KR20240007902A - compound - Google Patents

Abstract

[식 (I) 중, T¹ 및 T²는, 서로 독립적으로, 치환기를 갖고 있어도 되는 2가의 방향족 탄화수소기 또는 치환기를 갖고 있어도 되는 2가의 방향족 복소환기를 나타내고, L¹은, 치환기를 갖고 있어도 되는 탄소수 1∼12의 a가의 지방족 탄화수소기 또는 식 (i)로 나타내어지는 기를 나타내고, 당해 지방족 탄화수소기에 포함되는 메틸렌기의 적어도 1개는 -O-에 의해 치환되어 있고, a는 2 이상의 정수를 나타낸다.]

[식 (i) 중, T³은, 치환기를 갖고 있어도 되는 a가의 방향족 탄화수소기 또는 치환기를 갖고 있어도 되는 a가의 방향족 복소환기를 나타내고, L²는, 치환기를 갖고 있어도 되는 탄소수 1∼5의 2가의 지방족 탄화수소기를 나타내고, 당해 지방족 탄화수소기에 포함되는 메틸렌기의 적어도 1개는 -O-에 의해 치환되어 있다.]The object is to provide a compound capable of forming a color filter with excellent brightness. The above problem is solved by the compound represented by formula (I).

[In formula (I), T ¹ and T ² independently represent a divalent aromatic hydrocarbon group that may have a substituent or a divalent aromatic heterocyclic group that may have a substituent, and L ¹ may have a substituent. represents an a-valent aliphatic hydrocarbon group having 1 to 12 carbon atoms or a group represented by formula (i), at least one methylene group contained in the aliphatic hydrocarbon group is substituted with -O-, and a is an integer of 2 or more. indicates.]

[In formula (i), T ³ represents an a-valent aromatic hydrocarbon group which may have a substituent or an a-valent aromatic heterocyclic group which may have a substituent, and L ² represents 2 of 1 to 5 carbon atoms which may have a substituent. Represents an aliphatic hydrocarbon group, and at least one methylene group included in the aliphatic hydrocarbon group is substituted with -O-.]

Description

compound

The present invention relates to compounds, colored resin compositions, color filters, and display devices.

Color filters used in display devices such as liquid crystal displays, electroluminescence displays, and plasma displays, and solid-state imaging devices such as CCD and CMOS sensors are manufactured from colored resin compositions. As a colored resin composition for forming the color filter, various colorants are used, and examples of using compounds represented by the following formula (x1) or (x2) as the colorant, for example, are known (Patent Document 1).

[Formula 1]

Japanese Patent Laid-Open No. 2014-108975

However, the color filter formed from the colored resin composition containing the above compound sometimes does not have sufficiently satisfactory brightness. Therefore, the object of the present invention is to provide a compound capable of forming a color filter with excellent brightness.

The gist of the present invention is as follows.

[1] A compound represented by formula (I).

[Formula 2]

[In formula (I),

R ¹ to ^{R 4} and R ¹³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent.

R ⁵ to ^{R 12} each independently represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 5 carbon atoms which may have a substituent.

T ¹ and T ² independently represent a divalent aromatic hydrocarbon group that may have a substituent or a divalent aromatic heterocyclic group that may have a substituent.

L ¹ represents an a-valent aliphatic hydrocarbon group having 1 to 12 carbon atoms or a group represented by formula (i), which may have a substituent, and at least one methylene group contained in the aliphatic hydrocarbon group is substituted with -O- there is.

a represents an integer of 2 or more.

b and c independently represent an integer of 1 or more.

d represents an integer greater than or equal to 0.

X ^c- represents a c-valent anion.]

[Formula 3]

[In equation (i),

T ³ represents an a-valent aromatic hydrocarbon group which may have a substituent or an a-valent aromatic heterocyclic group which may have a substituent.

L ² represents a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a substituent, and at least one methylene group contained in the aliphatic hydrocarbon group is substituted with -O-.

* indicates the binding hand with T ^2. ]

[2] A colored resin composition containing a colorant and a resin, wherein the colorant contains the compound according to [1].

[3] The colored resin composition according to [2], further comprising a polymerizable compound and a polymerization initiator.

[4] A color filter formed from the colored resin composition according to [2] or [3].

[5] A display device including the color filter described in [4].

According to the present invention, a compound capable of forming a color filter with excellent brightness can be provided.

< Compound >

The compound of the present invention is a compound represented by formula (I) (hereinafter sometimes referred to as compound (I)). Hereinafter, the present invention will be described in detail using formula (I), but compound (I) also includes tautomers of formula (I).

[Formula 4]

[In formula (I),

R ¹ to ^{R 4} and R ¹³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent.

R ⁵ to ^{R 12} each independently represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 5 carbon atoms which may have a substituent.

T ¹ and T ² independently represent a divalent aromatic hydrocarbon group that may have a substituent or a divalent aromatic heterocyclic group that may have a substituent.

L ¹ represents an a-valent aliphatic hydrocarbon group having 1 to 12 carbon atoms or a group represented by formula (i), which may have a substituent, and at least one methylene group contained in the aliphatic hydrocarbon group is substituted with -O- there is.

a represents an integer of 2 or more.

b and c independently represent an integer of 1 or more.

d represents an integer greater than or equal to 0.

X ^c- represents a c-valent anion.]

[Formula 5]

[In equation (i),

T ³ represents an a-valent aromatic hydrocarbon group which may have a substituent or an a-valent aromatic heterocyclic group which may have a substituent.

L ² represents a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a substituent, and at least one methylene group contained in the aliphatic hydrocarbon group is substituted with -O-.

a has the same meaning as above.

* indicates the binding hand with T ^2. ]

Examples of the hydrocarbon group having 1 to 10 carbon atoms represented by R ¹ to R ⁴ and R ¹³ include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be saturated or unsaturated, and may be linear or alicyclic.

Examples of the saturated or unsaturated chain hydrocarbon groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-de. Straight-chain alkyl groups such as actual groups; Isopropyl group, (1-ethyl)propyl group, isobutyl group, sec-butyl group, tert-butyl group, (1-ethyl)butyl group, (2-ethyl)butyl group, (1-propyl)butyl group, Isopentyl group, neopentyl group, tert-pentyl group, (2-methyl)pentyl group, (1-ethyl)pentyl group, (3-ethyl)pentyl group, (1-propyl)pentyl group, (1-butyl) Pentyl group, isohexyl group, (2-methyl)hexyl group, (5-methyl)hexyl group, (2-ethyl)hexyl group, (1-butyl)hexyl group, (2-methyl)heptyl group, (2- Branched chain alkyl groups such as ethyl)heptyl group, (3-ethyl)heptyl group, (2-methyl)octyl group, and (2-ethyl)octyl group; Vinyl group, 1-propenyl group, 2-propenyl group (allyl group), (1-methyl)ethenyl group, 2-butenyl group, 3-butenyl group, 1,3-butadienyl group, (1-(2 Alkenyl groups such as -propenyl))ethenyl group, (1,2-dimethyl)propenyl group, and 2-pentenyl group; etc. can be mentioned.

Examples of the saturated or unsaturated alicyclic hydrocarbon group include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group; Cycloalkenyl groups such as cyclohexenyl group (e.g., cyclohexa-2-ene, cyclohexa-3-ene), cycloheptenyl group, and cyclooctenyl group; Norbornyl group, adamantyl group, bicyclo[2.2.2]octyl group, etc. can be mentioned.

Examples of aromatic hydrocarbon groups include aryl groups such as phenyl group, 1-naphthyl group, and 2-naphthyl group; o-tolyl group, m-tolyl group, p-tolyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group , 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethylphenyl group, 2-methyl-6-ethylphenyl group, 2,6-diethylphenyl group, o- Isopropylphenyl group, m-isopropylphenyl group, p-isopropylphenyl group, 2-methyl-6-isopropylphenyl group, 4-butylphenyl group, o-tert-butylphenyl group, m-tert-butylphenyl group, p-tert-butyl Alkylaryl groups such as phenyl groups; Alkenyl aryl groups such as 4-vinylphenyl group; etc. can be mentioned.

The hydrocarbon group having 1 to 10 carbon atoms may be a combination of two or more of the chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups listed above, as long as the upper limit of the carbon number is 10. Such groups include, for example, aralkyl groups such as benzyl group, phenethyl group, and 1-methyl-1-phenylethyl group; Arylalkenyl groups such as phenylethenyl group (phenylvinyl group); Arylalkynyl groups such as phenylethynyl group; 1-methylcyclopropyl group, 1-methylcyclohexyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 1,2-dimethylcyclohexyl group, 1,3-dimethylcyclo Hexyl group, 1,4-dimethylcyclohexyl group, 2,3-dimethylcyclohexyl group, 2,4-dimethylcyclohexyl group, 2,5-dimethylcyclohexyl group, 2,6-dimethylcyclohexyl group, 3, 4-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, 2,2-dimethylcyclohexyl group, 3,3-dimethylcyclohexyl group, 4,4-dimethylcyclohexyl group, 2,4,6-trimethyl an alicyclic hydrocarbon group bonded to one or more alkyl groups or alicyclic hydrocarbon groups such as cyclohexyl group, 2,2,6,6-tetramethylcyclohexyl group, and 3,3,5,5-tetramethylcyclohexyl group; An alkyl group bonded to one or more alicyclic hydrocarbon groups such as cyclopropylmethyl group, cyclopropylethyl group, cyclobutylmethyl group, cyclobutylethyl group, cyclopentylmethyl group, cyclopentylethyl group, cyclohexylmethyl group, 2-methylcyclohexylmethyl group, and cyclohexylethyl group; etc. can be mentioned.

Substituents that the hydrocarbon group having 1 to 10 carbon atoms may have (hereinafter sometimes referred to as substituent A) include halogen atom, hydroxy group, alkoxy group, formyl group, substituted or unsubstituted amino group, nitro group, cyano group, - SO ₃ ^- and -SO ₃ M may be at least one selected from the group consisting of M, where M represents a hydrogen atom or an alkali metal atom.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the alkoxy group include alkoxy groups having 1 to 4 carbon atoms, such as methoxy group, ethoxy group, propoxy group, and butoxy group.

Examples of the substituted amino group include an amino group having one or two hydrocarbon groups, and examples of the hydrocarbon group include groups exemplified as the above-mentioned hydrocarbon groups having 1 to 10 carbon atoms. Examples of substituted amino groups include N-methylamino group, N,N-dimethylamino group, N-ethylamino group, N,N-diethylamino group, N-propylamino group, N,N-dipropylamino group, and N-isopropyl. Amino group, N,N-diisopropylamino group, N-phenylamino group, N,N-diphenylamino group, N,N-ethylmethylamino group, N,N-methylphenylamino group, N,N-ethylphenylamino group, etc. there is.

Examples of the alkali metal atom include sodium and potassium.

Examples of the halogen atom represented by R ⁵ to ^{R 12} include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the hydrocarbon group having 1 to 5 carbon atoms represented by R ⁵ to ^{R 12} include aliphatic hydrocarbon groups having 1 to 5 carbon atoms, and specifically, the aliphatic hydrocarbon groups as R ¹ to R ⁴ and R ¹³ above. Among the groups, groups having 1 to 5 carbon atoms can be mentioned.

Examples of the substituent that the hydrocarbon group having 1 to 5 carbon atoms may have include the group exemplified as substituent A.

The divalent aromatic hydrocarbon group represented by T ¹ and T ² is a group in which, in an aromatic hydrocarbon ring, two hydrogen atoms directly bonded to the carbon atoms constituting the ring are replaced by bond hands. The aromatic hydrocarbon ring constituting the divalent aromatic hydrocarbon group may be either a mono-ring or a condensed ring, for example, a benzene ring, a naphthalene ring, an anthracene ring, and structures in which at least one hydrogen atom of these aromatic hydrocarbon rings is replaced by a hydrocarbon group, etc. can be mentioned. The hydrocarbon group includes groups exemplified as hydrocarbon groups having 1 to 10 carbon atoms represented by R ¹ to R ⁴ and R ¹³ , and is preferably a saturated chain hydrocarbon group, an aryl group, or an alkylaryl group, More preferably, it is a saturated chain hydrocarbon group having 1 to 4 carbon atoms. The number of hydrocarbon groups bonded to the aromatic hydrocarbon ring is preferably 0 to 4, and more preferably 0 to 3. Specific examples of the divalent aromatic hydrocarbon group include groups represented by the following formulas (Ta-1) to (Ta-8).

[Formula 6]

The divalent aromatic heterocyclic group represented by T ¹ and T ² is a group in which, in an aromatic heterocycle, two hydrogen atoms directly bonded to the atoms constituting the ring are replaced with bonding hands. The aromatic heterocycle constituting the divalent aromatic heterocyclic group may be either a monocyclic ring or a condensed ring, for example, a pyrrole ring, an oxazole ring, a pyrazole ring, an imidazole ring, a thiazole ring, a furan ring, a thiophene ring, and a pyridine ring. rings, pyrimidine rings, pyridazine rings, pyrazine rings, indole rings, benzimidazole rings, benzothiazole rings, quinoline rings, benzofuran rings, and structures in which at least one hydrogen atom of these aromatic heterocycles is replaced with a hydrocarbon group, etc. can be mentioned. The hydrocarbon group includes groups exemplified as hydrocarbon groups having 1 to 10 carbon atoms represented by R ¹ to R ⁴ and R ¹³ , and is preferably a saturated chain hydrocarbon group, an aryl group, or an alkylaryl group. The number of hydrocarbon groups bonded to the aromatic heterocycle is preferably 0 to 4, and more preferably 0 to 3.

Examples of the substituent that the divalent aromatic hydrocarbon group and the divalent aromatic heterocyclic group may have include the group exemplified as substituent A.

The a-valent aliphatic hydrocarbon group having 1 to 12 carbon atoms represented by L ¹ is a group in which a number of hydrogen atoms constituting the aliphatic hydrocarbon are replaced by bond hands. It is preferable that a number of bonding hands exist on different carbon atoms. Examples of the a-valent aliphatic hydrocarbon group include an a-valent chain hydrocarbon group, an a-valent alicyclic hydrocarbon group, and an a-valent group combining an a-valent alicyclic hydrocarbon group and an alicyclic hydrocarbon group.

The a-valent chain hydrocarbon group may be saturated or unsaturated, but is preferably an a-valent saturated chain hydrocarbon group. Examples of a-valent saturated chain hydrocarbon groups include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, and hexane. Alkanediyl groups such as -1,6-diyl group; Alkantriyl groups such as groups represented by the following formulas (a-1) to (a-2); alkanetetrayl groups such as groups represented by the following formula (a-3); etc. can be mentioned. The a-valent chain hydrocarbon group preferably has 1 to 8 carbon atoms, and more preferably 2 to 6 carbon atoms.

[Formula 7]

The a-valent alicyclic hydrocarbon group may be saturated or unsaturated, but it is preferable that it is an a-valent saturated alicyclic hydrocarbon group. Examples of the a-valent saturated alicyclic hydrocarbon group include divalent saturated alicyclic hydrocarbon groups such as cyclohexyl-1,2-diyl group, cyclohexyl-1,4-diyl group, and norbornane-2,5-diyl group; trivalent saturated alicyclic hydrocarbon groups such as cyclohexyl-1,3,5-triyl group; tetravalent saturated alicyclic hydrocarbon groups such as cyclohexyl-1,2,4,5-tetrayl group; etc. can be mentioned. The a-valent alicyclic hydrocarbon group preferably has 3 to 10 carbon atoms, and more preferably 3 to 6 carbon atoms.

Examples of a-valent groups obtained by combining a chain hydrocarbon group and an alicyclic hydrocarbon group include groups represented by the following formulas (a-5) to (a-7).

[Formula 8]

At least one methylene group contained in the a-valent aliphatic hydrocarbon group having 1 to 12 carbon atoms represented by L ¹ is substituted with -O-. However, none of the adjacent methylene groups are substituted with -O-. The number of methylene groups substituted by -O- is, for example, 1 to 6, but is preferably 1 or more and a or less, and more preferably a. The position of the methylene group substituted by -O- is not particularly limited, but it is preferable that at least one of the methylene groups adjacent to the bond held by the a-valent aliphatic hydrocarbon group is substituted with -O-, and the a-valent aliphatic hydrocarbon group has It is more preferable that all of the methylene groups adjacent to the bonding hand are substituted with -O-.

Groups in which at least one methylene group contained in an a-valent aliphatic hydrocarbon group is substituted with -O- specifically include groups represented by the following formulas (l-1a) to (l-24a), and the formula (l- Groups represented by 1a) to (l-16a), (l-18a) to (l-19a), and (l-22a) to (l-24a) are preferred, and groups represented by formulas (l-1a) and (l-10a) are preferred. ) to (l-16a), (l-18a) to (l-19a), (l-22a) to (l-24a) are more preferable, and the formulas (l-10a) to (l-16a) ) is more preferable.

[Formula 9]

Examples of the substituent that the a-valent aliphatic hydrocarbon group having 1 to 12 carbon atoms may have include the group exemplified as substituent A.

L ¹ is also the contribution represented by equation (i).

In formula (i), the a-valent aromatic hydrocarbon group represented by T ³ is a group in which, in an aromatic hydrocarbon ring, a number of hydrogen atoms directly bonded to the carbon atoms constituting the ring are replaced by bond hands. Examples of the aromatic hydrocarbon ring constituting the a-valent aromatic hydrocarbon group include the structures described above as the aromatic hydrocarbon ring constituting the divalent aromatic hydrocarbon group.

In formula (i), the a-valent aromatic heterocyclic group represented by T ³ is a group in which a hydrogen atom directly bonded to an atom constituting the ring in an aromatic heterocycle is replaced with a bond hand. Examples of the aromatic heterocycle constituting the a-valent aromatic heterocyclic group include the structures described above as the aromatic heterocycle constituting the divalent aromatic heterocyclic group.

Substituents that the a-valent aromatic hydrocarbon group and the a-valent aromatic heterocyclic group may have include the group exemplified as substituent A.

In formula (i), examples of the divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by L ² include a divalent chain hydrocarbon group having 1 to 5 carbon atoms and a divalent alicyclic hydrocarbon group having 1 to 5 carbon atoms.

The divalent chain hydrocarbon group may be saturated or unsaturated, but is preferably a divalent saturated chain hydrocarbon group. Examples of divalent saturated chain hydrocarbon groups include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, and pentane-1,5-diyl group. One example is Alkandi Diary.

The divalent alicyclic hydrocarbon group may be saturated or unsaturated, but is preferably a divalent saturated alicyclic hydrocarbon group. Examples of the divalent saturated alicyclic hydrocarbon group include cyclopropyl-1,2-diyl group and cyclobutyl-1,3-diyl group.

At least one methylene group contained in the divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by L ² is substituted with -O-. However, not all adjacent methylene groups are substituted with -O-. The number of methylene groups substituted by -O- is, for example, 1 to 3, and is preferably 1 to 2. The position of the methylene group substituted with -O- is not particularly limited, but it is preferable that the methylene group adjacent to the bond hand with T ² is substituted with -O-.

Groups in which at least one methylene group contained in a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms is substituted with -O- include groups represented by the following formulas (l-1b) to (l-12b), , Among them, groups represented by formulas (l-2b) to (l-5b) are preferable.

[Formula 10]

[In the formula, * represents a bond with T ² and ** represents a bond with T ^3. ]

Examples of the substituent that the divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms may have include the group exemplified as substituent A.

Specific examples of the group represented by formula (i) include groups represented by the following formulas (i1) to (i8).

[Formula 11]

[In formulas (i1) to (i8), L ⁱ¹ to L ⁱ⁸ each independently represent an alkanediyl group having 1 to 5 carbon atoms, and one methylene group contained in the alkanediyl group is substituted by -O- It is done. * indicates the binding hand with T ^2. ]

The position of the methylene group substituted with -O- is not particularly limited, but it is preferable that the methylene group adjacent to the bond hand with T ² is substituted with -O-.

A plurality of L ⁱ¹ to ^{L i8} may be the same or different, but they are preferably the same.

Examples of the c ^- valent anion represented by Anions, fluorine-containing anions, and anions containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and oxygen as essential elements can be mentioned.

Examples of the boron-containing anion and aluminum-containing anion include an anion represented by the following formula (4).

[Formula 12]

[In formula (4), W ¹ and W ² each independently represent a group having two substituents formed by releasing a proton from a monovalent proton donating substituent. M represents boron or aluminum.]

Groups having two substituents formed by releasing a proton from a monovalent proton donating substituent include compounds having at least two monovalent proton donating substituents (for example, hydroxy groups, carboxylic acid groups, etc.), each having two proton donating substituents. A group formed by releasing a proton from a group may be mentioned. The compounds include catechol which may have a substituent, 2,3-dihydroxynaphthalene which may have a substituent, 2,2'-biphenol which may have a substituent, and 3-hydroxy-2 which may have a substituent. -Naphthoic acid, 2-hydroxy-1-naphthoic acid, which may have a substituent, 1-hydroxy-2-naphthoic acid, which may have a substituent, binaphthol which may have a substituent, salicylic acid, which may have a substituent It is preferable that it is benzilic acid, which may have a substituent, or mandelic acid, which may have a substituent.

In the above example compounds, substituents include saturated hydrocarbon groups (eg, alkyl groups, cycloalkyl groups, etc.), halogen atoms, haloalkyl groups, hydroxy groups, amino groups, nitro groups, alkoxy groups, etc.

Salicylic acids that may have substituents include salicylic acid, 3-methylsalicylic acid, 3-tert-butylsalicylic acid, 3-methoxysalicylic acid, 3-nitrosalicylic acid, 4-trifluoromethylsalicylic acid, and 3,5-di-tert-butyl. Monoaminosalicylic acids such as salicylic acid, 3-aminosalicylic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, and 6-aminosalicylic acid; 3-hydroxysalicylic acid (2,3-dihydroxybenzoic acid), 4-hydroxysalicylic acid (2,4-dihydroxybenzoic acid), 5-hydroxysalicylic acid (2,5-dihydroxybenzoic acid), 6- Monohydroxysalicylic acids such as hydroxysalicylic acid (2,6-dihydroxybenzoic acid); Dihydroxysalicylic acids such as 4,5-dihydroxysalicylic acid and 4,6-dihydroxysalicylic acid; Monohalosalicylic acids such as 3-chlorosalicylic acid, 4-chlorosalicylic acid, 5-chlorosalicylic acid, 6-chlorosalicylic acid, 3-bromosalicylic acid, 4-bromosalicylic acid, 5-bromosalicylic acid, and 6-bromosalicylic acid; Dihalosalicylic acids such as 3,5-dichlorosalicylic acid, 3,5-dibromosalicylic acid, and 3,5-diiodosalicylic acid; Trihalosalicylic acids such as 3,5,6-trichlorosalicylic acid; etc. can be mentioned.

As benzyl acid which may have a substituent,

[Formula 13]

As mandelic acid which may have a substituent,

[Formula 14]

etc. can be mentioned.

Preferred anions among the anions represented by formula (4) include anions represented by the following formulas, anions (BC-1) to anions (BC-24) having substituents shown in the table, and anions (BC-24), each of which has the formula Examples include anions (BC-25) to anions (BC-28) represented by (BC-25), formula (BC-26), formula (BC-27), and formula (BC-28).

[Formula 15]

[Table 1]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

From the viewpoint of solubility in organic solvents, the anions represented by formula (4) include anion (BC-1), anion (BC-2), anion (BC-3), and anion (BC-25). ), anion (BC-26), and anion (BC-27) are preferred, and anion (BC-1), anion (BC-2), and anion (BC-25) are more preferred, and anion (BC-25) is more preferred. On (BC-1) and anion (BC-2) are more preferred.

Examples of fluorine-containing anions include groups represented by the following formulas (6), (7), (8), and (9).

[Formula 20]

[In formula (6), W ³ and W ⁴ each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms, or W ³ and W ⁴ together represent a fluorinated alkane group having 1 to 4 carbon atoms. Indicates diary.]

[Formula 21]

[In formula (7), W ⁵ to W ⁷ each independently represent a fluorine atom or a fluoroalkyl group having 1 to 4 carbon atoms.]

[Formula 22]

[In formula (8), Y ¹ represents a fluorinated alkanediyl group having 1 to 4 carbon atoms.]

[Formula 23]

[In formula (9), Y ² represents a fluoroalkyl group having 1 to 4 carbon atoms.]

In formulas (6), (7) and (9), a perfluoroalkyl group is preferable as the fluoroalkyl group having 1 to 4 carbon atoms. Examples of the perfluoroalkyl group include -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , -CF(CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , -CF ₂ CF(CF ₃ ) ₂ , -C(CF ₃ ) ₃ , etc.

In formulas (6) and (8), perfluoroalkanediyl group is preferable as the fluorinated alkanediyl group having 1 to 4 carbon atoms. Examples of perfluoroalkanediyl groups include -CF ₂ -, -CF ₂ CF ₂ -, -CF ₂ CF ₂ CF ₂ -, -C(CF ₃ ) ₂ -, -CF ₂ CF 2 CF _{2 CF 2} -, etc. there is.

The anion represented by formula (6) (hereinafter sometimes referred to as “anion (6)”) is an anion represented by formula (6-1) to formula (6-6), respectively (hereinafter referred to as “anion (6)”). (sometimes referred to as “on (6-1)” to “anion (6-6)”).

[Formula 24]

An anion (sometimes referred to as “anion (7)” hereinafter) represented by formula (7) includes anion (7-1) represented by the formula below.

[Formula 25]

An anion represented by formula (8) (hereinafter sometimes referred to as “anion (8)”) is an anion represented by formulas (8-1) to (8-4), respectively (hereinafter referred to as “anion (8-1)” to “sometimes referred to as anion (8-4)”).

[Formula 26]

The anion represented by formula (9) (hereinafter sometimes referred to as “anion (9)”) is an anion represented by formulas (9-1) to (9-4), respectively (hereinafter referred to as “anion (9-1)” to “sometimes referred to as anion (9-4)”).

[Formula 27]

The ^c- valent anion represented by anion), the solubility of compound (I) in an organic solvent can be improved. Among them, anion (6-1), anion (6-2), and anion (7-1) are preferable, and anion (6-2) is especially preferable.

Examples of the c ^- valent anion represented by Anions of heteropoly acids or isopoly acids are preferred, and anions of phosphotungstic acid, silicotungstic acid, and tungsten-based isopoly acids are more preferred.

Examples of the anions of heteropolyacids or isopolyacids containing tungsten as an essential element include Keggin-type phosphotungstic acid ion α-[PW ₁₂ O ₄₀ ] ^3- and Dawson-type phosphotungstic acid ion α-[P. ₂ W ₁₈ O ₆₂ ] ^6- , β-[P ₂ W ₁₈ O ₆₂ ] ^6- , Keggin type silicotungstate ion α-[SiW ₁₂ O ₄₀ ] ^4- , β-[SiW ₁₂ O ₄₀ ] ^4- , γ-[SiW ₁₂ O ₄₀ ] ^4- , and other examples include [P ₂ W ₁₇ O ₆₁ ] ^10- , [P ₂ W ₁₅ O ₅₆ ] ^12- , [H ₂ P ₂ W ₁₂ O ₄₈ ] ^12- , [NaP ₅ W ₃₀ O ₁₁₀ ] ^14- , α-[SiW ₉ O ₃₄ ] ^10- , γ-[SiW ₁₀ O ₃₆ ] ^8- , α-[SiW ₁₁ O ₃₉ ] ^8- , β-[SiW ₁₁ O ₃₉ ] ^8- , [W ₆ O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- , WO ₄ ^2- , etc.

Moreover, among anions other than the anions of heteropoly acid or isopoly acid containing tungsten as an essential element, an anion consisting of oxygen and at least one element selected from the group consisting of silicon and phosphorus is preferable.

Examples of such anions consisting of oxygen and at least one element selected from the group consisting of silicon and phosphorus include SiO ₃ ^2- and PO ₄ ^3- .

In particular, due to ease of synthesis and post-processing, heteropolyacid anions such as Keggin-type phosphotungstate ion, Dawson-type phosphotungstate ion, and Keggin-type silicotungstate ion, and isopolyacid anion such as [W ₁₀ O ₃₂ ] ^4- . This is desirable.

In formula (I), a plurality of R ¹ to R ¹³ , T ¹ , T ² , and L ¹ may be the same or different, but are preferably the same. Moreover, in formula (i), a plurality of L ² may be the same or different, but it is preferable that they are the same.

R ¹ to ^{R 4} are each independently a saturated chain hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, an aryl group having 6 to 10 carbon atoms which may have a substituent, or a C 7 to 10 group which may have a substituent. It is preferable that it is an alkylaryl group.

In particular, R ¹ and R ³ are each independently an aryl group having 6 to 10 carbon atoms which may have a substituent, or an alkylaryl group having 7 to 10 carbon atoms which may have a substituent, and R ² and R ⁴ are , each independently, is preferably a saturated chain hydrocarbon group having 1 to 10 carbon atoms which may have a substituent,

It is more preferable that R ¹ and R ³ are each independently a phenyl group which may have a substituent, and R ² and R ⁴ are each independently a saturated chain hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. ,

R ¹ and R ³ are each independently a phenyl group that may have a substituent, and has an alkyl group of 1 to 4 carbon atoms in at least one of the two bonding positions ortho to N bonded to the phenyl group. It is more preferable that R ² and R ⁴ are each independently a saturated chain hydrocarbon group having 1 to 6 carbon atoms which may have a substituent.

R ¹ and R ³ are each independently a phenyl group which may have a substituent, and which has an alkyl group of 1 to 4 carbon atoms at at least one of the two bonding positions ortho to N bonded to the phenyl group, Moreover, it is more preferable that R ² and R ⁴ are each independently a saturated chain hydrocarbon group having 2 to 6 carbon atoms which may have a substituent.

R ¹ and R ³ are each independently a phenyl group that may have a substituent, each having an alkyl group of 1 to 3 carbon atoms at two bonding positions ortho to N bonded to the phenyl group, and It is particularly preferable that R ² and R ⁴ each independently represent a saturated chain hydrocarbon group having 2 to 6 carbon atoms which may have a substituent.

Here, the substituents that the phenyl group may have include an alkyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxy group, an alkoxy group, a formyl group, a substituted or unsubstituted amino group, a nitro group, a cyano group, -SO ₃ ^- , and -SO ₃ M (M is the same as above); and at least one selected from the group consisting of, among others, an alkyl group having 1 to 4 carbon atoms, a halogen atom, an alkoxy group, and -SO ₃ ^- . At least one or more is preferable, and at least one or more selected from the group consisting of an alkyl group with 1 to 4 carbon atoms, an alkoxy group with 1 to 4 carbon atoms, and -SO ₃ ^- is more preferable.

In particular, when the phenyl group has an alkoxy group (preferably a methoxy group) as a substituent, the brightness of the resulting color filter can be further increased. The substitution position of the alkoxy group (preferably a methoxy group) is not particularly limited, but the effect can be further enhanced by bonding to a position para to N bonded to the phenyl group.

In the preferred embodiment of the above R ¹ to ^{R 4} , it is particularly preferred that R ¹ and R ³ each independently represent any of the groups represented by formulas (r1) to (r3). Additionally, one or more of the hydrogen atoms of the groups represented by formulas (r1) to (r3) may be substituted with -SO ₃ ^- .

[Formula 28]

[In the formula, R ^r1 to ^{R r4} each independently represent an alkyl group having 1 to 4 carbon atoms. * indicates a combined hand.]

R ^r1 to R ^r4 are preferably methyl groups.

R ⁵ to ^{R 12} are preferably hydrogen atoms.

R ¹³ is preferably a hydrocarbon group having 1 to 6 carbon atoms, which may have a hydrogen atom or a substituent, and more preferably a saturated chain hydrocarbon group having 1 to 6 carbon atoms, which may have a hydrogen atom or a substituent. is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group.

T ¹ is preferably a divalent aromatic hydrocarbon group that may have a substituent, and the aromatic hydrocarbon ring constituting the divalent aromatic hydrocarbon group is a benzene ring, a naphthalene ring, or at least one hydrogen atom of these rings has 1 to 10 carbon atoms. It is preferable that the structure is substituted with saturated chain hydrocarbon groups (preferably 1 to 4). As T ¹ , any of the groups represented by the above formulas (Ta-1) to (Ta-8) is more preferable, and the group represented by the above formulas (Ta-8) is particularly preferable.

T ² is preferably a divalent aromatic hydrocarbon group that may have a substituent, and the aromatic hydrocarbon ring constituting the divalent aromatic hydrocarbon group is a benzene ring, a naphthalene ring, or at least one hydrogen atom of these rings has 1 to 10 carbon atoms. It is preferable to have a structure in which the benzene ring or at least one hydrogen atom of the benzene ring is substituted with a saturated chain hydrocarbon group having 1 to 4 carbon atoms. As T ² , it is more preferable to be any of the groups represented by the following formulas (Tb-1) to (Tb-10), and (Tb-3), (Tb-5), (Tb-6), More preferably, it is any of the groups represented by (Tb-9) and (Tb-10), and the following formulas (Tb-5), (Tb-6), (Tb-9), (Tb-10) Any of the groups represented by is particularly preferable.

[Formula 29]

[In the formula, * represents a bond with L ¹ and ** represents a bond with a nitrogen atom.]

In formula (i), T ³ is an a-valent aromatic hydrocarbon group that may have a substituent, L ² is a divalent saturated chain hydrocarbon group having 1 to 5 carbon atoms, and at least one methylene group contained in the saturated chain hydrocarbon group is A group substituted by -O- is preferable, any of the groups represented by the formulas (i1) to (i8) is more preferable, and a group represented by the formula (i2) or (i3) is more preferable, Any of the groups represented by the following formulas (i-1) to (i-6) is particularly preferable.

[Formula 30]

[In the formula, * represents the bond with T ² .]

L ¹ is an a-valent aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, and at least one methylene group contained in the aliphatic hydrocarbon group is substituted with -O-, or a group of the above formula (i1) It is preferable that it is any of the groups represented by ~(i8),

A saturated a-valent chain hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, where at least one methylene group contained in the aliphatic hydrocarbon group is substituted with -O-, or a group of the above formula (i2) or formula ( The group represented by i3) is more preferable,

A saturated a-valent chain hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, where at least one methylene group contained in the aliphatic hydrocarbon group is substituted with -O-, or a group of the above formula (i-1) - Which of the groups represented by (i-6) is more preferable,

Any of the groups represented by the above formulas (l-10a) to (l-16a) or formulas (i-1) to (i-6) is particularly preferable.

The ^c- valent anion represented by More preferably, it is a halide ion or an anion of a heteropoly acid or isopoly acid containing tungsten as an essential element, and a halide ion, a Keggin-type phosphotungstic acid ion, or a Dawson-type phosphotungstic acid ion is more preferable.

The substituent (i.e., substituent A) of compound (I) is at least one selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group, a substituted or unsubstituted amino group, -SO ₃ ^- , and -SO ₃ M. Preferred, more preferably at least one selected from the group consisting of a halogen atom, an alkoxy group, -SO ₃ ^- , and -SO ₃ M.

a is preferably an integer of 2 or more and 6 or less, more preferably an integer of 2 or more and 4 or less, and still more preferably 2 or 3.

c is usually 1 to 14, preferably 1 to 12, more preferably 1 to 10, further preferably 1 to 6, and especially preferably 1 to 4.

b and d are determined depending on a, c, and the number of -SO ₃ ^- (hereinafter sometimes referred to as e) that compound (I) has as a substituent, and are generally It is adjusted so that the charge becomes 0. Therefore, usually a to d in formula (I) satisfy the relationship of formula (z) below.

[In the above formula, a to d have the same meaning as above. e represents the number of -SO ₃ ^- that compound (I) has as a substituent.]

e is an integer of 0 or more, preferably 0 or more (a+1) or less, more preferably 0 or more and a or less, and still more preferably 0 or a. In particular, when d is 1 or more, it is preferable that e is 0, that is, compound (I) does not have -SO ₃ ^- , and when d is 0, it is preferable that e=a.

In particular, from the viewpoint of heat ^resistance and solvent resistance, A compound with 0 is preferred.

Compound (I) is preferably a compound represented by formula (I-1) or formula (I-2).

[Formula 31]

[In formula (I-1),

R ¹⁰¹ and R ¹⁰³ are each independently a phenyl group which may have a substituent,

R ¹⁰² and R ¹⁰⁴ are each independently a saturated chain hydrocarbon group having 1 to 10 carbon atoms which may have a substituent,

R ¹⁰⁵ to ^{R 112} are hydrogen atoms,

R ¹¹³ is a hydrogen atom or a saturated chain hydrocarbon group having 1 to 6 carbon atoms which may have a substituent,

T ¹⁰¹ and T ¹⁰² are divalent aromatic hydrocarbon groups that may have substituents, and the aromatic hydrocarbon ring constituting the divalent aromatic hydrocarbon group is a benzene ring, a naphthalene ring, or at least one hydrogen atom of these rings has 1 to 4 carbon atoms. It is a structure substituted with a saturated chain hydrocarbon group,

L ¹⁰¹ is a saturated chain hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, and at least one methylene group contained in the aliphatic hydrocarbon group is substituted with -O-, or a group of formula (i) In the group represented by, T ³ is an a101-valent aromatic hydrocarbon group that may have a substituent, L ² is a divalent saturated chain hydrocarbon group having 1 to 5 carbon atoms, and at least one methylene group contained in the saturated chain hydrocarbon group is It is a group substituted by -O-,

a101 is 2 or 3,

d101 represents an integer of 1 or more,

b, c, and X ^c- have the same meaning as above.]

[Formula 32]

[In formula (I-2),

R ²⁰¹ and R ²⁰³ are each independently a phenyl group which may have a substituent,

R ²⁰² and R ²⁰⁴ are each independently a saturated chain hydrocarbon group having 1 to 10 carbon atoms which may have a substituent,

R ²⁰⁵ to ^{R 212} are hydrogen atoms,

R ²¹³ is a hydrogen atom or a saturated chain hydrocarbon group having 1 to 6 carbon atoms which may have a substituent,

T ²⁰¹ and T ²⁰² are divalent aromatic hydrocarbon groups that may have a substituent, and the aromatic hydrocarbon ring constituting the divalent aromatic hydrocarbon group is a benzene ring, a naphthalene ring, or at least one hydrogen atom of these rings has 1 to 4 carbon atoms. It is a structure substituted with a saturated chain hydrocarbon group,

L ²⁰¹ is a saturated chain hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, and at least one methylene group contained in the aliphatic hydrocarbon group is substituted with -O-, or a group of formula (i) In the group represented by, T ³ is an a201-valent aromatic hydrocarbon group that may have a substituent, L ² is a divalent saturated chain hydrocarbon group having 1 to 5 carbon atoms, and at least one methylene group contained in the saturated chain hydrocarbon group is It is a group substituted by -O-,

a201 and e201 are 2 or 3,

In the compound represented by formula (I-2), e201 of the hydrogen atoms of R ²⁰¹ to R ²¹³ , T ²⁰¹ , T ²⁰² , and L ²⁰¹ are substituted with -SO ₃ ^- .]

Substituents that the phenyl group represented by R ¹⁰¹ , R ¹⁰³ , R ²⁰¹ and R ²⁰³ may have include an alkyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxy group, an alkoxy group, formyl group, substituted or unsubstituted amino group, nitro group, and cyanogroup. and -SO ₃ M (M is a hydrogen atom or an alkali metal atom). Among them, an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. At least one selected from the group is preferred. The halogen atom, alkoxy group, substituted amino group, and alkali metal atom are the same as those described for the substituent A.

R ¹⁰¹ , R ¹⁰³ , R ²⁰¹ and R ²⁰³ are phenyl groups that may have substituents, and are at least one (preferably both) of the two bonding positions ortho to N bonded to the phenyl group. It is preferable that it is a group having an alkyl group having 1 to 4 carbon atoms. In particular, it is preferable that R ¹⁰¹ , R ¹⁰³ , R ²⁰¹ and R ²⁰³ each independently represent any of the groups represented by the above formulas (r1) to (r3).

R ¹⁰² , R ¹⁰⁴ , R ²⁰² and R ²⁰⁴ are preferably a saturated chain hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, and more preferably are a saturated chain hydrocarbon group having 2 to 6 carbon atoms. Substituents (hereinafter referred to as substituents B) that the saturated chain hydrocarbon groups represented by R ¹⁰² , R ¹⁰⁴ , R ²⁰² and R ²⁰⁴ may have include a halogen atom, a hydroxy group, an alkoxy group, a formyl group, a substituted or unsubstituted amino group, a nitro group, and at least one selected from the group consisting of a cyano group and -SO ₃ M (M is a hydrogen atom or an alkali metal atom). The halogen atom, alkoxy group, substituted amino group, and alkali metal atom are the same as those described for the substituent A.

Substituents that the saturated chain hydrocarbon group having 1 to 6 carbon atoms represented by R ¹¹³ and R ²¹³ may have include the group described as substituent B.

Examples of the substituent that the divalent aromatic hydrocarbon group represented by T ¹⁰¹ and T ²⁰¹ may have include the group described as substituent B. T ¹⁰¹ and T ²⁰¹ are preferably any of the groups represented by the above formulas (Ta-1) to (Ta-8), and more preferably are groups represented by the formula (Ta-8).

Substituents that the divalent aromatic hydrocarbon group represented by T ¹⁰² and T ²⁰² may have include the group described as substituent B, and among them, at least one selected from the group consisting of a halogen atom and an alkoxy group is preferable. T ¹⁰² and T ²⁰² are divalent aromatic hydrocarbon groups that may have substituents, and the aromatic hydrocarbon ring constituting the divalent aromatic hydrocarbon group is a benzene ring or at least one hydrogen atom of the benzene ring is a saturated chain hydrocarbon having 1 to 4 carbon atoms. It is preferable that it is a structure substituted with a group, more preferably any of the groups represented by the above formulas (Tb-1) to (Tb-10), and formulas (Tb-5), (Tb-6), (Tb Any of the groups represented by -9) and (Tb-10) is particularly preferable.

In formulas (I-1) and (I-2), an a-valent saturated chain hydrocarbon group having 1 to 8 carbon atoms represented by L ¹⁰¹ and L ²⁰¹ , an a-valent aromatic hydrocarbon group represented by T ³ , formula (i) Examples of the substituent that L ² may have include the group described as substituent B.

L ¹⁰¹ and L ²⁰¹ are a saturated a-valent chain hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, and at least one methylene group contained in the aliphatic hydrocarbon group is substituted with -O-, or the above It is preferable that it is any of the groups represented by formulas (i1) to (i8),

A saturated a-valent chain hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, where at least one methylene group contained in the aliphatic hydrocarbon group is substituted with -O-, or a group of the above formula (i2) or formula ( The group represented by i3) is more preferable,

Any of the groups represented by the above formulas (l-10a) to (l-16a) or formulas (i-1) to (i-6) is particularly preferable.

It is preferable that a201 and e201 are the same.

The compounds represented by formulas (I-1) and (I-2) preferably have a charge of 0.

Additionally, from the viewpoint of heat resistance and solvent resistance, the compound represented by formula (I-1) is preferable.

Compound (I) specifically includes compounds (I-1a-1) to (I-108a-1) and compounds (I-1a-2) to (I-108a-2) represented by the following formula (Ia), and compounds (I-1b) to (I-108b) represented by the following formula (Ib). In addition, the compound represented by formula (Ib) represents a compound in which b is 1 and d is 0 among compounds (I). In the compound represented by formula (Ib), e2 of any of the hydrogen atoms of R ^1b to R ^13b , T ^1b , T ^2b , and L ^1b are substituted with -SO ₃ ^- .

[Formula 33]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Formula 34]

[Table 7]

[Table 8]

[Table 9]

In Tables 2 to 9, H represents a hydrogen atom, Et represents an ethyl group, Pr represents an n-propyl group, r-1 to r-3 represent groups represented by the following formulas (r-1) to (r-3), Ta-8 represents a group represented by the following formula (Ta-8), and Tb-5 to Tb-6 and Tb-9 to Tb-10 represent a group represented by the following formula (Tb-5) to (Tb-6) and (Tb- 9) represents a group represented by to (Tb-10), i-1 and i-4 represent a group represented by the following formula (i-1) and (i-4), and l-13a represents a group represented by the following formula (l- It represents the group represented by 13a).

[Formula 35]

[In the formula, * represents a bond with a nitrogen atom.]

[Formula 36]

[In the formula, * represents the bonding hand.]

[Formula 37]

[In the formula, * represents a bond with L ^1a or L ^1b , and ** represents a bond with a nitrogen atom.]

[Formula 38]

[In the formula, * represents the bond with T ^2a or T ^2b .]

Compound (I) is preferably compound (I-1a-1) to (I-108a-1), and compound (I-1a-2) to (I-108a-2), and compound (I-1a-2) ) to (I-108a-2) are more preferable, compounds (I-1a-2) to (I-36a-2), compound (I-39a-2), compound (I-42a-2), compound (I-45a-2), compound (I-48a-2), compound (I-51a-2), and compound (I-54a-2) are more preferred.

Compound (I) can be produced, for example, by methods such as (1) to (3) below.

(1) Method for producing compound (I) (hereinafter sometimes referred to as compound (I')) wherein X ^c- is a halide ion.

Compound (I') can be produced, for example, by reacting a compound represented by formula (B-I) with a compound represented by formula (C-I).

[Formula 39]

[In formulas (BI) and (CI), R ¹ to ^{R 13} , T ² , L ¹ , and a each have the same meaning as above. T ^1B represents a group in which a bond different from the bond bonding hand bonding to the nitrogen atom in T ¹ is replaced with a hydrogen atom.]

The amount of the compound represented by formula (C-I) to be used is preferably 0.5 mol or more and 10 mol or less, and more preferably 1 mol or more and 4 mol or less, per 1 mole of the compound represented by formula (B-I).

The reaction temperature is preferably 30°C to 180°C, and more preferably 80°C to 130°C. The reaction time is preferably 1 hour to 12 hours, and more preferably 1 hour to 8 hours.

The above reaction may be carried out in the presence of an organic solvent or without a solvent, but from the viewpoint of yield, it is preferable to carry it out in an organic solvent. Examples of organic solvents include hydrocarbon solvents such as toluene and xylene; Halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform; Alcohol solvents such as methanol, ethanol, isopropanol, and butanol; Nitrohydrocarbon solvents such as nitrobenzene; Ketone solvents such as methyl isobutyl ketone; amide solvents such as 1-methyl-2-pyrrolidone; etc. can be mentioned. The amount of the organic solvent used is preferably 1 part by mass or more and 20 parts by mass or less, and more preferably 2 parts by mass or more and 10 parts by mass or less, based on 1 part by mass of the compound represented by formula (B-I).

From the viewpoint of yield, the above reaction is preferably carried out in the presence of a condensing agent. Examples of the condensing agent include phosphorus oxyhalides such as phosphoric acid, polyphosphoric acid, and phosphorus oxychloride, and thionyl halides such as sulfuric acid and thionyl chloride. When phosphorus oxyhalide, thionyl halide, etc. are used as the condensing agent and the relationship of formula (z1) is satisfied, compound (I') where X ^c- is a halide ion is obtained.

[In the above formula, a and b have the same meaning as a and b in formula (I). e represents the number of -SO ₃ ^- that compound (I') has as a substituent.]

The amount of the condensing agent used is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass, based on 1 part by mass of the compound represented by formula (B-I).

The method for obtaining compound (I') from the reaction mixture is not particularly limited, and various known methods can be employed. After extraction, the obtained residue may be purified by column chromatography, recrystallization, etc.

As a method for producing compound (B-I), various known methods can be used, for example, the method described in West German Patent Application P3928243.0. Additionally, if necessary, it may be further purified by known methods such as recrystallization or fractionation by chromatography.

Methods for producing compound (C-I) include various known methods. Additionally, if necessary, it may be further purified by known methods such as recrystallization or fractionation by chromatography.

(2) Method for producing compound (I) (hereinafter sometimes referred to as compound (I'')) wherein X ^c- is an anion other than a halide ion (hereinafter anion X ¹ ).

Compound (I'') can be produced by mixing compound (I') with an alkali metal salt of anion X ¹ or protonic acid. Alkali metals include lithium, sodium, and potassium.

The amount of alkali metal salt or ^protonic acid of ^anion However, for 1 mole of compound (I'), for example, it is preferably 0.5 mol or more and 8 mol or less, and more preferably 1 mol or more and 3 mol or less.

Mixing of compound (I') and an alkali metal salt or protonic acid of ^anion

Solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, acetonitrile, ethyl acetate, toluene, methanol, ethanol, isopropanol, acetone, tetrahydrofuran, Examples include oxalic acid, water, and chloroform.

Among them, from the viewpoint of solubility, at least one selected from the group consisting of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, methanol, ethanol, isopropanol, and water. Solvent is preferred.

The amount of solvent used is preferably 1 part by mass or more and 30 parts by mass or less, and more preferably 2 parts by mass or more and 20 parts by mass or less, based on 1 part by mass of compound (I').

When the solvent is water, an acid such as acetic acid or hydrochloric acid may be added.

The mixing temperature of compound (I') and an alkali metal salt or protonic acid of ^anion . The mixing time is preferably 1 hour to 72 hours, more preferably 2 hours to 24 hours, and still more preferably 3 hours to 12 hours.

When a solvent compatible with water is used, compound (I'') can be obtained by mixing the solution, stirring for an additional 1 to 3 hours as needed, and then removing the solvent. If necessary, the obtained compound (I'') may be washed with ion-exchanged water, methanol, etc.

When a solvent incompatible with water is used, the reaction mixture is mixed with ion-exchanged water, stirred for an additional 1 to 3 hours as needed, and then the organic layer is obtained by liquid separation to obtain compound (I''). A solution containing can be obtained. If necessary, the solution may be washed with ion-exchanged water. Compound (I'') can be obtained by removing the solvent from a solution containing compound (I'').

(3) Method for producing a compound (hereinafter sometimes referred to as compound (I''')) in which X ^c- does not exist (that is, d = 0)

Compound (I''') can be prepared by mixing compound (I') with sulfuric acid.

The amount of sulfuric acid used for compound (I') may be added in a stoichiometric ratio that balances the charge of the cation in compound (I') and -SO ₃ ^- , but 1 mole of compound (I') For example, it is 0.5 mol or more and 8 mol or less, and preferably 1 mol or more and 3 mol or less. Additionally, the sulfuric acid may be used as a reaction solvent. When sulfuric acid is used as a solvent, the amount of sulfuric acid used is, for example, 20 mol or more, preferably 25 mol or more, per 1 mol of compound (I'). In addition, when sulfuric acid is used as a solvent, the upper limit of the amount of sulfuric acid used is not particularly limited, but is, for example, 100 parts by mass or less, preferably 50 parts by mass or less, per 1 part by mass of compound (I').

The mixing temperature of compound (I') and sulfuric acid is preferably 0°C to 150°C, more preferably 10°C to 120°C, and even more preferably 20°C to 100°C. The mixing time is preferably 1 hour to 72 hours, more preferably 2 hours to 24 hours, and still more preferably 3 hours to 12 hours.

The mixture obtained by mixing compound (I') with sulfuric acid can be added to ice water to form a suspension and then filtered to obtain compound (I'''). Additionally, if necessary, it may be further purified by known methods such as recrystallization or fractionation by chromatography.

<Colored resin composition>

The colored resin composition of the present invention contains a colorant (hereinafter sometimes referred to as colorant (A)) and a resin (hereinafter sometimes referred to as resin (B)), wherein the colorant is compound (I). Includes.

The colored resin composition of the present invention further contains a polymerizable compound (hereinafter sometimes referred to as polymerizable compound (C)) and a polymerization initiator (hereinafter sometimes referred to as polymerization initiator (D)). It is desirable.

It is preferable that the colored resin composition of the present invention further contains a solvent (hereinafter sometimes referred to as solvent (E)).

The colored resin composition of the present invention may further contain a leveling agent (hereinafter sometimes referred to as leveling agent (F)).

In addition, in this specification, the compounds exemplified as each component can be used individually or in combination of multiple types, unless otherwise specified.

< Colorant (A) >

Colorant (A) contains compound (I). As a result, the brightness of the color filter obtained becomes good, and preferably, the color filter obtained can be made thinner. Moreover, when the colorant (A) contains compound (I), the heat resistance and/or solvent resistance of the resulting color filter are preferably also improved. Compound (I) includes the above-mentioned compound (I), and its preferred embodiments are also the same.

The colorant (A) contains a dye (hereinafter sometimes referred to as dye (A1-1)) and/or a pigment (hereinafter sometimes referred to as pigment (A1-2)) other than compound (I). You can stay. Hereinafter, dye (A1-1) and pigment (A1-2) may be collectively referred to as colorant (A1). These may be used individually, or may be used in combination of two or more types.

Dye (A1-1) is not particularly limited, as long as it does not contain compound (I), and known dyes can be used. Examples include solvent dyes, acid dyes, direct dyes, and mordant dyes. . Examples of dyes include compounds classified as dyes in the color index (published by The Society of Dyers and Colourists) and known dyes described in dyeing notes (Shikisensha). In addition, according to the chemical structure, azo dye, cyanine dye, triphenylmethane dye, xanthene dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squaryllium dye, and acridine. Dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, and phthalocyanine dyes can be mentioned. Among these, organic solvent-soluble dyes are preferred.

As dye (A1-1), specifically

C. I. Solvent Yellow 4, 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 117, 162, 163, 167, 189;

C. I. Solvent Red 24, 45, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172 , 175, 181, 207, 218, 222, 227, 230, 245, 247;

C. I. Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 77, 86, 99;

C. I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;

C. I. Solvent Blue 4, 5, 14, 18, 35, 36, 37, 38, 44, 45, 58, 59, 59:1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94 , 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;

C. I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35; C. I. Solvent dyes, etc.

C. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 , 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 1 84 , 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

C. I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76 , 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172 , 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 2 81 , 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;

C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173;

C. I. Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102;

C. I. Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45 , 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90:1, 91, 92, 93, 93:1 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147 , 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 2 36 , 242, 243, 249, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324:1, 335, 340;

C. I. Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80 , 104, 105, 106, 109; C. I. Acid dyes, etc.

C. I. Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102 , 108, 109, 129, 132, 136, 138, 141;

C. I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211 , 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

C. I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

C. I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

C. I. Direct Blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84 , 85, 86, 87, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150 , 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 1 95 , 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 2 45 , 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;

C. I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 79, 82; C. I. Direct dyes, etc.

C. I. Disperse Yellow 51, 54, 76;

C. I. Disperse Violet 26, 27;

C. I. dispers blue 1, 14, 56, 60; C. I. dispers dye, etc.

C. I. Basic Red 1, 9, 10;

C. I. Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66 , 67, 68, 81, 83, 88, 89;

C. I. Basic Violet 2;

C. I. Basic Green 1; C. I. basic dyes, etc.

C. I. Reactive Yellow 2, 76, 116;

C. I. Reactive Orange 16;

C.I. Reactive Red 36; C. I. Reactive dyes, etc.

C. I. Mordaunt Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

C. I. Mordaunt Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95;

C. I. Mordaunt Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

C. I. Mordaunt Violet 1, 1:1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28, 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58;

C. I. Mordaunt Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;

C. I. Mordaunt Green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53; C. I. Mordaunt dyes, etc.

C. I. Bat Green 1; Dyes with a color index (C.I.) number such as C.I. vat dye can be mentioned.

Pigment (A1-2) is not particularly limited and known pigments can be used as long as they do not contain compound (I). For example, they are classified as pigments in the Color Index (published by The Society of Dyers and Colourists). Included pigments can be used.

Pigments classified as pigments include, for example, C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109. , 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214, 231, etc.;

C. I. Orange pigments such as Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

C. I. Pigment Red 9, 97, 105, 122, 144, 166, 168, 176, 177, 180, 190, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, red pigments such as 269 and 273;

C. I. Blue pigments such as Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60;

C. I. Violet pigments such as Pigment Violet 1, 19, 23, 32, 36, and 38;

C. I. Green pigments such as Pigment Green 7, 36, 58, 59, 62, 63;

Brown pigments such as C.I. Pigment Brown 23 and 25;

C. I. Black pigments such as Pigment Black 1 and 7; can be mentioned.

As the colorant (A1), yellow, red or green dyes and/or pigments are preferred.

The colorant (A1) may, if necessary, undergo rosin treatment, surface treatment using a derivative into which an acidic group or basic group is introduced, grafting treatment on the surface of the colorant (A1) with a polymer compound, etc., atomization treatment using a sulfuric acid atomization method, etc., Washing treatment with an organic solvent or water to remove impurities, removal treatment using an ion exchange method for ionic impurities, etc. may be performed. It is preferable that the particle size of the colorant (A1) is approximately uniform.

When the colorant (A) further contains a colorant (A1), the content of compound (I) is, for example, 1% by mass or more, preferably 2% by mass or more, based on the total amount of colorant (A). , more preferably 10 mass% or more, further preferably 25 mass% or more, and particularly preferably 50 mass% or more. Moreover, when the colorant (A) further contains a colorant (A1), the content of compound (I) is, for example, less than 100% by mass with respect to the total amount of the colorant (A).

When the colored resin composition contains a solvent (E), a colorant-containing liquid containing the colorant (A) and the solvent (E) may be prepared in advance, and then the colored resin composition may be prepared using the colorant-containing liquid. When the colorant (A) is not soluble in the solvent (E), for example, when the colorant (A) contains a pigment (A1-2), the colorant-containing solution contains the colorant (A) in the solvent (E). It can be prepared by dispersing and mixing. The colorant-containing liquid may contain part or all of the solvent (E) contained in the colored resin composition.

The solid content in the colorant-containing liquid is preferably 0.01 mass% or more and 99.99 mass% or less, more preferably 0.1 mass% or more and 99.9 mass% or less, and still more preferably 0.1 mass% or more, relative to the total amount of the colorant-containing liquid. It is 99 mass% or less, more preferably 0.5 mass% or more and 90 mass% or less, and particularly preferably 1 mass% or more and 50 mass% or less.

The colorant (A) may be uniformly dispersed in the solution by dispersing the colorant (A) by containing a dispersant. When using two or more types of colorants (A) in combination, each may be dispersed individually, or multiple types may be mixed and dispersed.

Examples of the dispersing agent include surfactants, and may be any of cationic, anionic, nonionic, and amphoteric surfactants. Specifically, surfactants such as polyester-based, polyamine-based, and acrylic-based surfactants can be mentioned. These dispersants may be used individually or in combination of two or more types. Dispersants, as indicated by their brand names, include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Florene (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca Co., Ltd.), and EFKA (registered trademark). (manufactured by BASF), Ajispa (registered trademark) (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by Big Chemi Co., Ltd.), BYK (registered trademark) (manufactured by Big Chemi Co., Ltd.), etc. can be mentioned. As a dispersant, you may use resin (B) described later.

When using a dispersant, the amount of the dispersant (solid content) used is usually 1 part by mass or more and 10,000 parts by mass or less, preferably 5 parts by mass or more and 5,000 parts by mass or less, more preferably 100 parts by mass of the colorant (A). It is preferably 10 parts by mass or more and 1000 parts by mass or less, and more preferably 15 parts by mass or more and 800 parts by mass or less. If the amount of the dispersant used is within the above range, a colorant-containing liquid in a more uniformly dispersed state tends to be obtained.

The content rate of the colorant (A) is preferably 0.1% by mass or more and 50% by mass or less, more preferably 0.5% by mass or more and 40% by mass or less, and still more preferably 1% by weight, based on the total amount of solid content of the colored resin composition. It is more than 30% by mass and less than 30% by mass. If the content of the colorant (A) is within the above range, the color density when used as a color filter is sufficient, and the required amount of resin (B) can be contained in the composition, so a pattern with sufficient mechanical strength can be formed. desirable.

Here, the “total amount of solid content” in this specification refers to the amount excluding the content of the solvent from the total amount of the colored resin composition. The total amount of solid content and the content of each component relative to this can be measured by known analytical means such as liquid chromatography or gas chromatography, for example.

<Resin (B)>

The resin (B) is not particularly limited, but is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6].

Resin [K1]; A structural unit derived from at least one type of monomer (a) (hereinafter sometimes referred to as “(a)”) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and a cyclic ether structure having 2 to 4 carbon atoms. and a copolymer having a structural unit derived from monomer (b) (hereinafter sometimes referred to as “(b)”) having an ethylenically unsaturated bond;

Resin [K2]; A structural unit derived from (a), a structural unit derived from (b), and a monomer (c) copolymerizable with (a) (however, it is different from (a) and (b)) (hereinafter “(c)” A copolymer having a structural unit derived from (sometimes referred to as);

Resin [K3]; A copolymer having a structural unit derived from (a) and a structural unit derived from (c);

Resin [K4]; A copolymer having a structural unit derived from (a) with (b) added to the structural unit derived from (c);

Resin [K5]; A copolymer having a structural unit derived from (b) with (a) added to the structural unit derived from (c);

Resin [K6]; A copolymer having (a) added to the structural unit derived from (b), a structural unit obtained by further adding a carboxylic anhydride, and a structural unit derived from (c).

Examples of the monomer (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and o-, m-, and p-vinylbenzoic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene , 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene and 5-carboxy-6-ethylbicyclo. [2.2.1] Bicyclo unsaturated compounds containing a carboxyl group such as hept-2-ene;

Carboxylic acid anhydrides such as anhydrides of the above-mentioned unsaturated dicarboxylic acids excluding fumaric acid and mesaconic acid;

Unsaturated mono[(meth)acryloyloxyalkyl] of divalent or higher polyvalent carboxylic acids such as mono[2-(meth)acryloyloxyethyl] succinic acid and mono[2-(meth)acryloyloxyethyl] phthalate. esters;

unsaturated acrylates containing a hydroxy group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid; etc. can be mentioned.

Among these, acrylic acid, methacrylic acid, and maleic anhydride are preferable from the viewpoint of copolymerization reactivity and the solubility of the obtained resin in an aqueous alkaline solution.

In addition, in this specification, "(meth)acrylic acid" represents at least one type selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth)acryloyl” and “(meth)acrylate” also have the same meaning.

Monomer (b) is a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one member selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring (oxolane ring)) and an ethylenically unsaturated bond. refers to a polymerizable compound having . The monomer (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

As the monomer (b), for example, a monomer having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “monomer (b1)”), a monomer having an oxetanyl group and an ethylenically unsaturated bond (hereinafter, (sometimes referred to as “monomer (b2)”), a monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “monomer (b3)”), etc.

Examples of the monomer (b1) include a monomer having a structure obtained by epoxidizing an unsaturated aliphatic hydrocarbon (hereinafter sometimes referred to as “monomer (b1-1)”), and a monomer having a structure obtained by epoxidizing an unsaturated alicyclic hydrocarbon. and monomers (hereinafter sometimes referred to as “monomers (b1-2)”).

As the monomer (b1-1), a monomer having a glycidyl group and an ethylenically unsaturated bond is preferable. Monomer (b1-1) specifically includes glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether Dyl ether, α-methyl-p-vinylbenzylglycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis( Glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxy) Methyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) Styrene, etc. can be mentioned.

Monomers (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celoxide (registered trademark) 2000; manufactured by Daicel Co., Ltd.), and 3,4-epoxy. Cyclohexylmethyl (meth)acrylate (for example, Cyclomer (registered trademark) A400; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer ( Registered trademark) M100 (manufactured by Daicel Co., Ltd.), a compound represented by formula (BI), and a compound represented by formula (BII).

[Formula 40]

[In formula (BI) and formula (BII), R ^a and R ^b independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted by a hydroxy group. You can stay.

X ^a and X ^b independently represent a single bond, *-R ^c -, *-R ^c -O-, *-R ^c -S-, or *-R ^c -NH-.

R ^c represents an alkanediyl group having 1 to 6 carbon atoms.

* represents the bond with O.]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl group.

Examples of the alkyl group in which the hydrogen atom is substituted by hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, and 3-hydroxypropyl group. group, 1-hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc. can be mentioned.

R ^a and R ^b are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

Examples of alkanediyl groups include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, and pentane-1,5-diyl group. , hexane-1,6-diyl group, etc.

_{As X} ^{a and} _{_} and, more preferably, a single bond or a *-CH ₂ CH ₂ -O- group (* represents a bond with O).

Examples of the compound represented by formula (BI) include compounds represented by any of formulas (BI-1) to (BI-15). Among them, formula (BI-1), formula (BI-3), formula (BI-5), formula (BI-7), formula (BI-9) and formula (BI-11) to formula (BI-15) Compounds represented by are preferable, and compounds represented by formula (BI-1), formula (BI-7), formula (BI-9), and formula (BI-15) are more preferable.

[Formula 41]

Examples of the compound represented by formula (BII) include compounds represented by any of formulas (BII-1) to (BII-15), and among them, formula (BII-1) and formula (BII-3) , compounds represented by formula (BII-5), formula (BII-7), formula (BII-9) and formula (BII-11) to formula (BII-15) are preferred, and formula (BII-1), Compounds represented by formula (BII-7), formula (BII-9) and formula (BII-15) are more preferable.

[Formula 42]

The compound represented by formula (BI) and the compound represented by formula (BII) may be used individually, or the compound represented by formula (BI) and the compound represented by formula (BII) may be used in combination. When these are used together, the content ratio of the compound represented by formula (BI) and the compound represented by formula (BII) is preferably 5:95 to 95:5, more preferably 10:90 to 10:90, on a molar basis. It is 90:10, more preferably 20:80 to 80:20.

As the monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and a (meth)acryloyloxy group is more preferable. As monomer (b2), for example, 3-methyl-3-(meth)acryloyloxymethyloxetane, 3-ethyl-3-(meth)acryloyloxymethyloxetane, 3-methyl-3- (meth)acryloyloxyethyloxetane, 3-ethyl-3-(meth)acryloyloxyethyloxetane, etc.

As the monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group is more preferable. Examples of the monomer (b3) include tetrahydrofurfuryl acrylate (for example, Viscot V#150, manufactured by Osaka Organic Chemicals Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

Examples of monomer (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, and tert-butyl (meth)acrylate. , 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate , 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl (meth)acrylate (in the technical field, the common name is “dicyclofentanyl (meth)acrylate”) Also, it is sometimes called “tricyclodecyl (meth)acrylate”), tricyclo[5.2.1.0 ^2,6 ]decan-9-yl(meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decen-8-yl(meth)acrylate (in the technical field, it is commonly called "dicyclopentenyl(meth)acrylate"), tricyclo[5.2.1.0 ^2,6 ]decene- 9-yl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate ) (meth)acrylic acid esters such as acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate;

(meth)acrylic acid esters containing hydroxy groups such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconic acid;

Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybi Cyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2 -N, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept -2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept- 2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methyl Bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1] Hept-2-ene, 5-tert-Butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoc Cycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene and 5,6-bis(cyclohexyl oxide Bicyclo unsaturated compounds such as cycarbonyl)bicyclo[2.2.1]hept-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl- Dicarbonylimide derivatives such as 6-maleimide caproate, N-succinimidyl-3-maleimide propionate, and N-(9-acridinyl)maleimide;

Vinyl group-containing aromatic compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene; Vinyl group-containing nitriles such as (meth)acrylonitrile; Halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; Vinyl group-containing amides such as (meth)acrylamide; esters such as vinyl acetate; dienes such as 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene; etc. can be mentioned.

Among these, in terms of copolymerization reactivity and heat resistance, styrene, vinyltoluene, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl(meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decan-9 -yl(meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decen-8-yl(meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decen-9-yl(meth)acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene, 2-hydroxyethyl(meth)acrylate, and benzyl(meth)acrylate It is preferable to use at least one type selected from the group consisting of.

In resin [K1], the ratio of structural units derived from each is, among all structural units constituting resin [K1],

Structural unit derived from (a); 2~60 mol%

Structural unit derived from (b); 40∼98 mol%

It is desirable to be,

Structural unit derived from (a); 10 to 50 mol%

Structural unit derived from (b); 50 to 90 mol%

It is more preferable to be

If the ratio of the structural units of the resin [K1] is within the above range, the storage stability of the colored resin composition, developability when forming a colored pattern, and solvent resistance of the resulting color filter tend to be excellent.

Resin [K1] is, for example, the method described in the document "Experimental Methods for Polymer Synthesis" (written by Takayuki Otsu, Chemistry Dongin Co., Ltd., 1st edition, 1st printing, March 1, 1972) and the citations described in the document. It can be manufactured by referring to the literature.

Specifically, predetermined amounts of (a) and (b), a polymerization initiator, and a solvent are placed in a reaction vessel, for example, by replacing oxygen with nitrogen to create a deoxygenated atmosphere, and then heated and kept warm while stirring. Here's how to do it: In addition, the polymerization initiator and solvent used here are not particularly limited, and those commonly used in the field can be used. For example, as a polymerization initiator, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic peroxides (benzoyl peroxide, etc.) ) can be mentioned, and the solvent may be any solvent that dissolves each monomer, and examples of the solvent (E) described later as the solvent for the colored resin composition of the present invention include the solvent.

In addition, the obtained copolymer may be used as a solution after the reaction, a concentrated or diluted solution, or a solid (powder) taken out by a method such as reprecipitation. In particular, by using the solvent contained in the colored resin composition of the present invention as a solvent during this polymerization, the solution after the reaction can be used as is for preparing the colored resin composition of the present invention, so that the colored resin composition of the present invention can be prepared. The process can be simplified.

In resin [K2], the ratio of structural units derived from each is, among all structural units constituting resin [K2],

Structural unit derived from (a); 2~45 mol%

Structural unit derived from (b); 2~95 mol%

Structural unit derived from (c); 1 to 65 mol%

It is desirable to be,

Structural unit derived from (a); 5 to 40 mol%

Structural unit derived from (b); 5 to 80 mol%

Structural unit derived from (c); 5 to 60 mol%

It is more preferable to be

When the ratio of the structural units of the resin [K2] is within the above range, the storage stability of the colored resin composition, developability when forming a colored pattern, and the solvent resistance, heat resistance, and mechanical strength of the resulting color filter tend to be excellent. There is.

Resin [K2] can be produced, for example, in the same manner as the method described as the production method for resin [K1].

In resin [K3], the ratio of structural units derived from each is, among all structural units constituting resin [K3],

Structural unit derived from (a); 2~60 mol%

Structural unit derived from (c); 40∼98 mol%

It is desirable to be,

Structural unit derived from (a); 10 to 50 mol%

Structural unit derived from (c); 50 to 90 mol%

It is more preferable to be

Resin [K3] can be produced, for example, in the same manner as the method described as the method for producing resin [K1].

Resin [K4] is prepared by obtaining a copolymer of (a) and (c) and adding the cyclic ether having 2 to 4 carbon atoms of (b) to the carboxylic acid and/or carboxylic anhydride of (a). You can.

First, a copolymer of (a) and (c) is produced in the same manner as the method described as the method for producing resin [K1]. In this case, it is preferable that the ratio of structural units derived from each is the same as that contained in resin [K3].

Next, a portion of the carboxylic acid and/or carboxylic anhydride derived from (a) in the copolymer is reacted with the cyclic ether having 2 to 4 carbon atoms of (b).

Continuing with the production of the copolymers of (a) and (c), the atmosphere in the flask was changed from nitrogen to air, and (b), a reaction catalyst between carboxylic acid or carboxylic anhydride and cyclic ether (for example, tris ( Resin [K4] can be produced by placing dimethylaminomethyl)phenol, etc.) and a polymerization inhibitor (e.g., hydroquinone, etc.) in a flask and reacting at, for example, 60 to 130°C for 1 to 10 hours. there is.

The amount of (b) used is preferably 5 to 80 moles, more preferably 10 to 75 moles, per 100 moles of (a). By setting this range, the balance between the storage stability of the colored resin composition, developability when forming a pattern, and solvent resistance, heat resistance, mechanical strength, and sensitivity of the resulting pattern tends to become good. Since the reactivity of cyclic ether is high and unreacted (b) is unlikely to remain, (b) used in resin [K4] is preferably (b1), and (b1-1) is more preferable.

The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b), and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b), and (c).

Reaction conditions such as introduction method, reaction temperature and time can be adjusted appropriately taking into account the manufacturing equipment and the amount of heat generated by polymerization. In addition, as with the polymerization conditions, the introduction method and reaction temperature can be adjusted appropriately by taking into consideration the manufacturing equipment, the amount of heat generated by polymerization, etc.

As for resin [K5], in the first step, a copolymer of (b) and (c) is obtained in the same manner as the production method of resin [K1] described above. Similarly to the above, the obtained copolymer may be used as a solution after the reaction, a concentrated or diluted solution, or a solid (powder) taken out by a method such as reprecipitation.

The ratio of the structural units derived from (b) and (c) is, respectively, the structural units derived from (b) relative to the total number of moles of all structural units constituting the above copolymer; 5 to 95 mol%

Structural unit derived from (c); 5 to 95 mol%

It is desirable to be,

Structural unit derived from (b); 10 to 90 mol%

Structural unit derived from (c); 10 to 90 mol%

It is more preferable to be

In addition, under the same conditions as the method for producing resin [K4], the carboxylic acid or carboxylic anhydride of (a) is reacted with the cyclic ether derived from (b) of the copolymer of (b) and (c). By doing so, resin [K5] can be obtained.

The amount of (a) reacted with the above copolymer is preferably 5 to 80 moles per 100 moles of (b). Since the reactivity of cyclic ether is high and unreacted (b) is unlikely to remain, (b) used in resin [K5] is preferably (b1), and (b1-1) is more preferable.

Resin [K6] is a resin obtained by reacting resin [K5] with a carboxylic anhydride. A carboxylic acid anhydride is reacted with the hydroxy group generated by the reaction of a cyclic ether with a carboxylic acid or carboxylic anhydride.

Carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, and 1,2,3,6- Examples include tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride. The amount of carboxylic anhydride used is preferably 0.5 to 1 mol per 1 mol of (a).

Specific resins (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate/(meth)acrylic acid. Resins such as copolymers [K1]; Glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, glycidyl (meth)acrylate/styrene/(meth)acrylic acid copolymer, 3,4-epoxy tricyclo[5.2 .1.0 ^2,6 ]decyl acrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate/(meth)acrylic acid/N- Resins [K2] such as cyclohexylmaleimide/2-hydroxyethyl (meth)acrylate copolymer and 3-methyl-3-(meth)acryloyloxymethyloxetane/(meth)acrylic acid/styrene copolymer; Resins [K3] such as benzyl (meth)acrylate/(meth)acrylic acid copolymer and styrene/(meth)acrylic acid copolymer; A resin obtained by adding glycidyl (meth)acrylate to a benzyl (meth)acrylate/(meth)acrylic acid copolymer, and glycidyl (meth)acrylate to a tricyclodecyl (meth)acrylate/styrene/(meth)acrylic acid copolymer. ) Resins such as resins to which acrylates were added and resins to which glycidyl (meth)acrylate was added to tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer [K4]; A resin made by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate, tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate Resins [K5], such as a resin obtained by reacting (meth)acrylic acid with a copolymer; [K6], such as a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate with (meth)acrylic acid and further reacting tetrahydrophthalic anhydride. there is.

The resin (B) is more preferably at least one selected from the group consisting of resin [K1] and resin [K2], and is particularly preferably resin [K2].

The weight average molecular weight (Mw) of the resin (B) in terms of polystyrene is preferably 1,000 or more and 100,000 or less, more preferably 2,000 or more and 50,000 or less, and still more preferably 3,000 or more and 30,000 or less. If the weight average molecular weight is within the above range, the solubility of the unexposed portion in the developer is high, and the residual film rate and hardness of the resulting pattern tend to be high as well.

The dispersion degree [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1 or more and 6 or less, more preferably 1.001 or more and 4 or less, and still more preferably 1.01 or more. It is as follows.

The acid value (solid content conversion value) of the resin (B) is preferably 10 mg-KOH/g or more and 300 mg-KOH/g or less, and more preferably 20 mg-KOH/g or more and 250 mg-KOH/g or less. , more preferably 25 mg-KOH/g or more and 200 mg-KOH/g or less, even more preferably 30 mg-KOH/g or more and 150 mg-KOH/g or less, and particularly preferably 60 mg-KOH/g. It is more than KOH/g and less than 135 mg-KOH/g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be obtained, for example, by titration using an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 5 to 50 mass%, more preferably 10 to 40 mass%, and still more preferably 15 to 30 mass%, based on 100 mass% of solid content of the colored resin composition. When the content of the resin (B) is within the above range, the solubility of the unexposed portion in the developer tends to be high.

<Polymerizable Compound (C)>

The polymerizable compound (C) is a compound that can be polymerized by active radicals and/or acids generated from the polymerization initiator (D), and examples include compounds having a polymerizable ethylenically unsaturated bond, etc., and are preferred. It is a (meth)acrylic acid ester compound.

Examples of polymerizable compounds having one ethylenically unsaturated bond include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, and 2-hydroxy. Ethyl acrylate, N-vinylpyrrolidone, etc., and the above-mentioned monomer (a), monomer (b), and monomer (c) can be mentioned.

Examples of polymerizable compounds having two ethylenically unsaturated bonds include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and triacrylate. Examples include ethylene glycol di(meth)acrylate, bis(acryloyloxyethyl)ether of bisphenol A, and 3-methylpentanediol di(meth)acrylate.

The polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Such polymerizable compounds include, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, Pentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tris (2-(meth)acryloyloxyethyl)isocyanurate, ethylene glycol-modified pentaerythritol tetra(meth)acrylate, ethylene glycol-modified dipentaerythritol hexa(meth)acrylate, propylene glycol-modified pentaerythritol tetra(meth)acrylate ) Acrylate, propylene glycol-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, and caprolactone-modified dipentaerythritol hexa(meth)acrylate, etc., preferably At least one type selected from the group consisting of dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate can be mentioned.

The weight average molecular weight of the polymerizable compound (C) is preferably 50 or more and 4,000 or less, more preferably 70 or more and 3,500 or less, further preferably 100 or more and 3,000 or less, and even more preferably 150 or more and 2,900 or less. , and is particularly preferably 250 or more and 1,500 or less.

The content of the polymerizable compound (C) may be, for example, 1 mass% or more and 99 mass% or less, preferably 5 mass% or more and 90 mass% or less, more preferably is 10 mass% or more and 80 mass% or less, and is more preferably 12 mass% or more and 70 mass% or less.

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound that can initiate polymerization by generating active radicals, acids, etc. under the action of light or heat, and a known polymerization initiator can be used.

Examples of the polymerization initiator (D) include O-acyloxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds.

Examples of O-acyloxime compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl) ) Octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-(4 -phenylsulfanylphenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropane-1-one-2-imine , N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6 -{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1 -[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine and N-benzoyloxy-1-[9-ethyl-6-( and 2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-one-2-imine. In addition, as O-acyloxime compounds, Irgacure (registered trademark) OXE01, OXE02 (manufactured by BASF), N-1919 (manufactured by ADEKA Co., Ltd.), and TR-PBG327 (manufactured by Sangju Strong Electronic Materials Co., Ltd.) You may use commercially available products such as Among them, O-acyloxime compounds include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane- 1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, and TR-PBG327(N-acetoxy-1- At least one selected from the group consisting of (4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine) is preferred, and N-benzoyloxy-1-(4-phenylsulfanylphenyl) selected from the group consisting of octan-1-one-2-imine and TR-PBG327 (N-acetoxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine) At least one type is more preferable.

Alkylphenone compounds include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane. -1-one and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one, etc. As the alkylphenone compound, you may use commercial products such as Irgacure (registered trademark) 369, 907, and 379 (above, manufactured by BASF).

Alkylphenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1- oligomer of 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone, and benzyldimethylketal. can also be heard.

Examples of biimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3- dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, see Japanese Patent Application Laid-Open No. 6-75372, Japanese Patent Application Laid-Open No. 6-75373, etc.), 2 ,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5 ,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (e.g. , Japanese Patent Application Laid-Open No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, etc.) and a biimide in which the phenyl group at the 4,4',5,5'- position is substituted by a carboalkoxy group. Dazole compounds (for example, see Japanese Patent Application Laid-Open No. 7-10913, etc.) can be mentioned.

Triazine compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4- Methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl) )-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl 〕-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4 -bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine and 2,4-bis(trichloromethyl)-6- [2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, etc. are mentioned.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. You may use commercial products such as Irgacure (registered trademark) 819 (manufactured by BASF).

Furthermore, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, o-benzoylbenzoic acid methyl, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; Examples include 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds.

These are preferably used in combination with the polymerization initiation aid (D1) (particularly an amine compound) described later.

The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds, and biimidazole compounds, More preferably, it is a polymerization initiator containing an O-acyloxime compound.

The content of the polymerization initiator (D) is preferably 0.1 part by mass or more and 30 parts by mass or less, more preferably, with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C) contained in the colored resin composition. is 1 part by mass or more and 20 parts by mass or less. If the content of the polymerization initiator (D) is within the above range, the sensitivity increases and the exposure time tends to be shortened, thereby improving the productivity of the color filter.

<Polymerization initiation aid (D1)>

The colored resin composition of the present invention may contain a polymerization initiation aid (D1). The polymerization initiation aid (D1) is a compound or sensitizer used to promote polymerization of the polymerizable compound (C) whose polymerization was initiated by the polymerization initiator (D). When a polymerization initiation aid (D1) is included, it is usually used in combination with a polymerization initiator (D).

Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

Amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and 4-dimethylaminobenzoate 2. -Ethylhexyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone and 4,4'- Examples include bis(ethylmethylamino)benzophenone, and preferably 4,4'-bis(diethylamino)benzophenone. Moreover, as an amine compound, you may use a commercial item such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.).

Alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10-dibutoxy. Anthracene and 2-ethyl-9,10-dibutoxyanthracene can be mentioned.

Thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone. Santon, etc. can be mentioned.

Carboxylic acid compounds include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, and chlorophenyl alcohol. Examples include panylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

When using these polymerization initiation aids (D1), the content thereof is preferably 0.1 parts by mass or more and 30 parts by mass based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C) contained in the colored resin composition. Hereinafter, more preferably, it is 1 part by mass or more and 20 parts by mass or less.

<Solvent (E)>

The solvent (E) is not particularly limited, and solvents commonly used in the field can be used.

Solvent (E) is, for example, an ester solvent (a solvent containing -COO- in the molecule and not containing -O-), an ether solvent (a solvent containing -O- in the molecule and not containing -COO- solvent), ether ester solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule but not -COO-), alcohol solvent (solvent containing -COO- in the molecule) solvents containing OH but not containing -O-, -CO-, and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc. Two or more types of these solvents may be used in combination.

Ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, Examples include butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and propylene glycol. Monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1 , 4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetol and methyl anisole, etc. can be mentioned.

Ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2-methyl Methyl propionate, 2-ethoxy-2-methylethyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl Ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and dipropylene glycol methyl ether acetate.

Ketone solvents include 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, and 4-methyl-2- Pentanone, cyclopentanone, cyclohexanone, and isophorone can be mentioned.

Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene.

Examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

The solvent (E) is preferably a solvent containing at least one selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diacetone alcohol, and cyclohexanone.

The content of the solvent (E) is usually 99.99% by mass or less, preferably 40% by mass or more and 99% by mass or less, more preferably 50% by mass or more and 95% by mass or less, with respect to the total amount of the colored resin composition. More preferably, it is 70 mass% or more and 95 mass% or less, and even more preferably, it is 75 mass% or more and 90 mass% or less. In other words, the total amount of solid content of the colored resin composition is usually 0.01 mass% or more, preferably 1 mass% or more and 60 mass% or less, more preferably 5 mass% or more and 50 mass% or less, and even more preferably It is 5 mass% or more and 30 mass% or less, more preferably 10 mass% or more and 25 mass% or less. If the content of the solvent (E) is within the above range, the flatness during application becomes good and the color density is not insufficient when forming a color filter, so the display characteristics tend to be good.

<Leveling Agent (F)>

Examples of the leveling agent (F) include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having a fluorine atom. These may have a polymerizable group in the side chain.

Examples of silicone-based surfactants include surfactants having a siloxane bond in the molecule. Specifically, Toray Silicon DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (product name: Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324. , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan Joint Stock Company). You can.

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Florad (registered trademark) FC430, FC431 (made by Sumitomo 3M Co., Ltd.), Megapak (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30. , RS-718-K (manufactured by DIC Co., Ltd.), Ftop (registered trademark) EF301, EF303, EF351, EF352 (made by Mitsubishi Material Electronics Co., Ltd.), Surfron (registered trademark) S381, Examples include S382, SC101, SC105 (manufactured by AGC Co., Ltd.), and E5844 (manufactured by Daikin Fine Chemical Laboratories Co., Ltd.).

Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples include Megapak (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

When containing the leveling agent (F), the content rate of the leveling agent (F) is preferably 0.0005 mass% or more and 1 mass% or less, more preferably 0.001 mass% or more and 0.5 mass%, relative to the total amount of the colored resin composition. % or less, and more preferably 0.005 mass% or more and 0.1 mass% or less. Additionally, this content does not include the content of the above-described dispersant. If the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Other ingredients>

The colored resin composition may, if necessary, contain additives known in the art, such as fillers, other polymer compounds, adhesion promoters, adhesives, antioxidants, light stabilizers, and chain transfer agents.

<Method for producing colored resin composition>

The colored resin composition includes a colorant (A), a resin (B), a polymerizable compound (C) used as needed, a polymerization initiator (D), a polymerization initiation aid (D1), a solvent (E), and a leveling agent (F). ) and other ingredients. Mixing can be performed using known or customary equipment or conditions.

The colorant (A) may be used as a colorant-containing solution obtained by mixing it with part or all of the solvent (E) in advance and dispersing it using a bead mill or the like until the average particle diameter is about 0.2 μm or less. , it is preferable to use it as a colorant-containing liquid. At this time, part or all of the above-mentioned dispersant and resin (B) may be blended as needed. Additionally, the colorant (A) may be used as a colorant-containing liquid obtained by previously dissolving it in part or all of the solvent (E). The desired colored resin composition can be prepared by mixing the remaining components with the colorant-containing liquid obtained in this way to a predetermined concentration.

< Manufacturing method of color filter >

From the colored resin composition of the present invention, a color filter that may be a color conversion layer can be formed. Methods for forming a colored pattern include photolithographic methods, inkjet methods, and printing methods. Among them, the photolithographic method is preferable. The photolithographic method is a method of applying the colored resin composition to a substrate, drying it to form a colored resin composition layer, exposing the colored resin composition layer to light through a photomask, and developing the colored resin composition layer. In the photolithographic method, a colored coating film, which is a cured product of the colored resin composition layer, can be formed by not using a photomask during exposure and/or not developing. The colored pattern or colored coating film formed in this way is the color filter of the present invention.

The film thickness of the color filter to be produced is not particularly limited and can be adjusted appropriately depending on the purpose, use, etc., for example, is 0.1 μm or more and 30 μm or less, preferably 0.1 μm or more and 20 μm or less, and more preferably is 0.5 ㎛ or more and 6 ㎛ or less, more preferably 0.8 ㎛ or more and 4.5 ㎛ or less.

The substrate may be a glass plate such as quartz glass, borosilicate glass, aluminosilicate glass, or soda lime glass with a silica-coated surface, a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate, silicon, or aluminum on the substrate. Silver, silver/copper/palladium alloy thin films, etc. are used. Other color filter layers, resin layers, transistors, circuits, etc. may be formed on these substrates.

Formation of each color pixel by the photolithographic method can be performed using known or customary equipment and conditions. For example, it can be produced as follows.

First, the colored resin composition is applied onto a substrate, and then heated and dried (prebaked) and/or dried under reduced pressure to remove volatile components such as solvents and dried to obtain a smooth colored resin composition layer.

Application methods include spin coating, slit coating, and slit and spin coating.

The temperature when performing heat drying is preferably 30°C or higher and 120°C or lower, and more preferably 50°C or higher and 110°C or lower. Moreover, the heating time is preferably 10 seconds or more and 60 minutes or less, and more preferably 30 seconds or more and 30 minutes or less.

When performing reduced-pressure drying, it is preferably carried out under a pressure of 50 Pa or more and 150 Pa or less and a temperature range of 20°C or more and 25°C or less.

The film thickness of the colored resin composition layer is not particularly limited and may be appropriately selected depending on the film thickness of the target color filter.

Next, the colored resin composition layer is exposed through a photomask for forming the desired colored pattern. The pattern on the photomask is not particularly limited, and a pattern depending on the intended use is used. In addition, it is preferable to use exposure devices such as mask aligners and steppers because it is possible to uniformly irradiate parallel light to the entire exposure surface and to accurately align the photomask with the substrate on which the colored resin composition layer is formed. do. When forming a colored coating film, exposure may be performed without using a photomask.

As a light source used for exposure, a light source that generates light with a wavelength of 250 nm or more and 450 nm or less is preferable. For example, light below 350 nm can be cut using a filter that cuts this wavelength range, or light around 436 nm, 408 nm, and 365 nm can be cut using a bandpass filter that extracts these wavelength ranges. You can use it to selectively extract it. Specifically, mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, etc. can be mentioned.

A colored pattern is formed on the substrate by developing the colored resin composition layer after exposure by contacting it with a developing solution. By development, the unexposed portion of the colored resin composition layer is dissolved in the developing solution and removed. As a developing solution, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 mass% or more and 10 mass% or less, and more preferably 0.03 mass% or more and 5 mass% or less. Additionally, the developer may contain a surfactant.

The development method may be any of the paddle method, dipping method, and spray method. Additionally, the substrate may be tilted at an arbitrary angle during development.

It is preferable that the substrate after development is washed with water.

Additionally, it is preferable to post-bake the obtained colored pattern or colored coating film. The post-bake temperature is preferably 150°C or higher and 250°C or lower, and more preferably 160°C or higher and 240°C or lower. The post-bake time is preferably from 1 minute to 120 minutes, and more preferably from 10 minutes to 60 minutes.

<Display device>

The color filter is useful as a color filter used in display devices (eg, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

This application claims the benefit of priority based on Japanese Patent Application No. 2021-078791 filed on May 6, 2021. The entire content of the specification of Japanese Patent Application No. 2021-078791 filed on May 6, 2021 is incorporated herein by reference.

Example

Hereinafter, the present invention will be described in more detail through examples. In the examples, % and parts indicating content or usage are based on mass, unless otherwise specified.

In the following synthesis examples, the structure of the compound was confirmed by mass spectrometry (LC; Type 1200 manufactured by Agilent, MASS; Type LC/MSD6130 manufactured by Agilent).

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin in terms of polystyrene were measured by GPC method under the following conditions.

Device: HLC-8120GPC (manufactured by Tosoh Corporation)

Column: TSK-GELG2000HXL

Column temperature: 40℃

Solvent: Tetrahydrofuran

Flow rate: 1.0 mL/min

Solid content concentration of analysis sample: 0.001 to 0.01 mass%

Injection volume: 50 μL

Detector: RI

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.)

The ratio (Mw/Mn) of the weight average molecular weight and the number average molecular weight in terms of polystyrene obtained above was referred to as the degree of dispersion.

<Synthesis of pigments>

[Pigment Synthesis Example 1: Synthesis of Compound (B-I-1a)]

14.8 parts of 4-bromo-3,5-dimethylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 134 parts of N,N-dimethylformamide (manufactured by Kanto Chemical Co., Ltd.) were mixed, and 60% sodium hydride (Kanto Chemical Co., Ltd.) was mixed. 3.2 parts (manufactured by Chemical Co., Ltd.) were slowly added, and the temperature was raised to 40°C. 8.0 parts of 1,3,5-tris(bromomethyl)benzene (manufactured by Tokyo Chemical Industry Co., Ltd.) and 34 parts of N,N-dimethylformamide (manufactured by Kanto Chemical Co., Ltd.) were added dropwise and stirred for 5 hours. . After cooling to 10°C, 168 parts of water were added. After raising the temperature to 25°C, 168 parts of ethyl acetate (manufactured by Kanto Chemical Co., Ltd.) was added, and the ethyl acetate layer was extracted, concentrated, and dried under reduced pressure at 60°C. The compound represented by formula (B-I-1a) was obtained as 13.4 We obtained a wealth (yield 83%).

[Formula 43]

Identification of the compound represented by formula (B-I-1a)

(Mass spectrometry) Ionization mode = ESI +: m/z = 715.2

[Pigment Synthesis Example 2: Synthesis of Compound (B-I-1)]

Compound (B-I-1a) obtained in Pigment Synthesis Example 1: 10 parts, 1-naphthylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) 7.0 parts, palladium acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.38 parts, 2- 1.7 parts of dicyclohexylphosphino-2',6'-dimethoxybiphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.), 6.4 parts of tert-butoxy sodium (manufactured by Tokyo Chemical Industry Co., Ltd.), and dehydration 1 200 parts of 2-dimethoxyethane (manufactured by Kanto Chemical Co., Ltd.) were mixed and stirred at 93°C for 10 hours. After cooling to 25°C, the obtained mixture was filtered through Celite, and the filtrate was concentrated. The obtained residue was purified by silica gel column (solvent: chloroform) and dried under reduced pressure at 60°C to obtain 8.2 parts of the compound represented by the formula (B-I-1) (yield 65%).

[Formula 44]

Identification of the compound represented by formula (B-I-1)

(Mass spectrometry) Ionization mode = ESI +: m/z = 904.6

[Pigment Synthesis Example 3: Synthesis of Compound (C-I-1a)]

The following reaction was performed under a nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 0.27 parts of bis(dibenzylideneacetone)palladium(0) (manufactured by Tokyo Chemical Industry Co., Ltd.), 2-dicyclohexylphosphino-2',4',6' - 0.57 parts of triisopropyl biphenyl (manufactured by Sigma-Aldrich), 42.1 parts of sodium tert-butoxide (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 4,4'-dichlorobenzophenone (manufactured by Tokyo Kasei Kogyo Co., Ltd.) ) After adding 50 parts, a mixed solution of 48.3 parts of 2,6-dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 432 parts of toluene was added dropwise to the flask. This reaction solution was stirred for 2 hours while being heated to 80°C in an oil bath. After cooling the reaction liquid in an ice bath, it was filtered to obtain a solid and a filtrate. This solid is called crude A1, and the filtrate is called filtrate A1. The obtained crude A1 was washed with 50 parts of toluene and then washed twice with 250 parts of ion-exchanged water to obtain a solid. This solid is called crude B1. Filtrate A1, 50 parts of toluene, 229 parts of ion-exchanged water, and 20.8 parts of 35% hydrochloric acid were added to a flask equipped with a bottom discharge, stirred for 1 hour, and then separated to obtain an organic layer. The obtained organic layer was separated and washed with a mixture of 238 parts of ion-exchanged water and 12.5 parts of sodium carbonate, then dried with 150 parts of magnesium sulfate, and the solid was filtered and removed. The obtained organic layer was distilled to obtain a solid. This solid is called crude C1. Crude B1 and Crude C1 were added to a flask equipped with a stirring device, and a mass of acetonitrile 4 times the total mass of Crude B1 and Crude C1 was added and stirred for 1 hour. The solid obtained by filtering the mixed solution was washed with acetonitrile in an amount equal to 1 time the total mass of crude B1 and crude C1. The washed solid was dried at 60°C under reduced pressure to obtain 75.9 parts of the compound represented by the formula (C-I-1a). Yield 90.6%.

[Formula 45]

[Pigment Synthesis Example 4: Synthesis of Compound (C-I-1)]

The following reaction was performed under a nitrogen atmosphere. 50 parts of the compound represented by formula (C-I-1a) and 188 parts of N,N-dimethylformamide were added to a flask equipped with a cooling tube and a stirring device, and stirred for 30 minutes while cooling in an ice bath. 40 parts of potassium tert-butoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the flask, and the mixture was stirred for an additional hour while cooling in an ice bath. While the reaction solution was bathed in ice, 55.6 parts of iodoethane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. The reaction solution was heated to 35°C using an oil bath, stirred for 5 hours, and then allowed to cool to room temperature. 1000 parts of 10% sodium chloride aqueous solution was added to another flask equipped with a stirring device, and the reaction solution was added dropwise while stirring. After stirring for 30 minutes, a solid was obtained by filtration. The obtained solid was washed three times with 500 parts of ion-exchanged water and dried at 60°C under reduced pressure to obtain 53.0 parts of the compound represented by formula (C-I-1). Yield 93.5%.

[Formula 46]

[Pigment Synthesis Example 5: Synthesis of Compound (I-23a-1)]

The following reaction was performed under a nitrogen atmosphere. In a flask equipped with a cooling pipe and a stirring device, 6.8 parts of the compound represented by the formula (B-I-1) obtained in dye synthesis example 2, 11 parts of the compound represented by the formula (C-I-1) obtained in dye synthesis example 4, and toluene After adding 48 parts, 4.6 parts of phosphorus oxychloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added and stirred at 110°C for 8 hours. After the reaction mixture was cooled to room temperature, 200 parts of chloroform and 200 parts of saturated saline solution were poured, and the aqueous layer was removed by liquid separation. After the solvent was distilled off from the organic layer using an evaporator, the obtained blue-violet solid was purified by column chromatography. Additionally, 100 parts of chloroform and 500 parts of toluene were poured into the obtained blue-violet solid for washing, and then dried at 60°C under reduced pressure to obtain 7.5 parts of the compound represented by formula (I-23a-1) (yield 39%).

[Formula 47]

Identification of the compound represented by formula (I-23a-1)

(Mass spectrometry) Ionization mode = ESI +: m/z = 760.6, trivalent

[Pigment Synthesis Example 6: Synthesis of Compound (I-23a-2)]

The following reaction was performed under a nitrogen atmosphere. Into a flask equipped with a cooling tube and a stirring device, 4.3 parts of phosphotungstic acid hydrate (Keggin-type phosphotungstic acid; manufactured by Sigma-Aldrich Co., Ltd.), 12 parts of methanol, and 7.9 parts of water were added, and then mixed at 55°C. A phosphotungstic acid solution was prepared. 3.0 parts of the compound represented by the formula (I-23a-1) obtained in Pigment Synthesis Example 5 was added to the flask, and stirred at 55°C for 4 hours. After concentrating the reaction solution, 200 parts of water was added, dispersed for 1 hour, and then filtered to obtain a blue solid. Additionally, 800 parts of methanol was added to the blue solid, dispersed for 1 hour, filtered, and dried at 60°C under reduced pressure to obtain 4.7 parts of the compound represented by formula (I-23a-2) (yield 72%). .

[Formula 48]

Identification of the compound represented by formula (I-23a-2)

(Mass spectrometry) Ionization mode = MALDI +: m/z = 2280.0

Ionization mode = MALDI -: m/z = 2902.5

[Pigment Synthesis Example 7: Synthesis of Compound (B-I-2a)]

7.4 parts of 4-bromo-3,5-dimethylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 71 parts of N,N-dimethylformamide (manufactured by Kanto Chemical Co., Ltd.) were mixed, and 60% sodium hydride (Kanto Chemical Co., Ltd.) was mixed. 1.6 parts (manufactured by Chemical Co., Ltd.) was slowly added, and the temperature was raised to 40°C. 4.4 parts of 1,4-bis(bromomethyl)benzene (manufactured by Tokyo Chemical Industry Co., Ltd.) and 18 parts of N,N-dimethylformamide (manufactured by Kanto Chemical Co., Ltd.) were added dropwise, and stirred for 5 hours. After cooling to 10°C, 93 parts of water were added. After raising the temperature to 25°C, 93 parts of ethyl acetate (manufactured by Kanto Chemical Co., Ltd.) was added, and the ethyl acetate layer was extracted, concentrated, and dried under reduced pressure at 60°C. The compound represented by formula (B-I-2a) was obtained as 5.1. We obtained a wealth (yield 45%).

[Formula 49]

Identification of the compound represented by formula (B-I-2a)

(Mass spectrometry) Ionization mode = ESI +: m/z = 503.2

[Pigment Synthesis Example 8: Synthesis of Compound (B-I-2)]

9.5 parts of the compound represented by the formula (B-I-2a) obtained in Pigment Synthesis Example 7, 7.0 parts of 1-naphthylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.89 parts of palladium acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) part, 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 4.1 parts, tert-butoxy sodium (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 5.8 parts , and 190 parts of dehydrated 1,2-dimethoxyethane (manufactured by Kanto Chemical Co., Ltd.) were mixed and stirred at 93°C for 10 hours. After cooling to 25°C, the obtained mixture was filtered through Celite, and the filtrate was concentrated. The obtained residue was purified by silica gel column (solvent: chloroform) and dried under reduced pressure at 60°C to obtain 7.3 parts of the compound represented by the formula (B-I-2) (yield 61%).

[Formula 50]

Identification of the compound represented by formula (B-I-2)

(Mass spectrometry) Ionization mode = ESI +: m/z = 629.5

[Pigment Synthesis Example 9: Synthesis of Compound (I-5a-1)]

The following reaction was performed under a nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 4.0 parts of the compound represented by the formula (B-I-2) obtained in dye synthesis example 8, 22 parts of the compound represented by the formula (C-I-1) obtained in dye synthesis example 4, and toluene After adding 112 parts, 5.9 parts of phosphorus oxychloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added and stirred at 90°C for 6 and a half hours. Next, the reaction mixture was cooled to room temperature, 300 parts of chloroform was added thereto, the resulting solution was poured into 3,300 parts of ethyl acetate, and the resulting wet solid was filtered and washed with ethyl acetate. The obtained solid was dried at 60°C under reduced pressure and purified by column chromatography. When dried at 60°C under reduced pressure, 1.0 parts of the compound represented by formula (I-5a-1) was obtained (yield 10%).

[Formula 51]

Identification of the compound represented by formula (I-5a-1)

(Mass spectrometry) Ionization mode = ESI +: m/z = 774.6, divalent

[Pigment Synthesis Example 10: Synthesis of Compound (I-5a-2)]

The following reaction was performed under a nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 2.0 parts of phosphotungstic acid hydrate (manufactured by Sigma-Aldrich Co., Ltd.), 20 parts of dimethyl sulfoxide, and a dye represented by the formula (I-5a-1) obtained in Synthesis Example 9 0.6 parts of the compound was added and stirred at 45°C for 6 hours. After cooling to 25°C, 80 parts of distilled water was added to the reaction solution, dispersed for 1 hour, and then filtered to obtain a blue solid. Additionally, 60 parts of methanol was added to the blue solid, dispersed for 1 hour, filtered, and dried at 60°C under reduced pressure to obtain 1.8 parts of the compound represented by the formula (I-5a-2) (quantitative).

[Formula 52]

Identification of the compound represented by formula (I-5a-2)

(Mass spectrometry) Ionization mode = MALDI +: m/z = 1545.7

Ionization mode = MALDI -: m/z = 2902.5

[Pigment Synthesis Example 11: Synthesis of Compound (B-I-3a)]

4.0 parts of the compound represented by the formula (B-I-2a) obtained in Pigment Synthesis Example 7, 4.4 parts of 1-propylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), tris(dibenzylideneacetone)dipalladium (0) (Fuji 0.72 parts of 2-dicyclohexylphosphino-2'-(dimethylamino)biphenyl (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 0.92 parts, tert-butoxy sodium (Tokyo) 2.44 parts (manufactured by Kasei Kogyo Co., Ltd.) and 80 parts of dehydrated 1,2-dimethoxyethane (manufactured by Kanto Chemical Co., Ltd.) were mixed and stirred at 40°C for 2 hours. After cooling to 25°C, the obtained mixture was filtered through Celite, and the filtrate was concentrated. The obtained residue was purified by silica gel column (solvent: chloroform) and dried under reduced pressure at 60°C to obtain 3.24 parts of the compound represented by the formula (B-I-3a) (yield 89%).

[Formula 53]

Identification of the compound represented by formula (B-I-3a)

(Mass spectrometry) Ionization mode = ESI +: m/z = 461.5

[Pigment Synthesis Example 12: Synthesis of Compound (B-I-3)]

3.0 parts of the compound represented by the formula (B-I-3a) obtained in Pigment Synthesis Example 11, 2.70 parts of 1-bromonaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.177 parts of palladium acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) Part, 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.81 parts, tert-butoxy sodium (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.01 parts , and 60 parts of dehydrated 1,2-dimethoxyethane (manufactured by Kanto Chemical Co., Ltd.) were mixed and stirred at 93°C for 10 hours. After cooling to 25°C, the resulting mixture was filtered through Celite, and the filtrate was concentrated. The obtained residue was purified by silica gel column (solvent: chloroform) and dried under reduced pressure at 60°C to obtain 3.45 parts of the compound represented by the formula (B-I-3) (yield 74%).

[Formula 54]

Identification of the compound represented by formula (B-I-3)

(Mass spectrometry) Ionization mode = ESI +: m/z = 713.6

[Pigment Synthesis Example 13: Synthesis of Compound (I-17a-1)]

2.01 parts of a compound represented by formula (C-I-1) obtained in dye synthesis example 4, 1.35 parts of a compound represented by formula (B-I-3) obtained in dye synthesis example 12, phosphorus oxychloride (Fujifilm Wako Pure Chemical Industries, Ltd.) 0.75 parts of the product) and 9.9 parts of dehydrated toluene (manufactured by Kanto Chemical Co., Ltd.) were mixed and stirred at 100°C for 3 hours. After cooling to 25°C, the resulting mixture was concentrated. The obtained residue was purified by silica gel column (solvent: chloroform) and dried under reduced pressure at 60°C to obtain 2.31 parts of the compound represented by formula (I-17a-1) (yield 68%).

[Formula 55]

Identification of the compound represented by formula (I-17a-1)

(Mass spectrometry) Ionization mode = ESI +: m/z = 815.7, divalent

[Pigment Synthesis Example 14: Synthesis of Compound (I-17a-2)]

1.95 parts of the compound represented by formula (I-17a-1) obtained in Pigment Synthesis Example 13, 2.91 parts of phosphotungstic acid hydrate (manufactured by Sigma-Aldrich Co., Ltd.), and dehydrated dimethyl sulfoxide (manufactured by Kanto Chemical Co., Ltd.) 10.2 parts were mixed and stirred at 45°C for 6 hours. After cooling to 25°C, 78 parts of water were added, and the obtained blue precipitate was filtered. The obtained residue was dried under reduced pressure at 60°C, and 3.3 parts of the compound represented by the formula (I-17a-2) was obtained (yield 84%).

[Formula 56]

Identification of the compound represented by formula (I-17a-2)

(Mass spectrometry) Ionization mode = MALDI +: m/z = 1629.6

Ionization mode = MALDI -: m/z = 2902.5

[Pigment Synthesis Example 15: Synthesis of Compound (B-I-4a)]

2.76 parts of the compound represented by the formula (B-I-1a) obtained in Pigment Synthesis Example 1, 3.3 parts of 1-propylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), tris(dibenzylideneacetone)dipalladium (0) (Fuji 0.528 parts of 2-dicyclohexylphosphino-2'-(dimethylamino)biphenyl (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 0.69 parts, 1.77 parts of tert-butoxy sodium (manufactured by Tokyo Chemical Industry Co., Ltd.) and 54 parts of dehydrated 1,2-dimethoxyethane (manufactured by Kanto Chemical Co., Ltd.) were mixed and stirred at 40°C for 2 hours. After cooling to 25°C, the obtained mixture was filtered through Celite, and the filtrate was concentrated. The obtained residue was purified by silica gel column (solvent: chloroform) and dried under reduced pressure at 60°C to obtain 1.68 parts of the compound represented by the formula (B-I-4a) (yield 67%).

[Formula 57]

Identification of the compound represented by formula (B-I-4a)

(Mass spectrometry) Ionization mode = ESI +: m/z = 652.6

[Pigment Synthesis Example 16: Synthesis of Compound (B-I-4)]

0.82 parts of the compound represented by the formula (B-I-4a) obtained in Pigment Synthesis Example 15, 0.91 parts of 1-bromonaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.052 part of palladium acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) part, 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.24 part, tert-butoxy sodium (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.59 part , and 16 parts of dehydrated 1,2-dimethoxyethane (manufactured by Kanto Chemical Co., Ltd.) were mixed and stirred at 93°C for 10 hours. After cooling to 25°C, the resulting mixture was filtered through Celite, and the filtrate was concentrated. The obtained residue was purified by silica gel column (solvent: chloroform) and dried under reduced pressure at 60°C to obtain 1.2 parts of the compound represented by the formula (B-I-4) (yield 87%).

[Formula 58]

Identification of the compound represented by formula (B-I-4)

(Mass spectrometry) Ionization mode = ESI +: m/z = 1030.8

[Pigment Synthesis Example 17: Synthesis of Compound (I-35a-1)]

1.36 parts of a compound represented by formula (C-I-1) obtained in dye synthesis example 4, 0.90 parts of a compound represented by formula (B-I-4) obtained in dye synthesis example 16, phosphorus oxychloride (Fujifilm Wako Pure Chemical Industries, Ltd.) 0.52 parts of the product) and 6.8 parts of dehydrated toluene (manufactured by Kanto Chemical Co., Ltd.) were mixed and stirred at 100°C for 3 hours. After cooling to 25°C, the resulting mixture was concentrated. The obtained residue was purified by silica gel column (solvent: chloroform) and dried under reduced pressure at 60°C to obtain 1.36 parts of the compound represented by the formula (I-35a-1) (yield 62%).

[Formula 59]

Identification of the compound represented by formula (I-35a-1)

(Mass spectrometry) Ionization mode = ESI +: m/z = 802.7, trivalent

[Pigment Synthesis Example 18: Synthesis of Compound (I-35a-2)]

0.69 parts of the compound represented by the formula (I-35a-1) obtained in Pigment Synthesis Example 17, 1.18 parts of phosphotungstic acid hydrate (manufactured by Sigma-Aldrich Co., Ltd.), and dehydrated dimethyl sulfoxide (manufactured by Kanto Chemical Co., Ltd.) 3.6 parts were mixed and stirred at 45°C for 6 hours. After cooling to 25°C, 28 parts of water were added, and the resulting blue precipitate was filtered. The obtained residue was dried under reduced pressure at 60°C, and 1.3 parts of the compound represented by the formula (I-35a-2) was obtained (yield 89%).

[Formula 60]

Identification of the compound represented by formula (I-35a-2)

(Mass spectrometry) Ionization mode = MALDI +: m/z = 2405.9

Ionization mode = MALDI -: m/z = 2902.5

[Pigment Synthesis Example 19: Synthesis of Compound (B-I-5a)]

The following reaction was performed under a nitrogen atmosphere. Add 4.6 parts of 4-bromo-3,5-dimethylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.), 4.0 parts of potassium carbonate, and 17.4 parts of N,N-dimethylformamide to a flask equipped with a cooling pipe and a stirring device. After stirring at 25°C for 20 minutes, 2.5 parts of 1,4-dibromobutane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred at 60°C for 5 hours. After the reaction solution was allowed to cool, 200 parts of distilled water and 200 parts of ethyl acetate were added to separate the layers, and the aqueous layer was washed twice with 200 parts of ethyl acetate. The obtained organic layers were combined, dried over excess Na ₂ SO ₄ , and concentrated under reduced pressure to obtain a crude product. This was purified by silica gel column chromatography (developing phase: xane/toluene 3/1). After drying under reduced pressure at 60°C, 3.7 parts of the compound represented by formula (BI-5a) was obtained (yield 69%).

[Formula 61]

Identification of the compound represented by formula (B-I-5a)

(Mass spectrometry) Ionization mode = ESI +: m/z = 455.2

[Pigment Synthesis Example 20: Synthesis of Compound (B-I-5)]

3.95 parts of the compound represented by the formula (B-I-5a) obtained in Pigment Synthesis Example 19, 2.48 parts of 1-aminonaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.00 parts of tris(dibenzylideneacetone)dipalladium (0) , 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.71 parts, tert-butoxy sodium (manufactured by Tokyo Chemical Industry Co., Ltd.) 3.74 parts, and 40 parts of toluene were mixed and stirred at 110°C for 3 hours. After cooling to 25°C, the obtained mixture was filtered through Celite, and the filtrate was concentrated. The obtained residue was purified by silica gel column (solvent: chloroform) and dried under reduced pressure at 60°C to obtain 3.5 parts of the compound represented by the formula (B-I-5) (yield 70%).

[Formula 62]

Identification of the compound represented by formula (B-I-5)

(Mass spectrometry) Ionization mode = ESI +: m/z = 581.5

[Pigment Synthesis Example 21: Synthesis of Compound (C-I-5a)]

The same procedure as in dye synthesis example 3 except that 2,4,6-trimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 2,6-dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), formula ( A compound represented by C-I-5a) was obtained.

[Formula 63]

[Pigment Synthesis Example 22: Synthesis of Compound (C-I-5)]

The compound represented by the formula (C-I-5) was obtained in the same manner as in Pigment Synthesis Example 4 except that the compound represented by the formula (C-I-5a) was used instead of the compound represented by the formula (C-I-1a).

[Formula 64]

[Pigment Synthesis Example 23: Synthesis of Compound (I-40a-1)]

16.5 parts of a compound represented by formula (C-I-5) obtained in dye synthesis example 22, 7.5 parts of a compound represented by formula (B-I-5) obtained in dye synthesis example 20, phosphorus oxychloride (Fujifilm Wako Pure Chemical Industries, Ltd.) 5.9 parts (manufactured by Kanto Chemical Co., Ltd.) and 98 parts of dehydrated toluene (manufactured by Kanto Chemical Co., Ltd.) were mixed and stirred at 80°C for 3 hours. After cooling to 25°C, the resulting mixture was concentrated. The obtained residue was purified by silica gel column (solvent: chloroform) and dried under reduced pressure at 60°C to obtain 1.0 part of the compound represented by the formula (I-40a-1) (yield 5%).

[Formula 65]

Identification of the compound represented by formula (I-40a-1)

(Mass spectrometry) Ionization mode = ESI +: m/z = 777.7, divalent

[Pigment Synthesis Example 24: Synthesis of Compound (I-40a-2)]

1.3 parts of the compound represented by the formula (I-40a-1) obtained in Pigment Synthesis Example 23, 3.8 parts of phosphotungstic acid hydrate (manufactured by Sigma-Aldrich Co., Ltd.), and dehydrated dimethyl sulfoxide (manufactured by Kanto Chemical Co., Ltd.) 6.6 parts were mixed and stirred at 45°C for 6 hours. After cooling to 25°C, 80 parts of water were added, and the resulting blue precipitate was filtered. The obtained residue was dried under reduced pressure at 60°C, and 1.4 parts of the compound represented by the formula (I-40a-2) was obtained (yield 61%).

[Formula 66]

Identification of the compound represented by formula (I-40a-2)

(Mass spectrometry) Ionization mode = MALDI +: m/z = 1553.7

Ionization mode = MALDI -: m/z = 2902.5

[Pigment Synthesis Example 25: Synthesis of Compound (C-I-6a)]

In the same manner as in Pigment Synthesis Example 3 except that 2,6-dimethyl-4-methoxyaniline was used instead of 2,6-dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), the dye represented by formula (C-I-6a) was obtained. The compound was obtained.

[Formula 67]

[Pigment Synthesis Example 26: Synthesis of Compound (C-I-6)]

A compound represented by the formula (C-I-6) was obtained in the same manner as in Pigment Synthesis Example 4, except that the compound represented by the formula (C-I-6a) was used instead of the compound represented by the formula (C-I-1a).

[Formula 68]

[Pigment Synthesis Example 27: Synthesis of Compound (I-42a-1)]

4.7 parts of the compound represented by formula (C-I-6) obtained in dye synthesis example 26, 2.0 parts of compound represented by formula (B-I-5) obtained in dye synthesis example 20, phosphorus oxychloride (Fujifilm Wako Pure Chemical Industries, Ltd.) 1.6 parts of the product) and 6.0 parts of dehydrated toluene (manufactured by Kanto Chemical Co., Ltd.) were mixed and stirred at 80°C for 4 hours. After cooling to 25°C, the resulting mixture was concentrated. The obtained residue was purified by silica gel column (solvent: chloroform) and dried under reduced pressure at 60°C to obtain 0.7 parts of the compound represented by the formula (I-42a-1) (yield 10%).

[Formula 69]

Identification of the compound represented by formula (I-42a-1)

(Mass spectrometry) Ionization mode = ESI +: m/z = 809.7, divalent

[Pigment Synthesis Example 28: Synthesis of Compound (I-42a-2)]

0.7 parts of the compound represented by the formula (I-42a-1) obtained in Pigment Synthesis Example 27, 1.8 parts of phosphotungstic acid hydrate (manufactured by Sigma-Aldrich Co., Ltd.), and dehydrated dimethyl sulfoxide (manufactured by Kanto Chemical Co., Ltd.) 210 parts were mixed and stirred at 45°C for 6 hours. After cooling to 25°C, 300 parts of water were added, and the obtained blue precipitate was filtered. The obtained residue was dried under reduced pressure at 60°C, and 0.7 parts of the compound represented by the formula (I-42a-2) was obtained (yield 57%).

[Formula 70]

Identification of the compound represented by formula (I-42a-2)

(Mass spectrometry) Ionization mode = MALDI +: m/z = 1617.7

Ionization mode = MALDI -: m/z = 2902.5

[Pigment Synthesis Example 29: Synthesis of Compound (I-4a-1)]

The compound represented by the formula (I-4a-1) was obtained in the same manner as in Pigment Synthesis Example 9, except that the compound represented by the formula (C-I-5) was used instead of the compound represented by the formula (C-I-1).

[Formula 71]

Identification of the compound represented by formula (I-4a-1)

(Mass spectrometry) Ionization mode = MALDI +: m/z = 1601.9

[Pigment Synthesis Example 30: Synthesis of Compound (I-4a-2)]

The compound represented by the formula (I-4a-2) was prepared in the same manner as in Pigment Synthesis Example 10 except that the compound represented by the formula (I-4a-1) was used instead of the compound represented by the formula (I-5a-1). got it

[Formula 72]

Identification of the compound represented by formula (I-4a-2)

(Mass spectrometry) Ionization mode = MALDI +: m/z = 1601.9

Ionization mode = MALDI -: m/z = 2902.5

[Pigment Synthesis Example 31: Synthesis of Compound (x1)]

According to the contents described in Japanese Patent Application Laid-Open No. 2014-108975, a compound represented by the following formula (x1) was synthesized.

[Formula 73]

[Pigment Synthesis Example 32: Synthesis of Compound (x2)]

According to the contents described in Japanese Patent Application Laid-Open No. 2014-108975, a compound represented by the following formula (x2) was synthesized.

[Formula 74]

<Synthesis of resin>

Resin synthesis example 1

An appropriate amount of nitrogen was poured into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer to create a nitrogen atmosphere, 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were added, and the flask was heated to 85°C while stirring. Next, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-8-ylacrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-9-ylacrylate A mixed solution of 25 parts of lye (content ratio is 1:1 in molar ratio), 137 parts of N-cyclohexylmaleimide, 50 parts of 2-hydroxyethyl methacrylate, and 338 parts of propylene glycol monomethyl ether acetate was mixed over 5 hours. Dropped. Meanwhile, a solution prepared by dissolving 5 parts of 2,2-azobisisobutyronitrile in 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the solution was kept at 85°C for 4 hours and then cooled to room temperature to obtain a copolymer (resin B-1) solution with a viscosity of 23 mPas and a solid content of 25.6% as measured by a B-type viscometer (23°C). . The weight average molecular weight (Mw) of the produced copolymer was 8.0×10 ³ , the degree of dispersion was 2.1, and the acid value in terms of solid content was 109 mg-KOH/g. Resin B-1 has the following structural units.

[Formula 75]

[Example 1]

<Preparation of colorant dispersion (A-1) containing compound (I-23a-2)>

Compound (I-23a-2) 5 parts, acrylic dispersant 3 parts, Resin B-1 (solid content conversion) 2 parts, propylene glycol monomethyl ether acetate 79 parts, diacetone alcohol 10 parts, ethyl lactate 1 part, and 0.2 mm 300 parts of zirconia beads were mixed, and the resulting mixture was shaken for 1 hour using a paint conditioner (manufactured by LAU). Thereafter, the zirconia beads were removed by filtration to obtain a colorant dispersion (A-1).

<Preparation of colored resin composition>

(A) Colorant: Colorant dispersion (A-1) Part 245

(B) Resin: Resin (B-1) (converted to solid content) Part 45

(C) Polymerizable compound: Dipentaerythritol hexaacrylate

(Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 copies

(D) Polymerization initiator: TR-PBG327 (manufactured by Sangju Kanggyeon Electronic Materials Co., Ltd.) Part 3

(F) Surfactant: Fluorine-based surfactant (Megapac (registered trademark) F554; manufactured by DIC)

0.09 copies

(E) Solvent: propylene glycol monomethyl ether acetate (E-1) Part 506

(E) Solvent: Ethyl lactate (E-2) Part 27

was mixed to obtain a colored resin composition.

[Examples 2 to 7, Comparative Examples 1 to 2]

Colored resin compositions were obtained in the same manner as in Example 1, except that compound (I-23a-2) was changed to the following compounds.

Example 2: Compound (I-5a-2)

Example 3: Compound (I-17a-2)

Example 4: Compound (I-35a-2)

Example 5: Compound (I-40a-2)

Example 6: Compound (I-42a-2)

Example 7: Compound (I-4a-2)

Comparative Example 1: Compound (x1)

Comparative Example 2: Compound (x2)

< Production example 1 >

(Production of red resin composition)

(A) Colorant: Acid Red 52 (manufactured by Tokyo Chemical Industry Co., Ltd.) Part 8

(B) Resin: Resin (B-1) (converted to solid content) 50 copies

(C) Polymerizable compound: Dipentaerythritol hexaacrylate

(Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 copies

(D) Polymerization initiator: TR-PBG327 (manufactured by Sangju Kanggyeon Electronic Materials Co., Ltd.) Part 3

(F) Surfactant: Fluorine-based surfactant (Megapac (registered trademark) F554; manufactured by DIC)

0.09 copies

(E) Solvent: propylene glycol monomethyl ether acetate (E-1) Part 127

(E) Solvent: Ethyl lactate (E-2) Part 30

(E) Solvent: 4-hydroxy-4-methyl-2-pentanone (E-3) Part 472

was mixed to obtain a red resin composition.

<Formation of colored coating film (color filter)>

The colored resin composition obtained in Examples 1 to 7 and Comparative Examples 1 to 2 and the red resin composition obtained in Production Example 1 were applied to a 2-inch x 2-inch glass substrate (Eagle 2000; manufactured by Corning) by spin coating. Afterwards, it was prebaked at 100°C for 3 minutes to form a composition layer. After cooling, the composition layer was irradiated with light at an exposure dose of 60 mJ/cm2 (based on 365 nm) in an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon), and then post-baked in an oven at 230°C for 20 minutes. By performing this, a colored coating film was obtained.

<Measurement of transmission spectrum>

The transmission spectra of the colored coating films obtained from Examples 1 to 7, Comparative Examples 1 to 2, and Production Example 1 were measured using a colorimeter (OSP-SP-200) manufactured by Olympus.

<Calculation of brightness>

The CIE chromaticity coordinates and brightness (Y) when the colored resin compositions of Examples 1 to 7 or Comparative Examples 1 to 2 and the red resin composition of Production Example 1 were mixed in the ratios shown in Table 10 were obtained. CIE chromaticity coordinates and brightness (Y) are the transmission spectra obtained from the colored coating films of Examples 1 to 7 and Comparative Examples 1 to 2, respectively, the transmission spectrum obtained from the colored coating film of Production Example 1, and the characteristic function of the C light source. It was calculated, and the mixing ratios in Table 10 were all combinations of CIE chromaticity coordinates (x, y) = (0.150, 0.060). The values of brightness (Y) are shown in Table 10. The larger the value of Y, the higher the brightness.

[Table 10]

In Table 10, each notation represents the following coloring agent.

I-23a-2: Compound (I-23a-2)

I-5a-2: Compound (I-5a-2)

I-17a-2: Compound (I-17a-2)

I-35a-2: Compound (I-35a-2)

I-40a-2: Compound (I-40a-2)

I-42a-2: Compound (I-42a-2)

I-4a-2: Compound (I-4a-2)

x1: compound (x1)

x2: compound (x2)

AR52 : Acid Red 52

Claims (5)

A compound represented by formula (I).
[Formula 1]

[In formula (I),
R ¹ to ^{R 4} and R ¹³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent.
R ⁵ to ^{R 12} each independently represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 5 carbon atoms which may have a substituent.
T ¹ and T ² independently represent a divalent aromatic hydrocarbon group that may have a substituent or a divalent aromatic heterocyclic group that may have a substituent.
L ¹ represents an a-valent aliphatic hydrocarbon group having 1 to 12 carbon atoms or a group represented by formula (i), which may have a substituent, and at least one methylene group contained in the aliphatic hydrocarbon group is substituted with -O- there is.
a represents an integer of 2 or more.
b and c independently represent an integer of 1 or more.
d represents an integer greater than or equal to 0.
X ^c- represents a c-valent anion.]
[Formula 2]

[In equation (i),
T ³ represents an a-valent aromatic hydrocarbon group which may have a substituent or an a-valent aromatic heterocyclic group which may have a substituent.
L ² represents a divalent aliphatic hydrocarbon group having 1 to 5 carbon atoms which may have a substituent, and at least one methylene group contained in the aliphatic hydrocarbon group is substituted with -O-.
* indicates the binding hand with T ^2. ] A colored resin composition containing a colorant and a resin, wherein the colorant includes the compound according to claim 1. According to claim 2,
A colored resin composition further containing a polymerizable compound and a polymerization initiator. A color filter formed from the colored resin composition according to claim 2 or 3. A display device comprising the color filter according to claim 4.