JP2011102833A - Green photosensitive colored composition for color filter, and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a green photosensitive colored composition in which a light stabilizer is thoroughly dissolved and which suppresses aggregation of pigments and ensures superior stability of a dispersion, even when it is a green photosensitive colored composition for a color filter in which a green pigment and a yellow pigment are mixed. <P>SOLUTION: The green photosensitive colored composition includes: a transparent resin; a pigment carrier; a color material; a photopolymerization initiator; an ethylenically unsaturated monomer; and an organic solvent, wherein the color material is made of a mixture of a green pigment and a yellow pigment, wherein the green pigment is at least one selected from C.I. Pigment Green 7, 36 and 58 and the yellow pigment is at least one selected from C.I. Pigment Yellow 138, 139 and 150. The green photosensitive colored composition also includes a light stabilizer of a hindered amine compound having a molecular weight of 450-1,000 in a range of 0.1-20 mass% in the total solid content of the composition. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a coloring composition for a color filter, a color filter, and a liquid crystal display device used for producing a color filter used for a color liquid crystal display device, a color image pickup tube element, and the like.

  In the liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the amount of light passing through the first polarizing plate by controlling the degree of polarization of light passing through the first polarizing plate. Is a display device that performs display. A liquid crystal display device is capable of color display by providing a color filter between two polarizing plates, and has recently been used in televisions, personal computer monitors, and the like. There is an increasing demand for contrast.

  A color filter has two or more kinds of fine band (striped) filter segments arranged in parallel or intersecting with each other on the surface of a transparent substrate such as glass, or the fine filter segments are arranged in a fixed arrangement. It is made up of arranged ones. The filter segments are as fine as several μm to several hundreds of μm, and are regularly arranged in a predetermined arrangement for each hue.

  Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Yes. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to form them generally at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher. For this reason, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used.

  However, in general, a color filter in which a pigment is dispersed has a problem that the degree of polarization controlled by the liquid crystal is disturbed due to light scattering by the pigment. That is, since light leaks when light must be blocked (OFF state) or transmitted light attenuates when light must be transmitted (ON state), display devices in the ON state and the OFF state There is a problem that the upper luminance ratio (contrast ratio) is low.

The filter segment is formed using a color resist coating solution in which an initiator or an ethylenically unsaturated monomer is blended in the pigment dispersion. In order to achieve high brightness and high contrast of the color filter, first, the pigment contained in the filter segment is refined, and the refined pigment is stably put into a pigment carrier containing a resin or the like. It is necessary to prepare a dispersed dispersion. For example, Patent Document 1 discloses that yellow or / and orange organic pigments having an average primary particle diameter of 0.05 μm or less measured with an electron microscope have an average particle diameter of 0.08 to 0.3 μm measured by a photon correlation method. The coloring composition for color filters formed by dispersing in a transparent resin is disclosed. Patent Document 2 discloses a transparent resin, a pigment carrier, a blue pigment having a specific surface area of 90 to 140 m ² / g, a specific surface area larger than that of the blue pigment, and a specific surface area of 100 to 150 m ² / g. The coloring composition for color filters containing the purple pigment which is is disclosed.

However, if the finely divided pigment is strongly aggregated and cannot be dispersed completely, the brightness and contrast ratio of the color filter are decreased by going through the pigment finer process. Also, when the dispersion stability is low, the aggregation of pigment particles progresses over time, causing the viscosity of the colored composition to increase and poor fluidity. When forming a filter segment, the coating liquid is spin-coated on a glass substrate. A coating film having a uniform film thickness cannot be obtained due to poor spin coatability and leveling failure. In order to stabilize dispersions using such fine pigments, dispersion formulation optimization using pigment derivatives and resin-type dispersants has been carried out, and pigment derivatives, resin-type dispersants and binder resins have also been improved. I have been. For example, Patent Document 3 discloses a transparent copolymer obtained by copolymerizing a compound such as phenol ethylene oxide-modified (meth) acrylate and a compound having an ethylenically unsaturated double bond such as other (meth) acrylic acid. A technique is disclosed that exhibits an excellent dispersion effect for almost all pigments by using a resin as a pigment carrier.

  In recent years, liquid crystal display devices have been applied in TV monitor applications, personal computer monitor applications, mobile applications, and the like, and the level of demand for various characteristics is increasing for color filters used there. In particular, since color filters are used for a long period of time, there is a strong demand for quality such as heat resistance and light resistance.

  By the way, by using the above-described fine pigment, the stability such as light resistance is likely to deteriorate due to the increase in the surface area. In particular, light resistance may deteriorate in the green filter segment of the color filter. It has been known so far that the light resistance is deteriorated by a phthalocyanine complex dye and / or a phthalocyanine complex pigment. For example, in Patent Document 4, studies are made to contain nitrosonaphthols and benzophenones and / or bind them to side chains.

  In addition, studies have been made to add a light stabilizer as an improvement in light resistance of the color filter. For example, Patent Document 5 discusses the addition of compounds such as phosphites, benzotriazoles, benzophenones, hindered amines, salicylic acid esters, triazines, hindered phenols, and thioethers as light stabilizers. Has been made.

JP-A-10-130547 JP 2005-181383 A JP 2008-52239 A Japanese Patent No. 2661135 JP 2000-214580 A

However, the light resistance improvement in the green filter segment so far has not been sufficiently effective. In particular, the present inventors have confirmed that the light resistance deteriorates when a green pigment and a yellow pigment are mixed. In the examination so far, although a light stabilizer was added to the green dye to study the light resistance improvement, the light resistance of the mixed system of the green dye and the yellow dye has not been improved. In addition, there are problems that the addition of a light stabilizer does not sufficiently dissolve in the green photosensitive composition, and pigment aggregation occurs. Therefore, in the present invention, even in a green photosensitive coloring composition in which a green pigment and a yellow pigment are mixed, the light stabilizer is sufficiently dissolved in the photosensitive composition, thereby suppressing the aggregation of the pigment and improving the stability of the dispersion. It is an object to provide an excellent green photosensitive coloring composition and to provide a color filter having excellent light resistance using the same.

  As a result of extensive research by the inventor, the hindered amine compound having a specific molecular weight as a light stabilizer is in a specific addition amount range, thereby improving the light resistance in a green filter segment using a green pigment and a yellow pigment. As a result, the present invention has been found.

The invention according to claim 1 of the present invention is a green photosensitive coloring composition containing a transparent resin, a dye carrier, a coloring material, a photopolymerization initiator, an ethylenically unsaturated monomer, and an organic solvent.
The color material comprises a mixture of a green pigment and a yellow pigment, and the green pigment is C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 58, and the yellow pigment is C.I. I. A green photosensitive coloring composition which is at least one selected from Pigment Yellow 138, 139, 150,
And the light stabilizer of the hindered amine compound whose molecular weight is the range of 450-1000 is contained in the range of 0.1 mass%-20 mass% in the total solid of the said green photosensitive coloring composition, It is characterized by the above-mentioned. Is a green photosensitive coloring composition.

  The invention according to claim 2 of the present invention is a color filter comprising a green filter segment formed from the green photosensitive coloring composition according to claim 1.

  As described above, the green photosensitive coloring composition for a color filter of the present invention uses a green pigment and a yellow pigment by setting a hindered amine compound having a specific molecular weight as a light stabilizer in a specific addition amount range. A color fill with improved lightfastness in the green filter segment can be provided.

  Details of the present invention will be described below. These are examples of embodiments, and the present invention is not limited to these contents.

  A first embodiment of the present invention is a green photosensitive coloring composition containing a transparent resin, a dye carrier, a coloring material, a photopolymerization initiator, an ethylenically unsaturated monomer, and an organic solvent, wherein the coloring material is green It consists of a mixture of a pigment and a yellow pigment, and the green pigment is C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 58, and the yellow pigment is C.I. I. A green photosensitive coloring composition which is at least one selected from Pigment Yellow 138, 139 and 150, and the green photosensitive coloring composition is a light-stabilized hindered amine compound having a molecular weight in the range of 450 to 1000 It is a green photosensitive coloring composition characterized by containing an agent in 0.1 mass%-20 mass% in the total solid of a green photosensitive coloring composition. Moreover, the 2nd embodiment of this invention is a color filter provided with the green filter segment by the green photosensitive coloring composition which concerns on this invention.

As the addition amount of the hindered amine compound according to the present invention, the range of 0.1% by mass to 20% by mass in the total solid content of the green photosensitive coloring composition is optimal, and more preferably 0.5% by mass to The range of 10% by mass is good. If it is less than 0.1% by mass, a sufficient light resistance improvement effect cannot be achieved. If it exceeds 20% by mass, the brightness of the green filter segment may be reduced,
When the pattern is formed, the exposure sensitivity is lowered, and when dissolved in the green photosensitive coloring composition, problems such as precipitation occur.

  The molecular weight of the hindered amine compound according to the present invention is optimally in the range of 450 to 1000. If it is less than 450, heat resistance is inadequate and the effect of light resistance improvement cannot fully be exhibited. Moreover, when molecular weight exceeds 1000, when it dissolves in a green photosensitive coloring composition, precipitation will arise and a foreign material will generate | occur | produce. Furthermore, the hindered amine compound is colored by increasing the molecular weight, thereby causing a decrease in the brightness of the green filter segment. Even when the amount of the hindered amine compound added is too large, foreign matter is likely to be generated, and it is necessary to set the optimal molecular weight and amount.

  Examples of the hindered amine compound include a hindered amine compound having no hindered phenol skeleton and a hindered amine compound having a hindered phenol skeleton.

  As a commercial item of the hindered amine compound which does not have the said hindered phenol skeleton, Sanol LS-770 (made by Daiichi Sankyo Co., Ltd.), Adeka tab LA-57, Adeka tab LA-62, Adeka tab LA-63P, Adeka tab LA-67, ADK STAB LA-68LD, ADK STAB LA-77Y, ADK STAB LA-77G, ADK STAB LA-82, ADK STAB LA-87 (all manufactured by ADEKA), Sumisorb-577 (manufactured by Sumitomo Chemical), Viosorb-03, Viosorb-04 ( All are manufactured by Kyodo Yakuhin Co., Ltd.), Chimassorb 944LD (manufactured by Ciba Specialty Chemicals), Tinuvin-622LD (manufactured by Ciba Specialty Chemicals), and Goodrite UV-3034 (Good) and the hindered amine compound having a hindered phenol skeleton includes Tinuvin-144 (manufactured by Ciba Specialty Chemicals). This is an example of the hindered amine compound of the present invention, and is not limited to the above compounds.

  As the green coloring matter of the present invention, organic pigments or inorganic pigments can be used alone or in admixture of two or more. Among pigments, pigments having high color developability and high heat resistance, particularly pigments having high heat decomposition resistance are preferable, and organic pigments are usually used.

  Organic pigments that can be used as green pigments are listed by color index numbers. I. Pigment Green 7, 36, 58. At least one selected from Pigment Green 7, 36, 58.

  Organic pigments that can be used as yellow pigments are listed by color index numbers. I. Pigment Yellow 138, 139, 150. At least one selected from Pigment Yellow 138, 139, 150.

  Spectral characteristics of a general green color filter can be defined by x = 0.24 to 0.30, y = 0.60 (C light source), and 10 to 70 parts by mass of a yellow dye with respect to 100 parts by mass of a green dye. It is preferable to use it. When there are few yellow pigment | dyes, light resistance is also favorable and the deterioration of light resistance has been confirmed by the pigment ratio of a green pigment | dye and a yellow pigment | dye.

  Moreover, there exists a tendency for light resistance to improve most in the range whose total density | concentration of a green pigment | dye and a yellow pigment | dye is 20 mass%-50 mass% with respect to solid content in a green photosensitive coloring composition. If it is less than 20% by mass, a sufficient hue cannot be obtained, and in order to obtain a sufficient hue, there is a problem that the film thickness to be formed becomes thick. Further, when a transparent conductive film is formed on the patterned filter segment, there is a problem that wrinkles are generated on the pattern surface. On the other hand, when the dye concentration exceeds 50% by mass, the exposure sensitivity for patterning the photosensitive composition in producing a color filter is lowered, and the production cost is increased.

  The dye carrier contained in the coloring composition of the present invention is for dispersing a dye and is composed of a transparent resin, a precursor thereof, or a mixture thereof. The transparent resin is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. The transparent resin includes a thermoplastic resin, a thermosetting resin, and a photosensitive resin, and its precursor includes a monomer or an oligomer that is cured by heating or the like to form a transparent resin. Or a mixture of two or more. A pigment | dye carrier can be contained in the quantity of 20-900 mass parts with respect to a total of 100 mass parts of a green pigment | dye and a yellow pigment | dye.

  Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. And acrylic resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polybutadiene, polyethylene, polypropylene, polyimide resins, and the like. Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  Examples of the photosensitive resin include (meth) acrylic compounds having a reactive substituent such as an isocyanate group, an aldehyde group, and an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group, A resin obtained by reacting an acid and introducing a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the linear polymer is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

  Monomers and oligomers that are precursors of transparent resins include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) ) Acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, melamine (meth) acrylate, various acrylic esters such as epoxy (meth) acrylate and methacrylic acid Examples thereof include esters, (meth) acrylic acid, styrene, vinyl acetate, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, acrylonitrile and the like.

  In the coloring composition of the present invention, when the coating film is cured by ultraviolet rays, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2 -Hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate , Tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate Bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, methylolated melamine (meth) Various acrylic esters and methacrylic esters such as acrylic ester, epoxy (meth) acrylate, urethane acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth ) Acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like are used. These can be used alone or in admixture of two or more.

  As for content of a monomer and an oligomer, 10-300 mass parts is preferable with respect to a total of 100 mass parts of a green pigment and a yellow pigment, respectively, More preferably, it is 10-200 mass parts.

  When the coating film is cured by ultraviolet rays, a photopolymerization initiator may be added to the colored composition of the present invention. Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Acetophenone compounds such as hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl Benzoin compounds such as dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4 Benzophenone-based compounds such as methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4- Thioxanthone compounds such as diisopropylthioxanthone and 2,4-diethylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p- Methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis ( Trichloromethyl) -s-triazine, 2,4-bis (tri (Loromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)], O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′- Oxime ester compounds such as methoxy-naphthyl) ethylidene) hydroxylamine, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6 -Phosphine compounds such as trimethylbenzoyldiphenylphosphine oxide, quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, borate compounds, carbazole compounds, imidazole compounds, titanocene compounds, etc. It is done. These photopolymerization initiators can be used alone or in combination. A photoinitiator can be contained in the quantity of 0-200 mass parts with respect to a total of 100 mass parts of a green pigment | dye and a yellow pigment | dye.

  The above photopolymerization initiators can be used alone or in combination of two or more. As sensitizers, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10- Phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-diethylaminobenzophenone These compounds can also be used in combination. The sensitizer can be contained in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the photopolymerization initiator.

  In the coloring composition of the present invention, a green dye and a yellow dye, together with the photopolymerization initiator as necessary, in a dye carrier and a solvent, various types such as a three roll mill, a two roll mill, a sand mill, a kneader, and an attritor It can be produced by finely dispersing using a dispersing means. The colored composition of the present invention can also be produced by mixing a green pigment and a yellow pigment separately finely dispersed in a pigment carrier and a solvent. When the pigment is dispersed in the pigment carrier and the solvent as a pigment, a dispersion aid such as a resin-type pigment dispersant, a surfactant, or a pigment derivative can be appropriately contained. Since the dispersion aid is excellent in pigment dispersion and has a great effect of preventing re-aggregation of the pigment after dispersion, a coloring composition formed by dispersing the pigment in a dye carrier and a solvent using the dispersion aid is used. Thus, a coating film having more excellent transparency can be obtained. The dispersion aid can be contained in an amount of 0.1 to 100 parts by mass with respect to 100 parts by mass in total of the green pigment and the yellow pigment.

  The resin-type pigment dispersant has a pigment affinity part that has the property of adsorbing to the pigment and a part that is compatible with the dye carrier, and acts to stabilize the dispersion of the pigment on the dye carrier by adsorbing to the pigment. It is something to do. Specific examples of resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and the like Water-based dispersants such as oily dispersants such as salts, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based, and the like. These may be used alone or in admixture of two or more.

  Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines. These can be used alone or in admixture of two or more.

  As the pigment derivative, those close to the hue of the pigment to be used are preferable, but those having different hues may be used if the addition amount is small. The pigment derivative is a compound in which a substituent is introduced into an organic pigment, and the organic dye includes light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone which are not generally called dyes. Examples of the pigment derivative are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. These can be used alone or in combination of two or more.

  The colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Examples thereof include phosphine and phosphite. The storage stabilizer can be contained in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass in total of the green pigment and the yellow pigment.

  In addition, the coloring composition of the present invention may contain an adhesion improving agent such as a silane coupling agent in order to improve the adhesion to the substrate. Examples of the silane coupling agent include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β ( Aminoethyl) γ-aminopro Lutriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N Examples include aminosilanes such as -phenyl-γ-aminopropyltriethoxysilane, thiosilanes such as γ-mercaptopropyltrimethoxysilane, and γ-mercaptopropyltriethoxysilane. The silane coupling agent can be contained in an amount of 0 to 10 parts by mass with respect to 100 parts by mass in total of the green pigment and the yellow pigment.

  In addition, the coloring composition contains a solvent in order to make it easy to form a filter segment by applying a dry film thickness of 1 to 2.5 μm on a transparent substrate such as a glass substrate. Can do. Examples of the organic solvent contained in the coloring composition of the present invention include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, and dipropylene. Glycol monomethyl ether, dipropylene glycol mono nbutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mono nbutyl ether, methyl-n amyl ketone, propylene glycol monomethyl ether, toluene, methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, Isobutyl ketone, petroleum solvent, etc. They may be mixed and used these solvents. An organic solvent can be used in the quantity of 100-4000 mass parts with respect to a total of 100 mass parts of a green pigment | dye and a yellow pigment | dye.

  The amount of the solid content of the colored composition of the present invention is preferably 20 to 40% by mass. It is preferable that a pigment | dye is contained in the ratio of 20-50 mass% on the basis (100 mass%) of the total solid content of a coloring composition. More preferably, it is contained in a proportion of 25 to 45% by mass. The colored composition is removed by means of centrifugal separation, sintering filter, membrane filter, etc. to remove coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles It is preferable to carry out.

Each color filter segment of the color filter according to the present invention can be formed on a transparent substrate or a reflective substrate by a printing method or a photolithography method. As the transparent substrate, a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass whose surface is coated with silica, or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is used. As the reflective substrate, silicon or a substrate obtained by forming an aluminum, silver, silver / copper / palladium alloy thin film on the transparent substrate is used.

  When forming each color filter segment by a photolithography method, the colored composition prepared as a solvent developing type or alkali developing type colored resist material is applied to a transparent substrate such as spray coating, spin coating, slit coating, roll coating, etc. It is applied by a coating method so that the dry film thickness is 0.2 to 5 μm, preferably 1 to 2.5 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or an alkaline developer, or spraying the developer with a spray or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. . Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the printing method can be manufactured.

  In developing the colored composition, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution. In order to increase the UV exposure sensitivity, after coating and drying the colored resist material, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

  Each color filter segment can be manufactured by an electrodeposition method, a transfer method or the like in addition to the above method. The electrodeposition method is a method in which each color filter segment is electrodeposited on a transparent conductive film by electrophoresis of colloidal particles using a transparent conductive film formed on a transparent substrate. The transfer method is a method in which a filter segment layer is formed in advance on the surface of a peelable transfer base sheet, and this filter segment layer is transferred to a desired transparent substrate.

  If a black matrix is formed in advance before forming the filter segment on the transparent substrate or the reflective substrate, the contrast ratio of the liquid crystal display panel can be further increased. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. In addition, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then a filter segment may be formed. By forming the filter segment on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the luminance can be improved.

  On the color filter of the present invention, an overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed as necessary. The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal portion, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by pasting together. Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used for a liquid crystal display mode in which colorization is performed using a color filter.

  Specific examples of the present invention will be described below. In Examples and Comparative Examples, “part” means “part by mass”.

[Adjustment of photosensitive transparent resin]
570 parts of cyclohexanone is placed in a reaction vessel and heated to 80 ° C. while injecting nitrogen gas into the vessel. At the same temperature, 23 parts of methacrylic acid, 23 parts of methyl methacrylate, 35 parts of benzyl methacrylate, and paraffin as monomer (a) are obtained. A mixture of 22 parts of milphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toa Gosei Co., Ltd.), 48 parts of glycerol monomethacrylate and 3 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour for polymerization. Reaction was performed. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, then 1 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A polymer solution was obtained. Next, a mixture of 33 parts of 2-methacryloylethyl isocyanate, 0.4 part of dibutyltin laurate and 130 parts of cyclohexanone was added dropwise to 336 parts of the obtained transparent resin copolymer solution at 70 ° C. over 3 hours. Thus, a photosensitive transparent resin solution was obtained. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and the previously synthesized photosensitive transparent resin solution had a nonvolatile content of 20% by mass. Thus, cyclohexanone was added to prepare a photosensitive resin solution. The obtained transparent resin had a mass average molecular weight of 21,000.

[Adjustment of pigment dispersion resin]
70 parts of cyclohexanone is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and 12.3 parts of benzyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 5.3 parts of methacrylic acid at the same temperature. 2 parts of a mixture of 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toa Gosei Co., Ltd.) and 0.4 part of 2,2′-azobisisobutyronitrile as monomer (a) The polymerization reaction was carried out dropwise over time. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, then 0.2 part of azobisisobutyronitrile dissolved in 10 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A copolymer solution was obtained. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass. Thus, a resin solution used for pigment dispersion was prepared.

  Red, blue and green photosensitive coloring compositions were prepared as follows.

[Red photosensitive coloring composition]
A mixture having the following composition was uniformly stirred and mixed, then dispersed in a sand mill for 5 hours using glass beads having a diameter of 1 mm, and then filtered through a 5 μm filter to prepare a red pigment dispersion.
-Red pigment: C.I. I. Pigment Red 254 9 parts ("Ilgar Forred B-CF" manufactured by Ciba Specialty Chemicals)
-Red pigment: C.I. I. Pigment Red 177 1 part (“Chromophthal Red A2B” manufactured by Ciba Specialty Chemicals)
・ Dispersant (“Ajisper PB821” manufactured by Ajinomoto Fine Techno Co., Ltd.) 2 parts ・ Pigment dispersion resin (solid content 20%) 40 parts ・ Propylene glycol monomethyl ether acetate 48 parts Thereafter, a mixture having the following composition was stirred uniformly. After mixing, the mixture was filtered through a 5 μm filter to obtain a red photosensitive coloring composition.
-57 parts of the above dispersion of red pigment-18.3 parts of the above transparent resin (solid content 20%)-2.8 parts of polyfunctional monomer (DPPAH: dipentaerythritol pentaacrylate hexamethylene diisocyanate)
-Photoinitiator ("Irgacure 907" manufactured by Ciba Japan Co., Ltd.) 0.8 parts-Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd. 0.3 parts)-20.7 parts cyclohexanone [ Blue photosensitive coloring composition]
A mixture having the following composition was uniformly stirred and mixed, then dispersed in a sand mill for 5 hours using glass beads having a diameter of 1 mm, and then filtered through a 5 μm filter to prepare a blue pigment dispersion.
Blue pigment: C.I. I. Pigment Blue 15 9 parts ("Rionol Blue ES" manufactured by Toyo Ink Manufacturing Co., Ltd.)
Purple pigment: C.I. I. 1 part of Pigment Violet 23 ("Pariogen Violet 5890" manufactured by BASF)
-Dispersant ("Sols Birds 20000" manufactured by Zeneca) 2 parts-40 parts of the above dispersion resin (solid content 20%)-48 parts of propylene glycol monomethyl ether acetate Then, the mixture of the following composition was stirred and mixed to be uniform The mixture was filtered through a 5 μm filter to obtain a blue photosensitive coloring composition.
-57 parts of the above blue pigment dispersion-13.1 parts of the above transparent resin (solid content 20%)-3.3 parts of polyfunctional monomer (DPPAH: dipentaerythritol pentaacrylate hexamethylene diisocyanate)
・ Photoinitiator (“Irgacure 907” manufactured by Ciba Japan Co., Ltd.) 1.2 parts ・ Sensitizer (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts ・ Propylene glycol monomethyl ether acetate 25 parts [Green pigment dispersion 1]
A mixture of the following composition is stirred and mixed uniformly, then dispersed in a sand mill for 5 hours using a glass bead having a diameter of 1 mm, and then filtered through a 5 μm filter to produce a green pigment dispersion (green pigment dispersion 1). did.
Green pigment: C.I. I. 14 parts of Pigment Green 36 (“Rionol Green 6YK” manufactured by Toyo Ink Manufacturing Co., Ltd.)
-Dispersant ("Disperbyk-163" manufactured by Big Chemie) 2 parts-20 parts of the above dispersion resin (solid content 20%)-64 parts of propylene glycol monomethyl ether acetate [green pigment dispersion 2]
A mixture of the following composition is uniformly stirred and mixed, then dispersed in a sand mill for 5 hours using a glass bead having a diameter of 1 mm, and then filtered through a 5 μm filter to produce a green pigment dispersion (green pigment dispersion 2). did.
Green pigment: C.I. I. Pigment Green 7 14 parts (“Rionol Green YS-07” manufactured by Toyo Ink Manufacturing Co., Ltd.)
-Dispersant ("Disperbyk-163" manufactured by Big Chemie) 2 parts-20 parts of the above dispersion resin (solid content 20%)-64 parts of propylene glycol monomethyl ether acetate [green pigment dispersion 3]
A mixture of the following composition is uniformly stirred and mixed, then dispersed in a sand mill for 5 hours using a glass bead having a diameter of 1 mm, and then filtered through a 5 μm filter to produce a green pigment dispersion (green pigment dispersion 3). did.
Green pigment: C.I. I. 10 parts of Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC)
-Dispersant ("Disperbyk-161" manufactured by Big Chemie) 6 parts-20 parts of the above dispersion resin (solid content 20%)-64 parts of propylene glycol monomethyl ether acetate [yellow pigment dispersion 1]
A mixture of the following composition is stirred and mixed uniformly, then dispersed in a sand mill for 5 hours using glass beads having a diameter of 1 mm, and then filtered through a 5 μm filter to produce a yellow pigment dispersion (yellow pigment dispersion 1). did.
-Yellow pigment: C.I. I. 10 parts of Pigment Yellow 150 ("Funchon First Yellow Y-5688" manufactured by Bayer)
-Dispersant ("Disperbyk-163" manufactured by Big Chemie) 2 parts-40 parts of the above dispersion resin (solid content 20%)-48 parts of propylene glycol monomethyl ether acetate [yellow pigment dispersion 2]
A mixture of the following composition is uniformly stirred and mixed, then dispersed in a sand mill for 5 hours using glass beads having a diameter of 1 mm, and then filtered through a 5 μm filter to produce a yellow pigment dispersion (yellow pigment dispersion 2). did.
-Yellow pigment: C.I. I. 10 parts of Pigment Yellow 138 ("PALIOTOL YELLOW K0960-HD" manufactured by BASF)
-Dispersant ("Disperbyk-182" manufactured by Big Chemie) 2 parts-40 parts of the above dispersion resin (solid content 20%)-48 parts of propylene glycol monomethyl ether acetate [yellow pigment dispersion 3]
A mixture of the following composition is uniformly stirred and mixed, then dispersed in a sand mill for 5 hours using glass beads having a diameter of 1 mm, and then filtered through a 5 μm filter to produce a yellow pigment dispersion (yellow pigment dispersion 3). did.
-Yellow pigment: C.I. I. 10 parts of Pigment Yellow 139 (manufactured by BASF, “Pariotor Yellow D1819”)
-Dispersant ("Disperbyk-161" manufactured by Big Chemie) 2 parts-40 parts of the above dispersion resin (solid content 20%)-48 parts of propylene glycol monomethyl ether acetate <Examples 1-9>
Using the green pigment dispersions 1 to 3 and the yellow pigment dispersions 1 to 3, respectively, as shown in Table 1, the mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 5 μm filter. And the green photosensitive coloring compositions 1-9 used as Examples 1-9 of this invention were obtained.
Green pigment dispersion 48.9 parts Yellow pigment dispersion 17.1 parts Transparent resin (solid content 20%) 28.8 parts Polyfunctional monomer 2.5 parts (DPPAH: dipentaerythritol pentaacrylate hexamethylene Diisocyanate)
・ Light stabilizer 1 part ("TINUVIN 770DF" manufactured by Ciba Specialty Chemicals)
-Photoinitiator 0.56 parts ("Irgacure 379" manufactured by Ciba Specialty Chemicals)
-Photoinitiator 0.14 parts ("Irgacure OXE-02" manufactured by Ciba Specialty Chemicals)
Propylene glycol monomethyl ether acetate 6.6 parts Propylene glycol monomethyl ether acetate 20.25 parts The molecular weight of the light stabilizer used in the green photosensitive coloring compositions 1 to 9 is 480, and the added amount of the light stabilizer Was 4.3% by mass in the total solid content of the green photosensitive coloring composition. The pigment concentration in the total solid content of the green photosensitive coloring composition is 36.9% by mass for the green photosensitive coloring compositions 1 to 6, and 28.5% by mass for the green photosensitive coloring compositions 7 to 9. there were.

<Examples 10 to 12>
Using the green pigment dispersion 1 and the yellow pigment dispersion 1, as shown in Table 2, after adding light stabilizers having different molecular weights, the mixture having the following composition was stirred and mixed to be uniform, It filtered with a 5 micrometers filter, and obtained the green photosensitive coloring compositions 10-12 which are Examples 10-12 of this invention.

[Green photosensitive coloring composition 10]
Green pigment dispersion 1 48.9 parts Yellow pigment dispersion 1 17.1 parts Transparent resin (solid content 20%) 14.4 parts Polyfunctional monomer 1.3 parts (DPPAH: dipentaerythritol pentaacrylate) Hexamethylene diisocyanate)
-1 part of light stabilizer ("TINUVIN 765" manufactured by Ciba Specialty Chemicals)
-Photoinitiator 0.56 parts ("Irgacure 379" manufactured by Ciba Specialty Chemicals)
-Photoinitiator 0.14 parts ("Irgacure OXE-02" manufactured by Ciba Specialty Chemicals)
-Propylene glycol monomethyl ether acetate 6.6 parts-Propylene glycol monomethyl ether acetate 20.25 parts The molecular weight of the light stabilizer used in the green photosensitive coloring composition 10 is 510, and the addition amount of the light stabilizer is green. It was 5.2 mass% in the total solid of the photosensitive coloring composition. Moreover, in the green photosensitive coloring composition 10, the pigment | dye density | concentration in all the solid content was 44.8 mass%.

[Green photosensitive coloring composition 11]
Green pigment dispersion 1 48.9 parts Yellow pigment dispersion 1 17.1 parts Transparent resin (solid content 20%) 14.4 parts Polyfunctional monomer 1.3 parts (DPPAH: dipentaerythritol pentaacrylate) Hexamethylene diisocyanate)
・ Light stabilizer 1 part (“TINUVIN 114” manufactured by Ciba Specialty Chemicals)
-Photoinitiator 0.56 parts ("Irgacure 379" manufactured by Ciba Specialty Chemicals)
-Photoinitiator 0.14 parts ("Irgacure OXE-02" manufactured by Ciba Specialty Chemicals)
-Propylene glycol monomethyl ether acetate 6.6 parts-Propylene glycol monomethyl ether acetate 20.25 parts The molecular weight of the light stabilizer used in the color photosensitive coloring composition 11 is 690, and the addition amount of the light stabilizer is green. It was 5.2 mass% in the total solid of the photosensitive coloring composition. Moreover, in the green photosensitive coloring composition 11, the pigment | dye density | concentration in all the solid content was 44.8 mass%.

[Green photosensitive coloring composition 12]
Green pigment dispersion 1 48.9 parts Yellow pigment dispersion 1 17.1 parts Transparent resin (solid content 20%) 14.4 parts Polyfunctional monomer 1.3 parts (DPPAH: dipentaerythritol pentaacrylate) Hexamethylene diisocyanate)
・ Light stabilizer 1 part (“TINUVIN 152” manufactured by Ciba Specialty Chemicals)
-Photoinitiator 0.56 parts ("Irgacure 379" manufactured by Ciba Specialty Chemicals)
-Photoinitiator 0.14 parts ("Irgacure OXE-02" manufactured by Ciba Specialty Chemicals)
-Propylene glycol monomethyl ether acetate 6.6 parts-Propylene glycol monomethyl ether acetate 20.25 parts The molecular weight of the light stabilizer used in the green photosensitive coloring composition 12 is 757, and the addition amount of the light stabilizer is green. It was 5.2 mass% in the total solid of the photosensitive coloring composition. Moreover, in the green photosensitive coloring composition 12, the pigment | dye density | concentration in all the solid content was 44.8 mass%.

<Examples 13 and 14>
Using the above-mentioned green pigment dispersion 2 and yellow pigment dispersion 2, as shown in Table 2, the mixture of the following composition was stirred and mixed so as to change the pigment concentration and other formulations, and then a 5 μm filter. The green photosensitive coloring compositions 13 to 14 were obtained as Examples 13 and 14 of the present invention.

[Green photosensitive coloring composition 13]
Green pigment dispersion 2 48.9 parts Yellow pigment dispersion 2 17.1 parts Transparent resin (solid content 20%) 12.4 parts Polyfunctional monomer 1.0 part (DPPAH: dipentaerythritol pentaacrylate) Hexamethylene diisocyanate)
-Light stabilizer 1.7 parts ("TINUVIN 770DF" manufactured by Ciba Specialty Chemicals)
-Photoinitiator 0.56 parts ("Irgacure 379" manufactured by Ciba Specialty Chemicals)
-Photoinitiator 0.14 parts ("Irgacure OXE-02" manufactured by Ciba Specialty Chemicals)
-Propylene glycol monomethyl ether acetate 6.6 parts-Propylene glycol monomethyl ether acetate 20.25 parts The molecular weight of the light stabilizer used in the green photosensitive coloring composition 13 is 480, and the addition amount of the light stabilizer is green. It was 3.9 mass% in the total solid of the photosensitive coloring composition. Moreover, the pigment | dye density | concentration in all the solid content was 25.3 mass%.

[Green photosensitive coloring composition 14]
Green pigment dispersion 2 56.2 parts Yellow pigment dispersion 2 32.2 parts Transparent resin (solid content 20%) 11.3 parts Polyfunctional monomer 1.02 parts (DPPAH: dipentaerythritol pentaacrylate) Hexamethylene diisocyanate)
-0.7 parts of light stabilizer ("TINUVIN 770DF" manufactured by Ciba Specialty Chemicals)
・ Photoinitiator 0.65 parts ("Irgacure 379" manufactured by Ciba Specialty Chemicals)
-Photoinitiator 0.15 parts ("Irgacure OXE-02" manufactured by Ciba Specialty Chemicals)
-Propylene glycol monomethyl ether acetate 6.6 parts-Propylene glycol monomethyl ether acetate 20.25 parts The molecular weight of the light stabilizer used in the green photosensitive coloring composition 14 is 480, and the addition amount of the light stabilizer is green. It was 3.1 mass% in the total solid of a photosensitive coloring composition. Moreover, the pigment concentration in the total solid content was 49.4% by mass.

<Examples 15 and 16>
Using the green pigment dispersion 1 and the yellow pigment dispersion 1, as shown in Table 2, the composition of the light stabilizer was greatly changed, and a mixture having the following composition was stirred and mixed so as to be uniform. The green photosensitive coloring composition 15-16 as an Example of this invention was obtained by filtering with a filter.

[Green photosensitive coloring composition 15]
Green pigment dispersion 1 48.9 parts Yellow pigment dispersion 1 17.1 parts Transparent resin (solid content 20%) 28.8 parts Polyfunctional monomer 2.5 parts (DPPAH: dipentaerythritol pentaacrylate) Hexamethylene diisocyanate)
-Light stabilizer 0.02 part ("TINUVIN 770DF" manufactured by Ciba Specialty Chemicals)
-Photoinitiator 0.56 parts ("Irgacure 379" manufactured by Ciba Specialty Chemicals)
-Photoinitiator 0.14 parts ("Irgacure OXE-02" manufactured by Ciba Specialty Chemicals)
-Propylene glycol monomethyl ether acetate 6.6 parts-Propylene glycol monomethyl ether acetate 20.25 parts The molecular weight of the light stabilizer used in the green photosensitive coloring composition 15 is 480, and the addition amount of the light stabilizer is green. It was 0.1 mass% in the total solid of a photosensitive coloring composition. The pigment concentration in the total solid content was 38.6% by mass.

[Green photosensitive coloring composition 16]
Green pigment dispersion 1 48.9 parts Yellow pigment dispersion 1 17.1 parts Transparent resin (solid content 20%) 28.8 parts Polyfunctional monomer 2.5 parts (DPPAH: dipentaerythritol pentaacrylate) Hexamethylene diisocyanate)
・ 5.2 parts of light stabilizer (“TINUVIN 770DF” manufactured by Ciba Specialty Chemicals)
-Photoinitiator 0.56 parts ("Irgacure 379" manufactured by Ciba Specialty Chemicals)
-Photoinitiator 0.14 parts ("Irgacure OXE-02" manufactured by Ciba Specialty Chemicals)
-Propylene glycol monomethyl ether acetate 6.6 parts-Propylene glycol monomethyl ether acetate 20.25 parts The molecular weight of the light stabilizer used in the green photosensitive coloring composition 16 is 480, and the addition amount of the light stabilizer is green. It was 19 mass% in the total solid of the photosensitive coloring composition. Moreover, the pigment | dye density | concentration in all the solid content was 31.3 mass%.

<Comparative Examples 1-4>
Using the green pigment dispersion 1 and the yellow pigment dispersion 1, as shown in Table 3, a mixture having the following composition to which light stabilizers having different molecular weights were added was stirred and mixed so as to be uniform. It filtered with the filter and obtained the green photosensitive coloring compositions 17-20 used as Comparative Examples 1-4.

[Green photosensitive coloring composition 17]
Green pigment dispersion 1 48.9 parts Yellow pigment dispersion 1 17.1 parts Transparent resin (solid content 20%) 28.8 parts Polyfunctional monomer 2.5 parts (DPPAH: dipentaerythritol pentaacrylate) Hexamethylene diisocyanate)
・ Light stabilizer 1 part (Ciba Specialty Chemicals "CHIMASSORB 944 LD") Photoinitiator 0.56 parts (Ciba Specialty Chemicals "Irgacure 379")
-Photoinitiator 0.14 parts ("Irgacure OXE-02" manufactured by Ciba Specialty Chemicals)
Propylene glycol monomethyl ether acetate 6.6 parts Propylene glycol monomethyl ether acetate 20.25 parts The molecular weight of the light stabilizer used in the green photosensitive coloring composition 17 is 2100 to 3000, and the addition amount of the light stabilizer Was 4.3% by mass in the total solid content of the green photosensitive coloring composition. Moreover, the pigment concentration in the total solid content was 36.9% by mass.

[Green photosensitive coloring composition 18]
Green pigment dispersion 1 48.9 parts Yellow pigment dispersion 1 17.1 parts Transparent resin (solid content 20%) 28.8 parts Polyfunctional monomer 2.5 parts (DPPAH: dipentaerythritol pentaacrylate) Hexamethylene diisocyanate)
・ Light stabilizer 1 part ("TINUVIN 622 LD" manufactured by Ciba Specialty Chemicals)
-Photoinitiator 0.56 parts ("Irgacure 379" manufactured by Ciba Specialty Chemicals)
-Photoinitiator 0.14 parts ("Irgacure OXE-02" manufactured by Ciba Specialty Chemicals)
-Propylene glycol monomethyl ether acetate 6.6 parts-Propylene glycol monomethyl ether acetate 20.25 parts The molecular weight of the light stabilizer used in the green photosensitive coloring composition 18 is 3100-4000, and the addition amount of the light stabilizer Was 4.3% by mass in the total solid content of the green photosensitive coloring composition. Moreover, the pigment concentration in the total solid content was 36.9% by mass.

[Green photosensitive coloring composition 19]
Green pigment dispersion 1 48.9 parts Yellow pigment dispersion 1 17.1 parts Transparent resin (solid content 20%) 28.8 parts Polyfunctional monomer 2.5 parts (DPPAH: dipentaerythritol pentaacrylate) Hexamethylene diisocyanate)
-1 part of light stabilizer ("Ciasorb UV-3529" manufactured by Sun Chemical Co., Ltd.)
-Photoinitiator 0.56 parts ("Irgacure 379" manufactured by Ciba Specialty Chemicals)
-Photoinitiator 0.14 parts ("Irgacure OXE-02" manufactured by Ciba Specialty Chemicals)
-Propylene glycol monomethyl ether acetate 6.6 parts-Propylene glycol monomethyl ether acetate 20.25 parts The molecular weight of the light stabilizer used in the green photosensitive coloring composition 19 is 1700, and the addition amount of the light stabilizer is green. It was 4.3 mass% in the total solid of the photosensitive coloring composition. Moreover, the pigment concentration in the total solid content was 36.9% by mass.

[Green photosensitive coloring composition 20]
Green pigment dispersion 1 48.9 parts Yellow pigment dispersion 1 17.1 parts Transparent resin (solid content 20%) 28.8 parts Polyfunctional monomer 2.5 parts (DPPAH: dipentaerythritol pentaacrylate) Hexamethylene diisocyanate)
-1 part of light stabilizer ("Ciasorb UV-3853" manufactured by Sun Chemical Co., Ltd.)
-Photoinitiator 0.56 parts ("Irgacure 379" manufactured by Ciba Specialty Chemicals)
-Photoinitiator 0.14 parts ("Irgacure OXE-02" manufactured by Ciba Specialty Chemicals)
-Propylene glycol monomethyl ether acetate 6.6 parts-Propylene glycol monomethyl ether acetate 20.25 parts The molecular weight of the light stabilizer used in the green photosensitive coloring composition 20 is 419, and the addition amount of the light stabilizer is green. It was 4.3 mass% in the total solid of the photosensitive coloring composition. Moreover, the pigment concentration in the total solid content was 36.9% by mass.

<Comparative Examples 5, 6, 7><Example17>
As shown in Table 3, using the green pigment dispersion 1 and the yellow pigment dispersion 1, those without the addition of the light stabilizer, those with a large amount of the light stabilizer added, and the light stability as a contrast A mixture of the following composition was added with a normalizing agent, stirred and mixed so as to be uniform, and then filtered through a 5 μm filter to give green photosensitive coloring as Comparative Examples 5, 6, 7 and Example 17. Compositions 21, 22, 23 and 24 were obtained.

[Green photosensitive coloring composition 21]
Green pigment dispersion 1 48.9 parts Yellow pigment dispersion 1 17.1 parts Transparent resin (solid content 20%) 28.8 parts Polyfunctional monomer 3.5 parts (DPPAH: dipentaerythritol pentaacrylate) Hexamethylene diisocyanate)
-Photoinitiator 0.56 parts ("Irgacure 379" manufactured by Ciba Specialty Chemicals)
-Photoinitiator 0.14 parts ("Irgacure OXE-02" manufactured by Ciba Specialty Chemicals)
-Propylene glycol monomethyl ether acetate 6.6 parts-Propylene glycol monomethyl ether acetate 20.25 parts Green photosensitive coloring composition 21 has no light stabilizer added, and the dye concentration in the total solid content is 36.9 masses %Met.

[Green photosensitive coloring composition 22]
Green pigment dispersion 1 57.8 parts Yellow pigment dispersion 1 31.7 parts Transparent resin (solid content 20%) 7.2 parts Polyfunctional monomer 0.9 parts (DPPAH: dipentaerythritol pentaacrylate) Hexamethylene diisocyanate)
・ Photoinitiator 0.37 parts ("Irgacure 379" manufactured by Ciba Specialty Chemicals)
-Photoinitiator 0.14 parts ("Irgacure OXE-02" manufactured by Ciba Specialty Chemicals)
-Propylene glycol monomethyl ether acetate 6.0 parts-Propylene glycol monomethyl ether acetate 21.2 parts Green photosensitive coloring composition 22 has no light stabilizer added, and the dye concentration in the total solid content is 53.5 mass %Met.

[Green photosensitive coloring composition 23]
Green pigment dispersion 1 48.9 parts Yellow pigment dispersion 1 17.1 parts Transparent resin (solid content 20%) 20.0 parts Polyfunctional monomer 1.5 parts (DPPAH: dipentaerythritol pentaacrylate) Hexamethylene diisocyanate)
・ 6.5 parts of light stabilizer (“TINUVIN 770DF” manufactured by Ciba Specialty Chemicals)
-Photoinitiator 0.56 parts ("Irgacure 379" manufactured by Ciba Specialty Chemicals)
-Photoinitiator 0.14 parts ("Irgacure OXE-02" manufactured by Ciba Specialty Chemicals)
-Propylene glycol monomethyl ether acetate 6.6 parts-Propylene glycol monomethyl ether acetate 20.25 parts The molecular weight of the light stabilizer used in the green photosensitive coloring composition 23 is 480, and the addition amount of the light stabilizer is green. It was 25.1 mass% in the total solid of the photosensitive coloring composition. Further, the pigment concentration in the total solid content was 33.0% by mass.

[Green photosensitive coloring composition 24]
Green pigment dispersion 1 30.1 parts Yellow pigment dispersion 1 18.2 parts Transparent resin (solid content 20%) 45.5 parts Multifunctional monomer 4.5 parts (DPPAH: dipentaerythritol pentaacrylate) Hexamethylene diisocyanate)
-1 part of light stabilizer ("TINUVIN 770DF" manufactured by Ciba Specialty Chemicals)
・ Photoinitiator 1.02 parts ("Irgacure 379" manufactured by Ciba Specialty Chemicals)
-Photoinitiator 0.33 parts ("Irgacure OXE-02" manufactured by Ciba Specialty Chemicals)
Propylene glycol monomethyl ether acetate 6.6 parts Propylene glycol monomethyl ether acetate 20.25 parts The molecular weight of the light stabilizer used in the green photosensitive coloring composition 24 is 480, and the amount of light stabilizer added is green. It was 3.9 mass% in the total solid of the photosensitive coloring composition. Moreover, the pigment concentration in the total solid content was 23.6% by mass.

[Evaluation]
About the green photosensitive coloring compositions 1-24 obtained in the said Examples 1-17 and Comparative Examples 1-7, it evaluated by the following item. The results of green photosensitive coloring compositions 1-9 corresponding to Examples 1-9 are shown in Table 1, the results of green photosensitive coloring compositions 10-16 corresponding to Examples 10-16 are shown in Table 2, and Comparative Examples Table 3 shows the results of the green photosensitive coloring compositions 17 to 23 corresponding to 1 to 7 and the results of the green photosensitive coloring composition 24 corresponding to Example 17.

（異物評価）
緑色感光性着色組成物１〜２４を、それぞれ膜厚２μｍになるようにスピンコート法により３００×３００ｍｍサイズの基板上に塗布した後乾燥させ、目視及び顕微鏡で観察し、異物が３枚の基板中に５個以下のものを〇、異物が３枚の基板中に５個以上のものを×とした。

(Foreign substance evaluation)
The green photosensitive coloring compositions 1 to 24 are each applied to a 300 × 300 mm size substrate by spin coating so as to have a film thickness of 2 μm, dried, and observed visually and with a microscope. In the case of 5 or less in the substrate, ◯, and in the case of 5 or more foreign materials in the substrate of 3 sheets, the cross is indicated as x.

(Exposure sensitivity)
On the glass substrate, the green photosensitive coloring compositions 1 to 24 were each applied by spin coating so as to have a film thickness of 2 μm, dried, and then pre-baked at 70 ° C. for 20 minutes, and then the proxy. Ultraviolet exposure was performed through a photomask having a fine line pattern of 50 μm by a proximity exposure method using a miti aligner. The exposure amount was set to 7 levels of 50, 80, 100, 150, ²⁰⁰ , 250, 300, mJ / cm ² .
Next, shower development was performed using a 1.25% by mass aqueous sodium carbonate solution, followed by washing with water to complete patterning. The film thickness of the obtained filter segment was divided by the film thickness of the unexposed / undeveloped portion to calculate the remaining film ratio. Then, the exposure sensitivity curve was plotted with the horizontal axis representing the common logarithm of the exposure dose and the vertical axis representing the remaining film ratio after development. From the resulting exposure sensitivity curve, the minimum exposure amount of development after the residual film ratio reaches 85% or more as the sensitivity of the saturated exposure amount, i.e. green photosensitive coloring composition, and 〇 those less than 200 mJ / cm ^2, 200 mJ / Cm ² or more was determined as x.

(Light resistance)
A transparent conductive film (ITO) is vapor-deposited by sputtering on a substrate patterned with the green photosensitive coloring compositions 1 to 24, and the substrate is subjected to a light resistance evaluation apparatus (“Weather Meter Ci35A” manufactured by Atlas Co., Ltd.) for 200 hours. The color difference ΔEab before and after the light resistance evaluation was measured by light exposure. A case where ΔEab was 5 or less was marked as “◯”, and a case where ΔEab exceeded 5 was judged as “x”.

<Comparison result>
As shown in Table 1, Table 2 and Table 3, in the green photosensitive coloring compositions 1 to 17 which are the examples of the present invention, the selection of the pigment type and the molecular weight of the hindered amine which is the light stabilizer and the addition amount are set. By adjusting, there was no generation of foreign matters during coating, and a beautiful coating film could be formed. Also,
By having good exposure sensitivity, the productivity was excellent, the light resistance of the produced green filter segment could be improved, and a good filter segment could be obtained. On the other hand, Comparative Examples 1, 2, and 3 in which the molecular weight of the light stabilizer exceeded 1000 and Comparative Example 7 in which the addition amount of the light stabilizer exceeded 20% by mass had a large amount of foreign matters. Further, Comparative Example 7 in which the addition amount of the light stabilizer exceeded 20% by mass and Comparative Example 6 in which the light stabilizer was not added resulted in poor exposure sensitivity. Further, Comparative Example 2 in which the molecular weight of the light stabilizer exceeds 3000, Comparative Example 4 in which the molecular weight of the light stabilizer is less than 450, and Comparative Example 5 in which the light stabilizer is not added are insufficient light resistance. It became.

  From the results shown in Tables 1, 2, and 3, the following is clear. That is, a green dye of a green photosensitive coloring composition containing a transparent resin, a dye carrier comprising a precursor thereof or a mixture thereof, a green dye, a yellow dye, a photopolymerization initiator, an ethylenically unsaturated monomer, and an organic solvent Is C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment 58 and at least one selected from yellow pigments. I. In the green photosensitive coloring composition containing at least one selected from Pigment Yellow 138, 139, 150, the molecular weight of the light stabilizer of the hindered amine compound is in the range of 450 to 1000, and the addition amount is green photosensitive. Addition in the range of 0.1% by mass to 20% by mass in the total solid content of the coloring composition does not impair the exposure sensitivity for pattern formation, and does not generate foreign matter on the coated substrate. Sex coloring compositions can be provided. Moreover, generation | occurrence | production of the wrinkle of a pattern is not carried out, without impairing exposure sensitivity because the total density | concentration of the green pigment | dye in the total solid of a green photosensitive coloring composition and a yellow pigment | dye is the range of 20 mass%-50 mass%. The filter segment can be formed with an appropriate film thickness.

  Next, using the green photosensitive coloring composition of the present invention described above, R, G, and B color filters were produced by the following steps.

  First, the red photosensitive coloring composition was applied to a glass substrate provided with a stripe-shaped black matrix having a width of 20 μm and a thickness of 1.5 μm so as to have a film thickness of 2 μm by spin coating. After drying this, striped pattern exposure is performed with an exposure machine, and development is performed for 90 seconds with an alkaline developer (1.25% by mass aqueous sodium carbonate solution) to obtain a colored layer of striped red pixels. It was. Next, the green photosensitive coloring composition of the present invention is similarly applied by spin coating so that the film thickness becomes 2 μm, dried, and then the striped colored layer is combined with the above-described red pixel coloring layer by an exposure machine. By exposing and developing in the shifted place, the colored layer of the green pixel adjacent to the colored layer of the red pixel was obtained. Further, in the same manner as red and green, a blue colored composition was obtained with a thickness of 2 μm, and a colored layer of a colored pixel adjacent to the colored layer of the red and green pixels was obtained. Each of the color filters using the green photosensitive coloring composition of the present invention had excellent light resistance.

Claims (2)

In the green photosensitive coloring composition containing a transparent resin, a dye carrier, a color material, a photopolymerization initiator, an ethylenically unsaturated monomer, an organic solvent,
The color material comprises a mixture of a green pigment and a yellow pigment, and the green pigment is C.I. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 58, and the yellow pigment is C.I. I. A green photosensitive coloring composition which is at least one selected from Pigment Yellow 138, 139, 150,
And the light stabilizer of the hindered amine compound whose molecular weight is the range of 450-1000 is contained in the range of 0.1 mass%-20 mass% in the total solid of the said green photosensitive coloring composition, It is characterized by the above-mentioned. A green photosensitive coloring composition.   A color filter comprising a green filter segment formed from the green photosensitive coloring composition according to claim 1.