JP6503156B2 - Colored composition for solid-state imaging device and color filter - Google Patents

Description

  The present invention relates to a color filter attached to a solid-state imaging device such as a color liquid crystal display, a digital camera, a video camera, a copier, and a scanner, and a coloring composition for solid-state imaging device used for forming the color filter.

  Color filters attached to solid-state imaging devices such as color liquid crystal displays, digital cameras, video cameras, copiers and scanners are generally red (R), green (G), blue (B) on glass or solid-state imaging devices It is manufactured by providing colors such as the three primary colors of C and the complementary colors of cyan (C), magenta (M) and yellow (Y) as fine patterns.

  The color filter may be produced by a dyeing method using a dye as a coloring material, a dye dispersion method, a pigment dispersion method using a pigment as a coloring material, a printing method, an electrodeposition method, or the like. Among them, since the dye is a dye in the dyeing method or the dye dispersion method, there is a drawback that the heat resistance and the light resistance are somewhat inferior. Therefore, a pigment which is excellent in heat resistance and light resistance is used as a color material of the color filter, and a pigment dispersion method is often used as a manufacturing method from the accuracy and stability of the forming method.

  In the pigment dispersion method, a color resist is formed by mixing and preparing a photosensitive agent, an additive, etc. in a transparent resin in which pigment particles as a pigment are dispersed, and this color resist is coated on a substrate such as a spin coater. This is a method of forming a coating film, selectively exposing through a mask with an aligner, a stepper or the like, patterning by performing alkali development and thermosetting treatment, and repeating this operation to produce a color filter.

  However, in recent years, in color filters, particularly in digital cameras and in solid-state imaging devices, high definition, high brightness, and high color reproducibility are required, and further high transmittance of color filters, Excellent color separation is desired. At present, it is very difficult to make a coloring composition capable of achieving such excellent color degradability and high transmittance.

Unexamined-Japanese-Patent No. 2006-267792 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 solid-state imaging device by using a specific pigment, and is a coloring composition which is excellent in color decomposability and has high transmittance. And providing 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. It is possible to control the spectral characteristics by containing one or more selected from the group consisting of C.I. Pigment Yellow 185, thereby being excellent for color separation and high transmittance solid imaging devices. Found out.

  That is, the first aspect of the present invention is 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. Pigment Yellow 185, which is one or more selected from the group consisting of C.I. Pigment Yellow 185, and is a coloring composition for a solid-state imaging device.

In a second aspect of the present invention, the yellow pigment is C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, and C.I. I. Pigment Yellow 185, which is one or more selected from the group consisting of C.I. Pigment Yellow 185, is a coloring composition for a solid-state imaging device according to claim 1.
A third aspect of the present invention is a color filter comprising a filter segment formed from the coloring composition for 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. Pigment Yellow 185, and therefore, when a coating film is formed to have a film thickness of 0.5 to 1.2 μm and a transmittance of 650 nm of 2%, a short wavelength in the coating film The wavelength to be 50% of the spectral transmittance on the side is in the range of 475 nm to 495 nm, and the wavelength to be 50% of the spectral transmittance on the long wavelength side can be in the range of 580 nm to 590 nm. Also, C.I. I. Pigment green 58 is C.I. I. Compared to pigment green 36, its color characteristics exhibit high transmittance at the peak of the spectral transmittance, and the characteristic that the spectral transmittance changes to be low in the long wavelength region. Therefore, the transmissivity of 530 nm shows a high spectral transmissivity of 85% or more. Therefore, color separation is good.

  Next, the coloring composition for solid-state imaging devices of this invention is demonstrated in detail, mentioning a preferable embodiment. Here, a case of using a pigment dispersion method which is generally used in many cases will be specifically described.

  The coloring composition for solid-state imaging devices of the present invention contains a specific green pigment and a specific yellow pigment, and as a green pigment, 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. Pigment yellow 185, including one or more selected from the group consisting of C.I.

  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. Pigment yellow 185, so that the total of 1 to 50% by weight of the yellow pigment selected from the group consisting of C.I. Pigment Yellow 185 is such that the transmittance of 650 nm is 2% at a film thickness of 0.5 to 1.2 μm. When a coating film is formed, the wavelength at which the spectral transmittance of 50% 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 of 50% on the long wavelength side is 580 nm to 590 nm It can be done. Also, C.I. I. Pigment green 58 is C.I. I. Compared to pigment green 36, its color characteristics exhibit high transmittance at the peak of the spectral transmittance, and the characteristic that the spectral transmittance changes to be low in the long wavelength region. Therefore, it is preferable because the transmittance at 530 nm shows a high spectral transmittance as 85% or more.

In particular, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. It is preferable to contain 1 or more types selected from the group which consists of 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. C.I. pigment yellow 185 using one or more pigments selected from the group consisting of C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, or C.I. I. Pigment yellow 185, C.I. I. This is because the undesirable transmission peak in the wavelength range of 400 nm to 500 nm, which is the characteristic of pigment green 58, can be suppressed, and the spectral characteristic is 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. Pigment yellow 139, C.I. I. Pigment yellow 150, or C.I. I. When a coating film is formed such that the transmittance of 650 nm is 2% at a film thickness of 0.5 to 1.2 μm that the total amount of yellow pigment of pigment yellow 185 is 1 to 50% by weight. The wavelength to be 50% of the spectral transmittance on the wavelength side is in the range of 475 nm to 495 nm, and the wavelength to be 50% of the spectral transmittance on the long wavelength side can be in the range of 580 nm to 590 nm. Moreover, it is preferable in order that the transmittance | permeability of 530 nm may show a high spectral transmittance with 85% or more.

  And, when a coating film is formed so as to have a transmittance of 2% at a film thickness of 0.5 to 1.2 μm by using the coloring composition for a solid-state imaging device of the present invention, The wavelength at which the spectral transmittance on the wavelength side is 50% is in the range of 475 nm to 495 nm, the wavelength at which the spectral transmittance on the long wavelength side is 50% is in the range of 580 nm to 590 nm, and the transmittance at 530 nm is high at 85% or more It is possible to provide a green color filter that exhibits excellent transmittance and high color separation and high transmittance.

  That is, in the colored composition for 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. Pigment Yellow 185, and 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 | coating means. Of course, the green coating of the present invention can be diverted to a green filter segment or a color filter. It is also possible to form a color filter consisting only of green filter segments.

It is preferable that the coloring composition for solid-state imaging devices of this invention contains the pigment carrier comprised by transparent resin, its precursor, or mixtures thereof. This is to disperse the pigment well. The transparent resin is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength range of 400 to 700 nm in the visible light range. The transparent resin includes a thermoplastic resin, a thermosetting resin, and an active energy ray curable resin, and the precursor thereof includes a monomer or an oligomer which is cured by active energy ray irradiation to form a transparent resin. These can be used alone or in combination of two or more.
When the composition is cured by irradiation with ultraviolet light, a photopolymerization initiator or the like is added to the coloring composition for 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, polyester resin Acrylic resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resins, etc. may be mentioned. Moreover, as a thermosetting resin, an epoxy resin, benzoguanamine resin, rosin modified maleic resin, rosin modified fumaric resin, melamine resin, urea resin, a phenol resin etc. are mentioned, for example.

  As an active energy ray curable resin, (meth) acrylic having reactive substituents such as isocyanate group, aldehyde group and epoxy group on linear polymers having reactive substituents such as hydroxyl group, carboxyl group and amino group A resin or 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. In addition, a linear polymer containing an acid anhydride such as styrene-maleic anhydride copolymer or α-olefin-maleic anhydride copolymer is treated with a hydroxyl group-containing (meth) acrylic compound such as hydroxyalkyl (meth) acrylate. A half esterified one is 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 Chil glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, (meth) acrylic ester of methylolated melamine, epoxy (meth) acrylate, urethane Various acrylic esters and methacrylic esters such as acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide And N-vinylformamide, acrylonitrile and the like, and these can be used alone or in combination of two or more.

  The coloring composition for solid-state imaging devices of this invention can contain a photoinitiator etc. for hardening by ultraviolet irradiation. The compounding amount when using the photopolymerization initiator is preferably 5 to 200 parts by weight with respect to a total of 100 parts by weight of the pigment, and is 10 to 150 parts by weight from the viewpoint of photocurability and developability. Is more preferred.

  As a photopolymerization initiator, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1 -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, Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or Benzoin compounds such as dil dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyl diphenyl sulfide, or 3,3 ', 4 Benzophenone compounds such as 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diisopropyl thioxanthone, or 2,4-diethyl thioxanthone Thioxanthone compounds of the formula: 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphen) 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 phenyl phosphine oxide or 2,4,6-trimethyl benzoyl diphenyl phosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone; borate compounds; carbazole compounds; An imidazole compound; or a titanocene compound etc. are used.

The photopolymerization initiators described above are used singly or in combination of two or more, and as a sensitizer, α-acyloxy ester, acyl phosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone Compounds such as camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-diethylaminobenzophenone and the like It can also be used in combination.
The compounding amount when using the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator contained in the coloring composition, and from the viewpoint of photocurability and developability, 5 More preferably, it is 50 parts by weight.

  The coloring composition for solid-state imaging devices of the present invention can be prepared in the form of a solvent developing type or an alkali developing type coloring resist. The colored resist is obtained by dispersing a pigment in a pigment carrier containing a thermoplastic resin, a thermosetting resin, or a photosensitive resin and a monomer, and a pigment composition comprising a pigment or two or more pigments as needed. It can be finely dispersed in a pigment carrier using various dispersing means such as a triple roll mill, a double roll mill, a sand mill, a kneader, an attritor, etc. together with a photoinitiator. The colored composition of the present invention can also be produced by mixing several kinds of pigments separately dispersed in a pigment carrier.

  When the pigment is dispersed in the pigment carrier, dispersion aids such as resin type pigment dispersants and surfactants can be used as appropriate. Since the dispersing aid is excellent in dispersing the pigment and has a large effect of preventing reaggregation of the pigment after dispersing, when using a coloring composition in which the pigment is dispersed in the pigment carrier using the dispersing aid Is a color filter with excellent transparency.

  The resin type pigment dispersant has a pigment affinity site having a property of adsorbing to a pigment, and a site compatible with the pigment carrier, and functions to adsorb to the pigment and stabilize the dispersion of the pigment on the pigment carrier It is Specific examples of resin type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, polycarboxylic acid alkylamine Salts, polysiloxanes, long chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, and amides formed by reaction of poly (lower alkyleneimine) with polyesters having free carboxyl groups Dispersants such as salts, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinyl pyrrolidone, etc. Resin, water-soluble polymer compound, 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.

  As the surfactant, sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecyl benzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate And anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearic acid, monoethanolamine styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate ester, etc. Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts and ethylene oxide adducts thereof; alkyl dimethylamino There may be mentioned amphoteric surfactants such as alkyl betaines such as betaine acetate and alkyl imidazolines, which may be used alone or in combination of two or more.

The coloring composition for solid-state imaging device of the present invention is prepared by sufficiently dispersing the pigment in a pigment carrier and applying the filter segment on a transparent substrate such as a glass substrate to a dry film thickness of 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, ethyl benzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n amyl ketone, propylene glycol monomethyl ether toluene, methyl ethyl ketone And ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvents and the like, and these may be used alone or in combination. The solvent can be used in an amount of 800 to 4000 parts by weight with respect to a total of 100 parts by weight of pigment.

The coloring composition for solid-state imaging devices of the present invention can contain a storage stabilizer in order to stabilize the viscosity over 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 their methyl ethers, organics such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine. Phosphine, phosphite and the like can be mentioned.
The coloring composition for solid-state imaging device of the present invention may be coarse particles of 5 μm or more, preferably 1 μm or more, and more preferably 0.5 μm or more by means of centrifugation, sintered filter, membrane filter, etc. It is preferable to carry out removal of coarse particles and mixed dust.

  It is preferable that the coloring composition for solid-state image sensors of this invention contains a pigment in the ratio of 1.5 to 20 weight%. Also, in the color filter of the present invention, the pigment is contained in the final filter segment in a proportion of preferably 10 to 50% by weight, more preferably 35 to 50% by weight, the remainder being provided by the pigment carrier The resinous binder substantially consists of

  The colored composition of the present invention was coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more, by means of centrifugation, a sintered filter, membrane filter, etc. It is preferable to carry out dust removal.

  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 solid-state imaging device of the present invention.

  The blue filter segment is formed using a known blue coloring composition. Blue coloring compositions include, for example, C.I. I. Pigment blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 etc. can be included. Blue coloring compositions include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, etc. can be used in combination.

  In addition, the red filter segment is formed using a known red coloring composition. Examples of red coloring compositions 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, 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 yellow coloring compositions 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, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 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.

  Orange coloring compositions include, for example, C.I. I. Orange pigments such as CI Pigment Orange 36, 43, 51, 55, 59, 61 can be used.

The pigment composition for a solid-state imaging device of the present invention comprises 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 (hereinafter sometimes referred to as "specific basic group") selected from Is preferred.

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 an additional nitrogen, oxygen or sulfur atom. 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 optionally, an optionally substituted alkenyl or optionally substituted phenyl group having 2 to 36 carbon atoms having 1 to 36 carbon atoms. 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 each independently represent 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 a phenyl group which may be substituted. R ₄ , R ₅ , R ₆ and R ₇ are preferably unsubstituted or substituted alkyl groups having 1 to 4 carbon atoms.
Y _is, -NR 8 -Z-NR ₉ - represents a or a direct bond.
R ₈ and R ₉ each independently represent a hydrogen atom, an alkyl group having 1 to 36 carbon atoms which may be substituted, an alkenyl group having 2 to 36 carbon atoms which may be substituted, or may be substituted Represents a phenyl group. R ₈ and R ₉ are preferably each a hydrogen atom.
Z represents a C1-C36 optionally substituted alkylene group, a C2-36 optionally substituted alkenylene group, or an optionally substituted phenylene group. 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 azo dyes such as diketopyrrolopyrrole dyes, azo, disazo and polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine, flavanthrone and anth Anthraquinone dyes such as anthrone, indanthrone, pyranthrone, biolanthrone, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindolinone dyes, quinophthalone dyes, threne dyes, metal complexes Systemic dyes can be mentioned. Moreover, the organic pigment illustrated above may be sufficient.

  Pigment derivatives 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 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 is obtained by reacting 2-ylamino] aniline or the like.

Formula (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, a basic group can be obtained by introducing in advance the substituents represented by general formulas (1) to (4) into the diazo component or the coupling component, and then performing the coupling reaction. It is also possible to produce an azo pigment derivative having one.
In addition, the triazine derivative having a basic group of the present invention can be synthesized by various synthetic routes. For example, an amine component that uses cyanuric chloride as a starting material and forms a substituent represented by general formulas (1) to (4) in at least one chlorine of cyanuric chloride, such as N, N-dimethylaminopropylamine or N It is obtained by reacting methyl piperazine etc. and then reacting the remaining chlorine of cyanuric chloride with various amines or alcohols etc.

Examples of the amine component used to form the substituent 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 Pylamine, N, N-ethyl-hexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecoline, 3-pipecoline, 4 -Pipecoline, 2,4-lupetidine, 2,6-lupetidine, 3,5-lupetidine, 3-piperidinemethanol, pipecolic acid, isonipecotic acid, methyl isonipecotic acid, ethyl isonipecotic acid, 2-piperidine ethanol, pyrrolidine, 3-hydroxy Pyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecoline, N-aminoethyl morpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, N-aminopropyl-4-pipecoline, N-amino Propyl morpholine, N-methyl piperazine, N-butyl piperazine, N-methyl homo piperazine, 1-cyclopentyl piperazine, 1-amino-4-methyl piperazine, 1-cyclopentyl piperazine and the like can be mentioned.
The pigment derivatives can be used alone or in combination 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 produced by forming filter segments of each color on a transparent substrate using a colored composition of the present invention by printing method, electrodeposition method, photolithography method or the like on a substrate. Can.

  As a substrate, a glass plate, a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate or the like, 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 printing and drying of the coloring composition prepared as the various printing inks described above. Therefore, as a method for producing a color filter, it is excellent in mass productivity at low cost. ing. Furthermore, with the development of printing technology, printing of fine patterns with high dimensional accuracy and smoothness can be performed. In order to print, it is preferable to set it as a composition which an ink does not dry and solidify on the printing plate or on a blanket. In addition, it is important to control the flowability of the ink on the printing press, and the viscosity of the ink can be adjusted by a dispersant or an extender pigment.

  When forming each color filter segment by photolithography method, spray coating, spin coating, slit coating, roll coating, etc. are applied on a transparent substrate with the coloring composition prepared as the above-mentioned solvent development type or alkali development type coloring resist The coating is applied such that the dry film thickness is 0.2 to 5 μm, more preferably 0.5 to 1.5 μm, according to the method. The film dried if necessary is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Thereafter, the uncured area is removed by immersion in a solvent or an alkaline developer or by spraying the developer to remove a non-cured portion to form a desired pattern, and then the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to promote the polymerization of the colored resist, heating can be applied as needed. According to the photolithography method, it is possible to manufacture a color filter with higher accuracy than the above-mentioned printing method.

In the development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as an alkali developing solution, 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 ultraviolet exposure sensitivity, after applying and drying the colored resist, a water-soluble or alkali water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film for preventing polymerization inhibition by oxygen. After that, ultraviolet exposure can also be performed.

  The electrodeposition method is a method of producing a color filter by electrodepositing each color filter segment on a transparent conductive film by electrophoresis of colloidal particles using a transparent conductive film formed on a transparent substrate. is there. In the transfer method, a color filter layer is formed in advance on the surface of a transferable transfer base sheet, and the 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 thereby. In Examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively. Also, "PGMAc" means propylene glycol monomethyl ether acetate.

  First, a method of producing a resin solution used in Examples and Comparative Examples, a method of salt milling treatment of a pigment, a method of producing a pigment dispersion, and a method of producing a blue coloring composition and a red coloring composition will be described.

<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 monomers and a thermal polymerization initiator was added dropwise over 1 hour at the same temperature 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 Azobisisobutyro nitrile 10.0 parts After dropping and further reacting at 100 ° C. for 3 hours, A solution of 2.0 parts of ronitrile in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour to obtain a solution of an acrylic resin having a weight average molecular weight of about 40,000.
After cooling to room temperature, about 2 g of the resin solution is sampled, dried by heating at 180 ° C. for 20 minutes, non-volatile content is measured, and cyclohexanone is added to the resin solution synthesized above so that the non-volatile content is 20% by weight. An acrylic resin solution was prepared.

<Method of salt milling treatment of pigment>
(Yellow salt milled pigment production example)
Yellow pigment (CI pigment yellow 139, BASF "Paliotoll yellow D 1819") 250 g, sodium chloride 700 g, maleic acid resin (Arakawa Chemical Co. "Marquide No. 3002," acid value: 100) 107 g and polyethylene 160 g of glycol 300 g (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 3 hours. Next, this mixture is poured into about 3 liters of warm water and stirred for about 1 hour with a high speed mixer while heating to about 80 ° C. to form a slurry, and then filtered and washed with water to remove sodium chloride and solvent, 60 It dried in a hot-air oven for about 24 hours, and obtained "P.Y.139 salt milled pigment."

<Method of producing pigment dispersion>
(Production Example of Green Pigment Dispersion 1)
A mixture of the following composition was uniformly stirred and mixed, then dispersed with an Eiger mill for 10 hours using zirconia beads of 0.5 mm in diameter, 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 Corporation)
Dispersing agent 1.0 part (Nippon Lubrisol Co., Ltd. "Sol spars 20000")
Acrylic resin solution 35.0 parts PGMAc 52.0 parts

(Production Example of Green Pigment Dispersion 2)
A mixture of the following composition was uniformly stirred and mixed, then dispersed with an Eiger mill for 10 hours using zirconia beads of 0.5 mm in diameter, and then filtered 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)
Dispersing agent 1.0 part (Nippon Lubrisol Co., Ltd. "Sol spars 20000")
Acrylic resin solution 35.0 parts PGMAc 52.0 parts

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

C. I. Pigment green 36 12.0 parts (manufactured by Toyo Color Co., Ltd. "CF-G-6YK")
Dispersing agent 1.0 part (Nippon Lubrisol Co., Ltd. "Sol spars 20000")
Acrylic resin solution 35.0 parts PGMAc 52.0 parts

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

C. I. Pigment Yellow 150 10.0 parts ("E4GN" manufactured by LANXESS Co., Ltd.)
Dispersing agent 1.0 part (Nippon Lubrisol Co., Ltd. "Sol spars 20000")
Acrylic resin solution 45.0 parts PGMAc 44.0 parts

(Production Example of Yellow Pigment Dispersion 2)
In the preparation example of yellow pigment dispersion 1, C.I. I. A yellow pigment dispersion 2 was produced in the same manner as the yellow pigment dispersion 1 except that the pigment yellow 150 ("E4GN" manufactured by LANXCESS CO., LTD.) Was changed to "P.Y. 139 salt milling treated pigment". .

(Production Example of Yellow Pigment Dispersion 3)
In the preparation example of yellow pigment dispersion 1, C.I. I. Pigment Yellow 150 ("E4GN" manufactured by LANXESS Corporation) as a C.I. I. Pigment Yellow 83 (“LIONOL Yellow NBR” manufactured by Toyo Color Co., Ltd.) was prepared in the same manner as Yellow pigment dispersion 1, except that Yellow pigment dispersion 3 was produced.

(Production Example of Yellow Pigment Dispersion 4)
In the preparation example of yellow pigment dispersion 1, C.I. I. Pigment Yellow 150 ("E4GN" manufactured by LANXESS Corporation) as a C.I. 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 "Chromoftar yellow 2 RLTS" (manufactured by BASF Corp.).

(Production Example of Yellow Pigment Dispersion 5)
In the preparation example of yellow pigment dispersion 1, C.I. I. Pigment Yellow 150 ("E4GN" manufactured by LANXESS Corporation) as a C.I. I. Pigment Yellow 138 (“CF-Y-1010” manufactured by Toyo Color Co., Ltd.), except that it was changed to Yellow Pigment Dispersion 1, to prepare Yellow Pigment Dispersion 5.

(Production Example of Yellow Pigment Dispersion 6)
In the preparation example of yellow pigment dispersion 1, C.I. I. Pigment Yellow 150 ("E4GN" manufactured by LANXESS Corporation) as a C.I. I. Pigment Yellow 185 ("PALIOTOL YELLOW D 1155" manufactured by BASF Corp.) was prepared in the same manner as Yellow pigment dispersion 1, except that Yellow pigment dispersion 6 was produced.

<A method for producing a blue coloring composition and a red coloring composition>
(Example of production of blue coloring composition)
[Blue coloring composition 1]
A mixture of the following composition was uniformly stirred and mixed, then dispersed by 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 (manufactured by Toyo Color Co., Ltd. "Lionol Blue ES")
Dispersing agent 1.0 part (Nippon Lubrisol Co., Ltd. "Sol spars 20000")
Acrylic resin solution 35.0 parts PGMAc 52.0 parts

Thereafter, the mixture of the following composition was stirred and mixed so as to be uniform, and then filtered through a 0.45 μm filter to obtain a blue coloring composition 1.

Blue coloring dispersion 1 63.8 parts Photopolymerizing monomer 4.1 parts (Toon Gosei "Aronix M 402")
Acrylic resin solution 2.8 parts Photopolymerization initiator 1.1 parts (BASF Corporation "OXE-01": oxime ester initiator)
29.8 parts of PGMAc

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

C. I. Pigment Red 254 10.0 parts (“Irgafor Red B-CF” manufactured by BASF Corp.)
C. I. Pigment Red 177 2.0 parts (“Chromoftal Red A2B” manufactured by BASF Corp.)
Dispersing agent 1.0 part (Ajinomoto Fine Techno Co., Ltd. "Addisper PB 821")
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 the red coloring composition 1 was obtained.

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

Example 1
(Green coloring composition 1 (resist material 1))
The mixture of 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 coloring 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 part (BASF Co., Ltd. product "OXE-01": oxime ester initiator)
29.8 parts of PGMAc

[Examples 2 to 7 Comparative Examples 1 to 3]
(Green coloring composition 2 to 10 (resist materials 2 to 10))
Stir mixing and filtration are performed in the same manner as in the green colored composition 1 of Example 1 except that the composition and amount (parts) shown in Table 1 are changed, and green colored compositions 2 to 10 (resist materials 2 to 10) Got). Examples 2 to 6 are reference examples .

The pigment ratios of the green coloring compositions 1 to 8 (resist materials 1 to 8) are shown in Table 2.

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

The green coating film obtained by the coloring composition of [Example 1], [Example 2], and [Example 4] to [Example 7] has a wavelength of 475 nm-at which the spectral transmittance on the short wavelength side becomes 50%. A wavelength of 495 nm and a spectral transmittance of 50% on the long wavelength side satisfies a wavelength range of 580 nm to 590 nm. Moreover, the transmittance | permeability of 530 nm satisfy | fills the high transmittance | permeability of 85% or more, and it was excellent in color resolution.

  In particular, C.I. I. Pigment green 58 and C.I. I. Pigment green 7, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150 or C.I. I. When the pigment yellow 185 is contained, the film thickness is 0.9 μm or less, and it is possible to further reduce the film thickness.

  The green paint film obtained with the coloring composition of [Comparative Example 1] had a green pigment of C.I. I. Since only the pigment green 58 is used, the wavelength at which the spectral transmittance on the long wavelength side is 50% is 591.1 nm, and the color separation is deteriorated. In addition, the film thickness was as thick as 1.6 μm.

  The green paint film obtained with the coloring composition of [Comparative Example 2] had a green pigment of C.I. I. Since only pigment green 7 is used, the wavelength at which the spectral transmittance on the long wavelength side is 50% is 570.0 nm, and does not satisfy the range of 580 nm to 590 nm. In addition, the transmittance at 530 nm was less than 83.0% and 85%, and the color separation deteriorated. In addition, the film thickness was as thick as 1.9 μm.

  The green coating film obtained with the coloring composition of [Comparative Example 3] has C.I. I. Since the pigment green 58 was not contained, the transmittance at 530 nm fell below 84.8% and 85%, resulting in poor color separation.

Moreover, the coating film obtained from the green coloring composition for solid-state imaging devices of this invention, and a color filter had a spectral transmission factor with favorable 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, and C.I. I. Pigment yellow 150 or more selected from the group consisting of C.I. I. Pigment green 58 content is 45% by mass or more based on the total amount of the pigment, and C.I. I. The content of Pigment Green 7, the solid-state imaging device for coloring composition, which is a 5-10 wt% based on the pigment total amount.   Yellow pigments are C.I. I. Pigment yellow 150, The coloring composition for solid-state image sensors of Claim 1 characterized by the above-mentioned. A color filter comprising a filter segment formed from the coloring composition for a solid-state imaging device according to claim 1 or 2 on a substrate.