Coloring composition for cyan color filters and use thereof

Abstract

To provide a photosensitive coloring composition for cyan color filter with satisfactory stability over time, excellent in color characteristics (transmittance) and in substrate adhesion.SOLUTION: The coloring composition for cyan color filter contains a colorant and a basic resin type dispersant. The colorant contains a phthalocyanine pigment represented by the following general formula (1) or a blue phthalocyanine compound represented by the following general formula (2), and the phthalocyanine pigment represented by the following general formula (1) is included in the colorant 100% by mass from 40 to 95% by mass.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a cyan photosensitive coloring composition used in the production of a color filter for a solid-state imaging device or the like. [Background technology]

[0002] C-MOS(Complementary Metal Oxide Semiconductor) Solid-state imaging devices, such as complementary metal-oxide semiconductor (CCD) and charge-coupled devices (CCDs), typically perform color separation by arranging color filters with additive primary color filter segments—red filter layer segments (R), green filter segments (G), and blue filter segments (B)—at predetermined positions on their light-receiving elements. However, color filters with filter segments of cyan, magenta, and yellow (CMY), which correspond to the complementary colors of red, green, and blue, have recently attracted attention because they offer higher sensitivity than primary color filters. Complementary color filters are often used in video cameras and other devices that do not readily utilize auxiliary light sources such as flashes, contributing to increased sensitivity, particularly in nighttime photography. Color filters used in solid-state imaging devices are highly required to have high transmittance, i.e., brightness, and high reliability.

[0003] Among the CMY systems, cyan generally requires the ability to transmit light with wavelengths of 400nm to 600nm and block light above 600nm. Of the phthalocyanine pigments used for cyan, aluminum phthalocyanine pigments have excellent color properties for cyan.

[0004] Patent Document 1 discloses a coloring composition for a cyan color filter, which contains an aluminum phthalocyanine pigment and a basic pigment derivative. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2020-73989 Summary of the Invention [Problem to be solved by the invention]

[0006] However, conventional cyan coloring compositions have problems such as poor stability over time, and coatings formed from the compositions have insufficient transmittance in the wavelength range of 400 nm to 450 nm, which is important for cyan color, and poor adhesion to the substrate.

[0007] An object of the present invention is to provide a photosensitive coloring composition for a cyan color filter, which has good stability over time, is excellent in transmittance for cyan color, and is capable of forming a cyan filter segment with good substrate adhesion. [Means for solving the problem]

[0008] The present invention provides a coloring composition for a cyan color filter, comprising a colorant and a basic resin-type dispersant, The colorant contains a phthalocyanine pigment represented by the following general formula (1) and a blue phthalocyanine compound represented by the following general formula (2), The coloring composition for a cyan color filter contains a phthalocyanine pigment represented by the following general formula (1) in an amount of 40 to 95% by mass relative to 100% by mass of the colorant.

[0009] [ka]

[0010] (In general formula (1), X represents a halogen atom, and n represents an integer of 0 to 16. Y represents -OP(=O)RR, -OC(=O)R, or -OS(=O)R. R and R each independently represent a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted alkoxyl group, or an optionally substituted aryloxy group. R and R may be directly bonded to form a cyclic structure. R represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, or an optionally substituted heterocyclic group. R represents a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted heterocyclic group.) In the general formula (2), A represents any one of the metal elements Al, Cu, Zn, Ti, Cr, Co, and Ni. Y can only be present in the bond between A and Al, Ti, Cr, Co, or Ni, and represents the same structure as Y in general formula (1). There can be 0 to 16 Ls in one phthalocyanine skeleton, and each L independently represents a hydrogen atom, a halogen atom, a nitro group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an acidic functional group, a metal salt, or an amine salt. When A is Zn, there can be 0 to 4 halogen atoms, and when A is a metal other than Zn, there can be 0 to 16 halogen atoms. [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a photosensitive coloring composition for a cyan color filter, which is capable of forming a cyan color filter segment having good stability over time, excellent transmittance, and good substrate adhesion, a color filter, a display device, and a solid-state imaging device. DETAILED DESCRIPTION OF THE INVENTION

[0012] First, the terms used in this specification are defined. The terms "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", and "(meth)acrylamide" respectively mean "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", and "acrylamide and / or methacrylamide". "CI" stands for Color Index. The monomer is a compound containing an ethylenically unsaturated group bond.

[0013] The coloring composition for a cyan color filter (hereinafter referred to as the coloring composition) of the present invention contains a colorant and a basic resin-type dispersant, The colorant contains a phthalocyanine pigment represented by the following general formula (1) and a blue phthalocyanine compound represented by the following general formula (2), The coloring composition for a cyan color filter contains a phthalocyanine pigment represented by the following general formula (1) in an amount of 40 to 95% by mass relative to 100% by mass of the colorant.

[0014] [ka]

[0015] The coloring composition for cyan color filters of the present invention contains a phthalocyanine pigment represented by general formula (1) and a blue phthalocyanine compound represented by general formula (2) as colorants, and therefore exhibits excellent color characteristics that are difficult to obtain using the phthalocyanine pigment represented by general formula (1) alone. Furthermore, the use of a basic resin-type dispersant allows the colorant to be maintained in a well-dispersed state. This improves the transmittance in the 400-450 nm wavelength range, which is important for achieving cyan color, and also provides the unexpected effect of improving adhesion to the substrate.

[0016] <Coloring agent> The colorant contains a phthalocyanine pigment represented by general formula (1) and a blue phthalocyanine compound represented by general formula (2). Use of the phthalocyanine pigment represented by general formula (1) enables the formation of a cyan color filter with extremely low absorption in the 450 nm to 550 nm range and excellent cyan spectral characteristics.

[0017] The mass ratio of the phthalocyanine pigment represented by general formula (1) to the blue phthalocyanine compound represented by general formula (2) is preferably (1):(2)=40:60 to 95:5, more preferably 60:40 to 90:10, and even more preferably 70:30 to 85:15. When used in an appropriate ratio, the light transmittance of the cyan color is improved.

[0018] (Phthalocyanine pigment represented by general formula (1)) General formula (1) [ka]

[0019] In general formula (1), X represents a halogen atom, and n represents an integer of 0 to 16. Y represents -OP(=O)R1R2, -OC(=O)R3, or -OS(=O)2R4. R1 and R2 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent. R1 and R2 can be directly bonded to form the following cyclic structure. Note that * represents a bond to -Al.

[0020] [ka]

[0021] R3 represents a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent. R4 represents a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent.

[0022] The n of the halogen atom X is preferably 12 or less, more preferably 5 or less, which improves dispersibility and color properties.

[0023] In general formula (1), from the viewpoint of dispersibility and color properties, R 1 and R 2 At least one of the groups is an aryl group which may have a substituent, or an aryloxy group (-OR 3 In R 3 is an aryl group which may have a substituent) Preferred. 1 and R 2 represents an aryl group which may have a substituent, or an aryloxy group which may have a substituent (-OR 3 In R 3 is an aryl group which may have a substituent), and a phenyl group and a phenoxy group are even more preferred.

[0024] The content of the phthalocyanine pigment represented by general formula (1) is preferably 50 parts by mass or more in 100 parts by mass of the colorant, and more preferably 70 parts by mass or more in terms of the color characteristics of cyan color.

[0025] (Blue phthalocyanine compound represented by general formula (2)) By incorporating the blue phthalocyanine compound represented by general formula (2) as a colorant, the light transmittance of the cyan color is improved, and the stability over time of the colored composition and the photosensitive composition is also improved.

[0026] General formula (2) [ka]

[0027] In the general formula (2), A represents any one of the metal elements Al, Cu, Zn, Ti, Cr, Co, and Ni. Y can only be present in the bond between A and Al, Ti, Cr, Co, or Ni, and represents the same structure as Y in general formula (1). One phthalocyanine skeleton contains 0 to 16 L's. Each L independently represents a hydrogen atom, a halogen atom, a nitro group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an acidic functional group, a metal salt, or an amine salt. When A is Zn, the number of halogen atoms is preferably 0 to 4, and when A is a metal other than Zn, the number of halogen atoms is preferably 0 to 16.

[0028] Representative examples of Y in general formulas (1) and (2) are shown in Table 1. Note that * indicates the bonding position of the substituent to Al in general formula (1) or A in general formula (2). The present invention is not limited to these.

[0029] [Table 1]

[0030] Y is preferably a structure represented by —OP(═O)R 1 R 2 as shown in Table 1 as Y-1 to Y-15.

[0031] Examples of the halogen atom in L include fluorine, chlorine, bromine, and iodine.

[0032] Examples of the alkyl group in L which may have a substituent include linear, branched, monocyclic, and fused polycyclic alkyl groups having 1 to 18 carbon atoms. Examples of the "substituent" include halogen atoms such as chlorine, fluorine, and bromine, alkoxy groups such as methoxy, and nitro groups. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, an octadecyl group, a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, a 2-ethoxyethyl group, a 2-butoxyethyl group, a 2,2,3,3-tetrafluoropropyl group, a 2-nitropropyl group, an isopropyl group, an isopentyl group, a 2-ethylhexyl group, a sec-butyl group, a tert-butyl group, a sec-pentyl group, a tert-pentyl group, a tert-octyl group, a neopentyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a boronyl group, and a 4-decylcyclohexyl group.

[0033] Examples of the aryl group in L that may have a substituent include monocyclic or fused polycyclic aromatic groups having 6 to 18 carbon atoms. Examples of the "substituent" include halogen atoms such as chlorine, fluorine, and bromine, alkyl groups, alkoxy groups such as methoxy, amino groups, and nitro groups. Specific examples include phenyl, naphthyl, anthranyl, p-methylphenyl, p-bromophenyl, p-nitrophenyl, p-methoxyphenyl, 2,4-dichlorophenyl, pentafluorophenyl, 2-aminophenyl, 2-methyl-4-chlorophenyl, 4-methoxy-1-naphthyl, 6-methyl-2-naphthyl, 4,5,8-trichloro-2-naphthyl, anthraquinonyl, and 2-aminoanthraquinonyl.

[0034] (acidic functional group) L in general formula (2) is preferably an acidic functional group. Examples of the acidic functional group include a sulfo group, a carboxy group, a hydroxy group, and a phenol group. The number of functional groups, n, of the acidic functional group is preferably 1 to 3.

[0035] Among these, a sulfo group is preferred, and a functional group represented by the following general formula (3) or general formula (4) is more preferred. [ka]

[0036] General formula (3) represents a functional group that forms a salt with a sulfo group and a metal, and general formula (4) represents a functional group that forms a salt with a sulfo group and an amine compound. M2 represents, for example, a calcium atom, a barium atom, a strontium atom, a manganese atom, or an aluminum atom. i represents the valence of M2. R 159 ~R 162 each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a phenyl group which may have a substituent, or a polyoxyalkylene group, or R 159 ~R 162 represents an optionally substituted heterocycle containing a further nitrogen, oxygen or sulfur atom, which is formed by combining either of the above.

[0037] R 159 NR when is a hydrogen atom 160 , R 161 and R 162 The structure is shown below.

[0038] [Table 2]

[0039] Among these, alkylamines are preferred, primary amines having 6 to 36 carbon atoms are more preferred, and primary amines having 8 to 18 carbon atoms are particularly preferred.

[0040] When A is Cu and L is a hydrogen atom or a halogen atom, examples include CI Pigment Blue 15:2, 15:4, and 15:6. These are non-aggregating pigments that can easily form colored compositions with excellent viscosity stability. Among these, CI Pigment Blue 15:4 and 15:6 are preferred, and CI Pigment Blue 15:4 is more preferred.

[0041] (Other colorants) The colorant may further contain other colorants, which facilitates chromaticity adjustment. The other colorants are preferably blue pigments.

[0042] Examples of blue dyes include CI Pigment Blue 15, 15:1, 15:3, 15:5, 16, 22, 60, and 64.

[0043] The content of the colorant in the nonvolatile content of the colored composition is preferably 50 to 85 mass %, more preferably 60 to 80 mass %, and is preferably 25 to 75 mass %, more preferably 30 to 70 mass %, of the nonvolatile content of the photosensitive composition.

[0044] (Fine particle size of colorant) To obtain high light transmittance, it is preferable to use a colorant (organic pigment) whose particles have been refined by, for example, salt milling. The volume-average primary particle size of the colorant is preferably 10 nm or more to improve dispersibility. Furthermore, to improve color reproducibility, it is preferably 100 nm or less, more preferably 20 to 60 nm.

[0045] Salt milling is a process in which a mixture of a colorant, a water-soluble inorganic salt, and a water-soluble organic solvent is mechanically kneaded under heating using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill, and then the water-soluble inorganic salt and water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the colorant is crushed during salt milling by utilizing the high hardness of the inorganic salt. Optimizing the conditions for salt milling a colorant can produce a colorant with a very fine volume-average primary particle diameter and a narrow, sharp particle size distribution.

[0046] Examples of water-soluble inorganic salts that can be used include sodium chloride, barium chloride, potassium chloride, and sodium sulfate, but sodium chloride (table salt) is preferred from the standpoint of cost. From the standpoint of both processing efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000 mass%, and most preferably 300 to 1000 mass%, based on the total mass of the pigment (100 mass%).

[0047] The water-soluble organic solvent functions to moisten the colorant and water-soluble inorganic salt. It is not particularly limited as long as it dissolves (is miscible with) water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent becomes prone to evaporation, a high-boiling solvent with a boiling point of 120°C or higher is preferred for safety reasons. Examples of such solvents include 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and liquid polypropylene glycol. These water-soluble organic solvents are preferably used in an amount of 5 to 1000% by mass, and most preferably 50 to 500% by mass, based on the total mass of the colorant (100% by mass).

[0048] When the colorant is subjected to salt milling, a resin may be added as needed. Examples of the resin include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. The resin is preferably solid at room temperature (25°C) and insoluble in water, and more preferably partially soluble in the above-mentioned water-soluble organic solvents. The amount of resin used is preferably 2 to 200% by mass relative to 100 parts by mass of the colorant.

[0049] (Basic resin type dispersant) The basic resin-type dispersant preferably has an amine value of 10 to 300 mgKOH / g, more preferably 50 to 300 mgKOH / g. Using a basic resin-type dispersant with an appropriate amine value improves affinity for the colorant and dispersion stability. This dispersion stability is particularly improved when the colorant has an acidic functional group. When a phthalocyanine pigment represented by general formula (1) and a blue phthalocyanine compound represented by general formula (2) are mixed and dispersed (hereinafter also referred to as co-dispersion), a colored composition for color filters with excellent dispersibility and dispersion stability can be obtained by using a basic resin-type dispersant with an appropriate amine value as the resin-type dispersant used during dispersion.

[0050] The number average molecular weight of the basic resin-type dispersant is usually preferably 500 to 50000, and particularly preferably 3000 to 30000. A suitable number average molecular weight improves compatibility, making it easier to prepare a composition with a low viscosity.

[0051] Examples of the basic resin-type dispersant include vinyl-based, urethane-based, polyester-based, polyether-based, and polyamide-based resins. Further examples of the basic resin-type dispersant include a polymer having a primary amino group-containing monomer unit such as allylamine, or a comb-shaped basic resin-type dispersant obtained by modifying polyethyleneimine, polyethylenepolyamine, polyxylylenepoly(hydroxypropylene)polyamine, poly(aminomethylated)epoxy resin, or the like with a polyester resin, an acrylic resin, or a polyether resin, or the like.

[0052] Among these, vinyl resins are preferred because they are easy to design and have excellent resistance. Vinyl resins containing N,N-disubstituted amino group-containing monomer units and alkyl (meth)acrylate units are preferred. Unreacted monomers are called "monomers," and monomers that make up the resin after polymerization are called "monomer units."

[0053] Examples of the N,N-disubstituted amino group-containing monomer include N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylamide, and N,N-diethylaminoethyl (meth)acrylamide.

[0054] Examples of the alkyl (meth)acrylate include (meth)acrylic esters obtained by reacting an unsaturated monocarboxylic acid, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, or lauryl (meth)acrylate, with an alkyl alcohol having 1 to 18 carbon atoms.

[0055] Examples of other vinyl monomers include nitro group-containing vinyl monomers such as (meth)acrylonitrile, aromatic monomers such as styrene, α-methylstyrene, and benzyl (meth)acrylate, hydroxyl group-containing monomers such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and polyethylene glycol (meth)acrylate, amide group-containing monomers such as (meth)acrylamide, N-isopropylacrylamide, and diacetone acrylamide, monomers such as N-methylol (meth)acrylamide and dimethylol (meth)acrylamide, alkoxymethyl group-containing monomers such as N-methoxymethyl (meth)acrylamide and N-butoxymethyl (meth)acrylamide, olefins such as ethylene, propylene, and isoprene, dienes such as chloroprene and butadiene, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether, and fatty acid vinyls such as vinyl acetate and vinyl propionate.

[0056] Commercially available basic resin-type dispersants include, for example, DISPERBYK 161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2050, 2150, 2163, 2164, and BYK-LPN 6919 from BYK Japan, and SOLSPERSE 11200, 13240, 13650, and 13660 from Lubrizol Japan. 940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 38500, 39000, 53095, 56000, 7100, and EFKA4300, 4330, 4046, 4060, and 4080 from BASF Japan, but are not limited to these.

[0057] The content of the basic resin-type dispersant is preferably from 5 to 50% by mass, more preferably from 10 to 40% by mass, of the nonvolatile content of the colored composition.

[0058] <Resin-type dispersant containing quaternary ammonium salt groups> The coloring composition for a cyan color filter of the present invention preferably contains a resin-type dispersant having a quaternary ammonium salt group. The quaternary ammonium salt group may be directly bonded to the main chain, or may be bonded to the main chain via a divalent linking group. The quaternary ammonium salt group is preferably -N + R 42 R 43 R 44 Y - (However, R 42 , R 43 and R 44 each independently represents a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group; R 42 , R 43 and R 44 Two or more of Y may be bonded to each other to form a cyclic structure. - represents a counter anion.) It has a quaternary ammonium base represented by -N + R 42 R 43 R 44 In R 42 , R 43 and R 44 Examples of the cyclic structure formed by bonding two or more of the above include a 5- to 7-membered nitrogen-containing heterocyclic monocycle or a fused ring formed by condensing two of these. The nitrogen-containing heterocycle is preferably one that does not have aromaticity, and more preferably a saturated ring. Examples of the cyclic structure include the following structures.

[0059] [ka]

[0060] These cyclic structures may further have a substituent. -N + R 42 R 43 R 44 R in 42 , R 43 and R 44More preferred is an alkyl group having 1 to 4 carbon atoms which may have a substituent, or a phenyl group which may have a substituent, and a methyl group, an ethyl group, a propyl group, a butyl group, or a benzyl group is preferred.

[0061] The resin-type dispersant (B) having a quaternary ammonium salt group used in the colored composition for cyan color filter of the present invention is preferably an AB block copolymer and / or a BAB block copolymer. A: Block with a quaternary ammonium base in the side chain B: Block without quaternary ammonium base in the side chain

[0062] It is particularly preferable that the A block contains a constitutional unit represented by the following general formula (5).

[0063] General formula (5) [ka]

[0064] In general formula (5), R 45 , R 46 and R 47 each independently represents a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group; R 45 , R 46 and R 47 Two or more of the R may be bonded to each other to form a cyclic structure. 48 represents a hydrogen atom or a methyl group; Z represents a divalent linking group; Y - represents the counter anion. In the above general formula (5), examples of the divalent linking group Z include an alkylene group having 1 to 10 carbon atoms, an arylene group, -CONH-R 49 -group, -COO-R 50 -group (where R 49 and R 50is a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (-R'-OR"-: R' and R" are each independently an alkylene group). - As for Cl - , Br - , I - , ClO4 - , B.F. - , CH3COO - , PF6 - , R 49 -SO3 - , etc.

[0065] Two or more types of partial structures containing a specific quaternary ammonium base as described above may be contained in one A block. In this case, the two or more types of partial structures containing a quaternary ammonium base may be contained in the A block in the form of either random copolymerization or block copolymerization. A partial structure not containing a quaternary ammonium base may also be contained in the A block. Examples of such partial structures include partial structures derived from (meth)acrylic acid ester monomers described below. The content of such partial structures not containing a quaternary ammonium base in the A block is preferably 0 to 70% by mass, more preferably 0 to 50% by mass.

[0066] Examples of the B block constituting the block copolymer of the resin-type dispersant having a quaternary ammonium salt group include polymer structures obtained by copolymerizing comonomers such as styrene-based monomers such as styrene and α-methylstyrene; (meth)acrylic acid ester-based monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, glycidyl (meth)acrylate, benzyl (meth)acrylate, hydroxyethyl (meth)acrylate, ethyl glycidyl acrylate, and N,N-dimethylaminoethyl (meth)acrylate; (meth)acrylic acid salt-based monomers such as (meth)acrylic acid chloride; (meth)acrylamide-based monomers such as (meth)acrylamide, N-methylolacrylamide, N,N-dimethylacrylamide, and N,N-dimethylaminoethylacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether; crotonic acid glycidyl ether; and N-methacryloylmorpholine.

[0067] The resin-type dispersant containing a quaternary ammonium salt group used in the present invention is preferably an AB block or BAB block copolymer polymer compound composed of such an A block and a B block. Such block copolymers are produced, for example, by the living polymerization method described below. Here, living polymerization is a polymerization method that suppresses side reactions that occur in general radical polymerization and also allows polymerization growth to occur uniformly, making it easy to synthesize block polymers and resins with uniform molecular weights. The molecular weight of the polymer and the ratio of monomers to be block copolymerized can be freely controlled by the charging ratio of the polymerization initiator and vinyl monomer added during polymerization.

[0068] Examples of living polymerization methods include the nitroxide-mediated polymerization (NMP) method, which utilizes the dissociation and bonding of amine oxide radicals (see Reference 1); atom transfer radical polymerization (ATRP) method, which uses heavy metals such as copper, ruthenium, nickel, and iron and ligands that form complexes with them to polymerize halogen compounds as initiator compounds (see References 2, 3, and 4); reversible addition-fragmentation chain transfer (RAFT) method, which uses dithiocarboxylic acid esters, xanthates, and other initiator compounds to polymerize addition-polymerizable monomers and radical initiators (see Reference 5); Macromolecular Designvia Interchange of Xanthate (MADIX) method (see Reference 6); and degenerative transfer polymerization (Degenerative Transfer Polymerization) methods, which use heavy metals such as organotellurium, organobismuth, organoantimony, antimony halides, organogermanium, and germanium halides. These include the organotellurium-mediated living radical polymerization (TERP) method (see Reference 9), which controls polymerization through two processes: thermal dissociation of the bond between tellurium atoms and carbon and degenerative chain transfer.

[0069] (Reference 1)Chemical Review (2001)101,3661 (Reference document 2) Special table publication No. 2000-500516 (Reference document 3) Special table publication No. 2000-514479 (Reference 4)Chemical Review (2001)101,3689 (Reference document 5) Special table publication No. 2000-515181 (Reference 6) See the pamphlet for International Publication No. 1999-05099 (Reference 7) Japanese Patent Application Laid-Open No. 2007-277533 (Reference 8) Journal of American Chemical Society (2002) 124, 2874 (Reference 9) JP 2004-323693

[0070] Whether the resin-type dispersant having a quaternary ammonium salt group used in the present invention is an AB block copolymer or a BAB block copolymer, the A block / B block ratio constituting the copolymer is preferably 1 / 99 to 80 / 20, and particularly 5 / 95 to 60 / 40 (mass ratio), and within this range, good heat resistance and dispersibility can both be achieved. Furthermore, in the AB block copolymer and BAB block copolymer of the present invention, it is preferable that the monomer having a quaternary ammonium salt group accounts for 10 mass % or more of the total mass of the monomers constituting the copolymer, thereby enabling the resin-type dispersant (B) to be well adsorbed to the dye salt product (A) and exhibiting excellent dispersibility and storage stability.

[0071] Although resin-type dispersants containing quaternary ammonium salt groups may contain amino groups generated during the manufacturing process, it is preferable that they do not contain amino groups. Furthermore, the acid value of resin-type dispersants containing quaternary ammonium salt groups is preferably 0 to 50 mg KOH / g, and the molecular weight is preferably in the range of 1,000 to 100,000 in terms of mass average polystyrene. A molecular weight of 1,000 or more provides good storage stability, while a molecular weight of 100,000 or less provides good developability and resolution.

[0072] <Method of manufacturing a coloring composition for color filters> The coloring composition is prepared, for example, by dispersing a colorant, a basic resin-type dispersant, a solvent, and the like. The colorant is preferably subjected to a micronization treatment using a dispersing aid such as a dye derivative before the dispersion treatment. In this specification, the micronization treatment can be carried out by micronizing two types of colorants individually. Alternatively, multiple colorants (A) can be used and micronized all at once. In this specification, a coloring composition can be prepared for each type of colorant and then blended, or two types of colorants can be mixed and dispersed.

[0073] The dispersion treatment can be carried out using a dispersing device such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor. Among these, dispersion with beads using zirconium oxide or inorganic glass is preferred. Beads of different diameters may also be used.

[0074] After the dispersion treatment, it is preferable to remove coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and mixed dust from the colored composition using a means such as centrifugation at a gravitational acceleration of 3000 to 25000 G, a sintered filter, or a membrane filter.

[0075] The colored composition of the present invention can be prepared as a colored composition for a cyan color filter.

[0076] (covariance) In the method for producing a colored composition of the present invention, for example, a phthalocyanine pigment represented by general formula (1) and a blue phthalocyanine compound represented by general formula (2) are preferably co-dispersed in a basic resin-type dispersant using a media-type wet disperser. Co-dispersion refers to mixing two or more pigments and dispersing them under the same conditions. Co-dispersion can satisfactorily reduce the size and disperse the pigment particles, and can produce a colored composition for color filters that has excellent dispersion stability after dispersion. It goes without saying that this method is not limited to co-dispersion, and individual dispersion is also possible.

[0077] Co-dispersion can be achieved, for example, by mixing at least two pigments with a dispersant and pre-dispersing them using a homogenizer or the like, and then dispersing the mixture using various dispersing means such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor. Co-dispersion using a media-type wet disperser is preferred. Furthermore, the size of the zirconia beads used when dispersing using a media-type wet disperser is preferably 1.25 mm or less, and more preferably 0.5 mm or less.

[0078] In the present invention, when co-dispersing, it is more preferable to include at least one resin-type dispersant, since this can improve the dispersibility of the pigment.

[0079] <Resin-type dispersant> The coloring composition may contain a resin-type dispersant other than the basic resin-type dispersant. Examples of resin-type dispersants include polyurethanes, polyacrylates and other polycarboxylic acid esters, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof; oil-based dispersants such as amides formed by the reaction of poly(lower alkylene imines) with polyesters having free carboxyl groups, and salts thereof; water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohols, and polyvinylpyrrolidone; polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and phosphate esters.

[0080] The content of the resin-type dispersant is preferably 0.1 to 150 parts by mass, and more preferably 30 to 100 parts by mass, relative to 100 parts by mass of the colorant. When an appropriate amount is used, dispersibility is further improved.

[0081] (Acidic resin type dispersant) The resin-type dispersant is preferably an acidic resin-type dispersant. When an acidic resin-type dispersant is used together with a basic resin-type dispersant, the solubility in the developer is improved, and color residue after development can be suppressed. In terms of molecular structure, the acidic resin-type dispersant may be a straight-chain resin-type dispersant or a comb-type resin-type dispersant.

[0082] [Comb-type resin dispersant 1] Comb-shaped resin-type dispersant 1 can be synthesized by the methods described in, for example, WO2008 / 007776, JP2008-029901A, JP2009-155406A, and the like. The comb-shaped resin-type dispersant 1 is preferably a resin-type dispersant which is a reaction product between the hydroxyl groups of a hydroxyl group-containing polymer and the acid anhydride groups of a tetracarboxylic dianhydride, or a resin-type dispersant which is a polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product between the hydroxyl groups of a hydroxyl group-containing compound and the acid anhydride groups of a tetracarboxylic dianhydride.

[0083] [Comb-type resin dispersant 2] The comb-shaped resin-type dispersant 2 can be synthesized by the methods described in WO2008 / 007776, JP2009-155406A, JP2010-185934A, JP2011-157416A, and the like. Comb-shaped resin-type dispersant 2 is prepared by synthesizing a resin-type dispersant having a side chain by polymerizing an ethylenically unsaturated monomer having a thermally crosslinkable group such as a hydroxyl group, a t-butyl group, an oxetane skeleton, or a blocked isocyanate with other monomers in the presence of a reaction product between the hydroxyl group of a compound having a hydroxyl group and the acid anhydride group of a tetracarboxylic dianhydride. The resin-type dispersant is preferably obtained by subsequently reacting a monomer having an isocyanate group with the hydroxyl group in the side chain.

[0084] [Tetracarboxylic acid anhydride] Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride, propylene glycol ditrimellitic anhydride, butylene glycol ditrimellitic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyfuran) 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic) dianhydride, m-phenylene-bis(triphenylphthalic) dianhydride, bis(triphenylphthalic)-4,4'-diphenylether dianhydride, bis(triphenylphthalic)-4,4'-diphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)diphenylpropane dianhydride] ((oxy)phenyl)fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydrofuran Examples thereof include aromatic tetracarboxylic acid dianhydrides such as tetrahydro-1-naphthalene succinic dianhydride and 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride.

[0085] Among these, aromatic tetracarboxylic dianhydrides are preferred, and tetracarboxylic dianhydrides having two or more aromatic rings are more preferred. Aromatic carboxylic acids are preferred because their aromatic rings are easily adsorbed to the aromatic rings of phthalocyanine.

[0086] [Straight-chain resin-type dispersant 3] The linear resin-type dispersant 3 can be synthesized by the methods described in JP 2009-251481 A, JP 2007-23195 A, JP 1996-143651 A, etc. The linear resin-type dispersant 3 can be synthesized by adding the hydroxyl group of a vinyl polymer having one hydroxyl group at one end to the acid anhydride group of a tricarboxylic acid anhydride.

[0087] [Tricarboxylic acid anhydride] Examples of tricarboxylic acid anhydrides include aromatic tricarboxylic acid anhydrides such as benzenetricarboxylic acid anhydride (1,2,3-benzenetricarboxylic acid anhydride, trimellitic acid anhydride [1,2,4-benzenetricarboxylic acid anhydride], naphthalenetricarboxylic acid anhydride (1,2,4-naphthalenetricarboxylic acid anhydride, 1,4,5-naphthalenetricarboxylic acid anhydride, 2,3,6-naphthalenetricarboxylic acid anhydride, 1,2,8-naphthalenetricarboxylic acid anhydride), 3,4,4'-benzophenonetricarboxylic acid anhydride, 3,4,4'-biphenylethertricarboxylic acid anhydride, 3,4,4'-biphenyltricarboxylic acid anhydride, 2,3,2'-biphenyltricarboxylic acid anhydride, 3,4,4'-biphenylmethanetricarboxylic acid anhydride, and 3,4,4'-biphenylsulfonetricarboxylic acid anhydride. Among these, aromatic tricarboxylic acid anhydrides are preferred.

[0088] <Binder resin> The binder resin is preferably a resin having a transmittance of 80% or more over the entire wavelength range of 400 to 700 nm when a coating having a thickness of 2 μm is formed. The transmittance is preferably 95% or more. The binder resin is preferably a thermoplastic resin or a photosensitive resin. The binder resin is also preferably alkali-soluble. This allows the coating formed from the photosensitive coloring composition to be patterned by photolithography. The alkali-insoluble photosensitive resin and the alkali-soluble resin may have a thermosetting group. Examples of the thermosetting group include an epoxy group and an oxetanyl group.

[0089] Examples of alkali-soluble resins include resins having an acidic group such as a carboxyl group or a sulfonic group. Examples of alkali-soluble thermoplastic resins include acrylic resins having an acidic group, α-olefin / maleic acid (anhydride) copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, and isobutylene / maleic acid (anhydride) copolymers. Among these, acrylic resins having an acidic group and styrene / styrene sulfonic acid copolymers are preferred in terms of improving developability, heat resistance, and transparency.

[0090] The acid value of the alkali-soluble resin is preferably 20 to 300 mgKOH / g, which improves developability when forming a pattern by photolithography.

[0091] <Alkali-soluble photosensitive resin> Alkali-soluble photosensitive resins are photosensitive because they contain polymerizable unsaturated groups. Any known resin can be used as long as it is alkali-soluble and photosensitive, but resins synthesized by the following methods (i) and (ii) are preferred. When an alkali-soluble photosensitive resin is used, it undergoes three-dimensional crosslinking upon exposure to light, increasing the crosslink density and improving the chemical resistance of the coating.

[0092] [Method (i)] In method (i), for example, a polymer of an epoxy group-containing monomer and other monomers is first synthesized. Next, a monocarboxyl group-containing monomer is added to the epoxy group of the polymer, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to obtain an alkali-soluble photosensitive resin. The monocarboxyl group-containing monomer is a monomer having one carboxyl group.

[0093] Examples of epoxy group-containing monomers include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity.

[0094] Examples of the monocarboxyl group-containing monomer include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid, and (meth)acrylic acid substituted with haloalkyl, alkoxyl, halogen, nitro, or cyano at the α-position.

[0095] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc. The polybasic acid anhydride may have a carboxyl group that does not form an acid anhydride.

[0096] Examples of other monomers include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and ethoxypolyethylene glycol (meth)acrylate; Alternatively, examples include (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, and acryloylmorpholine; styrenes such as styrene and α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; and fatty acid vinyls such as vinyl acetate and vinyl propionate.

[0097] Also, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-triphenyl)maleimide, N-substituted maleimides such as N-(4-chlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, and 9-maleimidoacridine ethylene oxide (EO)-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of para-cumylphenol, EO-modified (meth)acrylate of nonylphenol, PO-modified (meth)acrylate of nonylphenol, etc.

[0098] In the method (ii), for example, a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other monomers are synthesized to prepare a polymer, and then the hydroxyl groups of the polymer are reacted with the isocyanate groups of an isocyanate group-containing monomer to synthesize an alkali-soluble photosensitive resin.

[0099] Examples of hydroxyl group-containing monomers include hydroxyalkyl methacrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3-, or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate. Other examples include polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to a hydroxyalkyl (meth)acrylate, and polyester mono(meth)acrylates obtained by addition polymerization of poly(γ-valerolactone), poly(ε-caprolactone), and / or poly(12-hydroxystearic acid). Among these, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferred, with glycerol mono(meth)acrylate being more preferred.

[0100] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0101] Monomers that can be used other than the above-mentioned monomers include the other monomers exemplified in the above method (i) as well as phosphate ester group-containing monomers.

[0102] The phosphate group-containing monomer is, for example, a compound obtained by reacting the hydroxyl group of a hydroxyl group-containing monomer with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid.

[0103] (thermoplastic resin) Thermoplastic resins are resins that are not alkali-soluble. Examples of thermoplastic resins include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. Among these, acrylic resins are preferred.

[0104] The weight-average molecular weight (Mw) of the binder resin is preferably 5,000 to 100,000, more preferably 10,000 to 80,000. The number-average molecular weight (Mn) is preferably 5,000 to 50,000. The Mw / Mn (molecular weight dispersity) is preferably 10 or less. The weight-average molecular weight (Mw) and number-average molecular weight (Mn) are polystyrene-equivalent molecular weights measured using a gel permeation chromatography (HLC-8220GPC, manufactured by Tosoh Corporation) with two TSK-GELSUPER HZM-N columns connected in series and tetrahydrofuran (THF) as the solvent.

[0105] The content of the binder resin is preferably 10 to 500 parts by mass with respect to 100 parts by mass of the colorant.

[0106] <Thermosetting compounds> The photosensitive coloring composition can contain a thermosetting compound. This improves the crosslink density during the heating process after forming a pattern on the coating by photolithography when producing a color filter, thereby improving heat resistance. In addition, the coloring agent is less likely to aggregate during the heating process, further improving the contrast ratio.

[0107] Thermosetting compounds include low molecular weight compounds and polymers (thermosetting resins). Examples of thermosetting compounds include epoxy compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, cardo compounds, and phenol compounds. Among these, epoxy compounds, melamine resins, cardo compounds, and oxetane compounds are preferred.

[0108] <Dispersion aid> When dispersing the colorant in the pigment carrier, a dispersant such as a dye derivative, a resin-type dispersant, a surfactant, etc. The dispersant has a significant effect of preventing reagglomeration of the colorant after dispersion, and therefore, a colored composition obtained by dispersing the colorant in the pigment carrier using the dispersant has good brightness and viscosity stability.

[0109] (dye derivatives) The coloring composition for color filters of the present invention can contain, as a dye derivative, a compound in which a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent has been introduced into an organic pigment, an anthraquinone, an acridone, or a triazine. Examples of such dye derivatives that can be used include those described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-2001-335717, JP-A-2003-128669, JP-A-2004-091497, JP-A-2007-156395, JP-A-2008-094873, JP-A-2008-094986, JP-A-2008-095007, JP-A-2008-195916, and Japanese Patent No. 4585781. These can be used alone or in combination of two or more. Compounds B-1 to B-50 in the present invention were also synthesized based on known methods for synthesizing dye derivatives.

[0110] The content of the dye derivative is preferably 1.0 part by mass or more, more preferably 3 parts by mass or more, and most preferably 5 parts by mass or more, relative to 100 parts by mass of the colorant from the viewpoint of improving dispersibility, and is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, from the viewpoint of heat resistance and light fastness.

[0111] <Organic solvent> Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3 -Methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diene ethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, cyclopentanone, cyclohexanone, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate,Examples of the dipropylene glycol monoethyl ether include dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

[0112] Among these, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone and cyclopentanone are preferred.

[0113] The amount of the organic solvent used is preferably 500 to 4000 parts by mass per 100 parts by mass of the colorant, in order to adjust the viscosity of the colored composition to an appropriate level.

[0114] The organic solvents can be used alone or in combination of two or more kinds.

[0115] <Photosensitive coloring composition for color filters> The photosensitive coloring composition for color filters preferably contains the coloring composition for color filters prepared as described above, a polymerizable compound, a photopolymerization initiator, and an organic solvent, and preferably further contains a binder resin. The photosensitive coloring composition for color filters is prepared by stirring and mixing the above materials. Further, filtration is carried out as necessary. The stirring and mixing may be carried out by the dispersion treatment already described. Furthermore, the timing of blending each material is arbitrary. It is preferable to remove coarse particles and the like in the same manner as above.

[0116] <Polymerizable compound> The polymerizable compound is a monomer or oligomer containing a polymerizable unsaturated group, such as an acid group-containing monomer, a urethane bond-containing monomer, or other monomer.

[0117] Examples of the acid group of the acid group-containing monomer include a sulfonic acid group, a carboxyl group, and a phosphoric acid group. Examples of the acid group-containing monomer include esters of dicarboxylic acids and free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid; and esters of polycarboxylic acids and monohydroxyalkyl (meth)acrylates. Specific examples include free carboxyl group-containing monoesters of monohydroxy oligoacrylates or monohydroxy oligomethacrylates, such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate, with dicarboxylic acids, such as malonic acid, succinic acid, glutaric acid, and phthalic acid; and free carboxyl group-containing oligoesters of tricarboxylic acids, such as propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, and benzene-1,3,5-tricarboxylic acid, with monohydroxy monoacrylates or monohydroxy monomethacrylates, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.

[0118] (urethane bond-containing monomer) Examples of the urethane bond-containing monomer include a polyfunctional urethane acrylate obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, and a polyfunctional urethane acrylate obtained by reacting an alcohol with a polyfunctional isocyanate and then reacting the alcohol with a (meth)acrylate having a hydroxyl group.

[0119] Examples of the (meth)acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and a carboxy(meth)acrylate, and a hydroxyl group-containing polyol polyacrylate.

[0120] Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanate.

[0121] Other monomers include, for example, 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, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, Examples of the acrylic acid esters include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, (meth)acrylic acid esters of methylolated melamine, epoxy (meth)acrylate, and various acrylic acid esters and methacrylic acid esters such as urethane acrylate, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, and acrylonitrile.

[0122] Among these, polymerizable compounds having three or more polymerizable unsaturated groups (hereinafter referred to as trifunctional or higher functional polymerizable compounds) are preferred.

[0123] Examples of the tri- or higher functional polymerizable compound include pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and dipentaerythritol penta(meth)acrylate.

[0124] Commercially available tri- or higher functional polymerizable compounds include, for example, KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R-684, GPO-303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, and DPCA-120 manufactured by Nippon Kayaku Co., Ltd., and Aronix M-303, M-305, M-306, M-309, and M-310 manufactured by Toagosei Co., Ltd. Examples include M-321, M-325, M-350, M-360, M-313, M-315, M-400, M-402, M-403, M-404, M-405, M-406, M-450, M-452, M-408, M-211B, and M-101A, Viscoat #310HP, #335HP, #700, #295, #330, #360, #GPT, #400, and #405 manufactured by Osaka Organic Chemical Co., Ltd., and NK Ester A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd.

[0125] The polymerizable compounds can be used alone or in combination of two or more kinds.

[0126] The content of the polymerizable compound is preferably 1 to 50 mass %, more preferably 2 to 40 mass parts, based on 100 mass % of the nonvolatile content of the photosensitive coloring composition. When an appropriate amount is added, the curability and developability are further improved.

[0127] <Photopolymerization initiator> The photopolymerization initiator (G) is, for example, 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)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4- acetophenone compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzil dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 3,3',4,4'-tetra(t- benzophenone compounds such as butylperoxycarbonyl)benzophenone; thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis( triazine-based compounds such as 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, and 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine;Examples of suitable compounds include oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime), or ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; and titanocene compounds.

[0128] Commercially available products include, for example, acetophenone compounds, all manufactured by IGM Resins, such as "Omnirad 907" (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one), "Omnirad 369E" (2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone), and "Omnirad 379EG" (2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone), and phosphine compounds, all manufactured by IGM Resins, such as "Omnirad 819" (bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide), "Omnirad TPO" (diphenyl-2,4,6-trimethylbenzoylphosphine oxide), etc.

[0129] Among these, oxime ester compounds are preferred.

[0130] (Oxime ester compounds) When oxime ester compounds absorb ultraviolet light, the NO bond of the oxime undergoes cleavage, generating iminyl radicals and alkyloxy radicals. These radicals further decompose to generate highly active radicals, allowing patterns to be formed with a small amount of exposure. When the organic pigment concentration of a photosensitive coloring composition is high, the ultraviolet transmittance of the coating film may decrease, resulting in a low degree of curing of the coating film. However, oxime ester compounds are preferably used because of their high quantum efficiency.

[0131] Preferred examples of the oxime ester photopolymerization initiator are shown below.

[0132] [ka] [ka]

[0133] Commercially available products include, for example, 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] (IRGACURE OXE-01), ethanone, 1-[ 9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (IRGACURE OXE 02), IRGACURE OXE 04 (all manufactured by BASF Japan), N-1919, NCI-831, NCI-930 (all manufactured by ADEKA), TRONLYTR-PBG-304, TRON LY TR-PBG-305, TRONLY TR-PBG-309, TRONLY TR TRONLY TR-PBG-345, TRONLY TR-PBG-358, TRONLY TR-PBG-3057 (all manufactured by Changzhou Strong New Materials Co., Ltd.), etc. Further examples include oxime ester photopolymerization initiators described in JP 2007-210991 A, JP 2009-179619 A, JP 2010-037223 A, JP 2010-215575 A, JP 2011-020998 A, etc.

[0134] The photopolymerization initiators can be used alone or in combination of two or more.

[0135] <Polymerization inhibitor> The photosensitive coloring composition may contain a polymerization inhibitor, which prevents photosensitivity due to diffracted light from the mask during exposure, making it easier to obtain a good pattern shape.

[0136] Examples of the polymerization inhibitor include alkyl catechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methyl catechol, 3-methyl catechol, 4-methyl catechol, 2-ethyl catechol, 3-ethyl catechol, 4-ethyl catechol, 2-propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-tert-butyl catechol, 3-tert-butyl catechol, 4-tert-butyl catechol, and 3,5-di-tert-butyl catechol; 2-methyl resorcinol, 4-methyl resorcinol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol, and 2-n-butyl alkylresorcinol compounds such as n-butylresorcinol, 2-tert-butylresorcinol, and 4-tert-butylresorcinol; alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, and 2,5-di-tert-butylhydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and tribenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite; pyrogallol; and phloroglucin.

[0137] The content of the polymerization inhibitor is preferably 0.01 to 1 part by mass in the nonvolatile content of the photosensitive coloring composition. When an appropriate amount is contained, a good pattern shape is easily obtained.

[0138] <UV absorber> The photosensitive coloring composition may contain an ultraviolet absorber. Examples of the ultraviolet absorber include benzotriazole compounds, triazine compounds, benzophenone compounds, salicylic acid ester compounds, cyanoacrylate compounds, and salicylate compounds. The ultraviolet absorber may be an oligomer or a polymer.

[0139] Among these, examples of benzotriazole-based organic compounds include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, and 2,2'-methylenebis[6-(benzotriazol-2-yl)-4-tert-octylphenol]. Examples of benzophenone-based organic compounds include 2,2-dihydroxy-4,4-dimethoxybenzophenone. Examples of triazine-based organic compounds include 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

[0140] Examples of commercially available products include "TINUVIN P" (absorbance 0.40), "TINUVIN 326" (absorbance 0.48), and "TINUVIN 360" (absorbance 0.40) manufactured by BASF Japan Ltd., "Seesorb 107" (absorbance 0.60) manufactured by Shipro Chemical Co., Ltd., and "ADK STAB LA-F70" (absorbance 0.90) manufactured by ADEKA Corporation.

[0141] The content of the ultraviolet absorber is preferably 5 to 70% by mass, based on 100% by mass of the total of the photopolymerization initiator and the ultraviolet absorber. When an appropriate amount is contained, a good pattern shape is easily obtained. When the photosensitive coloring composition contains a sensitizer, the content of the sensitizer is included in the content of the photopolymerization initiator.

[0142] <Sensitizer> The photosensitive coloring composition may contain a sensitizer. Examples of the sensitizer include polymethine dyes such as chalcone derivatives, unsaturated ketones typified by dibenzalacetone, 1,2-diketone derivatives typified by benzil and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, and oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyrazinoporphyrazine derivatives. Examples of the organic conductor include phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalylporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenyl glyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3', or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and 4,4'-diethylaminobenzophenone.

[0143] The content of the sensitizer is preferably 3 to 60 parts by mass, more preferably 5 to 50 parts by mass, relative to 100 parts by mass of the photopolymerization initiator. When an appropriate amount is contained, photocurability and developability are improved.

[0144] <Antioxidants> The photosensitive coloring composition can contain an antioxidant. The antioxidant prevents the coating film formed from the photosensitive coloring composition from yellowing due to oxidation during thermal curing or ITO annealing, thereby suppressing a decrease in the transmittance of the coating. In particular, when the colorant concentration of the photosensitive coloring composition is high, the content of the polymerizable compound is relatively reduced, and the coating is likely to yellow if the amount of photopolymerization initiator is increased or a thermosetting compound is added to address this. Therefore, by including an antioxidant, yellowing due to oxidation during the heating process can be prevented and a decrease in the transmittance of the coating can be suppressed.

[0145] Examples of the antioxidant include hindered phenol compounds, hindered amine compounds, phosphorus compounds, sulfur compounds, and hydroxylamine compounds. The antioxidant is preferably a compound that does not contain a halogen atom. Among these, hindered phenol compounds, hindered amine compounds, phosphorus compounds, and sulfur compounds are preferred from the viewpoint of achieving both transmittance and sensitivity of the coating film.

[0146] The antioxidants can be used alone or in combination of two or more.

[0147] The content of the antioxidant is preferably 0.5 to 5.0% by mass relative to 100% by mass of the nonvolatile content of the photosensitive coloring composition.

[0148] <Leveling Agent> The photosensitive coloring composition can contain a leveling agent. This improves the wettability of the coating to the transparent substrate during coating formation and the drying properties of the coating. Examples of leveling agents include dimethylpolysiloxane, silicone surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants. Of these, dimethylpolysiloxane is preferred, and the dimethylpolysiloxane preferably has a polyether structure or polyester structure in the main chain. Examples of commercially available products include dimethylpolysiloxanes having a polyether structure in the main chain, such as FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, and FZ-2207 manufactured by Toray Dow Corning Co., Ltd., and BYK-333 manufactured by BYK-Chemie Co., Ltd. Also, examples of dimethylpolysiloxanes having a polyester structure in the main chain, such as BYK-310 and BYK-370 manufactured by BYK-Chemie Co., Ltd.

[0149] The leveling agents can be used alone or in combination of two or more kinds.

[0150] The content of the leveling agent is preferably from 0.001 to 2.0 mass %, more preferably from 0.003 to 0.5 mass %, of the nonvolatile content of the photosensitive coloring composition.

[0151] <Curing agent, curing accelerator> The photosensitive coloring composition can contain a curing agent or a curing accelerator to aid in the curing of the thermosetting compound.As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, etc. are effective, but are not particularly limited thereto, and any curing agent may be used as long as it can react with the thermosetting resin.In addition, among these, compounds having two or more phenolic hydroxyl groups in one molecule and amine curing agents are preferred. Examples of the curing accelerator include amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivative bicyclic amidine compounds and salts thereof (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazoline, etc.), and the like. Examples of suitable curing accelerators include methyl methyl acrylate, methyl methacrylate, methyl methacrylate, methyl methacrylate (e.g., methyl methacrylate, methyl methacrylate), methyl methacrylate (e.g. ...

[0152] <Other additives> The photosensitive coloring composition may contain other additives such as a storage stabilizer and an adhesion improver. A storage stabilizer may be added to stabilize the viscosity over time. An adhesion improver such as a silane coupling agent may also be added to improve adhesion to the transparent substrate.

[0153] The storage stabilizer can improve the viscosity stability of the composition over time. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine, phosphites, etc. The amount of storage stabilizer used is preferably 0.1 to 10 parts by mass per 100 parts by mass of the colorant.

[0154] The adhesion promoter can improve the adhesion between the substrate and the coating. Examples of the adhesion improver include vinyl silanes such as vinyltris(β-methoxyethoxy)silane, vinylethoxysilane, and vinyltrimethoxysilane; (meth)acrylic silanes such as γ-methacryloxypropyltrimethoxysilane; β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)methyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane. Examples of the silane coupling agent include epoxy silanes such as N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The amount of the adhesion improver used is preferably 0.01 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the colorant.

[0155] (surfactant) Examples of surfactants include anionic surfactants such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium stearate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine styrene-acrylic acid copolymers, and polyoxyethylene alkyl ether phosphate esters; nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate esters, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyl betaines such as alkyldimethylaminoacetic acid betaine, and amphoteric surfactants such as alkylimidazolines. These may be used alone or in combination of two or more, but are not necessarily limited to these.

[0156] The content of the surfactant is preferably 0.1 to 55 parts by mass, and more preferably 0.1 to 45 parts by mass, relative to 100 parts by mass of the colorant. If the content of the surfactant is less than 0.1 part by mass, it is difficult to obtain the effect of adding it, and if the content is more than 55 parts by mass, the excess dispersant may affect dispersion.

[0157] <Color filter> The color filter of the present invention comprises a substrate and a filter segment formed from a photosensitive coloring composition for a cyan color filter, and preferably further comprises a magenta filter segment and a yellow filter segment.

[0158] The dyes used in the magenta and yellow filter segments will be described below. Known materials may be used as materials other than the dyes.

[0159] <Magenta dye> Examples of magenta colorants include magenta pigments, such as condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Examples of magenta pigments include CI Pigment Red 2, 3, 5, 6, 7, 23, 31, 48:2, 48:3, 48:4, 57:1, 81:1, 122, 123, 130, 144, 146, 149, 150, 166, 168, 169, 177, 179, 178, 181, 184, 185, 190, 194, 202, 206, 209, 220, 221, 224, 238, 254, 255, 269, 282, and CI Pigment Violet 19. Among these, CI Pigment Red 122, CI Pigment Red 150, and CI Pigment Red 282 are preferred because of their high transparency and coloring strength.

[0160] In addition to pigments, acid dyes and basic dyes can also be used, such as CI Acid Red 289, 52, and rhodamine dyes.

[0161] <Yellow colorant> The yellow colorant may be a yellow pigment or a yellow dye. Yellow pigments include, for example, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, and quinophthalone pigments described in Japanese Patent No. 4993026. Among these, CI Pigment Yellow 138, 139, 150, and 185 are preferred from the viewpoints of heat resistance, light fastness, and brightness.

[0162] Examples of yellow dyes include azo dyes, azo metal complex dyes, anthraquinone dyes, indigo dyes, thioindigo dyes, phthalocyanine dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, thiazine dyes, cationic dyes, quinophthalone dyes, cyanine dyes, nitro dyes, quinoline dyes, naphthoquinone dyes, and oxazine dyes.

[0163] <Color filter manufacturing method> The color filter of the present invention can be produced by a printing method or a photolithography method.

[0164] Formation of filter segments by printing methods allows for patterning by simply repeating the printing and drying of a coloring composition prepared as a printing ink, making it a low-cost and highly mass-producible method for producing color filters. Furthermore, advances in printing technology have made it possible to print fine patterns with high dimensional accuracy and smoothness. For printing, it is preferable to use a composition that prevents the ink from drying or solidifying on the printing plate or blanket. Controlling the fluidity of the ink on the printing press is also important, and the ink viscosity can be adjusted using dispersants and extender pigments.

[0165] When forming filter segments by photolithography, the colored composition prepared as the solvent-developable or alkali-developable colored resist material is applied to a transparent substrate by a coating method such as spray coating, spin coating, slit coating, or roll coating to a dry film thickness of 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern, which is placed in contact with or out of contact with the film. The film is then immersed in a solvent or alkali developer or sprayed with a developer to remove the uncured portions and form the desired pattern. The same process is then repeated for other colors to produce a color filter. Furthermore, heating can be applied as needed to promote polymerization of the colored resist material. Photolithography allows for the production of color filters with higher precision than the printing method.

[0166] During development, an aqueous solution of sodium carbonate, sodium hydroxide, or the like is used as an alkaline developer, and organic alkalis such as dimethylbenzylamine and triethanolamine can also be used. A defoaming agent or surfactant can also be added to the developer. To increase the sensitivity to ultraviolet light exposure, after coating and drying the colored resist material, a water-soluble or alkali-water-soluble resin, such as polyvinyl alcohol or a water-soluble acrylic resin, can be coated and dried to form a film that prevents polymerization inhibition by oxygen, followed by ultraviolet light exposure.

[0167] The color filter of the present invention can be produced by the above-mentioned method, as well as by an electrodeposition method, a transfer method, an inkjet method, or the like, and the coloring composition of the present invention can be used for any of these methods. The electrodeposition method is a method of producing a color filter by using a transparent conductive film formed on a substrate and electrodepositing each color filter segment onto the transparent conductive film by electrophoresis of colloidal particles. The transfer method is a method in which filter segments are formed in advance on the surface of a peelable transfer base sheet, and then the filter segments are transferred to a desired substrate.

[0168] A black matrix can be formed on a transparent or reflective substrate before forming each color filter segment. Examples of black matrices that can be used include, but are not limited to, multilayer films of chromium or chromium / chromium oxide, inorganic films such as titanium nitride, and resin films with a dispersed light-blocking agent. Thin-film transistors (TFTs) can also be formed on the transparent or reflective substrate beforehand, followed by the formation of each color filter segment. An overcoat film, a transparent conductive film, or the like can be formed on the color filter of the present invention as needed.

[0169] The color filter is bonded to the opposing substrate using a sealant, liquid crystal is injected through an injection port provided in the seal, the injection port is then sealed, and a polarizing film or a retardation film is bonded to the outside of the substrate as needed, thereby manufacturing a liquid crystal display panel.

[0170] Such LCD panels can be used in LCD display modes that use color filters, such as twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertically aligned (VA), and optically convex bend (OCB).

[0171] The display device of the present invention includes a color filter. The display device is preferably, for example, an image display device.

[0172] <Image display device> An image display device equipped with the color filter of the present invention will be described. The image display device of the present invention comprises the color filter of the present invention and a light source. Examples of light sources include cold cathode fluorescent lamps (CCFLs) and white LEDs. In the present invention, it is preferable to use a white LED because it broadens the red reproduction range. Figure 1 is a schematic cross-sectional view of an image display device 10 equipped with the color filter of the present invention. The device 10 shown in Figure 1 comprises a pair of transparent substrates 11 and 21 arranged at a distance from each other, with a liquid crystal LC sealed between them.

[0173] The liquid crystal LC is aligned according to a driving mode such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane Switching), VA (Vertical Alignment), or OCB (Optically Compensated Birefringence). A TFT (Thin Film Transistor) array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of, for example, ITO is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13. A polarizer 15 is formed on the outer surface of the transparent substrate 11.

[0174] On the other hand, a color filter 22 of the present invention is formed on the inner surface of the second transparent substrate 21. Red, green, and blue filter segments that make up the color filter 22 are separated by a black matrix (not shown).

[0175] A transparent protective film (not shown) is formed as needed to cover the color filter 22, and a transparent electrode layer 23 made of, for example, ITO is formed on top of that, and an alignment layer 24 is provided to cover the transparent electrode layer 23.

[0176] A polarizing plate 25 is formed on the outer surface of the transparent substrate 21. Below the polarizing plate 25, a backlight unit 30 is provided.

[0177] The white LED light source includes a blue LED with a fluorescent filter formed on the surface, and a blue LED with a fluorescent material contained in the resin package, and has a wavelength (λ3) in the range of 430 nm to 485 nm at which the emission intensity becomes maximum, a wavelength (λ4) in the range of 530 nm to 580 nm at which the emission intensity becomes maximum, and a wavelength (λ5) in the range of 600 nm to 650 nm at which the emission intensity becomes maximum, and the ratio (I4 / I3) of the emission intensity I3 at wavelength λ3 to the emission intensity I4 at wavelength λ4 is 0.2 or more and 0.4 or less. Therefore, a white LED light source (LED1) having spectral characteristics in which the ratio (I5 / I3) of the emission intensity I3 at wavelength λ3 to the emission intensity I5 at wavelength λ5 is 0.1 or more and 1.3 or less, or a white LED light source (LED2) having a wavelength (λ1) at which the emission intensity is maximum in the range of 430 nm to 485 nm, a peak wavelength (λ2) of the second emission intensity in the range of 530 nm to 580 nm, and a ratio (I2 / I1) of the emission intensity I1 at wavelength λ1 to the emission intensity I2 at wavelength λ2 is 0.2 or more and 0.7 or less is preferred.

[0178] Specific examples of the LED 1 include NSSW306D-HG-V1 (manufactured by Nichia Corporation) and NSSW304D-HG-V1 (manufactured by Nichia Corporation).

[0179] Specific examples of the LED 2 include NSSW440 (manufactured by Nichia Chemical Industries, Ltd.) and NSSW304D (manufactured by Nichia Chemical Industries, Ltd.).

[0180] <Color filter segment for solid-state imaging devices> In the present invention, the color filter segments for the solid-state imaging device can be formed using known methods, but since the filter segments for the imaging device are very fine, ranging from submicrons to several tens of microns, it is preferable to use optical lithography. An embodiment of the present invention is a method for producing a color filter having a color filter segment obtained by curing the color composition described above. The color filter segment includes a color filter segment obtained by curing the color composition according to the embodiment of the present invention described above. The color filter according to this embodiment includes the cyan, magenta, and yellow filter segments described above. The color filter segments other than those according to the present invention may be formed using a known coloring composition containing a color pigment, a color dye, or both a color pigment and a color dye. While the method for forming the color filter segments is not particularly limited, a photosensitive coloring composition that is a negative resist is typically used.

[0181] When forming color filter segments on corresponding photoelectric conversion elements, a negative color resist layer is formed by a negative green film formed from a negative photosensitive green composition. In this case, the thickness of the negative color resist layer is set in the range of 0.1 μm to 3.0 μm. The surface of the negative color resist layer formed by the negative color film is exposed to a pattern using a photomask in a number of areas corresponding to a number of photoelectric conversion elements to be formed. The photomask has dimensions 4 to 5 times larger than the dimensions of the pattern to be actually formed. During the exposure, the pattern is exposed by reducing the size to 1 / 4 to 1 / 5. This photomask is a 4 to 5 times reticle, and has a pattern four to five times larger than the size of the pattern exposed on the surface of the negative color resist layer. Using a stepper exposure device that does not require a photomask, the photomask pattern is reduced to 1 / 4 to 1 / 5 of its original size and exposed onto the surface of the negative color resist layer. Following the exposure step, an alkaline development treatment (development step) is carried out to dissolve the uncured portions after exposure into a developer, leaving the photocured portions. This development step allows the formation of a patterned film consisting of color filter segments.

[0182] The development method may be any of a dip method, shower method, spray method, paddle method, etc., and these may be combined with a swing method, spin method, ultrasonic method, etc. Uneven development can be prevented by wetting the surface to be developed with water or other liquid before contact with the developer. An organic alkaline developer is preferred as the developer, as it does not damage the underlying circuitry. The development temperature is usually 20°C to 30°C, and the development time is 10 to 90 seconds. Examples of alkaline agents contained in the developer include organic alkaline compounds such as aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene, and inorganic compounds such as sodium hydroxide, potassium hydroxide, sodium bicarbonate, and potassium bicarbonate. The developer is preferably an alkaline aqueous solution prepared by diluting the alkaline agent with pure water to a concentration of 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass. When using a developer made from such an alkaline aqueous solution, after development, the substrate is generally washed (rinsed) with pure water to remove excess developer, and then dried. Finally, the filter segments thus formed are subjected to a hardening treatment.

[0183] In the manufacturing method of the present invention, after the above-mentioned colored layer forming step, exposure step, and development step are performed, a curing step of curing the formed colored pattern by post-heating (post-baking) or post-exposure may be included as necessary. Post-baking is a heat treatment after development to complete the curing, and is usually a thermal curing treatment at 100°C to 270°C. In this case, it can be performed using g-rays, h-rays, i-rays, excimer lasers such as KrF and ArF, electron beams, X-rays, etc., but it is preferable to perform it at a low temperature of about 20 to 50°C using an existing high-pressure mercury lamp. Preferably, the irradiation time is 10 to 180 seconds, more preferably 30 to 60 seconds. When post-exposure and post-heating are used in combination, it is preferable to carry out post-exposure first. The colored layer forming step, the exposure step, and the development step (and, if necessary, the curing step) described above By repeating this process for the desired number of hues, color filter segments of the desired hues are produced.

[0184] <Solid-state imaging element> The solid-state imaging device of the present invention includes color filter segments. The solid-state imaging device may have, for example, the following configuration. A solid-state image sensor (CCD sensor, CMOS sensor, or organic CMOS sensor) is mounted on the substrate. The device has a plurality of photodiodes constituting a light receiving area (such as a sensor) and transfer electrodes made of polysilicon or the like. A light-shielding film made of tungsten or the like is provided on the photodiodes and the transfer electrodes, with only the light-receiving portions of the photodiodes being opened. A device protection film made of silicon nitride or the like is provided on the light-shielding film so as to cover the entire light-shielding film and the light-receiving portions of the photodiodes. and a color filter segment for a solid-state imaging device of the present invention is disposed on the device protective film. Furthermore, the device may have a configuration in which a focusing means (e.g., a microlens, etc.; the same applies below) is provided on the device protection layer and below the color filter segments (on the side closer to the substrate), or a configuration in which a focusing means is provided on the color filter segments. The organic CMOS sensor is composed of a thin-film panchromatic organic photoelectric conversion film as a photoelectric conversion layer and a CMOS signal readout substrate, and has a hybrid two-layer structure in which the organic material captures light and converts it into an electrical signal, while the inorganic material takes on the role of extracting the electrical signal to the outside, and in principle can achieve a 100% aperture ratio for incident light. The photoelectric conversion film is a structure-free continuous film that can be laid on the CMOS signal readout substrate, so it does not require expensive microfabrication processes and is suitable for miniaturizing filter segments. The arrangement of the color filter segments is not particularly limited, and any known method can be used. [Example]

[0185] The present invention will be described below based on examples. However, the present invention is not limited to these examples. Note that "parts" means "parts by mass" and "%" means "% by mass." Furthermore, "PGMAc" is propylene glycol monomethyl ether acetate. It should be noted that Example 78 is a reference example.

[0186] The methods for measuring the weight average molecular weight (Mw) of the resin, the average molecular weight of the basic resin-type dispersant, and the amine value of the basic resin-type dispersant, and the methods for calculating the number of halogen substitutions in the pigment and the halogen distribution width in the pigment are as follows.

[0187] (Weight average molecular weight of resin (Mw)) The weight-average molecular weight (Mw) of the resin was measured using a TSKgel column (manufactured by Tosoh Corporation) with a GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector, and was measured using THF as the developing solvent, and was expressed as polystyrene equivalent weight-average molecular weight (Mw).

[0188] (Average molecular weight of resin-type dispersant) The number average molecular weight (Mn) and weight average molecular weight (Mw) of the resin-type dispersant were measured using an HLC-8320GPC (manufactured by Tosoh Corporation) and a SUPER-AW3000 column. The eluent was a N,N-dimethylamine solution of 30 mM triethylamine and 10 mM LiBr. The polystyrene equivalent number average molecular weight (Mn) and weight average molecular weight (Mw) were measured using a dichloromethane solution.

[0189] (Acid value of acidic resin-type dispersant) The acid value of the acidic resin dispersant was measured by adding 80 ml of acetone and 10 ml of water to 0.5 to 1 g of resin solution, stirring to dissolve uniformly, and titrating the resin solution with a 0.1 mol / L KOH aqueous solution using an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) to measure the acid value (mg KOH / g) of the resin solution. The acid value per unit of nonvolatile content of the resin was then calculated from the acid value of the resin solution and the concentration of nonvolatile content of the resin solution.

[0190] (Amine value of basic resin type dispersant) The amine value of the basic resin-type dispersant is the total amine value (mgKOH / g) measured in accordance with the method of ASTM D 2074 and converted into nonvolatile content.

[0191] (Number of halogen substitutions in pigment) The number of halogen substitutions in the pigment was obtained by burning the pigment by an oxygen combustion flask method, absorbing the combustion product in water, analyzing the liquid by ion chromatography (ICS-2000 ion chromatography, manufactured by DIONEX Corporation), quantifying the amount of halogen, and converting it into the number of halogen substitutions.

[0192] (Halogen distribution width in pigment) The halogen distribution width in pigments was measured using a time-of-flight mass spectrometer (autofleXIII (TOF- The halogen content was determined using a Bruker Daltonics MS. The pigment powder was analyzed by mass spectrometry to obtain a mass spectrum. The signal intensity of the molecular ion peak corresponding to each component (each peak value) and the integrated value of each peak value (total peak value) were calculated, and the halogen content was determined from the ratio of each peak value to the total peak value. The halogen distribution width was determined by counting the number of peaks whose ratio of each peak value to the total peak value was 1% or more.

[0193] (Volume average primary particle size of pigment) The volume average primary particle size (MV) of a pigment was determined by measuring the minor and major axis diameters of 100 primary particles of the pigment using transmission electron micrographs (TEM), taking the average of the minor and major axis diameters as the particle size (d) of the pigment particle, and then determining the volume (V) of each particle by assuming that each pigment particle is a sphere with the determined particle size. This procedure was performed for 100 pigment particles, and the volume average primary particle size (MV) was calculated from the following formula. MV=Σ(V d) / Σ(V)

[0194] <Method of manufacturing finely processed pigment> (Fine Pigment (P-1)) A three-neck flask was charged with 500 parts of 98% sulfuric acid, 50 parts of the phthalocyanine pigment (P-11) represented by formula (50), and 129.3 parts of 1,2-dibromo-5,5-dimethylhydantoin (DBDMH), and the mixture was stirred and reacted at 20°C for 6 hours. The reaction mixture was then poured into 5,000 parts of ice water at 3°C, and the precipitated solid was collected by filtration and washed with water. 500 parts of a 2.5% aqueous sodium hydroxide solution and the collected residue were added to a beaker, and the mixture was stirred at 80°C for 1 hour. The mixture was then filtered, washed with water, and dried to obtain a pigment with an average of 10.1 bromine atoms substituted on the phthalocyanine ring. Next, 500 parts of N-methylpyrrolidone, 50 parts of the resulting pigment having an average of 10.1 bromine atoms substituted on the phthalocyanine ring, and 13.9 parts of diphenyl phosphate were added to a three-neck flask, heated to 90°C, and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain phthalocyanine pigment (P-1) represented by the following formula (51). The halogen distribution width of the pigment was 9, and the volume average primary particle diameter was 26 nm.

[0195] [ka]

[0196] (Fine Pigment (P-2)) A three-neck flask was charged with 500 parts of 98% sulfuric acid, 50 parts of the phthalocyanine pigment represented by formula (50), and 104.4 parts of 1,2-dibromo-5,5-dimethylhydantoin (DBDMH), followed by stirring and reaction at 20°C for 4 hours. The reaction mixture was then poured into 5,000 parts of ice water at 3°C, and the precipitated solid was collected by filtration and washed with water. 500 parts of 2.5% aqueous sodium hydroxide solution and the collected residue were added to a beaker and stirred at 80°C for 1 hour. The mixture was then filtered, washed with water, and dried to obtain a pigment with an average of 8.0 bromine atoms substituted on the phthalocyanine ring. Next, a three-neck flask was charged with 500 parts of N-methylpyrrolidone, 50 parts of the resulting pigment with an average of 8.0 bromine atoms substituted on the phthalocyanine ring, and 15.8 parts of diphenyl phosphate. The mixture was heated to 90°C and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain the phthalocyanine pigment (P-2) represented by the following formula (52). The halogen distribution width was 9. The volume average primary particle diameter of the pigment was 33 nm.

[0197] Formula (52) [ka]

[0198] (Fine Pigment (P-3)) 203 parts of aluminum bromide, 47 parts of sodium bromide, and 5 parts of ferric bromide were melted by heating, and 50 parts of the phthalocyanine pigment represented by formula (50) were added at 140°C. The temperature was raised to 160°C, and 215.4 parts of bromine were blown in while the mixture was reacted at 160°C for 7 hours. The reaction mixture was poured into 2,500 parts of ice water at 3°C, and the precipitated solid was collected by filtration and washed with water. The residue was washed with 1% aqueous hydrochloric acid, warm water, 1% aqueous sodium hydroxide, and warm water, and then dried to obtain 98 parts of brominated aluminum phthalocyanine. The resulting crude brominated aluminum phthalocyanine was dissolved in 980 parts of concentrated sulfuric acid and stirred at 50°C for 3 hours. The sulfuric acid solution was then poured into 9,800 parts of ice water at 3°C, and the precipitated solid was collected by filtration, washed with water, and dried. Next, 500 parts of 2.5% aqueous sodium hydroxide and the collected residue were added to a beaker and stirred at 80°C for 1 hour. Thereafter, the mixture was filtered, washed with water, and dried to obtain a pigment in which an average of 15.0 bromine atoms were substituted on the phthalocyanine ring. Next, 500 parts of N-methylpyrrolidone, 50 parts of the resulting pigment having an average of 15.0 bromine atoms substituted on the phthalocyanine ring, and 10.8 parts of diphenyl phosphate were added to a three-neck flask, heated to 90°C, and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain phthalocyanine pigment (P-3) represented by the following formula (53). The halogen distribution width was 4. The volume average primary particle diameter of the pigment was 40 nm.

[0199] Formula (53) [ka]

[0200] (Fine Pigment (P-4)) 500 parts of N-methylpyrrolidone, 50 parts of the pigment prepared in (P-2) in which an average of 8.0 bromine atoms were substituted on the phthalocyanine ring, and 13.8 parts of diphenylphosphinic acid were added to a three-neck flask, heated to 90°C, and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain the phthalocyanine pigment (P-4) represented by the following formula (54). The halogen distribution width was 9. The volume average primary particle diameter of the pigment was 45 nm.

[0201] Formula (54) [ka]

[0202] (Fine Pigment (P-5)) In a reaction vessel, 225 parts of phthalodinitrile and 78 parts of aluminum chloride anhydride were added to 1,250 parts of n-amyl alcohol and stirred. 266 parts of DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene) were added, and the mixture was heated and refluxed at 136°C for 5 hours. The reaction solution was cooled to 30°C while stirring, and poured into a mixed solvent of 5,000 parts of methanol and 10,000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent of 2,000 parts of methanol and 4,000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine. Furthermore, in the reaction vessel, chloroaluminum 100 parts of phthalocyanine were slowly added to 1,200 parts of concentrated sulfuric acid at room temperature. The mixture was stirred at 40°C for 3 hours, and the sulfuric acid solution was then poured into 24,000 parts of cold water at 3°C. The blue precipitate was filtered, washed with water, and dried to obtain 102 parts of aluminum phthalocyanine pigment (P-10) represented by the following formula (55).

[0203] Formula (55) [ka]

[0204] Next, 250 parts of aluminum chloride, 60 parts of sodium chloride, and 2.25 parts of iodine were added to a three-neck flask and stirred at 150°C for 30 minutes. 50 parts of the aluminum phthalocyanine pigment represented by formula (55) was added and dissolved by stirring at 155°C for 30 minutes. 58.5 parts of trichloroisocyanuric acid was then added and stirred at 190°C for 5 hours. The reaction mixture was then poured into 5,000 parts of ice water at 3°C, and the precipitated solid was collected by filtration and washed with water. 500 parts of 2.5% aqueous sodium hydroxide solution and the collected residue were added to a beaker and stirred at 80°C for 1 hour. The mixture was then filtered, washed with water, and dried to obtain a pigment with an average of 8.1 chlorine atoms substituted on the phthalocyanine ring. Next, 500 parts of N-methylpyrrolidone, 50 parts of the resulting pigment having an average of 8.1 bromine atoms substituted on the phthalocyanine ring, and 22.6 parts of diphenyl phosphate were added to a three-neck flask, heated to 90°C, and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain phthalocyanine pigment (P-5) represented by the following formula (56). The halogen distribution width was 8. The volume average primary particle diameter of the pigment was 36 nm.

[0205] Formula (56) [ka]

[0206] (Fine Pigment (P-6)) In a reaction vessel, 100 parts of the aluminum phthalocyanine pigment represented by formula (55) and 49.5 parts of diphenyl phosphate were added to 1,000 parts of methanol, heated to 40°C, and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain 114 parts of the aluminum phthalocyanine pigment represented by the following formula (57).

[0207] Formula (57) [ka]

[0208] Next, 100 parts of the above, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 6 hours at 70°C. This kneaded mixture was added to 3000 parts of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeated filtration and washing with water to remove the sodium chloride and diethylene glycol, the slurry was dried overnight at 80°C to obtain a micronized pigment (P-6). The volume average primary particle diameter of the pigment was 37 nm.

[0209] (Fine Pigment (P-7)) 100 parts of phthalocyanine green pigment CI Pigment Green 58 (DIC Corporation "FASTGENGREEN A110"), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho) and kneaded for 6 hours at 70°C. This kneaded mixture was added to 3000 parts of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeated filtration and water washing to remove the sodium chloride and diethylene glycol, the slurry was dried overnight at 80°C to obtain 97 parts of micronized pigment (P-7). The volume average primary particle diameter of the pigment was 36 nm.

[0210] (Fine Pigment (P-8)) The phthalocyanine pigment represented by formula (58) was obtained in the same manner as in the synthesis of the phthalocyanine pigment represented by formula (57), except that 43.2 parts of diphenylphosphinic acid was used instead of diphenyl phosphate. Subsequently, blue colorant (P-8) was produced in the same manner as blue colorant (P-6). The volume average primary particle diameter of the pigment was 29 nm.

[0211] Formula (58) [ka]

[0212] (Fine Pigment (P-9)) The phthalocyanine pigment represented by formula (59) was obtained in the same manner as in the synthesis of the phthalocyanine pigment represented by formula (57), except that 250 parts of 4-methylphthalodinitrile was used instead of phthalodinitrile and 28.0 parts of phenylphosphinic acid was used instead of diphenyl phosphate. Subsequently, a blue colorant (P-9) was produced in the same manner as the blue colorant (P-1). The volume average primary particle diameter of the pigment was 33 nm.

[0213] Formula (59) [ka]

[0214] (Fine Pigment (P-12)) The same procedure was used to prepare the finely divided pigment (P-6), except that the aluminum phthalocyanine pigment represented by formula (57) was replaced with LIONOL BLUE 7255-PS (CI Pigment Blue 15:2) manufactured by Toyocolor Co., Ltd., to obtain the finely divided pigment (P-12). The volume average primary particle diameter of the pigment was 30 nm.

[0215] (Fine Pigment (P-13)) The same procedure was used to prepare the finely divided pigment (P-6), except that the aluminum phthalocyanine pigment represented by formula (57) was replaced with LIONOL BLUE FG-7400-G (CI Pigment Blue 15:4) manufactured by Toyocolor Co., Ltd., to obtain the finely divided pigment (P-13). The volume average primary particle diameter of the pigment was 25 nm.

[0216] (Fine Pigment (P-14)) The same procedure was used to prepare the finely divided pigment (P-6), except that LIONOL BLUE ES (CI Pigment Blue 15:6) manufactured by Toyocolor Co., Ltd. was used instead of the aluminum phthalocyanine pigment represented by formula (57), to obtain the finely divided pigment (P-14). The volume average primary particle diameter of the pigment was 36 nm.

[0217] (Fine Pigment (P-15)) The same procedure was used to prepare the finely divided pigment (P-6), except that the aluminum phthalocyanine pigment represented by formula (57) was replaced with LIONOL BLUE FG-7330 (CI Pigment Blue 15:3) manufactured by Toyocolor Co., Ltd., to obtain the finely divided pigment (P-15). The volume average primary particle diameter of the pigment was 40 nm.

[0218] <Blue phthalocyanine compounds B-1 to B- 49 > Among the blue phthalocyanine compounds represented by general formula (2) used below, those represented by general formula (3) and B-1 to B- including general formula (4) 49 Shows. General formula (2) [ka]

[0219] [Table 3]

[0220] (B-50) Formula (63) [ka]

[0221] <Production of Acidic Resin-Type Dispersant Having Carboxyl Groups> (Production Example 1) (Acidic Resin-Type Dispersant C1 Having Carboxyl Groups) A reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer was charged with 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 parts of monobutyltin(IV) oxide as a catalyst. The atmosphere was then purged with nitrogen gas, and the mixture was heated and stirred at 120°C for 4 hours. After measuring the nonvolatile content to confirm that 98% had reacted, 73.3 parts of pyromellitic anhydride was added and the reaction was continued at 120°C for 2 hours. The reaction was terminated after measuring the acid value to confirm that at least 98% of the acid anhydride had been half-esterified. The resulting dispersant was a white solid at room temperature and had an acid value of 49 mgKOH / g. The nonvolatile content was adjusted with PGMAc to obtain an acidic resin-type dispersant (C1) solution with a nonvolatile content of 50%.

[0222] (Production Example 2) (Acidic Resin-Type Dispersant C2 Having Carboxyl Groups) A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 10 parts of methacrylic acid, 20 parts of methyl methacrylate, 90 parts of 2-methoxyethyl methacrylate, 40 parts of t-butyl methacrylate, 20 parts of n-butyl acrylate, 20 parts of t-butyl acrylate, and 50 parts of PGMAc, and the atmosphere was replaced with nitrogen gas. The reaction vessel was heated to 50°C with stirring, and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90°C, and a solution of 0.1 parts of 2,2'-azobisisobutyronitrile in 90 parts of PGMAc was added, and the reaction was continued for 7 hours. Measurement of the nonvolatile content confirmed that 95% had reacted. 35 parts of trimellitic anhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out for 7 hours at 100 ° C. After confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value, the reaction was terminated, and PGMAc was added to dilute the mixture so that the nonvolatile content was 50% by measuring the nonvolatile content, yielding an acidic resin-type dispersant (C2) with an acid value of 40 mg KOH / g and a weight-average molecular weight of 9000.

[0223] (Production Examples 3 to 7) (Carboxyl Group-Containing Resin-Type Dispersants C3 to C6) Synthesis was carried out in the same manner as in Production Example 2, except that the raw materials and amounts charged were used as shown in Table 2, to obtain resin-type dispersants (C3 to C6).

[0224] [Table 4]

[0225] <Method for producing basic resin-type dispersant> (Basic resin-type dispersant solution D1) B-block synthesis: A reactor equipped with a gas inlet tube, condenser, stirring blade, and thermometer was charged with 4.0 parts of AIBN (2,2'-azobisisobutyronitrile) and 133 parts of PGMAc, followed by 7.8 parts of ethyl acrylate (EA), 39.0 parts of methyl methacrylate (MMA), 31.2 parts of n-butyl methacrylate (BMA), and 5.0 parts of 2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO). The atmosphere was then purged with nitrogen for 30 minutes. The temperature of the reaction solution was then raised to 80°C with gentle stirring, and this temperature was maintained for 12 hours to allow living radical polymerization. A-block synthesis: Next, 22.0 parts of N,N-dimethylaminoethyl methacrylate (DM) was dissolved in this reaction solution, and the mixture was purged with nitrogen for 30 minutes. Living radical polymerization was then carried out at 80°C for 12 hours. After cooling to room temperature, approximately 2 g of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content. PGMAc was added to the previously synthesized dispersant to achieve a nonvolatile content of 50% by mass, preparing basic resin-type dispersant solution D1. GPC analysis revealed that the resin's Mw was 8100. The amine value per nonvolatile content was 79 mgKOH / g.

[0226] (Basic resin-type dispersant solutions D2 to D19) Basic resin-type dispersant solutions D2 to D19 were obtained in the same manner as basic resin-type dispersant solution 1, except that the compositions were changed as shown in Tables 5-1 and 5-2.

[0227] [Table 5-1]

[0228] [Table 5-2]

[0229] The abbreviations in Table 1 are as follows: DMAPMA: dimethylaminopropyl methacrylamide DMAPAA: dimethylaminopropylacrylamide DM-MC: N,N-dimethylaminoethyl methacrylate-methyl chloride salt DMAPAA-MC: dimethylaminopropylacrylamide-methyl chloride salt DMAPMA-MC: dimethylaminopropyl methacrylamide-methyl chloride salt DMAPAA-BC: dimethylaminopropylacrylamide-benzyl chloride salt DMAPAA-S: dimethylaminopropylacrylamide-propyl sulfonate CL5MA: 5 mol caprolactone adduct of 2-hydroxyethyl methacrylate (Daicel Chemical Industries, Ltd., Plaxel FM5) MMA: Methyl methacrylate tBA: tert-butyl acrylate AAm: Acrylamide acrylate

[0230] <Method for producing binder resin> (Preparation of binder resin solution 1) (Step 1: Polymerization of the resin main chain) 100 parts of PGMAc was placed in a reaction vessel equipped with a separable four-neck flask, a thermometer, a condenser, a nitrogen gas inlet tube, and a stirrer, and the vessel was heated to 120°C while nitrogen gas was injected into the vessel. At the same temperature, a mixture of 14 parts of styrene, 29 parts of dicyclopentanyl methacrylate, 57 parts of glycidyl methacrylate, and 1.0 part of azobisisobutyronitrile as a catalyst required for the reaction of the precursor at this stage was added dropwise from the dropping tube over 2.5 hours to carry out a polymerization reaction.

[0231] (Step 2: Reaction to epoxy groups) Next, the atmosphere in the flask was purged with air, and 29 parts of acrylic acid, 0.3 parts of trisdimethylaminomethylphenol as a catalyst required for the precursor reaction at this stage, and 0.3 parts of hydroquinone were added, and the reaction was carried out at 120°C for 5 hours, yielding a resin solution with a weight-average molecular weight (Mw) of approximately 10,500. The acrylic acid added forms an ester bond with the epoxy group terminal of the glycidyl methacrylate structural unit, so no carboxyl groups are generated in the resin structure.

[0232] (Step 3: Reaction with hydroxyl groups) Further, 46 parts of tetrahydrophthalic anhydride and 0.5 parts of triethylamine, which is a catalyst required for the reaction of the precursor at this stage, were added and reacted for 4 hours at 120°C. The carboxylic anhydride moiety of the added tetrahydrophthalic anhydride cleaved to generate two carboxyl groups, one of which formed an ester bond with a hydroxyl group in the resin structure, and the other formed a terminal carboxyl group.

[0233] (Step 4: Adjustment of non-volatile content) PGMAc was added so that the nonvolatile content became 50% by mass, to obtain binder resin solution 1. The weight average molecular weight (Mw) was 11,500, and the acid value was 103 mgKOH / g.

[0234] (Preparation of binder resin solution 2) A separable four-necked flask was equipped with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube, and a stirrer. 480.0 parts of cyclohexanone was charged into the reaction vessel, which was then heated to 80 ° C. and purged with nitrogen. From the dropping tube, 19.0 parts of meparacumylphenol ethylene oxide-modified acrylate (Toagosei Co., Ltd., Aronix M110), 28.0 parts of methacrylic acid, 22.4 parts of methyl methacrylate, 11.5 parts of glycerol monomethacrylate, 29.0 parts of benzyl methacrylate, 16.0 parts of n-butyl methacrylate, and 4.0 parts of 2,2'-azobisisobutyronitrile were added dropwise over 2 hours. After the dropwise addition, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, the nitrogen gas was stopped and dry air was injected into the entire copolymer solution for 1 hour while stirring. After cooling to room temperature, a mixture of 12.5 parts of 2-methacryloyloxyethyl isocyanate (Karens MOI, manufactured by Showa Denko K.K.), 0.1 parts of dibutyltin laurate, and 26.0 parts of cyclohexanone was added dropwise at 70 ° C over 3 hours. After the addition was completed, the reaction was continued for another hour to obtain an acrylic resin solution. After cooling to room temperature, approximately 2 parts of the resin solution was sampled and dried by heating at 180 ° C for 20 minutes to measure the nonvolatile content. Cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 50% by mass, and binder resin solution 2 with an acid value of 131 mg KOH / g was obtained.

[0235] (Preparation of binder resin solution 3) A separable four-necked flask was fitted with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube, and a stirrer. 700.0 parts of cyclohexanone was charged into the reaction vessel, which was then heated to 80°C and purged with nitrogen. Then, a mixture of 50.0 parts of paracumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 50.0 parts of methacrylic acid, 40 parts of methyl methacrylate, 55.2 parts of 2-hydroxyethyl methacrylate, and 4.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition was completed, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, the nitrogen gas supply was stopped and dry air was injected into the entire amount of the obtained copolymer solution for 1 hour while stirring, and then the solution was cooled to room temperature, and then a mixture of 59.9 parts of 2-methacryloyloxyethyl isocyanate (Karends MOI manufactured by Showa Denko K.K.), 0.4 parts of dibutyltin laurate, and 100.0 parts of cyclohexanone was added dropwise at 70°C over 3 hours. After the dropwise addition was completed, the reaction was continued for another 1 hour to obtain an acrylic resin solution. After cooling to room temperature, approximately 2 parts of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the non-volatile content. Cyclohexanone was added to the resin solution synthesized previously so that the non-volatile content became 50% by mass, and binder resin solution 3 with an acid value of 104 mgKOH / g was obtained.

[0236] (Preparation of binder resin solution 4) A separable four-neck flask was fitted with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube, and a stirrer. A reaction vessel was charged with 207 parts of cyclohexanone, heated to 80°C, and the atmosphere inside the reaction vessel was replaced with nitrogen. Then, a mixture of 37.5 parts of methacrylic acid, 27.5 parts of methyl methacrylate, 5.0 parts of n-butyl methacrylate, 18.7 parts of 2-hydroxyethyl methacrylate, and 1.33 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours through the dropping tube. After the dropwise addition was completed, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, the nitrogen gas was stopped and dry air was injected into the entire amount of the obtained copolymer solution for 1 hour while stirring. After cooling to room temperature, a mixture of 16.3 parts of 2-methacryloyloxyethyl isocyanate (Karens MOI manufactured by Showa Denko K.K.), 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone was added dropwise at 70 °C over 3 hours. After the dropwise addition was completed, the reaction was continued for another 1 hour to obtain an acrylic resin solution. After cooling to room temperature, approximately 2 parts of the resin solution was sampled and dried by heating at 180 °C for 20 minutes to measure the nonvolatile content. Cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 50% by mass, and binder resin solution 4 with an acid value of 233 mg KOH / g was obtained.

[0237] (Preparation of binder resin solution 5) 145 g of PGMAc was placed in a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, and the mixture was stirred and heated to 120 ° C while purging with nitrogen. Next, 10.1 parts of azobisisobutyronitrile per 100 parts of the monomer mixture was added to a monomer mixture consisting of 20.0 parts (0.1 mol) of a monomethacrylate having a dicyclopentadiene skeleton (FA-512M manufactured by Hitachi Chemical Co., Ltd.), 108.0 parts (1.5 mol) of methacrylic acid, and 31.0 parts (0.2 mol) of benzyl methacrylate. This mixture was added dropwise from the dropping funnel to the flask over 2 hours, and then aged at 120 ° C for another 2 hours with continued stirring. Next, the flask was purged with air, and 122.3 parts of glycidyl methacrylate (0.9 mol, 60 mol% of methacrylic acid), 0.9 g of tris(dimethylaminomethyl)phenol, and 0.145 parts of hydroquinone were added to the aged solution. The reaction was continued at 120°C for 6 hours, and terminated when the nonvolatile acid value reached 1.0. PGMAc was added to adjust the nonvolatile content to 50% by mass, yielding binder resin solution 5. The weight-average molecular weight (Mw) was 18,100, and the acid value was 117 mgKOH / g.

[0238] (Preparation of binder resin solution 6) 333 g of PGMAc was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube, and the atmosphere in the flask was changed from air to nitrogen. After that, the temperature was raised to 100°C, and then 70.5 parts of benzyl methacrylate, 71.1 parts of glycidyl methacrylate, 1.0 parts of tricyclohexyl methylpropional, and 1.0 parts of methylpropional were added. A mixture of 22.0 parts of decane-based monomethacrylate (Hitachi Chemical Co., Ltd. FA-513M) and 164 parts of PGMAc, plus 3.6 parts of azobisisobutyronitrile, was added dropwise from the addition funnel to the flask over 2 hours and stirred at 100 ° C for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 43.0 parts of methacrylic acid [0.5 mol (100 mol% relative to the glycidyl groups of the glycidyl methacrylate used in this reaction)], 0.9 parts of tris(dimethylaminomethyl)phenol, and 0.145 parts of hydroquinone were added to the flask. The reaction was continued for 6 hours at 110 ° C, and the reaction was terminated when the nonvolatile acid value reached 1 mg KOH / g. Next, 60.9 parts of tetrahydrophthalic anhydride and 0.8 parts of triethylamine were added, and the mixture was allowed to react for 3.5 hours at 120 ° C to obtain a binder resin solution. Approximately 2 g of the binder resin solution was sampled and dried by heating at 180°C for 20 minutes, and the nonvolatile content was measured. PGMAc was added to adjust the nonvolatile content to 50 mass %, and binder resin solution 6 with an acid value of 80 mgKOH / g was obtained.

[0239] (Preparation of binder resin solution 7) A separable four-neck flask was fitted with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube, and a stirrer. 196 parts of cyclohexanone was charged into the reaction vessel, which was then heated to 80°C. The atmosphere inside the reaction vessel was replaced with nitrogen. From the dropping tube, a mixture of 20.0 parts of benzyl methacrylate, 17.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of paracumylphenol ethylene oxide-modified acrylate (Aronix M110: manufactured by Toagosei Co., Ltd.), and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition was completed, the reaction was continued for another 3 hours to obtain an acrylic resin solution. After cooling to room temperature, approximately 2 parts of the resin solution was sampled and dried by heating at 180°C for 20 minutes, and the non-volatile content was measured. PGMAc was added to adjust the non-volatile content to 50% by mass, thereby obtaining binder resin solution 7 with an acid value of 94 mgKOH / g.

[0240] (Preparation of binder resin solution 8) A separable four-necked flask was equipped with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube, and a stirrer. 560.0 parts of cyclohexanone was charged into the reaction vessel, which was then heated to 80 ° C. and purged with nitrogen. 26.0 parts of methacrylic acid, 23.0 parts of methyl methacrylate, 23.0 parts of n-butyl methacrylate, 23.0 parts of paracumylphenol ethylene oxide-modified acrylate (Aronix M110: manufactured by Toagosei Co., Ltd.), 31.9 parts of glycerol monomethacrylate, and 4.0 parts of 2,2'-azobisisobutyronitrile were added dropwise over 2 hours. After the dropwise addition, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, the nitrogen gas flow was stopped and dry air was injected into the entire copolymer solution for 1 hour while stirring. After cooling to room temperature, a mixture of 52.2 parts of 2-methacryloyloxyethyl isocyanate (Karens MOI: Showa Denko K.K.), 0.4 parts of dibutyltin laurate, and 100.0 parts of cyclohexanone was added dropwise at 70°C over 3 hours. After the addition was completed, the reaction was continued for another hour to obtain an acrylic resin solution. After cooling to room temperature, approximately 2 parts of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content. Cyclohexanone was added to adjust the nonvolatile content to 50% by mass, yielding a binder resin solution 8 with an acid value of 95 mgKOH / g.

[0241] (Preparation of binder resin solution 9) A separable four-neck flask equipped with a thermometer, condenser, nitrogen gas inlet, dropping tube, and stirrer was charged with 520.0 parts of cyclohexanone and heated to 80°C. The atmosphere inside the reaction vessel was replaced with nitrogen, and a mixture of 7.0 parts of methacrylic acid, 7.0 parts of methyl methacrylate, 54.3 parts of 2-hydroxyethyl methacrylate, 66.0 parts of glycerol monomethacrylate, and 4.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours via the dropping tube. After the addition was completed, the reaction was continued for another 3 hours to obtain a copolymer resin solution. The nitrogen gas flow was stopped, and the resulting copolymer solution was stirred with dry air for 1 hour. After cooling to room temperature, a mixture of 64.8 parts of 2-methacryloyloxyethyl isocyanate (Karenz MOI: Showa Denko K.K.), 0.4 parts of dibutyltin laurate, and 100.0 parts of cyclohexanone was added dropwise over 3 hours at 70°C. After the dropwise addition was completed, the reaction was continued for another hour to obtain an acrylic resin solution. After cooling to room temperature, the nonvolatile content was measured, and cyclohexanone was added to adjust the nonvolatile content to 50% by mass, thereby obtaining binder resin solution 9 with an acid value of 23 mgKOH / g.

[0242] <Production of Cyan Colored Composition> [Example 1] (Preparation of Cyan Colored Composition (D-1)) The following mixture was stirred until uniform, and then mixed in an Eiger mill (Eiger Japan "Mini Model M-250MKII") using zirconia beads with a diameter of 0.5 mm. After dispersing for 5 hours, the mixture was filtered through a 5.0 μm filter to obtain a cyan colored composition (D-1). The cyan colored composition was adjusted with PGMAc to have a nonvolatile content of 20% by mass. Finely divided pigment (P-1): 11.2 parts Blue phthalocyanine compound (B-14): 2.8 parts Basic resin type dispersant solution (D1): 12.0 parts PGMAc: 74.0 copies

[0243] [Examples 2 to 98, Comparative Examples 1 to 5] (Preparation of Cyan Colored Compositions (D-2 to D-103)) Pigment dispersions (D-2 to D103) were obtained in the same manner as in the cyan colored composition (D-1), except that the compositions were changed as shown in Tables 6-1, 6-2, and 6-3.

[0244] [Table 6-1]

[0245] [Table 6-2]

[0246] [Table 6-3]

[0247] <Evaluation of Cyan Coloring Composition> The obtained cyan colored compositions (D-1 to D-103) were evaluated for viscosity stability and light transmittance by the following methods, and the evaluation results are shown in Tables 7-1, 7-2, and 7-3.

[0248] (Evaluation of Viscosity Stability of Cyan Colored Composition) The initial viscosity of the obtained cyan colored compositions (D-1 to D-103) immediately after dispersion and the viscosity over time after accelerated aging at 40°C for 1 week were measured using an E-type viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.) at 25°C and a rotation speed of 50 rpm. From the initial viscosity and viscosity over time values, the rate of viscosity change over time was calculated using the following formula, and the viscosity stability was evaluated on a two-level scale. ◎, ◯, and △ are practically usable. × is not practical (the same applies below). [Change in viscosity over time] = |([Initial viscosity] - [Viscosity over time]) / [Initial viscosity]| x 100 ◎: Change rate less than 2% ○: Change rate is 2% or more but less than 5% △: Change rate is 5% or more but less than 10% ×: Change rate 10% or more

[0249] (Measurement of Average Light Transmittance of Cyan Colored Composition) The photosensitive coloring composition described in the Examples was applied to a glass substrate using a spin coater to form a coating substrate with a film thickness of 0.5 μm, and the substrate was then heated on a hot plate at 70°C for 60 seconds. The light transmittance of the prepared substrate at wavelengths of 300 to 900 nm was measured using a spectrophotometer (Hitachi High-Tech Science Corporation, "U-3310"), and the light transmittance in the wavelength range described below was evaluated. ◯ and △ are practical. Transmittance 1 (evaluation of light transmittance in the wavelength range of 400 to 460 nm) 〇: 85% or more △: 80% or more but less than 85% ×: Less than 80% Transmittance 2 (average light transmittance evaluation in the wavelength range of 480 to 540 nm) 〇: 90% or more △: 80% or more but less than 90% ×: Less than 80% Transmittance 3 (average light transmittance evaluation in the wavelength range 620-680 nm) ○: Less than 10% △: 10% or more but less than 20% ×: 20% or more

[0250] [Table 7-1]

[0251] [Table 7-2]

[0252] [Table 7-3]

[0253] <Production of Photosensitive Coloring Composition> [Example 99] (Preparation of Photosensitive Coloring Composition (R-1)) A mixture of the following composition was stirred and mixed uniformly, and then filtered through a 1 μm filter to prepare a photosensitive coloring composition (R-1). Cyan coloring composition (D-1): 42.9 parts Binder resin solution 1: 3.5 parts Polymerizable compound (Aronix M-402: manufactured by Toagosei Co., Ltd.): 2.1 parts Polymerizable compound (Aronix M-350: manufactured by Toagosei Co., Ltd.): 2.1 parts Photopolymerization initiator (chemical formula (6b-2)): 0.19 parts UV absorber (TINUVIN 326): 0.2 parts Polymerization inhibitor solution (methylhydroquinone): 1.3 parts (Solution adjusted with PGMAc to a non-volatile content of 1% by mass) PGMAc: 43.4 parts Leveling agent solution: 4.3 parts (Toray Dow Corning "FZ-2122" (Solution adjusted with PGMAc to a non-volatile content of 1% by mass)

[0254] [Examples 100 to 231, Comparative Examples 6 to 10] (Preparation of Photosensitive Coloring Compositions (R-2 to 138)) The materials and blending amounts used in the photosensitive coloring composition (R-1) were changed as shown in Table 8-1, 8-2, 8-3, except that the photosensitive coloring composition (R-1) was carried out in the same manner as the photosensitive coloring composition (R-1), and photosensitive coloring compositions (R-2 to R-138) were obtained, respectively. Table 8-1, 8-2, 8-3, 8-4 of the ultraviolet absorber, polymerization inhibitor solution, and leveling agent solution blending amounts are the same as in Example 78.

[0255] [Table 8-1]

[0256] [Table 8-2]

[0257] [Table 8-3]

[0258] [Table 8-4]

[0259] The raw materials listed in Tables 8-1 to 8-4 are as follows. <Polymerizable compound> Urethane acrylate: Dipentaerythritol pentaacrylate hexamethylene diisocyanate (reaction product of dipentaerythritol pentaacrylate and hexamethylene diisocyanate) Aronix M-402 (manufactured by Toagosei Co., Ltd.: dipentaerythritol penta- and hexaacrylate) Aronix M-350 (manufactured by Toagosei Co., Ltd.: Trimethylolpropane EO-modified triacrylate) Aronix M-520 (manufactured by Toagosei: polybasic acid-modified special multifunctional acrylate with 3 or more functional groups) KAYARAD DPEA-12 (manufactured by Nippon Kayaku: acrylate monomer with five or more functional groups) KAYARAD DPCA-60 (manufactured by Nippon Kayaku: acrylate monomer with five or more functional groups)

[0260] <UV absorber> TINUVIN 326 (BASF Japan: benzotriazole compound): 2 -(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole (absorbance 0.5)

[0261] <Evaluation of Photosensitive Coloring Composition> The obtained photosensitive coloring compositions (R-1 to 138) were evaluated for light transmittance, viscosity stability, residue, development rate, and pattern formation by the following methods. The evaluation results are shown in Tables 9-1, 9-2, 9-3, and 9-4.

[0262] (Measurement of Average Light Transmittance of Photosensitive Composition) The photosensitive coloring composition described in the Examples was applied to a glass substrate using a spin coater to form a coating substrate with a film thickness of 0.5 μm, and the substrate was then heated on a hot plate at 70°C for 60 seconds. The light transmittance of the prepared substrate at wavelengths of 300 to 900 nm was measured using a spectrophotometer (Hitachi High-Tech Science Corporation, "U-3310"), and the light transmittance in the wavelength range described below was evaluated. ◯ and △ are practical. Transmittance 1 (evaluation of light transmittance in the wavelength range of 400 to 460 nm) 〇: 85% or more △: 80% or more but less than 85% ×: Less than 80% Transmittance 2 (average light transmittance evaluation in the wavelength range of 480 to 540 nm) 〇: 90% or more △: 80% or more but less than 90% ×: Less than 80% Transmittance 3 (average light transmittance evaluation in the wavelength range 620-680 nm) ○: Less than 10% △: 10% or more but less than 20% ×: 20% or more

[0263] (Evaluation of Viscosity Stability of Photosensitive Coloring Composition) The viscosity stability was measured in the same manner as in the evaluation of the cyan colored composition, and the composition was evaluated according to the following criteria: Excellent, Good, and Fair are practically usable. [Change in viscosity over time] = |([Initial viscosity] - [Viscosity over time]) / [Initial viscosity]| x 100 ◎: Change rate less than 2% ○: Change rate is 2% or more but less than 5% △: Change rate is 5% or more but less than 10% ×: Change rate 10% or more

[0264] <Residue evaluation> Hexamethyldisilazane was applied to an 8-inch (200 mm) silicon wafer, heated on a hot plate at 100°C for 60 seconds, and then heated on a hot plate at 230°C for 180 seconds to produce a silicon wafer with a hydrophobic surface. The photosensitive coloring composition obtained was applied onto the prepared silicon wafer using a spin coater so that the film thickness after drying would be 0.8 μm, and the wafer was subjected to a heat treatment using a hot plate at 70° C. for 100 seconds. The resulting coating was then exposed to light with a wavelength of 365 nm (exposure dose 3000 J / m) through a mask having an island pattern of 1.2 μm square using an i-line stepper exposure system FPA-3000 i4 (manufactured by Canon). 2 ). The exposed coating was then developed using a developing device (Act-8 manufactured by Tokyo Electron Ltd.). A 0.1% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) was used as the developer, and shower development was carried out at 23°C for 80 seconds. This was followed by rinsing with a spin shower using pure water to obtain a pattern. The obtained pattern was observed (magnification: 20,000x) using a scanning electron microscope (SEM) (S-8820 manufactured by Hitachi High-Technologies Corporation) to evaluate residues. The evaluation criteria are as follows: ◯ and △ are practical. ◯: No residue in non-image areas between patterns △: Residue with a maximum length of less than 0.10 μm is observed in the non-image area between patterns ×: Residues with a maximum length of 0.10 μm or more are observed in the non-image areas between patterns.

[0265] <Adhesion> Among the patterns produced for residue evaluation, a group of patterns with a pattern size of 1.2 μm were observed (magnification: 100 times) using an optical microscope (manufactured by Olympus Corporation). The evaluation criteria are as follows: ◯ and △ are practical. ○: No peeling or chipping of the pattern △: Pattern peeling and chipping is less than 10% in total ×: Pattern peeling and chipping total 10% or more

[0266] [Table 9-1]

[0267] [Table 9-2]

[0268] [Table 9-3]

[0269] [Table 9-4]

[0270] From the results in the above table, the photosensitive coloring compositions of Examples 99 to 231 exhibited good color properties as a cyan color, had good viscosity stability, and were also good in terms of residue and adhesion. On the other hand, Comparative Examples 6, 8, and 9 had good transmittance and adhesion, but very poor viscosity stability. Comparative Example 9 did not contain a basic resin-type dispersant, resulting in poor adhesion. Comparative Example 7 contained a green pigment, and Comparative Example 10 contained a small amount of aluminum phthalocyanine pigment, resulting in poor cyan color characteristics. Furthermore, since the adhesion evaluation was favorable, it is believed that when a solid-state imaging device having an adhesion layer on the partition surface is manufactured, it is possible to manufacture a color filter that does not suffer from poor adhesion to the adhesion layer.

[0271] <Color filter manufacturing> Next, a photosensitive red coloring composition prepared in the same manner as in Example 78 was applied to a silicon wafer substrate using a spin coater, except that the colorant used in the photosensitive coloring composition (R-1) was replaced with 14.0 parts of CI Pigment Red 122, to form a colored coating. Next, the coating was irradiated with 3000 J / m using an ultra-high pressure mercury lamp through a photomask. 2 The unexposed areas were then removed by spray development using an alkaline developer (aqueous solution of 0.05% by mass of tetramethylammonium hydroxide), and the substrate was then washed with ion-exchanged water and heated at 230°C for 5 minutes to form magenta filter segments.

[0272] Similarly, a photosensitive yellow coloring composition prepared in the same manner as in Example 78 was applied to a silicon wafer substrate using a spin coater, except that the colorant used in the photosensitive coloring composition (R-1) was replaced with 14.0 parts of CI Pigment Yellow 185, to form a colored coating. Next, the coating was irradiated with 3000 J / m using an ultra-high pressure mercury lamp through a photomask. 2 The unexposed areas were then removed by spray development using an alkaline developer (aqueous solution of 0.05% by mass of tetramethylammonium hydroxide), followed by washing with ion-exchanged water. The substrate was then heated at 230°C for 5 minutes to form yellow filter segments, thereby obtaining a color filter.

[0273] Similarly, the photosensitive coloring composition (R-6) was applied to a silicon wafer substrate using a spin coater to form a colored film. Next, the film was irradiated with 3000 J / m 2 using an ultra-high pressure mercury lamp through a photomask. 2 The substrate was then spray-developed with an alkaline developer consisting of a 0.05% by mass aqueous solution of tetramethylammonium hydroxide to remove the unexposed areas, and then washed with ion-exchanged water. The substrate was then heated at 230°C for 5 minutes to form cyan filter segments, thereby obtaining a color filter.

[0274] The color filter produced by using the photosensitive coloring composition for a cyan color filter for a solid-state imaging device of the present invention had good adhesion, little residue, good viscosity stability, and excellent color properties as a cyan color. Therefore, by using solid-state imaging elements equipped with this color filter in mobile phone cameras, in-vehicle sensors, surveillance cameras, etc., it will be possible to create devices with significantly improved long-distance imaging capabilities and image resolution.

Claims

1. A coloring composition for a cyan color filter, comprising a colorant and a basic resin-type dispersant, The colorant contains a phthalocyanine pigment represented by the following general formula (1) and a blue phthalocyanine compound represented by the following general formula (2), The colorant contains a phthalocyanine pigment represented by the following general formula (1) in an amount of 40 to 95% by mass relative to 100% by mass of the colorant, A coloring composition for a cyan color filter, wherein the blue phthalocyanine compound represented by the following general formula (2) is either (A) or (B) below: (A) one or more pigments selected from the group consisting of Pigment Blue 15:2, Pigment Blue 15:4, and Pigment Blue 15:6 (B) L in the general formula (2) is an acidic functional group represented by the following general formula (3) or general formula (4): 【Chemistry 1】 (In general formula (1), X represents a halogen atom, n represents an integer of 0 to 16, and Y represents -OP(=O)R １ R ２ , -OC(=O)R ３ , -OS(=O) ２ R ４ Represents R １ and R ２ each independently represents a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryloxy group which may have a substituent. １ and R ２ may be directly bonded to form a cyclic structure. ３ represents a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent. ４ represents a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent. In the general formula (2), A represents any one of the metal elements Al, Cu, Zn, Ti, Cr, Co, and Ni. Y can only be present in the bond between A and Al, Ti, Cr, Co, or Ni, and has the same structure as Y in general formula (1). There can be 0 to 16 L's in one phthalocyanine skeleton, and each L independently represents a hydrogen atom, a halogen atom, a nitro group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an acidic functional group, a metal salt, or an amine salt; when A is Zn, there can be 0 to 4 halogen atoms, and when A is a metal other than Zn, there can be 0 to 16 halogen atoms. 【Chemistry 2】 (M 2 represents a hydrogen atom, a calcium atom, a barium atom, a strontium atom, a manganese atom, or an aluminum atom. i represents the valence of M 2 . R 159 to R 162 each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a phenyl group or a polyoxyalkylene group which may have a substituent, or any of R 159 to R 162 taken together to form a heterocycle which further contains a nitrogen, oxygen or sulfur atom and which may have a substituent.

2. 2. The coloring composition for a cyan color filter according to claim 1, wherein the basic resin-type dispersant has an amine value of 10 to 300 mgKOH / g.

3. 3. The coloring composition for a cyan color filter according to claim 1, wherein the basic resin-type dispersant is a resin having a quaternary ammonium salt group.

4. A photosensitive coloring composition for a cyan color filter, comprising the coloring composition for a cyan color filter according to any one of claims 1 to 3, a polymerizable compound, a photopolymerization initiator, and an organic solvent.

5. The photosensitive coloring composition for a cyan color filter according to claim 4, further comprising a binder resin.

6. A color filter comprising a substrate and filter segments formed from the photosensitive coloring composition for a cyan color filter according to claim 4 or 5.

7. A display device comprising the color filter according to claim 6.

8. A solid-state imaging device comprising the color filter according to claim 6 .

Images