JP7767892B2 - Coloring composition for cyan color filters and use thereof - Google Patents

Description

The present invention relates to a cyan photosensitive coloring composition used in the manufacture of color filters for solid-state imaging devices and the like.

C-MOS (Complementary Metal Oxide Semiconductor)
Solid-state imaging devices, such as complementary metal-oxide semiconductor (CCD) and charge-coupled device (CCD), typically perform color separation by arranging color filters having additive primary color filter segments, i.e., red filter layer segments (R), green filter segments (G), and blue filter segments (B), at predetermined positions on their light-receiving elements. On the other hand, color filters having filter segments of cyan, magenta, and yellow (CMY), which correspond to the complementary colors of red, green, and blue, have been attracting attention in recent years because they offer higher sensitivity than primary color filters. Complementary color filters are often employed in video cameras and the like 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.

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

Patent Document 1 discloses a coloring composition for cyan color filters that contains an aluminum phthalocyanine pigment and a basic pigment derivative.

Japanese Patent Application Laid-Open No. 2020-73989

However, conventional cyan coloring compositions have had the problem of poor stability over time. Furthermore, coatings formed from these compositions have insufficient transmittance in the 400-450 nm wavelength range, which is important for cyan color, and also have poor adhesion to the substrate.

The present invention aims to provide a photosensitive coloring composition for cyan color filters that has good stability over time, excellent transmittance for cyan color, and can form cyan color filter segments with good substrate adhesion.

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:

(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 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. _R1 and _R2 may be directly bonded to form a cyclic structure. _{R3 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. R4 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 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.

The present invention described above provides a photosensitive coloring composition for cyan color filters that can form cyan color filter segments that have good stability over time, excellent transmittance, and good substrate adhesion, as well as color filters, display devices, and solid-state imaging devices.

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

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:

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 achieves excellent color characteristics that are difficult to achieve with 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 transmittance in the 400 nm to 450 nm wavelength range, which is important for cyan color, and also has the unexpected effect of improving adhesion to the substrate.

<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 that has extremely low absorption in the range of 450 nm to 550 nm and excellent cyan spectral characteristics.

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. Using an appropriate ratio improves the light transmittance of the cyan color.

(Phthalocyanine pigment represented by general formula (1))
General formula (1)

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.

_R3 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. _R4 represents a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted heterocyclic group.

The n value of the halogen atom X is preferably 12 or less, and more preferably 5 or less. This improves dispersibility and color properties.

In general formula (1), from the viewpoint of dispersibility and color properties, it is preferable that at least one of ^R1 and ^R2 is an aryl group which may have a substituent, or an aryloxy group which may have a substituent (in ^—OR3 , ^R3 is an aryl group which may have a substituent). ^R1 and ^R2 are more preferably an aryl group which may have a substituent, or an aryloxy group which may have a substituent (in ^—OR3 , ^R3 is an aryl group which may have a substituent), and a phenyl group or a phenoxy group is even more preferable.

The content of the phthalocyanine pigment represented by general formula (1) is preferably 50 parts by mass or more per 100 parts by mass of the colorant, and more preferably 70 parts by mass or more from the perspective of the color characteristics of the cyan color.

(Blue phthalocyanine compound represented by general formula (2))
By containing 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.

General formula (2)

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 are 0 to 16 L's in one phthalocyanine skeleton. Each L's 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.

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.

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

Halogen atoms in L include fluorine, chlorine, bromine, and iodine.

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

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

(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.

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.

General formula (3) represents a functional group in which a salt is formed between a sulfo group and a metal, and general formula (4) represents a functional group in which a salt is formed between 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 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.

When R ₁₅₉ is a hydrogen atom, examples of the structures of NR ₁₆₀ , R ₁₆₁ and R ₁₆₂ are shown below.

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.

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

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

Examples of blue pigments include C.I. Pigment Blue 15, 15:1, 15:3, 15:5, 16, 22, 60, and 64.

The colorant content is preferably 50 to 85% by mass, and more preferably 60 to 80% by mass, of the non-volatile content of the coloring composition. Furthermore, the colorant content is preferably 25 to 75% by mass, and more preferably 30 to 70% by mass, of the non-volatile content of the photosensitive composition.

(Fine particle size of colorant)
In order to obtain high light transmittance, it is preferable to use a colorant (organic pigment) in which the colorant particles are made fine by, for example, salt milling. The volume average primary particle diameter of the colorant is preferably 10 nm or more in order to improve dispersibility. Furthermore, in order to improve color reproducibility, it is preferably 100 nm or less, and more preferably 20 to 60 nm.

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 while heated using a kneading machine 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 rinsing with water. The water-soluble inorganic salt acts as a crushing aid, and the high hardness of the inorganic salt is used to crush the colorant during salt milling. Optimizing the conditions for salt milling the colorant makes it possible to obtain a colorant with an extremely fine volume average primary particle diameter and a narrow, sharp particle size distribution.

Water-soluble inorganic salts such as sodium chloride, barium chloride, potassium chloride, and sodium sulfate can be used, but sodium chloride (table salt) is preferred from a cost perspective. From the perspectives of both processing efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by mass, and most preferably 300 to 1000% by mass, based on the total mass of the pigment (100% by mass).

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, because 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).

When salt milling the colorant, a resin may be added as needed. Examples of resin types 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 water-soluble organic solvents listed above. The amount of resin used is preferably 2 to 200% by weight per 100 parts by weight of the colorant.

(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.

The number average molecular weight of the basic resin-type dispersant is generally preferably 500 to 50,000, and more preferably 3,000 to 30,000. A moderate number average molecular weight improves compatibility and makes it easier to prepare a composition with a low viscosity.

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.

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 referred to as "monomers," and monomers that make up the resin after polymerization are referred to as "monomer units."

Examples of N,N-disubstituted amino group-containing monomers 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.

Examples of alkyl (meth)acrylates include (meth)acrylic esters obtained by reacting unsaturated monocarboxylic acids, 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 alkyl alcohols having 1 to 18 carbon atoms.

Other vinyl monomers include, for example, 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 vinyl compounds such as vinyl acetate and vinyl propionate.

Commercially available basic resin-type dispersants include, for example, BYK Japan's DISPERBYK 161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2050, 2150, 2163, 2164, and BYK-LPN 6919, and Lubrizol Japan's SOLSPERSE 11200, 13240, 13650, and 13 Examples include, but are not limited to, 940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 38500, 39000, 53095, 56000, 7100, and EFKA 4300, 4330, 4046, 4060, and 4080 from BASF Japan.

The content of the basic resin-type dispersant is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass, of the non-volatile content of the coloring composition.

<Resin-type dispersant having a quaternary ammonium salt group>
The coloring composition for a cyan color filter of the present invention preferably contains a resin-type dispersant having a quaternary ammonium base. The quaternary ammonium base may be bonded directly to the main chain or may be bonded to the main chain via a divalent linking group. The quaternary ammonium base is preferably a quaternary ammonium base represented by -N ⁺ R ⁴² R ⁴³ R ⁴⁴ ·Y ^- (wherein R ⁴² , R ⁴³ , and R ⁴⁴ each independently represent a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group, and two or more of R ⁴² , R ⁴³ , and R ⁴⁴ may bond to each other to form a cyclic structure, and Y ^- represents a counter anion).
In -N ⁺ R ⁴² R ⁴³ R ⁴⁴ , examples of the cyclic structure formed by two or more of R ⁴² , R ⁴³ , and R ⁴⁴ bonding to each other 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 is more preferably a saturated ring. Examples of the cyclic structure include the following structures:

These cyclic structures may further have a substituent.
More preferred as R ⁴² , R ⁴³ and R ⁴⁴ in —N ⁺ R ⁴² R ⁴³ R ⁴⁴ are alkyl groups having 1 to 4 carbon atoms which may have a substituent, or phenyl groups which may have a substituent, and more preferred are methyl groups, ethyl groups, propyl groups, butyl groups and benzyl groups.

The resin-type dispersant (B) having a quaternary ammonium salt group used in the colored composition for a cyan color filter of the present invention is preferably an AB block copolymer and/or a BAB block copolymer.
A: Block having a quaternary ammonium base in the side chain B: Block not having a quaternary ammonium base in the side chain

It is particularly preferred that the A block contains a structural unit represented by the following general formula (5):

General formula (5)

In general formula (5), R ⁴⁵ , R ⁴⁶ and R ⁴⁷ each independently represent a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group, and two or more of R ⁴⁵ , R 46 and R ⁴⁷ may be bonded to each other to form a cyclic structure. R ⁴⁸ represents a hydrogen atom or a methyl ^group . Z represents a divalent linking group, and Y ⁻ represents a 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, a -CONH-R ⁴⁹ - group, and a -COO-R ⁵⁰ - group (wherein R ⁴⁹ and R ⁵⁰ are direct bonds, alkylene groups having 1 to 10 carbon atoms, or ether groups having 1 to 10 carbon atoms (-R'-O-R"-: R' and R" are each independently an alkylene group)). Examples of the counter anion Y ^- include Cl ^- , Br ^- , I ^- , ClO ₄ ^- , BF ^- , CH ₃ COO ^- , PF ₆ ^- , and R ⁴⁹ -SO ₃ ^- .

Two or more types of partial structures containing a specific quaternary ammonium base as described above may be contained in one A block. In such cases, the two or more types of partial structures containing a quaternary ammonium base may be contained in the A block in either a random copolymerization or block copolymerization manner. A partial structure that does not contain 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, as described below. The content of such partial structures that do not contain a quaternary ammonium base in the A block is preferably 0 to 70% by mass, more preferably 0 to 50% by mass.

Examples of the B block constituting the block copolymer of a resin-type dispersant having a quaternary ammonium salt group include polymer structures copolymerized with 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; crotonate glycidyl ether; and N-methacryloylmorpholine.

The resin-type dispersant containing a quaternary ammonium salt group used in the present invention is preferably an A-B block or B-A-B 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 ensures uniform polymerization growth, 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.

Living polymerization methods include, for example, 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, xanthate compounds, 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 (DT) methods, which use heavy metals such as organotellurium, organobismuth, organoantimony, antimony halides, organogermanium, and germanium halides. These include the organotellurium-mediated living radical polymerization (DT method) (see References 7 and 8), which controls polymerization through two processes: thermal dissociation of the bond between tellurium atoms and carbon and degenerative chain transfer (TERP method) (see Reference 9).

(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 document 4) Chemical Review (2001) 101,3689
(Reference 5) JP-A-2000-515181 (Reference 6) WO 1999-05099 (Reference 7) JP-A-2007-277533 (Reference 8) Journal of American Chemical Society (2002) 124, 2874
(Reference 9) JP 2004-323693

Whether the resin-type dispersant having a quaternary ammonium salt group used in the present invention is an A-B block copolymer or a B-A-B 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, both good heat resistance and dispersibility can be achieved.
Furthermore, in the A-B block copolymer and B-A-B block copolymer according to 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, whereby the resin-type dispersant (B) is well adsorbed to the dye salt form (A), and excellent dispersibility and storage stability are exhibited.

Note that resin-type dispersants containing quaternary ammonium salt groups may contain amino groups generated during the manufacturing process, but 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.

<Method of producing a coloring composition for color filters>
The coloring composition is prepared by, for example, 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 addition, the micronization treatment herein can be carried out by micronizing two types of colorants individually. Alternatively, multiple colorants (A) can be used and micronized all at once. In addition, 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.

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

After dispersion, it is preferable to remove coarse particles of 5 μm or larger, preferably 1 μm or larger, and more preferably 0.5 μm or larger, as well as any dust particles, from the coloring composition using a method such as centrifugation at a gravitational acceleration of 3,000 to 25,000 G, a sintered filter, or a membrane filter.

The coloring composition of the present invention can be prepared as a coloring composition for a cyan color filter.

(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 effectively reduce the size and disperse the pigment particles, and can also produce a colored composition for color filters that has excellent dispersion stability after dispersion. While this method is not limited to co-dispersion, individual dispersion is also possible.

Co-dispersion can be achieved, for example, by mixing at least two pigments with a dispersant and pre-dispersing them using a homogenizer or similar device, then dispersing the mixture using various dispersing means such as a kneader, two-roll mill, three-roll mill, ball mill, horizontal sand mill, vertical sand mill, annular bead mill, or 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.

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

<Resin-type dispersant>
The coloring composition may contain a resin-type dispersant other than the basic resin-type dispersant.
Resin-type dispersants, for example, polyurethane, polycarboxylic acid esters such as polyacrylate, 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; poly (lower alkylene imine) and amides formed by reaction with a polyester having a free carboxyl group, oil-based dispersants such as salts thereof; (meth) acrylic acid - styrene copolymer, (meth) acrylic acid - (meth) acrylic acid ester copolymer, styrene - maleic acid copolymer, polyvinyl alcohol, water-soluble resins and water-soluble polymer compounds such as polyvinylpyrrolidone, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide adduct, phosphate ester-based, and the like.

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, per 100 parts by mass of colorant. Using an appropriate amount will further improve dispersibility.

(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.

[Comb-shaped resin-type dispersant 1]
The 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.

[Comb-shaped resin-type 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, etc.
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, followed by reacting the hydroxyl group in the side chain with a monomer having an isocyanate group, which is preferred.

[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, and 2,3,6,7-naphthalene tetracarboxylic dianhydride. Anhydride, 3,3',4,4'-biphenylethertetracarboxylic acid dianhydride, 3,3',4,4'-dimethyldiphenylsilanetetracarboxylic acid dianhydride, 3,3',4,4'-tetraphenylsilanetetracarboxylic acid dianhydride, 1,2,3,4-furantetracarboxylic acid dianhydride, 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) aromatic tetracarboxylic acid dianhydrides such as 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)-4,4'-diphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, and 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride.

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

[Straight-chain resin-type dispersant 3]
The linear resin dispersant 3 can be synthesized by the methods described in JP-A Nos. 2009-251481, 2007-23195, and 1996-143651, etc. The linear resin 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.

[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], etc.), 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, etc.), 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.

<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 2 μm thick coating 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.

Examples of alkali-soluble resins include resins having acidic groups such as carboxyl groups and sulfonic groups. Examples of alkali-soluble thermoplastic resins include acrylic resins having acidic groups, 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 acidic groups and styrene/styrene sulfonic acid copolymers are preferred in terms of improved developability, heat resistance, and transparency.

The acid value of the alkali-soluble resin is preferably 20 to 300 mg KOH/g. Having a moderate acid value improves developability when forming patterns using photolithography.

<Alkali-soluble photosensitive resin>
The alkali-soluble photosensitive resin has photosensitivity due to the presence of polymerizable unsaturated groups. Any known resin can be used as the alkali-soluble photosensitive resin as long as it is alkali-soluble and photosensitive. However, 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.

[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.

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 standpoint of reactivity.

Examples of monocarboxyl group-containing monomers 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.

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. Note that polybasic acid anhydrides may also have carboxyl groups that do not form acid anhydrides.

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.

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-phenylene dimaleimide, N,N'-1,4-phenylene dimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide N-substituted maleimides such as N-isopropyl acrylate, ...

Method (ii) involves, for example, synthesizing a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other monomers to produce a polymer. 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.

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.

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

Monomers that can be used in addition to the above monomers include the other monomers exemplified in method (i) above, as well as phosphate ester group-containing monomers.

A phosphate ester 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.

(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.

The weight-average molecular weight (Mw) of the binder resin is preferably 5,000 to 100,000, and 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.

The binder resin content is preferably 10 to 500 parts by weight per 100 parts by weight of colorant.

<Thermosetting compound>
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.

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.

<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.

(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. Such dye derivatives include, for example, 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.

From the viewpoint of improving dispersibility, 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, per 100 parts by mass of the colorant. Furthermore, from the viewpoint of heat resistance and light fastness, the content is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less.

<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, and n-butyl benzene, 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 diethyl 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, dipropylene glycol monoethyl ether, 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, dibasic acid esters, and the like.

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.

The amount of organic solvent used is preferably 500 to 4,000 parts by mass per 100 parts by mass of colorant, in order to adjust the viscosity of the coloring composition to an appropriate level.

Organic solvents can be used alone or in combination of two or more types.

<Photosensitive Coloring Composition for Color Filter>
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.

<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.

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.

(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 further reacting the resulting alcohol with a (meth)acrylate having a hydroxyl group.

Examples of (meth)acrylates 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, reaction products of epoxy group-containing compounds and carboxy(meth)acrylates, and hydroxyl group-containing polyol polyacrylates.

Examples of polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanates.

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 include various acrylic acid esters and methacrylic acid esters such as 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 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.

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

Examples of trifunctional or higher functional polymerizable compounds include pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and dipentaerythritol penta(meth)acrylate.

Commercially available trifunctional or higher 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.

The polymerizable compounds can be used alone or in combination of two or more types.

The content of the polymerizable compound is preferably 1 to 50 mass %, and more preferably 2 to 40 mass parts, based on 100 mass % of the nonvolatile content of the photosensitive coloring composition. Adding an appropriate amount further improves curability and developability.

<Photopolymerization initiator>
Examples of the photopolymerization initiator (G) include acetophenone-based compounds such as 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, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; benzoin, benzoin methyl ether, benzo benzoin-based compounds such as benzoin ethyl ether, benzoin isopropyl ether, or benzil dimethyl ketal; benzophenone-based compounds such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone-based compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 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(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, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine triazine-based compounds such as azine; oxime ester-based 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-based compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; quinone-based compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate-based compounds; carbazole-based compounds; imidazole-based compounds; or titanocene-based compounds.

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), and the like.

Of these, oxime ester compounds are preferred.

(Oxime ester compounds)
When an oxime ester compound absorbs ultraviolet light, the N-O bond of the oxime undergoes cleavage, generating an iminyl radical and an alkyloxy radical. These radicals further decompose to generate highly active radicals, allowing for pattern formation 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.

Examples of preferred oxime ester photopolymerization initiators are listed below.

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 Ltd.), N-1919, NCI-831, NCI-930 (all manufactured by ADEKA Corporation), 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-A Nos. 2007-210991, 2009-179619, 2010-037223, 2010-215575, 2011-020998, etc.

Photopolymerization initiators can be used alone or in combination of two or more types.

<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.

Examples of polymerization inhibitors include alkyl catechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert-butylcatechol, and 3,5-di-tert-butylcatechol; 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, and 2-n-butylcatechol. Examples of suitable resorcinol compounds include alkylresorcinol compounds such as n-butylresorcinol, 4-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.

The content of the polymerization inhibitor is preferably 0.01 to 1 part by mass of the non-volatile content of the photosensitive coloring composition. An appropriate amount makes it easier to obtain a good pattern shape.

<Ultraviolet 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.

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-di-hydroxy-4,4-dimethoxybenzophenone. Examples of triazine-based organic compounds include 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

Commercially available products include, for example, BASF Japan's "TINUVIN P" (absorbance 0.40), "TINUVIN 326" (absorbance 0.48), and "TINUVIN 360" (absorbance 0.40), Shipro Kasei's "Seesorb 107" (absorbance 0.60), and ADEKA's "ADK STAB LA-F70" (absorbance 0.90).

The content of the UV absorber is preferably 5 to 70% by mass, with the total of the photopolymerization initiator and UV absorber being 100% by mass. An appropriate amount makes it easier to obtain a good pattern shape. Note that if the photosensitive coloring composition contains a sensitizer, the content of the sensitizer is included in the content of the photopolymerization initiator.

<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.

The content of the sensitizer is preferably 3 to 60 parts by weight, and more preferably 5 to 50 parts by weight, per 100 parts by weight of the photopolymerization initiator. When an appropriate amount is added, photocuring properties and developability are improved.

<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 the thermal process of thermal curing or ITO annealing, and can suppress 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, so that 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.

Examples of antioxidants include hindered phenol compounds, hindered amine compounds, phosphorus compounds, sulfur compounds, and hydroxylamine compounds. It is preferable that the antioxidant 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 high transmittance and high sensitivity of the coating.

Antioxidants can be used alone or in combination of two or more types.

The content of the antioxidant is preferably 0.5 to 5.0% by mass based on 100% by mass of the nonvolatile content of the photosensitive coloring composition.

<Leveling Agent> The photosensitive coloring composition can contain a leveling agent. This improves the wettability of the transparent substrate during film formation and the drying properties of the film. 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 Dow Corning Toray Co., Ltd., and BYK-333 manufactured by BYK-Chemie Co., Ltd. Furthermore, examples of dimethylpolysiloxanes having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK-Chemie Co., Ltd.

Leveling agents can be used alone or in combination of two or more types.

The content of the leveling agent is preferably 0.001 to 2.0% by mass, and more preferably 0.003 to 0.5% by mass, of the non-volatile content of the photosensitive coloring composition.

<Curing agent, curing accelerator>
The photosensitive coloring composition can contain a curing agent or a curing accelerator to assist 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 compounds that can be used include methyl methyl acrylate, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.), phosphorus compounds (e.g., triphenylphosphine, etc.), guanamine compounds (e.g., melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine-isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isocyanuric acid adduct, etc.). These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by mass per 100 parts by mass of the thermosetting resin.

<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.

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.

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 suitable silane coupling agents 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.

(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 of 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 can be used alone or in combination of two or more, but are not necessarily limited to these.

The surfactant content is preferably 0.1 to 55 parts by weight, and more preferably 0.1 to 45 parts by weight, per 100 parts by weight of colorant. If the surfactant content is less than 0.1 parts by weight, it will be difficult to achieve the desired effect, and if the content is more than 55 parts by weight, excess dispersant may affect dispersion.

<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.

The dyes used in the magenta and yellow filter segments are described below. Materials other than the dyes may be any known material.

<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 C.I. 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 C.I. Pigment Violet 19. Among these, C.I. Pigment Red 122 and C.I. Pigment Violet 19 are preferred because of their high transparency and coloring strength. Pigment Red 150, C.I. Pigment Red 282 are preferred.

In addition to pigments, acid dyes and basic dyes can also be used. Examples include C.I. Acid Red 289, 52, and rhodamine dyes.

<Yellow colorant>
The yellow colorant may be a yellow pigment or a yellow dye.
Yellow pigments include, for example, C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 171 6, 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, C.I. Pigment Yellow 138, 139, 150, and 185 are preferred from the viewpoints of heat resistance, light resistance, and brightness.

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.

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

When filter segments are formed by printing, patterns can be created simply by repeatedly printing and drying a colored composition prepared as printing ink, making it a low-cost and highly suitable method for mass production of 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 ink viscosity can be adjusted using dispersants and extender pigments.

When forming filter segments using 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 with a predetermined pattern, which is placed in contact with or out of contact with the film. The uncured portions are then removed by immersion in a solvent or alkali developer or sprayed with a developer, etc., to form the desired pattern. The same process can then be repeated for other colors to produce color filters. 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 described above.

For development, an aqueous solution of sodium carbonate, sodium hydroxide, or the like is used as the alkaline developer, and organic alkalis such as dimethylbenzylamine and triethanolamine can also be used. Antifoaming agents and surfactants can also be added to the developer. To increase UV exposure sensitivity, after coating and drying the colored resist material, a water-soluble or alkaline-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, before UV exposure.

The color filter of the present invention can be manufactured by the above-mentioned methods, as well as by electrodeposition, transfer, inkjet, and other methods, and the coloring composition of the present invention can be used in any of these methods. The electrodeposition method is a method of manufacturing 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 these filter segments are transferred to the desired substrate.

A black matrix can be formed before each color filter segment is formed on a transparent or reflective substrate. 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 before each color filter segment is formed. If necessary, an overcoat film or transparent conductive film can be formed on the color filter of the present invention.

The color filter is attached 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 retardation film is attached to the outside of the substrate as needed to produce a liquid crystal display panel.

Such liquid crystal display panels can be used in liquid crystal display modes that use color filters such as twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convex bend (OCB).

The display device of the present invention is equipped with a color filter. The display device is preferably, for example, an image display device.

<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 white LEDs because they broaden 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.

The liquid crystal LC is aligned according to the drive mode, such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane Switching), VA (Vertical Alignment), or OCB (Opticaly 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.

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

If necessary, a transparent protective film (not shown) is formed to cover the color filter 22, and a transparent electrode layer 23 made of, for example, ITO is formed on top of that. An alignment layer 24 is provided to cover the transparent electrode layer 23.

A polarizing plate 25 is formed on the outer surface of the transparent substrate 21. A backlight unit 30 is provided below the polarizing plate 15.

White LED light sources include those with a fluorescent filter formed on the surface of a blue LED and those with a fluorescent material contained in the resin package of a blue LED, and have a wavelength (λ3) in the range of 430 nm to 485 nm at which the emission intensity is maximized, a wavelength (λ4) in the range of 530 nm to 580 nm at which the emission intensity is maximized, and a wavelength (λ5) in the range of 600 nm to 650 nm at which the emission intensity is maximized, and the ratio (I4/I3) of the emission intensity I3 at wavelength λ3 to the emission intensity I4 at wavelength λ4 is between 0.2 and 0.4. 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 second emission intensity peak wavelength (λ2) in the range of 530 nm to 580 nm, and spectral characteristics in which the 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.

Specific examples of LED1 include NSSW306D-HG-V1 (manufactured by Nichia Corporation) and NSSW304D-HG-V1 (manufactured by Nichia Corporation).

Specific examples of LED2 include NSSW440 (manufactured by Nichia Corporation) and NSSW304D (manufactured by Nichia Corporation).

<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 colored composition described above. The color filter segment includes a color filter segment obtained by curing the colored 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.

When color filter segments are formed on corresponding photoelectric conversion elements, a negative color resist layer is formed from a negative green film formed from a negative photosensitive green composition, and the thickness of the negative color resist layer in this case is set in the range of 0.1 μm to 3.0 μm.
The surface of the negative color resist layer formed from the negative color film is exposed to pattern light using a photomask in multiple areas corresponding to the multiple photoelectric conversion elements to be formed. The photomask has dimensions 4 to 5 times the dimensions of the pattern to be actually formed, and is reduced to 1/4 to 1/5 during pattern exposure.
This photomask is a 4-5x reticle, and has a pattern that is 4-5 times larger than the size of the pattern to be exposed on the surface of the negative color resist layer. Then, using a stepper exposure device (not shown), the photomask pattern is reduced to 1/4 to 1/5 and exposed on the surface of the negative color resist layer.
Following the exposure step, an alkali 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.

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.
It is also possible to prevent uneven development by wetting the surface to be developed with water or the like before contacting it with the developer. As the developer, an organic alkaline developer is preferred, 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. As the developer, an alkaline aqueous solution obtained by diluting these alkaline agents with pure water to a concentration of 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass, is preferably used. When a developer comprising such an alkaline aqueous solution is used, 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.

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, if necessary. Post-baking is a heat treatment after development to ensure complete curing, and is usually a thermal curing treatment at 100°C to 270°C. When light is used, 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, and the irradiation time is 10 to 180 seconds, preferably 30 to 60 seconds. When post-exposure and post-baking are used in combination, it is preferable to perform 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.

<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.
The solid-state imaging device has a substrate on which a plurality of photodiodes constituting a light-receiving area of a solid-state imaging element (such as a CCD sensor, a CMOS sensor, or an organic CMOS sensor) and transfer electrodes made of polysilicon or the like. A light-shielding film made of tungsten or the like, with only the light-receiving portions of the photodiodes exposed, is disposed on the photodiodes and the transfer electrodes. A device protection film made of silicon nitride or the like is disposed on the light-shielding film so as to cover the entire light-shielding film and the light-receiving portions of the photodiodes. The solid-state imaging device has a color filter segment for the solid-state imaging element of the present invention disposed on the device protection 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 the light 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 the photoelectric conversion layer and a CMOS signal readout substrate, and has a two-layer hybrid structure in which the organic material captures light and converts it into an electrical signal, while the inorganic material extracts the electrical signal externally, and in principle can achieve a 100% aperture ratio for incident light.The organic 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.

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.

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, as well as the methods for calculating the number of halogen substitutions in the pigment and the halogen distribution width in the pigment, are as follows:

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

(Average molecular weight of resin-type dispersant)
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the resin-type dispersant are polystyrene-equivalent number average molecular weight (Mn) and weight average molecular weight (Mw) measured using an HLC-8320GPC (manufactured by Tosoh Corporation) as an apparatus, a SUPER-AW3000 column, and an N,N-dimethylformamide solution of 30 mM triethylamine and 10 mM LiBr as an eluent.

(Acid value of acidic resin-type dispersant)
The acid value of the acidic resin-type 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 aqueous KOH 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.

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

(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 resulting liquid with an ion chromatograph (ICS-2000 ion chromatograph, manufactured by DIONEX Corporation), quantifying the amount of halogen, and converting the amount into the number of halogen substitutions.

(Halogen distribution width in pigment)
The halogen distribution width in the pigment was measured using a time-of-flight mass spectrometer (autofleXIII (TOF-
The halogen content was determined using a mass spectrometry analyzer (MS) manufactured by Bruker Daltonics. The pigment powder was subjected to 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.

(Volume average primary particle diameter of pigment)
The volume-average primary particle size (MV) of the pigment was calculated by measuring the minor axis diameter and major axis diameter of 100 primary particles of the pigment using a transmission electron microscope (TEM) photograph, taking the average of the minor axis diameter and major axis diameter 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 having the determined particle size. This procedure was performed for 100 pigment particles, and the volume (V) of each particle was then calculated from the following formula.
MV=Σ(V・d)/Σ(V)

<Method of manufacturing finely treated pigment>
(Finely divided pigment (P-1))
To a three-neck flask, 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) were added and stirred, and the mixture was allowed to react at 20°C for 6 hours. Thereafter, the reaction mixture was 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. Thereafter, the mixture was collected by filtration, washed with water, and dried, yielding a pigment in which an average of 10.1 bromine atoms were 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 pigment had a halogen distribution width of 9 and a volume average primary particle diameter of 26 nm.

(Finely divided pigment (P-2))
To a three-neck flask, 500 parts of 98% sulfuric acid, 50 parts of the phthalocyanine pigment represented by the above formula (50), and 104.4 parts of 1,2-dibromo-5,5-dimethylhydantoin (DBDMH) were added, stirred, and allowed to react 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 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 collected by filtration, washed with water, and dried to obtain a pigment having an average of 8.0 bromine atoms substituted on the phthalocyanine ring. Next, 500 parts of N-methylpyrrolidone, 50 parts of the resulting pigment having an average of 8.0 bromine atoms substituted on the phthalocyanine ring, and 15.8 parts of diphenyl phosphate were added to a three-neck flask, heated to 90°C, and allowed to react for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain 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.

Formula (52)

(Fine Pigment (P-3))
203 parts of aluminum bromide, 47 parts of sodium bromide, and 5 parts of ferric bromide were heated to melt, 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, in that order, and then dried to obtain 98 parts of brominated aluminum phthalocyanine. The obtained 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 having an average of 15.0 bromine atoms 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.

Formula (53)

(Finely divided 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 are substituted on the phthalocyanine ring, and 13.8 parts of diphenylphosphinic acid were added to a three-neck flask, and 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 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.

Formula (54)

(Fine Pigment (P-5))
In a reaction vessel, 225 parts of phthalodinitrile and 78 parts of anhydrous aluminum chloride were added to 1,250 parts of n-amyl alcohol and stirred. To this was added 266 parts of DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene), the temperature was raised, and the mixture was 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 a reaction vessel, 100 parts of chloroaluminum 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 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).

Formula (55)

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 thereto and stirred at 155°C for 30 minutes to dissolve. 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 a 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.

Formula (56)

(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).

Formula (57)

Next, 100 parts of the stearate, 1,200 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 3,000 parts of warm water and stirred for 1 hour while heated 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 the micronized pigment (P-6). The volume average primary particle diameter of the pigment was 37 nm.

(Finely divided pigment (P-7))
100 parts of a phthalocyanine green pigment C.I. 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 washing with water to remove the sodium chloride and diethylene glycol, the mixture was dried at 80 ° C. overnight to obtain 97 parts of a micronized pigment (P-7). The volume average primary particle diameter of the pigment was 36 nm.

(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.

Formula (58)

(Finely divided 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 for blue colorant (P-1). The volume average primary particle diameter of the pigment was 33 nm.

Formula (59)

(Fine Pigment (P-12))
A micronized pigment (P-12) was obtained in the same manner as in the preparation of the micronized pigment (P-6), except that LIONOL BLUE 7255-PS (C.I. Pigment Blue 15:2) manufactured by Toyocolor Co., Ltd. was used instead of the aluminum phthalocyanine pigment represented by formula (57). The volume average primary particle diameter of the pigment was 30 nm.

(Fine Pigment (P-13))
A micronized pigment (P-13) was obtained in the same manner as in the preparation of the micronized pigment (P-6), except that LIONOL BLUE FG-7400-G (C.I. Pigment Blue 15:4) manufactured by Toyocolor Co., Ltd. was used instead of the aluminum phthalocyanine pigment represented by formula (57). The volume average primary particle diameter of the pigment was 25 nm.

(Finely divided pigment (P-14))
A micronized pigment (P-14) was obtained in the same manner as in the preparation of the micronized pigment (P-6), except that LIONOL BLUE ES (C.I. Pigment Blue 15:6) manufactured by Toyocolor Co., Ltd. was used instead of the aluminum phthalocyanine pigment represented by formula (57). The volume average primary particle diameter of the pigment was 36 nm.

(Finely divided pigment (P-15))
A micronized pigment (P-15) was obtained in the same manner as in the preparation of the micronized pigment (P-6), except that LIONOL BLUE FG-7330 (C.I. Pigment Blue 15:3) manufactured by Toyocolor Co., Ltd. was used instead of the aluminum phthalocyanine pigment represented by formula (57). The volume average primary particle diameter of the pigment was 40 nm.

<Blue Phthalocyanine Compounds B-1 to B- 49 >
Among the blue phthalocyanine compounds represented by general formula (2) used, B-1 to B -49 including those represented by general formula (3) and general formula (4) are shown below.
General formula (2)

(B-50)
Formula (63)

<Production of Acidic Resin-Type Dispersant Having Carboxyl Group>
(Production Example 1) (Acidic Resin-Type Dispersant C1 Having Carboxyl Groups)
A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a 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 confirming that 98% had reacted by measuring the nonvolatile content, 73.3 parts of pyromellitic anhydride was added, and the mixture was reacted at 120 ° C. for 2 hours. After confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value, the reaction was terminated. The resulting dispersant was a white solid at room temperature, and had an acid value of 49 mg KOH / g. The nonvolatile content was adjusted with PGMAc to obtain an acidic resin-type dispersant (C1) solution with a nonvolatile content of 50%.

(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, while the reaction was carried out 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 mixture was reacted for 7 hours at 100 ° C. After confirming that 98% or more of the acid anhydride had been half-esterified by acid value measurement, the reaction was terminated, and PGMAc was added to dilute the mixture so that the nonvolatile content was 50% by nonvolatile content measurement. An acidic resin-type dispersant (C2) with an acid value of 40 mg KOH / g and a weight average molecular weight of 9000 was obtained.

(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).

<Method for producing basic resin-type dispersant>
(Basic resin-type dispersant solution D1)
B-block synthesis: A reaction apparatus equipped with a gas inlet tube, a condenser, a stirring blade, and a 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), and the atmosphere was replaced with nitrogen for 30 minutes. The reaction solution was then gently stirred, the temperature was raised to 80°C, and this temperature was maintained for 12 hours to carry out 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, followed by living radical polymerization 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 so that the nonvolatile content was 50% by mass, to prepare basic resin-type dispersant solution D1. GPC measurement revealed that the resin had an Mw of 8100. The amine value per nonvolatile content was 79 mgKOH/g.

(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.

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

<Method for producing binder resin>
(Preparation of binder resin solution 1)
(Step 1: Polymerization of resin backbone)
100 parts of PGMAc was placed in a reaction vessel equipped with a thermometer, a condenser, a nitrogen gas inlet tube, and a stirrer in a separable four-neck flask, and heated to 120°C while injecting nitrogen gas 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.

(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 reaction of the precursor 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.

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

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

(Preparation of binder resin solution 2)
A separable four-necked flask was fitted 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, a mixture of 19.0 parts of meparacumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 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 was added dropwise over 2 hours. After completion of the dropping, 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, and then cooled to room temperature. A mixture of 12.5 parts of 2-methacryloyloxyethyl isocyanate (Karenz 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 completion of the dropwise addition, 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 a binder resin solution 2 having an acid value of 131 mg KOH / g was obtained.

(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. A reaction vessel was charged with 700.0 parts of cyclohexanone, the temperature was raised to 80 ° C., and the atmosphere in the reaction vessel was replaced with nitrogen. From the dropping tube, 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 completion of the dropping, 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 (Karenz 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 completion of the dropwise addition, 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, and the non-volatile content was measured. Cyclohexanone was added to the resin solution synthesized above so that the non-volatile content became 50% by mass, and binder resin solution 3 having an acid value of 104 mgKOH/g was obtained.

(Preparation of Binder Resin Solution 4)
A separable four-necked flask was equipped with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube, and a stirrer. 207 parts of cyclohexanone was charged into the reaction vessel, which was then heated to 80 ° C. After the atmosphere in the reaction vessel was replaced with nitrogen, 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 from the dropping tube. After completion of 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 amount of the obtained copolymer solution while stirring for 1 hour. After cooling to room temperature, a mixture of 16.3 parts of 2-methacryloyloxyethyl isocyanate (Showa Denko KARENZ MOI), 0.08 parts of dibutyltin laurate, and 26 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, 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 resin solution synthesized previously so that the nonvolatile content became 50% by mass, and binder resin solution 4 having an acid value of 233 mgKOH/g was obtained.

(Preparation of Binder Resin Solution 5)
A flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube was charged with 145 g of PGMAc, and the temperature was raised to 120 ° C. while stirring and replacing with nitrogen. Next, 20.0 parts (0.1 mol) of 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 were mixed with 10.1 parts of azobisisobutyronitrile per 100 parts of the monomer mixture. This was added dropwise from the dropping funnel to the flask over 2 hours, and the mixture was further stirred at 120 ° C. for 2 hours to perform aging. Next, the atmosphere in the flask was replaced with air, and 122.3 parts of glycidyl methacrylate (0.9 mol, 60 mol% of methacrylic acid), 0.9 g of trisdimethylaminomethylphenol, and 0.145 parts of hydroquinone were added to the aged solution, and the reaction was continued at 120°C for 6 hours. When the nonvolatile acid value reached 1.0, the reaction was terminated, and 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.

(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 a solution obtained by adding 3.6 parts of azobisisobutyronitrile to a mixture consisting of 70.5 parts of benzyl methacrylate, 71.1 parts of glycidyl methacrylate, 22.0 parts of a tricyclodecane-skeleton monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.), and 164 parts of PGMAc was added dropwise from the dropping funnel to the flask over 2 hours, and stirring was continued for a further 5 hours at 100°C. 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 group of the glycidyl methacrylate used in this reaction)], 0.9 parts of trisdimethylaminomethylphenol, and 0.145 parts of hydroquinone were added to the flask, and the reaction was continued for 6 hours at 110 ° C. 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 reaction was continued for 3.5 hours at 120 ° C. to obtain a binder resin solution. Approximately 2 g of the binder resin solution was sampled and heated to 180 ° C. for 20 minutes to dry the nonvolatile content, and PGMAc was added to adjust the nonvolatile content to 50% by mass, resulting in a binder resin solution 6 with an acid value of 80 mg KOH / g.

(Preparation of Binder Resin Solution 7)
A separable four-necked flask was equipped 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. and purged with nitrogen. 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 were added dropwise over 2 hours. After completion of the dropwise addition, 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 nonvolatile content was measured. PGMAc was added to adjust the nonvolatile content to 50% by mass, thereby obtaining binder resin solution 7 having an acid value of 94 mgKOH/g.

(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, and the temperature was raised to 80 ° C. After the atmosphere in the reaction vessel was replaced with nitrogen, a mixture of 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.) 22.0 parts, 31.9 parts of glycerol monomethacrylate, and 4.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of 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 amount of the obtained copolymer solution for 1 hour while stirring, and then cooled to room temperature. A mixture of 52.2 parts of 2-methacryloyloxyethyl isocyanate (Karenz 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 completion of the dropwise addition, 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 heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Cyclohexanone was added to adjust the nonvolatile content to 50% by mass, and a binder resin solution 8 having an acid value of 95 mg KOH / g was obtained.

(Preparation of Binder Resin Solution 9)
A separable four-necked flask was equipped with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube, and a stirrer. 520.0 parts of cyclohexanone was charged into the reaction vessel, and the temperature was raised to 80 ° C. After the atmosphere in the reaction vessel was replaced with nitrogen, 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 from the dropping tube. After completion of 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 total amount of the obtained copolymer solution while stirring for 1 hour. After cooling to room temperature, a mixture of 64.8 parts of 2-methacryloyloxyethyl isocyanate (Karenz MOI: manufactured by 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, 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 a binder resin solution 9 having an acid value of 23 mgKOH/g.

<Production of Cyan Colored Composition>
[Example 1]
(Preparation of Cyan Colored Composition (D-1))
The following mixture was stirred and mixed until uniform, and then the mixture was milled 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 parts

[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.

<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. The evaluation results are shown in Tables 7-1, 7-2, and 7-3.

(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 change in viscosity 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).
[Temporal viscosity change rate] = |([initial viscosity] - [temporal viscosity]) / [initial viscosity]| x 100
◎: Rate of change less than 2% ◯: Rate of change 2% or more but less than 5% △: Rate of change 5% or more but less than 10% ×: Rate of change 10% or more

(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)
○: 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 Less than 90% ×: Less than 80% Transmittance 3 (average light transmittance evaluation in the wavelength range 620 to 680 nm)
〇: Less than 10% △: 10% or more but less than 20% ×: 20% or more

<Production of Photosensitive Coloring Composition>
[Example 99]
(Preparation of Photosensitive Coloring Composition (R-1))
A mixture of the following components was stirred and mixed uniformly, and then filtered through a 1 μm filter to prepare a photosensitive coloring composition (R-1).
Cyan colored 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 Ultraviolet 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)

[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 Tables 8-1, 8-2, and 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. Tables 8-1, 8-2, 8-3, and 8-4 show the amounts of ultraviolet absorber, polymerization inhibitor solution, and leveling agent solution blended in the same manner as in Example 78.

The raw materials listed in Tables 8-1 to 8-4 are shown below.
<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 Co., Ltd.: polybasic acid-modified special multifunctional acrylate, trifunctional or higher)
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)

<Ultraviolet absorber>
TINUVIN 326 (manufactured by BASF Japan: benzotriazole-based compound): 2
-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole (absorbance 0.5)

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

(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)
○: 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 Less than 90% ×: Less than 80% Transmittance 3 (average light transmittance evaluation in the wavelength range 620 to 680 nm)
〇: Less than 10% △: 10% or more but less than 20% ×: 20% or more

(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.
[Temporal viscosity change rate] = |([initial viscosity] - [temporal viscosity]) / [initial viscosity]| x 100
◎: Rate of change less than 2% ◯: Rate of change 2% or more but less than 5% △: Rate of change 5% or more but less than 10% ×: Rate of change 10% or more

<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 thus 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 coating was then heat-treated using a hot plate at 70° C. for 100 seconds.
The resulting coating was then exposed to 365 nm wavelength light (exposure dose 3000 J/m 2 ) through a mask having a 1.2 μm square island pattern using an i-line stepper exposure system FPA-3000 i4 ( ^Canon ). The exposed coating was then developed using a developer (Act-8, Tokyo Electron Ltd.). A 0.1 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 resulting pattern was observed (magnification: 20,000x) using a scanning electron microscope (SEM) (S-8820, Hitachi High-Technologies Corporation), and residue was evaluated. The evaluation criteria are as follows: ◯ and △ are practically usable.
◯: No residue in non-image areas between patterns
△: Residues with a maximum length of less than 0.10 μm are observed in the non-image areas between the patterns. ×: Residues with a maximum length of 0.10 μm or more are observed in the non-image areas between the patterns.

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

From the results in the above table, the photosensitive coloring compositions of Examples 99 to 231 exhibited good color characteristics 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 color properties as a cyan color.
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.

<Production of Color Filters>
Next, on a silicon wafer substrate with a spin coater, the colorant used in the photosensitive coloring composition (R-1), C. I. Pigment Red 122 14.0 parts was replaced with a photosensitive red coloring composition prepared in the same manner as in Example 78, except that a colored coating was formed. Next, the coating was irradiated with 3000 J / m ² ultraviolet light using an ultra-high pressure mercury lamp through a photomask. Then, an alkaline developer (0.05% by mass tetramethylammonium hydroxide aqueous solution) was spray-developed to remove the unexposed portions, and then washed with ion-exchanged water, and the substrate was heated at 230 ° C. for 5 minutes to form a magenta color filter segment.

Similarly, on a silicon wafer substrate with a spin coater, the colorant used in the photosensitive coloring composition (R-1), C. I. Pigment Yellow 185 14.0 parts was replaced with a photosensitive yellow coloring composition prepared in the same manner as in Example 78, except that a colored coating was formed by applying the composition. Next, the coating was irradiated with 3000 J / m ² ultraviolet light using an ultra-high pressure mercury lamp through a photomask. Then, an alkaline developer (0.05% by mass tetramethylammonium hydroxide aqueous solution) was spray-developed to remove the unexposed portions, and then washed with ion-exchanged water. The substrate was heated at 230 ° C. for 5 minutes to form a yellow color filter segment, and a color filter was obtained.

Similarly, a photosensitive coloring composition (R-6) was applied to a silicon wafer substrate with a spin coater to form a colored coating. Next, the coating was irradiated with 3000 J/ ^m2 ultraviolet light using an ultra-high pressure mercury lamp through a photomask. Next, the unexposed portions were removed by spray development using an alkaline developer consisting of a 0.05% by mass aqueous solution of tetramethylammonium hydroxide, and then washed with ion-exchanged water. The substrate was heated at 230 ° C. for 5 minutes to form a cyan color filter segment, and a color filter was obtained.

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 (8)

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):
(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 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. _R1 and _R2 may be directly bonded to form a cyclic structure. _{R3 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. R4 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 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.

(M2 _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 _M2 .
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. 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. 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. 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. The photosensitive coloring composition for a cyan color filter according to claim 4 , further comprising a binder resin. 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 . A display device comprising the color filter according to claim 6 . A solid-state imaging device comprising the color filter according to claim 6 .