TWI813781B - Compound, colored resin composition, color filter and display device - Google Patents

Abstract

[Problem] The present invention provides a compound capable of forming a color filter excellent in heat resistance. [Solution] A compound represented by formula (I), a colored resin composition containing the same, a color filter and a display device. [In formula (I), R ¹ to R ⁸ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a carbon number 1 to 20 which may have a substituent. an alkoxy group; R ⁹ and R ¹⁰ each independently represent a divalent aliphatic hydrocarbon group with 1 to 20 carbon atoms that may have a substituent, and the methylene group contained in the aliphatic hydrocarbon group may be replaced with -O- ; R ¹¹ and R ¹² each independently represent a hydrocarbon group with 6 to 20 carbon atoms having an aromatic hydrocarbon ring. The hydrocarbon group may have a substituent, and the methylene group contained in the hydrocarbon group may be replaced with -O-; R ¹³ represents a hydrogen atom or a saturated hydrocarbon group with 1 to 8 carbon atoms]

Description

Compounds, colored resin compositions, color filters and display devices

The present invention relates to a compound.

Display devices such as liquid crystal displays, electroluminescence displays, and plasma displays, or solid-state imaging such as CCD (Charge-Coupled Device) or CMOS (Complementary Metal-Oxide-Semiconductor) sensors The color filters used in the components are made of colored resin compositions. As the coloring agent used in such a colored resin composition, compounds represented by formula (x) are known.

[Prior technical literature] [Patent Document] [Patent Document 1] Japanese Patent Application Publication No. 2015-86380

[Problem to be solved by the invention]

However, color filters formed from conventionally known colored resin compositions containing the above-mentioned compounds sometimes do not have sufficient heat resistance. Therefore, the present invention provides a compound capable of forming a color filter excellent in heat resistance. [Means to solve the problem]

The present invention includes the following inventions.

[1] A compound represented by formula (I), [In formula (I), R ¹ to R ⁸ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a carbon number 1 to 20 which may have a substituent. an alkoxy group; R ⁹ and R ¹⁰ each independently represent a divalent aliphatic hydrocarbon group with 1 to 20 carbon atoms that may have a substituent, and the methylene group contained in the aliphatic hydrocarbon group may be replaced with -O- ; R ¹¹ and R ¹² each independently represent a hydrocarbon group with 6 to 20 carbon atoms having an aromatic hydrocarbon ring. The hydrocarbon group may have a substituent, and the methylene group contained in the hydrocarbon group may be replaced with -O-; R ¹³ represents a hydrogen atom or a saturated hydrocarbon group having 1 to 8 carbon atoms].

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

[3] The colored resin composition as described in [2], further comprising a polymerizable compound and a polymerization initiator.

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

[5] A display device including the color filter as described in [4]. [Effects of the invention]

According to the present invention, a novel compound capable of forming a color filter excellent in heat resistance is provided.

＜Compound＞

The compound of the present invention is a compound represented by formula (I) (hereinafter, sometimes referred to as compound (I)). Although the present invention is described in detail below using formula (I), compound (I) also includes the resonance structure of formula (I) or the bonding of each group in formula (I) around a carbon-carbon single bond. A compound obtained by rotating an axis. [In formula (I), R ¹ to R ⁸ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a carbon number 1 to 20 which may have a substituent. The alkoxy group. R ⁹ and R ¹⁰ each independently represent a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and the methylene group contained in the aliphatic hydrocarbon group may be replaced with -O-. R ¹¹ and R ¹² each independently represent a hydrocarbon group having 6 to 20 carbon atoms having an aromatic hydrocarbon ring. The hydrocarbon group may have a substituent, and the methylene group contained in the hydrocarbon group may be replaced with -O-. R ¹³ represents a hydrogen atom or a saturated hydrocarbon group having 1 to 8 carbon atoms. ]

Examples of the halogen atom represented by R ¹ to R ⁸ include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ to R ⁸ may be linear, branched, or cyclic. Specific examples of linear or branched saturated hydrocarbon groups include: methyl, ethyl, propyl, isobutyl, butyl, tertiary butyl, hexyl, heptyl, octyl, nonyl, and decyl. , seventeen bases, eleven bases, etc. Examples of the cyclic saturated hydrocarbon group include: cyclopropyl, 1-methylcyclopropyl, cyclopentyl, cyclohexyl, 1,2-dimethylcyclohexyl, cyclooctyl, and 2,4,6-trimethyl cyclohexyl, 4-cyclohexylcyclohexyl, etc.

Examples of substituents for the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ to R ⁸ include: halogen atoms such as fluorine atoms, chlorine atoms, and iodine atoms; hydroxyl groups; -NR ^a R ^b (R ^a and R ^b are Each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms); nitro group; an alkoxy group having 1 to 10 carbon atoms such as methoxy, ethoxy, etc.; alkoxy groups having 1 to 10 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, etc. 1 to 10 alkoxycarbonyl groups, etc.

Examples of the alkoxy group having 1 to 20 carbon atoms represented by R ¹ to R ⁸ include groups in which -O- is bonded to the bonding end of the above-mentioned saturated hydrocarbon group having 1 to 20 carbon atoms. Specific examples include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, secondary butoxy, tertiary butoxy, pentyloxy, hexyloxy, heptyl Oxygen, octyloxy, 2-ethylhexyloxy, etc.

Examples of substituents for the alkoxy group having 1 to 20 carbon atoms represented by R ¹ to R ⁸ include: halogen atoms such as fluorine atoms, chlorine atoms, and iodine atoms; hydroxyl groups; -NR ^c R ^d (R ^c and R ^d are independently hydrogen atoms or alkyl groups with 1 to 20 carbon atoms); nitro; alkoxy groups with 1 to 10 carbon atoms such as methoxy and ethoxy; alkyl groups such as methoxycarbonyl and ethoxycarbonyl The carbon number of the oxy moiety is an alkoxycarbonyl group of 1 to 10, etc.

Among R ¹ to R ⁸ , R ¹ to R ⁴ are preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. In addition, when R ¹ to R ⁴ are hydrogen atoms or methyl groups, more preferably when R ¹ to R ⁴ are hydrogen atoms, R ⁵ to R ⁸ are preferably each independently a hydrogen atom, a hydroxyl group, A saturated hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent, or an alkoxy group having 1 to 20 carbon atoms, which may have a substituent, is more preferably a hydrogen atom or a hydroxyl group.

Preferably, two to four of R ¹ to R ⁸ (preferably R ⁵ to R ⁸ ) are independently hydroxyl groups.

The divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R ⁹ and R ¹⁰ may be either saturated or unsaturated, and is preferably saturated. In addition, the divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms may be linear, branched, or cyclic, and is preferably linear or branched.

Examples of the divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms include methylene, ethylidene, propane-1,3-diyl, butane-1,4-diyl, and pentane-1,5- Diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10- Diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane -1,15-diyl, hexadecane-1,16-diyl, heptadecan-1,17-diyl, propenylene and other divalent linear aliphatic hydrocarbon groups; ethane-1 ,1-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-2,2-diyl, pentane-2,4-diyl, 2-methylpropane-1 ,3-diyl, 2-methylpropane-1,2-diyl, 2,2-dimethylpropane-1,3-diyl, pentane-1,4-diyl, 2-methylbutanyl Alk-1,4-diyl and other divalent branched aliphatic hydrocarbon groups.

The cyclic divalent aliphatic hydrocarbon group may be monocyclic or polycyclic. Examples of the cyclic divalent aliphatic hydrocarbon group include cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, and cyclooctane-diyl. Monocyclic divalent aliphatic hydrocarbon groups such as 1,5-diyl; norbornane-1,4-diyl, norbornane-2,5-diyl, adamantane-1,5-diyl , adamantane-2,6-diyl and other polycyclic divalent aliphatic hydrocarbon groups.

The methylene group contained in the divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms may be replaced with -O-. Examples of the group in which the methylene group contained in the divalent aliphatic hydrocarbon group is replaced by -O- include groups represented by the following formula. In the following formula, the * on the left side represents the bonding end with the nitrogen atom, and the * on the right side represents the bonding end with the oxygen atom.

The divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R ⁹ and R ¹⁰ may have a substituent. Examples of the substituent include: halogen atoms such as fluorine atoms, chlorine atoms, and iodine atoms; hydroxyl groups; -NR ^e R ^f (R ^e and R ^f are each independently a hydrogen atom or an alkyl group with 1 to 20 carbon atoms); nitro; methoxycarbonyl, ethoxycarbonyl and other alkoxycarbonyl groups with 1 to 10 carbon atoms, etc. .

Examples of the hydrocarbon group having an aromatic hydrocarbon ring and having a carbon number of 6 to 20 represented by R ¹¹ and R ¹² include a group having a bonding end on the aromatic hydrocarbon ring (hereinafter referred to as an aromatic hydrocarbon group), a group having a carbon number of 7 to 20 aralkyl groups, etc. These may also have substituents.

Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and the like; a benzene ring is preferred.

Examples of the aromatic hydrocarbon group include phenyl, naphthyl, anthracenyl, phenanthrenyl, tolyl, styryl, trimethylphenyl, diisopropylphenyl, and the like. Among them, preferred are aromatic hydrocarbon groups having an alkyl group at the ortho position, examples of which include: 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, and 2,6-diisopropyl. Phenyl etc. Furthermore, if the alkyl group at the ortho position is large in size, the light resistance tends to be excellent.

When the aromatic hydrocarbon group has a substituent, it may have one substituent or a plurality of substituents. When the aromatic hydrocarbon group has a plurality of substituents, each substituent may be the same or different. Examples of the substituent include: hydroxyl group; carboxyl group; halogen atoms such as fluorine atom, chlorine atom, iodine atom, and bromine atom; alkoxy groups having 1 to 6 carbon atoms such as methoxy group and ethoxy group; sulfamide group ( sulfamoyl); alkylsulfonyl groups with 1 to 6 carbon atoms such as methylsulfonyl group; alkoxycarbonyl groups with 1 to 6 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group, etc.

The aforementioned hydrocarbon group having 1 to 14 carbon atoms may also have substituents such as a hydroxyl group, a carboxyl group, a halogen atom, and an alkoxy group.

When the aforementioned aromatic hydrocarbon group which may have a substituent has a methylene group, the methylene group may be replaced with -O-.

The above-mentioned aralkyl group having 7 to 20 carbon atoms can be exemplified by the aromatic hydrocarbon ring described above. Alkanediyl groups having 1 to 5 carbon atoms such as methylene, ethylidene, and propylene are bonded to the aromatic hydrocarbon ring. groups etc. Examples of the aralkyl group include benzyl group, phenylethyl group, naphthylmethyl group, naphthylethyl group, and the like.

The aforementioned aralkyl group having 7 to 20 carbon atoms may also have a substituent. When there are multiple substituents, each substituent may be the same or different. This substituent may be bonded to the aforementioned aromatic hydrocarbon ring or may be bonded to the aforementioned alkanediyl group. The substituent that may be bonded to the aromatic hydrocarbon ring is the same as the substituent of the aforementioned aromatic hydrocarbon group. The group is the same.

In the case where the aralkyl group having 7 to 20 carbon atoms which may have a substituent has a methylene group, the methylene group may also be replaced with -O-.

The saturated hydrocarbon group having 1 to 8 carbon atoms represented by R ¹³ may be linear, branched, or cyclic. Specific examples of linear or branched saturated hydrocarbon groups include methyl, ethyl, propyl, isobutyl, butyl, tertiary butyl, hexyl, heptyl, octyl, etc. Examples of the cyclic saturated hydrocarbon group include cyclopropyl, 1-methylcyclopropyl, cyclopentyl, cyclohexyl, 1,2-dimethylcyclohexyl, cyclooctyl, and the like.

Examples of the compound (I) include compounds represented by formulas (I-1) to formula (I-240) shown in Tables 1 to 3, and the like.

[Table 1]

[Table 2]

[table 3]

In Tables 1 to 3, A1-1 to A1-4 represent groups represented by the following formulas. In the following formula, the * on the left side represents the bonding end with the nitrogen atom, and the * on the right side represents the bonding end with the oxygen atom.

In Tables 1 to 3, A2-1 to A2-5 represent groups represented by the following formulas. In the following formula, * represents a bonding end.

In addition, as the compound (I), in addition to the compounds represented by the above-mentioned formula (I-1) to the formula (I-240), there can also be cited the compounds represented by the following formula (II), and preferably the compound represented by the formula ( II) The compound represented. The compound represented by formula (II) has good light resistance. [In formula (II), R ¹ to R ¹⁰ represent the same meaning as R ¹ to R ¹⁰ in formula (I); X ¹ and X ² independently represent a group consisting of a hydroxyl group and a carboxyl group. At least one of the selected groups is a hydrocarbon group, hydroxyl group and carboxyl group having 1 to 14 carbon atoms, and the methylene group contained in the hydrocarbon group can be replaced with -O-; R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom or a hydrocarbon group with a carbon number of 1 to 13; n1 and n2 each independently represent an integer from 1 to 5; however, the total carbon number of (X ¹ ) _n1 and (R ¹⁴ ) _5-n1 , and (X ² ) _n2 and The total carbon number of (R ¹⁵ ) _5-n2 is 14 or less]

Examples of the hydrocarbon group having 1 to 14 carbon atoms represented by X ¹ and X ² include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups combining these.

Examples of linear aliphatic hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and the like.

Examples of branched aliphatic hydrocarbon groups include isopropyl, secondary butyl, tertiary butyl, methylpentyl, ethylpentyl, methylhexyl, ethylhexyl, propylhexyl, and tertiary octyl. base, etc.; preferred examples include: isopropyl, secondary butyl, tertiary butyl, and ethylhexyl.

Examples of the cyclic aliphatic hydrocarbon group include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, adamantyl, and the like.

Examples of the aromatic hydrocarbon group include: phenyl group, naphthyl group, anthracenyl group, p-methylphenyl group, p-tertiary butylphenyl group, tolyl group, stubble group, cumenyl group, mesitylene Mesityl group, biphenyl, 2,6-diethylphenyl, 2-methyl-6-ethylphenyl, etc.

Examples of groups combining these include alkylcycloalkyl, cycloalkylalkyl, aralkyl, and the like.

The methylene group contained in the aforementioned hydrocarbon group having 1 to 14 carbon atoms may be replaced with -O-.

Examples of the hydrocarbon group having 1 to 13 carbon atoms represented by R ¹⁴ and R ¹⁵ include the same groups as those described as the hydrocarbon group having 1 to 14 carbon atoms represented by X ¹ and X ² .

n1 and n2 each independently represent an integer from 1 to 5, preferably 1 to 2.

The total carbon number of (X ¹ ) _n1 and (R ¹⁴ ) _5-n1 , and the total carbon number of (X ² ) _n2 and (R ¹⁵ ) _5-n2 are respectively 14 or less. When there are a plurality of X ¹ , X ² , R ¹⁴ and R ¹⁵ , each of X ¹ , X ² , R ¹⁴ and R ¹⁵ may be the same or different.

Examples of compound (II) include compounds represented by the following formula (II-a). Specifically, compounds represented by formulas (II-1) to formula (II-540) shown in Table 4 to Table 12, etc. .

[Table 4]

[table 5]

[Table 6]

[Table 7]

[Table 8]

[Table 9]

[Table 10]

[Table 11]

[Table 12]

In Tables 4 to 12, A1-1 to A1-4 represent the same groups as above.

In Tables 4 to 12, A3-1 to A3-3 represent groups represented by the following formulas. In the following formula, * represents a bonding end.

In Tables 4 to 12, A4-1 to A4-3 represent groups represented by the following formulas. In the following formula, * represents a bonding end.

The compound represented by formula (I) can be produced by reacting the compound represented by formula (pt1), the compound represented by formula (pt2), and the compound represented by formula (pt3). In this reaction, the total amount of the compound represented by the formula (pt1) and the compound represented by the formula (pt2) is preferably 1.5 mol to 2.5 mol per 1 mol of the compound represented by the formula (pt3). More.

＜Colored resin composition＞

The colored resin composition of the present invention contains a colorant (A) and a resin (B), wherein the colorant (A) contains a compound represented by formula (I).

The colored resin composition of the present invention preferably further contains a polymerizable compound (C) and a polymerization initiator (D).

The colored resin composition of the present invention may further include a polymerization starting aid (D1), a solvent (E), and a leveling agent (F).

In this specification, unless otherwise stated, the compounds exemplified as each component can be used alone or in combination of plural types.

＜Coloring agent (A)＞

The colored resin composition of the present invention contains compound (I) as the colorant (A). The content of the compound (I) is preferably 0.1 to 150 parts by mass, more preferably 0.3 to 100 parts by mass, and further preferably 0.5 to 80 parts by mass relative to 100 parts by mass of the resin (B). .

In the total amount of the colorant (A), the content rate of the compound (I) is preferably 20 mass% or more, more preferably 50 mass% or more, further preferably 80 mass% or more, and particularly preferably 90 mass% or more.

In addition to the compound (I) as the colorant (A), the colored resin composition of the present invention may also contain the dye (A1) and the pigment (A2) as the colorant (A).

The dye (A1) is not particularly limited, and conventional dyes can be used. Examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of dyes include compounds classified as substances having hues other than pigments in the Color Index (published by The Society of Dyers and Colourists), or dyeing notes ( The commonly known dyes recorded in the dyeing company). In addition, based on the chemical structure, examples include azo dyes, cyanine dyes, triphenylmethane dyes, dibenzopyran (xanthene) dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, and quinoneimine dyes. Methine dyes, azomethine dyes, squarylium dyes (excluding compound (I)), acridine dyes, styryl dyes, coumarin dyes, quinoline dyes and nitro dyes Dyes, etc. Among these, organic solvent-soluble dyes are preferred.

The pigment (A2) is not particularly limited, and conventional pigments can be used. For example, pigments classified as pigments in the Dye Index (published by The Society of Dyers and Colorists) can be used.

Examples of pigments include: 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, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and other yellow pigments; C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 and other red pigments; C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 60 and other blue pigments; C.I. Pigment Purple 1, 19, 23, 29, 32, 36, 38 and other purple pigments; C.I. Pigment Green 7, 36, 58 and other green pigments; C.I. Pigment Brown 23, 25 and other brown pigments; C.I. Pigment Black 1, 7 and other black pigments, etc.

The content rate of the coloring agent (A) is preferably 0.1 mass% to 70 mass%, more preferably 0.5 mass% to 60 mass%, further preferably 1 mass% to 60 mass%, based on the total solid content of the colored resin composition. 50% by mass.

Here, the "total amount of solid content" in this specification refers to the amount obtained by 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 the total amount can be measured by conventional analytical means such as liquid chromatography or gas chromatography.

＜Resin (B)＞

The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and more preferably has at least one monomer (a) selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride (hereinafter A resin having a structural unit called "(a)"). Resin (B) further preferably has at least one structural unit selected from the following group: monomer (b) derived from a cyclic ether structure having a carbon number of 2 to 4 and an ethylenically unsaturated bond (hereinafter referred to as In the case of "(b)"), the structural unit is derived from the monomer (c) copolymerizable with (a) (however, it is different from (a) and (b)) (hereinafter referred to as "(c)" case) structural units, and structural units with ethylenically unsaturated bonds in the side chain.

Specific examples of (a) include: acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, succinic acid mono[2-( meth)acryloxyethyl] ester, etc., preferably acrylic acid, methacrylic acid, and maleic anhydride.

(b) Preferably, it is a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxoacetate ring and a tetrahydrofuran ring) and (meth)propylene Cyloxy monomer.

Furthermore, in this specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. Expressions such as "(meth)acrylyl" and "(meth)acrylate" also have the same meaning.

Examples of (b) include: (meth)acrylic acid glycidyl ester, vinyl benzyl glycidyl ether, (meth)acrylic acid-3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl ester , 3-ethyl-3-(meth)acryloxymethyloxyethane, (meth)acrylic acid tetrahydrofurfuryl ester, etc., preferably glycidyl (meth)acrylate, (meth)acrylate Acrylic acid-3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl ester, 3-ethyl-3-(meth)acryloxymethyloxyethane.

Examples of (c) include: methyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, (meth)acrylate base) Tricyclo[5.2.1.0 ^2,6 ]decan-8-yl acrylate, (meth)acrylic acid benzyl ester, (meth)acrylic acid-2-hydroxyethyl ester, N-phenyl maleacyl ester Amine, N-cyclohexylmaleimide, N-benzylmaleimide, styrene, vinyltoluene, etc.; preferably styrene, vinyltoluene, (meth)acrylic acid-2-hydroxyethyl Ester, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, etc. are suitable.

The resin having a structural unit with an ethylenically unsaturated bond in the side chain can be obtained by adding (b) to the copolymer of (a) and (c), or by adding (b) to the copolymer of (b) and (c). Made into (a). This resin may be a resin obtained by adding (a) to the copolymer of (b) and (c) and further reacting a carboxylic acid anhydride.

The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, further preferably 5,000 to 30,000.

The dispersion degree [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, more preferably 1.2 to 4.

The acid value of the resin (B) is preferably 20 mg-KOH/g (mg-KOH/gram) to 170 mg-KOH/g in terms of solid content, and more preferably 30 mg-KOH/g to 150 mg- KOH/g, more preferably 40 mg-KOH/g to 135 mg-KOH/g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 gram of resin (B), and can be determined by titration using a potassium hydroxide aqueous solution, for example.

The content rate of resin (B) is preferably 30 mass % to 99.9 mass %, more preferably 50 mass % to 99.5 mass %, further preferably 70 mass % to 99 mass % relative to the total solid content of the colored resin composition. Mass %.

When the colored resin composition of the present invention contains the polymerizable compound (C) and the polymerization initiator (D), the content rate of the resin (B) relative to the total solid content of the colored resin composition is preferably: 7 mass% to 70 mass%, more preferably 13 mass% to 65 mass%, further preferably 17 mass% to 60 mass%.

<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). Examples thereof include polymerizable compounds having ethylenically unsaturated bonds, etc. Preferred are (meth)acrylate compounds.

Among these, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include: trimethylolpropane tri(meth)acrylate, neopentylerythritol tri(meth)acrylate, neopentylerythritol tetra(meth)acrylate, and dichloromethacrylate. Pentaerythritol penta(meth)acrylate, dineopenterythritol hexa(meth)acrylate, etc.

When the polymerizable compound (C) is contained, the content rate of the polymerizable compound (C) is preferably 5% by mass to 65% by mass, more preferably 13% by mass to 60% by mass relative to the total amount of solid content. %, more preferably 17% by mass to 55% by mass.

＜Polymerization initiator (D)＞

The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate active radicals, acids, etc. by the action of light or heat to initiate polymerization, and a conventional polymerization initiator can be used. Examples of polymerization initiators that generate active free radicals include: N-benzyloxy-1-(4-phenylhydrothiophenyl)butane-1-one-2-imine, N -Benzoyloxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylhydrogen) Thiophenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetyloxy-1-(4-phenylhydrothiophenyl)-3-cyclohexylpropane- 1-keto-2-imine, 2-methyl-2-morpholinyl-1-(4-methylhydrothiophenyl)propan-1-one, 2-dimethylamino-1- (4-morpholinylphenyl)-2-benzylbutan-1-one, 1-hydroxycyclohexylphenylketone, 2,4-bis(trichloromethyl)-6-sunfloweryl-1, 3,5-triazine, 2,4,6-trimethylbenzyldiphenylphosphine oxide, 2,2'-bis(2-chlorophenyl)-4,4',5,5' -Tetraphenylbiimidazole, etc.

When the polymerization initiator (D) is included, the content of the polymerization initiator (D) is preferably 0.1 parts by mass relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). to 30 parts by mass, more preferably 1 to 20 parts by mass, further preferably 2 to 10 parts by mass. When the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be high and the exposure time is shortened, so the productivity of the color filter is improved.

＜Polymerization starting aid (D1)＞

The polymerization initiating aid (D1) is a compound for accelerating the polymerization of a polymerizable compound started by a polymerization initiator, or is a sensitizer. When the polymerization initiating aid (D1) is included, it is usually used in combination with the polymerization initiator (D).

Examples of the polymerization starting aid (D1) include: 4,4'-bis(dimethylamino)benzophenone (commonly known as Michelone), 4,4'-bis(diethylamine) ) benzophenone, 9,10-dimethoxyanthracene, 2,4-diethyl thioxanthone (2,4-diethyl thioxanthone), N-phenylglycine, etc.

When using these polymerization starting aids (D1), the content is preferably 0.1 to 30 parts by mass relative to the total amount of 100 parts by mass of the resin (B) and the polymerizable compound (C). , more preferably 1 to 20 parts by mass. If the amount of the polymerization starting aid (D1) is within this range, a colored pattern can be formed with further high sensitivity, thereby tending to improve the productivity of the color filter.

＜Solvent (E)＞

The solvent (E) is not particularly limited, and solvents commonly used in this technical field can be used. Examples include: ester solvents (solvents that contain -COO- but not -O- in the molecule), ether solvents (solvents that contain -O- but do not contain -COO- in the molecule), ether ester solvents (solvents that contain - in the molecule) Solvents of COO- and -O-), ketone solvents (solvents that contain -CO- but not -COO- in the molecule), alcohol solvents (solvents that contain OH in the molecule and do not contain -O-, -CO- and -COO- solvents), aromatic hydrocarbon solvents, amide solvents, halogen solvents, dimethyl styrene, etc.

Examples of solvents include: Ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, n-butyl acetate, ethyl butyrate, butyl butyrate, ethyl pyruvate, methyl acetoacetate, cyclohexanol acetate and Ester solvents such as γ-butyrolactone (solvents that contain -COO- but do not contain -O- in the molecule); Ether solvents such as ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-1-butanol, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether ( Solvents containing -O- but not -COO- in the molecule); Methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethyl Ether ester solvents such as glycol monoethyl ether acetate (solvents containing -COO- and -O- in the molecule); 4-Hydroxy-4-methyl-2-pentanone (diacetone alcohol), heptanone, 4-methyl-2-pentanone, cyclohexanone and other ketone solvents (the molecule contains -CO- and does not contain -COO - solvent); Alcohol solvents such as butanol, cyclohexanol, and propylene glycol (solvents that contain OH in the molecule and do not contain -O-, -CO-, and -COO-); Amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone; Halogen solvents such as chloroform, chlorobenzene, dichloroethylene, trichlorethylene, etc.

As the solvent, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), N-methylpyrrolidone, chloroform, and ethyl lactate are more preferred. ester and ethyl 3-ethoxypropionate.

When the solvent (E) is included, the content rate of the solvent (E) is preferably 60 mass % to 95 mass %, more preferably 65 mass % to 92 mass % relative to the total amount of the colored resin composition of the present invention. Mass %. In other words, the total solid content of the colored resin composition is preferably 5 to 40 mass%, more preferably 8 to 35 mass%. If the content of the solvent (E) is within the above range, the flatness during coating will be good, and the color density will not be insufficient when forming the color filter, so the display characteristics will tend to be good.

＜Leveling agent (F)＞

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

Examples of polysiloxane-based surfactants include surfactants having siloxane bonds in the molecules. Specific examples include: Toray silicone C3PA, Toray silicone SH7PA, Toray silicone DC11PA, Toray silicone SH21PA, Toray silicone SH28PA, Toray silicone SH29PA, Toray silicone SH30PA, Toray silicone SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.); KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.); TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Japan Momentive Advanced Materials Co., Ltd.), etc. .

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specific examples include: Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Co., Ltd.); Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, Megafac RS-718-K (manufactured by DIC Co., Ltd.); Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.); Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Research Institute Co., Ltd.), etc.

Examples of the polysiloxane-based surfactant having fluorine atoms include surfactants having siloxane bonds and fluorocarbon chains in the molecule. Specific examples include: Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, and Megafac F443 (manufactured by DIC Co., Ltd.).

When the leveling agent (F) is included, the content of the leveling agent (F) is preferably 0.001 mass% to 0.2 mass%, more preferably 0.002 mass% to 0.1 relative to the total amount of the colored resin composition. Mass %. Furthermore, this content does not include the content of pigment dispersant. If the content of the leveling agent (F) is within the aforementioned range, the color filter can have good flatness.

＜Other ingredients＞

The colored resin composition of the present invention may also contain fillers, other polymer compounds, adhesion accelerators, antioxidants, light stabilizers, chain transfer agents and other additives commonly known in the technical field if necessary.

<Production method of colored resin composition>

The colored resin composition of the present invention can be obtained by combining the colorant (A) and the resin (B), and if necessary, the polymerizable compound (C), the polymerization initiator (D), and the polymerization initiating assistant (D1). ), solvent (E), leveling agent (F) and other ingredients are mixed and prepared.

＜Manufacturing method of color filter＞

Examples of methods for producing a colored pattern from the colored resin composition of the present invention include photolithography, inkjet, and printing. Among them, photolithography is preferred.

By making the colored resin composition contain the compound represented by formula (I), a color filter having particularly excellent heat resistance and light resistance can be produced. This color filter is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL (electroluminescence) devices, electronic paper, etc.) and solid-state imaging devices. [Example]

Hereinafter, the present invention will be described in more detail through examples, but the present invention is not limited by these examples. In the examples, % and parts indicating content or usage amount are based on mass unless otherwise specified.

In the following, the structure of the compound was confirmed by mass spectrometry (LC; Model 1200 manufactured by Agilent, MASS; LC/MSD model manufactured by Agilent).

(Synthesis example 1)

50 parts of 3-bromoanisole (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 36.1 parts of 2,4,6-trimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 434 parts of toluene (Kanto Chemical Co., Ltd.), and mix 30 parts of potassium hydroxide (manufactured by Kanto Chemical Co., Ltd.), 25 parts of water, and 2 parts of tetrabutylammonium bromide (Tokyo Chemical Industry Co., Ltd.) into the solution (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.4 parts of bis(tertiary butylphosphine)palladium(0) (manufactured by Tokyo Chemical Industry Co., Ltd.). After raising the temperature to 90°C and stirring for 5 hours, the organic layer was obtained by extraction, and the solvent was distilled off to obtain 52.1 parts of crude product. The obtained crude product was separated and purified using column chromatography to obtain 50.2 parts of the compound represented by formula (1-1). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 242.3 Accurate mass (Exact Mass): +241.2

(Synthesis example 2)

33 parts of the compound represented by formula (1-1), 26.8 parts of 4-chloro-4-oxybutyric acid methyl ester (manufactured by Tokyo Chemical Industry Co., Ltd.) and 286 parts of toluene (Kanto Chemical Co., Ltd. Manufacture), mix and heat while stirring at 100°C for 16 hours. After the reaction, the solvent was distilled off, and the crude product was separated and purified using column chromatography to obtain 30.7 parts of the compound represented by formula (1-2). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 356.2 Accurate mass (Exact Mass): +355.2

(Synthesis example 3)

10 parts of the compound represented by formula (1-2) was dissolved in 95 parts of methylene chloride (manufactured by Kanto Chemical Co., Ltd.), and the mixture was cooled to 0°C while stirring. While stirring, 28.2 parts of boron tribromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added dropwise. After the dropwise addition was completed, the temperature was slowly raised and stirred at 10°C for 4 hours. After the reaction, the solvent was distilled off under reduced pressure, a water-organic solvent extraction operation was performed, and the solvent was distilled off to obtain 9.1 parts of crude product. The crude product contained 48% of the compound represented by formula (1-3) and 36% of the compound represented by formula (1-4). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 342.2 Accurate mass (Exact Mass): +341.2 Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 328.1 Accurate mass (Exact Mass): +327.2

(Synthesis example 4)

A solution of 13.2 parts of thionyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 72 parts of methanol (manufactured by Kanto Chemical Co., Ltd.) was cooled to 0°C and added to the synthesis example while stirring. 9.1 parts of the crude product containing the compound represented by formula (1-3) and the compound represented by formula (1-4) obtained in 3. Warm up to room temperature and react for 16 hours. The solvent was distilled off under reduced pressure to obtain 8.3 parts of a crude product containing the compound represented by formula (1-3). The obtained crude product was purified using silica gel column chromatography to obtain 7.4 parts of the compound represented by formula (1-3). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 342.2 Accurate mass (Exact Mass): +341.2

(Synthesis example 5)

2 parts of the compound represented by formula (1-3), 26.3 parts of borane 1 M tetrahydrofuran solution (manufactured by Kanto Chemical Co., Ltd.), and 18 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.) were mixed at 0°C. Mix, warm to 10°C and stir for 5 hours. After the reaction is completed, water is added for quenching, and an organic solvent is used for extraction. The solvent was removed by distillation and the obtained crude product was purified by silica gel column chromatography to obtain 1.64 parts of the compound represented by formula (1-5). Identification: (Mass Analysis) Ionization Mode=ESI+: m/z=[M+H] ⁺ 300.2 Accurate Mass (Exact Mass): +299.2

(Example 1)

2.5 parts of the compound represented by formula (1-5) and 0.55 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) were dissolved in 50 parts of toluene (manufactured by Kanto Chemical Co., Ltd.) and 50 parts of n-butanol (manufactured by Kanto Chemical Co., Ltd.) were heated while stirring at 110°C for 6 hours. After the reaction, the solvent was distilled off, and the obtained crude product was separated and purified using silica gel column chromatography to obtain 2.7 parts of the compound represented by formula (I-147). Identification: (Mass Analysis) Ionization Mode=ESI+: m/z=[M+H] ⁺ 677.4 Accurate Mass (Exact Mass): +676.4

(Synthesis example 6)

Mix 10 parts of the compound represented by formula (1-1), 7.4 parts of methylmalonide chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 87 parts of toluene (manufactured by Kanto Chemical Co., Ltd.) in Heat while stirring at 100°C for 16 hours. After the reaction, the solvent was distilled off, and the obtained crude product was separated and purified using column chromatography to obtain 9.1 parts of the compound represented by formula (1-6). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 342.2 Accurate mass (Exact Mass): +341.2

(Synthesis Example 7)

8.1 parts of the compound represented by formula (1-6) was dissolved in 107 parts of methylene chloride (manufactured by Kanto Chemical Co., Ltd.), and the mixture was cooled to 0°C while stirring. While stirring, 24 parts of boron tribromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added dropwise. After the dropwise addition was completed, the temperature was slowly raised and stirred at 23°C for 3 hours. After the reaction, the organic layer was extracted and concentrated to obtain 7.2 parts of the compound represented by formula (1-7). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 314.1 Accurate mass (Exact Mass): +313.1

(Synthesis example 8)

A solution of 10.6 parts of thionyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 55.5 parts of methanol (manufactured by Kanto Chemical Co., Ltd.) was cooled to 0°C, and 5 parts were added while stirring. Compounds represented by formula (1-7). The temperature was raised to 23°C and allowed to react for 16 hours. The solvent was distilled off under reduced pressure to obtain 6.8 parts of a crude product containing the compound represented by formula (1-8). The obtained crude product was purified using silica gel column chromatography to obtain 5.6 parts of the compound represented by formula (1-8). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 328.2 Accurate mass (Exact Mass): +327.15

(Synthesis example 9)

5.5 parts of the compound represented by formula (1-8), 92.3 parts of borane 1 M tetrahydrofuran solution (manufactured by Kanto Chemical Co., Ltd.), and 49 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.) were mixed at 0°C. Mix, warm to 23°C and stir for 3 hours. After the reaction is completed, water is added for quenching, and an organic solvent is used for extraction. The solvent was removed by distillation and the obtained crude product was purified by silica gel column chromatography to obtain 2.6 parts of the compound represented by formula (1-9). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 286.2 Accurate mass (Exact Mass): +285.2

(Example 2)

2 parts of the compound represented by formula (1-9) and 0.4 part of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were dissolved in 69 parts of toluene (manufactured by Kanto Chemical Co., Ltd.) and 16 parts of n-butanol (manufactured by Kanto Chemical Co., Ltd.) were heated while stirring at 120° C. for 4 hours. After the reaction, the solvent was distilled off, and the obtained crude product was separated and purified using silica gel column chromatography to obtain 1.3 parts of the compound represented by formula (I-27). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 649.7 Accurate mass (Exact Mass): +648.3

(Synthesis Example 10)

Make 7 parts of mesityl bromide (manufactured by Tokyo Chemical Industry Co., Ltd.), 4.8 parts of 5-methoxy-2-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.39 parts Palladium acetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.84 parts of 4,5'-bis(diphenylphosphino)-9,9'-dimethyldibenzopiran (Tokyo Chemical Industry Co., Ltd.) (manufactured by Tokyo Chemical Industry Co., Ltd.) and 6.8 parts of tertiary sodium butoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 126 parts of toluene (manufactured by Kanto Chemical Co., Ltd.) and heated to reflux at 105°C for 1 hour. After the reaction is completed, water is added and the organic layer is extracted. The obtained crude product is separated and purified using silica gel column chromatography to obtain 7 parts of the compound represented by formula (1-15). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 256.2 Accurate mass (Exact Mass): +255.2

(Synthesis Example 11)

6 parts of the compound represented by formula (1-15) and 33 parts of monoethyl succinate chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 20 parts of toluene (manufactured by Kanto Chemical Co., Ltd.), and heated at 90°C for 8 hours. After the reaction, water was added, the organic layer was extracted, and repulped and washed with 300 parts of hexane (manufactured by Kanto Chemical Co., Ltd.) to obtain 4 parts of the compound represented by formula (1-16). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 384.0 Accurate mass (Exact Mass): +383.2

(Synthesis Example 12)

4.2 parts of the compound represented by formula (1-16) was dissolved in 20 parts of methylene chloride (manufactured by Kanto Chemical Co., Ltd.), and 46 parts of boron tribromide (manufactured by Fujifilm and Wako Pure Chemical Industries, Ltd.) was added ) and stir. After the reaction, water was added to the reaction mixture for quenching, and the mixture was extracted with ethyl acetate solvent and concentrated to obtain 5 parts of the compound represented by formula (1-17). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 370.3 Accurate mass (Exact Mass): +369.2

(Synthesis Example 13)

Dissolve 4 parts of the compound represented by formula (1-17) in 40 parts of dehydrated tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.), cool to 0°C, and add 105 parts of borane 1 M tetrahydrofuran while stirring. Solution (manufactured by Kanto Chemical Co., Ltd.). The temperature was raised to 23°C, and after further stirring for 20 hours, water was added for quenching, and extraction was performed with an organic solvent. The solvent was removed by distillation to obtain 2.8 parts of the compound represented by formula (1-18). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 314.3 Accurate mass (Exact Mass): +313.2

(Example 3)

0.7 part of the compound represented by formula (1-18) and 0.12 part of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) were dissolved in 2 parts of toluene (manufactured by Kanto Chemical Co., Ltd.) and 3 parts of n-butanol (manufactured by Kanto Chemical Co., Ltd.) were heated while stirring at 110°C for 13 hours. After the reaction is completed, the solvent is distilled off, and the obtained crude product is separated and purified using silica gel column chromatography to obtain 0.1 part of the compound represented by formula (I-150). Identification: (Mass Analysis) Ionization Mode=ESI+: m/z=[M+H] ⁺ 705.8 Accurate Mass (Exact Mass): +704.4

(Synthesis Example 14)

20 parts of 2,6-diisopropylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), 22.4 parts of 3-bromoanisole (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.6 part of palladium acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) Co., Ltd.), 0.9 parts of 1 mol/L (mol/L) tri-tertiary butylphosphine·hexane solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 21.7 parts of tertiary butylphosphonium Sodium alkoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 228 parts of toluene (manufactured by Kanto Chemical Co., Ltd.) and heated to reflux at 110°C for 5 hours. After the reaction, water was added and the organic layer was extracted. The obtained crude product was separated and purified using silica gel column chromatography to obtain 32 parts of the compound represented by formula (1-19). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 284.2 Accurate mass (Exact Mass): +283.2

(Synthesis Example 15)

5 parts of the compound represented by formula (1-19) were dissolved in 85 parts of dimethylformamide (manufactured by Fuji Film and Wako Pure Chemical Industries, Ltd.) under an ice bath. 3.5 parts of sodium hydride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was slowly added thereto. After stirring for 10 minutes, 3.8 parts of 1-bromo-4-methoxybutane (manufactured by Tokyo Chemical Industry Co., Ltd.) was slowly added, and then the temperature was raised to 120° C. and heated to reflux. After the reaction is completed, water is slowly added again under an ice bath for quenching, the organic layer is extracted, and the obtained crude product is separated and purified using silica gel column chromatography to obtain 6.5 parts of formula (1-20) represented by compound. Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 370.5 Accurate mass (Exact Mass): +369.5

(Synthesis Example 16)

Dissolve 5 parts of the compound represented by formula (1-20) in 100 parts of methylene chloride (manufactured by Kanto Chemical Co., Ltd.), and add 147 parts of boron tribromide (manufactured by Fuji Film and Wako Pure Chemical Industries, Ltd. ) and stir. After the reaction, the reaction mixture was quenched by adding water, extracted with ethyl acetate, and concentrated. The obtained crude product was separated using a silica gel column to obtain 3.8 parts of a mixture containing 78% of the compound represented by formula (1-21-1) and 22% of the compound represented by formula (1-21-2) ( Hereinafter, there are cases called mixtures (1-21)). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 342.4 Accurate mass (Exact Mass): +341.2 Identification: (Mass Analysis) Ionization Mode=ESI+: m/z=[M+H] ⁺ 356.5 Accurate Mass (Exact Mass): +355.3

(Example 4 to Example 5)

Dissolve 4.5 parts of the mixture (1-21) and 0.45 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) in 30 parts of toluene (manufactured by Kanto Chemical Co., Ltd.) and 30 parts of n-butanol (manufactured by Kanto Chemical Co., Ltd.), and heated while stirring at 120°C for 3.5 hours. After the reaction is completed, the solvent is distilled off, and silica column chromatography is used for separation and purification to obtain 1 part of the compound represented by formula (I-171) and 1 part of the compound represented by formula (I-177). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 761.4 Accurate mass (Exact Mass): +760.5 Identification: (Mass Analysis) Ionization Mode=ESI+: m/z=[M+H] ⁺ 775.7 Accurate Mass (Exact Mass): +774.5

(Synthesis Example 17)

10 parts of 2,4,6-trimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.), 16 parts of 1-bromo-3,5-dimethoxybenzene (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.83 parts of palladium acetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.1 parts of 4,5'-bis(diphenylphosphino)-9,9'-dimethyldibenzopiran (made by Tokyo Chemical Industry Co., Ltd.) Co., Ltd.) and 14.2 parts of tertiary sodium butoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 180 parts of toluene (manufactured by Kanto Chemical Co., Ltd.) and heated to reflux at 105°C for 3 hours. After the reaction is completed, water is added and the organic layer is extracted. The obtained crude product is separated and purified using silica gel column chromatography to obtain 19 parts of the compound represented by formula (1-22). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 272.5 Accurate mass (Exact Mass): +271.2

(Synthesis Example 18)

7.5 parts of the compound represented by formula (1-22) and 13.6 parts of monoethyl succinate chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 150 parts of toluene (manufactured by Kanto Chemical Co., Ltd.), and heated at 100°C for 5 hours. After the reaction, the solvent was distilled off, and the obtained crude product was separated and purified using silica gel column chromatography to obtain 10 parts of the compound represented by formula (1-23). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 400.5 Accurate mass (Exact Mass): +399.2

(Synthesis Example 19)

2.7 parts of the compound represented by formula (1-23) was dissolved in 30 parts of methylene chloride (manufactured by Kanto Chemical Co., Ltd.), and 7.7 parts of boron tribromide (manufactured by Fujifilm and Wako Pure Chemical Industries, Ltd.) was added ) and stir. After the reaction, the reaction mixture was quenched by adding water, extracted with ethyl acetate solvent, and concentrated to obtain 2.2 parts of the compound represented by formula (1-24). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 372.3 Accurate mass (Exact Mass): +371.2

(Synthesis example 20)

Dissolve 0.25 parts of the compound represented by formula (1-24) in 7 parts of dehydrated tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.), cool to 0°C, and add 0.4 parts of borane 1 M tetrahydrofuran while stirring. Solution (manufactured by Kanto Chemical Co., Ltd.). The temperature was raised to 23°C, and after further stirring for 20 hours, water was added for quenching, and the organic solvent was concentrated to obtain 0.12 parts of the compound represented by formula (1-25). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 316.3 Accurate mass (Exact Mass): +315.2

(Example 6)

0.4 part of the compound represented by formula (1-25) and 0.07 part of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) were dissolved in 3 parts of toluene (manufactured by Kanto Chemical Co., Ltd.) and 4.5 parts of n-butanol (manufactured by Kanto Chemical Co., Ltd.) were heated while stirring at 110°C for 3 hours. After the reaction, the solvent was distilled off, and the obtained crude product was washed with water and acetone to obtain 0.22 parts of the compound represented by formula (I-145). Identification: (Mass Analysis) Ionization Mode=ESI+: m/z=[M+H] ⁺ 709.7 Accurate Mass (Exact Mass): +708.3

(Synthesis Example 21)

Dissolve 62 parts of 2,2-dimethyl-malonate monomethyl ester (manufactured by Alfa Chemical Co., Ltd.) in 413 parts of methylene chloride (manufactured by Kanto Chemical Co., Ltd.) and cool to 0°C, while stirring, 5 parts of dimethylformamide (manufactured by Kanto Chemical Co., Ltd.) and 81 parts of oxalyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) were added dropwise. Thereafter, the temperature was raised to 23°C and stirred for 1 hour. After the reaction is completed, the reaction mixture is concentrated to obtain 54 parts of the compound represented by formula (1-26). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 165.1 Accurate mass (Exact Mass): +164.0

(Synthesis example 22)

46 parts of 2,4,6-trimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 219 parts of dimethylformamide (manufactured by Kanto Chemical Co., Ltd.). While stirring this solution at 23°C, 50.4 parts of the compound represented by the above formula (1-26) was added dropwise. After completion of the dropwise addition, stir for 1 hour. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain 46 parts of a crude product containing a compound represented by the following formula (1-27). The crude product was separated and purified using silica gel column chromatography to obtain 40 parts of the compound represented by formula (1-27). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 264.1 Accurate mass (Exact Mass): +263.2

(Synthesis example 23)

14.4 parts of lithium aluminum hydride (powder) (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 40 parts of dimethyl ether (manufactured by Kanto Chemical Co., Ltd.) and stirred. The mixed solution was cooled to 0°C. On the other hand, 10 parts of the compound represented by the above formula (1-27) was put into 40 parts of dimethyl ether (manufactured by Kanto Chemical Co., Ltd.), and stirred to dissolve. The solution containing the compound represented by formula (1-27) was added dropwise to the solution containing the above-mentioned lithium aluminum hydride (powder) over 15 minutes while cooling to 0° C. and stirring. Thereafter, the temperature was slowly raised to 80°C and reacted at 80°C for 3 days. After the reaction, the reaction mixture was put into 200 parts of water, extracted with water and toluene, and concentrated to obtain 7.0 parts of crude product. The crude product was separated and purified using silica gel column chromatography to obtain 2.9 parts of the compound represented by formula (1-28). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 222.1 Accurate mass (Exact Mass): +221.2

(Synthesis Example 24)

7.8 parts of the compound represented by formula (1-28) was dissolved in 108 parts of methylene chloride (manufactured by Kanto Chemical Co., Ltd.), cooled to 0°C, and 3.6 parts of imidazole (Tokyo Chemical Co., Ltd.) was added while stirring. Chemical Industry Co., Ltd.) and 6.4 parts of tertiary butyldimethylsilyl chloride (Tokyo Chemical Industry Co., Ltd.). The temperature was raised to 23°C and stirred for a further 16 hours. After the reaction, an extraction operation was performed using water and an organic solvent to obtain 7.8 parts of crude product. The obtained crude product was separated and purified using column chromatography to obtain 7.2 parts of the compound represented by formula (1-29). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 336.4 Accurate mass (Exact Mass): +335.3

(Synthesis example 25)

Dissolve 50 parts of bromophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 30 parts of imidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) in 500 parts of methylene chloride (manufactured by Kanto Chemical Co., Ltd.) and cool to After 0°C, 48 parts of tertiary butyldimethylsilyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After the dropwise addition was completed, the temperature was raised to 23°C and stirred for 16 hours. After the reaction is completed, water is added and the organic layer is extracted. After the solvent is concentrated, the mixture is separated and purified by silicone column chromatography to obtain 74 parts of the compound represented by formula (1-10). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 287.0 Accurate mass (Exact Mass): +286.0

(Synthesis example 26)

20 parts of the compound represented by formula (1-10) was added to 31 parts of 1,4-dioxane (manufactured by Kanto Chemical Co., Ltd.) and dissolved. Furthermore, 3.2 parts of N,N-dimethylethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 20.9 parts of sodium iodide (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.7 parts of Copper(I) iodide (manufactured by Fuji Film and Wako Pure Chemical Industries, Ltd.). It was added to a pressurized vessel and reacted at 120°C for 6 hours. After the reaction was completed, the mixture was extracted with water and toluene solvents and concentrated to obtain 20 parts of crude product. The crude product was separated and purified using silica gel column chromatography to obtain 10.5 parts of the compound represented by formula (1-30). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 335.1 Accurate mass (Exact Mass): +334.0

(Synthesis Example 27)

9.6 parts of the compound represented by formula (1-29) and 9.6 parts of the compound represented by formula (1-30) were put into 84 parts of toluene (manufactured by Kanto Chemical Co., Ltd.) and dissolved. 6.8 parts of tertiary sodium butoxide (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.4 parts of tertiary butylphosphonium tetrafluoroborate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.52 parts of Tris(diphenylmethylacetone)dipalladium(0) (manufactured by Tokyo Chemical Industry Co., Ltd.) and dissolved. The mixed solution was irradiated with microwaves and reacted at 140°C for 1 hour. Thereafter, the solvent was distilled off under reduced pressure, water was added, and an extraction operation was performed using an organic solvent. The solvent was distilled off to obtain 9.6 parts of a crude product. The crude product was separated and purified using silica gel column chromatography to obtain 1.8 parts of a crude product containing a compound represented by formula (1-31) (hereinafter, sometimes referred to as crude product (1-31)). . Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 542.4 Accurate mass (Exact Mass): +541.4

(Synthesis example 28)

1.8 parts of the crude product (1-31) was dissolved in 17.8 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.), and after cooling to 0°C, 9.2 parts of tetrabutylammonium fluoride 1 M tetrahydrofuran solution ( (Manufactured by Tokyo Chemical Industry Co., Ltd.), after the dropwise addition, stir at 23°C for 16 hours. After the reaction, water was added, tetrahydrofuran was distilled off, and the obtained crude product was extracted with an organic solvent. After concentration, 1.4 parts of the crude product of the compound represented by formula (1-32) was obtained. The crude product thus obtained was separated and purified by column chromatography to obtain 0.76 parts of the compound represented by formula (1-32). Identification: (Mass Analysis) Ionization Mode=ESI+: m/z=[M+H] ⁺ 314.2 Accurate Mass (Exact Mass): +313.2

(Example 7)

0.4 part of the compound represented by formula (1-32) and 0.072 part of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) were dissolved in 14 parts of toluene (manufactured by Kanto Chemical Co., Ltd.) and 3.24 parts of n-butanol (manufactured by Kanto Chemical Co., Ltd.) were heated while stirring at 140° C. for 3 hours. After the reaction, the solvent was distilled off, and the crude product was separated and purified using silica gel column chromatography to obtain 0.25 parts of the compound represented by formula (I-87). Identification: (Mass Analysis) Ionization Mode=ESI+: m/z=[M+H] ⁺ 705.8 Accurate Mass (Exact Mass): +704.4

(Synthesis Example 29)

45 parts of 4-amino-3,5-stylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 400 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.). 127 parts of di-tertiary butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to this solution and dissolved. Stir and react at 23°C for 16 hours. After the reaction was completed, the solvent was distilled off to obtain 51 parts of crude product. The obtained crude product was stirred and purified in a mixed solvent of 90 parts of ethyl acetate (manufactured by Kanto Chemical Co., Ltd.) and 272 parts of n-hexane (manufactured by Kanto Chemical Co., Ltd.) at 23°C for 2 hours to obtain 47 parts of the compound represented by formula (1-33). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 238.3 Accurate mass (Exact Mass): +237.1

(Synthesis Example 30)

20 parts of 2-bromoethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 333 parts of dichloromethane (manufactured by Kanto Chemical Co., Ltd.). 32.4 parts of triethylamine (manufactured by Kanto Chemical Co., Ltd.) and 0.156 part of 4-dimethylaminopyridine (manufactured by Kanto Chemical Co., Ltd.) were added to this solution, and 28.95 parts of triethylamine (manufactured by Kanto Chemical Co., Ltd.) were added while stirring. grade butyldimethylsilyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and dissolved. Stir and react at 23°C for 16 hours. The solvent was removed by distillation to obtain 20 parts of crude product. The obtained crude product was separated and purified using column chromatography to obtain 20 parts of the compound represented by formula (1-34). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 239.1 Accurate mass (Exact Mass): +238.0

(Synthesis Example 31)

47 parts of the compound represented by formula (1-33) were dissolved in 141.5 parts of the bromine compound represented by formula (1-34) and 447 parts of dimethylformamide (manufactured by Kanto Chemical Co., Ltd.). 138.2 parts of potassium carbonate (manufactured by Kanto Chemical Co., Ltd.) was added to the solution, and the mixture was stirred and reacted at 70°C for 16 hours. After the reaction, the solvent was distilled off, and an organic solvent was used for extraction to obtain 49 parts of crude product. The obtained crude product was separated and purified using column chromatography to obtain 41 parts of the compound represented by formula (1-35). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+Ht-Bu ⁺ ] ⁺ 339.2 Accurate mass (Exact Mass): +395.3

(Synthesis example 32)

41 parts of the compound represented by formula (1-35) was dissolved in 424 parts of 1,4-dioxane (manufactured by Kanto Chemical Co., Ltd.), and 263 parts of hydrogen chloride (approximately 4 mol/liter 1, 4-dioxane solution) (manufactured by Tokyo Chemical Industry Co., Ltd.), stirred at 23°C for 1 hour and deprotected. After the reaction was completed, the solvent was distilled off to obtain 36 parts of crude product. The obtained crude product was separated and purified using column chromatography to obtain 22 parts of the compound represented by formula (1-36). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 182.2 Accurate mass (Exact Mass): +181.1

(Synthesis example 33)

22 parts of the compound represented by formula (1-36) were dissolved in 293 parts of dichloromethane (manufactured by Kanto Chemical Co., Ltd.). 10.8 parts of imidazole (manufactured by Kanto Chemical Co., Ltd.) and 22 parts of tertiary butyldimethylsilyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to this solution and dissolved. Stir and react at 23°C for 16 hours. The solvent was removed by distillation to obtain 23 parts of crude product. The obtained crude product was separated and purified using column chromatography to obtain 20 parts of the compound represented by formula (1-37). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 296.3 Accurate mass (Exact Mass): +295.2

(Synthesis Example 34)

Dissolve 15 parts of the compound represented by formula (1-10) in 14.5 parts of the compound represented by formula (1-37) and 130 parts of toluene (manufactured by Kanto Chemical Co., Ltd.), and mix 5.7 Parts of potassium hydroxide (manufactured by Kanto Chemical Co., Ltd.), 15 parts of water, 2 parts of tetrabutylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.26 parts of bis(tertiary-tertiary butylphosphine) ) Palladium(0) (manufactured by Tokyo Chemical Industry Co., Ltd.). After raising the temperature to 90°C and stirring for 20 minutes, the organic layer was obtained by extraction, and the solvent was distilled off to obtain 15 parts of crude product. The obtained crude product was separated and purified using column chromatography to obtain 12 parts of the compound represented by formula (1-38). Identification: (Mass Analysis) Ionization Mode=ESI+: m/z=[M+H] ⁺ 502.4 Accurate Mass (Exact Mass): +501.3

(Synthesis Example 35)

12 parts of the compound represented by formula (1-38), 11.9 parts of methyl 4-chloro-4-oxybutyrate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 41.6 parts of toluene (Kanto Chemical Co., Ltd. Manufacture), mix and heat while stirring at 90°C for 1 hour. After the reaction, the solvent was distilled off, and the obtained crude product was separated and purified using column chromatography to obtain 5.9 parts of the compound represented by formula (1-39). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 616.3 Accurate mass (Exact Mass): +615.3

(Synthesis Example 36)

5.9 parts of the compound represented by formula (1-39) was dissolved in 52.4 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.), and after cooling to 0°C, 11 parts of tetrabutylammonium fluoride 1 M was added dropwise. Tetrahydrofuran solution (manufactured by Tokyo Chemical Industry Co., Ltd.), after the dropwise addition, stirred at 23°C for 2 hours. After the reaction is completed, water is added, the tetrahydrofuran solvent is distilled off, and the obtained crude product is extracted with an organic solvent. After concentration, 4.3 parts of the compound represented by formula (1-40) is obtained. Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 388.2 Accurate mass (Exact Mass): +387.2

(Synthesis Example 37)

4.3 parts of the compound represented by formula (1-40), 56.4 parts of borane 1 M tetrahydrofuran solution (manufactured by Kanto Chemical Co., Ltd.), and 38.2 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.) were mixed at 0°C. Mix, warm to 23°C and stir for 16 hours. After the reaction is completed, water is added for quenching, and an organic solvent is used for extraction. The solvent was removed by distillation and the obtained crude product was purified by silica gel column chromatography to obtain 2.3 parts of the compound represented by formula (1-41). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 346.3 Accurate mass (Exact Mass): +345.2

(Example 8)

2.3 parts of the compound represented by formula (1-41) and 0.38 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) were dissolved in 80 parts of toluene (manufactured by Kanto Chemical Co., Ltd.) and 19 parts of n-butanol (manufactured by Kanto Chemical Co., Ltd.) were heated while stirring at 120°C for 4 hours. After the reaction, the solvent was distilled off, and the obtained crude product was separated and purified using silica gel column chromatography to obtain 1.3 parts of the compound represented by formula (II-135). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 769.8 Accurate mass (Exact Mass): +768.4

(Synthesis Example 38)

Dissolve 100 parts of 3-iodoanisole (manufactured by Tokyo Chemical Industry Co., Ltd.) and 85.5 parts of 4-bromo-2,6-dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) in 72 parts of water In a mixed solvent with 867 parts of toluene (manufactured by Kanto Chemical Co., Ltd.). While stirring this solution at 23°C, 48 parts of potassium hydroxide (manufactured by Kanto Chemical Co., Ltd.), 5 parts of tetrabutylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.2 parts bis(tertiary-tertiary butylphosphine)palladium(0) (manufactured by Tokyo Chemical Industry Co., Ltd.). The mixed solution was heated to 90°C and reacted for 16 hours. After the reaction was completed, water and toluene solvents were used for extraction and concentration to obtain 96.8 parts of crude product. The crude product was separated and purified using silica gel column chromatography to obtain 60.2 parts of the compound represented by formula (1-42). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 306.0 Accurate mass (Exact Mass): +305.0

(Synthesis Example 39)

60 parts of the compound represented by formula (1-42) and 29.5 parts of 4-chloro-4-oxybutyric acid methyl ester (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 520 parts of toluene at 23°C. (manufactured by Kanto Chemical Co., Ltd.), the temperature was raised to 100°C and reacted for 16 hours. After the reaction, a water-toluene solvent was used for extraction, and after concentration, 64.2 parts of crude product were obtained. The crude product was separated and purified using silica gel column chromatography to obtain 55.1 parts of the compound represented by formula (1-43). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 419.9 Accurate mass (Exact Mass): +419.1

(Synthesis Example 40)

55 parts of the compound represented by formula (1-43) was dissolved in 732 parts of methylene chloride (manufactured by Kanto Chemical Co., Ltd.), and the mixture was cooled to 0°C while stirring. While stirring, 197 parts of boron tribromide (manufactured by Fuji Film and Wako Pure Chemical Industries, Ltd.) was added dropwise. Stir at 23°C for 3 hours. After the reaction is completed, the solvent is distilled off under reduced pressure, and a water-organic solvent extraction operation is performed to obtain a compound containing 66% of the compound represented by the following formula (1-44) and 23% of the compound represented by the following formula (1-45). A mixture of 47.3 parts of the compound. Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 392.1 Accurate mass (Exact Mass): +391.0

(Synthesis Example 41)

A solution containing 37.9 parts of thionyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 377 parts of methanol (manufactured by Kanto Chemical Co., Ltd.) was cooled to 0°C and stirred while adding the solution containing A mixture of 47.3 parts of 66% of the compound represented by the above formula (1-44) and 23% of the compound represented by the following formula (1-45). The temperature was raised to 23°C and allowed to react for 16 hours. The solvent was distilled off under reduced pressure to obtain 45.4 parts of a crude product containing the compound represented by formula (1-45). The obtained crude product was purified using silica gel column chromatography to obtain 40.2 parts of the compound represented by formula (1-45). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 406.1 Accurate mass (Exact Mass): +405.1

(Synthesis Example 42)

40 parts of the compound represented by Formula (1-45) was dissolved in 355 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.) and stirred. Cool to 0°C and add dropwise 442 parts of borane 1 M tetrahydrofuran solution (manufactured by Kanto Chemical Co., Ltd.). After the dropwise addition, the temperature was raised to 10° C. and stirred for 3 hours. Water was added and the organic layer was obtained by extraction. The solvent was distilled off to obtain 37.3 parts of the compound represented by formula (1-46). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 364.1 Accurate mass (Exact Mass): +363.08

(Synthesis Example 43)

32 parts of the compound represented by formula (1-46) was dissolved in 638 parts of methylene chloride (manufactured by Kanto Chemical Co., Ltd.), cooled to 0°C, and 17.9 parts of imidazole (Tokyo Chemical Co., Ltd.) was added while stirring. (manufactured by Chemical Industry Co., Ltd.) and 29.1 parts of tertiary butyldimethylsilyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.). The temperature was raised to 23° C., and the mixture was further stirred for 16 hours to perform silylation. After the reaction, an extraction operation was performed using water and an organic solvent to obtain 45.8 parts of crude product. The crude product thus obtained was separated and purified by column chromatography to obtain 40.9 parts of the compound represented by formula (1-47). Identification: (Mass Analysis) Ionization Mode=ESI+: m/z=[M+H] ⁺ 592.3 Accurate Mass (Exact Mass): +591.3

(Synthesis Example 44)

20 parts of the compound represented by formula (1-47) and 29 parts of methyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 475 parts of dimethylformamide (manufactured by Kanto Chemical Co., Ltd.) . 26.2 parts of diisopropylethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.05 parts of tris(o-tolyl)phosphine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.758 parts of palladium acetate were added to this solution. (II) (manufactured by Tokyo Chemical Industry Co., Ltd.), stir at 23°C for 30 minutes. The temperature was raised to 140°C, stirred for 32 hours and allowed to react. Here, 14.5 parts of methyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 26.2 parts of diisopropylethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were additionally added. Further, react at 140°C for 2 days. Thereafter, the solvent was distilled off under reduced pressure, water was added, and an extraction operation was performed using an organic solvent. The solvent was distilled off to obtain 17.2 parts of a crude product (hereinafter, sometimes referred to as crude product (1-48)). The crude product contains 40% of the compound represented by formula (1-48-1) and 40% of the compound represented by formula (1-48-2). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 484.5 Accurate mass (Exact Mass): +483.3 Identification: (Mass Analysis) Ionization Mode=ESI+: m/z=[M+H] ⁺ 598.3 Accurate Mass (Exact Mass): +597.4

(Synthesis Example 45)

17.2 parts of the crude product (1-48) was dissolved in 155.4 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.), and after cooling to 0°C, 62.6 parts of tetrabutylammonium fluoride 1 M tetrahydrofuran solution ( (Manufactured by Tokyo Chemical Industry Co., Ltd.), after the dropwise addition, stir at 23°C for 16 hours. After the reaction, water was added, the tetrahydrofuran solvent was distilled off, and the obtained crude product was extracted with an organic solvent. After concentration, 13.72 parts of the crude product of the compound represented by formula (1-49) was obtained. The crude product thus obtained was separated and purified by column chromatography to obtain 8.1 parts of the compound represented by formula (1-49). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 370.2 Accurate mass (Exact Mass): +369.2

(Synthesis Example 46)

6.87 parts of the compound represented by formula (1-49) was dissolved in 59.5 parts of methanol (manufactured by Kanto Chemical Co., Ltd.), and 0.69 parts of palladium/carbon (Pd 10%) (Fuji Film) was added under a normal pressure hydrogen flow. manufactured by Wako Pure Chemical Industries, Ltd.) and stirred at 23°C for 16 hours. After the reaction was completed, the reaction mixture was filtered, and the solvent was distilled off to obtain 5.49 parts of crude product. The crude product thus obtained was separated and purified by column chromatography to obtain 4.26 parts of the compound represented by formula (1-50). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 372.1 Accurate mass (Exact Mass): +371.2

(Synthesis Example 47)

4.2 parts of the compound represented by formula (1-50), 2.85 parts of lithium hydroxide monohydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 33.3 parts of methanol (manufactured by Kanto Chemical Co., Ltd.) and 37.3 parts Mix 21 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.) and 21 parts of water and stir at 23°C for 16 hours. After the reaction, the solvent was distilled off, and the crude product was purified using silica gel column chromatography to obtain 3.11 parts of the compound represented by formula (1-51). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 358.0 Accurate mass (Exact Mass): +357.2

(Example 9)

3 parts of the compound represented by formula (1-51) and 0.48 part of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were dissolved in 104 parts of toluene (manufactured by Kanto Chemical Co., Ltd.) and 24.3 parts of n-butanol (manufactured by Kanto Chemical Co., Ltd.) were heated while stirring at 120° C. for 4 hours. After the reaction, the solvent was distilled off, and the obtained crude product was separated and purified using silica gel column chromatography to obtain 0.70 parts of the compound represented by formula (II-129). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 793.7 Accurate mass (Exact Mass): +792.4

(Synthesis Example 48)

100 parts of 1,3-dimethoxybenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 1,330 parts of methylene chloride (manufactured by Kanto Chemical Co., Ltd.) and cooled to 0°C. While stirring this solution, 463 parts of bromine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After the dropwise addition is completed, the temperature is raised to 23°C and stirred for 3 hours. After the reaction was completed, the mixture was extracted with water and methylene chloride solvent and concentrated to obtain 110 parts of the compound represented by formula (1-52). Identification: (Mass Analysis) Ionization Mode=ESI+: m/z=[M+H] ⁺ 295.0 Accurate Mass (Exact Mass): +293.9

(Synthesis Example 49)

25 parts of the compound represented by formula (1-52) was dissolved in 111 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.), cooled to -78°C, and 234.2 parts of n-butyl was added dropwise while stirring. Lithium 2.5 M hexane solution (manufactured by Aldrich Co., Ltd.). After the addition, the mixture was stirred for 45 minutes while maintaining -78°C, and 156 parts of methyl iodide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise while maintaining cooling to -78°C. After adding, the temperature was raised to 23°C and stirred for 5 hours. After the reaction is completed, the reaction mixture is added little by little to 500 parts of ice water. Thereafter, an extraction operation was performed using a water-toluene solvent, and after concentration, 21 parts of crude product were obtained. The crude product was separated and purified using silica gel column chromatography to obtain 17 parts of the compound represented by formula (1-53). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 167.1 Accurate mass (Exact Mass): +166.1

(Synthesis example 50)

13.5 parts of the compound represented by formula (1-53) was dissolved in 200 parts of methylene chloride (manufactured by Kanto Chemical Co., Ltd.), and the mixture was cooled to 0°C while stirring. While stirring, 65 parts of bromine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. Thereafter, the temperature was raised to 23°C and stirred for 16 hours. After the reaction, the solvent was distilled off under reduced pressure, and a water-methylene chloride solvent extraction operation was performed to obtain 21 parts of a crude product containing the compound represented by formula (1-54). The obtained crude product was purified using silica gel column chromatography to obtain 15 parts of the compound represented by formula (1-54). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 323.0 Accurate mass (Exact Mass): +321.9

(Synthesis Example 51)

14 parts of the compound represented by formula (1-54) was dissolved in 124 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.), cooled to -78°C, and 22 parts of butyl was added dropwise while stirring. Lithium 1.6 M hexane solution (manufactured by Aldrich Co., Ltd.). After adding, stir for 1 hour while maintaining -78°C. Thereafter, 50 parts of water was added dropwise while stirring while maintaining -78°C. Thereafter, an extraction operation was performed using a water-toluene solvent, and after concentration, 12.5 parts of a crude product containing the compound represented by formula (1-55) was obtained. The crude product was separated and purified using silica gel column chromatography to obtain 10.4 parts of the compound represented by formula (1-55). Identification: (Mass Analysis) Ionization Mode=ESI+: m/z=[M+H] ⁺ 245.1 Accurate Mass (Exact Mass): +244.0

(Synthesis example 52)

10.4 parts of the compound represented by formula (1-55) was dissolved in 200 parts of methylene chloride (manufactured by Kanto Chemical Co., Ltd.), and the mixture was cooled to 0°C while stirring. While stirring, 64 parts of boron tribromide (manufactured by Fuji Film and Wako Pure Chemical Industries, Ltd.) was added dropwise. Stir at 23°C for 3 hours. After the reaction, the solvent was distilled off under reduced pressure, and a water-organic solvent extraction operation was performed to obtain 11 parts of a crude product containing the compound represented by formula (1-56). The obtained crude product was purified using silica gel column chromatography to obtain 8.9 parts of the compound represented by formula (1-56). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 217.0 Accurate mass (Exact Mass): +216.0

(Synthesis example 53)

8.9 parts of the compound represented by formula (1-56) was dissolved in 50 parts of dimethylformamide (manufactured by Kanto Chemical Co., Ltd.), and 28.3 parts of potassium carbonate (Kanto Chemical Co., Ltd.) was added while stirring the solution. Chemical Co., Ltd.). Furthermore, 29.4 parts of (2-bromoethoxy)-tertiary butyldimethylsilane (manufactured by Aldrich Co., Ltd.) was added. The solution was warmed to 70°C and stirred for 16 hours. After the reaction, the solvent was distilled off under reduced pressure, and a water-organic solvent extraction operation was performed to obtain 20.6 parts of a crude product containing the compound represented by formula (1-57). The obtained crude product was purified using silica gel column chromatography to obtain 15.7 parts of the compound represented by formula (1-57). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 533.2 Accurate mass (Exact Mass): +532.2

(Synthesis example 54)

25 parts of 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 333 parts of methylene chloride (manufactured by Kanto Chemical Co., Ltd.), and the mixture was cooled to 0°C while stirring. While stirring this solution at 0°C, 20.3 parts of imidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and further 41.4 parts of tertiary butyldimethylsilyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added ). Thereafter, the temperature was raised to 23°C and stirred for 16 hours. After the reaction, a water-organic solvent extraction operation was performed to obtain 48 parts of a crude product containing the compound represented by formula (1-58). The obtained crude product was purified using silica gel column chromatography to obtain 42 parts of the compound represented by formula (1-58). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 224.1 Accurate mass (Exact Mass): +223.1

(Synthesis example 55)

12.9 parts of the compound represented by formula (1-57) and 4.5 parts of the compound represented by formula (1-58) were dissolved in 312 parts of toluene (manufactured by Kanto Chemical Co., Ltd.). 18 parts of water was put into this solution, and while stirring, 3.4 parts of potassium hydroxide (manufactured by Kanto Chemical Co., Ltd.), 0.5 part of tetrabutylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.51 part of bis(tertiary butylphosphine)palladium(0) (manufactured by Tokyo Chemical Industry Co., Ltd.) and stirred at 23°C for 30 minutes. Thereafter, the temperature was raised to 105°C and reacted for 3 hours. Thereafter, water was added, an extraction operation was performed using an organic solvent, and the solvent was distilled off to obtain 12.8 parts of a crude product. The obtained crude product was purified using silica gel column chromatography to obtain 10.2 parts of the compound represented by formula (1-59). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 676.4 Accurate mass (Exact Mass): +675.4

(Synthesis example 56)

10 parts of the compound represented by formula (1-59) and 2.7 parts of methyl 4-chloro-4-oxybutyrate (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 87 parts of toluene at 23°C. (manufactured by Kanto Chemical Co., Ltd.), the temperature was raised to 105°C and reacted for 16 hours. After the reaction, an extraction operation was performed using a water-toluene solvent, and after concentration, 10.3 parts of a crude product containing the compound represented by formula (1-60) was obtained. Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 790.4 Accurate mass (Exact Mass): +789.5

(Synthesis example 57)

10 parts of the crude product containing the compound represented by formula (1-60) was dissolved in 26.6 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.), and after cooling to 0°C, 47.4 parts of tetrabutyl fluoride was added dropwise After the dropwise addition of 1 M ammonium chloride solution in tetrahydrofuran (manufactured by Tokyo Chemical Industry Co., Ltd.), stir at 23°C for 16 hours. After the reaction, water was added, the tetrahydrofuran solvent was distilled off, and the obtained crude product was extracted with an organic solvent. After concentration, 7.87 parts of the crude product of the compound represented by formula (1-61) was obtained. The crude product thus obtained was separated and purified by column chromatography to obtain 4.1 parts of the compound represented by formula (1-61). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 448.3 Accurate mass (Exact Mass): +447.2

(Synthesis example 58)

4 parts of the compound represented by Formula (1-61) were dissolved in 36 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.) and stirred. Cool to 0°C and add dropwise 39.2 parts of borane 1 M tetrahydrofuran solution (manufactured by Kanto Chemical Co., Ltd.). After the dropwise addition, the temperature was raised to 23°C and stirred for 5 hours. Then, water was added and the organic layer was obtained by extraction. The solvent was distilled off to obtain 3.54 parts of a crude product containing the compound represented by formula (1-62). The crude product thus obtained was separated and purified by column chromatography to obtain 2.5 parts of the compound represented by formula (1-62). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 406.2 Accurate mass (Exact Mass): +405.2

(Example 10)

2.5 parts of the compound represented by formula (1-62) and 0.70 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) were dissolved in 108.4 parts of toluene (manufactured by Kanto Chemical Co., Ltd.) and 40.5 parts of n-butanol (manufactured by Kanto Chemical Co., Ltd.) were heated while stirring at 120° C. for 16 hours. After the reaction, the solvent was distilled off, and the obtained crude product was separated and purified using silica gel column chromatography to obtain 1.81 parts of the compound represented by formula (II-138). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 889.8 Accurate mass (Exact Mass): +888.4

(Synthesis Example 59)

Make 10 parts of 2-(1-adamantyl)-4-bromoanisole (manufactured by Tokyo Chemical Industry Co., Ltd.), 4 parts of 3-aminoanisole (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.35 parts of palladium acetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.90 part of 4,5'-bis(diphenylphosphino)-9,9'-dimethyldibenzopiran (made by Tokyo Chemical Industry Co., Ltd.) Co., Ltd.) and 6 parts of tertiary sodium butoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 180 parts of toluene (manufactured by Kanto Chemical Co., Ltd.) and heated to reflux at 105°C for 2 hours. After the reaction is completed, water is added, the organic layer is extracted, and concentrated to obtain 25 parts of the compound represented by formula (1-63). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 364.5 Accurate mass (Exact Mass): +363.2

(Synthesis example 60)

8 parts of the compound represented by formula (1-63) and 11 parts of monoethyl succinate chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 160 parts of toluene (manufactured by Kanto Chemical Co., Ltd.), and heated to 90°C. After the reaction, the solvent was concentrated and separated and purified using column chromatography to obtain 8 parts of the compound represented by formula (1-64). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 492.3 Accurate mass (Exact Mass): +491.3

(Synthesis Example 61)

8 parts of the compound represented by formula (1-64) was dissolved in 150 parts of methylene chloride (manufactured by Kanto Chemical Co., Ltd.), and 195 parts of boron tribromide (Fuji Film and Wako Pure Chemical Industries, Ltd.) was added manufacturing) and stir. After the reaction, the reaction mixture was put into 200 parts of water, extracted with ethyl acetate solvent, and concentrated to obtain 12 parts of the compound represented by formula (1-65). Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 464.0 Accurate mass (Exact Mass): +463.2

(Synthesis example 62)

Dissolve 12 parts of the compound represented by formula (1-65) in 70 parts of dehydrated tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.), cool to 0°C, and add 117 parts of borane 1 M while stirring. Tetrahydrofuran solution (manufactured by Kanto Chemical Co., Ltd.). The temperature was raised to 23°C, and after further stirring for 16 hours, water was added for quenching, and then the organic solvent was concentrated, and the obtained crude product was separated and purified using column chromatography to obtain 2.5 parts of formula (1-66) the compound represented. Identification: (Mass analysis) Ionization mode=ESI+: m/z=[M+H] ⁺ 408.0 Accurate mass (Exact Mass): +407.3

(Example 11)

2.5 parts of the compound represented by formula (1-66) and 0.32 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) were dissolved in 8 parts of toluene (manufactured by Kanto Chemical Co., Ltd.) and 10 parts of n-butanol (manufactured by Kanto Chemical Co., Ltd.) were heated while stirring at 110°C for 2 hours. After the reaction, the solvent was distilled off, and the crude product was purified using silica gel column chromatography to obtain 0.5 part of the compound represented by formula (II-372). Identification: (Mass Analysis) Ionization Mode=ESI+: m/z=[M+H] ⁺ 893.0 Accurate Mass (Exact Mass): +892.5

(Resin synthesis example 1)

Circulate an appropriate amount of nitrogen in a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace it with a nitrogen environment. Add 280 parts of propylene glycol monomethyl ether acetate and heat to 80°C while stirring. Then, the following mixed solution was added dropwise over 5 hours: 38 parts of acrylic acid, 289 parts of acrylic acid-3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl ester and acrylic acid-3, A mixture of 4-epoxy tricyclic [5.2.1.0 ^2,6 ] decane-9-yl ester (mixing ratio is 1:1) and 125 parts of propylene glycol monomethyl ether acetate. On the other hand, a mixed solution in which 33 parts of 2,2-azobis (2,4-dimethylvaleronitrile) was dissolved in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the dropwise addition, the flask was kept at 80°C for 4 hours, and then cooled at room temperature to obtain a Type B viscosity (23°C) of 125 mPa·s and a solid content of 35.1 % copolymer (resin (B-1)) solution. The weight average molecular weight Mw of the produced copolymer is 9200, the dispersion degree is 2.08, and the acid value of the solid content is 77 mg-KOH/g. Resin (B-1) has the following structural units.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin in terms of polystyrene were measured using the gel permeation chromatography (GPC) method under the following conditions. Device: HLC-8120GPC (manufactured by Tosoh Corporation) Column: TSK-GELG2000HXL Column temperature: 40°C Solvent: tetrahydrofuran (THF) Flow rate: 1.0 ml/min (mL/min) Solid content concentration of the liquid to be tested: 0.001 mass% to 0.01 mass% Injection volume: 50 microliters (μL) Detector: RI Calibration standard materials: TSK standard polystyrene (STANDARD POLYSTYRENE) F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.)

The ratio (Mw/Mn) of the polystyrene-converted weight average molecular weight and the number average molecular weight obtained above was defined as the degree of dispersion.

[Example 12 to Example 22, Comparative Example 1]

[Preparation of colored resin composition]

Each component was mixed so that it might become the composition shown in Table 13, and the colored resin composition was obtained.

[Table 13] In Table 13, each component system represents the following compounds. Colorant (A-1): a compound represented by formula (I-147) Colorant (A-2): a compound represented by formula (I-27) Colorant (A-3): formula (I-150) The compound coloring agent (A-4) represented by the formula (I-171): the compound coloring agent (A-5) represented by the formula (I-177): the compound coloring agent (A-6) represented by the formula (I-177): Compound coloring agent (A-7) represented by Formula (I-145): Compound coloring agent (A-8) represented by Formula (I-87): Compound coloring agent (A-9) represented by Formula (II-135) ): Compound colorant (A-10) represented by formula (II-129): Compound colorant (A-11) represented by formula (II-138): Compound colorant represented by formula (II-372) (Ax): compound represented by formula (x) Resin (B-1): Resin (B-1) (solid content conversion) Solvent (E-1): Propylene glycol monomethyl ether acetate Solvent (E-2): Diacetone alcohol Solvent (E-3): N - Methylpyrrolidone solvent (E-4): Chloroform leveling agent (F-1): Polyether modified silicone oil ("Toray silicone SH8400" manufactured by Toray Dow Corning Co., Ltd.)

＜Preparation of color filter (colored coating) 1＞

The colored resin composition was coated on a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Corporation) by spin coating, and then prebaked at 100°C for 3 minutes to obtain a colored coating film.

＜Measurement of Chroma＞

The chromaticity of the colored coating is a function of the spectrum measured using a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.) and the characteristics of the C light source, as specified by the International Commission on Illumination (CIE) ) is obtained by using the xy chromaticity coordinates (x, y) of the XYZ color system and the stimulus value Y.

＜Heat resistance evaluation＞

The obtained colored coating film was heated in an oven at 230°C for 2 hours.

The chromaticity was measured before and after heating, and the color difference ΔEab* was calculated based on the measured value using the method described in JIS Z 8730:2009 (7. Calculation method of color difference). The results are shown in Table 14. The smaller ΔEab* is, the smaller the color change is. In addition, if the heat resistance of the colored coating film is good, the colored pattern made of the same colored resin composition can also be said to have good heat resistance.

＜Evaluation of light resistance＞

An ultraviolet cutoff filter (COLORED OPTICAL GLASS L38; manufactured by Hoya Co., Ltd.; cuts light below 380 nanometers) was placed on the obtained colored coating film, and a light resistance testing machine (Suntest CPS+) was used from the upper surface: Manufactured by Toyo Seiki Co., Ltd.) and exposed to xenon light for 48 hours.

The chromaticity was measured before and after irradiation, and the color difference ΔEab* was calculated based on the measured value using the method described in JIS Z 8730:2009 (7. Calculation method of color difference). The results are shown in Table 14. The smaller ΔEab* is, the smaller the color change is. Furthermore, as shown in Table 14, Examples 12 to 22 had not only good heat resistance but also good light resistance.

[Table 14]

[Example 23 to Example 33]

[Preparation of colored resin composition]

Each component was mixed so that it might become the composition shown in Table 15, and the colored resin composition was obtained.

[Table 15] In Table 15, each component system represents the following compounds. Polymerizable compound (C-1): dipenterythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) Polymerization initiator (D-1): N-acetyloxy -1-(4-phenylhydrothiophenyl)-3-cyclohexylpropane-1-one-2-imine (PBG-327; oxime compound; manufactured by Changzhou Qianli Electronic New Materials Co., Ltd.) Other symbol systems It means the same meaning as above.

＜Preparation 2 of color filter (colored coating film) and heat resistance evaluation＞

The colored resin composition was coated on a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Incorporated) using spin coating, and then prebaked at 100°C for 3 minutes to form a colored composition layer. After leaving it to cool, use an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) to form an exposure on the substrate at an exposure dose of 100 millijoules/square centimeter (mJ/cm ² ) (365 nanometer basis) in an atmospheric environment. The upper colored composition layer is irradiated with light. After light irradiation, post-baking is performed in an oven at 230°C for 30 minutes to obtain a colored coating film.

The color was measured before and after post-baking, and the color difference ΔEab* was calculated based on the measured value using the method described in JIS Z 8730:2009 (7. Calculation method of color difference). The results are shown in Table 16.

[Table 16] [Industrial availability]

According to the compound of the present invention, a color filter excellent in heat resistance can be formed.

without

without

Claims (5)

A compound represented by formula (I),

In formula (I), R ¹ to R ⁸ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a saturated hydrocarbon group having 1 to 20 carbon atoms that may have a substituent, or a saturated hydrocarbon group having 1 to 20 carbon atoms that may have a substituent. Alkoxy group; R ⁹ and R ¹⁰ each independently represent a divalent aliphatic hydrocarbon group with 1 to 20 carbon atoms that may have a substituent, and the methylene group contained in the aliphatic hydrocarbon group may be replaced with -O-, The divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms is methylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, or hexane-1 ,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane- 1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1,15-diyl , Hexadecane-1,16-diyl, Heptadecan-1,17-diyl, propenyl, ethane-1,1-diyl, propane-1,1-diyl, propane-1, 2-diyl, propane-2,2-diyl, pentane-2,4-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, 2,2-dimethylpropane-1,3-diyl, pentane-1,4-diyl, 2-methylbutane-1,4-diyl, cyclobutane-1,3-diyl , cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, cyclooctane-1,5-diyl, norbornane-1,4-diyl, norbornane-2 , 5-diyl, adamantane-1,5-diyl, or adamantane-2,6-diyl; R ¹¹ and R ¹² each independently represent a hydrocarbon group with an aromatic hydrocarbon ring having 6 to 20 carbon atoms. , the hydrocarbon group may have a substituent, and the methylene group contained in the hydrocarbon group may be replaced by -O-; R ¹³ represents a hydrogen atom or a saturated hydrocarbon group with 1 to 8 carbon atoms. A colored resin composition includes a colorant and a resin, wherein the colorant includes the compound described in claim 1. The colored resin composition as described in claim 2 further includes a polymerizable compound and a polymerization initiator. A color filter formed from the colored resin composition as described in claim 2 or 3. A display device including the color filter as described in claim 4.