JP2015169880A - Colored composition for solid-state imaging device, and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color filter having excellent color reproducibility and a high transmittance, to be used for a color liquid crystal display device, a solid-state imaging device, or the like, and a colored composition and a green coating film for forming the color filter.SOLUTION: A colored composition for a solid-state imaging device is provided, which comprises a green pigment and a yellow pigment. The green pigment comprises C.I. Pigment Green 58 and C.I. Pigment Green 7, while the yellow pigment comprises at least one pigment selected from the group consisting of C.I. Pigment Yellow 83, C.I. Pigment Yellow 110, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, and Pigment Yellow 185. A green coating film and a color filter using the above colored composition are also disclosed.

Description

  The present invention relates to a color filter mounted on a solid-state image sensor such as a color liquid crystal display, a digital camera, a video camera, a copy, or a scanner, and a coloring composition for a solid-state image sensor used for forming the color filter.

  Color filters mounted on solid-state image sensors such as color liquid crystal displays, digital cameras, video cameras, copies, and scanners are generally red (R), green (G), and blue (B) on glass and solid-state image sensors. And the complementary colors of cyan (C), magenta (M), and yellow (Y) are provided as fine patterns.

  The color filter manufacturing method includes a dyeing method using a dye as a color material, a dye dispersion method, a pigment dispersion method using a pigment as a color material, a printing method, and an electrodeposition method. Among these, the dyeing method or the dyeing and dispersing method has a disadvantage that the heat resistance and the light resistance are slightly inferior because the dye is a dye. Therefore, a pigment having excellent heat resistance and light resistance is used as the color material of the color filter, and the pigment dispersion method is often used as the manufacturing method because of the accuracy and stability of the forming method.

  In the pigment dispersion method, a color resist is formed by mixing and blending a photosensitive agent or an additive in a pigment in which pigment particles, which are pigments, are dispersed in a transparent resin, and this color resist is applied onto a substrate by a coating device such as a spin coater. In this method, a color filter is produced by forming a coating film by the above, performing selective exposure through a mask with an aligner or a stepper, patterning by alkali development and thermosetting, and repeating this operation.

  However, in recent years, in color filters, particularly for digital cameras and solid-state image sensors, high definition, high brightness, and high color reproducibility have been demanded. Excellent color separation is desired. Therefore, it is very difficult to obtain a coloring composition that can achieve such excellent color separation and high transmittance.

JP 2006-267992 A JP 2008-040404 A JP 2006-104243 A

  Therefore, the present invention makes it possible to control the spectral characteristics required for a color filter for a solid-state imaging device by using a specific pigment, and has excellent color separation and high transmittance. And a color filter using the same.

  In the coloring composition of the present invention, the green pigment is C.I. I. Pigment green 58 and C.I. I. Pigment Green 7 and the yellow pigment is C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150 and C.I. I. By including at least one selected from the group consisting of CI Pigment Yellow 185, it becomes possible to control spectral characteristics, and therefore, excellent in color separation and high transmittance for solid-state imaging devices. Is found.

  That is, the first aspect of the present invention is a coloring composition for a solid-state imaging device containing a green pigment and a yellow pigment, wherein the green pigment is C.I. I. Pigment green 58 and C.I. I. Pigment Green 7 and the yellow pigment is C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150 and C.I. I. 1. A colored composition for a solid-state imaging device, comprising at least one selected from the group consisting of CI Pigment Yellow 185.

In the second embodiment of the present invention, the yellow pigment is C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, and C.I. I. The colored composition for a solid-state imaging device according to claim 1, comprising at least one selected from the group consisting of CI Pigment Yellow 185.
A third aspect of the present invention is a color filter comprising a filter segment formed from the colored composition for a solid-state imaging device on a substrate.

  In the coloring composition for a solid-state imaging device of the present invention, the green pigment is C.I. I. Pigment green 58 and C.I. I. Pigment Green 7 and the yellow pigment is C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150 and C.I. I. Since it contains one or more selected from the group consisting of CI Pigment Yellow 185, when the coating film is formed so that the transmittance at 650 nm is 2% with a film thickness of 0.5 to 1.2 μm, the short wavelength in the coating film The wavelength at which the spectral transmittance on the side is 50% is in the range of 475 nm to 495 nm, and the wavelength at which the spectral transmittance on the long wavelength side is 50% is in the range of 580 nm to 590 nm. In addition, C.I. I. Pigment Green 58 is a C.I. I. Compared to Pigment Green 36, the color characteristic has a characteristic that the spectral transmittance has a high transmittance at the peak of the spectral transmittance, and the spectral transmittance is low in the long wavelength region. For this reason, the transmittance at 530 nm is as high as 85% or higher. Therefore, color separation is good.

  Next, the coloring composition for solid-state image sensors of the present invention will be described in detail with reference to preferred embodiments. Here, a case where a pigment dispersion method which is generally used is used will be specifically described.

  The coloring composition for a solid-state imaging device of the present invention contains a specific green pigment and a specific yellow pigment, and C.I. I. Pigment green 58 and C.I. I. Pigment Green 7 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150 and C.I. I. 1 or more types selected from the group consisting of CI Pigment Yellow 185 are included.

  The content of each pigment is 5 to 85% by weight of pigment green 58, 5 to 60% by weight of pigment green 7 in the total amount of pigment (100% by weight), C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150 and C.I. I. One or more yellow pigments selected from the group consisting of CI Pigment Yellow 185 are 1 to 50% by weight in total so that the transmittance at 650 nm is 2% with a film thickness of 0.5 to 1.2 μm. When the coating film is formed, the wavelength at which the spectral transmittance on the short wavelength side of the coating film is 50% is in the range of 75 nm to 495 nm, and the wavelength at which the spectral transmittance on the long wavelength side is 50% is in the range of 580 nm to 590 nm. It can be. In addition, C.I. I. Pigment Green 58 is a C.I. I. Compared to Pigment Green 36, the color characteristic has a characteristic that the spectral transmittance has a high transmittance at the peak of the spectral transmittance, and the spectral transmittance is low in the long wavelength region. Therefore, it is preferable because the transmittance at 530 nm is as high as 85% or higher.

In particular, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. It is preferable to include one or more selected from the group consisting of CI Pigment Yellow 185.
C. I. Pigment green 58, C.I. I. Pigment Green 7 and C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, and C.I. I. By using a pigment containing one or more selected from the group consisting of CI Pigment Yellow 185, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, or C.I. I. Pigment Yellow 185 is C.I. I. This is because an undesirable transmission peak in the 400 nm to 500 nm wavelength region, which is a characteristic of the pigment green 58, can be suppressed, and the spectral characteristics are excellent.

  When these pigments are used, the content of each pigment is 5 to 85% by weight of pigment green 58 and 5 to 60% by weight of pigment green 7 in the total amount of pigment (100% by weight). , C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, or C.I. I. When the coating film was formed such that the pigment yellow 185 pigments totaled 1 to 50% by weight and the transmittance at 650 nm was 2% with a film thickness of 0.5 to 1.2 μm, The wavelength at which the spectral transmittance on the wavelength side is 50% is in the range of 475 nm to 495 nm, and the wavelength at which the spectral transmittance on the long wavelength side is 50% is in the range of 580 nm to 590 nm. Moreover, it is preferable because the transmittance at 530 nm is as high as 85% or more.

  And when the coating film was formed so that the transmittance | permeability of 650 nm might be set to 2% by the film thickness of 0.5-1.2 micrometers by using the coloring composition for solid-state image sensors of this invention, it is short in this coating film. A wavelength with a spectral transmittance of 50% on the wavelength side is in the range of 475 nm to 495 nm, a wavelength with a spectral transmittance of 50% on the long wavelength side is in the range of 580 nm to 590 nm, and the transmittance at 530 nm is as high as 85% or higher. The green color filter which has the outstanding color separation property and high transmittance which show the transmittance | permeability can be provided.

  That is, in the coloring composition for a solid-state imaging device of the present invention, C.I. I. Pigment green 58, and C.I. I. Pigment Green 7 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150 and C.I. I. By including at least one selected from the group consisting of CI Pigment Yellow 185, when the green coating film or color filter having a film thickness of 0.5 to 1.2 μm is formed using the coloring composition, the above-described spectral characteristics are achieved. it can. In addition, a green coating film means what coated and apply | coated the coloring composition for solid-state image sensors of this invention to a base material, and can be obtained by a well-known coating and application means. Naturally, the green coating film of the present invention can be applied to a green filter segment or a color filter. In addition, a color filter including only a green filter segment can be formed.

It is preferable that the coloring composition for solid-state image sensors of this invention contains the pigment carrier comprised by transparent resin, its precursor, or those mixtures. This is for favorably dispersing the pigment. The transparent resin is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Transparent resins include thermoplastic resins, thermosetting resins, and active energy ray curable resins, and precursors thereof include monomers or oligomers that are cured by irradiation with active energy rays to form transparent resins. These can be used alone or in admixture of two or more.
When the composition is cured by ultraviolet irradiation, a photopolymerization initiator or the like is added to the colored composition for a solid-state imaging device.

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

  As the active energy ray-curable resin, a (meth) acryl having a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amino group. A resin in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the linear polymer by reacting a compound or cinnamic acid is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

  As monomers and oligomers, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate , Polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol Tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopen Tylglycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate, epoxy (meth) acrylate, urethane Various acrylates and methacrylates such as acrylates, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide , N-vinylformamide, acrylonitrile and the like, and these can be used alone or in admixture of two or more.

  The colored composition for a solid-state imaging device of the present invention can contain a photopolymerization initiator and the like for curing by ultraviolet irradiation. The blending amount when using the photopolymerization initiator is preferably 5 to 200 parts by weight with respect to 100 parts by weight of the total pigment, and 10 to 150 parts by weight from the viewpoint of photocurability and developability. Is more preferable.

  Examples of the photopolymerizable initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, -Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl]- Acetophenone compounds such as 1- [4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or Benzoin compounds such as dimethyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, 4 Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, etc. 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) Nyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro Methyl) -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, or 2,4-trichloromethyl- Triazine compounds such as (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], Or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) Phosphine compounds such as phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds; An imidazole compound; or a titanocene compound or the like is used.

The above photopolymerization initiators are used alone or in combination of two or more. As sensitizers, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone. , Camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, etc. It can also be used together.
It is preferable that the compounding quantity at the time of using a sensitizer is 3-60 weight part with respect to 100 weight part of photoinitiators contained in a coloring composition, and it is 5 from a viewpoint of photocurability and developability. More preferably, it is -50 weight part.

  The colored composition for a solid-state imaging device of the present invention can be adjusted in the form of a solvent development type or alkali development type colored resist. The colored resist is a dispersion of a pigment in a pigment carrier containing a thermoplastic resin, a thermosetting resin or a photosensitive resin and a monomer, and a pigment composition composed of a pigment or two or more pigments is used as necessary. In addition to the photoinitiator, it can be produced by finely dispersing in a pigment carrier using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, and an attritor. The colored composition of the present invention can also be produced by mixing several types of pigments separately dispersed on a pigment carrier.

  When dispersing the pigment in the pigment carrier, a dispersion aid such as a resin-type pigment dispersant and a surfactant can be appropriately used. The dispersion aid is excellent in dispersing the pigment and has a great effect of preventing re-aggregation of the pigment after dispersion. Therefore, when a coloring composition obtained by dispersing the pigment in the pigment carrier using the dispersion aid is used. Provides a color filter excellent in transparency.

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

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

The coloring composition for a solid-state imaging device of the present invention is obtained by sufficiently dispersing a pigment in a pigment carrier and applying the filter segment 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 included to facilitate formation.
Examples of the solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, 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. A solvent can be used in the quantity of 800-4000 weight part with respect to a total of 100 weight part of a pigment.

The colored composition for a solid-state imaging device of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time of the composition.
Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Examples thereof include phosphine and phosphite.
The colored composition for a solid-state imaging device of the present invention has a coarse particle of 5 μm or more, preferably a coarse particle of 1 μm or more, more preferably 0.5 μm or more by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove coarse particles and mixed dust.

  The colored composition for a solid-state imaging device of the present invention preferably contains a pigment in a proportion of 1.5 to 20% by weight. In the color filter of the present invention, the pigment is preferably contained in the final filter segment in a proportion of 10 to 50% by weight, more preferably 35 to 50% by weight, and the remainder is provided by the pigment carrier. It consists essentially of a resinous binder.

  The coloring composition of the present invention is mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more and coarse particles by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove dust.

  The color filter of the present invention comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment. Here, at least one green filter segment is formed using the coloring composition for a solid-state imaging device of the present invention.

  The blue filter segment is formed using a known blue coloring composition. Examples of the blue coloring composition include C.I. I. Blue pigments such as CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 can be included. Blue coloring compositions include C.I. I. Purple violet pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 can be used in combination.

  The red filter segment is formed using a known red coloring composition. Examples of the red coloring composition include C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 246, 254, 255, 264, Red pigments such as 272 can be used. A yellow coloring composition and an orange coloring composition can be used in combination with the red coloring composition.

  Examples of the yellow coloring composition include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 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, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 17 It can be used yellow pigments such 177,179,180,181,182,185,187,188,193,194,199.

  Examples of the orange coloring composition include C.I. I. Orange pigments such as CI Pigment Orange 36, 43, 51, 55, 59, and 61 can be used.

The pigment composition for a solid-state imaging device of the present invention includes a basic group of the following general formula (1), a basic group of the general formula (2), a basic group of the general formula (3), and a base of the general formula (4). Containing at least one derivative selected from a pigment derivative, an anthraquinone derivative, a triazine derivative or an acridone derivative having at least one basic group selected from a functional group (hereinafter sometimes referred to as “specific basic group”) It is preferable.

In the general formulas (1) to (4), X represents —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond.
n represents an integer of 1 to 10, preferably an integer of 1 to 3.
R ₁ and R ₂ each independently represent an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or an optionally substituted phenyl group. Or R ₁ and R ₂ combine to form an optionally substituted heterocycle containing additional nitrogen, oxygen or sulfur atoms. R ₁ and R ₂ are preferably unsubstituted or substituted alkyl groups having 1 to 5 carbon atoms.
R ₃ represents an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or an optionally substituted phenyl group. R ₃ is preferably an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms.

R ₄ , R ₅ , R ₆ and R ₇ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or Represents an optionally substituted phenyl group. R ₄ , R ₅ , R ₆ and R ₇ are preferably unsubstituted or substituted alkyl groups having 1 to 4 carbon atoms.
Y represents —NR ₈ —Z—NR ₉ — or a direct bond.
R ₈ and R ₉ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or optionally substituted. Represents a phenyl group. R ₈ and R ₉ are preferably each a hydrogen atom.
Z represents an alkylene group having 1 to 36 carbon atoms which may be substituted, an alkenylene group having 2 to 36 carbon atoms which may be substituted, or a phenylene group which may be substituted. Z is preferably an unsubstituted or substituted phenylene group.

R represents a substituent represented by the following general formula (5) or a substituent represented by the following general formula (6). In the following general formula (5) and general formula (6), R _{1 to} R ₇ and n are as defined above.
Q represents a hydroxyl group, an alkoxyl group, a substituent represented by the following general formula (5) or a substituent represented by the following general formula (6). Q is preferably a substituent represented by the following general formula (5).

  Examples of the organic dye constituting the pigment derivative having a basic group include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo, and polyazo, phthalocyanine dyes, diaminodianthraquinones, anthrapyrimidines, flavantrons, and anants. Anthraquinone dyes such as anthrone, indanthrone, pyranthrone, violanthrone, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindolinone dyes, quinophthalone dyes, selenium dyes, metal complexes Systematic dyes. Moreover, the organic pigment illustrated previously may be sufficient.

  A pigment derivative having a basic group can be synthesized by various synthetic routes. For example, after introducing a substituent represented by the following formulas (7) to (10) into an organic dye, it reacts with the substituent to form a substituent represented by the general formulas (1) to (4). Amine components such as N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] -1,3,5-triazine- It can be obtained by reacting 2-ylamino] aniline or the like.

Equation (7) _-SO 2 Cl
Formula (8) -COCl
Equation ₍₉₎ -CH ₂ NHCOCH 2 Cl
Formula (10) -CH2Cl

When the organic dye is an azo dye, the basic group is introduced by introducing the substituents represented by the general formulas (1) to (4) into the diazo component or the coupling component in advance and then performing a coupling reaction. An azo pigment derivative having the same can also be produced.
The triazine derivative having a basic group of the present invention can be synthesized by various synthetic routes. For example, starting from cyanuric chloride, an amine component that forms a substituent represented by the general formulas (1) to (4) on at least one chlorine of cyanuric chloride, such as N, N-dimethylaminopropylamine or N It is obtained by reacting methylpiperazine or the like and then reacting the remaining chlorine of cyanuric chloride with various amines or alcohols.

Examples of the amine component used to form the substituents represented by the general formulas (1) to (4) include dimethylamine, diethylamine, N, N-ethylisopropylamine, N, N-ethylpropylamine. N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine, di Butylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N-methyloctadecylamine, Didecylamine, diallylamine, N N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylamino Amylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N, N-diethylaminopentylamine, N , N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N-methyl-laurylamino The Pyramine, N, N-ethyl-hexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecholine, 3-pipecholine, 4 -Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-piperidinemethanol, Pipecolic acid, Isonipecotate, Methyl isonipecotate, Ethyl isonipecotate, 2-Piperidinethanol, Pyrrolidine, 3-hydroxy Pyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecholine, N-aminopropyl-4-pipecholine, N-amino Examples thereof include propylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine and the like.
The pigment derivatives can be used alone or in admixture of two or more.

  The content of the pigment derivative having a specific basic group is preferably 0.001 to 40% by weight, more preferably 1 to 25% by weight, based on the pigment.

  Then, the color filter which comprises the filter segment formed from the coloring composition for solid-state image sensors of this invention is demonstrated.

  The color filter of the present invention is manufactured by forming each color filter segment on a transparent substrate using the coloring composition of the present invention on a substrate by a printing method, an electrodeposition method, a photolithography method or the like. Can do.

  As the substrate, a glass plate, a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, a silicon wafer, or the like is used.

  The formation of each color filter segment by the printing method can be patterned simply by repeating the printing and drying of the colored composition prepared as the above various printing inks. Therefore, the color filter manufacturing method is low-cost and excellent in mass productivity. ing. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  When each color filter segment is formed by photolithography, the colored composition prepared as the solvent development type or alkali development type color resist is applied on a transparent substrate, such as spray coating, spin coating, slit coating, roll coating, etc. By a method, it apply | coats so that a dry film thickness may be 0.2-5 micrometers, More preferably, it is 0.5-1.5 micrometers. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above 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, after coating and drying the colored resist, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

  The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a transparent substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. is there. The transfer method is a method in which a color filter layer is formed in advance on the surface of a peelable transfer base sheet, and this color filter layer is transferred to a desired transparent substrate.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively. “PGMAc” means propylene glycol monomethyl ether acetate.

  First, the manufacturing method of the resin solution used for the Example and the comparative example, the salt milling method of a pigment, the manufacturing method of a pigment dispersion, and the manufacturing method of a blue coloring composition and a red coloring composition are demonstrated.

<Method for producing resin solution>
(Acrylic resin solution)
A reaction vessel was charged with 800 parts of cyclohexanone, heated to 100 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomer and thermal polymerization initiator was added dropwise at the same temperature over 1 hour to carry out a polymerization reaction.
Styrene 60.0 parts Methacrylic acid 60.0 parts Methyl methacrylate 65.0 parts Butyl methacrylate 65.0 parts Azobisisobutyronitrile 10.0 parts After the addition, the reaction was further carried out at 100 ° C for 3 hours, and then azobisisobuty A solution of 2.0 parts of nitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour to obtain an acrylic resin solution having a weight average molecular weight of about 40000.
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. To prepare an acrylic resin solution.

<Salt milling method of pigment>
(Example of yellow salt milled pigment production)
250 g of yellow pigment (CI Pigment Yellow 139, “Pariotor Yellow D1819” manufactured by BASF), 700 g of sodium chloride, 107 g of maleic acid resin (“Marquide No. 3002” manufactured by Arakawa Chemical Co., Ltd., acid value: 100) and polyethylene 160 g of glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) 160 g was charged into a stainless gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 3 hours. Next, this mixture was poured into about 3 liters of warm water, heated to about 80 ° C. and stirred for about 1 hour with a high speed mixer to form a slurry, filtered, washed with water to remove sodium chloride and solvent, It was dried in a hot air oven at 0 ° C. for about 24 hours to obtain “PYY139 salt milled pigment”.

<Method for producing pigment dispersion>
(Production Example of Green Pigment Dispersion 1)
A mixture having the following composition was stirred and mixed uniformly, then dispersed with an Eiger mill for 10 hours using zirconia beads having a diameter of 0.5 mm, and then filtered with a 1.0 μm filter to prepare a green pigment dispersion 1.

C. I. Pigment Green 58 12.0 parts ("FASTOGEN GREEN A110" manufactured by DIC)
Dispersant 1.0 part (“Solspers 20000” manufactured by Nippon Lubrizol)
Acrylic resin solution 35.0 parts PGMAc 52.0 parts

(Production Example of Green Pigment Dispersion 2)
A mixture having the following composition was uniformly stirred and mixed, and then dispersed with an Eiger mill for 10 hours using zirconia beads having a diameter of 0.5 mm, followed by filtration with a 1.0 μm filter to prepare a green pigment dispersion 2.

C. I. Pigment Green 7 12.0 parts (“Fastgen Green S” manufactured by DIC Corporation)
Dispersant 1.0 part (“Solspers 20000” manufactured by Nippon Lubrizol)
Acrylic resin solution 35.0 parts PGMAc 52.0 parts

(Production Example of Green Pigment Dispersion 3)
A mixture having the following composition was uniformly stirred and mixed, and then dispersed with an Eiger mill for 10 hours using zirconia beads having a diameter of 0.5 mm, followed by filtration with a 1.0 μm filter to prepare a green pigment dispersion 3.

C. I. Pigment Green 36 12.0 parts (“CF-G-6YK” manufactured by Toyocolor Co., Ltd.)
Dispersant 1.0 part (“Solspers 20000” manufactured by Nippon Lubrizol)
Acrylic resin solution 35.0 parts PGMAc 52.0 parts

(Production Example of Yellow Pigment Dispersion 1)
A mixture having the following composition was uniformly stirred and mixed, and then dispersed with an Eiger mill for 10 hours using zirconia beads having a diameter of 0.5 mm, followed by filtration with a 1.0 μm filter to prepare a yellow pigment dispersion 1.

C. I. Pigment Yellow 150 10.0 parts ("E4GN" manufactured by LANXESS)
Dispersant 1.0 part (“Solspers 20000” manufactured by Nippon Lubrizol)
Acrylic resin solution 45.0 parts PGMAc 44.0 parts

(Production Example of Yellow Pigment Dispersion 2)
C. of Production Example of Yellow Pigment Dispersion 1 I. A yellow pigment dispersion 2 was prepared in the same manner as the yellow pigment dispersion 1 except that Pigment Yellow 150 (“E4GN” manufactured by LANXESS) was changed to “P.Y.139 salt milled pigment”. .

(Production Example of Yellow Pigment Dispersion 3)
C. of Production Example of Yellow Pigment Dispersion 1 I. Pigment Yellow 150 (“E4GN” manufactured by LANXESS Corporation) I. A yellow pigment dispersion 3 was prepared in the same manner as the yellow pigment dispersion 1 except that the pigment yellow 83 was changed to “Pigment Yellow 83” (“LIONOL Yellow NBR” manufactured by Toyocolor Co., Ltd.).

(Production Example of Yellow Pigment Dispersion 4)
C. of Production Example of Yellow Pigment Dispersion 1 I. Pigment Yellow 150 (“E4GN” manufactured by LANXESS Corporation) I. A yellow pigment dispersion 4 was produced in the same manner as the yellow pigment dispersion 1 except that the pigment yellow 110 was changed to “Chromophthal Yellow 2RLTS” manufactured by BASF Corporation.

(Production Example of Yellow Pigment Dispersion 5)
C. of Production Example of Yellow Pigment Dispersion 1 I. Pigment Yellow 150 (“E4GN” manufactured by LANXESS Corporation) I. A yellow pigment dispersion 5 was produced in the same manner as the yellow pigment dispersion 1 except that the pigment yellow 138 was changed to “CF-Y-1010” manufactured by Toyocolor Co., Ltd.

(Production Example of Yellow Pigment Dispersion 6)
C. of Production Example of Yellow Pigment Dispersion 1 I. Pigment Yellow 150 (“E4GN” manufactured by LANXESS Corporation) I. A yellow pigment dispersion 6 was produced in the same manner as the yellow pigment dispersion 1 except that the pigment yellow 185 was changed to “PALIOTOL YELLOW D1155” manufactured by BASF Corporation.

<The manufacturing method of a blue coloring composition and a red coloring composition>
(Production example of blue coloring composition)
[Blue coloring composition 1]
A mixture having the following composition was stirred and mixed uniformly, then dispersed in a sand mill for 5 hours using a glass bead having a diameter of 1 mm, and then filtered through a 5 μm filter to prepare a blue pigment dispersion 1.

C. I. Pigment Blue 15: 6 12.0 parts ("Rionol Blue ES" manufactured by Toyocolor Co., Ltd.)
Dispersant 1.0 part (“Solspers 20000” manufactured by Nippon Lubrizol)
Acrylic resin solution 35.0 parts PGMAc 52.0 parts

Then, after stirring and mixing the mixture of the following composition so that it might become uniform, it filtered with a 0.45 micrometer filter, and obtained the blue coloring composition 1.

Blue colored dispersion 1 63.8 parts Photopolymerizable monomer 4.1 parts ("Aronix M402" manufactured by Toagosei Co., Ltd.)
Acrylic resin solution 2.8 parts Photopolymerization initiator 1.1 parts ("OXE-01" manufactured by BASF Corporation: oxime ester initiator)
29.8 parts of PGMAc

(Production example of red coloring composition)
[Red coloring composition 1]
A mixture having the following composition was stirred and mixed uniformly, then dispersed in a sand mill for 5 hours using glass beads having a diameter of 1 mm, and then filtered through a 5 μm filter to prepare a red pigment dispersion 1.

C. I. Pigment Red 254 10.0 parts ("Irgafore Red B-CF" manufactured by BASF Corporation)
C. I. 2.0 parts of Pigment Red 177 (“Chromophthal Red A2B” manufactured by BASF Corporation)
Dispersant 1.0 part ("Ajisper PB821" manufactured by Ajinomoto Fine Techno Co., Ltd.)
Acrylic resin solution 35.0 parts PGMAc 52.0 parts

Then, after stirring and mixing the mixture of the following composition so that it might become uniform, it filtered with a 0.45 micrometer filter, and obtained the red coloring composition 1. FIG.

Red colored dispersion 1 63.8 parts Photopolymerizable monomer 2.5 parts ("Aronix M402" manufactured by Toagosei Co., Ltd.)
Acrylic resin solution 2.8 parts Photopolymerization initiator 1.1 parts ("OXE-01" manufactured by BASF Corporation: oxime ester initiator)
29.8 parts of PGMAc

[Example 1]
(Green coloring composition 1 (resist material 1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 0.6 μm filter to obtain a green colored composition 1 (resist material 1).

Green pigment dispersion 1 39.0 parts Green pigment dispersion 2 6.0 parts Yellow pigment dispersion 1 14.4 parts Yellow pigment dispersion 2 3.6 parts Acrylic resin solution 2.6 parts Photopolymerizable monomer 3.5 Department (“Aronix M402” manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator 1.1 parts (“OXE-01” manufactured by BASF Corporation: oxime ester initiator)
29.8 parts of PGMAc

[Examples 2-7 Comparative Examples 1-3]
(Green coloring composition 2 to 10 (resist material 2 to 10))
Except having changed into the composition shown in Table 1, and the compounding quantity (part), it stirred and mixed and filtered by the same method as the green coloring composition 1 of Example 1, and the green coloring compositions 2-10 (resist materials 2-10) )

Table 2 shows the pigment ratios of the green coloring compositions 1 to 8 (resist materials 1 to 8).

  The obtained green coloring composition is applied to a glass substrate with a spin coater, dried, exposed, developed, and dried again so that the transmittance at 650 nm is 2% with a film thickness of 0.5 to 1.2 μm. A coating film was formed. The spectral transmittance was measured for the transmittance of the obtained coating film using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). The results are shown in Table 3.

  The green coating film obtained with the colored composition of [Example 1] to [Example 7] has a short wavelength side spectral transmittance of 50%, a wavelength of 475 nm to 495 nm, and a long wavelength side spectral transmittance of 50. % Wavelength satisfies the wavelength range of 580 nm to 590 nm. Further, the transmittance at 530 nm satisfied a high transmittance of 85% or more, and the color separation was excellent.

  In particular, C.I. I. Pigment green 58 and C.I. I. Pigment Green 7 and C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150 or C.I. I. When Pigment Yellow 185 was included, the film thickness was 0.9 μm or less, and the film thickness could be further reduced.

  The green paint film obtained with the colored composition of [Comparative Example 1] has a green pigment of C.I. I. Since only Pigment Green 58 was used, the wavelength at which the spectral transmittance on the long wavelength side was 50% was 591.1 nm, and color separation was poor. Further, the film thickness was 1.6 μm, which was a thick film.

  The green paint obtained with the colored composition of [Comparative Example 2] has a green pigment of C.I. I. Since only Pigment Green 7 was used, the wavelength at which the spectral transmittance on the long wavelength side was 50% was 570.0 nm, which did not satisfy the range of 580 nm to 590 nm. Further, the transmittance at 530 nm was 83.0%, which was lower than 85%, and the color separation deteriorated. Further, the film thickness was 1.9 μm, which was a thick film.

  The green coating film obtained with the coloring composition of [Comparative Example 3] is C.I. I. Since Pigment Green 58 was not included, the transmittance at 530 nm was 84.8%, which was lower than 85%, and color separation deteriorated.

Moreover, the coating film obtained from the green coloring composition for solid-state image sensors of this invention and a color filter had a spectral transmittance with good color separation.

Claims (3)

  A coloring composition for a solid-state imaging device, comprising a green pigment and a yellow pigment, wherein the green pigment is C.I. I. Pigment green 58 and C.I. I. Pigment Green 7 and the yellow pigment is C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150 and C.I. I. A coloring composition for a solid-state imaging device, comprising at least one selected from the group consisting of CI Pigment Yellow 185.   The yellow pigment is C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, and C.I. I. The colored composition for a solid-state imaging device according to claim 1, comprising at least one selected from the group consisting of CI Pigment Yellow 185. A color filter comprising a filter segment formed from the colored composition for a solid-state imaging device according to claim 1 or 2 on a substrate.