JP6922155B2 - Green photosensitive coloring composition, color filter and color display device using it - Google Patents

Description

The present invention relates to a green photosensitive coloring composition used for a color filter used in a color display device such as a liquid crystal display device or an EL (electroluminescence) display device, and a color filter and a color display device using the same.

Color display devices are widely used from small-area devices such as mobile phones and digital cameras to large-area devices such as personal computer display devices and televisions. These color display devices are required to have higher performance such as brightness, color reproducibility, and contrast, and even in color filters, which are members of the color display devices, higher brightness and higher color reproduction are required. Sexuality, high contrast, etc. are desired.

The color filter has two or more types of filter segments (pixels) having different hues and a black matrix for partitioning them on the surface of a transparent substrate such as glass, and has an active element such as a TFT (thin film transistor). A color liquid crystal display device, which is a kind of color display device, is provided by combining the liquid crystal display with a polarizing plate and a backlight unit after injecting the liquid crystal into the gap portion.

In order to achieve the wide color reproduction range and high brightness desired for a color filter, recently, in order to form a green filter segment constituting a color filter, a phthalocyanine pigment (for example, a brominated copper phthalocyanine pigment is used for forming a CI. Pigment Green 36, CI Pigment Green 7 made of chlorinated copper phthalocyanine pigment, CI Pigment Green 58 made of chlorinated brominated zinc phthalocyanine pigment, etc.) are used.

However, phthalocyanine is an excellent colorant and at the same time a material also known as an organic semiconductor, and it is known that it becomes a phthalocyanine radical and stabilizes when irradiated with light, particularly under low oxygen concentration (Patent Document 1, Patent Document 1, 2. See Non-Patent Document 1).

This reaction to light is an extremely useful reaction when considering application to solar cells and the like, but it has become a big problem when phthalocyanine is used as a colorant. That is, since the absorption wavelength of the phthalocyanine radical is different from that of the ground state phthalocyanine, the color of the phthalocyanine radical changes when used as a colorant.

In addition, this phenomenon is more likely to occur with zinc phthalocyanine than with copper phthalocyanine, and a remarkable color change is observed.

This phenomenon becomes apparent especially when it is used in a state where it is completely shielded from air, that is, under a low oxygen concentration, such as a liquid crystal display device or an EL display device, and improvement is desired.

As an attempt to solve the color change associated with the generation of radicals by light irradiation as described above, an organic compound having an ultraviolet absorbing function or an antioxidant function is added as a light stabilizer to the photopolymerizable composition for forming a filter segment. (See Patent Documents 3 and 4). However, the effect of this technique is insufficient, and the suitability of pigment dispersion for use in a pigment dispersion method using a pigment that has undergone miniaturization treatment in recent years as a colorant, or a color filter by a photolithography method, There were many problems to be solved such as photolithography suitability.

Japanese Patent No. 2949230 Japanese Patent No. 2958461 Japanese Unexamined Patent Publication No. 2000-214580 Japanese Patent No. 5657452

"Parthalocyanine-Chemistry and Function-", edited by Hirofusa Shirai and Nagao Kobayashi, published by IPC, 1997.

The present invention eliminates the problem of using a phthalocyanine pigment in a color filter for a liquid crystal display device, eliminates the color change due to light irradiation, and provides a highly reliable green photosensitive coloring composition and a color filter using the same. It is an object of the present invention to provide a color display device.

In view of the above, the present invention is a coloring composition containing at least (a) a dye, (b) a pigment dispersant, (c) a transparent resin, (d) a photopolymerizable monomer, and (e) a photopolymerization initiator. The dye (a) is a zinc halide phthalocyanine compound, and the isoindole having a phthalocyanine structure contained in at least one compound among the compound that becomes the dye (a) or a derivative that may be contained. It is a green photosensitive coloring composition characterized in that one hydrogen atom at the α-position of the ring is substituted with a cyano group or an N-substituted maleimide group.

Further, in the uniform of the present invention, when the dye (a) or the dye derivative which may be contained contains a phthalocyanine structure, the molar ratio of the cyano group or the N-substituted maleimide group to the phthalocyanine structure is 1. It is a green photosensitive coloring composition characterized by being ~ 16.

In the uniform of the present invention, when the dye (a) or the dye derivative which may be contained contains a quinophthalone structure, the molar ratio of the cyano group or the N-substituted maleimide group to the quinophthalone structure is 1 to 8. It is a green photosensitive coloring composition characterized by the above.

The uniform form of the present invention is a green photosensitive coloring composition characterized in that the zinc halide phthalocyanine contained in the dye (a) is chlorinated zinc phthalocyanine.

Uniform body of the present invention, on a transparent substrate, at least the black matrix, a color filter having a plurality of colored filter segments comprising green filter segment, a green filter formed by using the pre-Symbol green photosensitive coloring composition It is a color filter characterized by having segments.

The uniform of the present invention is a color display device including the color filter.

According to the green photosensitive coloring composition of the present invention, it is possible to provide a green photosensitive coloring composition, a color filter, and a color display device, which are difficult to change color even when irradiated with light under a low oxygen concentration.

Hereinafter, typical embodiments for carrying out the present invention will be described, but the present invention is not limited to the following embodiments.

First, the green photosensitive coloring composition of the present invention will be described.

The green photosensitive coloring composition of the present invention contains (a) dye, (b) pigment dispersant, (c) transparent resin, (d) photopolymerizable monomer, and (e) photopolymerization initiator as essential components thereof. Is what you do. Further, it may contain additives such as a dye derivative, a solvent, a dispersant, a photosensitizer, a chain transfer agent, and a storage stabilizer.

(A) Dyes and Dye Derivatives Examples of the green dye or dye derivative that can be used in the green coloring composition of the present invention include C.I. I. Pigment Green 7, 10, 36, 37, 58, 59, etc., or Japanese Patent No. 5581566, International Publication No. 2015/122372, Japanese Patent Application Laid-Open No. 2015-11124, Japanese Patent No. 5568804, Japanese Patent Application Laid-Open No. 2010-007084. , The green pigment described in International Publication No. 2014/021086. In particular, C.I. I. Halogenated zinc phthalocyanine containing a brominated zinc phthalocyanine pigment represented by Pigment Green 58 is effective for increasing the transmittance.

It is preferable to use a yellow dye or a dye derivative in combination with the green photosensitive coloring composition of the present invention in order to adjust the hue.

The yellow pigment or pigment derivative that can be used in the green coloring composition of the present invention is, for example, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37 , 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104 , 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154. , 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193. , 194, 198, 199, 213, 214, etc., C.I. I. SolventYello2, 3, 7, 12, 13, 14, 16, 18, 19, 21, 25, 25: 1, 27, 28, 29, 30, 33, 34, 36, 42, 43, 44, 47, 56, 62, 72, 73, 77, 79, 81, 82, 83, 83: 1, 88, 89, 90, 93, 94, 96, 98, 104, 107, 114, 116, 117, 124, 130, 131, 133, 135, 141, 143, 145, 146, 157, 160: 1, 161, 162, 163, 167, 169, 172, 174, 175, 176, 179, 180, 181, 182, 183, 184, 185, 186, 187, 189, 190, 191 and C.I. I. BasicYello 11, 23, 25, 28, 41, C.I. I. DirectYellow26, 27, 28, 33, 44, 50, 86, 142, C.I. I. SulfurYellow4, C.I. I. ReactiveYello1, 2, 4, 14, 16, C.I. I. VatYellow2, 12, 20, 33, C.I. I. Disperse Yellow 3, 4, 5, 7, 23, 33, 42, 60, 64, etc., Japanese Patent Application Laid-Open No. 2009-145721, Japanese Patent Application Laid-Open No. 2013-120309, Japanese Patent No. 4525122, Japanese Patent Application Laid-Open No. 2014-177627, Examples thereof include the yellow dyes described in Japanese Patent Application Laid-Open No. 2013-231165, Japanese Patent Application Laid-Open No. 2013-151668, and Japanese Patent Application Laid-Open No. 2014-051641. Among these, from the viewpoint of increasing brightness, C.I. I. Pigment Yellow 138 and C.I. I. It is preferable to use Pigment Yellow 150.

Further, in the green photosensitive coloring composition of the present invention, coloring components other than green and yellow, such as a blue pigment, a blue dye, a red pigment, and a red dye, may be used in combination in order to adjust the hue.

Examples of coloring components other than green and yellow include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 81: 4, 146, 168, 177, 178, 184, 185, 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272, 279, C.I. I. Pigment Orange 43, 71, 73, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, C.I. I. Direct Blue 1, 2, 6, 8, 15, 22, 25, 41, 71, 76, 77, 78, 80, 86, 90, 98, 106, 108, 120, 158, 160, 163, 165, 168, 192 , 193, 194, 195, 196, 199, 200, 201, 202, 203, 207, 225, 226, 236, 237, 246, 248, 249, C.I. I. Acid Blue 1, 7, 9, 15, 22, 23, 25, 27, 29, 40, 41, 43, 45, 54, 59, 60, 62, 72, 74, 78, 80, 82, 83, 90, 92, 93, 100, 102, 103, 104, 112, 113, 117, 120, 126, 127, 129, 130, 131, 138, 140, 142, 143, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 229, 234, 236, C.I. I. Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, Source Blue 4, 5, 35, 45, 59, 67, 70, 90, 97, 101, 104, 122, C.I. I. Solvent Orange 1, 2, 3, 4, 5, 7, 11, 14, 20, 23, 25, 31, 40: 1, 41, 45, 54, 56, 58, 60, 62, 63, 70, 75, 77, 80, 81, 86, 99, 102, 103, 105, 106, 107, 108, 109, 110, 111, 112, 113, C.I. I. SolventRed1, 2, 3, 4, 8, 16, 17, 18, 19, 23, 24, 25, 26, 27, 30, 33, 35, 41, 43, 45, 48, 49, 52, 68, 69, 72, 73, 83: 1, 84: 1, 89, 90, 90: 1, 91, 92, 106, 109, 110, 111, 118, 119, 122, 124, 125, 127, 130, 132, 135, 141, 143, 145, 146, 149, 150, 151, 155, 160, 161, 164, 164: 1, 165, 166, 168, 169, 172, 175, 179, 180, 181, 182, 195, 196, 197, 198, 207, 208, 210, 212, 214, 215, 218, 222, 223, 225, 227, 229, 230, 233, 234, 235, 236, 238, 239, 240, 241, 242, 243, 244, 245, 247, 248, C.I. I. AcidRed6, 11, 26, 60, 88, 111, 186, 215, C.I. I. AcidYello 17, 23, 25, 36, 38, 42, 44, 72, 78, C.I. I. BasicRed1, 2, 13, 14, 22, 27, 29, 39, C.I. I. DirectRed4, 23, 31, 75, 76, 79, 80, 81, 83, 84, 149, 224, C.I. I. Direct Orange 26, 29, 34, 37, 72, C.I. I. SulfurRed 5, 6, 7, C.I. I. VatRed 13, 21, 23, 28, 29, 48, C.I. I. VatOrange 2, 5, 11, 15, 18, 20, C.I. I. ReactiveRed8, 22, 46, 120, C.I. I. Reactive Orange 1, 4, 7, 13, 16, 20, C.I. I. DisperseRed4, 11, 54, 55, 58, 65, 73, 127, 129, 141, 196, 210, 229, 354, 356, C.I. I. Disperse Orange 13, 29, 30, and the like can be mentioned.

A dye derivative is a compound in which a substituent is introduced into an organic dye. In addition to the above, the dye derivative includes a substituent having an amine site, an imine site, an ammonium site, an amide site, an imide site, a urethane bond site and the like as a basic dye derivative. Examples of those having an acidic group include a sulfo group, a sulfonat group, a sulfonamide group, a sulfonic acid group and a carboxyl group.
Organic dyes also include pale yellow aromatic polycyclic compounds such as naphthalene and anthraquinone, which are not generally called dyes. Examples of the dye derivative are described in JP-A-63-305173, Japanese Patent Publication No. 57-15620, Japanese Patent Publication No. 59-40172, Japanese Patent Application Laid-Open No. 63-17102, Japanese Patent Publication No. 5-1469, and the like. These can also be used alone or in admixture of two or more.

The present invention is characterized in that at least one of (a) a dye or a dye derivative that may be contained contains a cyano group or an N-substituted maleimide group. (A) By containing a cyano group or an N-substituted maleimide group in the dye or dye derivative, the phthalocyanine anion radical generated by light irradiation can be inactivated to the basal phthalocyanine, and the color change can be suppressed.

The structures of these compounds are shown in the following chemical formulas (1) to (4).

In these chemical formulas, Dye represents a dye or dye derivative residue, and examples thereof include those shown above. R may be substituted containing, for example, S, SO2, CO, N, O, alkyl groups, optionally substituted alkenyl groups, optionally substituted phenyl groups, N, S, O atoms. Heterocyclic residues can be mentioned. n is the number of bonds of a cyano group or an N-substituted maleimide group per Dye.

When the (a) dye containing the cyano group or the N-substituted maleimide group or the dye derivative which may be contained contains a phthalocyanine structure, the molar ratio of the cyano group or the N-substituted maleimide group to the phthalocyanine structure is 1 to 1. It is preferably 16. If the molar ratio of the cyano group or the N-substituted maleimide group to the phthalocyanine structure is less than 1, a large effect of improving light resistance cannot be obtained, and if it is larger than 16, the chromaticity and lightness are significantly different from those of the original dye or dye derivative. Or, the stability may deteriorate.

When the (a) dye containing the cyano group or the N-substituted maleimide group or the dye derivative which may be contained contains a quinophthalone structure, the molar ratio of the cyano group or the N-substituted maleimide group to the quinophthalone structure is 1 to 1. It is preferably 8. If the molar ratio of the cyano group or the N-substituted maleimide group to the quinophthalone structure is less than 1, a large effect of improving light resistance cannot be obtained, and if it is larger than 8, the chromaticity and lightness are significantly different from those of the original dye or dye derivative. Or, the stability may deteriorate.

(B) The pigment dispersant will be described later.

(C) Transparent Resin The transparent resin that can be used in the green photosensitive coloring composition of the present invention has 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. Can be used. The transparent resin includes a thermoplastic resin, a non-photosensitive resin such as a thermosetting resin, and a photosensitive resin, and these may be used alone or in combination of two or more. The resin may have an imide structure, a cyano group or an N-substituted maleimide group.

The molecular weight of the transparent resin is preferably in the range of 3,000 to 100,000. If the molecular weight of the transparent resin is less than 3,000, the linearity of the color filter pattern deteriorates during development, the film loss rate increases, and the cross-sectional shape of the color filter pattern deteriorates. On the contrary, if it is 100,000 or more, the development time becomes slow and the productivity decreases. Therefore, more preferably, the range is 20,000 to 60,000.

The non-photosensitive transparent resin is a resin that does not have an ethylenically unsaturated double bond, and examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, and polychloride. Vinyl, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, polyester resin, acrylic resin, alkyd resin, styrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polybutadiene, etc. Can be mentioned.

Examples of the thermosetting resin include epoxy resin, benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, phenol resin, melamine resin, urea resin, and polyimide resin, and melamine resin or epoxy resin. Is preferable. However, most of these resins do not show alkali solubility.

The photosensitive resin is an ethylene unsaturated double bond obtained by reacting a linear polymer having a reactive functional group with a (meth) acrylic compound having a substituent capable of reacting with the reactive functional group, silicic acid, or the like. Examples thereof include a resin in which a bond is introduced into the linear polymer. Further, an ethylene unsaturated double bond is formed by reacting a (meth) acrylic compound having a reactive functional group, silicic acid, or the like with a linear polymer having a substituent capable of reacting with the reactive functional group. Examples thereof include the resin introduced into the state polymer. Examples of the reactive functional group include a hydroxyl group, a carboxyl group and an amino group, and examples of the substituent capable of reacting with the reactive functional group include an isocyanate group, an aldehyde group and an epoxy group.

Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is used as a (meth) acrylic compound having a hydroxyl group such as a hydroxyalkyl (meth) acrylate. The one half-esterified with the above can also be used as a photosensitive resin.

The amount of ethylenically unsaturated double bonds introduced into the photosensitive transparent resin via a hydroxyl group or the like, which indicates the susceptibility to photocuring, is indicated by the "double bond equivalent" of the obtained photosensitive transparent resin. .. The double bond equivalent of the photosensitive transparent resin is preferably 200 to 1200, more preferably 300 to 900. When the double bond equivalent of the photosensitive transparent resin is less than 200, the proportion of the ethylenically unsaturated monomer having a reactive substituent that introduces an ethylenically unsaturated double bond becomes high, and various properties are maintained. It is not possible to copolymerize a sufficient amount of other ethylenically unsaturated monomers. If it exceeds 1200, sufficient sensitivity cannot be obtained because the number of ethylenically unsaturated double bonds is small.

(D) Photopolymerizable Monomer The photopolymerizable monomer used in the green photosensitive coloring composition of the present invention contains one or more ethylenically unsaturated double bonds in one molecule. Further, it is preferable that one molecule contains two or more ethylenically unsaturated double bonds. These photopolymerizable monomers may be used alone or in combination of two or more. Further, the photopolymerizable monomer may have an imide structure, a cyano group or an N-substituted maleimide group in the resin.

Examples of the photopolymerizable monomer include N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-laurylmaleimide, and 1.2-bismaleimide. Etan, 1,4-bismaleimidebutane, 1,6-bismaleimidehexane, 4,4'-bismaleimidediphenylmethane, 4-aminophenylmaleimide, N-methoxycarbonylmaleimide, 3-maleimidepropionic acid, 4-maleimidebutyric acid, Maleimides such as 6-maleimidehexanoic acid, 4-nitrophenylmaleimide, 3-maleimide propionate N-succinimidyl, maleimide (meth) acrylates, N-acrylicoxysuccinimide, N-acrylicoxyphthalimide, N-acryloyloxyethyl Compounds having both an imide structure such as hexahydrophthalimide and a (meth) acryloyl group, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol (meth) Acryloyl, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, 3-methylpentanediol di (meth) acrylate, diethylene glycol bis β- (meth) acryloyloxypropinate, trimethylol ethanetri (meth) acrylate, trimethylpropantri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (2-hydroxy) Ethyl) isocyanate di (meth) acrylate, pentaerythritol tetra (meth) acrylate, 2,3-bis (meth) acryloyloxyethyloxymethyl [2.2.1] heptane, poly 1,2-butadiene di (meth) acrylate , 1,2-bis (meth) acryloyloxymethylhexane, nonaethylene glycol di (meth) acrylate, tetradecaneethylene glycol di (meth) acrylate, 10-decanediol (meth) acrylate, 3,8-bis (meth) acryloyl Oxymethyltricyclo [5.2.10] decane, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propa , 1,4-Bis ((meth) acryloyloxymethyl) cyclohexane, hydroxypivalic acid ester neopentyl glycol di (meth) acrylate, ethoxylated bisphenol A diacrylate, propoxylated bisphenol A diacrylate, propoxylated ethoxylated bisphenol A Diacrylate, ethoxylated bisphenol B diacrylate, propoxylated bisphenol B diacrylate, propoxylated ethoxylated bisphenol B diacrylate, ethoxylated bisphenol E diacrylate, propoxylated bisphenol E diacrylate, propoxylated ethoxylated bisphenol E diacrylate, ethoxy Typical examples include various acrylic acid esters such as bisphenol F diacrylate, propoxylated bisphenol F diacrylate, and propoxylated ethoxylated bisphenol F diacrylate, and methacrylic acid esters. As the photopolymerizable monomer, if necessary, a photopolymerizable monomer copolymerized with each other may be used.

In the present invention, "(meth) acrylate" means both "acrylate" and "methacrylate". Moreover, "(meth) acryloyl group" means both "acryloyl group" and "methacryloyl group". For example, "urethane (meth) acrylate" indicates both "urethane acrylate" and "urethane methacrylate".

(E) Photopolymerization initiator The photopolymerization initiator used in the green photosensitive coloring composition of the present invention includes an oxime ester-based photopolymerization initiator, an acetophenone-based compound, a benzoin-based compound, a benzophenone-based compound, and a thioxanson-based compound. Examples thereof include triazine-based compounds, phosphine-based compounds, quinone-based compounds, borate-based compounds, carbazole-based compounds, imidazole-based compounds, and titanosen-based compounds.

Particularly preferred oxime ester-based photopolymerization initiators include etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (0-acetyloxime), 1 , 2-Octadion-1- [4- (phenylthio)-, 2- (O-benzoyloxime)] and the like.

Examples of acetophenone compounds include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, and 1-hydroxy. Cyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- 1-on and the like can be mentioned.

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyl dimethyl ketal.

Examples of the benzophenone compound include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylicized benzophenone, 4-benzoyl-4'-methyldiphenylsulfide and the like. Examples of the thioxanthone compound include thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone and the like.

Examples of triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, and 2- (p-methoxyphenyl) -4,6-bis. (Trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-pipenyl-4,6-bis (trichloromethyl) -s-triazine, 2 , 4-Bis (trichloromethyl) -6-styryl s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphtho-1) -Il) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine And so on.

Examples of the phosphine compound include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like.

Examples of the quinone compound include 9,10-phenanthrene quinone, camphorquinone, and ethyl anthraquinone.

(solvent)
The green coloring composition of the present invention is photosensitively colored in order to facilitate the formation of a filter segment by applying it on a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. A solvent can also be used to optimize the viscosity of the composition and to sufficiently disperse the colorant in the photosensitive coloring composition.
As the solvent, water, an organic solvent and the like can be used. Examples of the organic solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-N-amyl ketone. , Propylene glycol monomethyl ether toluene, methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent and the like, and these are used alone or in combination. The solvent can be used in an amount of preferably 800 to 4000 parts by mass, more preferably 1000 to 2500 parts by mass with respect to 100 parts by mass of the coloring material.

(Dispersant)
Dispersants such as resin-type pigment dispersants, pigment derivatives, and surfactants can be used as appropriate. Since the dispersant is excellent in dispersing the pigment and has a great effect of preventing the reaggregation of the pigment after dispersion, when a coloring composition obtained by dispersing the pigment in the photosensitive coloring composition using the dispersant is used. A color filter having excellent transparency can be obtained. The amount of the dispersant added is not particularly limited, but is preferably 0.1 to 40 parts by mass, more preferably 0.1 to 30 parts by mass, and further preferably 1 to 1 part by mass with respect to 100 parts by mass of the coloring pigment. It can be used in an amount of 10 parts by mass.

(Resin type dispersant)
The resin-type pigment dispersant has a pigment-affinitive portion having a property of adsorbing to the pigment and a portion compatible with the photosensitive transparent resin and the non-photosensitive transparent resin, and is adsorbed on the pigment to make the pigment photosensitive. It functions to stabilize the dispersion in the coloring composition.
Examples of the resin-type pigment dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, and poly. Siloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly (lower alkyleneimine) with polyesters having free carboxyl groups, and salts thereof. Used. In addition, water-soluble resins such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, and polyvinylpyrrolidone, and water-soluble. Polymer compounds, polyester-based, modified polyacrylates, ethylene oxide / propylene oxide adducts and the like are also used. These can be used alone or in admixture of two or more.

Examples of commercially available resin-type pigment dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, manufactured by Big Chemie. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, or Lactimon, LactimoN-WS or Bykumen Etc., SOLPERS E-3000, 9000, 13240, 13650, 13940, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32600, 34750, 36600, 38500, 41000 , 41090, 53095, etc., EFKA-46, 47, 48, 452, LP4008, 4009, LP4010, LP4050, LP4055, 400, 401, 402, 403, 450, 451, 453, 4540, 4550, manufactured by Fuka Chemicals. LP4560, 120, 150, 1501, 1502, 1503 and the like can be mentioned.

(Surfactant)
Examples of the surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalin sulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate, and lauryl. Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymer; polyoxyethylene oleyl ether, polyoxyethylene Nonionic surfactants such as lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts. Examples thereof include alkyl betaines such as alkyl dimethylamino acetate betaine and amphoteric surfactants such as alkyl imidazoline, which can be used alone or in admixture of two or more.

(Photosensitizer)
A photosensitizer can be added to the green photosensitive coloring composition of the present invention in addition to the polymerization initiator. As the photosensitizer, an amine compound can be exemplified. For example, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4-dimethylaminobenzoate. With 2-ethylhexyl acid, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone, etc. be.

In addition, α-acyloxime ester, acylphosphine oxide, methylphenylglycilate, benzyl, 9,10-phenanthrene quinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalofenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone and the like can also be used as a sensitizer. The amount of these sensitizers used is preferably 0.5 to 60% by mass, more preferably 3 to 40% by mass, based on the total amount of the photopolymerization initiator and the sensitizer.

(Chain transfer agent)
The green photosensitive coloring composition of the present invention can further contain a polyfunctional thiol that acts as a chain transfer agent. The polyfunctional thiol may be used alone or in combination of two or more. The content of the polyfunctional thiol is preferably 0.05 to 100 parts by mass, more preferably 0.1 to 60 parts by mass with respect to 100 parts by mass of the pigment.

(Storage stabilizer)
The green photosensitive coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Further, an adhesion improver such as a silane coupling agent can be contained in order to improve the adhesion with the transparent substrate. The storage stabilizer can be used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the pigment in the photosensitive coloring composition.

The method for obtaining the color filter of the present invention will be described below. The color filter of the present invention is a color filter having at least a plurality of color filter segments on a transparent substrate and having filter segments formed by using the green photosensitive coloring composition of the present invention. Color filters include an additive color filter segment comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment, and at least one magenta color filter segment, at least one cyan filter segment. And there are reduced color mixing types that include at least one yellow filter segment.

The red filter segment can be formed using a conventional red photosensitive coloring composition. The red photosensitive coloring composition is described in, for example, C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 81: 4, 146, 168, 177, 178, 184, It is a composition obtained by using a red pigment such as 185, 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272, 279. The red photosensitive coloring composition includes C.I. I. Orange pigments such as Pigment Orange 43, 71, 73 can be used in combination.

The green filter segment can be formed using the green photosensitive coloring composition of the present invention.

Further, the blue filter segment can be formed by using a usual blue photosensitive coloring composition. Instead of the green pigment, the blue photosensitive coloring composition is described in, for example, C.I. I. It is a composition obtained by using a blue pigment such as Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 and the like. For the blue photosensitive coloring composition, as a direct dye, C.I. I. Direct Blue 1, 2, 6, 8, 15, 22, 25, 41, 71, 76, 77, 78, 80, 86, 90, 98, 106, 108, 120, 158, 160, 163, 165, 168, 192 , 193, 194, 195, 196, 199, 200, 201, 202, 203, 207, 225, 226, 236, 237, 246, 248, 249, etc., as acid dyes, C.I. I. Acid Blue 1, 7, 9, 15, 22, 23, 25, 27, 29, 40, 41, 43, 45, 54, 59, 60, 62, 72, 74, 78, 80, 82, 83, 90, 92, 93, 100, 102, 103, 104, 112, 113, 117, 120, 126, 127, 129, 130, 131, 138, 140, 142, 143, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 229, 234, 236, etc., as basic dyes, C.I. I. Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, As the oil-soluble dyes such as 67 and 68, dyes such as Sovent Blue 4, 5, 35, 45, 59, 67, 70, 90, 97, 101, 104 and 122 can also be used.

The color filter of the present invention can be manufactured by forming filter segments of each color on a transparent substrate by a photolithography method. As the transparent substrate, a substrate having a certain transmittance with respect to visible light can be used. A glass plate or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is used. When a light-shielding pattern is used, a transparent substrate on which a pattern made of a metal thin film such as chromium or a light-shielding resin is previously attached by a known method may be used.

Each color filter segment is formed on the transparent substrate by the following method by a photolithography method. That is, the photosensitive coloring composition is applied onto a transparent substrate by a coating method such as spray coating, spin coating, slit coating or roll coating so that the dry film thickness is 0.2 to 5 μm.

If necessary, the dried film is exposed to ultraviolet rays through a mask having a predetermined pattern provided in contact with or without contact with the film. Then, it is necessary to immerse it in a solvent or an alkaline developer, or spray the developer with a spray or the like to remove the uncured portion to form a desired pattern, and then to promote the polymerization of the photosensitive coloring composition. Heating can also be applied accordingly. According to the photolithography method, a color filter having higher accuracy than the printing method can be manufactured.

At the time of development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as the alkaline developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant can be added to the developing solution. In order to increase the UV exposure sensitivity, the photosensitive coloring composition is applied and dried, and then a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to prevent polymerization inhibition by oxygen. After forming, ultraviolet exposure can also be performed.

By repeating the above series of steps by changing the photosensitive coloring composition and the pattern and repeating the process as many times as necessary, a color filter having a coloring pattern in which the required number of colors is combined, that is, a filter segment of a plurality of colors can be obtained.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to this as long as it does not deviate from the gist of the present invention.

First, a method for preparing a resin-type dispersant solution, a transparent resin solution, a pigment dispersion, and a photosensitive composition used in Examples and Comparative Examples will be described.

[Preparation of resin-type dispersant solution]
A commercially available resin-type dispersant (EFKA4300 manufactured by BASF) and propylene glycol monomethyl ether acetate were used to prepare a 40% by weight non-volatile content solution, which was used as a resin-type dispersant solution.

[Preparation of pigment dispersion resin solution]
Put 370 parts of cyclohexanone in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a separable 4-neck flask, heat to 80 ° C while injecting nitrogen gas into the vessel, and methacrylic acid at the same temperature. 23 parts of acid (MAA), 17 parts of 2-hydroxyethyl methacrylate (HEMA), 25 parts of N-butyl methacrylate (BMA), 22 parts of benzyl methacrylate (BzMA), paracumylphenol ethylene oxide-modified acrylate (manufactured by Toa Synthetic Co., Ltd.) A mixture of 13 parts of "Aronix (registered trademark) M110") and 12.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction. After completion of the dropping, the mixture was further reacted at 80 ° C. for 3 hours, then a solution prepared by dissolving 3.0 parts of azobisisobutyronitrile in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour to carry out the acrylic resin. A solution was obtained. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and cyclohexanone was added to the previously synthesized resin solution so that the non-volatile content was 20% by mass. To prepare a pigment-dispersed resin.

[Preparation of transparent resin solution]
Put 70 parts of cyclohexanone in the reaction vessel, heat to 80 ° C while injecting nitrogen gas into the vessel, and at the same temperature, 50 parts of cyclohexylmaleimide as N-substituted maleimide, 15 parts of hydroxyethyl methacrylate, and 12 parts of methacrylic acid. A mixture of 23 parts of methyl methacrylate and 0.4 parts of azobisisobutyronitrile was added dropwise over 2 hours to carry out a polymerization reaction. After completion of the dropping, the reaction was further carried out 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 to prevent non-dropping. A photosensitive transparent resin copolymer solution was obtained. After cooling to room temperature, about 2 g of the non-photosensitive transparent resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. A non-photosensitive resin solution was prepared by adding cyclohexanone so as to obtain a transparent resin solution.

[Preparation of pigments or pigment derivatives]
-Synthesis Example 1: Green compound 1 (phthalocyanine compound having a maleimide group)
In a 200 ml 4-port flask, 5.9 g of 4,5-dichlorophthalonitrile, 1.6 g of 3-methylmaleimidephthalonitrile, and 10 ml of methylnaphthalene are charged, and 30 ml of a methylnaphthalene solution containing 1.8 g of zinc iodide is added thereto. Added. It was heated at 190-200 ° C. for 6 hours in a nitrogen atmosphere. The precipitate was collected by filtration, washed in the order of methanol, N-methylpyrrolidone, and methanol, dried, and phthalocyanine compound 5 containing ZN-hexachloro-maleimide phthalocyanine represented by the following chemical formula (5) as a main product. .51 g was obtained.

This compound was dispersed in 285 times the amount of 95% concentrated sulfuric acid, stirred for 6 hours, then poured into 10 times the amount of concentrated sulfuric acid in ice water, and the precipitated crystals were collected by filtration, washed with water, and dried for pigmentation. rice field.

-Synthesis Example 2: Green compound 2 (phthalocyanine compound having a cyano group)
5.9 g of 4,5-dichlorophthalonitrile, 1.6 g of 3-cyanophthalonitrile, and 10 ml of methylnaphthalene are charged in a 200 ml 4-port flask, and 30 ml of a methylnaphthalene solution containing 1.8 g of zinc iodide is added thereto. bottom. It was heated at 190-200 ° C. for 6 hours in a nitrogen atmosphere. The precipitate was collected by filtration, washed in the order of methanol, N-methylpyrrolidone, and methanol, dried, and phthalocyanine compound 5 containing ZN-hexachloro-cyanophthalocyanine represented by the following chemical formula (6) as a main product. 0.02 g was obtained.

-Synthesis Example 3: Yellow compound 1 (quinophthalone compound having a maleimide group)
20.5 g of maleimide and 7.4 g of paraformaldehyde were alternately added little by little under stirring to 560 g of 3.6 mass% fuming sulfuric acid at 25 ° C. The mixture was heated to 50 ° C. and stirred at this temperature for 30 minutes. C. I. After adding 100 g of Pigment Yellow 138 (BASF's "PALIOTOL YELLOW K0 961HD"), the mixture was heated to 100 ° C. and stirred at this temperature for an additional 3 hours. The reaction mixture was then added to 3500 g of water and stirred at 60 ° C. for 30 minutes. The product precipitated in this manner is filtered off, washed to neutrality with water, dried at 90 ° C. in a vacuum drying shelf, and 101.2 g of the phthalocyanine compound represented by the following chemical formula (7) is a gold-yellow powder. Obtained as.

-Synthesis Example 4: Yellow compound 2 (quinophthalone compound having a cyano group)
1200 g of chlorosulfonic acid and C.I. I. 200 g of Pigment Yellow 138 (“PALIOTOL YELLOW K0 961HD” manufactured by BASF) was heated to 120 ° C. and stirred at this temperature for 2 hours. After cooling to ≦ 80 ° C. and adding 123 g of thionyl chloride, the mixture was further stirred at 80 ° C. for 30 minutes. After cooling to 25 ° C., the reaction mixture was added to 3500 g of the ice / water mixture, in which the amount of ice not exceeding 3 ° C. was added. After stirring for 15 minutes, the precipitated product was filtered off and washed with water until sulfate-free. A mixture consisting of 614 g of this water-containing product (content about 18.5%) and 1000 g of ice / water-mixture were cooled to <2 ° C. The pH value of the mixture was adjusted to 8.7 by the addition of about 8 g of sodium carbonate. Subsequently, a mixture consisting of 10 g of cyanamide and 100 g of water adjusted to a pH value of 7 with 8.15 g of glacial acetic acid was added dropwise under stirring over 30 minutes. At that time, the pH-value lowered to 5.7 was adjusted to 7 by adding sodium carbonate. After stirring for 1 hour, the product was filtered off, washed neutrally with water and dried in a vacuum drying shelf at 90 ° C. 92 g of the quinophthalone compound represented by the following chemical formula (8) was obtained as a yellow powder.

[Preparation of pigment dispersion]
・ Red pigment dispersion PR
After uniformly stirring and mixing the mixture having the following composition, the mixture was dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) for 5 hours using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. A red pigment dispersion PR was prepared.
In the following, "part" means a mass part.
Red pigment 1: C.I. I. Pigment Red 254 7.5 copies (BASF's "Irgafore Red B-CF")
Red pigment 2: C.I. I. Pigment Red 177 1.2 copies (BASF's "Chromoftal Red A2B")
Yellow pigment 1: C.I. I. Pigment Yellow 150 1.0 copy (Lanxess "E4GN")
Diketopyrrolopyrrole pigment derivative 2.3 parts Resin type dispersant solution 3.0 parts Pigment dispersion resin solution 34.0 parts Propylene glycol monomethyl ether acetate 51.0 parts

-Green pigment dispersion PG-1
A green pigment dispersion PG-1 was prepared in the same manner as the red pigment dispersion PR using a mixture having the following composition. The green compound and the yellow compound shown below are the compounds shown in the above-mentioned Synthesis Examples 1 to 4.
Green pigment 1: C.I. I. Pigment Green58 4.5 copies (DIC Corporation "Fastgen Green A110")
Green compound 1 4.5 parts Yellow pigment 1: C.I. I. Pigment Yellow138 3.0 copies (BASF's "PALIOTOL YELLOW K0 961HD")
Resin type dispersant solution 3.0 parts Pigment dispersion resin solution 34.0 parts Propylene glycol monomethyl ether acetate 51.0 parts

-Green pigment dispersion PG-2
A green pigment dispersion PG-2 was prepared in the same manner as the red pigment dispersion PR using a mixture having the following composition.
Green pigment 1: C.I. I. Pigment Green58 4.5 copies (DIC Corporation "Fastgen Green A110")
Green compound 2 4.5 parts Yellow pigment 1: C.I. I. Pigment Yellow138 3.0 copies (BASF's "PALIOTOL YELLOW K0 961HD")
Resin type dispersant solution 3.0 parts Pigment dispersion resin solution 34.0 parts Propylene glycol monomethyl ether acetate 51.0 parts

-Green pigment dispersion PG-3
A green pigment dispersion PG-3 was prepared in the same manner as the red pigment dispersion PR using a mixture having the following composition.
Green pigment 1: C.I. I. Pigment Green58 9.0 copies (DIC Corporation "Fastgen Green A110")
Yellow pigment 1: C.I. I. Pigment Yellow138 1.5 copies (BASF's "PALIOTOL YELLOW K0 961HD")
Yellow compound 1 1.5 parts Resin type dispersant solution 3.0 parts Pigment dispersion resin solution 34.0 parts Propylene glycol monomethyl ether acetate 51.0 parts

-Green pigment dispersion PG-4
A green pigment dispersion PG-4 was prepared in the same manner as the red pigment dispersion PR using a mixture having the following composition.
Green pigment 1: C.I. I. Pigment Green58 9.0 copies (DIC Corporation "Fastgen Green A110")
Yellow pigment 1: C.I. I. Pigment Yellow138 1.5 copies (BASF's "PALIOTOL YELLOW K0 961HD")
Yellow compound 2 1.5 parts Resin type dispersant solution 3.0 parts Pigment dispersion resin solution 34.0 parts Propylene glycol monomethyl ether acetate 51.0 parts

-Green pigment dispersion PG-5
A green pigment dispersion PG-1 was prepared in the same manner as the red pigment dispersion PR using a mixture having the following composition.
Green pigment 1: C.I. I. Pigment Green58 4.5 copies (DIC Corporation "Fastgen Green A110")
Green compound 1 4.5 parts Yellow pigment 1: C.I. I. Pigment Yellow138 1.5 copies (BASF's "PALIOTOL YELLOW K0 961HD")
Yellow compound 1 1.5 parts Resin type dispersant solution 3.0 parts Pigment dispersion resin solution 34.0 parts Propylene glycol monomethyl ether acetate 51.0 parts

-Green pigment dispersion PG-6
A green pigment dispersion PG-1 was prepared in the same manner as the red pigment dispersion PR using a mixture having the following composition.
Green pigment 1: C.I. I. Pigment Green58 4.5 copies (DIC Corporation "Fastgen Green A110")
Green compound 1 4.5 parts Yellow pigment 1: C.I. I. Pigment Yellow138 1.5 copies (BASF's "PALIOTOL YELLOW K0 961HD")
Yellow compound 2 1.5 parts Resin type dispersant solution 3.0 parts Pigment dispersion resin solution 34.0 parts Propylene glycol monomethyl ether acetate 51.0 parts

-Green pigment dispersion PG-7
A green pigment dispersion PG-1 was prepared in the same manner as the red pigment dispersion PR using a mixture having the following composition.
Green pigment 1: C.I. I. Pigment Green58 4.5 copies (DIC Corporation "Fastgen Green A110")
Green compound 2 4.5 parts Yellow pigment 1: C.I. I. Pigment Yellow138 1.5 copies (BASF's "PALIOTOL YELLOW K0 961HD")
Yellow compound 1 1.5 parts Resin type dispersant solution 3.0 parts Pigment dispersion resin solution 34.0 parts Propylene glycol monomethyl ether acetate 51.0 parts

-Green pigment dispersion PG-8
A green pigment dispersion PG-1 was prepared in the same manner as the red pigment dispersion PR using a mixture having the following composition.
Green pigment 1: C.I. I. Pigment Green58 4.5 copies (DIC Corporation "Fastgen Green A110")
Green compound 2 4.5 parts Yellow pigment 1: C.I. I. Pigment Yellow138 1.5 copies (BASF's "PALIOTOL YELLOW K0 961HD")
Yellow compound 2 1.5 parts Resin type dispersant solution 3.0 parts Pigment dispersion resin solution 34.0 parts Propylene glycol monomethyl ether acetate 51.0 parts

-Green pigment dispersion PG-9
A green pigment dispersion PG-5 was prepared in the same manner as the red pigment dispersion PR using a mixture having the following composition.
Green pigment 1: C.I. I. Pigment Green58 9.0 copies (DIC Corporation "Fastgen Green A110")
Yellow pigment 1: C.I. I. Pigment Yellow138 3.0 copies (BASF's "PALIOTOL YELLOW K0 961HD")
Resin type dispersant solution 3.0 parts Pigment dispersion resin solution 34.0 parts Propylene glycol monomethyl ether acetate 51.0 parts

・ Blue pigment dispersion PB
A blue pigment dispersion PB was prepared in the same manner as the red pigment dispersion PR using a mixture having the following composition.
Blue pigment 1: C.I. I. Pigment Blue 15: 6 9.8 copies (BASF's "Heliogen Blue L-6700F")
Purple Pigment 1: C.I. I. Pigment Violet 23 2.2 Part ("Rio Nogen Violet R-6200" manufactured by Toyo Color Co., Ltd.)
Resin type dispersant solution 2.4 parts Pigment dispersion resin solution 25.6 parts Propylene glycol monomethyl ether acetate 60.0 parts

[Adjustment of red photosensitive coloring composition]
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a red photosensitive coloring composition.
-Pigment dispersion: Red pigment dispersion PR 50.0 parts-Transparent resin 7.0 parts-Photopolymerizable monomer: Polybasic acid-modified acrylic oligomer "Aronix M520" manufactured by Toa Synthetic Co., Ltd. 4.0 parts-Photopolymerization initiator : BASF "Irgacure (registered trademark) OXE02" 1.8 parts ・ Organic solvent: Propylene glycol monomethyl ether acetate 37.2 parts

[Adjustment of green photosensitive coloring composition]
<Examples 1 to 8, Comparative Example 1>
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a green photosensitive coloring composition.
-Pigment dispersion: 50.0 parts of the pigment dispersion prepared above shown in Table 1. 12.0 parts of transparent resin-Photopolymerizable monomer: Polybasic acid-modified acrylic oligomer "Aronix M520" manufactured by Toa Synthetic Co., Ltd. 4.0 Part-Photopolymerization initiator 1: BASF "Irgacure 379" 0.7 part-Photopolymerization initiator 2: BASF "Irgacure 907" 0.4 part-Photopolymerization initiator 3: BASF " Irgacure OXE02 ”0.1 part ・ Organic solvent: propylene glycol monomethyl ether acetate 32.8 parts

[Adjustment of blue photosensitive coloring composition]
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a blue photosensitive coloring composition.
-Pigment dispersion: Blue pigment dispersion PB 35.0 parts-Transparent resin 12.0 parts-Photopolymerizable monomer: Polybasic acid-modified acrylic oligomer "Aronix M520" manufactured by Toa Synthetic Co., Ltd. 4.0 parts-Photopolymerization initiator : BASF "Irgacure OXE02" 1.8 parts ・ Organic solvent: Propylene glycol monomethyl ether acetate 47.2 parts

[Making color filters]
A filter segment was formed using the obtained photosensitive coloring composition. A red photosensitive composition was applied to a glass substrate on which a striped resin black matrix (thickness 1.2 μm) was formed in advance by spinless coating so that the finished film thickness was 2.3 μm. After drying at 90 ° C. for 5 minutes, the light of a high-pressure mercury lamp is irradiated at 50 mJ / cm ² through a striped photomask for forming a red filter segment, developed with an alkaline developer for 60 seconds, and the striped red color is formed. Obtained a filter segment. Then, it was treated at 230 ° C. for 20 minutes to harden the film.

Next, the green photosensitive coloring composition was also applied by a spinless coat so that the finished film thickness was 2.3 μm. After drying at 90 ° C. for 5 minutes, the mixture was exposed and developed through a photomask so that a pattern was formed at a position adjacent to the above-mentioned red filter segment to obtain a striped green filter segment. Then, it was treated at 230 ° C. for 20 minutes to harden the film.

Further, in exactly the same manner as in red and green, the blue photosensitive coloring composition was also applied by spinless coating so that the finished film thickness was 2.3 μm. After drying at 90 ° C. for 5 minutes, a blue filter segment was obtained by exposing and developing through a photomask so that a pattern was formed at a position adjacent to the red and green filter segments. This gave a color filter having striped filter segments of three colors of red, green, and blue on a transparent substrate.

The alkaline developer has the following composition.
Sodium carbonate 1.5% by mass
Sodium hydrogen carbonate 0.5% by mass
Anionic surfactant (Kao / Perirex NBL) 8.0% by mass
Water 90.0% by mass

[Manufacturing of liquid crystal display panel]
An overcoat layer was formed on the coloring composition side of the obtained color filter, and a polyimide oriented layer was formed on the overcoat layer. Then, a polarizing plate was formed on the other surface of the glass substrate. On the other hand, a TFT array and a pixel electrode were formed on one surface of another (second) non-alkali glass substrate having a plate thickness of 0.7 mm.

The two glass substrates prepared in this manner are opposed to each other so that the electrode layers face each other, and the spacer beads are used to align the two glass substrates while keeping the distance between the two substrates constant, leaving an opening for injecting the liquid crystal composition. The periphery was sealed with an LCD sealant "Photorec (registered trademark) S". Then, the liquid crystal composition for use was injected through the opening, and the opening was sealed. Then, it was heated in a clean oven at 190 ° C. for 60 minutes to obtain a liquid crystal display panel.

[Light resistance evaluation]
The produced liquid crystal display panel is irradiated with a xenon weather meter Ci35A (manufactured by ALTAS) for ^{200 hours under the conditions of an illuminance of 0.5 mW / cm 2} (340 nm), a temperature of 63 ° C., and a humidity of 50%, and the spectroscopy is performed before and after the test. Using a microspectrophotometer (LCF-1100 manufactured by Otsuka Electronics Co., Ltd.), the spectral characteristics of the green filter segment with the C light source were evaluated, and ΔE ^* ab was calculated. A non-alkali glass having a plate thickness of 0.7 mm was used as a reference for the measurement.
The criteria for evaluating the light resistance were: ◯: ΔE ^* ab ≦ 3, ×: ΔE ^* ab> 3. The results of the light resistance evaluation are shown in Table 1 below.

[Manufacturing of liquid crystal display device]
The obtained liquid crystal display panel was provided with an optical compensation layer optimized for wide viewing angle display. Further, a liquid crystal display device was obtained in combination with a backlight unit.

As a result of turning on the backlight of the obtained liquid crystal display device and observing the appearance, the color display characteristics of Examples 1 to 8 were good. In Comparative Example 1, ^{the value of ΔE *} ab was too large and was not good.

As shown in the results of Table 1, by using the green pigment dispersions of Examples 1 to 8, a color filter having a good light resistance evaluation result could be obtained.

As described above, by using the green photosensitive coloring composition of the present invention, it is possible to provide a color filter and a color display device having excellent light resistance.

Claims (6)

At least (a) dye,
(B) Pigment dispersant,
(C) Transparent resin,
(D) Photopolymerizable monomer,
(E) A coloring composition containing a photopolymerization initiator.
The dye (a) is zinc phthalocyanine halide, and the α-position of the isoindole ring of the phthalocyanine structure contained in at least one compound among the compound serving as the dye or the derivative which may be contained in the dye (a). A green photosensitive colored product, wherein one hydrogen atom of the above is substituted with a cyano group or an N-substituted maleimide group. The green photosensitive according to claim 1, wherein the dye (a) or a dye derivative which may be contained has a molar ratio of a cyano group or an N-substituted maleimide group to 1 to 16 with respect to a phthalocyanine structure. Sexual coloring composition. (A) The claim is characterized in that when the dye or the dye derivative which may be contained contains a quinophthalone structure, the molar ratio of the cyano group or the N-substituted maleimide group to the quinophthalone structure is 1 to 8. The green photosensitive coloring composition according to 1 or 2. The green photosensitive coloring composition according to any one of claims 1 to 3, wherein the zinc halide phthalocyanine contained in the dye (a) is a chlorinated zinc phthalocyanine. A color filter having at least a black matrix and a plurality of coloring filter segments including a green filter segment on a transparent substrate, using the green photosensitive coloring composition according to any one of claims 1 to 4. A color filter characterized by having a green filter segment. A color display device including the color filter according to claim 5.