JP2006259716A - Photosensitive coloring composition and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive coloring composition with which no scum (floating residue) is produced on a pixel, and a highly precise pattern comforming to a mask design is formed with high sensitivity, and which is also excellent in adhesion strength to a substrate and so on. <P>SOLUTION: In the photosensitive coloring composition containing a coloring agent, an alkali soluble resin, a photopolymerization initiator, a reactive monomer, and an organic solvent as components, a fluorene structure containing bifunctional monomer with a specified structure is used as the reactive monomer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a photosensitive coloring composition, particularly a photosensitive coloring composition suitable for a color filter of a color liquid crystal display device such as a color liquid crystal television and a computer color liquid crystal display, and a color filter using the same.

  In order to colorize a liquid crystal display, a color filter is used in which pixels of three colors R (red), G (green), and B (blue) are arranged in a line shape or a mosaic shape on a transparent substrate. For example, a TFT (thin film transistor) color liquid crystal display that is widely used at present is called a backlight in which a liquid crystal is sealed between a transparent glass substrate on which a color filter is formed and a transparent glass substrate on which a TFT is formed. The light source is made up of. When light emitted from the backlight passes through the liquid crystal panel, an image is displayed by controlling the transmittance by the voltage applied to the liquid crystal.

  Conventionally, many methods for producing a color filter using an acrylic photosensitive coloring composition have been proposed. Among these, negative-type (exposed-part curable) photosensitive compositions mainly comprising an acrylic acid polymer and a monomer having an ethylenically unsaturated group, a photopolymerization initiator, and a colorant are widely used. Curing of such a photosensitive composition is initiated by decomposing or activating the photopolymerization initiator by ultraviolet irradiation to generate free radicals, which activate the ethylenically unsaturated compounds present in the vicinity. It progresses when it is converted to radical polymerization. When forming a color filter using such a negative photosensitive composition, after applying a negative photosensitive composition containing a colorant on a normal substrate and irradiating ultraviolet rays through a photomask. The pixel pattern is formed by developing and dissolving the ultraviolet non-irradiated portion with a developer.

  However, when trying to form a color filter from such a negative photosensitive composition, when developing with an alkali developer, the pixel portion cured by irradiation with radiation expands with the alkali developer, resulting in a pixel. In some cases, the resolution of the pattern is lowered or the pixel pattern is deformed. In addition, the adhesion strength of the pixel pattern is reduced by development, and there is a disadvantage that the pixel pattern is peeled off from the substrate after the pixel array is formed. Furthermore, there are problems such as the occurrence of scum (floating) on the obtained pixel pattern, and it has been difficult to manufacture a highly accurate pixel array. Therefore, even when a fine pixel array is formed, a negative photosensitive coloring composition that can form a pixel array with high accuracy and excellent adhesion strength to the substrate without generating scum on the pixel. Development of was desired.

  As a conventional method for producing a high-precision pixel array, a photosensitive coloring composition mainly composed of an alkali-soluble resin, a polyfunctional monomer, a photopolymerization initiator, and a coloring agent is used. A photosensitive coloring composition containing a mixture of erythritol hexaacrylate and dipentaerythritol pentaacrylate has been proposed (see, for example, Patent Documents 1 to 3). However, it has been difficult to produce a highly accurate pixel array simply by using these methods.

  Moreover, sensitivity is improved by containing 0.01 to 20% by mass of a thiophosphite compound in a photosensitive coloring composition mainly composed of an alkali-soluble resin, an ethylenically unsaturated compound, a photopolymerization initiator, and a colorant. There has been proposed a method for producing a practical coloring composition by improving and shortening the exposure time (see, for example, Patent Document 4).

  However, it is difficult to produce a high-accuracy pixel array only by improving the sensitivity, and it is more developable and has a carboxyl group and an ethylenically unsaturated group in the side chain as a method for producing a sharp pattern at the edge. A photosensitive coloring composition containing an acrylic copolymer as a binder component and containing a coloring component, a polyfunctional thiol compound, and a photopolymerization initiator has been proposed (for example, see Patent Document 5).

Furthermore, the photosensitive coloring composition containing the monofunctional monomer which has an imidazole ring in a molecule | numerator is included in the photosensitive coloring composition which has an alkali-soluble resin, a polyfunctional monomer, a photoinitiator, and a coloring agent as a main component. It has been proposed (see, for example, Patent Document 6). However, even if these methods are used, they are not sufficient for the level of a highly accurate pixel array.
JP-A-7-140656 (Claim 1 etc.) JP-A-10-104412 (Claim 2 etc.) JP 2000-81508 A (Claim 4 etc.) JP-A-5-255419 (Claim 1 etc.) JP-A-5-281734 (Claim 1 etc.) JP 2001-21713 A (Claim 1 etc.)

  An object of the present invention is a photosensitive coloring composition that has high sensitivity and excellent adhesion strength to a substrate, can form a high-definition pattern as designed, and does not generate scum (float) on a pixel. Is to provide things.

  In order to solve the above problems, the present invention has the following configuration. That is, a photosensitive coloring composition containing a colorant, an alkali-soluble resin, a photopolymerization initiator, a reactive monomer, and an organic solvent, and the fluorene represented by the following general formula (1) as the reactive monomer A photosensitive coloring composition containing a structure-containing bifunctional monomer and a color filter using the same.

(Here, R ₁ represents an oxygen atom or —ORO—, wherein R represents an alkyl group having 1 to 6 carbon atoms, and R ₂ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

  By using the photosensitive coloring composition of the present invention, it is possible to form a high-definition and sharp pattern as designed, even when a fine pixel array is formed, and scum is formed on the pixel. A pixel array that does not occur and has excellent adhesion strength with the substrate can be obtained.

  The present invention forms the above-mentioned problem, that is, the photosensitive coloring composition, which does not generate scum (floating) on the pixel, has high sensitivity, and has a high-definition pattern with excellent adhesion strength to the substrate. As a result of diligent investigations, we have found that this problem can be solved at once by using a specific bifunctional monomer.

  As the colorant used in the photosensitive coloring composition of the present invention, dyes, organic pigments, inorganic pigments and the like can be used, and organic pigments are preferable from the viewpoint of heat resistance and transparency. Among them, those having high transparency and excellent light resistance, heat resistance, and chemical resistance are preferable. When specific examples of typical organic pigments are represented by color index (CI) numbers, the following are preferably used, but they are not limited to these.

  Examples of yellow pigments include pigment yellow (hereinafter abbreviated as PY) 12, 13, 17, 20, 24, 83, 86, 93, 95, 109, 110, 117, 125, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 168, 185, etc. are used.

  Examples of orange pigments include pigment orange (hereinafter abbreviated as PO) 13, 36, 38, 43, 51, 55, 59, 61, 64, 65, 71, and the like.

  Examples of red pigments include pigment red (hereinafter abbreviated as PR) 9, 48, 97, 122, 123, 144, 149, 166, 168, 177, 179, 180, 192, 209, 215, 216, 217. 220, 223, 224, 226, 227, 228, 240, 254, etc. are used.

  Examples of purple pigments include pigment violet (hereinafter abbreviated as PV) 19, 23, 29, 30, 32, 37, 40, 50, and the like.

  Examples of blue pigments include pigment blue (hereinafter abbreviated as PB) 15, 15: 3, 15: 4, 15: 6, 22, 60, 64, and the like.

Examples of green pigments include pigment green (hereinafter abbreviated as PG) 7, 10, 36, and the like.
These pigments may be subjected to surface treatment such as rosin treatment, acidic group treatment, basic treatment and the like, if necessary.

  The pigment is, for example, a color filter R (red), G (green), or B (blue) three-color pixel, chromaticity characteristics of a CRT (cathode ray tube) phosphor, liquid crystal used in a backlight or a liquid crystal display. Toned and used in combination with several colors to suit the characteristics.

  Taking the case of R (red) as an example, a combination of PR-254 and PR-177, a combination of PR-254 and PY-138, a combination of PR-254 and PY-139, a combination of PR-209 and PO-38 The chromaticity is adjusted by combination or the like.

  In the case of G (green), PG-7, PG-36 and the above yellow pigment, for example, PY-17, PY-83, PY-138, PY-139, PY-150, etc. To adjust the chromaticity.

  Moreover, the photosensitive coloring composition of this invention can also be used for resin black matrix. In the case of the photosensitive coloring composition for resin black matrix, a coloring agent that is insoluble in the organic solvent and water used and serves as a light-shielding agent is used. For example, in addition to pigment black 7 or carbon black as organic pigments, inorganic pigments or metal oxides such as graphite, iron oxide, manganese oxide, and titanium black can be used as a light shielding agent.

  These light-shielding agents can be mixed and used as required, and pigments of other colors can be added, but from the viewpoint of light-shielding properties and dispersibility, it is preferable to contain carbon black. Carbon black can be subjected to surface treatment such as resin treatment, acid treatment, and basic treatment, and the pH is preferably 2 to 5. A pH greater than 5 is not preferred because the solubility of the unexposed areas tends to deteriorate during development, and carbon black having a pH less than 2 is not preferred because it is substantially difficult to produce.

  The pH of carbon black can be determined by adding 10 mass times pure water to carbon black, boiling for 10 minutes, cooling to room temperature, and measuring the mud with a glass electrode pH meter.

  The photosensitive coloring composition of the present invention may be produced by a method of directly dispersing a colorant in a resin solution using a disperser. However, when a pigment is used as the colorant, it is difficult to disperse uniformly. Therefore, a pigment dispersion in which a pigment is dispersed in advance in an organic solvent is prepared, and this pigment dispersion is a resin solution, and in some cases, a resin, a polymer dispersant, a photopolymerization initiator, a solution containing a polymerizable monomer, It is preferable to manufacture by the method of mixing. The method for dispersing the pigment is not particularly limited, and various methods such as a ball mill, a sand grinder, a three-roll mill, and a high-speed impact mill are employed.

  The pigment dispersion is produced by dispersing a pigment in an organic solvent using a disperser. The organic solvent is not particularly limited, for example, methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, (Poly) alkylene glycol ether solvents such as diethylene glycol monomethyl ether, or aliphatic esters such as propylene glycol monoethyl ether acetate, ethyl acetoacetate, methyl-3-methoxypropionate, 3-methyl-3-methoxybutyl acetate Or aliphatic alcohols such as ethanol, 3-methyl-3-methoxybutanol, cyclopentanone, cyclohexanone What ketones can be used, these alone, or may be used two or more mixed solvents is also preferred. Mixing with other solvents is also preferably used.

  However, as described later, when the coloring composition of the present invention is applied to a substrate by a die coating method, the boiling point is selected from the viewpoint of uniformity of film thickness and prevention of pigment aggregates from forming in the discharge slit portion. It is preferred to use a relatively high solvent. On the other hand, if the boiling point is too high, the drying property is deteriorated. Specifically, it is preferable to use a solvent having a boiling point in the range of 150 ° C. or higher and 220 ° C. or lower.

  For example, methyl benzoate (boiling point 200 ° C.), ethyl benzoate (boiling point 213 ° C.), diethyl oxalate (boiling point 185 ° C.), diethyl malonate (boiling point 199 ° C.), 3-methoxybutyl acetate (boiling point 173 ° C.), 3-methoxy -3-methyl-butyl acetate (bp 188 ° C.), 2-ethylbutyl acetate (bp 162 ° C.), 2-butoxyethyl acetate (bp 192 ° C.), 2-ethylhexyl acetate (bp 199 ° C.), cyclohexyl acetate (bp 174 ° C), benzyl acetate (boiling point 214 ° C), methyl acetoacetate (boiling point 172 ° C), ethyl acetoacetate (boiling point 181 ° C), propylene glycol monoethyl ether acetate (boiling point 158 ° C), isopentylpropionate (boiling point 160 ° C) ), Ethyl-3-ethoxy Ropioneto (boiling point 170 ° C.), propylene glycol monomethyl ether propionate (boiling point 160 ° C.) can be preferably used.

  In particular, from the viewpoint of the resin component, the solubility in the photopolymerization initiator, the dispersion stability of the pigment, and the like, an acetate ester or propionate ester solvent is preferable. In addition, from the viewpoint of safety and environment, it does not fall under the category of hazardous air pollutants specified in the 1990 Amended Air Cleanup Act, and the title III313 of the amended Superfund Act and Rebirth Act established in 1986 More preferably, it is a solvent that does not fall under TOXIC CHEMICAL REPORTING and has low toxicity. From the above viewpoint, particularly preferred solvents are 3-methoxy-butyl acetate (flash point 60 ° C.), 3-methoxy-3-methyl-butyl. Acetate (flash point 73 ° C), 2-ethylbutyl acetate (flash point 57 ° C), 2-ethylhexyl acetate (flash point 88 ° C), propylene glycol monoethyl ether acetate (flash point 52 ° C), isopentylpropionate ( Flash point 63 ° C), ethyl-3-ethoxy Lopionate (flash point: 58 ° C.) and propylene glycol monomethyl ether propionate (flash point: 56 ° C.), and a solvent having a flash point of 60 ° C. or higher can be handled more safely. Of these, 3-methoxy-3-methyl-butyl acetate is most preferable because it has almost no odor and is easily available. These can be used alone or mixed with other solvents. The concentration of the pigment in the pigment dispersion is preferably 5 to 90% by mass, more preferably 5 to 20% by mass with respect to the entire pigment dispersion.

  Furthermore, in the pigment dispersion, various dispersants are preferably used in order to further improve the dispersion stability. Examples thereof include a method using a low molecular pigment derivative described in JP-B-4-3841 and JP-A-11-295515. Examples of the polymeric pigment dispersant include, for example, JP-A-54-37082, JP-A-9-169821, JP-A-2000-95992, JP-A-2000-155209, JP-A-2001-59906. High molecular pigment dispersants having a basic group, such as those described in Japanese Patent Publication No. Gazette, can be used. In addition to the low-molecular pigment dispersant and the high-molecular pigment dispersant described above, addition of an alkali-soluble resin, which will be described later, is preferably performed because the dispersion stability can be further increased.

  The photosensitive coloring composition of the present invention needs to contain at least an alkali-soluble resin, a photopolymerization initiator, and a reactive monomer in addition to the colorant and the organic solvent described later.

  The photosensitive coloring composition of the present invention needs to contain an alkali-soluble resin. Among the alkali-soluble resins, an acrylic resin having a carboxyl group or a polyimide precursor such as polyamic acid is preferable in that a pattern can be easily formed by development or etching. In particular, it is more preferable to use an acrylic resin having a carboxyl group as the alkali-soluble resin because a photosensitive coloring composition that can be produced relatively easily by the addition of a photopolymerization initiator and a polymerizable monomer can be obtained.

  In the photosensitive coloring composition of the present invention, if necessary, a resin generally used for a color filter, for example, acrylic resin, alkyd resin, melamine resin, polyvinyl alcohol, polyamide, polyamideimide, polyimide, polyimide precursor, etc. Various resins can be used.

  The acrylic resin having a carboxyl group is preferably a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid and the like. These may be used alone or in combination with other copolymerizable ethylenically unsaturated compounds. Specific examples of the copolymerizable ethylenically unsaturated compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate, methacryl Isopropyl acid, n-butyl acrylate, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-acrylate -Unsaturated carboxylic acid alkyl esters such as pentyl, n-pentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, styrene, p-methylstyrene , Aromatic vinyl compounds such as o-methylstyrene, m-methylstyrene and α-methylstyrene, aminoalkyl esters of unsaturated carboxylic acids such as aminoethyl acrylate, glycidyl esters of unsaturated carboxylic acids such as glycidyl acrylate and glycidyl methacrylate, acetic acid Carboxylic acid vinyl esters such as vinyl and vinyl propionate, vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile, aliphatic conjugated dienes such as 1,3-butadiene and isoprene, acryloyl groups at the ends, or Examples include, but are not limited to, polystyrene having a methacryloyl group, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate, and polybutyl methacrylate. Not to. In particular, a quaternary copolymer selected from methacrylic acid and / or acrylic acid and methyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, and styrene, having a weight average molecular weight Mw of 9000 to 100,000 (gel permeation) A polymer having an acid value of 70 to 150 (mg KOH / g) measured by chromatography and converted using a standard polystyrene calibration curve is preferable from the viewpoint of solubility in a solvent and solubility in an alkali developer. If it is out of the above range, the solubility in a solvent and the solubility in an alkali developer may decrease, which is not preferable.

  Further, when an acrylic polymer having an ethylenically unsaturated group in the side chain is used, the sensitivity at the time of pixel patterning is improved, so that it can be preferably used. As an ethylenically unsaturated group, an acryl group and a methacryl group are preferable. Such an acrylic polymer can be subjected to an addition reaction of an ethylenically unsaturated compound having a glycidyl group or an alicyclic epoxy group to the carboxyl group of the acrylic (co) polymer. As a specific example of an acrylic polymer having an ethylenically unsaturated group in the side chain, a photocurable resin that is a copolymer described in Japanese Patent No. 3120476, JP-A-8-262221, or a commercially available acrylic polymer. Examples thereof include resin “Cyclomer P” (manufactured by Daicel Chemical Industries, Ltd.). In particular, an acrylic polymer having an ethylenically unsaturated group in the side chain, a polymer having a weight average molecular weight Mw of 9000 to 100,000 and an acid value of 70 to 150 (mgKOH / g) is photosensitive property, solubility in an ester solvent, alkali development Most preferable from the viewpoint of solubility in the liquid.

  The reactive monomer used in the photosensitive coloring composition of the present invention must contain at least a fluorene structure-containing bifunctional monomer represented by the following general formula (1).

(Here, R ₁ represents an oxygen atom or —ORO—, wherein R represents an alkyl group having 1 to 6 carbon atoms, and R ₂ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. )
The fluorene structure-containing bifunctional monomer can form a sharp and fine pattern as designed, has excellent adhesion strength with the substrate, and can generate scum on the pixel. In view of the absence, bisphenoxyethanol fluorene acrylate represented by the following structural formula (2) is most preferable.

  As the reactive monomer, in addition to the fluorene structure-containing bifunctional monomer, for example, bisphenol A diglycidyl ether (meth) acrylate, poly (meth) acrylate carbamate, modified bisphenol A epoxy (meth) acrylate, adipic acid 1,6 -Hexanediol (meth) acrylic acid ester, phthalic anhydride propylene oxide (meth) acrylic acid ester, trimellitic acid diethylene glycol (meth) acrylic acid ester, rosin modified epoxy di (meth) acrylate, alkyd modified (meth) acrylate, etc. Oligomer or tripropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, triacryl formal, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. alone Or it can mix and use. In addition, the following monofunctional monomers can be used in combination, for example, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, n-butyl methacrylate, glycidyl methacrylate, lauryl ( There are meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate and the like, and a mixture of two or more of these or a mixture with other compounds is used.

  The photosensitive coloring composition of the present invention preferably contains a trifunctional or higher polyfunctional acrylic monomer in addition to the fluorene structure-containing bifunctional monomer as a reactive monomer. By containing a trifunctional or higher polyfunctional acrylic monomer, it is possible to improve the sensitivity and to improve the solubility of the ultraviolet non-irradiated part in an alkali developer. The trifunctional or higher polyfunctional acrylic monomer is not particularly limited, but dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate are particularly preferable for obtaining a highly sensitive photosensitive coloring composition.

  When the fluorene structure-containing bifunctional monomer and the trifunctional or higher polyfunctional acrylic monomer are used in combination, the content of the fluorene structure-containing bifunctional monomer to be a reactive monomer is 15 to 85% by mass, more preferably The content of the trifunctional or higher polyfunctional acrylic monomer is 10 to 85% by mass, more preferably 30 to 70% by mass. By setting the content of the fluorene structure-containing bifunctional monomer to 15% by mass or more, it is possible to form a sharp pattern particularly as designed, has excellent adhesion strength with the substrate, and has a scum on the pixel. It is possible to obtain a photosensitive coloring composition that does not generate (floating). In addition, by setting the content of the trifunctional or higher polyfunctional acrylic monomer to 10% by mass or more, particularly high sensitivity and solubility of the ultraviolet non-irradiated part can be improved.

  In addition to the fluorene structure-containing bifunctional monomer and the trifunctional or higher polyfunctional acrylic monomer, it is preferable to contain dicyclopentanedienyl diacrylate as the reactive monomer. The fluorene structure-containing bifunctional monomer to be made into a reactive monomer is in the range of 20 to 60% by mass, the trifunctional or higher polyfunctional acrylic monomer is in the range of 20 to 60% by mass, and the dicyclopentanedienyl diacrylate is in the range of 20 to 60% by mass. It is preferable to use them in a mixed state.

  As the same bifunctional monomer, the fluorene structure-containing bifunctional monomer is superior to dicyclopentanedienyl diacrylate in that it forms a sharp pattern according to the design dimensions, but it dissolves the ultraviolet non-irradiated part. In terms of sex, dicyclopentanedienyl diacrylate is slightly better. By using the fluorene structure-containing difunctional monomer, the trifunctional or higher polyfunctional acrylic monomer, and dicyclopentanedienyl diacrylate within the content range, ultraviolet irradiation is not performed without reducing the patterning performance. It becomes possible to improve the solubility of the part.

  By combining with selection of these bifunctional monomers and polyfunctional monomers, it is possible to control the sensitivity and processability characteristics of the photosensitive coloring composition.

  Examples of the photopolymerization initiator used in the present invention include inorganic compounds such as benzophenone compounds, acetophenone compounds, thioxanthone compounds, imidazole compounds, benzothiazole compounds, benzoxazole compounds, triazine compounds, phosphorus compounds, and titanates. Known photopolymerization initiators can be used.

  For example, benzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyldimethyl Ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propane, 2-benzyl-2 -Dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4-methyl) benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,1- (9-ethyl) -6- (2-methyl Nzoyl) -9H-carbazol-3-yl), 1,2-octanedione, 1- [4- (phenylthio)-, 2- (o-benzoyloxime), t-butylanthraquinone, 1-chloroanthraquinone, 2, 3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2- Phenylanthraquinone, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 4- (p-methoxyphenyl) -2,6-di- (trichloro) Methyl) -s-triazine and the like. Further, it is preferable to add a sensitizing aid such as an aromatic or aliphatic tertiary amine because the sensitivity can be further improved. Moreover, these photoinitiators can also be used in combination of 2 or more types. Among these photopolymerization initiators, 1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl), trade name “CGI242” manufactured by Ciba Specialty Chemicals Co., Ltd. is included. It is preferable from the viewpoint of improving sensitivity. Although there is no limitation in particular as the addition amount of a photoinitiator, Preferably it is 2-30 mass% with respect to the photosensitive coloring composition total solid, More preferably, it is 5-25 mass%.

  The coloring composition of the present invention needs to contain at least an organic solvent. Although it does not specifically limit as an organic solvent, For example, the said (poly) alkylene glycol ether solvent, aliphatic ester, aliphatic alcohol, ketones etc. can be used. However, when the coloring composition of the present invention is applied to a substrate by a die coating method, it is not particularly limited, but for the same reason as in the case of the solvent that can be used for the dispersion, it is 150 ° C. or higher and 220 ° C. Solvents having boiling points in the following ranges are preferred, and they are preferably contained in an amount of 40% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more based on the total solvent.

  Among the solvents having a boiling point in the range of 150 ° C. or higher and 220 ° C. or lower, a more preferable solvent is 3-methoxy-butyl acetate (flash point 60 ° C.) for the same reason as the solvent that can be used for the pigment dispersion. 3-methoxy-3-methyl-butyl acetate (flash point 73 ° C.), 2-ethylbutyl acetate (flash point 57 ° C.), 2-ethylhexyl acetate (flash point 88 ° C.), propylene glycol monoethyl ether acetate (flash point 52) ° C), isopentyl propionate (flash point 63 ° C), ethyl-3-ethoxypropionate (flash point 58 ° C), propylene glycol monomethyl ether propionate (flash point 56 ° C), and flash point 60. Solvents higher than ℃ are preferable because they can be handled more safely, and in particular, 3-methoxy-3-methyl-butyl Seteto is most preferable. These are used alone or in appropriate combination as a mixed solvent of two or more kinds of solvents. In addition, combinations with solvents other than those described above are also preferably performed.

  In the photosensitive coloring composition of the present invention, the colorant is usually used in the range of 5 to 80% by mass, preferably 10 to 60% by mass in the total solid content of the photosensitive coloring composition. The ratio of these colorants to the total solid content of the photosensitive coloring composition is appropriately adjusted according to the required color purity. In particular, when high color purity is required, the higher the colorant ratio, the higher the color purity when matched to the target film thickness, which is preferable. Specifically, the addition amount of the colorant is preferably 40% by mass to 60% by mass, and more preferably 45% by mass to 55% by mass. When it is less than 40% by mass, the resin content is relatively increased, so that the film thickness of the coating film is increased and liquid crystal display elements may be disturbed when the liquid crystal display element is used. When the amount is large, the solubility and adhesion during development are likely to deteriorate, such being undesirable.

  When such a high color purity is required, the addition amount of the colorant in the above range is preferable. However, since the irradiation light irradiated at the time of exposure is absorbed by the colorant and other components, the coating is applied. Irradiation light does not reach the lower part of the film sufficiently, and it is extremely difficult to form an appropriate pattern with the photosensitive coloring composition having the conventional constitution. If the photosensitive coloring composition of the present invention is used, a sharp pattern can be formed even if sufficient irradiation light does not reach the lower part of the film. Specifically, i-line (365 nm) transmittance is preferable. Is particularly effective when producing a color filter in a range of 5% or less, more preferably 2% or less. The transmittance at i-line can be calculated by using, for example, an ultraviolet spectrophotometer “MultiSpec-1500” manufactured by Shimadzu Corporation, and assuming that the transmittance of a substrate on which no color filter is formed is 100%.

  In order to improve the adhesion of the colored layer to the substrate, it is also preferable to add a silane coupling agent to the colored composition of the present invention.

  Further, for the purpose of improving the coating property of the photosensitive coloring composition and the surface uniformity of the colored layer, or for the purpose of improving the dispersibility of the pigment, a surfactant is added to the coloring composition of the present invention. Can be added. The amount of the surfactant added is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass, based on the pigment. If the added amount is less than this range, the effect of improving the coating property, the uniformity of the colored film surface, or the pigment dispersibility is small, and if it is too much, the coating property is poor or the pigment is aggregated. Since there are cases, it is not preferable.

  Specific examples of such surfactants include anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether sulfate triethanolamine, cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride, and lauryldimethylamine oxide. Amphoteric surfactants such as lauryl carboxymethyl hydroxyethyl imidazolium betaine, and nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and sorbitan monostearate are preferably used. Such surfactants can be used alone or in combination. Such a surfactant can be added at any time during or before or after the pigment dispersion step. However, care should be taken because the dispersibility of the pigment may change depending on the point of addition.

  Next, the example of the manufacturing method of the color filter using the photosensitive coloring composition of this invention is demonstrated. As a method of applying the photosensitive coloring composition on the substrate, a method of applying to the substrate by a spin coater, a bar coater, a blade coater, a roll coater, a die coater, a screen printing method, or the like, or immersing the substrate in the coloring composition Various methods such as spraying the coloring composition onto the substrate can be used. Among these, the die coater coating is most preferable because the liquid-saving property and large plate coating property of the coloring composition are excellent. .

  In addition, as such a substrate, a transparent substrate such as soda glass, non-alkali glass, borosilicate glass, or quartz glass, or a semiconductor substrate such as silicon or gallium-arsenide is usually used, but is not particularly limited thereto. When applying the photosensitive coloring composition of the present invention on such a substrate, if the substrate surface is treated with an adhesion aid such as a silane coupling agent, the adhesion between the colored film and the substrate can be improved. it can.

  As described above, after the photosensitive coloring composition of the present invention is applied on the substrate, the solvent is removed by air drying, reduced pressure drying, heat drying or the like to form a coating film. In particular, after providing a vacuum drying step, additional heating and drying in an oven or a hot plate eliminates coating defects caused by convection and improves the yield. The drying under reduced pressure is preferably performed in the range of normal temperature to 100 ° C., 5 seconds to 10 minutes, atmospheric pressure 500 to 5 Pa, more preferably atmospheric pressure 100 to 10 Pa. Heat drying is preferably performed using an oven, a hot plate or the like at a temperature of 50 to 120 ° C. for 10 seconds to 30 minutes. Thereafter, an oxygen barrier film may be provided on the coating film as necessary. Subsequently, a mask is placed on the coating film and irradiated with ultraviolet rays using an exposure apparatus. Next, development is performed with an alkaline developer. Here, it is preferable to use an alkaline developer added with 0.01 to 1% by mass of a surfactant such as a nonionic surfactant as the developer because a better pattern can be obtained.

  Although it does not specifically limit as an alkaline substance used for an alkaline developing solution, For example, inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n- Primary amines such as propylamine, secondary amines such as diethylamine and di-n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, and tetraalkylammonium hydroxides such as tetramethylammonium hydroxide (TMAH) , Quaternary ammonium salts such as choline, triethanolamine, diethanolamine, monoethanolamine, dimethylaminoethanol, diethylaminoethanol and other alcohol amines, pyrrole, piperidine, 1,8-dia Bicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3,0] -5-nonane, organic alkalis such as cyclic amines such as morpholine, and the like.

  The concentration of the alkaline substance in the developer is usually 0.01 to 50% by mass. Preferably it is 0.05-10 mass%, More preferably, it is 0.1-1 mass%. The developer is preferably an aqueous aqueous developer in terms of working environment and waste developer treatment. In the case of using an aqueous alkaline aqueous developer, a water-soluble organic solvent such as ethanol, γ-butyrolactone, dimethylformamide, or N-methyl-2-pyrrolidone may be appropriately added to the developer.

  The development method uses an immersion method, a spray method, a paddle method or the like, but is not particularly limited. After the development or etching, the oxygen blocking film that has become unnecessary is removed as necessary. A washing step with pure water or the like may be added as appropriate after development.

  The coating film pattern of the obtained colored composition then becomes a colored pixel patterned by heat treatment. The heat treatment is usually performed in air, in a nitrogen atmosphere, or in a vacuum at 150 to 300 ° C, preferably 180 to 250 ° C, continuously or stepwise for 0.25 to 5 hours. Done.

  When a colored pattern is sequentially formed for an arbitrary number of colors by the above method, a color filter for a liquid crystal display device having a pixel composed of a colored layer provided in a desired pattern can be produced. Here, the patterning order of the coloring composition is not limited. Although the number of colors is arbitrary, three colors of RGB, or six colors provided with a dark color portion and a light color portion for each of the RGB colors are preferable.

  Moreover, a black matrix, a protective film, a transparent conductive film, etc. can be formed as needed. The position where these are formed, the order of formation, the formation method, and the like are not particularly limited. As an example, a black matrix is formed on a substrate, a colored layer is formed thereon, a protective film is further formed thereon, and a transparent conductive film is formed thereon.

  EXAMPLES Hereinafter, although this invention is demonstrated in more detail using an Example, the scope of the present invention is not restrict | limited at all by this.

(Evaluation methods)
1. Pattern shape The pattern shape after exposure, development and post-baking (220 ° C. × 30 minutes) was subjected to planar observation (with or without meandering) using an optical microscope (Olympus Sales Co., Ltd., BH3-MJL), scanning electron microscope Cross-section observation (taper shape) was performed using (S-4800, manufactured by Hitachi, Ltd.).

In cross-sectional observation, the lower width and the upper width were equal, or the lower width was wider than the upper width, and the lower taper was narrower than the upper width, and the reverse taper was lower. A pattern having no forward meandering and a forward taper shape was determined as a good pattern and judged according to the following criteria.
◎: Observed about 10 patterns, all are forward tapered and no meandering ○: Observed about 10 patterns, meandering is seen, but the meandering width is all 2 μm or less, and becomes a forward tapered shape 1. What is observed: 10 patterns are observed, and even one meander having a width of 2 μm or more is seen or a reverse taper shape. Pattern reproducibility UV light containing each wavelength of i-line: 365 nm, h-line: 405 nm, and g-line: 436 nm on the coating film through a photomask (manufactured by HOYA, negative mask, stripe design line width 50 μm, 200 μm gap) Was exposed at an exposure amount of 100 mJ / cm ² , and the obtained line width with respect to the designed line width of 50 μm after development and post-baking (220 ° C. × 30 minutes) was measured and determined according to the following criteria.
A: The obtained line width is in the range of 50 μm to 53 μm. ○: The obtained line width is in the range of 53 μm to 56 μm. X: The obtained line width is thicker than 56 μm. Adhesiveness Via a photomask (manufactured by HOYA, negative mask, stripe design line width 5 μm, 200 μm gap), the coating film is irradiated with ultraviolet rays including wavelengths of i-line: 365 nm, h-line: 405 nm, and g-line: 436 nm. Exposure was performed at 60 mJ / cm ² and 30 mJ / cm ² , and the adhesiveness of the pattern after development and post-baking (220 ° C. × 30 minutes) was observed with an optical microscope, and determined according to the following criteria.
A: Observation is performed on 10 patterns exposed at an exposure amount of 30 mJ / cm ² , and all the patterns are not missing. ○: Observation is performed on 10 patterns exposed at an exposure amount of 60 mJ / cm ² , and all patterns are missing. None: X: 10 patterns exposed at an exposure amount of 60 mJ / cm ² were observed, and at least one pattern was missing. Solubility in developer Using the above-mentioned alkali developer, shower development is performed with an automatic developing device (AD-2000), and the time until the radiation non-irradiated portion is dissolved and development is completed is measured. Judgment was made.
◎: Development completed within 40 seconds from the start of development ○: Development completed within 60 seconds from the start of development Δ: Development completed within 80 seconds from the start of development ×: 80 seconds elapsed from the start of development 4. Development is not completed afterwards. Sensitivity Shows the minimum required exposure required to form a pattern that does not have surface roughness even when developed. Via a photomask (manufactured by HOYA Co., Ltd., negative mask, stripe design line width 50 μm, 200 μm gap), ultraviolet rays containing wavelengths of i-line: 365 nm, h-line: 405 nm and g-line: 436 nm were applied to the coating film at 200 mJ. The exposure amount was reduced as needed, with the maximum exposure amount being / cm ^2, and the minimum exposure amount in a range where the pattern surface was not roughened after development was defined as the minimum required exposure amount. A sensitivity level that does not cause surface roughness at an exposure dose of 40 mJ / cm ² is required.

6). Scum On a pixel after exposure, development and post-baking (220 ° C. × 30 minutes), using an optical microscope (BH3-MJL manufactured by Olympus Sales Co., Ltd.), a 5-field scum with a field of view of 0.5 × 0.5 mm Was observed and judged according to the following criteria.
○: No scum was observed ×: Even one scum was observed Example 1
12 parts by weight of a 46/15/39 (weight ratio) mixture of Pigment Green 36, Pigment Green 7 and Pigment Yellow 150 as a colorant, an acrylic block copolymer polymer dispersant (EFKA Additives Co., Ltd., EFKA) -4330) as a binder resin and 5 parts by weight of a 70% by mass methoxypropyl acetate solution by the method described in Example 1 of Japanese Patent No. 3120476, a methyl methacrylate / methacrylic acid / styrene copolymer (weight composition ratio 30 / 40/30) synthesized, glycidyl methacrylate added, re-precipitated with purified water, filtered and dried, and obtained by acrylic polymer having characteristics of average molecular weight Mw 40,000 and acid value 110 (mgKOH / g) 11 parts by weight (hereinafter referred to as polymer A), solvent and Then, 72 parts by weight of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) was mixed, and then dispersed using a mill type disperser filled with zirconia beads to obtain a pigment dispersion.

  Next, 0.04 part by weight of polymer A with respect to 100 parts by weight of the pigment dispersion, and a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate as a polyfunctional monomer (“Kayacure” manufactured by Nippon Kayaku Co., Ltd.) "DPHA (hereinafter referred to as DPHA)" is 5.60 parts by weight, and bisphenoxyethanol full orange acrylate represented by the structural formula (2) as a bifunctional monomer (BPEFA manufactured by Osaka Gas Chemical Co., Ltd., hereinafter referred to as BPEFA) is used. 5.60 parts by weight, 1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl) as a photopolymerization initiator (CGI242 manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.60 parts by weight of 2- (4-methyl) benzyl-2-dimethyl 3.20 parts by weight of tilamino-1- (4-morpholinophenyl) -butanone-1 (CGI113 manufactured by Ciba Specialty Chemicals Co., Ltd., hereinafter referred to as CGI113), and 3-methacryloxypropyltri as an adhesion improver 0.38 parts by weight of methoxysilane (KBM503 manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter referred to as KBM503), 0.08 parts by weight of MegaFac R-08 (manufactured by Dainippon Chemical Co., Ltd.) as a surfactant, and A photosensitive coloring composition was prepared by mixing 56.5 parts by weight of PGMEA as a solvent.

Using a spin coater (manufactured by Mikasa Co., Ltd., 1H-D2 type) on the substrate surface of the liquid composition on an alkali-free glass (manufactured by Nippon Electric Glass Co., Ltd., OA10: 50 mm × 70 mm, thickness 0.7 mm). After coating, the substrate was heat-dried (prebaked) for 10 minutes in a 90 ° C. inert oven (manufactured by Davyespec Corp., PERFECTOTVEN PV-210) to form a coating film having a thickness of 1.89 μm. Then, after cooling this board | substrate to room temperature, using an exposure machine (Union optics Co., Ltd. product, ultraviolet exposure machine PEM-6M), a photomask (HOYA Co., Ltd. product, negative mask, stripe design line width 50 micrometers, 200 micrometers gap) ), The coating film was exposed to ultraviolet rays containing wavelengths of i-line: 365 nm, h-line: 405 nm, and g-line: 436 nm at an exposure dose of 100 mJ / cm ² .

  Next, an aqueous solution at 23 ° C. containing 0.05% by mass of potassium hydroxide and 1.67% by mass of Emulgen A-60 (manufactured by Kao Corporation) was used as a developing solution, and the substrate was used as an automatic developing device (Mikasa Co., Ltd.). ) Manufactured by AD-2000), washed with pure water, and air-dried. The development time was set to (unirradiated part dissolution time + 30) seconds. Furthermore, it heat-dried (post-baking) for 30 minutes in 220 degreeC inert oven (Dabaye specs Co., Ltd. product, HIGHTEMPOVEN PV-110), and produced the green color filter on the board | substrate.

  The evaluation results are shown in Table 1. When the obtained green color filter was observed with an optical microscope, a good pattern with sharp edges was obtained, and the taper shape was a forward taper. Also, no pattern loss or damage was observed, and the obtained line width was 54 μm with respect to the mask design line width of 50 μm, which was a value close to the design dimension. The adhesion of the obtained pixel to the substrate was excellent, and the solubility and sensitivity of the non-irradiated part were very good. No scum was observed on the pixels.

Example 2
12 parts by weight of a 46/15/39 (weight ratio) mixture of Pigment Green 36, Pigment Green 7 and Pigment Yellow 150 as a colorant, an acrylic block copolymer polymer dispersant (EFKA Additives Co., Ltd., EFKA) -4330) 5 parts by weight of a 70% by mass methoxypropyl acetate solution, 11 parts by weight of polymer A as a binder resin, and 72 parts by weight of PGMEA as a solvent were dispersed using a mill type disperser filled with zirconia beads, A dispersion was obtained.

  Next, 0.04 parts by weight of polymer A, 2.24 parts by weight of DPHA as a polyfunctional monomer, 8.96 parts by weight of BPEFA as a bifunctional monomer, and 100% by weight of this pigment dispersion 1.60 parts by weight of CGI242 as an initiator, 3.20 parts by weight of CGI113, 0.38 parts by weight of KBM503 as an adhesion improver, 0.08 parts by weight of MegaFac R-08 as a surfactant, and solvent As a mixture, 56.5 parts by weight of PGMEA was mixed to prepare a photosensitive coloring composition.

  Next, a green color filter was produced on the substrate in the same manner as in Example 1. The obtained color filter was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

  When the obtained green color filter was observed with an optical microscope, a very good pattern with sharp edges was obtained, and the taper shape was a forward taper. Also, no pattern loss or damage was observed, and the obtained line width was 52 μm with respect to the mask design line width of 50 μm, which was almost as designed. The adhesion of the obtained pixel to the substrate was also excellent, and the solubility and sensitivity of the radiation non-irradiated part were good. Further, no scum was observed on the pixel.

Example 3
12 parts by weight of a 46/15/39 (weight ratio) mixture of Pigment Green 36 and Pigment Green 7 and Pigment Yellow 150 as a colorant, an acrylic block copolymer polymer dispersant (EFKA Additives Co., Ltd., EFKA) -4330) 5 parts by weight of a 70% by mass methoxypropyl acetate solution, 11 parts by weight of polymer A as a binder resin, and 72 parts by weight of PGMEA as a solvent were dispersed using a mill type disperser filled with zirconia beads, A dispersion was obtained.

  Next, with respect to 100 parts by weight of this pigment dispersion, 0.04 part by weight of polymer A, 3.36 parts by weight of DPHA as a polyfunctional monomer, 4.48 parts by weight of BPEFA as a bifunctional monomer, 3.36 parts by weight of dicyclopentanedienyl diacrylate (“Kayacure” R-684, hereinafter referred to as R-684, manufactured by Nippon Kayaku Co., Ltd.) as a functional monomer, and 1.60 of CGI242 as a photopolymerization initiator Parts by weight, 3.20 parts by weight of CGI113, 0.38 parts by weight of KBM503 as an adhesion improver, 0.08 parts by weight of MegaFac R-08 as a surfactant, and 56.5 parts by weight of PGMEA as a solvent Thus, a photosensitive coloring composition was prepared.

  Next, a green color filter was produced on the substrate in the same manner as in Example 1. The obtained color filter was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

  When the obtained green color filter was observed with an optical microscope, a very good pattern with sharp edges was obtained, and the taper shape was a forward taper. Also, no pattern loss or damage was observed, and the obtained line width was 52 μm with respect to the mask design line width of 50 μm, which was almost as designed. The adhesion of the obtained pixel to the substrate was also excellent, and the solubility and sensitivity of the radiation non-irradiated part were very good. Further, no scum was observed on the pixel.

Example 4
12 parts by weight of a 46/15/39 (weight ratio) mixture of Pigment Green 36 and Pigment Green 7 and Pigment Yellow 150 as a colorant, an acrylic block copolymer polymer dispersant (EFKA Additives Co., Ltd., EFKA) -4330) 5 parts by weight of a 70% by mass methoxypropyl acetate solution, 11 parts by weight of polymer A as a binder resin, and 72 parts by weight of PGMEA as a solvent were dispersed using a mill type disperser filled with zirconia beads, A dispersion was obtained.

  Next, with respect to 100 parts by weight of this pigment dispersion, 0.04 part by weight of polymer A, 10.08 parts by weight of DPHA as a polyfunctional monomer, 1.12 parts by weight of BPEFA as a bifunctional monomer, photopolymerization 1.60 parts by weight of CGI242 as an initiator, 3.20 parts by weight of CGI113, 0.38 parts by weight of KBM503 as an adhesion improver, 0.08 parts by weight of MegaFac R-08 as a surfactant, and solvent As a mixture, 56.5 parts by weight of PGMEA was mixed to prepare a photosensitive coloring composition.

  Next, a green color filter was produced on the substrate in the same manner as in Example 1. The obtained color filter was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

  When the obtained green color filter was observed with an optical microscope, meandering was observed at the edge of the pattern, but all the meandering widths were as small as 2 μm or less. The obtained line width was 55 μm with respect to the mask design line width of 50 μm, which was a slightly thicker pattern than the design, but no pattern loss or damage was observed, and the adhesion of the pixel to the substrate was excellent. Both the solubility and sensitivity of the non-irradiated part were very good. Further, no scum was observed on the pixel.

Example 5
12 parts by weight of a 46/15/39 (weight ratio) mixture of Pigment Green 36 and Pigment Green 7 and Pigment Yellow 150 as a colorant, an acrylic block copolymer polymer dispersant (EFKA Additives Co., Ltd., EFKA) -4330) 5 parts by weight of a 70% by mass methoxypropyl acetate solution, 11 parts by weight of polymer A as a binder resin, and 72 parts by weight of PGMEA as a solvent were dispersed using a mill type disperser filled with zirconia beads, A dispersion was obtained.

  Next, with respect to 100 parts by weight of this pigment dispersion, 0.04 part by weight of polymer A, 1.12 parts by weight of DPHA as a polyfunctional monomer, and 10.08 parts by weight of BPEFA as a bifunctional monomer, photopolymerization 1.60 parts by weight of CGI242 as an initiator, 3.20 parts by weight of CGI113, 0.38 parts by weight of KBM503 as an adhesion improver, 0.08 parts by weight of MegaFac R-08 as a surfactant, and solvent As a mixture, 56.5 parts by weight of PGMEA was mixed to prepare a photosensitive coloring composition.

  Next, a green color filter was produced on the substrate in the same manner as in Example 1. The obtained color filter was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

  When the obtained green color filter was observed with an optical microscope, a very good pattern with sharp edges was obtained, and the taper shape was a forward taper. Further, no missing or broken pattern was observed, and the obtained line width was 51 μm as designed with respect to the mask design line width of 50 μm. Also, the adhesion of the obtained pixel to the substrate was excellent. The dissolution time of the non-irradiated part was slightly longer and a slightly lower value of sensitivity was obtained, but it was within the usable level range. Further, no scum was observed on the pixel.

Example 6
After mixing 20 parts by weight of carbon black “MA100” manufactured by Mitsubishi Chemical Corporation having a pH of 3.5 as a colorant, 8 parts by weight of polymer A as a binder resin, and 72 parts by weight of PGMEA as a solvent, zirconia beads are filled. Was dispersed using a mill-type disperser to obtain a black pigment dispersion.

  Next, 5 parts by weight of BPEFA as a fluorene structure-containing bifunctional monomer, 5 parts by weight of DPHA as a polyfunctional monomer, and 1.6 parts by weight of CGI242 as a photopolymerization initiator are added to 100 parts by weight of this black pigment dispersion. Part, 3.2 parts by weight of CGI113 and 55.2 parts by weight of PGMEA as a solvent were mixed to prepare a photosensitive black composition for a resin black matrix.

  Next, in the same manner as in Example 1, a black color filter (resin black matrix) was produced on the substrate so that the film thickness after heating and drying was 1.0 μm. The obtained color filter was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

  When the obtained black color filter was observed with an optical microscope and a scanning electron microscope, a very good pattern with sharp edges was obtained, and the taper shape was a forward taper. Also, no pattern loss or damage was observed, and the obtained line width was 52 μm with respect to the mask design line width of 50 μm, which was almost as designed. The adhesion of the obtained pixel to the substrate was also excellent, and the solubility and sensitivity of the radiation non-irradiated part were good. Further, no scum was observed on the pixel.

Example 7
After mixing 20 parts by weight of carbon black “MA100” manufactured by Mitsubishi Chemical Corporation having a pH of 3.5 as a colorant, 8 parts by weight of polymer A as a binder resin, and 72 parts by weight of PGMEA as a solvent, zirconia beads are filled. Was dispersed using a mill type disperser to obtain a black pigment dispersion.

  Next, 3 parts by weight of BPEFA as a fluorene structure-containing bifunctional monomer, 7 parts by weight of DPHA as a polyfunctional monomer, and 1.6 parts by weight of CGI 242 as a photopolymerization initiator with respect to 100 parts by weight of this black pigment dispersion Part, 3.2 parts by weight of CGI113 and 55.2 parts by weight of PGMEA as a solvent were mixed to prepare a photosensitive black composition for a resin black matrix.

  Next, in the same manner as in Example 1, a black color filter (resin black matrix) was produced on the substrate so that the film thickness after heating and drying was 1.0 μm. The obtained color filter was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

  When the obtained black color filter was observed with an optical microscope and a scanning electron microscope, some meandering was observed at the edge of the pattern, but the meandering width was all smaller than 2 μm, and the taper shape was forward tapered. Was made. Also, no pattern loss or damage was observed, and the obtained line width was 52.5 μm with respect to the mask design line width of 50 μm, which was almost as designed. The adhesion of the obtained pixel to the substrate was also excellent, and the solubility and sensitivity of the radiation non-irradiated part were good. Further, no scum was observed on the pixel.

Example 8
After mixing 20 parts by weight of carbon black “MA100” manufactured by Mitsubishi Chemical Corporation having a pH of 3.5 as a colorant, 8 parts by weight of polymer A as a binder resin, and 72 parts by weight of PGMEA as a solvent, zirconia beads are filled. Was dispersed using a mill-type disperser to obtain a black pigment dispersion.

  Next, 5 parts by weight of BPEFA as a fluorene structure-containing bifunctional monomer, 2.5 parts by weight of DPHA as a polyfunctional monomer, and R-684 as a bifunctional monomer with respect to 100 parts by weight of this black pigment dispersion. 2.5 parts by weight, 1.6 parts by weight of CGI242 as a photopolymerization initiator, 3.2 parts by weight of CGI113, and 55.2 parts by weight of PGMEA as a solvent are mixed to prepare a photosensitive black composition for a resin black matrix. Prepared.

  Next, in the same manner as in Example 1, a black color filter (resin black matrix) was produced on the substrate so that the film thickness after heating and drying was 1.0 μm. The obtained color filter was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

  When the obtained black color filter was observed with an optical microscope and a scanning electron microscope, a very good pattern with sharp edges was obtained, and the taper shape was a forward taper. Also, no pattern loss or damage was observed, and the obtained line width was 51 μm with respect to the mask design line width of 50 μm, which was almost as designed. The adhesion of the obtained pixel to the substrate was also excellent, and the solubility and sensitivity of the radiation non-irradiated part were good. Further, no scum was observed on the pixel.

Example 9
After mixing 20 parts by weight of carbon black “# 2350” manufactured by Mitsubishi Chemical Corporation having a pH of 2.5 as a colorant, 8 parts by weight of polymer A as a binder resin, and 72 parts by weight of PGMEA as a solvent, zirconia beads are filled. The resulting mixture was dispersed using a mill type disperser to obtain a black pigment dispersion.

  Next, 5 parts by weight of BPEFA as a fluorene structure-containing bifunctional monomer, 2.5 parts by weight of DPHA as a polyfunctional monomer, and R-684 as a bifunctional monomer with respect to 100 parts by weight of this black pigment dispersion. 2.5 parts by weight, 1.6 parts by weight of CGI242 as a photopolymerization initiator, 3.2 parts by weight of CGI113, and 55.2 parts by weight of PGMEA as a solvent are mixed to prepare a photosensitive black composition for a resin black matrix. Prepared.

  Next, in the same manner as in Example 1, a black color filter (resin black matrix) was produced on the substrate so that the film thickness after heating and drying was 1.0 μm. The obtained color filter was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

  When the obtained black color filter was observed with an optical microscope and a scanning electron microscope, a very good pattern with sharp edges was obtained, and the taper shape was a forward taper. Also, no pattern loss or damage was observed, and the obtained line width was 50.5 μm with respect to the mask design line width of 50 μm, almost as designed. The adhesion of the obtained pixel to the substrate was also excellent, and the solubility and sensitivity of the radiation non-irradiated part were good. Further, no scum was observed on the pixel.

Example 10
After mixing 20 parts by weight of carbon black “# 990” manufactured by Mitsubishi Chemical Corporation having a pH of 7.0 as a colorant, 8 parts by weight of polymer A as a binder resin, and 72 parts by weight of PGMEA as a solvent, zirconia beads are filled. The resulting mixture was dispersed using a mill type disperser to obtain a black pigment dispersion.

  Next, 5 parts by weight of BPEFA as a fluorene structure-containing bifunctional monomer, 2.5 parts by weight of DPHA as a polyfunctional monomer, and R-684 as a bifunctional monomer with respect to 100 parts by weight of this black pigment dispersion. 2.5 parts by weight, 1.6 parts by weight of CGI242 as a photopolymerization initiator, 3.2 parts by weight of CGI113, and 55.2 parts by weight of PGMEA as a solvent are mixed to prepare a photosensitive black composition for a resin black matrix. Prepared.

  Next, in the same manner as in Example 1, a black color filter (resin black matrix) was produced on the substrate so that the film thickness after heating and drying was 1.0 μm. The obtained color filter was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

  When the obtained black color filter was observed with an optical microscope and a scanning electron microscope, some meandering was observed at the edge of the pattern, but the meandering width was all smaller than 2 μm, and the taper shape was forward tapered. Was made. Also, no pattern loss or damage was observed, and the obtained line width was a little thicker at 54 μm than the mask design line width of 50 μm, but it was a pattern close to the design. Further, the adhesion and sensitivity of the obtained pixel with the substrate were excellent. The dissolution time of the non-irradiated part was slightly longer, but was within the usable level range. Further, no scum was observed on the pixel.

Comparative Example 1
12 parts by weight of a 46/15/39 (weight ratio) mixture of Pigment Green 36, Pigment Green 7 and Pigment Yellow 150 as a colorant, an acrylic block copolymer polymer dispersant (EFKA Additives Co., Ltd., EFKA) -4330) 5 parts by weight of a 70% by mass methoxypropyl acetate solution, 11 parts by weight of polymer A as a binder resin, and 72 parts by weight of PGMEA as a solvent were dispersed using a mill type disperser filled with zirconia beads, A dispersion was obtained.

  Next, with respect to 100 parts by weight of this pigment dispersion, 0.04 part by weight of polymer A, BPEFA is not added as a reactive monomer, only 11.2 parts by weight of DPHA, and 1 CGI 242 as a photopolymerization initiator. .60 parts by weight, 3.20 parts by weight of CGI113, 0.38 parts by weight of KBM503 as an adhesion improver, 0.08 parts by weight of MegaFac R-08 as a surfactant, and 56.5 parts by weight of PGMEA as a solvent Were mixed to prepare a photosensitive coloring composition.

  Next, a green color filter was produced on the substrate in the same manner as in Example 1. The obtained color filter was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

  When the obtained green color filter was observed with an optical microscope, meandering was observed at the pattern edge portion, and the taper shape was inversely tapered. Further, the obtained line width was 60 μm with respect to the mask design line width of 50 μm, which was significantly thicker than the design dimension. Although the solubility and sensitivity of the non-irradiated part were very good, the adhesion of the obtained pixel to the substrate was poor, and scum was observed on the pixel.

Comparative Example 2
After mixing 20 parts by weight of carbon black “MA100” manufactured by Mitsubishi Chemical Corporation having a pH of 3.5 as a colorant, 8 parts by weight of polymer A as a binder resin, and 72 parts by weight of PGMEA as a solvent, zirconia beads are filled. Was dispersed using a mill-type disperser to obtain a black pigment dispersion.

  Next, 10 parts by weight of DPHA as a polyfunctional monomer, 1.6 parts by weight of CGI242 as a photopolymerization initiator, 3.2 parts by weight of CGI113, and PGMEA55 as a solvent with respect to 100 parts by weight of this black pigment dispersion .2 parts by weight was mixed to prepare a photosensitive black composition for a resin black matrix.

  Next, in the same manner as in Example 1, a black color filter (resin black matrix) was produced on the substrate so that the film thickness after heating and drying was 1.0 μm. The obtained color filter was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

  When the obtained black color filter was observed with an optical microscope and a scanning electron microscope, meandering was observed at the edge of the pattern, and the taper shape was inversely tapered. The obtained line width was 53.5 μm with respect to the mask design line width of 50 μm, which was a pattern close to the design while being slightly thicker, but the adhesion between the pattern and the substrate was poor, and a lack was observed. Furthermore, although there was no problem with the solubility of the non-irradiated part, the sensitivity was poor and scum was observed on the pixels.

Comparative Example 3
After mixing 20 parts by weight of carbon black “# 990” manufactured by Mitsubishi Chemical Corporation having a pH of 7.0 as a colorant, 8 parts by weight of polymer A as a binder resin, and 72 parts by weight of PGMEA as a solvent, zirconia beads are filled. The resulting mixture was dispersed using a mill type disperser to obtain a black pigment dispersion.

  Next, 10 parts by weight of DPHA as a polyfunctional monomer, 1.6 parts by weight of CGI242 as a photopolymerization initiator, 3.2 parts by weight of CGI113, and PGMEA55 as a solvent with respect to 100 parts by weight of this black pigment dispersion .2 parts by weight was mixed to prepare a photosensitive black composition for a resin black matrix.

  Next, in the same manner as in Example 1, a black color filter (resin black matrix) was produced on the substrate so that the film thickness after heating and drying was 1.0 μm. The obtained color filter was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

  When the obtained black color filter was observed with an optical microscope and a scanning electron microscope, meandering was observed at the edge of the pattern, and the taper shape was inversely tapered. Although the obtained line width was a pattern close to the design while being slightly thick at 54.5 μm with respect to the mask design line width of 50 μm, the adhesion between the pattern and the substrate was poor, and a lack was observed. Furthermore, the dissolution time of the non-irradiated part was slightly longer, the sensitivity was poor, and scum was observed on the pixels.

Claims (8)

A photosensitive coloring composition containing a colorant, an alkali-soluble resin, a photopolymerization initiator, a reactive monomer, and an organic solvent, wherein the reactive monomer contains a fluorene structure represented by the following general formula (1) A photosensitive coloring composition comprising a bifunctional monomer.

(Here, R ₁ represents an oxygen atom or —ORO—, wherein R represents an alkyl group having 1 to 6 carbon atoms, and R ₂ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) The photosensitive coloring composition according to claim 1, wherein the fluorene structure-containing bifunctional monomer is bisphenoxyethanol fluorene acrylate. The photosensitive coloring composition according to claim 1 or 2, further comprising a trifunctional or higher polyfunctional acrylic monomer as the reactive monomer. The content of the fluorene structure-containing bifunctional monomer, which is a reactive monomer, is 15 to 85 mass%, and the content of a trifunctional or higher polyfunctional acrylic monomer is 10 to 85 mass%. 3. The photosensitive coloring composition according to 3. The photosensitive coloring composition according to claim 3 or 4, further comprising dicyclopentanedienyl diacrylate as the reactive monomer. The reactive monomer has a fluorene structure-containing difunctional monomer content of 20 to 60% by mass, a trifunctional or higher polyfunctional acrylic monomer content of 20 to 60% by mass, and dicyclopentanedienyl diacrylate. Content is 20-60 mass%, The photosensitive coloring composition of Claim 5 characterized by the above-mentioned. The photosensitive coloring composition according to claim 1, comprising carbon black having a pH of 2 to 5 as the coloring agent. A color filter in which pixels of one color or a plurality of colors are provided in a pattern, wherein the pixels have a colored layer, and at least one of the colored layers is according to any one of claims 1 to 7. A color filter formed of a photosensitive coloring composition.