JP7101111B2 - Compound - Google Patents

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JP7101111B2
JP7101111B2 JP2018240241A JP2018240241A JP7101111B2 JP 7101111 B2 JP7101111 B2 JP 7101111B2 JP 2018240241 A JP2018240241 A JP 2018240241A JP 2018240241 A JP2018240241 A JP 2018240241A JP 7101111 B2 JP7101111 B2 JP 7101111B2
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JP2019163233A (en
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俊雄 上田
章太 森脇
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Dongwoo Fine Chem Co Ltd
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Priority to KR1020207020600A priority patent/KR20200122300A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/007—Squaraine dyes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

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Description

本発明は化合物に関する。 The present invention relates to compounds.

液晶表示装置、エレクトロルミネッセンス表示装置及びプラズマディスプレイ等の表示装置やＣＣＤやＣＭＯＳセンサなどの固体撮像素子に使用されるカラーフィルタは、着色樹脂組成物から製造される。このような着色樹脂組成物に用いられる着色剤として、式（ｘ）で表される化合物が知られている。

Figure 0007101111000001
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.
Figure 0007101111000001

特開２０１５－８６３８０号公報Japanese Unexamined Patent Publication No. 2015-86380

しかし、従来から知られる上記の化合物を含む着色樹脂組成物から形成されるカラーフィルタは、耐熱性を十分に満足できない場合があった。そこで本発明は、耐熱性に優れたカラーフィルタを形成しうる化合物を提供する。 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.

本発明は、以下の発明を含む。
［１］ 式（Ｉ）で表される化合物。

Figure 0007101111000002

［式（Ｉ）中、
Ｒ1～Ｒ8は、それぞれ独立に、水素原子、ヒドロキシ基、置換基を有していてもよい炭素数１～２０のアルキル基、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～Ｒ12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の炭化水素基を表し、Ｒ9～Ｒ12のうち少なくとも一つは、カルボキシ基を置換基として有する炭素数１～２０の脂肪族炭化水素基であり、かつ、Ｒ9～Ｒ12のうち少なくとも一つは、置換基を有していてもよい炭素数６～２０の芳香族炭化水素基であり、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。］
［２］ 着色剤及び樹脂を含み、着色剤が、［１］に記載の式（Ｉ）で表される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］に記載の着色樹脂組成物。
［４］ ［２］又は［３］に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］に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).
Figure 0007101111000002
[In formula (I),
R 1 to R 8 each independently have a hydrogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and 1 to 20 carbon atoms which may have a substituent. Represents an alkoxy group.
R 9 to R 12 each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and at least one of R 9 to R 12 uses a carboxy group as a substituent. It is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and at least one of R 9 to R 12 is an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. Yes, the methylene group contained in the aliphatic hydrocarbon group may be replaced with —O—. ]
[2] A colored resin composition containing a colorant and a resin, wherein the colorant contains a compound represented by the formula (I) according to [1].
[3] The colored resin composition according to [2], which further comprises 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].

本発明によれば、耐熱性に優れたカラーフィルタを形成可能な新規な化合物が提供される。 INDUSTRIAL APPLICABILITY According to the present invention, a novel compound capable of forming a color filter having excellent heat resistance is provided.

＜化合物＞
本発明に係る化合物は、式（Ｉ）で表される化合物（以下、化合物（Ｉ）ということがある）である。以下、式（Ｉ）を用いて本発明について詳述するが、化合物（Ｉ）には、式（Ｉ）の共鳴構造が含まれ、さらに式（Ｉ）またはその共鳴構造式中の各基を炭素－炭素単結合または炭素－窒素単結合の結合軸周りに回転させて得られる化合物も含まれることとする。 <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) contains a resonance structure of the formula (I), and each group in the formula (I) or its resonance structural formula is further added. Compounds obtained by rotating around the bond axis of a carbon-carbon single bond or a carbon-nitrogen single bond are also included.

Figure 0007101111000003
Figure 0007101111000003

［式（Ｉ）中、
Ｒ1～Ｒ8は、それぞれ独立に、水素原子、ヒドロキシ基、置換基を有していてもよい炭素数１～２０のアルキル基、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～Ｒ12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の炭化水素基を表し、Ｒ9～Ｒ12のうち少なくとも一つは、カルボキシ基を置換基として有する炭素数１～２０の脂肪族炭化水素基であり、かつ、Ｒ9～Ｒ12のうち少なくとも一つは、置換基を有していてもよい炭素数６～２０の芳香族炭化水素基であり、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。］ [In formula (I),
R 1 to R 8 each independently have a hydrogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and 1 to 20 carbon atoms which may have a substituent. Represents an alkoxy group.
R 9 to R 12 each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and at least one of R 9 to R 12 uses a carboxy group as a substituent. It is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and at least one of R 9 to R 12 is an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. Yes, the methylene group contained in the aliphatic hydrocarbon group may be replaced with —O—. ]

Ｒ1～Ｒ8で表される炭素数１～２０のアルキル基は、直鎖状、分岐鎖状及び環状の何れであってもよい。直鎖状又は分岐鎖状のアルキル基としては、具体的には、メチル基、エチル基、プロピル基、イソブチル基、ブチル基、ｔｅｒｔ－ブチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ヘプタデシル基、ウンデシル基等が挙げられる。環状のアルキル基としては、シクロプロピル基、１－メチルシクロプロピル基、シクロペンチル基、シクロヘキシル基、１，２－ジメチルシクロヘキシル基、シクロオクチル基、２，４，６－トリメチルシクロヘキシル基、４－シクロヘキシルシクロヘキシル基等が挙げられる。
Ｒ1～Ｒ8で表される炭素数１～２０のアルキル基の置換基としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；ヒドロキシ基；－ＮＲaＲb(Ｒa及びＲbは、それぞれ独立に、水素原子または炭素数１～２０のアルキル基である)；ニトロ基；メトキシ基、エトキシ基等の炭素数１～１０のアルコキシ基；メトキシカルボニル基、エトキシカルボニル基等の炭素数１～１０のアルコキシカルボニル基；等が挙げられる。 The alkyl 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 alkyl 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 thereof include a decyl group, a heptadecyl group and an undecyl group. The cyclic alkyl 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-cyclohexylcyclohexyl. The group etc. can be mentioned.
As the substituent of the alkyl group having 1 to 20 carbon atoms represented by R 1 to R 8 , a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a hydroxy group; -NR a R b (R a ). And R b are independently hydrogen atoms or alkyl groups having 1 to 20 carbon atoms); nitro group; alkoxy groups having 1 to 10 carbon atoms such as methoxy group and ethoxy group; methoxycarbonyl group and ethoxycarbonyl group. Etc., an alkoxycarbonyl group having 1 to 10 carbon atoms; and the like.

Ｒ1～Ｒ8で表される炭素数１～２０のアルコキシ基としては、上記炭素数１～２０のアルキル基の結合手に－Ｏ－が結合した基が挙げられる。具体的には、メトキシ基、エトキシ基、ｎ－プロポキシ基、イソプロポキシ基、ｎ－ブトキシ基、ｓｅｃ－ブトキシ基、ｔｅｒｔ－ブトキシ基、ペンチルオキシ基、ヘキシルオキシ基、ヘプチルオキシ基、オクチルオキシ基、２－エチルヘキシルオキシ基等が挙げられる。
Ｒ1～Ｒ8で表される炭素数１～２０のアルコキシ基の置換基としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；ヒドロキシ基；－ＮＲcＲd(Ｒc及びＲdは、それぞれ独立に、水素原子または炭素数１～２０のアルキル基である)；ニトロ基；メトキシ基、エトキシ基等の炭素数１～１０のアルコキシ基；メトキシカルボニル基、エトキシカルボニル基等の炭素数１～１０のアルコキシカルボニル基；等が挙げられる。 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 alkyl 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 halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a hydroxy group; -NR c R d (R c) . And R d are independently hydrogen atoms or alkyl groups having 1 to 20 carbon atoms); nitro groups; alkoxy groups having 1 to 10 carbon atoms such as methoxy groups and ethoxy groups; methoxycarbonyl groups and ethoxycarbonyl groups. Etc., an alkoxycarbonyl group having 1 to 10 carbon atoms; and the like.

Ｒ1～Ｒ8のうち、Ｒ1～Ｒ4は特に水素原子であることが好ましい。またＲ5～Ｒ8は、それぞれ独立に、水素原子、ヒドロキシ基、置換基を有していてもよい炭素数１～２０のアルキル基、または置換基を有していてもよい炭素数１～２０のアルコキシ基であることが好ましく、水素原子またはヒドロキシ基であることがより好ましい。 Of R 1 to R 8 , R 1 to R 4 are particularly preferably hydrogen atoms. Further, R 5 to R 8 independently have a hydrogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or 1 to 1 carbon atoms which may have a substituent. It is preferably an alkoxy group of 20, more preferably a hydrogen atom or a hydroxy group.

Ｒ1～Ｒ8（好ましくはＲ5～Ｒ8）のうち２個～４個が、それぞれ独立に、ヒドロキシ基であることが好ましい。 It is preferable that 2 to 4 of R 1 to R 8 (preferably R 5 to R 8 ) are independently hydroxy groups.

Ｒ9～Ｒ12で表される炭素数１～２０の炭化水素基としては、炭素数１～２０の脂肪族炭化水素基または炭素数６～２０の芳香族炭化水素基等が例示される。 Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R 9 to R 12 include an aliphatic hydrocarbon group having 1 to 20 carbon atoms and an aromatic hydrocarbon group having 6 to 20 carbon atoms.

炭素数１～２０の脂肪族炭化水素基は、飽和及び不飽和の何れであってもよく、飽和が好ましい。また炭素数１～２０の脂肪族炭化水素基は、直鎖状、分岐鎖状及び環状の何れであってもよく、直鎖状または分岐鎖状が好ましい。 The aliphatic hydrocarbon group having 1 to 20 carbon atoms may be saturated or unsaturated, and saturation is preferable. The aliphatic hydrocarbon group having 1 to 20 carbon atoms may be linear, branched or cyclic, and is preferably linear or branched.

炭素数１～２０の直鎖状または分岐鎖状の脂肪族炭化水素としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ビニル基、１－プロペニル基、２－プロペニル基（アリル基）等の直鎖状脂肪族炭化水素基；イソプロピル基、イソブチル基、イソペンチル基、ネオペンチル基、２－エチルヘキシル基等の分岐鎖状脂肪族炭化水素基等が挙げられる。該脂肪族炭化水素基の炭素数は、好ましくは１～１５であり、より好ましくは１～１０である。
環状の脂肪族炭化水素基は、単環でも多環でもよい。該環状の脂肪族炭化水素基としては、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基等が挙げられる。該環状の脂肪族炭化水素基の炭素数は、好ましくは３～８であり、より好ましくは３～６である。 Linear or branched aliphatic hydrocarbons having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, vinyl group and 1-. Linear aliphatic hydrocarbon groups such as propenyl group and 2-propenyl group (allyl group); branched chain aliphatic hydrocarbon groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group and 2-ethylhexyl group. Can be mentioned. The aliphatic hydrocarbon group preferably has 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms.
The cyclic aliphatic hydrocarbon group may be monocyclic or polycyclic. Examples of the cyclic aliphatic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like. The cyclic aliphatic hydrocarbon group preferably has 3 to 8 carbon atoms, and more preferably 3 to 6 carbon atoms.

前記炭素数１～２０の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。該脂肪族炭化水素基に含まれるメチレン基が－Ｏ－に置き換わっている基としては、例えば、下記式で表される基が挙げられる。下記式中、＊は結合手を表す。 The methylene group contained in the 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 aliphatic hydrocarbon group is replaced with —O— include a group represented by the following formula. In the following formula, * represents a bond.

Figure 0007101111000004
Figure 0007101111000004

炭素数６～２０の芳香族炭化水素基としては、フェニル基、キシリル基、トリメチルフェニル基、ジプロピルフェニル基、ジ（２，２－ジメチルプロピル）フェニル基、ナフチル基等が挙げられる。前記芳香族炭化水素基の炭素数は、好ましくは６～１６であり、より好ましくは６～１２であり、さらに好ましくは６～９である。 Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a xsilyl group, a trimethylphenyl group, a dipropylphenyl group, a di (2,2-dimethylpropyl) phenyl group, a naphthyl group and the like. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 16, more preferably 6 to 12, and even more preferably 6 to 9.

Ｒ9～Ｒ12で表される炭素数１～２０の炭化水素基は置換基を有していてもよく、該置換基としては、カルボキシ基；フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；メトキシ基、エトキシ基等の炭素数１～１０のアルコキシ基；ヒドロキシ基；スルファモイル基；メトキシカルボニル基、エトキシカルボニル基等の炭素数１～１０のアルコキシカルボニル基；等が挙げられる。 The hydrocarbon group having 1 to 20 carbon atoms represented by R 9 to R 12 may have a substituent, and the substituent includes a carboxy group; a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. Halogen atom; alkoxy group having 1 to 10 carbon atoms such as methoxy group and ethoxy group; hydroxy group; sulfamoyl group; alkoxycarbonyl group having 1 to 10 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group; and the like.

Ｒ9～Ｒ12のうち少なくとも一つは、カルボキシ基を置換基として有する炭素数１～２０の脂肪族炭化水素基である。前記カルボキシ基を置換基として有する炭素数１～２０の脂肪族炭化水素基は、カルボキシ基を、好ましくは１～２個、より好ましくは１個有することが望ましい。また、前記カルボキシ基は、カルボキシ基を置換基として有する炭素数１～２０の脂肪族炭化水素基の少なくとも末端に結合していることが望ましい。このようなカルボキシ基を置換基として有する炭素数１～２０の脂肪族炭化水素基としては、例えば、下記式で表される基が挙げられる。下記式中、＊は結合手を表す。 At least one of R 9 to R 12 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms having a carboxy group as a substituent. The aliphatic hydrocarbon group having 1 to 20 carbon atoms having the carboxy group as a substituent preferably has 1 to 2 carboxy groups, more preferably 1 carboxy group. Further, it is desirable that the carboxy group is bonded to at least the terminal of an aliphatic hydrocarbon group having 1 to 20 carbon atoms having a carboxy group as a substituent. Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms having such a carboxy group as a substituent include a group represented by the following formula. In the following formula, * represents a bond.

Figure 0007101111000005
Figure 0007101111000005

Ｒ9～Ｒ12のうち少なくとも一つは、置換基を有していてもよい炭素数６～２０の芳香族炭化水素基である。該置換基を有していてもよい炭素数６～２０の芳香族炭化水素基としては、好ましくはフェニル基、キシリル基、トリメチルフェニル基、ジプロピルフェニル基、ジ（２，２－ジメチルプロピル）フェニル基または；２，４－ジフルオロフェニル基、２，４－ジクロロフェニル基、２，４－ジブロモフェニル基、２，４－ジヨードフェニル基などの置換基としてハロゲン原子を２つ有するフェニル基であり、より好ましくは２，４－ジメチルフェニル基、２，４，６－トリメチルフェニル基または２，４－ジフルオロフェニル基である。 At least one of R 9 to R 12 is an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. The aromatic hydrocarbon group having 6 to 20 carbon atoms which may have the substituent is preferably a phenyl group, a xsilyl group, a trimethylphenyl group, a dipropylphenyl group or a di (2,2-dimethylpropyl). A phenyl group or a phenyl group having two halogen atoms as a substituent such as a 2,4-difluorophenyl group, a 2,4-dichlorophenyl group, a 2,4-dibromophenyl group and a 2,4-diiodophenyl group. , More preferably a 2,4-dimethylphenyl group, a 2,4,6-trimethylphenyl group or a 2,4-difluorophenyl group.

化合物（Ｉ）において、Ｒ9及びＲ12が、それぞれ独立に、カルボキシ基を置換基として有する炭素数１～２０の脂肪族炭化水素基であり、Ｒ10及びＲ11が、それぞれ独立に、置換基を有していてもよい炭素数６～２０の芳香族炭化水素基であることが望ましい。 In compound (I), R 9 and R 12 are independently substituted aliphatic hydrocarbon groups having 1 to 20 carbon atoms having a carboxy group as a substituent, and R 10 and R 11 are independently substituted, respectively. It is desirable that it is an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a group.

化合物（Ｉ）としては、表１～３に示す、式（Ｉ－１）～式（Ｉ－１８０）で表される化合物等が挙げられる。
化合物（Ｉ）は、
好ましくは式（Ｉ－１）～式（Ｉ－９０）、式（Ｉ－１２１）～式（Ｉ－１８０）で表される化合物であり、
より好ましくは式（Ｉ－１）～式（Ｉ－３０）、式（Ｉ－１２１）～式（Ｉ－１５０）で表される化合物であり、
さらに好ましくは式（Ｉ－１）～式（Ｉ－３）、式（Ｉ－１９）～式（Ｉ－２１）、式（Ｉ－１２７）～式（Ｉ－１２９）で表される化合物である。 Examples of the compound (I) include compounds represented by the formulas (I-1) to (I-180) shown in Tables 1 to 3.
Compound (I) is
It is preferably a compound represented by the formulas (I-1) to (I-90) and the formulas (I-121) to (I-180).
More preferably, it is a compound represented by the formulas (I-1) to (I-30) and the formulas (I-121) to (I-150).
More preferably, it is a compound represented by the formulas (I-1) to (I-3), the formula (I-19) to the formula (I-21), and the formulas (I-127) to the formula (I-129). be.

Figure 0007101111000006
Figure 0007101111000006

Figure 0007101111000007
Figure 0007101111000007

Figure 0007101111000008
Figure 0007101111000008

表１～３中、ｐｈ１～ｐｈ１０は、下記式で表される基を表す（＊は結合手を意味する）。 In Tables 1 to 3, ph1 to ph10 represent groups represented by the following formulas (* means a bond).

Figure 0007101111000009
Figure 0007101111000009

表１～３中、ｃａ１～ｃａ６は、下記式で表される基を表す（＊は結合手を意味する）。 In Tables 1 to 3, ca1 to ca6 represent groups represented by the following formulas (* means a bond).

Figure 0007101111000010
Figure 0007101111000010

式（Ｉ）で表される化合物は、式（ｐｔ１）で表される化合物と、式（ｐｔ２）で表される化合物と、式（ｐｔ３）で表される化合物を、反応させることにより製造できる。本反応において、式（ｐｔ１）で表される化合物及び式（ｐｔ２）で表される化合物の合計使用量は、式（ｐｔ３）で表される化合物１ｍｏｌに対し、１．５～２．５ｍｏｌであることが好ましい。 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.

Figure 0007101111000011
Figure 0007101111000011

［式（ｐｔ１）～式（ｐｔ２）、式（Ｉ）中、Ｒ1～Ｒ12は前記に同じ。］ [In the formulas (pt1) to (pt2) and the formula (I), R1 to R12 are the same as described above. ]

＜着色樹脂組成物＞
本発明の着色樹脂組成物は、着色剤（Ａ）及び樹脂（Ｂ）を含み、着色剤（Ａ）が、式（Ｉ）で表される化合物を含む。
本発明の着色樹脂組成物は、さらに重合性化合物（Ｃ）及び重合開始剤（Ｄ）を含むことが好ましい。
本発明の着色樹脂組成物は、さらに重合開始助剤（Ｄ１）、溶剤（Ｅ）、レベリング剤（Ｆ）を含んでいてもよい。
本明細書において、各成分として例示する化合物は、特に断りのない限り、単独で又は複数種を組合せて使用することができる。 <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.

＜着色剤（Ａ）＞
本発明の着色樹脂組成物は、着色剤（Ａ）として、化合物（Ｉ）を含む。化合物（Ｉ）の含有量は、樹脂（Ｂ）１００質量部に対して、０．１～１５０質量部であることが好ましく、０．５～１００質量部であることがより好ましく、１～８０質量部であることがさらに好ましい。
化合物（Ｉ）の含有率は、着色剤（Ａ）の総量中、５０質量％以上であることが好ましく、８０質量％以上であることがより好ましく、９０質量％以上であることがさらに好ましい。 <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 0.5 to 100 parts by mass, and 1 to 80 parts by mass with respect to 100 parts by mass of the resin (B). It is more preferably by mass.
The content of the compound (I) is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, based on the total amount of the colorant (A).

本発明の着色樹脂組成物は、着色剤（Ａ）として、化合物（Ｉ）の他に、染料（Ａ１）と顔料（Ａ２）とを含んでいてもよい。 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).

染料（Ａ１）は、特に限定されず公知の染料を使用することができ、例えば、溶剤染料、酸性染料、直接染料、媒染染料等が挙げられる。染料としては、例えば、カラーインデックス（Ｔｈｅ Ｓｏｃｉｅｔｙ ｏｆ Ｄｙｅｒｓ ａｎｄ Ｃｏｌｏｕｒｉｓｔｓ出版）でピグメント以外で色相を有するものに分類されている化合物や、染色ノート（色染社）に記載されている公知の染料が挙げられる。また、化学構造によれば、アゾ染料、シアニン染料、トリフェニルメタン染料、キサンテン染料、フタロシアニン染料、アントラキノン染料、ナフトキノン染料、キノンイミン染料、メチン染料、アゾメチン染料、スクアリリウム染料（ただし、化合物（Ｉ）を除く。）、アクリジン染料、スチリル染料、クマリン染料、キノリン染料及びニトロ染料等が挙げられる。これらのうち、有機溶剤可溶性染料が好ましい。 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 the dye include compounds classified as having a hue other than pigment in the Color Index (The Society of Dyers and Colorists Publishing), and known dyes described in Dyeing Note (Color Dyeing Co., Ltd.). 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 preferable.

顔料（Ａ２）としては、特に限定されず公知の顔料を使用することができ、例えば、カラーインデックス（Ｔｈｅ Ｓｏｃｉｅｔｙ ｏｆ Ｄｙｅｒｓ ａｎｄ Ｃｏｌｏｕｒｉｓｔｓ出版）でピグメントに分類されている顔料が挙げられる。
顔料としては、例えば、Ｃ．Ｉ．ピグメントイエロー１、３、１２、１３、１４、１５、１６、１７、２０、２４、３１、５３、８３、８６、９３、９４、１０９、１１０、１１７、１２５、１２８、１３７、１３８、１３９、１４７、１４８、１５０、１５３、１５４、１６６、１７３、１９４、２１４などの黄色顔料；
Ｃ．Ｉ．ピグメントオレンジ１３、３１、３６、３８、４０、４２、４３、５１、５５、５９、６１、６４、６５、７１、７３などのオレンジ色顔料；
Ｃ．Ｉ．ピグメントレッド９、９７、１０５、１２２、１２３、１４４、１４９、１６６、１６８、１７６、１７７、１８０、１９２、２０９、２１５、２１６、２２４、２４２、２５４、２５５、２６４、２６５などの赤色顔料；
Ｃ．Ｉ．ピグメントブルー１５、１５：３、１５：４、１５：６、６０などの青色顔料；Ｃ．Ｉ．ピグメントバイオレット１、１９、２３、２９、３２、３６、３８などのバイオレット色顔料；
Ｃ．Ｉ．ピグメントグリーン７、３６、５８などの緑色顔料；
Ｃ．Ｉ．ピグメントブラウン２３、２５などのブラウン色顔料；
Ｃ．Ｉ．ピグメントブラック１、７などの黒色顔料；等が挙げられる。 As the pigment (A2), a known pigment can be used without particular limitation, and examples thereof include pigments classified as pigments in the Color Index (The Society of Dyers and Colorists Publishing).
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. Black pigments such as Pigment Blacks 1 and 7; and the like.

着色剤（Ａ）の含有率は、着色樹脂組成物の固形分の総量に対しては、好ましくは０．１～７０質量％であり、より好ましくは０．５～６０質量％であり、さらに好ましくは１～５０質量％である。
ここで、本明細書における「固形分の総量」とは、着色樹脂組成物の総量から溶剤の含有量を除いた量のことをいう。固形分の総量及びこれに対する各成分の含有量は、例えば、液体クロマトグラフィー又はガスクロマトグラフィーなどの公知の分析手段で測定することができる。 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.

＜樹脂（Ｂ）＞
樹脂（Ｂ）は、特に限定されないが、アルカリ可溶性樹脂であることが好ましく、不飽和カルボン酸及び不飽和カルボン酸無水物からなる群から選ばれる少なくとも１種（ａ）（以下「（ａ）」という場合がある）に由来する構造単位を有する樹脂がより好ましい。樹脂（Ｂ）は、さらに、炭素数２～４の環状エーテル構造とエチレン性不飽和結合とを有する単量体（ｂ）（以下「（ｂ）」という場合がある）に由来する構造単位、（ａ）と共重合可能な単量体（ｃ）（ただし、（ａ）及び（ｂ）とは異なる。）（以下「（ｃ）」という場合がある）に由来する構造単位、並びに、側鎖にエチレン性不飽和結合を有する構造単位からなる群から選ばれる少なくとも一種の構造単位を有することが好ましい。 <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.

（ａ）としては、具体的には、例えば、アクリル酸、メタクリル酸、無水マレイン酸、イタコン酸無水物、３，４，５，６－テトラヒドロフタル酸無水物、こはく酸モノ〔２－（メタ）アクリロイルオキシエチル〕等が挙げられ、好ましくは、アクリル酸、メタクリル酸、無水マレイン酸である。 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.

（ｂ）は、炭素数２～４の環状エーテル構造（例えば、オキシラン環、オキセタン環及びテトラヒドロフラン環からなる群から選ばれる少なくとも１種）と（メタ）アクリロイルオキシ基とを有する単量体が好ましい。
尚、本明細書において、「（メタ）アクリル酸」とは、アクリル酸及びメタクリル酸よりなる群から選ばれる少なくとも１種を表す。「（メタ）アクリロイル」及び「（メタ）アクリレート」等の表記も、同様の意味を有する。
（ｂ）としては、例えば、グリシジル（メタ）アクリレート、ビニルベンジルグリシジルエーテル、３，４－エポキシトリシクロ［５．２．１．０2,6］デシル（メタ）アクリレート、３－エチル－３－（メタ）アクリロイルオキシメチルオキセタン、テトラヒドロフルフリル（メタ）アクリレート等が挙げられ、好ましくは、グリシジル（メタ）アクリレート、３，４－エポキシトリシクロ［５．２．１．０2,6］デシル（メタ）アクリレート、３－エチル－３－（メタ）アクリロイルオキシメチルオキセタンである。 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 kind 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.

（ｃ）としては、例えば、メチル（メタ）アクリレート、ブチル（メタ）アクリレートシクロヘキシル（メタ）アクリレート、２－メチルシクロヘキシル（メタ）アクリレート、トリシクロ［５．２．１．０2,6］デカン－８－イル（メタ）アクリレート、ベンジル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、Ｎ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミド、Ｎ－ベンジルマレイミド、スチレン、ビニルトルエン等が挙げられ、好ましくは、スチレン、ビニルトルエン、２－ヒドロキシエチル（メタ）アクリレート、Ｎ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミド、Ｎ－ベンジルマレイミド等が好ましい。 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.

側鎖にエチレン性不飽和結合を有する構造単位を有する樹脂は、（ａ）と（ｃ）との共重合体に（ｂ）を付加させるか、（ｂ）と（ｃ）との共重合体に（ａ）を付加させることにより製造することができる。該樹脂は、（ｂ）と（ｃ）との共重合体に（ａ）を付加させさらにカルボン酸無水物を反応させた樹脂であってもよい。 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.

樹脂（Ｂ）のポリスチレン換算の重量平均分子量は、好ましくは３，０００～１００，０００であり、より好ましくは５，０００～５０，０００であり、さらに好ましくは５，０００～３０，０００である。
樹脂（Ｂ）の分散度［重量平均分子量（Ｍｗ）／数平均分子量（Ｍｎ）］は、好ましくは１．１～６であり、より好ましくは１．２～４である。 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.

樹脂（Ｂ）の酸価は、固形分換算で、好ましくは２０～１７０ｍｇ－ＫＯＨ／ｇであり、より好ましくは３０～１５０ｍｇ－ＫＯＨ／ｇ、さらに好ましくは４０～１３５ｍｇ－ＫＯＨ／ｇである。ここで酸価は樹脂（Ｂ）１ｇを中和するために必要な水酸化カリウムの量（ｍｇ）として測定される値であり、例えば水酸化カリウム水溶液を用いて滴定することにより求めることができる。 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. ..

樹脂（Ｂ）の含有率は、着色樹脂組成物の固形分の総量に対しては、好ましくは３０～９９．９質量％であり、より好ましくは５０～９９．５質量％であり、さらに好ましくは７０～９９質量％である。
本発明の着色樹脂組成物が重合性化合物（Ｃ）及び重合開始剤（Ｄ）を含む場合、樹脂（Ｂ）の含有率は、着色樹脂組成物の固形分の総量に対しては、好ましくは７～７０質量％であり、より好ましくは１３～６５質量％であり、さらに好ましくは１７～６０質量％である。 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 relative to the total solid content of the colored resin composition. It is 7 to 70% by mass, more preferably 13 to 65% by mass, and even more preferably 17 to 60% by mass.

＜重合性化合物（Ｃ）＞
重合性化合物（Ｃ）は、重合開始剤（Ｄ）から発生した活性ラジカル及び／又は酸によって重合しうる化合物であり、例えば、重合性のエチレン性不飽和結合を有する化合物等が挙げられ、好ましくは（メタ）アクリル酸エステル化合物である。 <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.

中でも、重合性化合物（Ｃ）は、エチレン性不飽和結合を３つ以上有する重合性化合物であることが好ましい。このような重合性化合物としては、例えば、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等が挙げられる。 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.

重合性化合物（Ｃ）の重量平均分子量は、好ましくは１５０以上２，９００以下、より好ましくは２５０以上１，５００以下である。 The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, and more preferably 250 or more and 1,500 or less.

重合性化合物（Ｃ）を含む場合、重合性化合物（Ｃ）の含有率は、着色樹脂組成物の固形分の総量に対して、７～６５質量％であることが好ましく、より好ましくは１３～６０質量％であり、さらに好ましくは１７～５５質量％である。 When the polymerizable compound (C) is contained, the content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 65% by mass, based on the total solid content of the colored resin composition. It is 60% by mass, more preferably 17 to 55% by mass.

＜重合開始剤（Ｄ）＞
重合開始剤（Ｄ）は、光や熱の作用により活性ラジカル、酸等を発生し、重合を開始しうる化合物であれば特に限定されることなく、公知の重合開始剤を用いることができる。活性ラジカルを発生する重合開始剤としては、例えば、Ｎ－ベンゾイルオキシ－１－（４－フェニルスルファニルフェニル）ブタン－１－オン－２－イミン、Ｎ－ベンゾイルオキシ－１－（４－フェニルスルファニルフェニル）オクタン－１－オン－２－イミン、Ｎ－ベンゾイルオキシ－１－（４－フェニルスルファニルフェニル）－３－シクロペンチルプロパン－１－オン－２－イミン、Ｎ－アセチルオキシ－１－（４－フェニルスルファニルフェニル）－３－シクロヘキシルプロパン－１－オン－２－イミン、２－メチル－２－モルホリノ－１－（４－メチルスルファニルフェニル）プロパン－１－オン、２－ジメチルアミノ－１－（４－モルホリノフェニル）－２－ベンジルブタン－１－オン、１－ヒドロキシシクロヘキシルフェニルケトン、２，４－ビス（トリクロロメチル）－６－ピペロニル－１，３，５－トリアジン、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド、２，２’－ビス（２－クロロフェニル）－４，４’，５，５’－テトラフェニルビイミダゾール等が挙げられる。 <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.

重合開始剤（Ｄ）を含む場合、重合開始剤（Ｄ）の含有量は、樹脂（Ｂ）及び重合性化合物（Ｃ）の合計量１００質量部に対して、好ましくは０．１～３０質量部であり、より好ましくは１～２０質量部である。重合開始剤（Ｄ）の含有量が、前記の範囲内にあると、高感度化して露光時間が短縮される傾向があるためカラーフィルタの生産性が向上する。 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. 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.

＜重合開始助剤（Ｄ１）＞
重合開始助剤（Ｄ１）は、重合開始剤によって重合が開始された重合性化合物の重合を促進するために用いられる化合物、もしくは増感剤である。重合開始助剤（Ｄ１）を含む場合、通常、重合開始剤（Ｄ）と組み合わせて用いられる。
重合開始助剤（Ｄ１）としては、４，４’－ビス（ジメチルアミノ）ベンゾフェノン（通称ミヒラーズケトン）、４，４’－ビス（ジエチルアミノ）ベンゾフェノン、９，１０－ジメトキシアントラセン、２，４－ジエチルチオキサントン、Ｎ－フェニルグリシン等が挙げられる。 <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.

これらの重合開始助剤（Ｄ１）を用いる場合、その含有量は、樹脂（Ｂ）及び重合性化合物（Ｃ）の合計量１００質量部に対して、好ましくは０．１～３０質量部、より好ましくは１～２０質量部である。重合開始助剤（Ｄ１）の量がこの範囲内にあると、さらに高感度で着色パターンを形成することができ、カラーフィルタの生産性が向上する傾向にある。 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.

＜溶剤（Ｅ）＞
溶剤（Ｅ）は、特に限定されず、当該分野で通常使用される溶剤を用いることができる。例えば、エステル溶剤（分子内に－ＣＯＯ－を含み、－Ｏ－を含まない溶剤）、エーテル溶剤（分子内に－Ｏ－を含み、－ＣＯＯ－を含まない溶剤）、エーテルエステル溶剤（分子内に－ＣＯＯ－と－Ｏ－とを含む溶剤）、ケトン溶剤（分子内に－ＣＯ－を含み、－ＣＯＯ－を含まない溶剤）、アルコール溶剤（分子内にＯＨを含み、－Ｏ－、－ＣＯ－及び－ＣＯＯ－を含まない溶剤）、芳香族炭化水素溶剤、アミド溶剤、ジメチルスルホキシド等が挙げられる。 <Solvent (E)>
The solvent (E) is not particularly limited, and a solvent usually used in the art can be used. For example, ester solvent (solvent containing -COO- in the molecule and not containing -O-), ether solvent (solvent containing -O- in the molecule and not containing -COO-), ether ester solvent (solvent in the molecule). 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, dimethylsulfoxide and the like.

溶剤としては、
乳酸エチル、乳酸ブチル、２－ヒドロキシイソブタン酸メチル、酢酸ｎ－ブチル、酪酸エチル、酪酸ブチル、ピルビン酸エチル、アセト酢酸メチル、シクロヘキサノールアセテート及びγ－ブチロラクトン等のエステル溶剤（分子内に－ＣＯＯ－を含み、－Ｏ－を含まない溶剤）；
エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテル、３－メトキシ－１－ブタノール、ジエチレングリコールジメチルエーテル、ジエチレングリコールメチルエチルエーテル等のエーテル溶剤（分子内に－Ｏ－を含み、－ＣＯＯ－を含まない溶剤）；
３－メトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、３－メトキシブチルアセテート、プロピレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート等のエーテルエステル溶剤（分子内に－ＣＯＯ－と－Ｏ－とを含む溶剤）；
４－ヒドロキシ－４－メチル－２－ペンタノン（ジアセトンアルコール）、ヘプタノン、４－メチル－２－ペンタノン、シクロヘキサノン等のケトン溶剤（分子内に－ＣＯ－を含み、－ＣＯＯ－を含まない溶剤）；
ブタノール、シクロヘキサノール、プロピレングリコール等のアルコール溶剤（分子内にＯＨを含み、－Ｏ－、－ＣＯ－及び－ＣＯＯ－を含まない溶剤）；
Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド及びＮ－メチルピロリドン等のアミド溶剤；等が挙げられる。
溶剤としては、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル、４－ヒドロキシ－４－メチル－２－ペンタノン（ジアセトンアルコール）、乳酸エチル及び３－エトキシプロピオン酸エチルがより好ましい。 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; and the like.
As the solvent, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethyl lactate and ethyl 3-ethoxypropionate are more preferable.

溶剤（Ｅ）を含む場合、溶剤（Ｅ）の含有率は、本発明の着色樹脂組成物の総量に対して、好ましくは６０～９５質量％であり、より好ましくは６５～９２質量％である。言い換えると、着色樹脂組成物の固形分の総量は、好ましくは５～４０質量％、より好ましくは８～３５質量％である。溶剤（Ｅ）の含有量が前記の範囲内にあると、塗布時の平坦性が良好になり、またカラーフィルタを形成した際に色濃度が不足しないために表示特性が良好となる傾向がある。 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. ..

＜レベリング剤（Ｆ）＞
レベリング剤（Ｆ）としては、シリコーン系界面活性剤、フッ素系界面活性剤及びフッ素原子を有するシリコーン系界面活性剤等が挙げられる。これらは、側鎖に重合性基を有していてもよい。
シリコーン系界面活性剤としては、分子内にシロキサン結合を有する界面活性剤等が挙げられる。具体的には、トーレシリコーンＤＣ３ＰＡ、同ＳＨ７ＰＡ、同ＤＣ１１ＰＡ、同ＳＨ２１ＰＡ、同ＳＨ２８ＰＡ、同ＳＨ２９ＰＡ、同ＳＨ３０ＰＡ、同ＳＨ８４００（商品名：東レ・ダウコーニング（株）製）、ＫＰ３２１、ＫＰ３２２、ＫＰ３２３、ＫＰ３２４、ＫＰ３２６、ＫＰ３４０、ＫＰ３４１（信越化学工業（株）製）、ＴＳＦ４００、ＴＳＦ４０１、ＴＳＦ４１０、ＴＳＦ４３００、ＴＳＦ４４４０、ＴＳＦ４４４５、ＴＳＦ４４４６、ＴＳＦ４４５２及びＴＳＦ４４６０（モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製）等が挙げられる。 <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. ..

前記のフッ素系界面活性剤としては、分子内にフルオロカーボン鎖を有する界面活性剤等が挙げられる。具体的には、フロラード（登録商標）ＦＣ４３０、同ＦＣ４３１（住友スリーエム（株）製）、メガファック（登録商標）Ｆ１４２Ｄ、同Ｆ１７１、同Ｆ１７２、同Ｆ１７３、同Ｆ１７７、同Ｆ１８３、同Ｆ５５４、同Ｒ３０、同ＲＳ－７１８－Ｋ（ＤＩＣ（株）製）、エフトップ（登録商標）ＥＦ３０１、同ＥＦ３０３、同ＥＦ３５１、同ＥＦ３５２（三菱マテリアル電子化成（株）製）、サーフロン（登録商標）Ｓ３８１、同Ｓ３８２、同ＳＣ１０１、同ＳＣ１０５（旭硝子（株）製）及びＥ５８４４（（株）ダイキンファインケミカル研究所製）等が挙げられる。 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.).

前記のフッ素原子を有するシリコーン系界面活性剤としては、分子内にシロキサン結合及びフルオロカーボン鎖を有する界面活性剤等が挙げられる。具体的には、メガファック（登録商標）Ｒ０８、同ＢＬ２０、同Ｆ４７５、同Ｆ４７７及び同Ｆ４４３（ＤＩＣ（株）製）等が挙げられる。 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).

レベリング剤（Ｆ）を含む場合、レベリング剤（Ｆ）の含有量は、着色樹脂組成物の総量に対して、好ましくは０．００１～０．２質量％であり、より好ましくは０．００２～０．１質量％である。尚、この含有量に、顔料分散剤の含有量は含まれない。レベリング剤（Ｆ）の含有量が前記の範囲内にあると、カラーフィルタの平坦性を良好にすることができる。 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.

＜その他の成分＞
本発明の着色樹脂組成物は、必要に応じて、充填剤、他の高分子化合物、密着促進剤、酸化防止剤、光安定剤、連鎖移動剤等、当該技術分野で公知の添加剤を含んでもよい。 <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.

＜着色樹脂組成物の製造方法＞
本発明の着色樹脂組成物は、着色剤（Ａ）及び樹脂（Ｂ）、並びに必要に応じて用いられる重合性化合物（Ｃ）、重合開始剤（Ｄ）、重合開始助剤（Ｄ１）、溶剤（Ｅ）、レベリング剤（Ｆ）及びその他の成分を混合することにより調製できる。 <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, which are used as necessary. It can be prepared by mixing (E), the leveling agent (F) and other components.

＜カラーフィルタの製造方法＞
本発明の着色樹脂組成物から着色パターンを製造する方法としては、フォトリソグラフ法、インクジェット法、印刷法等が挙げられる。中でも、フォトリソグラフ法が好ましい。 <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. Above all, the photolithography method is preferable.

着色樹脂組成物が、式（Ｉ）で表される化合物を含むことにより、特に耐熱性に優れたカラーフィルタを作製することができる。該カラーフィルタは、表示装置（例えば、液晶表示装置、有機ＥＬ装置、電子ペーパー等）及び固体撮像素子に用いられるカラーフィルタとして有用である。 When the colored resin composition contains the compound represented by the formula (I), a color filter having particularly excellent heat 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, an electronic paper, etc.) and a solid-state image sensor.

以下、実施例によって本発明をより詳細に説明するが、本発明はこれらの実施例によって限定されるものではない。例中、含有量ないし使用量を表す％および部は、特に断らないかぎり質量基準である。
以下において、化合物の構造は質量分析（ＬＣ；Ａｇｉｌｅｎｔ製１２００型、ＭＡＳＳ；Ａｇｉｌｅｎｔ製ＬＣ／ＭＳＤ型）で確認した。 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).

（合成例１）
１－ブロモ－３，５－ジメトキシベンゼン（東京化成工業（株）製）１００部、２，４－ジメチルアニリン（東京化成工業（株）製）５５部、水酸化カリウム（和光純薬工業（株）製）５１部、テトラブチルアンモニウムブロマイド（東京化成工業（株）製）１．５部、ビス（トリｔ－ブチルホスフィン）パラジウム（アルドリッチ（株）製）２．３部、水１００部及びトルエン１０００部（関東化学（株）製）を混合し、９０℃で１時間撹拌しながら加熱した。反応終了後、有機層に水及び酢酸エチルを加えた後で分液し有機層を得た。そして有機層を硫酸マグネシウムで乾燥させ、エバポレーターで溶媒を留去して、式（１－１）で表される化合物を１１３部得た。 (Synthesis Example 1)
1-bromo-3,5-dimethoxybenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) 100 parts, 2,4-dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) 55 parts, potassium hydroxide (Wako Pure Chemical Industry Co., Ltd.) ) 51 parts, tetrabutylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.5 parts, bis (trit-butylphosphine) palladium (manufactured by Aldrich Co., Ltd.) 2.3 parts, water 100 parts and toluene 1000 parts (manufactured by Kanto Chemical Industry Co., Ltd.) were mixed and heated at 90 ° C. for 1 hour with stirring. After completion of the reaction, water and ethyl acetate were added to the organic layer, and then the liquid was separated to obtain an organic layer. Then, the organic layer was dried over magnesium sulfate, and the solvent was distilled off with an evaporator to obtain 113 parts of the compound represented by the formula (1-1).

同定：（質量分析）イオン化モード＝ＥＳＩ＋：ｍ／ｚ＝［Ｍ＋Ｈ］+２５８．２
Ｅｘａｃｔ Ｍａｓｓ：＋２５７．１ Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] + 258.2
Exact Mass: +257.1

Figure 0007101111000012
Figure 0007101111000012

（合成例２）
式（１－１）で表される化合物７０部、４－クロロ－４－オキソ酪酸メチル１０部（東京化成工業（株）製）５３部及びトルエン（関東化学（株）製）７００部を混合し、１００℃で１６時間撹拌しながら加熱した。反応終了後溶媒を留去し、得られた粗生成物にヘキサン（関東化学（株）製）７００部を加えて２時間撹拌して固体をろ別することにより、式（１－２）で表される化合物を９０部得た。 (Synthesis Example 2)
70 parts of the compound represented by the formula (1-1), 10 parts of methyl 4-chloro-4-oxobutyrate (manufactured by Tokyo Chemical Industry Co., Ltd.) 53 parts and 700 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, 700 parts of hexane (manufactured by Kanto Chemical Co., Inc.) was added to the obtained crude product, and the mixture was stirred for 2 hours to separate the solid by the formula (1-2). 90 parts of the represented compound was obtained.

同定：（質量分析）イオン化モード＝ＥＳＩ＋：ｍ／ｚ＝［Ｍ＋Ｈ］+３７２．２
Ｅｘａｃｔ Ｍａｓｓ：＋３７１．１ Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] + 372.2
Exact Mass: +371.1

Figure 0007101111000013
Figure 0007101111000013

（合成例３）
式（１－２）で表される化合物３４部をジクロロメタン３４０部（関東化学（株）製）に溶解して０℃に冷却し、三臭化ホウ素（東京化成工業（株）製）９２部を滴下した。滴下終了後１０℃に昇温して３時間撹拌した後、水を加えて有機層を抽出により取得し、溶媒を留去し粗生成物Ａを８９部得た。粗生成物Ａには、式（１－３）で表される化合物が４４％、式（１－３－１）で表される化合物が５３％含まれていた。 (Synthesis Example 3)
34 parts of the compound represented by the formula (1-2) was dissolved in 340 parts of dichloromethane (manufactured by Kanto Chemical Co., Ltd.) and cooled to 0 ° C., and 92 parts of boron tribromide (manufactured by Tokyo Chemical Industry Co., Ltd.). Was dropped. 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 89 parts of crude product A. The crude product A contained 44% of the compound represented by the formula (1-3) and 53% of the compound represented by the formula (1-3-1).

同定：（質量分析）イオン化モード＝ＥＳＩ＋：ｍ／ｚ＝［Ｍ＋Ｈ］+３４４．２
Ｅｘａｃｔ Ｍａｓｓ：＋３４３．１ 式（１－３）
同定：（質量分析）イオン化モード＝ＥＳＩ＋：ｍ／ｚ＝［Ｍ＋Ｈ］+３３０．２
Ｅｘａｃｔ Ｍａｓｓ：＋３２９．１ 式（１－３－１） Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] + 344.2
Exact Mass: +343.1 Equation (1-3)
Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] + 330.2
Exact Mass: +329.1 equation (1-3-1)

Figure 0007101111000014
Figure 0007101111000014

（合成例４）
粗生成物Ａ８９部をメタノール（関東化学（株）製）３７０部に溶解させ、０℃に冷却後、塩化チオニル（東京化成工業（株）製）５１部を加えた。２３℃で１６時間撹拌し、反応終了後水を加えて溶媒を留去して、得られた粗生成物をシリカゲルカラムクロマトグラフィーで分離精製を行い、式（１－３）で表される化合物を５３部得た。 (Synthesis Example 4)
89 parts of the crude product A was dissolved in 370 parts of methanol (manufactured by Kanto Chemical Co., Inc.), cooled to 0 ° C., and then 51 parts of thionyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. The mixture was stirred at 23 ° C. for 16 hours, water was added after the reaction was completed, the solvent was distilled off, and the obtained crude product was separated and purified by silica gel column chromatography, and the compound represented by the formula (1-3) was separated. Was obtained 53 copies.

同定：（質量分析）イオン化モード＝ＥＳＩ＋：ｍ／ｚ＝［Ｍ＋Ｈ］+３４４．２
Ｅｘａｃｔ Ｍａｓｓ：＋３４３．１ Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] + 344.2
Exact Mass: +343.1

（合成例５）
式（１－３）で表される化合物５３部をテトラヒドロフラン（関東化学（株）製）５３０部に溶解させ０℃に冷却したのち、ボラン１Ｍテトラヒドロフラン溶液（関東化学（株）製）４６０部を滴下し、滴下終了後２０℃で５時間撹拌した。反応終了後水を加え、溶媒を留去して得られた粗生成物をカラムクロマトグラフィーで分離精製を行って式（１－４）で表される化合物を２５部得た。 (Synthesis Example 5)
After dissolving 53 parts of the compound represented by the formula (1-3) in 530 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.) and cooling to 0 ° C., 460 parts of a borane 1M tetrahydrofuran solution (manufactured by Kanto Chemical Co., Ltd.) was added. The mixture was added dropwise, and after completion of the addition, the mixture was stirred at 20 ° C. for 5 hours. After completion of the reaction, water was added, the solvent was distilled off, and the obtained crude product was separated and purified by column chromatography to obtain 25 parts 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］+３３０．３
Ｅｘａｃｔ Ｍａｓｓ：＋３２９．２ Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] + 330.3
Exact Mass: +329.2

Figure 0007101111000015
Figure 0007101111000015

（合成例６）
式（１－４）で表される化合物４部、水酸化リチウム一水和物（和光純薬工業（株）製）２．５部、メタノール（関東化学（株）製）２０部及びテトラヒドロフラン（関東化学（株）製）２０部を混合し、２３℃で５時間撹拌した。反応終了後溶媒を留去し、得られた粗生成物をシリカゲルカラムクロマトグラフィーで精製し、式（１－５）で表される化合物を１．７部得た。 (Synthesis Example 6)
4 parts of the compound represented by the formula (1-4), 2.5 parts of lithium hydroxide monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.), 20 parts of methanol (manufactured by Kanto Chemical Industries, Ltd.) and tetrahydrofuran ( 20 parts (manufactured by Kanto Chemical Industries, Ltd.) were mixed and stirred at 23 ° C. for 5 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 1.7 parts of the compound represented by the formula (1-5).

同定：（質量分析）イオン化モード＝ＥＳＩ＋：ｍ／ｚ＝［Ｍ＋Ｈ］+３１６．１
Ｅｘａｃｔ Ｍａｓｓ：＋３１５．２ Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] + 316.1
Exact Mass: +315.2

Figure 0007101111000016
Figure 0007101111000016

実施例１
式（１－５）で表される化合物１．７部及び３，４－ジヒドロキシ－３－シクロブテン－１，２－ジオン（和光純薬工業（株）製）０．３部をトルエン（関東化学（株）製）６５部、ｎ－ブタノール（関東化学（株）製）１７部に溶解させ、１２０℃で２時間撹拌しながら加熱した。反応終了後、溶媒を留去し得られた粗生成物をシリカゲルカラムクロマトグラフィーで分離精製を行い、式（１－６）で表される化合物を０．８５部得た。 Example 1
1.7 parts of the compound represented by the formula (1-5) and 0.3 part of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Wako Pure Chemical Industries, Ltd.) in toluene (Kanto Chemical Industries, Ltd.) It was dissolved in 65 parts (manufactured by Kanto Chemical Industries, Ltd.) and 17 parts of n-butanol (manufactured by Kanto Chemical Industries, Ltd.) and heated at 120 ° C. for 2 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 0.85 parts of the compound represented by the formula (1-6).

同定：（質量分析）イオン化モード＝ＥＳＩ＋：ｍ／ｚ＝［Ｍ＋Ｈ］+７０９．３
Ｅｘａｃｔ Ｍａｓｓ：＋７０８．３ Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] + 709.3
Exact Mass: +708.3

Figure 0007101111000017
Figure 0007101111000017

（合成例７）
ｍ－ブロモフェノール（東京化成工業（株）製）５０部及びイミダゾール（東京化成工業（株）製）３０部をジクロロメタン（関東化学（株）製）５００部に溶解させ０℃に冷却後、ｔｅｒｔ－ブチルジメチルクロロシラン（東京化成工業（株）製）４８部を滴下した。滴下終了後２３℃へ昇温し１６時間撹拌した。反応終了後水を加えて有機層を抽出し、溶媒を濃縮後シリカゲルカラムクロマトグラフィーで分離精製を行い、式（１－７）で表される化合物を７４部得た。 (Synthesis Example 7)
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 (1-7).

同定：（質量分析）イオン化モード＝ＥＳＩ＋：ｍ／ｚ＝［Ｍ＋Ｈ］+２８７．０
Ｅｘａｃｔ Ｍａｓｓ：＋２８６．０ Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] + 287.0
Exact Mass: +286.0

Figure 0007101111000018
Figure 0007101111000018

（合成例８）
２，４－ジメチルアニリン（東京化成工業（株）製）１５部、式（１－７）で表される化合物３５部、水酸化カリウム（和光純薬工業（株）製）１４部、テトラブチルアンモニウムブロミド（東京化成工業（株）製）２部及びビス（トリ－ｔｅｒｔ－ブチルホスフィン）パラジウム（０）（アルドリッチ（株）製）０．６部をトルエン（関東化学（株）製）２５０部及び水１５部に溶解させ、９０℃に加熱して３０分撹拌した。反応終了後有機層を抽出して濃縮し、シリカゲルカラムクロマトグラフィーで分離精製を行い式（１－８）で表される化合物を１４部得た。 (Synthesis Example 8)
2,4-Dimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) 15 parts, compound represented by formula (1-7) 35 parts, potassium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) 14 parts, tetrabutyl 2 parts of ammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.6 part of bis (tri-tert-butylphosphine) palladium (0) (manufactured by Aldrich Co., Ltd.) 250 parts of toluene (manufactured by Kanto Chemical Co., Ltd.) And 15 parts of water, heated to 90 ° C. and stirred for 30 minutes. After completion of the reaction, the organic layer was extracted and concentrated, and separated and purified by silica gel column chromatography to obtain 14 parts of the compound represented by the formula (1-8).

同定：（質量分析）イオン化モード＝ＥＳＩ＋：ｍ／ｚ＝［Ｍ＋Ｈ］+３２８．３
Ｅｘａｃｔ Ｍａｓｓ：＋３２７．２ Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] + 328.3
Exact Mass: +327.2

Figure 0007101111000019
Figure 0007101111000019

（合成例９）
式（１－８）で表される化合物１４部及び４－クロロ－４－オキソ酪酸メチル１０部（東京化成工業（株）製）をトルエン（関東化学（株）製）２５５部に溶解させ、９０℃に昇温して１時間撹拌した。反応終了後、水を加えて有機層を抽出し、溶媒を濃縮後シリカゲルクロマトグラフィーで分離精製を行い、式（１－９）で表される化合物を１５部得た。 (Synthesis Example 9)
14 parts of the compound represented by the formula (1-8) and 10 parts of methyl 4-chloro-4-oxobutyrate (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 255 parts of toluene (manufactured by Kanto Chemical Industry Co., Ltd.). The temperature was raised to 90 ° C. and the mixture was stirred for 1 hour. 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 chromatography to obtain 15 parts of the compound represented by the formula (1-9).

同定：（質量分析）イオン化モード＝ＥＳＩ＋：ｍ／ｚ＝［Ｍ＋Ｈ］+４４２．３
Ｅｘａｃｔ Ｍａｓｓ：＋４４１．２ Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] + 442.3
Exact Mass: +441.2

Figure 0007101111000020
Figure 0007101111000020

（合成例１０）
式（１－９）で表される化合物１５部をテトラヒドロフラン（関東化学（株）製）１５０部に溶解させ、０℃に冷却後にフッ化テトラ－ｎ－ブチルアンモニウム１Ｍテトラヒドロフラン溶液（東京化成工業（株）製）１５部を滴下した。滴下終了後２３℃に昇温し、２時間撹拌した。反応終了後、溶媒を濃縮し、シリカゲルカラムクロマトグラフィーで分離精製を行い、式（１－１０）で表される化合物を１２部得た。 (Synthesis Example 10)
15 parts of the compound represented by the formula (1-9) is dissolved in 150 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.), cooled to 0 ° C., and then tetra-n-butylammonium fluoride 1M tetrahydrofuran solution (Tokyo Chemical Industry Co., Ltd. (Tokyo Chemical Industry Co., Ltd.) Co., Ltd.) 15 parts were added dropwise. After completion of the dropping, the temperature was raised to 23 ° C., and the mixture was stirred for 2 hours. After completion of the reaction, the solvent was concentrated and separated and purified by silica gel column chromatography to obtain 12 parts of the compound represented by the formula (1-10).

同定：（質量分析）イオン化モード＝ＥＳＩ＋：ｍ／ｚ＝［Ｍ＋Ｈ］+３２８．２
Ｅｘａｃｔ Ｍａｓｓ：＋３２７．２ Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] + 328.2
Exact Mass: +327.2

Figure 0007101111000021
Figure 0007101111000021

（合成例１１）
式（１－１０）で表される化合物１２部をテトラヒドロフラン（関東化学（株）製）２４０部に溶解させ０℃に冷却後、ボラン－１Ｍテトラヒドロフラン溶液（関東化学（株）製）１８０部を滴下した。滴下終了後３０分撹拌し、水を加えたのちテトラヒドロフランを濃縮し、酢酸エチルで有機層を抽出した。溶媒を濃縮後シリカゲルカラムクロマトグラフィーで分離精製を行い、式（１－１１）で表される化合物を６部得た。 (Synthesis Example 11)
After dissolving 12 parts of the compound represented by the formula (1-10) in 240 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.) and cooling to 0 ° C., 180 parts of borane-1M tetrahydrofuran solution (manufactured by Kanto Chemical Co., Ltd.) was added. Dropped. After completion of the dropping, the mixture was stirred for 30 minutes, water was added, tetrahydrofuran was concentrated, and the organic layer was extracted with ethyl acetate. After concentrating the solvent, separation and purification were performed by silica gel column chromatography to obtain 6 parts of the compound represented by the formula (1-11).

同定：（質量分析）イオン化モード＝ＥＳＩ＋：ｍ／ｚ＝［Ｍ＋Ｈ］+３１４．２
Ｅｘａｃｔ Ｍａｓｓ：＋３１３．２ Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] + 314.2
Exact Mass: +313.2

Figure 0007101111000022
Figure 0007101111000022

（合成例１２）
式（１－１１）で表される化合物６部及び水酸化リチウムー水和物（和光純薬工業（株））０．２部をメタノール（関東化学（株）製）２０部、テトラヒドロフラン（関東化学（株）製）２０部、水１０部に溶解させ、２３℃で１時間撹拌した。反応終了後、有機溶媒を濃縮し、酢酸エチルで有機層を抽出し、シリカゲルカラムクロマトグラフィーで分離精製を行って式（１－１２）で表される化合物を４部得た。 (Synthesis Example 12)
6 parts of the compound represented by the formula (1-11) and 0.2 part of lithium hydroxide-hydrate (Wako Pure Chemical Industries, Ltd.), 20 parts of methanol (manufactured by Kanto Chemical Co., Ltd.), tetrahydrofuran (Kanto Chemical Co., Ltd.) It was dissolved in 20 parts and 10 parts of water (manufactured by Co., Ltd.) and stirred at 23 ° C. for 1 hour. After completion of the reaction, the organic solvent was concentrated, the organic layer was extracted with ethyl acetate, and separation and purification were performed by silica gel column chromatography to obtain 4 parts of the compound represented by the formula (1-12).

同定：（質量分析）イオン化モード＝ＥＳＩ＋：ｍ／ｚ＝［Ｍ＋Ｈ］+３００．２
Ｅｘａｃｔ Ｍａｓｓ：＋２９９．２ Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] + 300.2
Exact Mass: +299.2

Figure 0007101111000023
Figure 0007101111000023

実施例２
式（１－１２）で表される化合物４部及び３，４－ジヒドロキシ－３－シクロブテン－１，２－ジオン（和光純薬工業（株）製）０．８部をトルエン（関東化学（株）製）４０部、ｎ－ブタノール（関東化学（株）製）１０部に溶解させ、１４０℃に昇温し、２時間
撹拌した。溶媒を濃縮後、シリカゲルカラムクロマトグラフィーで分離精製を行い、式（１－１３）で表される化合物を１．６部得た。 Example 2
4 parts of the compound represented by the formula (1-12) and 0.8 part of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Wako Pure Chemical Industries, Ltd.) in toluene (Kanto Kagaku Co., Ltd.) )) And 10 parts of n-butanol (manufactured by Kanto Chemical Industries, Ltd.), the temperature was raised to 140 ° C., and the mixture was stirred for 2 hours. After concentrating the solvent, separation and purification were performed by silica gel column chromatography to obtain 1.6 parts of the compound represented by the formula (1-13).

同定：（質量分析）イオン化モード＝ＥＳＩ＋：ｍ／ｚ＝［Ｍ＋Ｈ］+６７７．３
Ｅｘａｃｔ Ｍａｓｓ：＋６７６．３ Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] + 677.3
Exact Mass: +676.3

Figure 0007101111000024
Figure 0007101111000024

（合成例１３）
３－ブロモアニソール（東京化成工業（株）製）１００部を２，４，６－トリメチルアニリン（東京化成工業（株）製）７２部とトルエン（関東化学（株）製）８６８部に溶解させ、この溶液に水酸化カリウム（関東化学（株）製）６０部、水５０部、テトラノルマルブチルアンモニウムブロミド（東京化成工業（株）製）４部、ビス(トリ－ｔ－ブチルホスフィン)パラジウム（０）（東京化成工業（株）製）２．８部を混合した。９０℃に昇温して５時間撹拌した後、水を加えたのち酢酸エチルで有機層を抽出した。溶媒を留去し粗生成物を１０４部得た。得られた粗生成物をカラムクロマトグラフィーで分離精製を行って式（１－１４）で表される化合物を１００部得た。 (Synthesis Example 13)
Dissolve 100 parts of 3-bromoanisole (manufactured by Tokyo Chemical Industry Co., Ltd.) in 72 parts of 2,4,6-trimethylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 868 parts of toluene (manufactured by Kanto Chemical Industry Co., Ltd.). , 60 parts of potassium hydroxide (manufactured by Kanto Chemical Co., Ltd.), 50 parts of water, 4 parts of tetranormal butylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.), bis (tri-t-butylphosphine) palladium ( 0) (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.8 parts were mixed. The temperature was raised to 90 ° C., the mixture was stirred for 5 hours, water was added, and then the organic layer was extracted with ethyl acetate. The solvent was distilled off to obtain 104 parts of a crude product. The obtained crude product was separated and purified by column chromatography to obtain 100 parts of the compound represented by the formula (1-14).

同定：（質量分析）イオン化モード＝ＥＳＩ＋：ｍ／ｚ＝［Ｍ＋Ｈ］+２４２．２
Ｅｘａｃｔ Ｍａｓｓ：＋２４１．２ Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] + 242.2
Exact Mass: +241.2

Figure 0007101111000025
Figure 0007101111000025

（合成例１４）
１，４－ジオキサン－２，６－ジオン（東京化成工業（株）製）１５０部とメタノール（関東化学（株）製）５９５部を混合し、撹拌しながら７０℃まで昇温し２時間反応させた。得られた反応液を濃縮し１５３部の粗生成物を得た。続いて、この粗生成物１５３部を０℃に冷却した塩化チオニル（東京化成工業（株）製）３９４部の中へ撹拌しながら徐々に投入した。室温で１６時間撹拌し、反応終了後濃縮し、式（１－１５）で表される化合物１４４部を得た。この酸塩化物はメタノールと反応させメチルエステル化しジメチル ２，２－オキシジアセテートに変換し同定した。 (Synthesis Example 14)
Mix 150 parts of 1,4-dioxane-2,6-dione (manufactured by Tokyo Chemical Industry Co., Ltd.) and 595 parts of methanol (manufactured by Kanto Chemical Co., Inc.), raise the temperature to 70 ° C. with stirring, and react for 2 hours. I let you. The obtained reaction solution was concentrated to obtain 153 parts of a crude product. Subsequently, 153 parts of this crude product was gradually poured into 394 parts of thionyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) cooled to 0 ° C. with stirring. The mixture was stirred at room temperature for 16 hours, and after completion of the reaction, the mixture was concentrated to obtain 144 parts of the compound represented by the formula (1-15). This acid chloride was identified by reacting with methanol to methyl esterify and convert to dimethyl 2,2-oxydiacetate.

式（１－１５）のメチルエステル体；ジメチル ２，２－オキシジアセテート
同定：（質量分析）イオン化モード＝ＥＳＩ＋：ｍ／ｚ＝［Ｍ＋Ｈ］+１６２．９
Ｅｘａｃｔ Ｍａｓｓ：＋１６２．１ Methyl ester compound of formula (1-15); dimethyl 2,2-oxydiacetate identification: (mass spectrometry) ionization mode = ESI +: m / z = [M + H] + 162.9
Exact Mass: +162.1.

Figure 0007101111000026
Figure 0007101111000026

（合成例１５）
式（１－１４）で表される化合物８４部と式（１－１５）で表される化合物１１６部をトルエン（関東化学（株）製）１０９３部に溶解させ９０℃に昇温し５時間撹拌した。反応終了後水を加え、有機溶媒による抽出操作を施して、濃縮後式（１－１６）で表される化合物の粗生成物８６部得た。こうして得られた粗生成物をカラムクロマトグラフィーで分離精製を行って式（１－１６）で表される化合物を４２部得た。 (Synthesis Example 15)
84 parts of the compound represented by the formula (1-14) and 116 parts of the compound represented by the formula (1-15) were dissolved in 1093 parts of toluene (manufactured by Kanto Chemical Co., Inc.) and heated to 90 ° C. for 5 hours. Stirred. After completion of the reaction, water was added and an extraction operation was carried out with an organic solvent to obtain 86 parts of a crude product of the compound represented by the formula (1-16) after concentration. The crude product thus obtained was separated and purified by column chromatography to obtain 42 parts of the compound represented by the formula (1-16).

同定：（質量分析）イオン化モード＝ＥＳＩ＋：ｍ／ｚ＝［Ｍ＋Ｈ］+３７２．３
Ｅｘａｃｔ Ｍａｓｓ：＋３７１．２ Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] + 372.3
Exact Mass: +371.2

Figure 0007101111000027
Figure 0007101111000027

（合成例１６）
式（１－１６）で表される化合物４０部をテトラヒドロフラン（関東化学（株）製）５３３部に溶解させ０℃に冷却したのち、テトラヒドロフランボラン１Ｍ・テトラヒドロフラン溶液（シグマアルドリッチ（株）製）５８１部を滴下し、滴下終了後室温まで昇温し２時間撹拌した。反応終了後水を加え、テトラヒドロフラン溶媒を留去して得られた粗生成物に有機溶媒による抽出操作を施して、濃縮後式（１－１７）で表される化合物の粗生成物４０部を得た。こうして得られた粗生成物をカラムクロマトグラフィーで分離精製を行って式（１－１７）で表される化合物を３０部得た。 (Synthesis Example 16)
40 parts of the compound represented by the formula (1-16) was dissolved in 533 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.) and cooled to 0 ° C., and then a 1M-tetrahydrofuran solution (manufactured by Sigma Aldrich Co., Ltd.) 581. The part was dropped, and after the dropping was completed, the temperature was raised to room temperature and the mixture was stirred for 2 hours. After completion of the reaction, water was added, and the crude product obtained by distilling off the tetrahydrofuran solvent was subjected to an extraction operation with an organic solvent to obtain 40 parts of the crude product of the compound represented by the formula (1-17) after concentration. Obtained. The crude product thus obtained was separated and purified by column chromatography to obtain 30 parts of the compound represented by the formula (1-17).

同定：（質量分析）イオン化モード＝ＥＳＩ＋：ｍ／ｚ＝［Ｍ＋Ｈ］+３３０．３
Ｅｘａｃｔ Ｍａｓｓ：＋３２９．２０ Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] + 330.3
Exact Mass: +329.20

Figure 0007101111000028
Figure 0007101111000028

（合成例１７）
式（１－１７）で表される化合物２８．６部をトルエン（関東化学（株）製）４８６部に溶解させ、この溶液にテトラブチルアンモニウムブロミド（東京化成工業（株）製）８．４部を滴下し、０℃で５分間撹拌した。さらに０℃で撹拌しながら５０％水酸化ナトリウム水溶液（富士フイルム和光純薬（株）製）を３８０部投入し、さらに３－ブロモプロピオン酸 ｔ－Ｂｕエステル（シグマアルドリッチ（株）製）１４５．２部を投入した。その後、８０℃まで昇温し１６時間撹拌して反応させた。反応終了後水を加え、得られた反応混合物に有機溶媒による抽出操作を施して、濃縮後式（１－１８）で表される化合物の粗生成物２８部得た。こうして得られた粗生成物をカラムクロマトグラフィーで分離精製を行って式（１－１８）で表される化合物を１２部得た。 (Synthesis Example 17)
28.6 parts of the compound represented by the formula (1-17) is dissolved in 486 parts of toluene (manufactured by Kanto Chemical Industry Co., Ltd.), and tetrabutylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) 8.4 is dissolved in this solution. The portion was added dropwise, and the mixture was stirred at 0 ° C. for 5 minutes. Further, 380 parts of a 50% aqueous sodium hydroxide solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added while stirring at 0 ° C., and further, 3-bromopropionic acid t-Bu ester (manufactured by Sigma-Aldrich Co., Ltd.) 145. Two copies were put in. Then, the temperature was raised to 80 ° C., and the mixture was stirred for 16 hours to react. After completion of the reaction, water was added, and the obtained reaction mixture was subjected to an extraction operation with an organic solvent to obtain 28 parts of a crude product of the compound represented by the formula (1-18) after concentration. The crude product thus obtained was separated and purified by column chromatography to obtain 12 parts of the compound represented by the formula (1-18).

同定：式（１－１８）で表される化合物の同定はｔ－Ｂｕエステル体である式（１－１８－１）で表される化合物に変換して行った。
（質量分析）イオン化モード＝ＥＳＩ＋：ｍ／ｚ＝［Ｍ＋Ｈ］+４５８．３
Ｅｘａｃｔ Ｍａｓｓ：＋４５７．２８ Identification: The compound represented by the formula (1-18) was identified by converting it into a compound represented by the formula (1-18-1) which is a t-Bu ester compound.
(Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] + 458.3
Exact Mass: +457.28

Figure 0007101111000029
Figure 0007101111000029

Figure 0007101111000030
Figure 0007101111000030

（合成例１８）
式（１－１８）で表される化合物１０部をＮ－メチルピロリドン（関東化学（株）製）５２部に溶解させた。この溶液にエタンチオール（東京化成工業（株）製）３．１部を滴下し、滴下終了後、１００℃に昇温し、１６時間撹拌した。反応終了後水を加え、粗生成物を含む溶液から有機溶媒による抽出操作を施して、濃縮後式（１－１９）で表される化合物の粗生成物９．４部を得た。こうして得られた粗生成物をカラムクロマトグラフィーで分離精製を行って式（１－１９）で表される化合物７．６部を得た。 (Synthesis Example 18)
10 parts of the compound represented by the formula (1-18) was dissolved in 52 parts of N-methylpyrrolidone (manufactured by Kanto Chemical Co., Inc.). 3.1 parts of ethanethiol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to this solution, and after the addition was completed, the temperature was raised to 100 ° C. and the mixture was stirred for 16 hours. After completion of the reaction, water was added, and the solution containing the crude product was subjected to an extraction operation with an organic solvent to obtain 9.4 parts of the crude product of the compound represented by the formula (1-19) after concentration. The crude product thus obtained was separated and purified by column chromatography to obtain 7.6 parts of the compound represented by the formula (1-19).

同定：（質量分析）イオン化モード＝ＥＳＩ＋：ｍ／ｚ＝［Ｍ＋Ｈ］+３８８．１
Ｅｘａｃｔ Ｍａｓｓ：＋３８７．２ Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] + 388.1
Exact Mass: +387.2

Figure 0007101111000031
Figure 0007101111000031

実施例３
式（１－１９）で表される化合物４．１部及び３，４－ジヒドロキシ－３－シクロブテン－１，２－ジオン（和光純薬工業（株）製）０．６部をトルエン（関東化学（株）製）１４６部、ｓｅｃ－ブタノール（関東化学（株）製）３４部に溶解させ、１２０℃で９時間撹拌しながら加熱した。反応終了後、溶媒を留去し得られた粗生成物をシリカゲルカラムクロマトグラフィーで分離精製を行い、式（１－２０）で表される化合物を１．３部得た。 Example 3
4.1 parts of the compound represented by the formula (1-19) and 0.6 part of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Wako Pure Chemical Industries, Ltd.) in toluene (Kanto Chemical Industries, Ltd.) It was dissolved in 146 parts (manufactured by Kanto Chemical Industries, Ltd.) and 34 parts of sec-butanol (manufactured by Kanto Chemical Industries, Ltd.) and heated at 120 ° C. for 9 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 (1-20).

同定：（質量分析）イオン化モード＝ＥＳＩ＋：ｍ／ｚ＝［Ｍ＋Ｈ］+８５３．９
Ｅｘａｃｔ Ｍａｓｓ：＋８５２．４ Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] + 853.9
Exact Mass: +852.4

Figure 0007101111000032
Figure 0007101111000032

（合成例１９）
２，４－ジフルオロアニリン（東京化成工業（株）製）６６部と式（１－７）で表される化合物１４７部をトルエン（関東化学（株）製）８６８部に溶解させた。この溶液に水６６部を投入し、撹拌しながら、水酸化カリウム（関東化学（株）製）５７部、テトラブチルアンモニウムブロミド（東京化成工業（株）製）８．２部、ビス(トリ－ｔｅｒｔ－ブチルホスフィン)パラジウム（０）（東京化成工業（株）製）２．６１部を加え３０分間室温で撹拌した。その後、９０℃まで昇温し１時間反応させた。その後、水を加え有機溶媒による抽出操作を施し、溶媒を留去し７２部の粗生成物を得た。得られた粗生成物をシリカゲルカラムクロマトグラフィーで精製し、式（１－２１）で表される化合物を６６部得た。 (Synthesis Example 19)
66 parts of 2,4-difluoroaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 147 parts of the compound represented by the formula (1-7) were dissolved in 868 parts of toluene (manufactured by Kanto Chemical Co., Inc.). Add 66 parts of water to this solution, and while stirring, 57 parts of potassium hydroxide (manufactured by Kanto Chemical Co., Ltd.), 8.2 parts of tetrabutylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.), and bis (tri-). tert-Butylphosphine) Palladium (0) (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.61 parts was added, and the mixture was stirred at room temperature for 30 minutes. Then, the temperature was raised to 90 ° C. and the reaction was carried out for 1 hour. Then, water was added and an extraction operation was carried out with an organic solvent, and the solvent was distilled off to obtain 72 parts of a crude product. The obtained crude product was purified by silica gel column chromatography to obtain 66 parts of the compound represented by the formula (1-21).

同定：（質量分析）イオン化モード＝ＥＳＩ＋：ｍ／ｚ＝［Ｍ＋Ｈ］+３３６．２
Ｅｘａｃｔ Ｍａｓｓ：＋３３５．１５ Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] + 336.2
Exact Mass: +335.15

Figure 0007101111000033
Figure 0007101111000033

（合成例２０）
式（１－２１）で表される化合物６６部と４－クロロ－４－オキソ酪酸メチル（東京化成工業（株）製）５９部をトルエン（関東化学（株）製）４００部に室温で溶解させ、９０℃まで昇温し５時間反応させた。反応終了後、水－トルエン溶媒で抽出操作して、濃縮後式（１－２２）で表される化合物を含む６４部の粗生成物を得た。 (Synthesis Example 20)
66 parts of the compound represented by the formula (1-21) and 59 parts of methyl 4-chloro-4-oxobutyrate (manufactured by Tokyo Chemical Industry Co., Ltd.) are dissolved in 400 parts of toluene (manufactured by Kanto Chemical Industry Co., Ltd.) at room temperature. The temperature was raised to 90 ° C. and the reaction was carried out for 5 hours. After completion of the reaction, extraction operation was carried out with a water-toluene solvent to obtain 64 parts of a crude product containing the compound represented by the formula (1-22) after concentration.

同定：（質量分析）イオン化モード＝ＥＳＩ＋：ｍ／ｚ＝［Ｍ＋Ｈ］+３３６．２
Ｅｘａｃｔ Ｍａｓｓ：＋３３５．１５ Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] + 336.2
Exact Mass: +335.15

Figure 0007101111000034
Figure 0007101111000034

（合成例２１）
式（１－２２）で表される化合物６４部をテトラヒドロフラン（関東化学（株）製）８５４部に溶解させ０℃に冷却したのち、テトラブチルアンモニウムフルオリド－１Ｍ・テトラヒドロフラン溶液（東京化成工業（株）製）５８部を滴下し、滴下終了後室温で２時間撹拌させた。反応終了後水を加え、テトラヒドロフラン溶媒を留去して得られた粗生成物に有機溶媒による抽出操作を施して、濃縮後式（１－２３）で表される化合物の粗生成物６２部得た。こうして得られた粗生成物をカラムクロマトグラフィーで分離精製を行って式（１－２３）で表される化合物を５１部得た。 (Synthesis Example 21)
64 parts of the compound represented by the formula (1-22) was dissolved in 854 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.) and cooled to 0 ° C., and then a tetrabutylammonium fluoride-1M-tetrahydrofuran solution (Tokyo Chemical Industry Co., Ltd. (Tokyo Chemical Industry Co., Ltd.) (Manufactured by Co., Ltd.) 58 parts were added dropwise, and after completion of the addition, the mixture was stirred at room temperature for 2 hours. After completion of the reaction, water was added, and the crude product obtained by distilling off the tetrahydrofuran solvent was subjected to an extraction operation with an organic solvent to obtain 62 parts of the crude product of the compound represented by the formula (1-23) after concentration. rice field. The crude product thus obtained was separated and purified by column chromatography to obtain 51 parts of the compound represented by the formula (1-23).

同定：（質量分析）イオン化モード＝ＥＳＩ＋：ｍ／ｚ＝［Ｍ＋Ｈ］+３３６．２
Ｅｘａｃｔ Ｍａｓｓ：＋３３５．１ Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] + 336.2
Exact Mass: +335.1

Figure 0007101111000035
Figure 0007101111000035

（合成例２２）
式（１－２３）で表される化合物５０部をテトラヒドロフラン（関東化学（株）製）８８８部に溶解させ撹拌した。０℃に冷却して、ボラン－テトラヒドロフラン錯体溶液１Ｍ（シグマ－アルドリッチ（株）製）６７０部を滴下した。滴下終了後１５℃まで昇温して１時間撹拌した後、水を加えて有機層を抽出により取得し、溶媒を留去し式（１－２４）で表される化合物を含む粗生成物５０部を得た。こうして得られた粗生成物をカラムクロマトグラフィーで分離精製を行って式（１－２４）で表される化合物を２６部得た。 (Synthesis Example 22)
50 parts of the compound represented by the formula (1-23) was dissolved in 888 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Inc.) and stirred. After cooling to 0 ° C., 670 parts of a borane-tetrahydrofuran complex solution (manufactured by Sigma-Aldrich Co., Ltd.) was added dropwise. After completion of the dropping, the temperature is raised to 15 ° C., the mixture is stirred for 1 hour, water is added to obtain an organic layer by extraction, the solvent is distilled off, and the crude product containing the compound represented by the formula (1-24) 50 is contained. I got a part. The crude product thus obtained was separated and purified by column chromatography to obtain 26 parts of the compound represented by the formula (1-24).

同定：（質量分析）イオン化モード＝ＥＳＩ＋：ｍ／ｚ＝［Ｍ＋Ｈ］+３２２．２
Ｅｘａｃｔ Ｍａｓｓ：＋３２１．１ Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] + 322.2
Exact Mass: +321.1

Figure 0007101111000036
Figure 0007101111000036

（合成例２３）
式（１－２４）で表される化合物２４．６部をテトラヒドロフラン（関東化学（株）製）２１４部、メタノール（関東化学（株）製）１９２部と水１２０部の混合溶媒に溶解させ、さらに水酸化リチウム一水和物（シグマ－アルドリッチ（株）製）１９．３部を投入し撹拌した。室温で２時間撹拌した後、有機溶媒を減圧留去し希塩酸水を加えて有機溶媒を加えて抽出し、抽出溶媒を留去し式（１－２５）で表される化合物を含む粗生成物２４部を得た。こうして得られた粗生成物をカラムクロマトグラフィーで分離精製を行って式（１－２５）で表される化合物を１３．８部得た。 (Synthesis Example 23)
24.6 parts of the compound represented by the formula (1-24) was dissolved in a mixed solvent of 214 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.), 192 parts of methanol (manufactured by Kanto Chemical Co., Ltd.) and 120 parts of water. Further, 19.3 parts of lithium hydroxide monohydrate (manufactured by Sigma-Aldrich Co., Ltd.) was added and stirred. After stirring at room temperature for 2 hours, the organic solvent was distilled off under reduced pressure, dilute hydrochloric acid water was added, the organic solvent was added for extraction, the extraction solvent was distilled off, and the crude product containing the compound represented by the formula (1-25) was contained. Obtained 24 copies. The crude product thus obtained was separated and purified by column chromatography to obtain 13.8 parts of the compound represented by the formula (1-25).

同定：（質量分析）イオン化モード＝ＥＳＩ＋：ｍ／ｚ＝［Ｍ＋Ｈ］+３０８．２
Ｅｘａｃｔ Ｍａｓｓ：＋３０７．１ Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] + 308.2
Exact Mass: +307.1

Figure 0007101111000037
Figure 0007101111000037

実施例４
式（１－２５）で表される化合物７．２部及び３，４－ジヒドロキシ－３－シクロブテン－１，２－ジオン（和光純薬工業（株）製）１．３４部をトルエン（関東化学（株）製）２５２部、ｎ－ブタノール（関東化学（株）製）３０部、ｔ－ブタノール（東京化成工業（株）製）２８部に溶解させ、１１０℃で４時間撹拌しながら加熱した。反応終了後、溶媒を留去し得られた粗生成物をシリカゲルカラムクロマトグラフィーで分離精製を行い、式（１－２６）で表される化合物を１．０４部得た。 Example 4
7.2 parts of the compound represented by the formula (1-25) and 1.34 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Wako Pure Chemical Industries, Ltd.) in toluene (Kanto Kagaku Co., Ltd.) It was dissolved in 252 parts (manufactured by Kanto Chemical Industries, Ltd.), 30 parts of n-butanol (manufactured by Kanto Chemical Industries, Ltd.), and 28 parts of t-butanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and heated at 110 ° 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 1.04 parts of the compound represented by the formula (1-26).

同定：（質量分析）イオン化モード＝ＥＳＩ＋：ｍ／ｚ＝［Ｍ＋Ｈ］+６９２．８
Ｅｘａｃｔ Ｍａｓｓ：＋６９２．２ Identification: (Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] + 692.8
Exact Mass: +692.2

Figure 0007101111000038
Figure 0007101111000038

（樹脂合成例１）
還流冷却器、滴下ロート及び撹拌機を備えたフラスコ内に窒素を適量流し窒素雰囲気に置換し、プロピレングリコールモノメチルエーテルアセテート２８０部を入れ、撹拌しながら８０℃まで加熱した。次いで、アクリル酸３８部、３，４－エポキシトリシクロ［５．２．１．０2,6］デカン－８－イルアクリレート及び３，４－エポキシトリシクロ［５．２．１．０2,6］デカン－９－イルアクリレートの混合物（混合割合は１：１）２８９部、プロピレングリコールモノメチルエーテルアセテート１２５部の混合溶液を５時間かけて滴下した。一方、２，２－アゾビス（２，４－ジメチルバレロニトリル）３３部をプロピレングリコールモノメチルエーテルアセテート２３５部に溶解した混合溶液を６時間かけて滴下した。滴下終了後、フラスコ内を８０℃で４時間保持した後、室温で冷却して、Ｂ型粘度（２３℃）１２５ｍＰａ・ｓ、固形分３５．１％の共重合体（樹脂（Ｂ－１））溶液を得た。生成した共重合体の重量平均分子量Ｍｗは９２００、分散度２．０８、固形分酸価７７ｍｇ－ＫＯＨ／ｇであった。樹脂（Ｂ－１）は下記構造単位を有する。 (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 the 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.

Figure 0007101111000039
Figure 0007101111000039

樹脂のポリスチレン換算の重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）の測定は、ＧＰＣ法により以下の条件で行った。
装置 ；ＨＬＣ－８１２０ＧＰＣ（東ソー（株）製）
カラム ；ＴＳＫ－ＧＥＬＧ２０００ＨＸＬ
カラム温度 ；４０℃
溶媒 ；ＴＨＦ
流速 ；１．０ｍＬ／ｍｉｎ
被検液固形分濃度；０．００１～０．０１質量％
注入量 ；５０μＬ
検出器 ；ＲＩ
校正用標準物質 ；ＴＳＫ ＳＴＡＮＤＡＲＤ ＰＯＬＹＳＴＹＲＥＮＥ
Ｆ－４０、Ｆ－４、Ｆ－２８８、Ａ－２５００、Ａ－５００
（東ソー（株）製）
上記で得られたポリスチレン換算の重量平均分子量及び数平均分子量の比（Ｍｗ／Ｍｎ
）を分散度とした。 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)
Ratio of weight average molecular weight and number average molecular weight in terms of polystyrene obtained above (Mw / Mn)
) Was taken as the degree of dispersion.

［実施例５～７、比較例１］
［着色樹脂組成物の調製］
表４に示す組成となるように各成分を混合して着色樹脂組成物を得た。 [Examples 5 to 7, Comparative Example 1]
[Preparation of colored resin composition]
Each component was mixed so as to have the composition shown in Table 4 to obtain a colored resin composition.

Figure 0007101111000040
Figure 0007101111000040

表４中、各成分は以下の化合物を表す。
着色剤（Ａ－１）：式（１－６）で表される化合物
着色剤（Ａ－２）：式（１－１３）で表される化合物
着色剤（Ａ－３）：式（１－２０）で表される化合物
着色剤（Ａ－ｘ）：式（ｘ）で表される化合物

Figure 0007101111000041

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
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 4, each component represents the following compound.
Colorant (A-1): Compound represented by formula (1-6) Colorant (A-2): Compound represented by formula (1-13) Colorant (A-3): Formula (1- 20) Compound Colorant (AX): Compound represented by formula (x)
Figure 0007101111000041
Resin (B-1): Resin (B-1) (in terms of solid content)
Solvent (E-1): Propylene glycol monomethyl ether acetate Solvent (E-2): Diacetone alcohol Leveling agent (F-1): Polyether-modified silicone oil ("Torre Silicone SH8400" manufactured by Toray Dow Corning Co., Ltd.)

＜カラーフィルタ（着色塗膜）の作製１＞
５ｃｍ角のガラス基板（イーグル２０００；コーニング社製）上に、着色樹脂組成物を、スピンコート法で塗布したのち、１００℃で３分間プリベークして、着色塗膜を得た。 <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.

＜色度の測定＞
着色塗膜の色度は、測色機（ＯＳＰ－ＳＰ－２００；オリンパス（株）製）を用いて測定した分光と、Ｃ光源の特性関数とから、ＣＩＥのＸＹＺ表色系におけるｘｙ色度座標（ｘ、ｙ）と刺激値Ｙとして求めた。 <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 Co., Ltd.) 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.

＜耐熱性評価＞
得られた着色塗膜をオーブン中、２３０℃で２時間加熱した。
加熱前後で色度の測定を行い、該測定値からＪＩＳ Ｚ ８７３０：２００９（７．色差の計算方法）に記載される方法で色差△Ｅａｂ＊を計算し、結果を表５に示した。△Ｅａｂ＊は小さいほど色変化が小さいことを意味する。また、着色塗膜の耐熱性が良好であれば、同じ着色樹脂組成物から作製された着色パターンも、耐熱性は良好であるといえる。 <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 5. 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.

＜耐光性評価＞
得られた着色塗膜の上に紫外線カットフィルター（ＣＯＬＯＲＥＤ ＯＰＴＩＣＡＬ ＧＬＡＳＳ Ｌ３８；ホヤ社製；３８０ｎｍ以下の光をカットする）を配置し、その上面から耐光性試験機（サンテストＣＰＳ＋：東洋精機社製）にて、キセノンランプ光を４８時間照射した。
照射前後で色度の測定を行い、該測定値からＪＩＳ Ｚ ８７３０：２００９（７．色差の計算方法）に記載される方法で色差△Ｅａｂ＊を計算し、結果を表５に示した。△Ｅａｂ＊は小さいほど色変化が小さいことを意味する。なお表５に示すように、実施例５～７は、耐熱性だけでなく耐光性も良好であった。 <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 5. ΔEab * means that the smaller the color, the smaller the color change. As shown in Table 5, Examples 5 to 7 had good light resistance as well as heat resistance.

Figure 0007101111000042
Figure 0007101111000042

［実施例８～１０］
［着色樹脂組成物の調製］
表６に示す組成となるように各成分を混合して着色樹脂組成物を得た。 [Examples 8 to 10]
[Preparation of colored resin composition]
Each component was mixed so as to have the composition shown in Table 6 to obtain a colored resin composition.

Figure 0007101111000043
Figure 0007101111000043

表６中、各成分は以下の化合物を表す。
重合性化合物（Ｃ－１）： ジペンタエリスリトールヘキサアクリレート（カヤラッド（登録商標）ＤＰＨＡ；日本化薬（株）製）
重合開始剤（Ｄ－１）：Ｎ－アセチルオキシ－１－（４－フェニルスルファニルフェニル）－３－シクロヘキシルプロパン－１－オン－２－イミン（ＰＢＧ－３２７；オキシム化合物；常州強力電子新材料（株）製）
その他の符号は、上記と同じものを表す。 In Table 6, 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.

＜カラーフィルタ（着色塗膜）の作製２と耐熱性評価＞
５ｃｍ角のガラス基板（イーグル２０００；コーニング社製）上に、着色樹脂組成物をスピンコート法で塗布したのち、１００℃で３分間プリベークして、着色組成物層を形成した。放冷後、基板上に形成された着色組成物層に、露光機（ＴＭＥ－１５０ＲＳＫ；トプコン（株）製）を用いて、大気雰囲気下、１００ｍＪ／ｃｍ2の露光量（３６５ｎｍ基準）で光照射した。光照射後、オーブン中、２３０℃で３０分間ポストベークを行い、着色塗膜を得た。
ポストベーク前後で色度の測定を行い、該測定値からＪＩＳ Ｚ ８７３０：２００９（７．色差の計算方法）に記載される方法で色差△Ｅａｂ＊を計算し、結果を表７に示した。 <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 7.

Figure 0007101111000044
Figure 0007101111000044

本発明の化合物によれば、耐熱性に優れるカラーフィルタを形成することができる。 According to the compound of the present invention, a color filter having excellent heat resistance can be formed.

Claims (5)

式（Ｉ）で表される化合物。
Figure 0007101111000045
 ［式（Ｉ）中、
Ｒ1～Ｒ 4 は、水素原子を表す。
Ｒ 5 ～Ｒ 8 は、それぞれ独立に、水素原子またはヒドロキシ基を表し、Ｒ 5 ～Ｒ 8 のうち２～４個は、ヒドロキシ基である。
Ｒ9 及びＲ12は、それぞれ独立に、カルボキシ基を置換基として有する炭素数１～２０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。
Ｒ 10 及びＲ 11 は、それぞれ独立に、置換基としてメチル基及びプロピル基から選択される１種以上を有していてもよい炭素数６～２０の芳香族炭化水素基を表す。］ A compound represented by the formula (I).
Figure 0007101111000045
 [In formula (I),
R 1 to R 4 represent hydrogen atoms .
R 5 to R 8 independently represent a hydrogen atom or a hydroxy group, and 2 to 4 of R 5 to R 8 are hydroxy groups.
R 9 and R 12 each independently represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms having a carboxy group as a substituent, and the methylene group contained in the aliphatic hydrocarbon group is replaced with —O—. May be.
R 10 and R 11 each independently represent an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have one or more selected from a methyl group and a propyl group as substituents. ] 着色剤及び樹脂を含み、着色剤が、請求項１に記載の式（Ｉ）で表される化合物を含む着色樹脂組成物。 A colored resin composition containing a colorant and a resin, wherein the colorant contains the compound represented by the formula (I) according to claim 1. さらに、重合性化合物及び重合開始剤を含む請求項２に記載の着色樹脂組成物。 The colored resin composition according to claim 2, further comprising a polymerizable compound and a polymerization initiator. 請求項２又は３に記載の着色樹脂組成物から形成されるカラーフィルタ。 A color filter formed from the colored resin composition according to claim 2 or 3. 請求項４に記載のカラーフィルタを含む表示装置。 A display device including the color filter according to claim 4.
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