JP7046775B2 - Compound - Google Patents

Description

The present invention relates to compounds.

Color filters used in display devices such as liquid crystal displays, electroluminescence display devices and plasma displays, and solid-state image pickup devices such as CCDs and CMOS sensors are manufactured from colored resin compositions. As a colorant used in such a colored resin composition, a compound represented by the formula (x) is known.

Japanese Unexamined Patent Publication No. 2015-86380

However, a color filter formed from a conventionally known colored resin composition containing the above compound may not sufficiently satisfy the heat resistance. Therefore, the present invention provides a compound capable of forming a color filter having excellent heat resistance.

［式（Ｉ）中、
Ｒ¹～Ｒ⁸は、それぞれ独立に、水素原子、ハロゲン原子、ヒドロキシ基、置換基を有していてもよい炭素数１～２０の飽和炭化水素基、又は置換基を有していてもよい炭素数１～２０のアルコキシ基を表す。
Ｒ⁹及びＲ¹⁰は、それぞれ独立に、置換基を有していてもよい炭素数１～２０の２価の脂肪族炭化水素基を表し、該脂肪族炭化水素基に含まれるメチレン基は－Ｏ－に置き換わっていてもよい。
Ｒ¹¹及びＲ¹²は、それぞれ独立に、芳香族炭化水素環を有する炭素数６～２０の炭化水素基を表し、該炭化水素基は置換基を有していてもよく、該炭化水素基に含まれるメチレン基は－Ｏ－に置き換わっていてもよい。
Ｒ¹³は、水素原子又は炭素数１～８の飽和炭化水素基を表す。］
［２］ 着色剤及び樹脂を含み、着色剤が［１］記載の化合物を含む着色樹脂組成物。
［３］ さらに、重合性化合物及び重合開始剤を含む［２］記載の着色樹脂組成物。
［４］ ［２］又は［３］記載の着色樹脂組成物から形成されるカラーフィルタ。
［５］ ［４］記載のカラーフィルタを含む表示装置。 The present invention includes the following inventions.
[1] A compound represented by the formula (I).

[In formula (I),
Each of R ¹ to R ⁸ may independently have a hydrogen atom, a halogen atom, a hydroxy group, a saturated hydrocarbon group having 1 to 20 carbon atoms, or a substituent. Represents an alkoxy group having 1 to 20 carbon atoms.
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 is-. It 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, and the hydrocarbon group may have a substituent, and the hydrocarbon group may have a substituent. The included methylene 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 according to [1].
[3] The colored resin composition according to [2], further comprising a polymerizable compound and a polymerization initiator.
[4] A color filter formed from the colored resin composition according to [2] or [3].
[5] A display device including the color filter according to [4].

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

<Compound>
The compound according to the present invention is a compound represented by the formula (I) (hereinafter, may be referred to as compound (I)). Hereinafter, the present invention will be described in detail using the formula (I), but the compound (I) has a resonance structure of the formula (I) and a bond axis of a carbon-carbon single bond in which each group in the formula (I) is bonded. Compounds obtained by rotating around are also included.

[In formula (I),
Each of R ¹ to R ⁸ may independently have a hydrogen atom, a halogen atom, a hydroxy group, a saturated hydrocarbon group having 1 to 20 carbon atoms, or a substituent. Represents an alkoxy group having 1 to 20 carbon atoms.
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 is-. It 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, and the hydrocarbon group may have a substituent, and the hydrocarbon group may have a substituent. The included methylene 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 the linear or branched saturated hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isobutyl group, a butyl group, a tert-butyl group, a hexyl group, a heptyl group, an octyl group and a nonyl group. Examples include a group, a decyl group, a heptadecyl group, an undecyl group and the like. The cyclic saturated hydrocarbon group includes a cyclopropyl group, a 1-methylcyclopropyl group, a cyclopentyl group, a cyclohexyl group, a 1,2-dimethylcyclohexyl group, a cyclooctyl group, a 2,4,6-trimethylcyclohexyl group and a 4-. Cyclocyclohexyl group and the like can be mentioned.
As the substituent of the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹ to R ⁸ , a fluorine atom, a chlorine atom, a halogen atom such as iodine; a hydroxy group; -NR ^a R ^b (R ^a and R). ^b is an independently hydrogen atom or an alkyl group having 1 to 20 carbon atoms); a nitro group; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group; a methoxycarbonyl group, an ethoxycarbonyl group and the like. An alkoxycarbonyl group having 1 to 10 carbon atoms; and the like can be mentioned.

Examples of the alkoxy group having 1 to 20 carbon atoms represented by R ¹ to R ⁸ include a group in which —O— is bonded to the bond of the saturated hydrocarbon group having 1 to 20 carbon atoms. Specifically, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, and an octyloxy group. , 2-Ethylhexyloxy group and the like.
As the substituent of the alkoxy group having 1 to 20 carbon atoms represented by R ¹ to R ⁸ , a fluorine atom, a chlorine atom, a halogen atom such as iodine; a hydroxy group; -NR ^c R ^d (R ^c and R ^d are , Each independently is 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 a methoxy group and an ethoxy group; an alkoxy group such as a methoxycarbonyl group and an ethoxycarbonyl group. Examples thereof include an alkoxycarbonyl group having 1 to 10 carbon atoms in the portion.

Of R ¹ to R ⁸ , R ¹ to R ⁴ are preferably hydrogen atoms or methyl groups, and more preferably hydrogen atoms. Further, 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 independently hydrogen atoms, hydroxy groups, and substituents, respectively. It is preferably a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom, or an alkoxy group having 1 to 20 carbon atoms which may have a substituent, and is a hydrogen atom or a hydroxy group. Is more preferable.

It is preferable that 2 to 4 of R ¹ to R ⁸ (preferably R ⁵ to R ⁸ ) are independently hydroxy groups.

The divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R ⁹ and R ¹⁰ may be saturated or unsaturated, and saturation is preferable. 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 a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5-diyl group. Hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonan-1,9-diyl group, decane-1,10-diyl group, undecane-1,11 -Diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane Divalent linear aliphatic hydrocarbon groups such as -1,17-diyl group and propenylene group; ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group. , Propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, 2,2-dimethylpropane- Examples thereof include a divalent branched chain aliphatic hydrocarbon group such as a 1,3-diyl group, a pentane-1,4-diyl group and a 2-methylbutane-1,4-diyl group.
The cyclic divalent aliphatic hydrocarbon group may be monocyclic or polycyclic. Examples of the cyclic divalent aliphatic hydrocarbon group include cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, and cyclooctane-1,5-diyl. Monocyclic divalent aliphatic hydrocarbon groups such as groups; norbornan-1,4-diyl group, norbornan-2,5-diyl group, adamantan-1,5-diyl group, adamantan-2,6-diyl Examples thereof include a polycyclic divalent aliphatic hydrocarbon group such as a group.

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 with —O— include a group represented by the following formula. In the following formula, * on the left side represents a bond with a nitrogen atom, and * on the right side represents a bond with an oxygen atom.

The divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by R ⁹ and R ¹⁰ may have a substituent, and the substituent may be a halogen such as a fluorine atom, a chlorine atom or iodine. Atomic; hydroxy group; -NR ^e R ^f (R ^e and R ^f are independently hydrogen atoms or alkyl groups having 1 to 20 carbon atoms); nitro group; carbons such as methoxycarbonyl group and ethoxycarbonyl group. An alkoxycarbonyl group having a number of 1 to 10; and the like can be mentioned.

Examples of the hydrocarbon group having 6 to 20 carbon atoms having an aromatic hydrocarbon ring represented by R ¹¹ and R ¹² include a group having a bond to the aromatic hydrocarbon ring (hereinafter referred to as an aromatic hydrocarbon group). Examples thereof include an aralkyl group having 7 to 20 carbon atoms. These may have substituents.
Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring and the like, and a benzene ring is preferable.
Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a trill group, a xylyl group, a trimethylphenyl group and a diisopropylphenyl group. Among them, an aromatic hydrocarbon group having an alkyl group at the ortho position is preferable, and examples thereof include a 2,6-dimethylphenyl group, a 2,4,6-trimethylphenyl group and a 2,6-diisopropylphenyl group. Further, when the alkyl group at the ortho position is bulky, the light resistance tends to be excellent.
When the aromatic hydrocarbon group has a substituent, it may have one or a plurality of the substituents. When the aromatic hydrocarbon group has a plurality of substituents, the respective substituents may be the same or different. The substituents include a hydroxy group; a carboxy group; a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom and a bromine atom; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; a sulfamoyl group; a methylsulfonyl group. Examples thereof include an alkylsulfonyl group having 1 to 6 carbon atoms; an alkoxycarbonyl group having 1 to 6 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group; and the like.
The hydrocarbon group having 1 to 14 carbon atoms may have a substituent such as a hydroxy group, a carboxy group, a halogen atom, or an alkoxy group.

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

The aralkyl group having 7 to 20 carbon atoms is a group in which an alkandiyl group having 1 to 5 carbon atoms such as a methylene group, an ethylene group and a propylene group is bonded to the aromatic hydrocarbon ring described in the aromatic hydrocarbon group. Can be mentioned. Examples of the aralkyl group include a benzyl group, a phenylethyl group, a naphthylmethyl group, a naphthylethyl group and the like.
The aralkyl group having 7 to 20 carbon atoms may have a substituent, and when there are a plurality of substituents, the respective substituents may be the same or different. The substituent may be bonded to the aromatic hydrocarbon ring or the alkanediyl group, and the substituent that can be bonded to the aromatic hydrocarbon ring is a substituent of the aromatic hydrocarbon group. It is the same as the group described.

When the aralkyl group having 7 to 20 carbon atoms which may have the substituent has a methylene group, the methylene group may 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 the linear or branched saturated hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isobutyl group, a butyl group, a tert-butyl group, a hexyl group, a heptyl group, an octyl group and the like. Can be mentioned. Examples of the cyclic saturated hydrocarbon group include a cyclopropyl group, a 1-methylcyclopropyl group, a cyclopentyl group, a cyclohexyl group, a 1,2-dimethylcyclohexyl group, a cyclooctyl group and the like.

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

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

Further, examples of the compound (I) include compounds represented by the following formulas (II) in addition to the compounds represented by the above formulas (I-1) to (I-240), which are represented by the formula (II). It is preferably the compound represented. The compound represented by the formula (II) has good light resistance.

[In formula (II),
R ¹ to R ¹⁰ have the same meanings as those in the formula (I).
X ¹ and X ² each independently represent a hydrocarbon group having 1 to 14 carbon atoms, a hydroxy group and a carboxy group having at least one group selected from the group consisting of a hydroxy group and a carboxy group, and the hydrocarbon group. The methylene group contained in may be replaced with —O—.
R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 13 carbon atoms.
n1 and n2 each independently represent an integer of 1 to 5.
However, 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 14 or less, respectively. ]

Examples of the hydrocarbon group having 1 to 14 carbon atoms represented by X ¹ and X ² include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a group combining these.
Examples of the linear aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group and a dodecyl group. Be done.
Examples of the branched aliphatic hydrocarbon group include an isopropyl group, a sec-butyl group, a tert-butyl group, a methylpentyl group, an ethylpentyl group, a methylhexyl group, an ethylhexyl group, a propylhexyl group and a tert-octyl group. Examples thereof include an isopropyl group, a sec-butyl group, a tert-butyl group and an ethylhexyl group.
Examples of the cyclic aliphatic hydrocarbon group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an adamantyl group and the like.
Examples of the aromatic hydrocarbon group include phenyl group, naphthyl group, anthryl group, p-methylphenyl group, p-tert-butylphenyl group, tolyl group, xylyl group, cumenyl group, mesityl group, biphenyl group, 2,6-. Examples thereof include a diethylphenyl group and a 2-methyl-6-ethylphenyl group.
Examples of the group combining these include an alkylcycloalkyl group, a cycloalkylalkyl group, an aralkyl group and the like.

The methylene group contained in the 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 above as the hydrocarbon group having 1 to 14 carbon atoms represented by X ¹ and X ² . Be done.

n1 and n2 each independently represent an integer of 1 to 5, and more 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 14 or less, respectively. When there are a plurality of X ¹ , X ² , R ¹⁴ and R ¹⁵ , the respective X ¹ , X ² , R ¹⁴ and R ¹⁵ may be the same or different.

Examples of the compound (II) include compounds represented by the following formulas (II-a), specifically represented by the formulas (II-1) to (II-540) shown in Tables 4 to 12. Compounds and the like can be mentioned.

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

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

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

The compound represented by the formula (I) can be produced by reacting the compound represented by the formula (pt1) with the compound represented by the formula (pt2) and the compound represented by the 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 1.5 to 2.5 mol with respect to 1 mol of the compound represented by the formula (pt3). It is preferable to have.

<Colored resin composition>
The colored resin composition of the present invention contains a colorant (A) and a resin (B), and the colorant (A) contains a compound represented by the 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 contain a polymerization initiation aid (D1), a solvent (E), and a leveling agent (F).
In the present specification, the compounds exemplified as each component may be used alone or in combination of a plurality of kinds unless otherwise specified.

<Colorant (A)>
The colored resin composition of the present invention contains the 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 0.5 by mass with respect to 100 parts by mass of the resin (B). It is more preferably to 80 parts by mass.
The content of the compound (I) is preferably 20% by mass or more, more preferably 50% by mass or more, still more preferably 80% by mass or more, based on the total amount of the colorant (A). It is particularly preferable that it is 90% by mass or more.

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

The dye (A1) is not particularly limited, and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of dyes include compounds classified by the Color Index (The Society of Dyers and Colorists) as having a hue other than pigments, and known dyes described in dyeing notes (color dyeing company). Be done. According to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, and squarylium dyes (however, compound (I)) are used. Excludes), aclysine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes and the like. Of these, organic solvent-soluble dyes are preferred.

As the pigment (A2), known pigments can be used without particular limitation, and examples thereof include pigments classified as pigments in the Color Index (published by The Society of Dyers and Colorists).
Examples of the pigment include C.I. 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, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
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. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other violet pigments;
C. I. Pigment Green 7, 36, 58 and other green pigments;
C. I. Pigment brown 23, 25 and other brown pigments;
C. I. Examples thereof include black pigments such as Pigment Black 1 and 7.

The content of the colorant (A) is preferably 0.1 to 70% by mass, more preferably 0.5 to 60% by mass, and further, with respect to the total solid content of the colored resin composition. It is preferably 1 to 50% by mass.
Here, the "total amount of solid content" in the present specification means an amount obtained by subtracting 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 of solid content can be measured by a known analytical means such as, for example, liquid chromatography or gas chromatography.

<Resin (B)>
The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (a) (hereinafter, “(a)”). A resin having a structural unit derived from) is more preferable. The resin (B) is a structural unit derived from a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter, may be referred to as “(b)”). Structural units derived from the monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter sometimes referred to as "(c)"), and sides. It is preferable to have at least one structural unit selected from the group consisting of structural units having an ethylenically unsaturated bond in the chain.

Specifically, as (a), for example, acrylic acid, methacrylic acid, maleic anhydride, itaconic acid anhydride, 3,4,5,6-tetrahydrophthalic acid anhydride, succinic acid mono [2- (meth). ) Acryloyloxyethyl] and the like, preferably acrylic acid, methacrylic acid, maleic anhydride.

As (b), a monomer having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxylan ring, an oxetane ring and a tetrahydrofuran ring) and a (meth) acryloyloxy group is preferable. ..
In addition, in this specification, "(meth) acrylic acid" represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as "(meth) acryloyl" and "(meth) acrylate" have the same meaning.
Examples of (b) include glycidyl (meth) acrylate, vinylbenzyl glycidyl ether, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate, and 3-ethyl-3-. Examples thereof include (meth) acryloyloxymethyloxetane, tetrahydrofurfuryl (meth) acrylate, and the like, preferably glycidyl (meth) acrylate, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl ( Meta) acrylate, 3-ethyl-3- (meth) acryloyloxymethyloxetane.

Examples of (c) include methyl (meth) acrylate, butyl (meth) acrylate cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, and tricyclo [5.2.1.0 ^2,6 ] decane-8. -Il (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, styrene, vinyltoluene and the like can be mentioned, with preference given to styrene. , Vinyl toluene, 2-hydroxyethyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and the like are preferable.

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

The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000. ..
The dispersity [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

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

The content of the resin (B) is preferably 30 to 99.9% by mass, more preferably 50 to 99.5% by mass, still more preferably, with respect to the total solid content of the colored resin composition. Is 70 to 99% by mass.
When the colored resin composition of the present invention contains the polymerizable compound (C) and the polymerization initiator (D), the content of the resin (B) is preferably 7 with respect to the total solid content of the colored resin composition. It is about 70% by mass, more preferably 13 to 65% by mass, still more preferably 17 to 60% by mass.

<Polymerizable compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by an active radical and / or an acid generated from the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, which is preferable. Is a (meth) acrylic acid ester compound.

Above all, 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, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (dipentaerythritol hexa). Meta) Acrylate and the like can be mentioned.

When the polymerizable compound (C) is contained, the content of the polymerizable compound (C) is preferably 5 to 65% by mass, more preferably 13 to 60% by mass, based on the total amount of solids. , More preferably 17 to 55% by mass.

<Polymer Initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound that can initiate polymerization by generating active radicals, acids and the like by the action of light or heat, and a known polymerization initiator can be used. Examples of the polymerization initiator that generates an active radical include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-on-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl). ) Octane-1-on-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-on-2-imine, N-acetyloxy-1- (4-phenyl) Sulfanylphenyl) -3-cyclohexylpropane-1-on-2-imine, 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-) Morphorinophenyl) -2-benzylbutane-1-one, 1-hydroxycyclohexylphenylketone, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4,6-trimethylbenzoyl Examples thereof include diphenylphosphine oxide, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole and the like.

When the polymerization initiator (D) is contained, the content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Parts, more preferably 1 to 20 parts by mass, still more 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 increased and the exposure time tends to be shortened, so that the productivity of the color filter is improved.

<Polymerization initiation aid (D1)>
The polymerization initiator (D1) is a compound or a sensitizer used to promote the polymerization of the polymerizable compound initiated by the polymerization initiator. When the polymerization initiator (D1) is contained, it is usually used in combination with the polymerization initiator (D).
Examples of the polymerization initiation aid (D1) include 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 9,10-dimethoxyanthracene, and 2,4-diethylthioxanthone. , N-Phenylglycine and the like.

When these polymerization initiation aids (D1) are used, the content thereof is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is preferably 1 to 20 parts by mass. When the amount of the polymerization initiation aid (D1) is within this range, a coloring pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

<Solvent (E)>
The solvent (E) is not particularly limited, and a solvent usually used in the art can be used. For example, an ester solvent (solvent containing -COO- in the molecule and not containing -O-), an ether solvent (solvent containing -O- in the molecule and not containing -COO-), an ether ester solvent (intramolecular). Solvent containing -COO- and -O-), Ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (solvent containing OH in the molecule, -O-,- CO- and -COO-free solvents), aromatic hydrocarbon solvents, amide solvents, halogen-based solvents, dimethylsulfoxide and the like.

As a solvent,
Ester solvents such as ethyl lactate, butyl lactate, methyl 2-hydroxyisobutate, n-butyl acetate, ethyl butyrate, butyl butyrate, ethyl pyruvate, methyl acetoacetate, cyclohexanol acetate and γ-butyrolactone (intramolecular-COO- Solvent containing —O— but not —O—);
Ether solvents such as ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-1-butanol, diethylene glycol dimethyl ether, and diethylene glycol methyl ethyl ether (solvents containing -O- in the molecule and not -COO-). );
Ether ester solvents such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate (intramolecular-COO- Solvent containing -O-);
Ketone solvents such as 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), heptanone, 4-methyl-2-pentanone, cyclohexanone (solvents containing -CO- in the molecule and not -COO-) ;
Alcohol solvents such as butanol, cyclohexanol and propylene glycol (solvents containing OH in the molecule and not -O-, -CO- and -COO-);
Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone;
Halogen-based solvents such as chloroform, chlorobenzene, dichloroethylene and trichlorethylene; and the like.
As the solvent, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), N-methylpyrrolidone, chloroform, ethyl lactate and ethyl 3-ethoxypropionate are more suitable. preferable.

When the solvent (E) is contained, the content of the solvent (E) is preferably 60 to 95% by mass, more preferably 65 to 92% by mass, based on the total amount of the colored resin composition of the present invention. .. In other words, the total solid content of the colored resin composition is preferably 5 to 40% by mass, more preferably 8 to 35% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating is good, and the color density is not insufficient when the color filter is formed, so that the display characteristics tend to be good. ..

<Leveling agent (F)>
Examples of the leveling agent (F) include a silicone-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom. These may have a polymerizable group in the side chain.
Examples of the silicone-based surfactant include a surfactant having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324. , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (manufactured by Momentive Performance Materials Japan GK) and the like. ..

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafuck (registered trademark) F142D, F171, F172, F173, F177, F183, F554, and F554. R30, RS-718-K (manufactured by DIC Co., Ltd.), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S381, Examples thereof include S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.).

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

When the leveling agent (F) is contained, the content of the leveling agent (F) is preferably 0.001 to 0.2% by mass, more preferably 0.002 to 0.2% by mass, based on the total amount of the colored resin composition. It is 0.1% by mass. The content of the pigment dispersant is not included in this content. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Other ingredients>
The colored resin composition of the present invention contains, if necessary, additives known in the art such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents and the like. But it may be.

<Manufacturing method of colored resin composition>
The colored resin composition of the present invention comprises a colorant (A) and a resin (B), as well as a polymerizable compound (C), a polymerization initiator (D), a polymerization initiator (D1), and a solvent used as needed. It can be prepared by mixing (E), the leveling agent (F) and other components.

<Manufacturing method of color filter>
Examples of the method for producing a colored pattern from the colored resin composition of the present invention include a photolithography method, an inkjet method, a printing method and the like. Of these, the photolithography method is preferable.

When the colored resin composition contains the compound represented by the formula (I), a color filter having particularly excellent heat resistance and light resistance can be produced. The color filter is useful as a color filter used in a display device (for example, a liquid crystal display device, an organic EL device, electronic paper, etc.) and a solid-state image sensor.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. In the examples,% and parts indicating the content or the amount used are based on mass unless otherwise specified.
In the following, the structure of the compound was confirmed by mass spectrometry (LC; Agilent 1200 type, MASS; Agilent LC / MSD type).

(Synthesis Example 1)
50 parts of 3-bromoanisole (manufactured by Tokyo Chemical Industry Co., Ltd.) to 36.1 parts of 2,4,6-trimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 434 parts of toluene (manufactured by Kanto Chemical Industry Co., Ltd.) Dissolve and dissolve in this solution 30 parts of potassium hydroxide (manufactured by Kanto Chemical Co., Ltd.), 25 parts of water, 2 parts of tetrabutylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.), bis (tri-tert-butylphosphine) palladium. (0) 1.4 parts (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed. 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 a crude product. The obtained crude product was separated and purified by column chromatography to obtain 50.2 parts of the compound represented by the formula (1-1).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 242.3
Exact Mass: +241.2

(Synthesis Example 2)
33 parts of the compound represented by the formula (1-1), 26.8 parts of methyl 4-chloro-4-oxobutyrate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 286 parts of toluene (manufactured by Kanto Chemical Co., Inc.) are mixed. Then, the mixture was heated at 100 ° C. for 16 hours with stirring. After completion of the reaction, the solvent was distilled off, and the obtained crude product was separated and purified by column chromatography to obtain 30.7 parts of the compound represented by the formula (1-2).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 356.2
Exact Mass: +355.2

(Synthesis Example 3)
10 parts of the compound represented by the formula (1-2) was dissolved in 95 parts of methylene chloride (manufactured by Kanto Chemical Co., Inc.) and cooled to 0 ° C. with stirring. 28.2 parts of boron tribromide (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise with stirring. After completion of the dropping, the temperature was gradually raised and the mixture was stirred at 10 ° C. for 4 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, a water-organic solvent extraction operation was carried out, and the solvent was distilled off to obtain 9.1 parts of a crude product. It contained 48% of the compound represented by the formula (1-3) and 36% of the compound represented by the formula (1-4).

同定：（質量分析）イオン化モード＝ＥＳＩ＋：ｍ／ｚ＝［Ｍ＋Ｈ］⁺３４２．２
Ｅｘａｃｔ Ｍａｓｓ：＋３４１．２

同定：（質量分析）イオン化モード＝ＥＳＩ＋：ｍ／ｚ＝［Ｍ＋Ｈ］⁺３２８．１
Ｅｘａｃｔ Ｍａｓｓ：＋３２７．２

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 342.2
Exact Mass: +341.2

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 328.1
Exact Mass: +327.2

(Synthesis Example 4)
The formula obtained in Synthesis Example 3 while cooling a solution of 13.2 parts of thionyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 72 parts of methanol (manufactured by Kanto Chemical Co., Ltd.) to 0 ° C. and stirring. 9.1 parts of a crude product containing the compound represented by (1-3) and the compound represented by the formula (1-4) was charged. The temperature was raised to room temperature and the reaction was carried out 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 the formula (1-3). The obtained crude product was purified by silica gel column chromatography to obtain 7.4 parts of the compound represented by the formula (1-3).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 342.2
Exact Mass: +341.2

(Synthesis Example 5)
2 parts of the compound represented by the formula (1-3), 26.3 parts of borane 1M tetrahydrofuran solution (manufactured by Kanto Chemical Co., Ltd.) and 18 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.) are mixed at 0 ° C. and 10 ° C. The temperature was raised to 5 and the mixture was stirred for 5 hours. After completion of the reaction, water was added to quench the reaction, and the mixture was extracted with an organic solvent. The crude product obtained by distilling off the solvent was purified by silica gel column chromatography to obtain 1.64 parts of the compound represented by the formula (1-5).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 300.2
Exact Mass: +299.2

(Example 1)
2.5 parts of the compound represented by the formula (1-5) and 0.55 part of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Wako Pure Chemical Industries, Ltd.) in toluene (Kanto) It was dissolved in 50 parts of Chemical Industries, Ltd. and 50 parts of n-butanol (manufactured by Kanto Chemical Industries, Ltd.) and heated at 110 ° C. for 6 hours with stirring. After completion of the reaction, the solvent was distilled off and the obtained crude product was separated and purified by silica gel column chromatography to obtain 2.7 parts of the compound represented by the formula (I-147).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 677.4
Exact Mass: +676.4

(Synthesis Example 6)
10 parts of the compound represented by the formula (1-1), 7.4 parts of methylmalonyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 87 parts of toluene (manufactured by Kanto Chemical Co., Inc.) are mixed and 16 at 100 ° C. It was heated with stirring for hours. After completion of the reaction, the solvent was distilled off, and the obtained crude product was separated and purified by column chromatography to obtain 9.1 parts of the compound represented by the formula (1-6).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 342.2
Exact Mass: +341.2

(Synthesis Example 7)
8.1 parts of the compound represented by the formula (1-6) was dissolved in 107 parts of methylene chloride (manufactured by Kanto Chemical Co., Inc.) and cooled to 0 ° C. with stirring. 24 parts of boron tribromide (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise with stirring. After completion of the dropping, the temperature was gradually raised and the mixture was stirred at 23 ° C. for 3 hours. After completion of the reaction, the organic layer was extracted and concentrated to obtain 7.2 parts of the compound represented by the formula (1-7).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 314.1
Exact Mass: +313.1

(Synthesis Example 8)
Formula (1-7) while cooling a solution of 10.6 parts of thionyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 55.5 parts of methanol (manufactured by Kanto Chemical Co., Inc.) to 0 ° C. and stirring. 5 parts of the compound represented by is added. The temperature was raised to 23 ° C. and the reaction was carried out 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 the formula (1-8). The obtained crude product was purified by silica gel column chromatography to obtain 5.6 parts of the compound represented by the formula (1-8).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 328.2
Exact Mass: +327.15

(Synthesis Example 9)
5.5 parts of the compound represented by the formula (1-8), 92.3 parts of borane 1M tetrahydrofuran solution (manufactured by Kanto Chemical Co., Ltd.), and 49 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.) are mixed at 0 ° C. The temperature was raised to 23 ° C. and the mixture was stirred for 3 hours. After completion of the reaction, water was added to quench the reaction, and the mixture was extracted with an organic solvent. The solvent was distilled off, and the obtained crude product was purified by silica gel column chromatography to obtain 2.6 parts of the compound represented by the formula (1-9).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 286.2
Exact Mass: +285.2

(Example 2)
2 parts of the compound represented by the formula (1-9) and 0.4 part of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Wako Pure Chemical Industries, Ltd.) in toluene (Kanto Kagaku (Kanto Kagaku Co., Ltd.) It was dissolved in 69 parts (manufactured by Kanto Chemical Industries, Ltd.) and 16 parts of n-butanol (manufactured by Kanto Chemical Industries, Ltd.) and heated at 120 ° C. for 4 hours with stirring. After completion of the reaction, the solvent was distilled off and the obtained crude product was separated and purified by silica gel column chromatography to obtain 1.3 parts of the compound represented by the formula (I-27).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 649.7
Exact Mass: +648.3

(Synthesis Example 10)
Mesityl bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) 7 parts, 5-methoxy-2-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.8 parts, palladium acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.39 parts 4,5'-bis (diphenylphosphino) -9,9'-dimethylxanthene (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.84 parts, sodium-tert-butoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) 6. Eight parts were dissolved in 126 parts of toluene (manufactured by Kanto Chemical Industry Co., Ltd.), and heated and refluxed at 105 ° C. for 1 hour. After completion of the reaction, water was added to extract the organic layer, and the obtained crude product was separated and purified by silica gel column chromatography to obtain 7 parts of the compound represented by the formula (1-15).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M ⁺ H] +256.2
Exact Mass: +255.2

(Synthesis Example 11)
6 parts of the compound represented by the formula (1-15) and 33 parts of succinic acid monoethyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) are dissolved in 20 parts of toluene (manufactured by Kanto Chemical Co., Inc.) and 8 at 90 ° C. Heated for hours. After completion of the reaction, water was added to extract the organic layer, and repulp washing was performed with 300 parts of hexane (manufactured by Kanto Chemical Co., Inc.) to obtain 4 parts of the compound represented by the formula (1-16).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 384.0
Exact Mass: +383.2

(Synthesis Example 12)
4.2 parts of the compound represented by the formula (1-16) is dissolved in 20 parts of methylene chloride (manufactured by Kanto Chemical Industries, Ltd.), and 46 parts of boron tribromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) is dissolved. It was charged and stirred. After completion of the reaction, water was added to the reaction mixture for quenching, extraction with an ethyl acetate solvent and concentration to obtain 5 parts of the compound represented by the formula (1-17).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 370.3
Exact Mass: +369.2

(Synthesis Example 13)
4 parts of the compound represented by the formula (1-17) is dissolved in 40 parts of dehydrated tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.), cooled to 0 ° C., and a borane 1M tetrahydrofuran solution (manufactured by Kanto Chemical Co., Ltd.) is stirred. ) 105 copies were put in. After raising the temperature to 23 ° C. and stirring for another 20 hours, water was added for quenching, and the mixture was extracted with an organic solvent. The solvent was distilled off to obtain 2.8 parts of the compound represented by the formula (1-18).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 314.3
Exact Mass: +313.2

(Example 3)
0.7 part of the compound represented by the formula (1-18) and 0.12 part of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Wako Pure Chemical Industries, Ltd.) in toluene (Kanto) It was dissolved in 2 parts of Chemical Industries, Ltd. and 3 parts of n-butanol (manufactured by Kanto Chemical Industries, Ltd.) and heated at 110 ° C. for 13 hours with stirring. After completion of the reaction, the solvent was distilled off and the obtained crude product was separated and purified by silica gel column chromatography to obtain 0.1 part of the compound represented by the formula (I-150).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 705.8
Exact Mass: +704.4

(Synthesis Example 14)
2,6-Diisopropylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) 20 parts, 3-bromoanisole (manufactured by Tokyo Chemical Industry Co., Ltd.) 22.4 parts, palladium acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.6 Toluene (1 mol / L tri-tert-butylphosphine / hexane solution (manufactured by Wako Pure Chemical Industries, Ltd.) 0.9 parts, sodium tert-butoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) 21.7 parts It was dissolved in 228 parts (manufactured by Kanto Chemical Industry Co., Ltd.) and heated and refluxed at 110 ° C. for 5 hours. After completion of the reaction, water was added to extract the organic layer, and the obtained crude product was separated and purified by silica gel column chromatography to obtain 32 parts of the compound represented by the formula (1-19).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 284.2
Exact Mass: +283.2

(Synthesis Example 15)
Five parts of the compound represented by the formula (1-19) were dissolved in 85 parts of dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.) under an ice bath. 3.5 parts of sodium hydride (manufactured by 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 reflux was performed by heating. After completion of the reaction, 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 by silica gel column chromatography and represented by the formula (1-20). 6.5 parts of the compound was obtained.

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 370.5
Exact Mass: +369.5

(Synthesis Example 16)
5 parts of the compound represented by the formula (1-20) is dissolved in 100 parts of methylene chloride (manufactured by Kanto Chemical Industries, Ltd.), and 147 parts of boron tribromide (manufactured by Wako Pure Chemical Industries, Ltd.) is added. And stirred. After completion of the reaction, water was added to the reaction mixture for quenching, extraction with ethyl acetate and concentration. The obtained crude product is separated by a silica gel column, and a mixture containing 78% of the compound represented by the formula (1-21-1) and 22% of the compound represented by the formula (1-21-2) (hereinafter referred to as a mixture). A mixture (1-21) may be referred to as 3.8 parts).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 342.4
Exact Mass: +341.2

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 356.5
Exact Mass: +355.3

(Examples 4 to 5)
4.5 parts of the mixture (1-21) and 0.45 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Wako Pure Chemical Industries, Ltd.) in toluene (manufactured by Kanto Chemical Industries, Ltd.) ) 30 parts, n-butanol (manufactured by Kanto Chemical Industries, Ltd.) was dissolved in 30 parts and heated at 120 ° C. for 3.5 hours with stirring. After completion of the reaction, the solvent was distilled off and separated and purified by silica gel column chromatography to obtain 1 part of the compound represented by the formula (I-171) and 1 part of the compound represented by the formula (I-177). ..

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 761.4
Exact Mass: +760.5

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 775.7
Exact Mass: +774.5

(Synthesis Example 17)
2,4,6-trimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) 10 parts, 1-bromo-3,5-dimethoxybenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) 16 parts, palladium acetate (Tokyo Chemical Industry Co., Ltd.) ) 0.83 parts, 4,5'-bis (diphenylphosphino) -9,9'-dimethylxanthene (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.1 parts, sodium tert-butoxide (Tokyo Chemical Industry (Tokyo Chemical Industry Co., Ltd.) 14.2 parts (manufactured by Kanto Chemical Industry Co., Ltd.) was dissolved in 180 parts of toluene (manufactured by Kanto Chemical Industry Co., Ltd.), and heated and refluxed at 105 ° C. for 3 hours. After completion of the reaction, water was added to extract the organic layer, and the obtained crude product was separated and purified by silica gel column chromatography to obtain 19 parts of the compound represented by the formula (1-22).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 272.5
Exact Mass: +271.2

(Synthesis Example 18)
7.5 parts of the compound represented by the formula (1-22) and 13.6 parts of succinic acid monoethyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 150 parts of toluene (manufactured by Kanto Chemical Co., Inc.). It was heated at 100 ° C. for 5 hours. After completion of the reaction, the solvent was distilled off, and the obtained crude product was separated and purified by silica gel column chromatography to obtain 10 parts of the compound represented by the formula (1-23).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 400.5
Exact Mass: +399.2

(Synthesis Example 19)
2.7 parts of the compound represented by the formula (1-23) is dissolved in 30 parts of methylene chloride (manufactured by Kanto Chemical Industries, Ltd.), and boron tribromide (manufactured by Wako Pure Chemical Industries, Ltd.) 7.7. The parts were put in and stirred. After completion of the reaction, water was added to the reaction mixture for quenching, extraction with an ethyl acetate solvent and concentration to obtain 2.2 parts of the compound represented by the formula (1-24).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 372.3
Exact Mass: +371.2

(Synthesis Example 20)
0.25 part of the compound represented by the formula (1-24) is dissolved in 7 parts of dehydrated tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.), cooled to 0 ° C., and a borane 1M tetrahydrofuran solution (Kanto Chemical Co., Ltd.) is stirred. ) Manufactured) 0.4 part was added. The temperature was raised to 23 ° C., the mixture was further stirred for 20 hours, water was added and quenched, and then the organic solvent was concentrated to obtain 0.12 parts of the compound represented by the formula (1-25).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 316.3
Exact Mass: +315.2

(Example 6)
0.4 part of the compound represented by the formula (1-25) and 0.07 part of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Wako Pure Chemical Industries, Ltd.) in toluene (Kanto) It was dissolved in 3 parts of Chemical Industries, Ltd. and 4.5 parts of n-butanol (manufactured by Kanto Chemical Industries, Ltd.) and heated at 110 ° C. for 3 hours with stirring. After completion of 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 the formula (I-145).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 709.7
Exact Mass: +708.3

(Synthesis Example 21)
62 parts of 2,2-dimethyl-malonic acid monomethyl ester (manufactured by Alfa Chemistry Co., Ltd.) was dissolved in 413 parts of methylene chloride (manufactured by Kanto Chemical Industry Co., Ltd.), cooled to 0 ° C., and stirred while dimethylformamide (dichloroformamide). 5 parts (manufactured by Kanto Chemical Co., Ltd.) and 81 parts of oxalyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) were added dropwise. Then, the temperature was raised to 23 ° C. and the mixture was stirred for 1 hour. After completion of the reaction, the reaction mixture was concentrated to obtain 54 parts of the compound represented by the formula (1-26).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 165.1
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., Inc.). While stirring this solution at 23 ° C., 50.4 parts of the compound represented by the above formula (1-26) was added dropwise. After the dropping was completed, the mixture was stirred for 1 hour. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain 46 parts of a crude product containing the compound represented by the following formula (1-27). This crude product was separated and purified by silica gel column chromatography to obtain 40 parts of the compound represented by the formula (1-27).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 264.1
Exact Mass: +263.2

(Synthesis Example 23)
14.4 parts of lithium aluminum hydride (powder) (manufactured by Tokyo Chemical Industry Co., Ltd.) was put into 40 parts of dimethyl ether (manufactured by Kanto Chemical Co., Inc.) 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., Inc.) and stirred to dissolve. The solution containing the compound represented by this formula (1-27) was added dropwise to the above solution containing lithium aluminum hydride (powder) over 15 minutes while cooling to 0 ° C. and stirring. Then, the temperature was gradually raised to 80 ° C. and the reaction was carried out at 80 ° C. for 3 days. After completion of the reaction, the reaction mixture was poured into 200 parts of water, extracted with water and toluene, and concentrated to obtain 7.0 parts of a crude product. This crude product was separated and purified by silica gel column chromatography to obtain 2.9 parts of the compound represented by the formula (1-28).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 222.1
Exact Mass: +221.2

(Synthesis Example 24)
7.8 parts of the compound represented by the formula (1-28) is dissolved in 108 parts of methylene chloride (manufactured by Kanto Chemical Industry Co., Ltd.), cooled to 0 ° C., and imidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) while stirring. ) 3.6 parts and 6.4 parts of tert-butyldimethylchlorosilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. The temperature was raised to 23 ° C., and the mixture was further stirred for 16 hours. After completion of the reaction, an extraction operation with water and an organic solvent was carried out to obtain 7.8 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 7.2 parts of the compound represented by the formula (1-29).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 336.4
Exact Mass: +335.3

(Synthesis Example 25)
50 parts of m-bromophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 30 parts of imidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) are dissolved in 500 parts of dichloromethane (manufactured by Kanto Chemical Industry Co., Ltd.), cooled to 0 ° C., and then tert. -48 parts of butyldimethylchlorosilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of the dropping, the temperature was raised to 23 ° C. and the mixture was stirred for 16 hours. After completion of the reaction, water was added to extract the organic layer, the solvent was concentrated, and the residue was separated and purified by silica gel column chromatography to obtain 74 parts of the compound represented by the formula (1-10).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 287.0
Exact Mass: +286.0

(Synthesis Example 26)
20 parts of the compound represented by the formula (1-10) was put into 31 parts of 1,4-dioxane (manufactured by Kanto Chemical Co., Inc.) and dissolved. Further, in this solution, 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.), copper iodide (I) (Fuji Film). 2.7 parts (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed. This was placed in a pressurized container and reacted at 120 ° C. for 6 hours. After completion of the reaction, the mixture was extracted with water and a toluene solvent and concentrated to obtain 20 parts of a crude product. This crude product was separated and purified by silica gel column chromatography to obtain 10.5 parts of the compound represented by the formula (1-30).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 335.1
Exact Mass: +334.0

(Synthesis Example 27)
9.6 parts of the compound represented by the formula (1-29) and 9.6 parts of the compound represented by the formula (1-30) were added to 84 parts of toluene (manufactured by Kanto Chemical Co., Inc.) and dissolved. To this solution, 6.8 parts of sodium tert-butoxide (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.4 part of tri-tert-butylphosphonium tetrafluoroborate (manufactured by Tokyo Chemical Industry Co., Ltd.), tris (dibenzylideneacetone) ) DiPalladium (0) (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.52 part was added and dissolved. The mixed solution was irradiated with microwaves and reacted at 140 ° C. for 1 hour. Then, the solvent was distilled off under reduced pressure, water was added, and an extraction operation with an organic solvent was carried out, and the solvent was distilled off to obtain 9.6 parts of a crude product. This crude product is separated and purified by silica gel column chromatography, and the crude product containing the compound represented by the formula (1-31) (hereinafter, may be referred to as crude product (1-31)) 1.8. I got a copy.

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 542.4
Exact Mass: +541.4

(Synthesis Example 28)
After dissolving 1.8 parts of the crude product (1-31) in 17.8 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.) and cooling to 0 ° C., tetrabutylammonium fluoride 1M tetrahydrofuran solution (Tokyo Chemical Industry Co., Ltd.) ) Manufactured) 9.2 parts were added dropwise, and after completion of the addition, the mixture was stirred at 23 ° C. for 16 hours. After completion of the reaction, water was added, and the crude product obtained by distilling off tetrahydrofuran was subjected to an extraction operation with an organic solvent, and after concentration, 1.4 parts of the crude product of the compound represented by the formula (1-32) was subjected to an extraction operation. Obtained. The crude product thus obtained was separated and purified by column chromatography to obtain 0.76 parts of the compound represented by the formula (1-32).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 314.2
Exact Mass: +313.2

(Example 7)
0.4 part of the compound represented by the formula (1-32) and 0.072 part of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Wako Pure Chemical Industries, Ltd.) in toluene (Kanto) It was dissolved in 14 parts of Chemical Industries, Ltd. and 3.24 parts of n-butanol (manufactured by Kanto Chemical Industries, Ltd.) and heated at 140 ° C. for 3 hours with stirring. After completion of the reaction, the solvent was distilled off and the obtained crude product was separated and purified by silica gel column chromatography to obtain 0.25 part of the compound represented by the formula (I-87).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 705.8
Exact Mass: +704.4

(Synthesis Example 29)
45 parts of 4-amino-3,5-xylenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 400 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Inc.). 127 parts of di-tert-butyl dicarbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to this solution and dissolved. The mixture was stirred and reacted at 23 ° C. for 16 hours. After completion of the reaction, the solvent was distilled off to obtain 51 parts of a crude product. The obtained crude product was purified by stirring in a mixed solvent of 90 parts of ethyl acetate (manufactured by Kanto Chemical Co., Inc.) and 272 parts of n-hexane (manufactured by Kanto Chemical Co., Inc.) at 23 ° C. for 2 hours, according to the formula (1). Forty-seven parts of the compound represented by −33) were obtained.

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 238.3
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., Inc.). 32.4 parts of triethylamine (manufactured by Kanto Chemical Industry Co., Ltd.) and 0.156 parts of 4-dimethylaminopyridine (manufactured by Kanto Chemical Co., Ltd.) are added to this solution, and tert-butyldimethylsilyl chloride (Tokyo Chemical Industry Co., Ltd.) is added while stirring. 28.95 parts (manufactured by Kogyo Co., Ltd.) was added and dissolved. The mixture was stirred and reacted at 23 ° C. for 16 hours. The solvent was distilled off to obtain 20 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 20 parts of the compound represented by the formula (1-34).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 239.1
Exact Mass: +238.0

(Synthesis Example 31)
47 parts of the compound represented by the formula (1-33) were dissolved in 141.5 parts of the bromo compound represented by the formula (1-34) and 447 parts of dimethylformamide (manufactured by Kanto Chemical Co., Inc.). 138.2 parts of potassium carbonate (manufactured by Kanto Chemical Co., Inc.) was added to this solution, and the mixture was stirred and reacted at 70 ° C. for 16 hours. After completion of the reaction, the solvent was distilled off and an extraction operation with an organic solvent was carried out to obtain 49 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 41 parts of the compound represented by the formula (1-35).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H-t-Bu ⁺ ] ⁺ 339.2
Exact Mass: +395.3

(Synthesis Example 32)
41 parts of the compound represented by the formula (1-35) was dissolved in 424 parts of 1,4-dioxane (manufactured by Kanto Chemical Industry Co., Ltd.), and hydrogen chloride (about 4 mol / L 1,4-dioxane solution) (Tokyo Chemical Industry Co., Ltd.) was dissolved. 263 parts (manufactured by Kogyo Co., Ltd.) were added and stirred at 23 ° C. for 1 hour for deprotection. After completion of the reaction, the solvent was distilled off to obtain 36 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 22 parts of the compound represented by the formula (1-36).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 182.2
Exact Mass: +181.1

(Synthesis Example 33)
22 parts of the compound represented by the formula (1-36) was dissolved in 293 parts of dichloromethane (manufactured by Kanto Chemical Co., Inc.). 10.8 parts of imidazole (manufactured by Kanto Chemical Co., Inc.) and 22 parts of tert-butyldimethylsilyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to this solution and dissolved. The mixture was stirred and reacted at 23 ° C. for 16 hours. The solvent was distilled off to obtain 23 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 20 parts of the compound represented by the formula (1-37).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 296.3
Exact Mass: +295.2

(Synthesis Example 34)
15 parts of the compound represented by the formula (1-10) are dissolved in 14.5 parts of the compound represented by the formula (1-37) and 130 parts of toluene (manufactured by Kanto Chemical Industry Co., Ltd.), and hydroxide is added to this solution. Potassium (manufactured by Kanto Chemical Co., Ltd.) 5.7 parts, water 15 parts, tetrabutylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) 2 parts, bis (tri-tert-butylphosphine) palladium (0) (Tokyo Chemical Industry Co., Ltd.) 0.26 part (manufactured by Kogyo Co., Ltd.) was mixed. After raising the temperature to 90 ° C. and stirring for 20 minutes, an organic layer was obtained by extraction, and the solvent was distilled off to obtain 15 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 12 parts of the compound represented by the formula (1-38).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 502.4
Exact Mass: +501.3

(Synthesis Example 35)
12 parts of the compound represented by the formula (1-38), 11.9 parts of methyl 4-chloro-4-oxobutyrate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 41.6 parts of toluene (manufactured by Kanto Chemical Co., Inc.) Was mixed and heated at 90 ° C. for 1 hour with stirring. After completion of the reaction, the solvent was distilled off, and the obtained crude product was separated and purified by column chromatography to obtain 5.9 parts of the compound represented by the formula (1-39).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 616.3
Exact Mass: +615.3

(Synthesis Example 36)
After dissolving 5.9 parts of the compound represented by the formula (1-39) in 52.4 parts of tetrahydrofuran (manufactured by Kanto Chemical Industry Co., Ltd.) and cooling to 0 ° C., tetrabutylammonium fluoride 1M tetrahydrofuran solution (Tokyo Chemical Industry Co., Ltd.) 11 parts (manufactured by Kogyo Co., Ltd.) were added dropwise, and the mixture was stirred at 23 ° C. for 2 hours after the completion of the addition. After completion of the reaction, water was added, the tetrahydrofuran solvent was distilled off, and the obtained crude product was subjected to an extraction operation with an organic solvent to obtain 4.3 parts of the compound represented by the formula (1-40) after concentration. ..

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 388.2
Exact Mass: +387.2

(Synthesis Example 37)
4.3 parts of the compound represented by the formula (1-40), 56.4 parts of borane 1M tetrahydrofuran solution (manufactured by Kanto Chemical Co., Ltd.), 38.2 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.) at 0 ° C. The mixture was mixed, heated to 23 ° C., and stirred for 16 hours. After completion of the reaction, water was added, the mixture was quenched, and the mixture was extracted with an organic solvent. The solvent was distilled off, and the obtained crude product was purified by silica gel column chromatography to obtain 2.3 parts of the compound represented by the formula (1-41).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 346.3
Exact Mass: +345.2

(Example 8)
2.3 parts of the compound represented by the formula (1-41) and 0.38 part of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Wako Pure Chemical Industries, Ltd.) in toluene (Kanto) It was dissolved in 80 parts of Chemical Industries, Ltd. and 19 parts of n-butanol (manufactured by Kanto Chemical Industries, Ltd.) and heated at 120 ° C. for 4 hours with stirring. After completion of the reaction, the solvent was distilled off and the obtained crude product was separated and purified by silica gel column chromatography to obtain 1.3 parts of the compound represented by the formula (II-135).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 769.8
Exact Mass: +768.4

(Synthesis Example 38)
3-Iodoanisole (manufactured by Tokyo Chemical Industry Co., Ltd.) 100 parts and 4-bromo-2,6-dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) 85.5 parts, 72 parts of water and toluene (Kanto Kagaku Co., Ltd.) )) Dissolved in 867 parts of a mixed solvent. 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.), bis (tri-tert-butylphosphine) palladium. (0) 2.2 copies (manufactured by Tokyo Chemical Industry Co., Ltd.) were introduced. The mixed solution was heated to 90 ° C. and reacted for 16 hours. After completion of the reaction, the mixture was extracted with water and a toluene solvent and concentrated to obtain 96.8 parts of a crude product. This crude product was separated and purified by silica gel column chromatography to obtain 60.2 parts of the compound represented by the formula (1-42).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 306.0
Exact Mass: +305.0

(Synthesis Example 39)
60 parts of the compound represented by the formula (1-42) and 29.5 parts of methyl 4-chloro-4-oxobutyrate (manufactured by Tokyo Chemical Industry Co., Ltd.) are added to 520 parts of toluene (manufactured by Kanto Chemical Co., Inc.) 23. It was dissolved at ° C., heated to 100 ° C., and reacted for 16 hours. After completion of the reaction, extraction operation was carried out with a water-toluene solvent to obtain 64.2 parts of a crude product after concentration. This crude product was separated and purified by silica gel column chromatography to obtain 55.1 parts of the compound represented by the formula (1-43).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 419.9
Exact Mass: +419.1

(Synthesis Example 40)
55 parts of the compound represented by the formula (1-43) was dissolved in 732 parts of methylene chloride (manufactured by Kanto Chemical Co., Inc.) and cooled to 0 ° C. with stirring. 197 parts of boron tribromide (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise with stirring. The mixture was stirred at 23 ° C. for 3 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and a water-organic solvent extraction operation was performed. 66% of the compound was represented by the following formula (1-44) and 23% was represented by the following formula (1-45). A mixture of 47.3 parts containing the above compounds was obtained.

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 392.1
Exact Mass: +391.0

(Synthesis Example 41)
A solution prepared by dissolving 37.9 parts of thionyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 377 parts of methanol (manufactured by Kanto Chemical Co., Ltd.) is cooled to 0 ° C. and stirred while stirring the above formula (1) of 66%. A mixture of 47.3 parts containing the compound represented by −44) and 23% of the compound represented by the following formula (1-45) was added. The temperature was raised to 23 ° C. and the reaction was carried out 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 the formula (1-45). The obtained crude product was purified by silica gel column chromatography to obtain 40.2 parts of the compound represented by the formula (1-45).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 406.1
Exact Mass: +405.1

(Synthesis Example 42)
40 parts of the compound represented by the formula (1-45) was dissolved in 355 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Inc.) and stirred. After cooling to 0 ° C., 442 parts of a borane 1M tetrahydrofuran solution (manufactured by Kanto Chemical Co., Inc.) was added dropwise. After completion of the dropping, the temperature was raised to 10 ° C. and the mixture was stirred for 3 hours, water was added to obtain an organic layer by extraction, and the solvent was distilled off to obtain 37.3 parts of the compound represented by the formula (1-46). rice field.

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 364.1
Exact Mass: +363.08

(Synthesis Example 43)
32 parts of the compound represented by the formula (1-46) is dissolved in 638 parts of methylene chloride (manufactured by Kanto Chemical Industry Co., Ltd.), cooled to 0 ° C., and imidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) 17 with stirring. .9 parts and 29.1 parts of tert-butyldimethylchlorosilane (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. The temperature was raised to 23 ° C., and the mixture was further stirred for 16 hours for silylation. After completion of the reaction, an extraction operation with water and an organic solvent was carried out to obtain 45.8 parts of a crude product. The crude product thus obtained was separated and purified by column chromatography to obtain 40.9 parts of the compound represented by the formula (1-47).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 592.3
Exact Mass: +591.3

(Synthesis Example 44)
20 parts of the compound represented by the 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., Inc.). 26.2 parts of diisopropylethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.05 parts of tri (ortho-tolyl) phosphine (manufactured by Tokyo Chemical Industry Co., Ltd.), palladium (II) acetate (Tokyo Chemical Industry Co., Ltd.) (Made by Co., Ltd.) 0.758 parts were added and stirred at 23 ° C. for 30 minutes. The temperature was raised to 140 ° C., and the mixture was stirred for 32 hours 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. The reaction was further carried out at 140 ° C. for 2 days. After that, the solvent was distilled off under reduced pressure, water was added, an extraction operation was performed with an organic solvent, and the solvent was distilled off to obtain 17.2 parts of a crude product (hereinafter, may be referred to as a crude product (1-48)). Got This crude product contained 40% of the compound represented by the formula (1-48-1) and 40% of the compound represented by the formula (1-48-2).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 484.5
Exact Mass: +483.3

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 598.3
Exact Mass: +597.4

(Synthesis Example 45)
After dissolving 17.2 parts of the crude product (1-48) in 155.4 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.) and cooling to 0 ° C., tetrabutylammonium fluoride 1M tetrahydrofuran solution (Tokyo Chemical Industry Co., Ltd.) ) Manufactured) 62.6 parts were added dropwise, and after completion of the addition, the mixture was stirred at 23 ° C. for 16 hours. After completion of the reaction, water was added, the tetrahydrofuran solvent was distilled off, and the crude product obtained was subjected to an extraction operation with an organic solvent. After concentration, the crude product of the compound represented by the formula (1-49) was subjected to the extraction operation. I got 72 copies. The crude product thus obtained was separated and purified by column chromatography to obtain 8.1 parts of the compound represented by the formula (1-49).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 370.2
Exact Mass: +369.2

(Synthesis Example 46)
6.87 parts of the compound represented by the formula (1-49) was dissolved in 59.5 parts of methanol (manufactured by Kanto Chemical Industries, Ltd.), and palladium / carbon (Pd 10%) (Fuji) under a normal pressure hydrogen stream. 0.69 parts of Wako Pure Chemical Industries, Ltd. (manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred at 23 ° C. for 16 hours. After completion of the reaction, the reaction mixture was filtered and the solvent was distilled off to obtain 5.49 parts of a crude product. The crude product thus obtained was separated and purified by column chromatography to obtain 4.26 parts of the compound represented by the formula (1-50).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 372.1
Exact Mass: +371.2

(Synthesis Example 47)
4.2 parts of the compound represented by the formula (1-50), 2.85 parts of lithium hydroxide monohydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), methanol (manufactured by Kanto Chemical Industries, Ltd.) 33. 3 parts, 37.3 parts of tetrahydrofuran (manufactured by Kanto Chemical Industries, Ltd.) and 21 parts of water were mixed and stirred at 23 ° C. for 16 hours. After completion of the reaction, the solvent was distilled off, and the obtained crude product was purified by silica gel column chromatography to obtain 3.11 parts of the compound represented by the formula (1-51).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 358.0
Exact Mass: +357.2

(Example 9)
3 parts of the compound represented by the formula (1-51) and 0.48 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Wako Pure Chemical Industries, Ltd.) in toluene (Kanto Kagaku (Kanto Kagaku Co., Ltd.) It was dissolved in 104 parts (manufactured by Kanto Chemical Industries, Ltd.) and 24.3 parts of n-butanol (manufactured by Kanto Chemical Industries, Ltd.) and heated at 120 ° C. for 4 hours with stirring. After completion of the reaction, the solvent was distilled off and the obtained crude product was separated and purified by silica gel column chromatography to obtain 0.70 parts of the compound represented by the formula (II-129).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 793.7
Exact Mass: +792.4

(Synthesis Example 48)
100 parts of 1,3-dimethoxybenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 1330 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 completion of the dropping, the temperature was raised to 23 ° C. and the mixture was stirred for 3 hours. After completion of the reaction, the mixture was extracted with water and a methylene chloride solvent and concentrated to obtain 110 parts of the compound represented by the formula (1-52).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 295.0
Exact Mass: +293.9

(Synthesis Example 49)
Twenty-five parts of the compound represented by the formula (1-52) was dissolved in 111 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.), cooled to −78 ° C., and stirred with n-butyllithium 2.5M hexane solution (Aldrich Co., Ltd.). ) 234.2 parts were added dropwise. After the addition, the mixture was stirred at −78 ° C. for 45 minutes, and 156 parts of iodomethane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise while being cooled to −78 ° C. After charging, the temperature was raised to 23 ° C. and the mixture was stirred for 5 hours. After completion of the reaction, the reaction mixture was gradually poured into 500 parts of ice water. Then, the extraction operation was carried out with a water-toluene solvent to obtain 21 parts of a crude product after concentration. This crude product was separated and purified by silica gel column chromatography to obtain 17 parts of the compound represented by the formula (1-53).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 167.1
Exact Mass: +166.1

(Synthesis Example 50)
13.5 parts of the compound represented by the formula (1-53) was dissolved in 200 parts of methylene chloride (manufactured by Kanto Chemical Co., Inc.) and cooled to 0 ° C. with stirring. 65 parts of bromine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise with stirring. Then, the temperature was raised to 23 ° C. and the mixture was stirred for 16 hours. After completion of 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 the formula (1-54). The obtained crude product was purified by silica gel column chromatography to obtain 15 parts of the compound represented by the formula (1-54).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 323.0
Exact Mass: +321.9

(Synthesis Example 51)
14 parts of the compound represented by the formula (1-54) was dissolved in 124 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.), cooled to −78 ° C., and stirred with a butyllithium 1.6M hexane solution (manufactured by Aldrich Co., Ltd.). ) 22 parts were dropped and added. After charging, the mixture was stirred at −78 ° C. for 1 hour. Then, 50 parts of water was added dropwise while stirring at −78 ° C. Then, the extraction operation was carried out with a water-toluene solvent, and after concentration, 12.5 parts of a crude product containing the compound represented by the formula (1-55) was obtained. This crude product was separated and purified by silica gel column chromatography to obtain 10.4 parts of the compound represented by the formula (1-55).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M ⁺ H] +245.1
Exact Mass: +244.0

(Synthesis Example 52)
10.4 parts of the compound represented by the formula (1-55) was dissolved in 200 parts of methylene chloride (manufactured by Kanto Chemical Co., Inc.) and cooled to 0 ° C. with stirring. While stirring, 64 parts of boron tribromide (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise. The mixture was stirred at 23 ° C. for 3 hours. After completion of 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 the formula (1-56). The obtained crude product was purified by silica gel column chromatography to obtain 8.9 parts of the compound represented by the formula (1-56).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 217.0
Exact Mass: +216.0

(Synthesis Example 53)
8.9 parts of the compound represented by the formula (1-56) is dissolved in 50 parts of dimethylformamide (manufactured by Kanto Chemical Co., Inc.), and potassium carbonate (manufactured by Kanto Chemical Co., Inc.) 28. Three copies were put in. Further, 29.4 parts of (2-bromoethoxy) -tert-butyldimethylsilane (manufactured by Aldrich Co., Ltd.) was added. The temperature of this solution was raised to 70 ° C. and the mixture was stirred for 16 hours. After completion of 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 the formula (1-57). The obtained crude product was purified by silica gel column chromatography to obtain 15.7 parts of the compound represented by the formula (1-57).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 533.2
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 cooled to 0 ° C. with 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 tert-butyldimethylchlorosilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. .. After that, the temperature was raised to 23 ° C. and the mixture was stirred for 16 hours. After completion of the reaction, a water-organic solvent extraction operation was carried out to obtain 48 parts of a crude product containing the compound represented by the formula (1-58). The obtained crude product was purified by silica gel column chromatography to obtain 42 parts of the compound represented by the formula (1-58).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 224.1
Exact Mass: +223.1

(Synthesis Example 55)
12.9 parts of the compound represented by the formula (1-57) and 4.5 parts of the compound represented by the formula (1-58) were dissolved in 312 parts of toluene (manufactured by Kanto Chemical Co., Inc.). 18 parts of water is added to this solution, and while stirring, 3.4 parts of potassium hydroxide (manufactured by Kanto Chemical Co., Ltd.), 0.5 parts of tetrabutylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.), and bis ( Tory-tert-butylphosphine) palladium (0) (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.51 part was added and stirred at 23 ° C. for 30 minutes. Then, the temperature was raised to 105 ° C. and the reaction was carried out for 3 hours. Then, water was added and an extraction operation was carried out with an organic solvent, and the solvent was distilled off to obtain 12.8 parts of a crude product. The obtained crude product was purified by silica gel column chromatography to obtain 10.2 parts of the compound represented by the formula (1-59).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 676.4
Exact Mass: +675.4

(Synthesis Example 56)
10 parts of the compound represented by the formula (1-59) and 2.7 parts of methyl 4-chloro-4-oxobutyrate (manufactured by Tokyo Chemical Industry Co., Ltd.) are added to 87 parts of toluene (manufactured by Kanto Chemical Co., Inc.) 23. It was dissolved at ° C., heated to 105 ° C., and reacted for 16 hours. After completion of the reaction, extraction operation was carried out with a water-toluene solvent to obtain 10.3 parts of a crude product containing the compound represented by the formula (1-60) after concentration.

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 790.4
Exact Mass: +789.5

(Synthesis Example 57)
10 parts of the crude product containing the compound represented by the formula (1-60) was dissolved in 26.6 parts of tetrahydrofuran (manufactured by Kanto Chemical Industry Co., Ltd.), cooled to 0 ° C., and then tetrabutylammonium fluoride 1M tetrahydrofuran solution. 47.4 parts (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, and after completion of the addition, the mixture was stirred at 23 ° C. for 16 hours. After completion of the reaction, water was added, the tetrahydrofuran solvent was distilled off, and the crude product obtained was subjected to an extraction operation with an organic solvent. After concentration, the crude product of the compound represented by the formula (1-61) was 7.87. I got a part. The crude product thus obtained was separated and purified by column chromatography to obtain 4.1 parts of the compound represented by the formula (1-61).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 448.3
Exact Mass: +447.2

(Synthesis Example 58)
4 parts of the compound represented by the formula (1-61) was dissolved in 36 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Inc.) and stirred. The mixture was cooled to 0 ° C., and 39.2 parts of a borane 1M tetrahydrofuran solution (manufactured by Kanto Chemical Co., Inc.) was added dropwise. After completion of the dropping, the temperature was raised to 23 ° C., the mixture was stirred for 5 hours, water was added to obtain an organic layer by extraction, the solvent was distilled off, and the crude product containing the compound represented by the formula (1-62) 3 was added. Obtained .54 copies. The crude product thus obtained was separated and purified by column chromatography to obtain 2.5 parts of the compound represented by the formula (1-62).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 406.2
Exact Mass: +405.2

(Example 10)
2.5 parts of the compound represented by the formula (1-62) and 0.70 part of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Wako Pure Chemical Industries, Ltd.) in toluene (Kanto) It was dissolved in 108.4 parts (manufactured by Chemical Industries, Ltd.) and 40.5 parts of n-butanol (manufactured by Kanto Chemical Industries, Ltd.) and heated at 120 ° C. for 16 hours with stirring. After completion of the reaction, the solvent was distilled off and the obtained crude product was separated and purified by silica gel column chromatography to obtain 1.81 parts of the compound represented by the formula (II-138).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 889.8
Exact Mass: +888.4

(Synthesis Example 59)
2- (1-adamantyl) -4-bromoanisole (manufactured by Tokyo Chemical Industry Co., Ltd.) 10 parts, 3-aminoanisole (manufactured by Tokyo Chemical Industry Co., Ltd.) 4 parts, palladium acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) ) 0.35 parts, 4.5'-bis (diphenylphosphino) -9,9'-dimethylxanthene (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.90 parts, sodium tert-butoxide (Tokyo Chemical Industry Co., Ltd.) 6 parts were dissolved in 180 parts of toluene (manufactured by Kanto Chemical Industry Co., Ltd.), and heated and refluxed at 105 ° C. for 2 hours. After completion of the reaction, water was added to extract the organic layer and concentrated to obtain 25 parts of the compound represented by the formula (1-63).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 364.5
Exact Mass: +363.2

(Synthesis Example 60)
8 parts of the compound represented by the formula (1-63) and 11 parts of succinic acid monoethyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) are dissolved in 160 parts of toluene (manufactured by Kanto Chemical Co., Inc.) and heated to 90 ° C. did. After completion of the reaction, the solvent was concentrated and separated and purified by column chromatography to obtain 8 parts of the compound represented by the formula (1-64).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 492.3
Exact Mass: +491.3

(Synthesis Example 61)
Eight parts of the compound represented by the formula (1-64) are dissolved in 150 parts of methylene chloride (manufactured by Kanto Chemical Industries, Ltd.) and added to 195 parts of boron tribromide (manufactured by Wako Pure Chemical Industries, Ltd.). And stirred. After completion of the reaction, the reaction mixture was poured into 200 parts of water, extracted with an ethyl acetate solvent and concentrated to obtain 12 parts of the compound represented by the formula (1-65).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 464.0
Exact Mass: +463.2

(Synthesis Example 62)
Twelve parts of the compound represented by the formula (1-65) are dissolved in 70 parts of dehydrated tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.), cooled to 0 ° C., and a borane 1M tetrahydrofuran solution (manufactured by Kanto Chemical Co., Ltd.) is stirred. ) 117 copies were put in. The temperature was raised to 23 ° C., the mixture was further stirred for 16 hours, water was added for quenching, the organic solvent was concentrated, and the obtained crude product was separated and purified by column chromatography and represented by the formula (1-66). 2.5 parts of the compound to be obtained was obtained.

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 408.0
Exact Mass: +407.3

(Example 11)
2.5 parts of the compound represented by the formula (1-66) and 0.32 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Wako Pure Chemical Industries, Ltd.) in toluene (Kanto) It was dissolved in 8 parts of Chemical Industries, Ltd. and 10 parts of n-butanol (manufactured by Kanto Chemical Industries, Ltd.) and heated at 110 ° C. for 2 hours with stirring. After completion of the reaction, the solvent was distilled off, and the obtained crude product was purified by silica gel column chromatography to obtain 0.5 part of the compound represented by the formula (II-372).

Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 893.0
Exact Mass: +892.5

(Resin Synthesis Example 1)
An appropriate amount of nitrogen was poured into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace it with a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80 ° C. with stirring. Then 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate and 3,4-epoxytricyclo [5.2.2.10 ^{2, 6} ] A mixed solution of 289 parts of a mixture of decane-9-ylacrylate (mixing ratio: 1: 1) and 125 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a mixed solution prepared by dissolving 33 parts of 2,2-azobis (2,4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropping, the inside of the flask was held at 80 ° C. for 4 hours, and then cooled at room temperature to obtain a copolymer (resin (B-1)) having a B-type viscosity (23 ° C.) of 125 mPa · s and a solid content of 35.1%. ) A solution was obtained. The weight average molecular weight Mw of the produced copolymer was 9200, the dispersity was 2.08, and the solid content acid value was 77 mg-KOH / g. The resin (B-1) has the following structural units.

The polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by the GPC method under the following conditions.
Equipment; HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature; 40 ° C
Solvent; THF
Flow velocity; 1.0 mL / min
Test solution solid content concentration; 0.001 to 0.01% by mass
Injection volume; 50 μL
Detector; RI
Calibration standard; TSK STANDARD POLYSTYRENE
F-40, F-4, F-288, A-2500, A-500
(Made by Tosoh Corporation)
The ratio (Mw / Mn) of the polystyrene-equivalent weight average molecular weight and the number average molecular weight obtained above was defined as the degree of dispersion.

[Examples 12 to 22, Comparative Example 1]
[Preparation of colored resin composition]
Each component was mixed so as to have the composition shown in Table 13 to obtain a colored resin composition.

樹脂（Ｂ－１）：樹脂（Ｂ－１）（固形分換算）
溶剤（Ｅ－１）：プロピレングリコールモノメチルエーテルアセテート
溶剤（Ｅ－２）：ジアセトンアルコール
溶剤（Ｅ－３）：Ｎ－メチルピロリドン
溶剤（Ｅ－４）：クロロホルム
レベリング剤（Ｆ－１）：ポリエーテル変性シリコーンオイル（東レ・ダウコーニング（株）製「トーレシリコーンＳＨ８４００」） In Table 13, each component represents the following compound.
Colorant (A-1): Compound represented by formula (I-147) Colorant (A-2): Compound represented by formula (I-27) Colorant (A-3): Formula (I-) Compound represented by 150) Colorant (A-4): Compound represented by formula (I-171) Colorant (A-5): Compound represented by formula (I-177) Colorant (A-) 6): Compound represented by the formula (I-145) Coloring agent (A-7): Compound represented by the formula (I-87) Coloring agent (A-8): Represented by the formula (II-135) Compound Colorant (A-9): Compound represented by the formula (II-129) Colorant (A-10): Compound represented by the formula (II-138) Colorant (A-11): Formula ( Compound represented by II-372) Colorant (Ax): Compound represented by formula (x)

Resin (B-1): Resin (B-1) (in terms of solid content)
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): Poly Ether-modified silicone oil ("Torre Silicone SH8400" manufactured by Toray Dow Corning Co., Ltd.)

<Preparation of color filter (colored coating film) 1>
A colored resin composition was applied onto a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Inc.) by a spin coating method, and then prebaked at 100 ° C. for 3 minutes to obtain a colored coating film.

<Measurement of chromaticity>
The chromaticity of the colored coating film is determined by the spectroscopy measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation) and the characteristic function of the C light source, and the xy chromaticity in the XYZ color system of CIE. It was obtained as the coordinates (x, y) 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 from the measured values by the method described in JIS Z 8730: 2009 (7. Color difference calculation method), and the results are shown in Table 14. ΔEab * means that the smaller the color, the smaller the color change. Further, if the heat resistance of the colored coating film is good, it can be said that the coloring pattern produced from the same colored resin composition also has good heat resistance.

<Light resistance evaluation>
An ultraviolet cut filter (COLORED OPTICAL GLASS L38; manufactured by Hoya) is placed on the obtained colored coating film, and a light resistance tester (Suntest CPS +: manufactured by Toyo Seiki Co., Ltd.) is placed on the upper surface thereof. ), The xenon lamp light was irradiated for 48 hours.
The chromaticity was measured before and after irradiation, and the color difference ΔEab * was calculated from the measured values by the method described in JIS Z 8730: 2009 (7. Color difference calculation method), and the results are shown in Table 14. ΔEab * means that the smaller the color, the smaller the color change. As shown in Table 14, Examples 12 to 22 had good light resistance as well as heat resistance.

[Examples 23 to 33]
[Preparation of colored resin composition]
Each component was mixed so as to have the composition shown in Table 15 to obtain a colored resin composition.

In Table 15, each component represents the following compound.
Polymerizable compound (C-1): Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization Initiator (D-1): N-Acetyloxy-1- (4-phenylsulfanylphenyl) -3-cyclohexylpropane-1-on-2-imine (PBG-327; oxime compound; Changzhou strong electron new material ( Made by Co., Ltd.)
Other symbols represent the same as above.

<Making a color filter (colored coating film) 2 and heat resistance evaluation>
A colored resin composition was applied onto a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Inc.) by a spin coating method, and then prebaked at 100 ° C. for 3 minutes to form a colored composition layer. After allowing to cool, the colored composition layer formed on the substrate was exposed to light at an exposure amount of 100 mJ / cm ² (based on 365 nm) under an atmospheric atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation). Irradiated. After light irradiation, post-baking was performed at 230 ° C. for 30 minutes in an oven to obtain a colored coating film.
The chromaticity was measured before and after the post-bake, and the color difference ΔEab * was calculated from the measured values by the method described in JIS Z 8730: 2009 (7. Color difference calculation method), and the results are shown in Table 16.

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

Claims (5)

A compound represented by the formula (I).

[In formula (I),
Each of R ¹ to R ⁸ may independently have a hydrogen atom, a halogen atom, a hydroxy group, a saturated hydrocarbon group having 1 to 20 carbon atoms, or a substituent. Represents an alkoxy group having 1 to 20 carbon atoms.
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 is-. It may be replaced with O- ,
The divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms is a methylene group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, or a hexane-1. , 6-Diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonan-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group , Dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, heptadecane-1, 17-diyl group, propenylene group, ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-2,2-diyl group, pentane-2,4- Diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, 2,2-dimethylpropane-1,3-diyl group, pentane-1,4-diyl group, 2-Methylbutane-1,4-diyl group, cyclobutane-1,3-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,5-diyl group, norbornan It is a -1,4-diyl group, a norbornan-2,5-diyl group, an adamantan-1,5-diyl group, or an adamantan-2,6-diyl group.
R ¹¹ and R ¹² each independently represent a hydrocarbon group having 6 to 20 carbon atoms having an aromatic hydrocarbon ring, and the hydrocarbon group may have a substituent, and the hydrocarbon group may have a substituent. The included methylene group may be replaced with —O—.
R ¹³ represents a hydrogen atom or a saturated hydrocarbon group having 1 to 8 carbon atoms. ] A colored resin composition containing a colorant and a resin, wherein the colorant contains the compound according to claim 1. The colored resin composition according to claim 2, further comprising a polymerizable compound and a polymerization initiator. A color filter formed from the colored resin composition according to claim 2 or 3. A display device including the color filter according to claim 4.