JP2017129674A - Green photosensitive coloring composition, and color filter and color display device employing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a highly-reliable green photosensitive coloring composition that solves the problem of color change with light irradiation, which occurs when using a phthalocyanine pigment in a color filter for a liquid crystal display device, and a color filter prepared therewith, and a color display device comprising the same.SOLUTION: A green photosensitive coloring composition comprises (a) a coloring pigment, (b) a pigment dispersant, (c) a transparent resin, (d) a photopolymerizable monomer, and (e) a photopolymerization initiator. The (a) coloring pigment at least comprises phthalocyanine, and the (b) pigment dispersant is a copolymer comprising an imide structure.SELECTED DRAWING: None

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, a color filter using the same, and a color display device.

  Color display devices are widely spread 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 that are members of color display devices, higher brightness and higher color reproduction are required. And higher contrast are desired.

  The color filter has two or more kinds of filter segments (pixels) having different hues on a surface of a transparent substrate such as glass, and a black matrix that partitions them, 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 with a polarizing plate and a backlight unit after injecting liquid crystal into the gap and injecting liquid crystal into the gap.

  In order to achieve the wide color gamut and high luminance desired for color filters, recently, the formation of the green filter segment constituting the color filter has been carried out by using a phthalocyanine pigment (for example, CI consisting of brominated copper phthalocyanine pigment). 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 known as an organic semiconductor, and is known to be stabilized as a phthalocyanine radical by light irradiation particularly under a low oxygen concentration (Patent Document 1, 2, see Non-Patent Document 1).

  This reaction to light is a very useful reaction when considering application to solar cells and the like, but it is a serious problem when phthalocyanine is used as a colorant. That is, the absorption wavelength of the phthalocyanine radical deviates from that of the phthalocyanine in the ground state, so that when used as a colorant, the color appears to change.

  This phenomenon is more likely to occur with zinc phthalocyanine than with copper phthalocyanine, and a significant color change is observed.

  This phenomenon is particularly apparent when it is used in a state of being completely cut off from air, such as a liquid crystal display device or an EL display device, and improvement is desired.

  As an attempt to solve the color change accompanying radical generation 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. The technique which performs is known (refer patent document 3, 4). However, this technique is insufficient in effect, and in order to be used for a color dispersion by a pigment dispersion method using a pigment that has been subjected to a recent micronization treatment as a colorant, or a color filter by a photolithography method, the dispersibility of the pigment, There were many problems to be solved such as suitability for photolithography.

Japanese Patent No. 2949230 Japanese Patent No. 2958461 JP 2000-214580 A Japanese Patent No. 5657452

“Phthalocyanine: Chemistry and Function”, edited by Shigeyoshi Shirai and Nagao Kobayashi, IPC, 1997.

  The present invention eliminates a color change caused by light irradiation, which has been a problem when using a phthalocyanine pigment in a color filter for a liquid crystal display device, a highly reliable green photosensitive coloring composition, and a color filter using the same An object is to provide a color display device.

  In order to solve the above problems, the present invention contains at least (a) a color pigment, (b) a pigment dispersant, (c) a transparent resin, (d) a photopolymerizable monomer, and (e) a photopolymerization initiator. A photosensitive coloring composition comprising: (a) the colored pigment contains at least phthalocyanine; and (b) the pigment dispersant is a copolymer containing an imide structure. It is.

  Moreover, this invention is a green photosensitive coloring composition characterized by the imide structure contained in the said (b) pigment dispersant being N-substituted maleimide.

  The present invention is the green photosensitive coloring composition, wherein the N-substituted maleimide contained in the pigment dispersant (b) is cyclohexylmaleimide.

  The present invention is characterized in that the blending ratio of the (b) pigment dispersant (pigment dispersant / colored pigment) to the total amount of the (a) colored pigment containing at least phthalocyanine is 0.45 or less by weight. Is a green photosensitive coloring composition.

  The present invention is the green photosensitive coloring composition, wherein the phthalocyanine contained in the color pigment (a) is zinc halide phthalocyanine.

  The present invention is a color filter having a plurality of colored filter segments including at least a black matrix and a green filter segment on a transparent substrate, wherein the green filter segment uses the above-mentioned green photosensitive coloring composition. Is a color filter.

  The present invention is a color display device comprising the above color filter.

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

  Although the typical form for implementing this invention is described below, this invention is not limited to the following embodiment.

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

The green photosensitive coloring composition of the present invention comprises (a) a color pigment, (b) a pigment dispersant, (c) a transparent resin, (d) a photopolymerizable monomer, and (e) a photopolymerization initiator as essential components. It contains.
Moreover, you may contain additives, such as a solvent, a photosensitizer, a chain transfer agent, and a storage stabilizer.

(A) Coloring pigment Examples of the coloring pigment that can be used in the green photosensitive coloring composition of the present invention include C.I. I. Green pigments such as Pigment Green 7, 10, 36, 37, 58, and 59 can be used. In particular, C.I. I. A halogenated zinc phthalocyanine pigment containing a brominated zinc phthalocyanine pigment represented by Pigment Green 58 is effective for increasing the transmittance.

  In the green photosensitive coloring composition of the present invention, it is preferable to use a yellow pigment or a yellow dye in combination in order to adjust the hue.

Examples of the yellow pigment that can be used in the green photosensitive coloring composition of the present invention include 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. can be used.
Among these, from the viewpoint of increasing the brightness, C.I. I. Pigment Yellow 138 and C.I. I. It is preferable to use Pigment Yellow 150.

  Examples of yellow dyes that can be used in the green photosensitive coloring composition of the present invention include C.I. I. Solvent Yellow 2, 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, C.I. I. Basic Yellow 11, 23, 25, 28, 41, C.I. I. Direct Yellow 26, 27, 28, 33, 44, 50, 86, 142, C.I. I. Sulfur Yellow 4, C.I. I. Reactive Yellow 1, 2, 4, 14, 16, C.I. I. Vat Yellow 2, 12, 20, 33, C.I. I. Disperse Yellow 3, 4, 5, 7, 23, 33, 42, 60, 64 etc. are mentioned.

  Moreover, in order to adjust a hue, you may use together coloring components other than green and yellow, such as a blue pigment, a blue dye, a red pigment, and a red dye, in the green photosensitive coloring composition of this invention.

  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, Sent 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. SolventRed 1, 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, 23 , 236,238,239,240,241,242,243,244,245,247,248, C. I. Acid Red 6, 11, 26, 60, 88, 111, 186, 215, C.I. I. Acid Yellow 17, 23, 25, 36, 38, 42, 44, 72, 78, C.I. I. Basic Red 1, 2, 13, 14, 22, 27, 29, 39, C.I. I. DirectRed 4, 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. Vat Orange 2, 5, 11, 15, 18, 20, C.I. I. Reactive Red 8, 22, 46, 120, C.I. I. Reactive Orange 1, 4, 7, 13, 16, 20, C.I. I. Disperse Red 4, 11, 54, 55, 58, 65, 73, 127, 129, 141, 196, 210, 229, 354, 356, C.I. I. Disperse Orange 13, 29, 30 etc. are mentioned.

(B) Pigment dispersant

  The (b) pigment dispersant in the present invention is a resin type dispersant that is a copolymer containing at least an imide structure.

  The (b) pigment dispersant has a pigment affinity part having the property of adsorbing to the pigment, and a part compatible with the photosensitive transparent resin and the non-photosensitive transparent resin. It functions to stabilize dispersion in the photosensitive resin composition.

In the present invention, (b) the imide structure contained in the pigment dispersant includes N-substituted maleimide cyclohexyl maleimide, phenyl maleimide, methyl maleimide, ethyl maleimide, n-butyl maleimide, lauryl maleimide, or cyclohexyl which is N-succinimide. Succinimide, phenyl succinimide, methyl succinimide, ethyl succinimide, n-butyl succinimide, lauryl succinimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-benzylmaleimide, N- Cyclohexylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimid -6-maleimide caproate, cyclohexyl phthalimide is N- succinimidyl-3- maleimido propionate or N- substituted phthalimide, phenyl phthalimide, methyl phthalimide, ethyl phthalimide, n- butyl phthalimide, and the like lauryl phthalimide.
Among these, a copolymer containing cyclohexylmaleimide is particularly preferable because of its excellent dispersibility and transparency.

  These N-position substituted maleimides can be used alone or in admixture of two or more. The copolymerization ratio of N-substituted maleimide is preferably 3 to 80% by weight, more preferably 5 to 50% by weight. By setting it as the said range, the phthalocyanine anion radical generate | occur | produced by light irradiation can be deactivated to the ground state phthalocyanine, and a color change can be suppressed.

(B) As a pigment dispersant, in addition to the imide structure, specifically, polycarboxylic acid ester such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, ammonium polycarboxylate Salt, polycarboxylic acid alkylamine salt, polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, poly (lower alkylene imine) and reaction with polyester having free carboxyl group Oil-based dispersants such as amides and salts thereof, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic ester copolymers, styrene-maleic acid copolymers, polyvinyl Water-soluble resins such as alcohol and polyvinylpyrrolidone, water-soluble polymer compounds, Reester, modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester, etc. are used, and these can be used alone or in combination of two or more, but are not necessarily limited to these. Absent.

  As a site | part with high affinity to the dispersion medium of (b) pigment dispersant in the green photosensitive coloring composition of this invention, at least 1 sort (s) of polymer unit chosen from polyester, polyether, and poly (meth) acrylate is preferable.

  For example, as polyester, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol 1,4-bis (hydroxymethyl) cyclohesan, bisphenol A, hydrogenated bisphenol A, hydroxypivalylhydroxypivalate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol, One or more alcohols such as glycerin or hexanetriol, succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid ,Guru Conic acid, 1,2,5-hexanetricarboxylic acid, 1,4-cyclohexanehycarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexa And polyester polyols obtained by cocondensation with one or more carboxylic acids such as tricarboxylic acid or 2,5,7-naphthalenetricarboxylic acid.

  For example, as the polyether, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexane Diol, 1,4-bis (hydroxymethyl) cyclohesan, bisphenol A, hydrogenated bisphenol A, hydroxypivalylhydroxypivalate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol , Alcohols such as glycerin or hexanetriol, ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether Others include modified polyether polyols and the like obtained by ring-opening polymerization of various (cyclic) ether bond-containing compounds such as allyl glycidyl ether.

  For example, as poly (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (Meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, oxetane (meth) acrylate, etc. Alkoxypolyalkylene glycol (meth) acrylates such as xypolypropylene glycol (meth) acrylate and ethoxypolyethylene glycol (meth) acrylate, (meth) acrylamide, and N, N-dimethyl (meth) acrylamide, N, N-diethyl (meta) ) N-substituted (meth) acrylamides such as acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, acryloylmorpholine, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl ( Examples include homopolymers and copolymers such as amino group-containing (meth) acrylates such as (meth) acrylate and nitriles such as (meth) acrylonitrile. These may be used alone or in combination, or may be in the form of a block polymer, graft polymer or random polymer.

(B) The content of the pigment dispersant is at least 0.45 or less by weight ratio of the pigment dispersant (pigment dispersant / colored pigment) with respect to the total amount of the (a) colored pigment containing at least phthalocyanine. It is preferable that The ratio is more preferably 0.05 to 0.4, and still more preferably 0.1 to 0.3. (B) Although the content of the pigment dispersant is preferably as small as possible, in order to ensure dispersibility as a pigment dispersion and to realize a high contrast ratio, the ratio of the dispersant to the pigment is set to 0.05 or more. Is preferred.

  In the present invention, the pigment dispersant containing an imide structure may be used in combination with one or more dispersants, and usable dispersants are not particularly limited.

The pigment dispersant that can be used is not particularly limited, and for example, cationic, anionic, nonionic, amphoteric, silicone, and fluorine-based surfactants can be used. It is preferable to use a molecular dispersant.
Examples of the polymer surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, etc. Polyoxyethylene alkylphenyl ethers; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes.

  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 SOLSPERS E-3000, 9000, 13240, 13650, 13940, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32 manufactured by Abyssia 00, 32500, 32600, 34750, 36600, 38500, 41000, 41090, 53095, etc., EFKA-46, 47, 48, 452, LP4008, 4009, LP4010, LP4050, LP4055, 400, 401, 402, etc. 403, 450, 451, 453, 4300, 4540, 4550, LP4560, 120, 150, 1501, 1502, 1503, and the like.

  The acid value of the pigment dispersant containing the imide structure of the present invention is preferably 200 mgKOH / g or less, more preferably 40 to 200 mgKOH / g, and most preferably 40 to 150 mgKOH / g, from the viewpoint of dispersion stability. The weight average molecular weight (Mw) of the pigment dispersant in the present invention is preferably in the range of 1000 to 50000, more preferably in the range of 1000 to 30000.

  As a solvent (dispersion solvent) for preparing the pigment dispersion composition, an organic solvent is preferably used. As an organic solvent, in order to prepare the photosensitive coloring composition mentioned later, the organic solvent used as a dilution solvent can be used.

  The dispersion solvent is usually used in an amount of 1 to 10 parts by weight, preferably 2 to 9 parts by weight, based on the pigment 1.

  The pigment dispersion composition in the present invention can be prepared by using a part or all of the pigment dispersant shown above in a conventionally known pigment dispersion composition preparation procedure. That is, a color pigment containing at least phthalocyanine, a pigment dispersant containing the imide structure, and, if necessary, other pigment dispersants and pigment dispersion resins as solvents are mixed in a solvent in any order, and the kneader The pigment dispersion composition can be prepared by dispersing using a known dispersing machine such as a roll mill, an attritor, a super mill, a dissolver, a homomixer, or a sand mill.

  Specifically, a method in which a mixture of an organic pigment and a binder is added and dispersed in a solvent, a method in which a pigment and a binder are added and dispersed in a solvent; a liquid in which only the pigment is dispersed in the solvent; and a binder only in the solvent Examples thereof include a method of mixing the prepared liquid or a method of adding a binder to a liquid in which only the pigment is dispersed in a solvent.

In this way, a pigment dispersion composition having excellent pigment particle dispersibility is obtained. This pigment dispersion composition is used as a preliminary preparation for preparing a coating liquid excellent in pigment dispersibility.
However, if a pigment or a pigment dispersant is directly added and mixed with a binder component in a diluent solvent, sufficient dispersibility may not be obtained. In contrast, the pigment dispersion composition according to the present invention is mixed with an additional amount of the binder and other components, or the pigment dispersion composition according to the present invention, the additional amount of the binder, and other components are mixed into the solid content. By adding to a solvent (dilution solvent) for adjusting the concentration, a coating liquid excellent in pigment dispersibility can be easily prepared.

(C) Transparent resin The transparent resin that can be used in the green photosensitive coloring composition of the present invention preferably has a transmittance of 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 non-photosensitive resin such as a thermoplastic resin and a thermosetting resin, and a photosensitive resin. These may be used alone or in combination of two or more.

  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 reduction 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 is delayed and the productivity is lowered. Therefore, the range of 20,000 to 60,000 is more preferable.

  The non-photosensitive transparent resin is a resin that does not have an ethylenically unsaturated double bond. Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, and polychlorinated resin. 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. Is mentioned.

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

  As the photosensitive resin, a linear polymer having a reactive functional group is reacted with a (meth) acrylic compound having a substituent capable of reacting with the reactive functional group, cinnamic acid, etc. Examples thereof include resins in which a bond is introduced into the linear polymer. In addition, a linear polymer having a substituent capable of reacting with the reactive functional group is reacted with a (meth) acrylic compound having a reactive functional group, cinnamic acid, or the like, to thereby form an ethylenically unsaturated double bond. Resin introduced into the 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.

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

  The amount of ethylenically unsaturated double bonds introduced through a hydroxyl group or the like into the photosensitive transparent resin, which indicates the ease of photocuring, is indicated by the “double bond equivalent” of the resulting photosensitive transparent resin. . The double bond equivalent of the photosensitive transparent resin is preferably 200 to 1200, and more preferably 300 to 900. When the double bond equivalent of the photosensitive transparent resin is less than 200, the ratio of the ethylenically unsaturated monomer having a reactive substituent for introducing an ethylenically unsaturated double bond is increased, and various characteristics are maintained. A sufficient amount of other ethylenically unsaturated monomers cannot be copolymerized. When it exceeds 1200, sufficient sensitivity cannot be obtained because the number of ethylenically unsaturated double bonds is small.

  In the green photosensitive coloring composition of the present invention, from the viewpoint of suppressing the photoreaction of phthalocyanine molecules during light irradiation, it is preferable to avoid introduction of a urethane bond part or an amino group serving as an electron donating component. And addition of a monomer having an epoxy group and an unsaturated double bond to a copolymer of a monomer having an unsaturated double bond and another monomer copolymerizable with the monomer A photosensitive resin containing a unit structure having a polymerizable unsaturated bond is preferably used.

(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. Moreover, it is preferable that two or more ethylenically unsaturated double bonds are contained in one molecule. These photopolymerizable monomers may be used alone or in combination of two or more. Further, the photopolymerizable monomer may have an imide structure, particularly 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. Ethane, 1,4-bismaleimide butane, 1,6-bismaleimide hexane, 4,4′-bismaleimide diphenylmethane, 4-aminophenylmaleimide, N-methoxycarbonylmaleimide, 3-maleimidopropionic acid, 4-maleimidobutyric acid, Maleimides such as 6-maleimidohexanoic acid, 4-nitrophenylmaleimide, N-succinimidyl 3-maleimidopropionate, and maleimide (meth) acrylates, N-acryloxysuccinimide, N-acryloxyphthale 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, such as imide, N-acryloyloxyethylhexahydrophthalimide and other imide structures and compounds having both (meth) acryloyl groups , Neopentyl glycol (meth) acrylate, 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, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythri Tall tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (2-hydroxyethyl) 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, tetradecane ethylene glycol di (meth) Acrylate, 10-decanediol (meth) acrylate, 3,8-bis (meth) acryloyloxymethyltricyclo [5.2.10] decane, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) Prop 1,4-bis ((meth) acryloyloxymethyl) cyclohexane, hydroxypivalate ester neopentyl glycol di (meth) acrylate, ethoxylated bisphenol A diacrylate, propoxylated bisphenol A diacrylate, propoxylated ethoxylated bisphenol A di Acrylate, 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, ethoxylated Bisphenol F diacrylate, propoxylated bisphenol F diacrylate, propoxylated ethylene Of various acrylic acid esters and methacrylic acid esters such as bisphenol F diacrylate and the like as a typical example. As the photopolymerizable monomer, a copolymerized photopolymerizable monomer may be used if necessary.

  In the present invention, “(meth) acrylate” refers to both “acrylate” and “methacrylate”. Further, “(meth) acryloyl group” means both “acryloyl group” and “methacryloyl group”. For example, “urethane (meth) acrylate” indicates both “urethane acrylate” and “urethane methacrylate”.

  The blending amount of the photopolymerizable monomer is preferably 5 to 400 parts by weight with respect to 100 parts by weight of the pigment, and more preferably 10 to 300 parts by weight from the viewpoint of photocurability and developability.

(E) Photopolymerization initiator As the photopolymerization initiator used in the green photosensitive coloring composition of the present invention, an oxime ester photopolymerization initiator, an acetophenone compound, a benzoin compound, a benzophenone compound, a thioxanthone compound, Examples include triazine compounds, phosphine compounds, quinone compounds, borate compounds, carbazole compounds, imidazole compounds, titanocene compounds, and the like.

  Particularly preferred oxime ester photoinitiators include ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-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-methylpropan-1-one, and 1-hydroxy. Cyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- 1-one etc. are mentioned.

  Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyl dimethyl ketal.

  Examples of the benzophenone-based compound include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and the like.

  Examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 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-pienyl-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-naphth-1) -Yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4'-me Kishisuchiriru) -6-triazine.

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

In addition, examples of the quinone compound include 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

(solvent)
In order to make it easy to form a filter segment by applying the green coloring composition of the present invention on a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm, A solvent can be used to optimize the viscosity of the composition and sufficiently disperse the colorant uniformly in the photosensitive resin composition.

  As the solvent, water, an organic solvent, or 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, and 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. These may be used alone or in combination. The solvent can be used in an amount of preferably 800 to 4000 parts by weight, more preferably 1000 to 2500 parts by weight with respect to 100 parts by weight of the colorant.

(Dye derivative)
A pigment derivative is a compound in which a substituent is introduced into an organic pigment. Organic dyes include light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone which are not generally called dyes. Examples of the dye derivatives are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. These can be used singly or in combination of two or more.

(Surfactant)
Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, lauryl sulfate monoethanolamine, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer; polyoxyethylene oleyl ether, polyoxyethylene Lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate, polyethylene glycol Nonionic surfactants such as nolaurate; cationic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkylbetaines such as alkyldimethylaminoacetic acid betaine, and amphoteric surfactants such as alkylimidazoline These can be used alone or in admixture of two or more.

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

  Α-acyloxime ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone or the like can also be used as a sensitizer. The amount of these sensitizers used is preferably 0.5 to 60% by weight, more preferably 3 to 40% by weight, based on the total amount of photopolymerization initiator and sensitizer.

(Chain transfer agent)
The green photosensitive coloring composition of the present invention can further contain a polyfunctional thiol that functions as a chain transfer agent. A polyfunctional thiol can be used individually by 1 type or in mixture of 2 or more types. The content of the polyfunctional thiol is preferably 0.05 to 100 parts by weight, more preferably 0.1 to 60 parts by weight with respect to 100 parts by weight of the pigment.

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

  Hereinafter, a method for obtaining the color filter of the present invention will be described. The color filter of the present invention is a color filter having filter segments of a plurality of colors on at least a transparent substrate and having a filter segment formed using the green photosensitive coloring composition of the present invention. The color filter includes an additive color mixture 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 filter segment, at least one cyan filter segment, And a subtractive color type with at least one yellow filter segment.

  The red filter segment can be formed using a normal red photosensitive coloring composition. Examples of the red photosensitive coloring composition 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, It is a composition obtained by using red pigments such as 185, 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272, and 279. The red photosensitive coloring composition includes C.I. I. An orange pigment 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.

Moreover, a blue filter segment can be formed using a normal blue photosensitive coloring composition. The blue photosensitive coloring composition can be replaced with, for example, C.I. I. 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, 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, 199, 200, 201, 202, 203, 207, 225, 226, 236, 237, 246, 248, 249, etc. 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. 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 Saven 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. In the case of using the light shielding pattern, it is sufficient to use a transparent substrate in which a metal thin film such as chromium or a pattern made of a light shielding resin is attached in a known method in advance.

Each color filter segment is formed on the transparent substrate by the following method by photolithography. 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 or non-contact with the film.
Then, after immersing in a solvent or an alkaline developer, or spraying the developer with a spray or the like to remove the uncured portion and forming a desired pattern, it is necessary to promote polymerization of the photosensitive coloring composition. Heating can be applied accordingly. According to such a photolithography method, a color filter with higher accuracy than the printing method can be manufactured.

  In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution. In order to increase the UV exposure sensitivity, a film that prevents polymerization inhibition by oxygen by applying and drying a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin after coating and drying the photosensitive coloring composition. Ultraviolet exposure can also be performed after forming.

  By repeating the above-described series of steps by changing the photosensitive coloring composition and pattern as many times as necessary, it is possible to obtain a color filter including a colored pattern in which a necessary number of colors are combined, that is, a plurality of color filter segments. .

  The present invention will be specifically described with reference to the following examples. However, the present invention is not limited to this without departing from the spirit of the present invention.

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

[Preparation of Pigment Dispersant Solution 1]
In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 100 parts of methyl methacrylate, 100 parts of n-butyl acrylate, 50 parts of cyclohexylmaleimide as N-substituted maleimide, 40 parts of propylene glycol monomethyl ether acetate was charged and replaced with nitrogen gas. After heating the inside of the reaction vessel to 80 ° C. and adding 12 parts of 3-mercapto-1,2-propanediol, 0.2 part of 2,2′-azobisisobutyronitrile is divided into 20 portions. It was added every minute and reacted for 12 hours at 80 ° C., and it was confirmed by solid content measurement that 95% had reacted.

  Next, as the second stage synthesis, 30 parts of pyromellitic anhydride, 160 parts of propylene glycol monomethyl ether acetate, and 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added. Then, the mixture was reacted at 120 ° C. for 7 hours. It was confirmed by titration that 98% or more of the acid anhydride had been half-esterified, and the reaction was completed. After completion of the reaction, a pigment dispersant solution 1 having an acid value of 45 mgKOH / g and a weight average molecular weight of 9,500 per solid content was prepared by adding propylene glycol monomethyl ether acetate so that the nonvolatile content was 40% by weight. It was.

[Preparation of Pigment Dispersant Solution 2]
In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 100 parts of methyl methacrylate, 100 parts of n-butyl acrylate, 35 parts of N-phenylmaleimide as N-substituted maleimide, 40 parts of propylene glycol monomethyl ether acetate was charged and replaced with nitrogen gas. After heating the inside of the reaction vessel to 80 ° C. and adding 12 parts of 3-mercapto-1,2-propanediol, 0.2 part of 2,2′-azobisisobutyronitrile is divided into 20 portions. It was added every minute and reacted for 12 hours at 80 ° C., and it was confirmed by solid content measurement that 95% had reacted.

  Next, as the second stage synthesis, 30 parts of pyromellitic anhydride, 160 parts of propylene glycol monomethyl ether acetate, and 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added. Then, the mixture was reacted at 120 ° C. for 7 hours. It was confirmed by titration that 98% or more of the acid anhydride had been half-esterified, and the reaction was completed. After the reaction was completed, propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 40% by weight, and a pigment dispersant solution 2 having an acid value of 80 mgKOH / g and a weight average molecular weight of 7800 per solid content was obtained.

[Preparation of Pigment Dispersant Solution 3]
A commercially available pigment dispersant (EFKA4300 manufactured by BASF) and a propylene glycol monomethyl ether acetate were used to prepare a solution having a nonvolatile content of 40% by weight and used as the pigment dispersant solution 3.

  Thus, the pigment dispersant solution 1 and the pigment dispersant solution 2 containing an imide structure and the pigment dispersant solution 3 not containing an imide structure were prepared.

[Preparation of pigment dispersion resin solution]
Place 370 parts of cyclohexanone in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer in a separable four-necked flask, and heat to 80 ° C. while injecting nitrogen gas into the vessel. Acid (MAA) 23 parts, 2-hydroxyethyl methacrylate (HEMA) 17 parts, n-butyl methacrylate (BMA) 25 parts, benzyl methacrylate (BzMA) 22 parts, paracumylphenol ethylene oxide modified acrylate (manufactured by Toagosei 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 dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then a solution in which 3.0 parts of azobisisobutyronitrile was dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A solution was obtained. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Thus, a pigment dispersion resin was prepared.

[Preparation of transparent resin solution]
70 parts of cyclohexanone is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and 12.3 parts of benzyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 5.3 parts of methacrylic acid at the same temperature. (B) A mixture of 7.4 parts of paracumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toa Gosei Co., Ltd.) and 0.4 part of azobisisobutyronitrile as a photopolymerizable monomer is added dropwise over 2 hours. Then, a polymerization reaction was performed.

  After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, then 0.2 parts of azobisisobutyronitrile dissolved in 10 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. 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 heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Cyclohexanone was added so that a non-photosensitive resin solution was prepared to obtain a transparent resin solution. The weight average molecular weight Mw of the obtained transparent resin was 20000.

[Preparation of pigment dispersion]
・ Red pigment dispersion PR
After uniformly stirring and mixing a mixture having the following composition, using a zirconia bead having a diameter of 1 mm, the mixture was dispersed for 5 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan), and then filtered with a 5 μm filter. A red pigment dispersion PR was prepared.
Red pigment 1: C.I. I. Pigment Red 254 7.5 parts ("Irga Four Red B-CF" manufactured by BASF)
Red pigment 2: C.I. I. Pigment Red 177 1.2 parts (BASF "Chromoval Red A2B")
Yellow pigment 1: C.I. I. Pigment Yellow 150 1.0 part ("E4GN" manufactured by LANXESS)
Diketopyrrolopyrrole pigment derivative 2.3 parts Pigment dispersant solution 3 3.0 parts Pigment dispersion resin solution 34.0 parts
(Organic solvent) 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.
Green pigment 1: C.I. I. Pigment Green 58 9.0 parts (“Fastgen Green A110” manufactured by DIC)
Yellow pigment 2: C.I. I. Pigment Yellow 138 3.0 parts (BASF "PALIOTOL YELLOW K0 961HD")
Pigment dispersant solution 1 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 Green 58 9.0 parts (“Fastgen Green A110” manufactured by DIC)
Yellow pigment 2: C.I. I. Pigment Yellow 138 3.0 parts (BASF "PALIOTOL YELLOW K0 961HD")
Pigment dispersant solution 2 3.0 parts Pigment dispersion resin solution 34.0 parts Propylene glycol monomethyl ether acetate 51.0 parts

Green pigment dispersion PG-3
Using a mixture having the following composition, a green pigment dispersion PG-3 was prepared in the same manner as the red pigment dispersion PR.
Green pigment 1: C.I. I. Pigment Green 58 9.0 parts (“Fastgen Green A110” manufactured by DIC)
Yellow pigment 2: C.I. I. Pigment Yellow 138 3.0 parts (BASF "PALIOTOL YELLOW K0 961HD")
Pigment dispersant solution 1 2.0 parts Pigment dispersant solution 3 1.0 part 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 Green 58 9.0 parts (“Fastgen Green A110” manufactured by DIC)
Yellow pigment 2: C.I. I. Pigment Yellow 138 3.0 parts (BASF "PALIOTOL YELLOW K0 961HD")
Pigment dispersant solution 1 0.5 parts Pigment dispersant solution 3 2.5 parts Pigment dispersion resin solution 34.0 parts Propylene glycol monomethyl ether acetate 51.0 parts

Green pigment dispersion PG-5
Using a mixture having the following composition, a green pigment dispersion PG-5 was prepared in the same manner as the red pigment dispersion PR.
Green pigment 1: C.I. I. 12 parts of Pigment Green 58 (DIC Corporation "Fastgen Green A110")
Yellow pigment 2: C.I. I. 0.6 parts of Pigment Yellow 138 (BASF “PALIOTOL YELLOW K0 961HD”)
Pigment dispersant solution 1 2.4 parts Pigment dispersion resin solution 34.0 parts Propylene glycol monomethyl ether acetate 51.0 parts

Green pigment dispersion PG-6
Using a mixture having the following composition, a green pigment dispersion PG-6 was prepared in the same manner as the red pigment dispersion PR.
Green pigment 1: C.I. I. Pigment Green 58 4.5 parts ("Fastgen Green A110" manufactured by DIC)
Yellow pigment 2: C.I. I. Pigment Yellow 138 4.5 parts ("PALIOTOL YELLOW K0 961HD" manufactured by BASF)
Pigment dispersant solution 1 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-7 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 Green 58 4.5 parts ("Fastgen Green A110" manufactured by DIC)
Yellow pigment 2: C.I. I. Pigment Yellow 138 4.5 parts ("PALIOTOL YELLOW K0 961HD" manufactured by BASF)
Pigment dispersant solution 1 3.0 parts Pigment dispersion resin solution 34.0 parts Propylene glycol monomethyl ether acetate 51.0 parts

Green pigment dispersion PG-8
Using a mixture having the following composition, a green pigment dispersion PG-8 was prepared in the same manner as the red pigment dispersion PR.
Green pigment 2: C.I. I. Pigment Green 36 9.0 parts ("Rionol (registered trademark) Green 6YK" manufactured by Toyo Ink Co., Ltd.)
Yellow pigment 2: C.I. I. Pigment Yellow 138 3.0 parts (BASF "PALIOTOL YELLOW K0 961HD")
Pigment dispersant solution 1 3.0 parts Pigment dispersion resin solution 34.0 parts Propylene glycol monomethyl ether acetate 51.0 parts

Green pigment dispersion PG-9
Using a mixture having the following composition, a green pigment dispersion PG-9 was prepared in the same manner as the red pigment dispersion PR.
Green pigment 1: C.I. I. Pigment Green 58 9.0 parts (“Fastgen Green A110” manufactured by DIC)
Yellow pigment 2: C.I. I. Pigment Yellow 138 3.0 parts (BASF "PALIOTOL YELLOW K0 961HD")
Pigment dispersant solution 3 3.0 parts Pigment dispersion resin solution 34.0 parts Propylene glycol monomethyl ether acetate 51.0 parts

Green pigment dispersion PG-10
Using a mixture having the following composition, a green pigment dispersion PG-10 was prepared in the same manner as the red pigment dispersion PR.
Green pigment 2: C.I. I. Pigment Green 36 9.0 parts ("Rionol Green 6YK" manufactured by Toyo Ink Co., Ltd.)
Yellow pigment 2: C.I. I. Pigment Yellow 138 3.0 parts (BASF "PALIOTOL YELLOW K0 961HD")
Pigment dispersant solution 3 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 parts ("Heliogen (registered trademark) Blue L-6700F" manufactured by BASF)
Purple pigment 1: C.I. I. Pigment Violet 23 2.2 parts (Toyocolor "Rionogen Violet R-6200")
Pigment dispersant solution 3 2.4 parts Pigment dispersion resin solution 25.6 parts Propylene glycol monomethyl ether acetate 60.0 parts

[Adjustment of red photosensitive resin composition]
The following mixture was stirred and mixed to be uniform, and then filtered through a 1 μm filter to prepare a red photosensitive resin composition.
-Pigment dispersion: 50.0 parts of red pigment dispersion PR-Transparent resin: 7.0 parts of transparent resin solution-Photopolymerizable monomer: 4.0 parts of M520-Photopolymerization initiator: "Irgacure (registered by BASF) Trademark) OXE02 "1.8 parts Organic solvent: 37.2 parts propylene glycol monomethyl ether acetate

[Adjustment of green photosensitive resin composition]
<Examples 1-8, Comparative Examples 1-2>
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 resin composition.
Pigment dispersion: 50.0 parts of the pigment dispersion prepared previously shown in Table 1. Transparent resin: 12.0 parts of transparent resin solution Photopolymerizable monomer: 4.0 parts of photopolymerizable monomer shown in Table 1 Photopolymerization initiator 1: 0.7 part of BASF "Irgacure 379" Photopolymerization initiator 2: BASF "Irgacure 907" 0.4 part Photopolymerization initiator 3: BASF "Irgacure" OXE02 "0.1 part Organic solvent: 32.8 parts propylene glycol monomethyl ether acetate

<Example 9>
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 resin composition.
Pigment dispersion: 50.0 parts of previously prepared pigment dispersion shown in Table 1. Transparent resin: 10.0 parts of transparent resin solution Photopolymerizable monomer 1: Photopolymerizable monomer 1 3.0 shown in Table 1 Part / Photopolymerizable monomer 2: 3.0 parts / Photopolymerizable monomer 2 shown in Table 1 / Photopolymerization initiator 1: 0.7 parts manufactured by BASF “Irgacure 379” / Photopolymerization initiator 2: manufactured by BASF "Irgacure 907" 0.4 parts-Photopolymerization initiator 3: "Irgacure OXE02" manufactured by BASF 0.1 parts-Organic solvent: Propylene glycol monomethyl ether acetate 32.8 parts

Specific contents of the composition of the photopolymerizable monomer described in Table 1 below and the above Examples and Comparative Examples are shown below.
M520: polybasic acid-modified acrylic oligomer
("Aronix M520" manufactured by Toagosei Co., Ltd.)
M145: maleimide acrylate
("Aronix M145" manufactured by Toagosei Co., Ltd.)

[Adjustment of blue photosensitive coloring composition]
The following mixture was stirred and mixed to be uniform, and then filtered through a 1 μm filter to prepare a blue photosensitive resin composition.
Pigment dispersion: 35.0 parts of blue pigment dispersion PB Transparent resin: 12.0 parts of transparent resin solution Photopolymerizable monomer: 4.0 parts of M520 Photopolymerization initiator: “Irgacure 907” manufactured by BASF 1.8 parts, organic solvent: 47.2 parts propylene glycol monomethyl ether acetate

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

  Next, the green photosensitive composition was similarly applied by spinless coating so that the finished film thickness was 2.3 μm. After drying at 90 ° C. for 5 minutes, the film was exposed and developed through a photomask so that a pattern was formed adjacent to the above-mentioned red filter segment, thereby obtaining a stripe-shaped green filter segment. Then, it hardened | cured by processing for 20 minutes at 230 degreeC.

  Further, in the same manner as red and green, the blue photosensitive composition was similarly 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 adjacent to the red and green filter segments. Thus, a color filter having striped filter segments of three colors of red, green and blue on the transparent substrate was obtained.

The alkaline developer has the following composition.
Sodium carbonate 1.5% by weight
Sodium bicarbonate 0.5% by weight
Anionic surfactant (Kao Perillex NBL) 8.0% by weight
90.0% by weight of water

[Production of liquid crystal display panel]
An overcoat layer was formed on the colored composition side of the obtained color filter, and a polyimide alignment layer was formed thereon. And the polarizing plate was formed in the other surface of this glass substrate. On the other hand, another (second) non-alkali glass substrate having a thickness of 0.7 mm was prepared, and a TFT array and a pixel electrode were formed on one surface thereof.

  The two glass substrates prepared in this manner face each other so that the electrode layers face each other, and are aligned while using a spacer bead to keep the distance between the two substrates constant, leaving a liquid crystal composition injection opening. The periphery was sealed with an LCD sealant “PHOTOREC S”. Next, a liquid crystal composition was injected from the opening to seal the opening. Then, it heated at 190 degreeC for 60 minutes in clean oven, and obtained the liquid crystal display panel.

[Light resistance evaluation]
The prepared liquid crystal display panel was 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%. Using a spectrophotometer (LCF-1100 manufactured by Otsuka Electronics Co., Ltd.), spectral characteristics were evaluated with a green light source C light source (CIE standard light source), and ΔE ^* ab was calculated. Note that alkali-free glass having a thickness of 0.7 mm was used as a reference for measurement.
The judgment criteria for light resistance evaluation were as follows: ○: ΔE ^* ab ≦ 3, ×: ΔE ^* ab> 3. The results of light resistance evaluation are shown in Table 1.

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

  The backlight of the obtained liquid crystal display device was turned on and the appearance was observed. As a result, the color display characteristics were good.

  As shown in the results of Table 1, by using the green pigment dispersions of Examples 1 to 9, a color filter having good light resistance evaluation results could be obtained. Examples 1 to 9 all use an N-substituted maleimide having an imide structure as a pigment dispersant solution, and Comparative Examples 1 and 2 use those not containing an imide structure.

  As described above, by using the green pigment dispersion of the present invention, it is possible to provide a color filter excellent in light resistance and a color display device.

Claims (7)

  A photosensitive coloring composition containing at least (a) a coloring pigment, (b) a pigment dispersant, (c) a transparent resin, (d) a photopolymerizable monomer, and (e) a photopolymerization initiator, A green photosensitive coloring composition characterized in that a) the colored pigment contains at least phthalocyanine and the (b) pigment dispersant is a copolymer containing an imide structure.   The green photosensitive coloring composition according to claim 1, wherein the imide structure contained in the pigment dispersant (b) is an N-substituted maleimide.   The green photosensitive coloring composition according to claim 1 or 2, wherein the N-substituted maleimide contained in the pigment dispersant (b) is cyclohexylmaleimide.   The blending ratio (pigment dispersant / colored pigment) of the (b) pigment dispersant with respect to the total amount of the (a) colored pigment containing at least phthalocyanine is 0.45 or less by weight ratio, Item 4. The green photosensitive coloring composition according to any one of Items 1 to 3.   The green photosensitive coloring composition according to any one of claims 1 to 4, wherein the phthalocyanine contained in the (a) colored pigment is a halogenated zinc phthalocyanine.   A green photosensitive coloring composition according to any one of claims 1 to 5, wherein the color filter has a plurality of colored filter segments including at least a black matrix and a green filter segment on a transparent substrate. A color filter characterized by using an object.   A color display device comprising the color filter according to claim 6.