァセトフエノン、 p-tert-ブチルァセトフエ ノン等のァセトフエノン類、ベンゾフエノン、 p, p' -ビス（N, N-ジメチルァミノ）ベンゾ フエノン等のベンゾフエノン類、ベンゾインェチルエーテル、ベンゾイン- tert-ブチル エーテル等のベンゾインエーテル類、 2-メチル -1- [4- (メチルチオ）フエ-ル] -2-モ ルフォリノプロパン- 1-オン、 2-ベンジル- 2- (N, N-ジメチルァミノ）- 1- (4-モルフオリ ノフエ-ル）ブタン- 1-オン等のひ-アミノアルキルフエノン類、 2, 4, 6-トリス（トリクロ口 メチル）- 1 , 3, 5-トリアジン、 2- (4-メトキシフエ-ル）- 4, 6-ビス（トリクロロメチル） -1 , 3, 5-トリアジン等のトリアジン類、過酸化べンゾィル、 3, 3' , 4, A' -テトラ（tert- ブチルペルォキシカルボ-ル）ベンゾフエノン等の有機過酸化物類、チォキサントン 、 2, 4-ジェチルチオキサントン等の硫黄ィ匕合物類等を挙げることができる。これらは 単独で用いても、 2種以上を併用してもよい。 [0030] Examples of the photopolymerization initiator of component (D) include acetophenones such as acetophenone and p-tert-butylacetophenone, benzophenones such as benzophenone and p, p'-bis (N, N-dimethylamino) benzophenone. Benzoin ethers such as benzoinethyl ether and benzoin-tert-butyl ether, 2-methyl-1- [4- (methylthio) phenol] -2-morpholinopropan-1-one, 2-benzyl- 2-Aminoalkylphenones such as 2- (N, N-dimethylamino) -1- (4-morpholinophenol) butan-1-one, 2, 4, 6-tris (trichloromethyl) -1, 3,5-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine and other triazines, benzoyl peroxide, 3, 3 ', 4, A'-tetra (tert-butylperoxycarbol) benzophenone Peroxides, Chiokisanton And sulfur compounds such as 2,4-jetylthioxanthone. These may be used alone or in combination of two or more.
[0031] 光重合開始剤の配合率は、露光感度等に応じて適宜選択されるが、成分 (A)に対 して 0. 1〜20重量％であることが好ましぐ更には 0. 5〜15重量％であることが好ま しい。含有割合が 0. 1重量％未満では、感光性が不十分となり、反対に 20重量％を 超えると、レジストインキとしての保存安定性に欠ける。  [0031] The blending ratio of the photopolymerization initiator is appropriately selected according to the exposure sensitivity and the like, but is preferably 0.1 to 20% by weight with respect to the component (A). It is preferably 5 to 15% by weight. If the content is less than 0.1% by weight, the photosensitivity becomes insufficient. On the other hand, if it exceeds 20% by weight, the storage stability as a resist ink is insufficient.
[0032] 本発明のカラーフィルター用組成物は、上記必須成分を含有する限りその製法は 限定されないが、顔料、分散剤 (以下、成分 (E)ともいう)及び溶剤を主成分とする顔 料分散液を予め製作し (以下、これを顔料分散体とも称する)、その後、成分 (A)及び (D)、必要により加えられる榭脂類及びその他の成分と混合することが有利である。  [0032] The production method of the color filter composition of the present invention is not limited as long as it contains the above-mentioned essential components, but is a pigment mainly composed of a pigment, a dispersant (hereinafter also referred to as component (E)) and a solvent. It is advantageous to make the dispersion in advance (hereinafter also referred to as pigment dispersion) and then mix with components (A) and (D), optionally added rosins and other components.
[0033] ここで、顔料分散体は、前記のサブフタロシアニン系顔料、分散剤及び溶剤を含有 するが、顔料分散体中の全固形分は 1〜40重量％であることが好ましぐ更には 5〜 35重量％であることが好ましい。顔料の配合率は、顔料分散体中 1〜25重量％であ ることが好ましぐ更には 5〜20重量％であることが好ましい。また、分散剤の配合率 は、顔料に対して 10〜60重量％であることが好ましぐ 20〜50重量％であることが より好ましい。なお、全固形分とは乾燥、硬化後に残存する成分をいう。顔料分散体 は顔料を分散剤と共に溶剤中に分散させることで得られるが、その製作方法は、特 に制限されるものではなぐ公知の方法が利用できる。例えばペイントシェーカー、ビ ーズミル等による分散処理等を挙げることができる。  [0033] Here, the pigment dispersion contains the above-mentioned subphthalocyanine pigment, dispersant and solvent, and it is preferable that the total solid content in the pigment dispersion is 1 to 40% by weight. It is preferably 5 to 35% by weight. The blending ratio of the pigment is preferably 1 to 25% by weight in the pigment dispersion, and more preferably 5 to 20% by weight. Further, the blending ratio of the dispersant is preferably 10 to 60% by weight, more preferably 20 to 50% by weight with respect to the pigment. The total solid content means a component remaining after drying and curing. The pigment dispersion can be obtained by dispersing the pigment in a solvent together with a dispersant, but the production method is not particularly limited, and a known method can be used. For example, a dispersion treatment using a paint shaker or a bead mill can be used.
[0034] 成分 (E)の分散剤を用いる場合、その種類は特に限定されるものではないが、分散 安定性に優れる点から、 (a)ポリ（低級アルキレンィミン)及び (b)ポリアリルァミンから 選ばれる 1種以上の含窒素化合物に、遊離のカルボキシル基を有する（i)ポリエステ ル、（ii)ポリアミド及び (iii)ポリエステルアミドカも選ばれる 1種以上のカルボキシル基 含有ィ匕合物を反応させてアミド又は塩を形成させてなるグラフトポリマーを用いること が好ましい。  [0034] When the dispersant of component (E) is used, the type thereof is not particularly limited, but from the viewpoint of excellent dispersion stability, it can be derived from (a) poly (lower alkyleneimine) and (b) polyallylamin. One or more selected nitrogen-containing compounds are reacted with (i) polyester having a free carboxyl group, (ii) polyamide, and (iii) polyester amideca. It is preferable to use a graft polymer obtained by forming an amide or salt.
[0035] (a)ポリ（低級アルキレンィミン）は、一級（-NH )、二級（-NH-)及び三級（-Nく）のァ  [0035] (a) Poly (lower alkyleneimine) is a primary (—NH 2), secondary (—NH—) and tertiary (—N) alkyl.
2  2
ミノ基を低級アルキレン鎖 (-R -、例えば- CH CH -)で結合した分枝構造を有するポ  A polymer having a branched structure in which a mino group is connected by a lower alkylene chain (-R-, for example, -CH CH-).
2 2  twenty two
リマーであり、（b)ポリアリルアミンは、 [- CH - CH(CH NH )-]なる構造を有するポリマ  (B) polyallylamine is a polymer having a structure of [—CH—CH (CH NH) —]
2 2 2 η 一である。また、（i)、（ii)及び ( )のカルボキシル基含有ィ匕合物は、末端又は側鎖等 に少なくとも 1つのカルボキシル基を有し、これが（a)及び (b)の- NH等の少なくとも 2 2 2 η It is one. In addition, the carboxyl group-containing compound (i), (ii) and () has at least one carboxyl group at the terminal or side chain, and this is a group such as -NH in (a) and (b). at least
2  2
一部と反応して- NHCO-又は ΝΗ +·— OCO-等を形成してグラフトポリマーを形成する  Reacts with part to form -NHCO- or ΝΗ + ·-OCO- etc. to form graft polymer
3  Three
[0036] 上記グラフトポリマーは、顔料に吸着してアンカーの役割を果たす塩基性部分 (a) 又は (b)と、立体反発効果により分散性を付与する高分子鎖部分 (i、 ii又は )を共に 有する分散剤である。このようなグラフトポリマーの製造方法は公知であり、例えば特 公昭 63-30057号公報及び特開平 9-169821号公報に開示されている。 [0036] The graft polymer comprises a basic part (a) or (b) that acts as an anchor by adsorbing to a pigment, and a polymer chain part (i, ii, or) that imparts dispersibility by a steric repulsion effect. Both are dispersants. Such a method for producing a graft polymer is known and disclosed in, for example, Japanese Patent Publication No. 63-30057 and Japanese Patent Laid-Open No. 9-169821.
[0037] また、グラフトポリマーの塩基性部分のサブフタロシアニン系顔料への吸着性をより 高めるために、顔料骨格に酸性の官能基を導入した顔料誘導体型の分散助剤を分 散剤と併用することもできる。上記の分散助剤は、色相の点力 青色、紫色のものが 好ましぐ例えば銅フタロシアニンのスルホン酸誘導体、サブフタロシアニンのスルホ ン酸誘導体、キナクリドンのスルホン酸誘導体、カルバゾールジォキサジンのスルホ ン酸誘導体等を挙げることができる。 [0037] Further, in order to further enhance the adsorptivity of the basic portion of the graft polymer to the subphthalocyanine pigment, a pigment derivative type dispersion aid in which an acidic functional group is introduced into the pigment skeleton is used in combination with the dispersant. You can also. The above-mentioned dispersion aids are preferably those having a hue of blue or purple. For example, sulfonic acid derivatives of copper phthalocyanine, sulfonic acid derivatives of subphthalocyanine, sulfonic acid derivatives of quinacridone, and sulfonates of carbazole dioxazine. An acid derivative etc. can be mentioned.
[0038] なお、成分 (E)の分散剤は、上記のようなグラフトポリマーに限定されず、分散能を 有するものをいい、分散剤、分散促進剤等として市販されているもの又はその同等品 をいう。榭脂類の中には、顔料の表面に吸着して顔料を分散させる働きを有するもの がある。このような榭脂類は分散能を有するので分散剤に含まれる。したがって、（A) 感光性榭脂及び Z又は単量体が分散能を有する場合は、これを分散剤として用い てもよい。ただし、高粘度物質である榭脂類は一般に分散を安定させる作用（分散安 定能）は有するが分散能を有さず、このように分散能を有さないものは分散剤とは扱 わない。本発明において、分散剤は必須成分ではないが、これを使用する場合には 榭脂成分の一構成成分となり得る。 [0038] The dispersant of component (E) is not limited to the graft polymer as described above, and refers to a dispersant having a dispersibility, which is commercially available as a dispersant, a dispersion accelerator, or the like. Say. Some greaves have the function of adsorbing on the surface of the pigment and dispersing the pigment. Such rosins are included in the dispersant because they have dispersibility. Therefore, when (A) the photosensitive resin and Z or the monomer has a dispersibility, this may be used as a dispersant. However, coffins, which are high viscosity substances, generally have an action to stabilize dispersion (dispersion stability) but do not have dispersibility, and those that do not have such dispersibility are treated as dispersants. Absent. In the present invention, the dispersant is not an essential component, but when it is used, it can be a constituent component of the resin component.
[0039] 本発明のカラーフィルター用組成物は、上記成分以外に現像性や塗膜形成能を向 上させる目的で、バインダー榭脂成分として、アルカリ溶解性を有する榭脂を加えて もよい。例えば、ポリエチレンオキサイド、ポリビュルピロリドン、ポリアミド、ポリウレタン 、ポリエステル、ポリエーテル等が挙げられる力 主鎖又は側鎖にカルボキシル基を 含有しアルカリ現像性に優れるものが好ましい。このようなものには、例えばアクリル 酸 (共)重合体、（メタ)アクリル酸 (共)重合体、マレイン酸 (共)重合体等のビニル榭 脂類が挙げられる。この他に、水酸基を有する榭脂に酸無水物を付加させたものな ども有用である。これらは単独で用いても、 2種以上を併用してもよい。 [0039] In addition to the above components, the color filter composition of the present invention may contain an alkali-soluble resin as a binder resin component for the purpose of improving developability and coating film-forming ability. For example, polyethylene oxide, polybutylpyrrolidone, polyamide, polyurethane, polyester, polyether, and the like are preferred. Those having a carboxyl group in the main chain or side chain and having excellent alkali developability are preferred. For example, acrylic Examples thereof include vinyl resins such as acid (co) polymers, (meth) acrylic acid (co) polymers, and maleic acid (co) polymers. In addition to this, the addition of an acid anhydride to rosin having a hydroxyl group is also useful. These may be used alone or in combination of two or more.
[0040] 本発明のカラーフィルター用組成物は、必須成分として前記の成分 (A)〜（D)を含 有するが、全固形分は 1〜40重量％であることが好ましぐ更には 5〜30重量％であ ることが好ましい。 [0040] The composition for a color filter of the present invention contains the above-mentioned components (A) to (D) as essential components, but the total solid content is preferably 1 to 40% by weight. It is preferably ˜30% by weight.
[0041] カラーフィルター用組成物を製作する方法としては、予め前記サブフタロシアニン 顔料を単独で又は他の顔料と共に分散剤を用いて溶剤に分散させた顔料分散体を 製作し、これと榭脂成分、光重合開始剤等を配合する方法や、サブフタロシアニン系 顔料を榭脂組成物中に直接分散させる方法等を挙げることができるが、カラーフィル ター用組成物の安定性の点力も前者の方法が好ましい。また、サブフタロシアニン系 顔料を溶解できる高溶解性溶剤を用いてサブフタロシアニン系顔料を、感光性榭脂 を含む組成物中に溶解させてカラーレジストインキとする方法もあるが、耐光性、耐 熱性及び耐溶剤性の点で難があるために、サブフタロシアニン系顔料を分散する方 法が最も好ましい。  [0041] As a method for producing a composition for a color filter, a pigment dispersion in which the above-mentioned subphthalocyanine pigment is dispersed in a solvent using a dispersant alone or together with other pigments is prepared, and this is a resin component. , A method of blending a photopolymerization initiator and the like, a method of directly dispersing a subphthalocyanine pigment in a resin composition, and the like, but the former method also has the point of stability of the composition for a color filter. Is preferred. There is also a method of dissolving a subphthalocyanine pigment in a composition containing a photosensitive resin using a highly soluble solvent capable of dissolving the subphthalocyanine pigment to form a color resist ink. In view of solvent resistance, it is most preferable to disperse the subphthalocyanine pigment.
[0042] 本発明のカラーフィルター用組成物を硬化して得られる硬化物は、当該組成物を 基板等に塗布し、光照射、加熱等で硬化させることによって得られる。組成物を塗布 する方法としては公知の方法が利用でき、例えばスピンコーター、バーコ一ター、ダ イコーター等の塗布装置による塗布を挙げることができる。塗布後は、ホットプレート、 IRオーブン等を用いて乾燥を行なうことがよ!、。  [0042] A cured product obtained by curing the composition for a color filter of the present invention is obtained by applying the composition to a substrate or the like and curing it by light irradiation, heating or the like. As a method for applying the composition, a known method can be used, and examples thereof include application by a coating apparatus such as a spin coater, a bar coater, and a die coater. After application, dry using a hot plate, IR oven, etc.!
[0043] 塗布された組成物を光照射する方法も公知の方法が利用でき、露光光源は特に限 定されるものではないが、例えばキセノンランプ、ハロゲンランプ、タングステンランプ 、超高圧水銀灯、高圧水銀灯、中圧水銀灯、低圧水銀灯等のランプ光源等が用いら れる。しかし、塗布及び光照射の方法は上記の方法に限定されない。  [0043] A known method can be used for irradiating the coated composition with light, and the exposure light source is not particularly limited. For example, a xenon lamp, a halogen lamp, a tungsten lamp, an ultra-high pressure mercury lamp, a high-pressure mercury lamp Lamp light sources such as medium-pressure mercury lamps and low-pressure mercury lamps are used. However, the coating and light irradiation methods are not limited to the above methods.
[0044] かかる光源にて画像露光を行った後、現像すれば基板上に画像を形成することが できる。現像液としては、未露光部分を溶解し露光部分溶解しない現像液であれば いかなるものも用いることができる。具体時には、種々の添加物を含んだアルカリ溶 液であり、添加物としては、有機溶剤、緩衝剤、界面活性剤等を含有することができ る。現像処理方法については特に制限はないが、浸漬現像、スプレー現像、ブラシ 現像、超音波現像等の方法が用いられる。 [0044] An image can be formed on a substrate by developing after image exposure with such a light source. Any developer can be used as long as it dissolves the unexposed part and does not dissolve the exposed part. Specifically, it is an alkaline solution containing various additives, and the additives can contain organic solvents, buffers, surfactants, and the like. The The development processing method is not particularly limited, but methods such as immersion development, spray development, brush development and ultrasonic development are used.
[0045] 塗膜の強度を上げるため、熱風オーブンによる加熱硬化を行うことが望ま 、。組 成物の硬化条件につ!、ては特に制約はな!、が、組成物を硬化して得られる硬化膜 の変色、褪色を防ぐために、加熱については 250°C以下で 1時間以内とすることが好 ましい。なお、上記のカラーフィルター用組成物の硬化膜を用いてカラーフィルター を製作する方法としては、公知の方法を利用できる。  [0045] In order to increase the strength of the coating film, it is desirable to perform heat curing with a hot air oven. There are no particular restrictions on the curing conditions of the composition! However, in order to prevent discoloration or discoloration of the cured film obtained by curing the composition, heating should be performed at 250 ° C or less for 1 hour or less. It is preferable to do. In addition, as a method for producing a color filter using the cured film of the color filter composition, a known method can be used.
図面の簡単な説明  Brief Description of Drawings
[0046] [図 1]モデルカラーフィルターの分光透過率を示すグラフである。  FIG. 1 is a graph showing the spectral transmittance of a model color filter.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0047] 以下、実施例により本発明を具体的に説明するが、本発明は以下の実施例に限定 されるものでない。なお、以下における「部」はいずれも重量部を示す。 [0047] The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples. In the following, “part” means part by weight.
[0048] 製造例 1 [0048] Production Example 1
トクロロナフタレン 600部にテトラクロ口フタ口-トリル 150部をカ卩え、窒素雰囲気下 、室温で 30分攪拌したのち、三塩化硼素 48部を滴下する。その後、 180°Cまでゆつ くり加熱し、 10〜60分加熱撹拌を行なう。放冷後、析出物を濾取して、メタノール、ァ セトン、トルエンの順で洗浄し乾燥して、下式 (4)で示されるクロ口-ドデカクロロサブ フタロシアニン硼素錯体 119部（収率 75%)を得た。  Add 600 parts of tetrachlorophthalate-tolyl to 600 parts of tochloronaphthalene and stir at room temperature for 30 minutes in a nitrogen atmosphere, and then add 48 parts of boron trichloride dropwise. Then slowly heat to 180 ° C and stir for 10-60 minutes. After allowing to cool, the precipitate was collected by filtration, washed with methanol, acetone, and toluene in this order, dried, and 119 parts (yield 75) of the black mouth-dodecachlorosubphthalocyanine boron complex represented by the following formula (4). %).
[0049] Q| Q|  [0049] Q | Q |
Figure imgf000016_0001
[0050] 製造例 2
Figure imgf000016_0001
[0050] Production Example 2
製造例 1で得たクロ口-ドデカクロロサブフタロシアニン硼素錯体 100部に、 1-クロ口 ナフタレン 1120部、メタノール 449部、トリェチルァミン 31部を加え、攪拌しながら 3 時間加熱還流した。放冷後、メタノール、水、アセトンで洗浄し乾燥して、下式（5)で 示されるメトキシ-ドデカクロロサブフタロシアニン硼素錯体 96部（収率 97%)を得た。  To 100 parts of the black mouth-dodecachlorosubphthalocyanine boron complex obtained in Production Example 1, 1120 parts of 1-black naphthalene, 449 parts of methanol and 31 parts of triethylamine were added and heated to reflux with stirring for 3 hours. The mixture was allowed to cool, washed with methanol, water, and acetone and dried to obtain 96 parts (yield 97%) of a methoxy-dodecachlorosubphthalocyanine boron complex represented by the following formula (5).
[0051]  [0051]
Figure imgf000017_0001
Figure imgf000017_0001
[0052] 製造例 3 [0052] Production Example 3
製造例 2で得たメトキシ -ドデカクロロサブフタロシアニン硼素錯体 102部を濃硫酸 5 10部に溶解させ、この溶液を氷水中に滴下し、析出した固体を濾取乾燥して、サブ フタロシアニン顔料 100部を得た。このサブフタロシアニン顔料 100部に分散剤 40部 及びプロピレングリコールモノメチルエーテルアセテート 860部を、メディアを充填し た容器に配合し、ペイントシェーカーを用いて 6時間の分散処理を行い、濾過してメ ディアを除去し、分散液 1000部を製作した。ここで、分散剤には、ポリアリルァミンに 遊離のカルボキシル基を有するポリエステルを反応させてアミドを形成させたグラフト ポリマーを用いた。ここで、ペイントシェーカーのメディアには、 0. 4mm φガラスビー ズを充填率 40%あるいは 0. 4mm φジルコ-ァビーズを充填率 15%で用いた。こう して得られた分散液の固形分濃度は 14重量％、全固形分中の着色材の割合は 71. 4重量％であり、低粘度かつ低チクソトロピー性を示すものであった。  Dissolve 102 parts of the methoxy-dodecachlorosubphthalocyanine boron complex obtained in Production Example 2 in 10 parts of concentrated sulfuric acid, add this solution dropwise to ice water, filter and dry the precipitated solid, and add 100 parts of subphthalocyanine pigment. Got. Mix 100 parts of this subphthalocyanine pigment with 40 parts of a dispersant and 860 parts of propylene glycol monomethyl ether acetate in a container filled with media, disperse using a paint shaker for 6 hours, and filter the media. Removal of 1000 parts of dispersion was made. Here, a graft polymer obtained by reacting polyallylamine with a polyester having a free carboxyl group to form an amide was used as the dispersant. Here, as the media of the paint shaker, 0.4 mm φ glass beads were used at a filling rate of 40%, or 0.4 mm φ zirco beads were used at a filling rate of 15%. The dispersion thus obtained had a solid content concentration of 14% by weight, and the ratio of the coloring material in the total solid content was 71.4% by weight, indicating low viscosity and low thixotropy.
[0053] 製造例 4 製造例 1で得たクロロードデカクロロサブフタロシアニン硼素錯体 100部に、トルェ ン 578部、 1—クロ口エタノール 286部、トリェチルァミン 72部をカロえ、攪拌しながら 3 時間加熱還流した。放冷後、メタノール、アセトンで洗浄し乾燥して、下式 (6)で示さ れるクロロェトキシードデカクロロサブフタロシアニン硼素錯体 82部（収率 78%)を得 [0053] Production Example 4 To 100 parts of the chlorodedecachlorosubphthalocyanine boron complex obtained in Production Example 1, 578 parts of toluene, 286 parts of 1-necked ethanol and 72 parts of triethylamine were heated and refluxed for 3 hours with stirring. After standing to cool, it was washed with methanol and acetone and dried to obtain 82 parts (yield 78%) of a chloroethodededecachlorosubphthalocyanine boron complex represented by the following formula (6).
[0054] [0054]
Figure imgf000018_0001
Figure imgf000018_0001
[0055] 実施例 1 [0055] Example 1
ビスフエノールフルオレン骨格を有するエポキシアタリレート榭脂の 54. 2重量％プ ロピレンダリコールモノメチルエーテルアセテート溶液 (新日鐡ィ匕学社製商品名： V- 2 59ME) 130部、ジペンタエリスリトールへキサアタリレート 47部、ビフエ-ル骨格を有 するエポキシ榭脂（ジャパンエポキシレジン社製商品名：ェピコート YX4000HK) 17 部、 2-メチル -1- [4- (メチルチオ）フエ-ル]- 2-モルフォリノプロパン- 1-オン 7部、 p , p' -ビス（N, N-ジェチルァミノ）ベンゾフエノン 1部、ジエチレングリコールジメチル エーテル 196部、プロピレングリコールモノメチルエーテルアセテート 75部、界面活 性剤 1部及びシランカップリング剤 1部を配合し、十分に攪拌して、弱アルカリ溶液に 可溶な感光性榭脂を含む組成物 475部を製作した。  130 parts of dipentaerythritol hexane, 54.2 wt% polypropylene alcohol monomethyl ether acetate solution of bisphenol fluorene skeleton with bisphenol fluorene skeleton (trade name: V-2 59ME, manufactured by Nippon Steel Chemical Co., Ltd.) 47 parts of acrylate, epoxy resin with biphenyl skeleton (trade name: Epicoat YX4000HK, manufactured by Japan Epoxy Resin Co., Ltd.) 17 parts, 2-methyl-1- [4- (methylthio) phenol] -2-morphol 7 parts Linopropan-1-one, 1 part p, p'-bis (N, N-jetylamino) benzophenone, 196 parts diethylene glycol dimethyl ether, 75 parts propylene glycol monomethyl ether acetate, 1 part surfactant and silane coupling 475 parts of a composition containing photosensitive resin soluble in a weak alkaline solution was prepared by mixing 1 part of the agent and stirring thoroughly.
[0056] この感光性榭脂を含む組成物 475部に、製造例 3で得られた分散液 525部を配合 し、均一な溶液になるまで十分に攪拌してカラーフィルター用組成物 1000部を製作 した。この組成物の固形分濃度は 21. 6重量％、全固形分中の顔料分の割合は 24. 3重量％であり、低粘度かつ低チクソトロピー性を示すものであった。 [0056] To 475 parts of the composition containing the photosensitive resin, 525 parts of the dispersion obtained in Production Example 3 was blended, and stirred sufficiently until a uniform solution was obtained. Production did. This composition had a solid content concentration of 21.6% by weight, and a pigment content in the total solid content of 24.3% by weight, indicating low viscosity and low thixotropy.
[0057] このカラーフィルター用組成物を、 5インチ角、厚さ lmmの青板ガラス基板上にスピ ンコーターを用いて塗布した。このとき、スピンコーターの回転数を変化させて試験片 を製作した。この試験片を乾燥した後、フォトマスクを被せて 200mj/cm2の紫外線 露光を行い露光部のカラーレジストインキを硬化させた。次いで試験片を 0. 4%炭酸 ナトリウム水溶液で 60秒間アルカリ現像して未露光部のカラーレジストインキを除去し 、これを乾燥した。最後に試験片を熱硬化して、モデルカラーフィルターとしてのカラ 一レジストインキの硬化膜を製作した。 [0057] This composition for a color filter was applied on a blue plate glass substrate having a size of 5 inches square and a thickness of 1 mm using a spin coater. At this time, test pieces were manufactured by changing the rotation speed of the spin coater. After drying this test piece, it was covered with a photomask and exposed to UV light of 200 mj / cm 2 to cure the color resist ink in the exposed area. Next, the test piece was alkali-developed with a 0.4% aqueous sodium carbonate solution for 60 seconds to remove the unexposed color resist ink and dried. Finally, the test piece was thermally cured to produce a cured film of color resist ink as a model color filter.
[0058] 製作したモデルカラーフィルターの分光透過率、色度 (X値、 y値)及び明度 (Y値） は、色度計 (東京電色社製商品名：カラーアナライザー TC-1800MK2)を用いて測 定したが、このときの測色用の光は補助標準イルミナント Cとした。本実施例で得られ たモデルカラーフィルターの分光透過率を図 1に、色度及び明度を表 1に示す。  [0058] The spectral transmittance, chromaticity (X value, y value), and brightness (Y value) of the model color filter produced were measured using a chromaticity meter (trade name: Color Analyzer TC-1800MK2 manufactured by Tokyo Denshoku Co., Ltd.) The light for colorimetry at this time was auxiliary standard illuminant C. The spectral transmittance of the model color filter obtained in this example is shown in FIG. 1, and the chromaticity and brightness are shown in Table 1.
[0059] 実施例 2  [0059] Example 2
着色材を製造例 4で得たクロロェトキシードデカクロロサブフタロシアニン硼素錯体 に変更した以外は製造例 3と同様な方法にて分散液を得た。この分散液を使用した 以外は、実施例 1と同様にしてカラーフィルター用組成物を作製した。この組成物に ついて実施例 1と同様な方法にて、モデルカラーフィルターを製作し、分光透過率及 び色度、明度を測定した。  A dispersion was obtained in the same manner as in Production Example 3, except that the colorant was changed to the chloroethodese decachlorosubphthalocyanine boron complex obtained in Production Example 4. A color filter composition was prepared in the same manner as in Example 1 except that this dispersion was used. With respect to this composition, a model color filter was produced in the same manner as in Example 1, and the spectral transmittance, chromaticity, and brightness were measured.
[0060] 実施例 3 [0060] Example 3
ビスフエノールフルオレン骨格を有するエポキシアタリレート榭脂のプロピレングリコ ールモノメチルエーテルアセテート溶液を、メタクリル酸 Zベンジルメタタリレート共重 合体のプロピレングリコールモノメチルエーテルアセテート溶液（メタクリル酸：ベンジ ルメタクリレー卜（モル比率） =0. 28 : 0. 72、 Mw31000、酸価 104)に変更した以外 は実施例 1と同様にしてカラーフィルター用組成物を作製した。この組成物について 実施例 1と同様な方法にて、モデルカラーフィルターを製作し、分光透過率及び色度 Propylene glycol monomethyl ether acetate solution of epoxy attalate resin having bisphenol fluorene skeleton is mixed with propylene glycol monomethyl ether acetate solution of methacrylic acid Zbenzyl methacrylate copolymer (methacrylic acid: benzyl methacrylate) (molar ratio) A composition for a color filter was prepared in the same manner as in Example 1 except that the value was changed to = 0.28: 0.72, Mw31000, acid value 104). For this composition, a model color filter was produced in the same manner as in Example 1, and the spectral transmittance and chromaticity were
、明度を測定した。 The brightness was measured.
[0061] 比較例 1 着色材をビグメント 'バイオレット 23に変更した以外は製造例 3と同様な方法にて分 散液を得た。この分散液を使用した以外は、実施例 1と同様にしてカラーフィルター 用組成物を作製した。この組成物について実施例 1と同様な方法にて、モデルカラ 一フィルターを製作し、分光透過率及び色度、明度を測定した。 [0061] Comparative Example 1 A dispersion was obtained in the same manner as in Production Example 3, except that the colorant was changed to pigment 'violet 23'. A color filter composition was prepared in the same manner as in Example 1 except that this dispersion was used. For this composition, a model color filter was produced in the same manner as in Example 1, and the spectral transmittance, chromaticity, and brightness were measured.
[0062] 比較例 2  [0062] Comparative Example 2
着色材を下式（7)で示されるクロ口-サブフタロシアニン硼素錯体顔料に変更した以 外は製造例 3と同様な方法にて分散液を得た。この分散液を使用した以外は、実施 例 1と同様にしてカラーフィルター用組成物を作製した。この組成物にっ 、て実施例 1と同様な方法にて、モデルカラーフィルターを製作し、分光透過率及び色度、明度 を測定した。  A dispersion was obtained in the same manner as in Production Example 3, except that the colorant was changed to a black mouth-subphthalocyanine boron complex pigment represented by the following formula (7). A color filter composition was prepared in the same manner as in Example 1 except that this dispersion was used. With this composition, a model color filter was produced in the same manner as in Example 1, and the spectral transmittance, chromaticity, and brightness were measured.
[0063]  [0063]
Figure imgf000020_0001
Figure imgf000020_0001
[0064] 図 1及び表 1に各実施例及び比較例で得られたモデルカラーフィルターについて、 分光透過率及び色度、明度を測定した結果を示す。 FIG. 1 and Table 1 show the results of measuring the spectral transmittance, chromaticity, and brightness of the model color filters obtained in the examples and comparative examples.
[0065] 本発明のカラーフィルター用組成物から成るモデルカラーフィルタ一は、三波長型 蛍光ランプの青の発光を効果的に透過し、赤及び緑の発光を効果的に遮光すること ができる高明度、高彩度を有するものであった。表 1からも明らかなように、青く（X値 力 S小さく）且つ大幅に明度が向上 (Y値が増大)している。また、その硬化膜は、膜厚 均一で凝集析出物等のな 、塗布性良好なものであった。  [0065] The model color filter comprising the color filter composition of the present invention can effectively transmit the blue light emission of the three-wavelength fluorescent lamp, and can effectively block the red and green light emission. And had high saturation. As is clear from Table 1, the color is blue (X value force S is small) and the brightness is greatly improved (Y value is increased). Further, the cured film had a uniform film thickness and good coatability without aggregated precipitates.
[0066] [表 1] X y Y 実施例 1 0. 148 0. 052 4. 4 [0066] [Table 1] X y Y Example 1 0. 148 0. 052 4.4
実施例 2 0. 151 0. 052 4. 4  Example 2 0. 151 0. 052 4. 4
実施例 3 0. 148 0. 052 4. 2  Example 3 0. 148 0. 052 4.2
比較例 1 0. 183 0. 052 3. 3  Comparative Example 1 0. 183 0. 052 3.3
比較例 2 0. 202 0. 052 3. 4 産業上の利用可能性  Comparative Example 2 0. 202 0. 052 3.4 Industrial Applicability
本発明におけるカラーフィルター用組成物は、耐熱性に優れ、高明度、高彩度を有 するため、高品位の液晶ディスプレイ等の製造を可能にする点できわめて有用であ る。  The color filter composition of the present invention has excellent heat resistance, high brightness, and high saturation, so that it is extremely useful in terms of enabling production of a high-quality liquid crystal display or the like.

Claims

請求の範囲 The scope of the claims
[1] (A)感光性樹脂及び Z又は単量体、 (B)着色材、 (C)溶剤及び (D)光重合開始剤 を含有して成るカラーフィルター用組成物にぉ 、て、着色材成分として下記 OLE丄 IN K1一般式（1)で示されるサブフタロシア-ンィ匕合物からなる顔料 OLE丄 INK1を全着 色材中 0. 5重量％以上含有し、前記組成物中の (B)着色材と榭脂固形分 (R)との重 量比で表される（B)Z(R)が 0. 05〜： L 5の範囲であることを特徴とするカラーフィル ター用組成物。  [1] A color filter composition containing (A) a photosensitive resin and Z or monomer, (B) a coloring material, (C) a solvent, and (D) a photopolymerization initiator, and then colored. As a material component, a pigment OLE 丄 INK1 comprising a subphthalocyanine compound represented by the following general formula (1) is contained in an amount of 0.5% by weight or more in all the coloring materials, (B) For color filters characterized by the fact that (B) Z (R), expressed as the weight ratio of the colorant to the solid content of resin (R), is in the range of 0.05 to L5. Composition.
Figure imgf000022_0001
Figure imgf000022_0001
但し、 X〜X は水素原子又はハロゲン原子を示し、 Yは置換基を有してもよいアルWhere X to X represent a hydrogen atom or a halogen atom, and Y represents an alkyl which may have a substituent.
1 12 1 12
キル基、ァリール基、アルコキシ基又はァリールォキシ基を示す。  A kill group, an aryl group, an alkoxy group or an aryloxy group;
[2] 一般式（1)で表されるサブフタロシア-ンィ匕合物において、 X〜X の少なくとも 6個 [2] In the subphthalocyanine compound represented by the general formula (1), at least 6 of X to X
1 12  1 12
がハロゲン原子である請求項 1記載のカラーフィルター用組成物。  2. The color filter composition according to claim 1, wherein is a halogen atom.
[3] 一般式（1)で表されるサブフタロシアニン化合物において、 X〜X のすべてがハロ [3] In the subphthalocyanine compound represented by the general formula (1), all of X to X are halo.
1 12  1 12
ゲン原子である請求項 1記載のカラーフィルター用組成物。  2. The color filter composition according to claim 1, wherein the color filter composition is a gen atom.
[4] 更に、分散剤として、（a)ポリ（低級アルキレンィミン)及び (b)ポリアリルアミンカもな る群力も選ばれる少なくとも 1種の含窒素化合物に、（i)ポリエステル、（ii)ポリアミド及 び (iii)ポリエステルアミド力 成る群力 選ばれる少なくとも 1種の遊離のカルボキシ ル基を有する化合物を反応させて得られるグラフトポリマーを含有する請求項 1〜3 の、、ずれかに記載のカラーフィルター用組成物。 [4] Further, as a dispersant, (a) a poly (lower alkyleneimine) and (b) at least one nitrogen-containing compound that also has a polyallylamine group power is selected, (i) a polyester, (ii) Polyamide and (iii) Polyester amide force Group force comprising a graft polymer obtained by reacting at least one selected compound having a free carboxyl group. The composition for a color filter according to any one of the above.
[5] (A)感光性榭脂及び Z又は単量体が、フルオレン骨格を有するエポキシアタリレー トからなる請求項 1〜4のいずれかに記載のカラーフィルター用組成物。 [5] The composition for a color filter according to any one of [1] to [4], wherein (A) the photosensitive resin and Z or the monomer comprises an epoxy atalate having a fluorene skeleton.
[6] 請求項 1〜5の 、ずれかに記載のカラーフィルター用組成物を硬化して得られる硬 化物。 [6] A cured product obtained by curing the color filter composition according to any one of claims 1 to 5.
[7] 青色画素を形成する硬化膜が請求項 6記載の硬化物からなるカラーフィルター。  [7] The color filter comprising the cured product according to [6], wherein the cured film forming a blue pixel.
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