TWI664240B - Compound and colored curable resin composition - Google Patents

Compound and colored curable resin composition Download PDF

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TWI664240B
TWI664240B TW104104201A TW104104201A TWI664240B TW I664240 B TWI664240 B TW I664240B TW 104104201 A TW104104201 A TW 104104201A TW 104104201 A TW104104201 A TW 104104201A TW I664240 B TWI664240 B TW I664240B
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芦田徹
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南韓商東友精細化工有限公司
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00Diaryl- or thriarylmethane dyes
    • C09B11/04Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10Amino derivatives of triarylmethanes
    • C09B11/12Amino derivatives of triarylmethanes without any OH group bound to an aryl nucleus
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00Diaryl- or thriarylmethane dyes
    • C09B11/02Diaryl- or thriarylmethane dyes derived from diarylmethanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00Dyes not provided for by a single group of this subclass
    • C09B69/008Dyes containing a substituent, which contains a silicium atom
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00Dyes not provided for by a single group of this subclass
    • C09B69/02Dyestuff salts, e.g. salts of acid dyes with basic dyes
    • C09B69/06Dyestuff salts, e.g. salts of acid dyes with basic dyes of cationic dyes with organic acids or with inorganic complex acids
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/20Filters
    • G02B5/22Absorbing filters
    • G02B5/223Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/13Devices 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
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1335Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509Filters, e.g. light shielding masks
    • G02F1/133514Colour filters

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  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
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Abstract

一種式(A-VI)所示之化合物。 A compound represented by the formula (A-VI).

[式(A-VI)中,R1A至R8A各自獨立地表示氫原子、鹵原子、硝基、羥基,或碳數1至20的烷基(在構成該烷基的碳原子間可插入氧原子)。 [In the formula (A-VI), R 1A to R 8A each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 20 carbon atoms (can be inserted between the carbon atoms constituting the alkyl group) Oxygen atom).

R9A至R12A各自獨立地表示氫原子、可具有取代基之碳數1至20的烷基(在構成該烷基的碳原子間可插入氧原子)或可具有取代基之芳基。但是,R9A至R12A中的至少一者係包含矽原子。 R 9A to R 12A each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbons which may have a substituent (an oxygen atom may be inserted between carbon atoms constituting the alkyl group), or an aryl group which may have a substituent. However, at least one of R 9A to R 12A includes a silicon atom.

Gg-表示相對陰離子。 G g- represents a relative anion.

g表示任意的自然數。 g represents an arbitrary natural number.

D表示可具有取代基之芳基,或可具有取代基之雜芳基。] D represents an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. ]

Description

化合物及著色硬化性樹脂組成物 Compound and colored hardening resin composition

本發明係有關化合物及著色硬化性樹脂組成物。 The present invention relates to a compound and a coloring curable resin composition.

作為彩色濾光片的領域所使用的染料,係在日本特表2010-520508號公報中記載有二(三)-芳基(雜)色素及三-芳基(雜)-碳陽離子顏料。 As a dye used in the field of color filters, Japanese Patent Application Publication No. 2010-520508 describes a di (tri) -aryl (hetero) pigment and a tri-aryl (hetero) -carbocation pigment.

本發明係包括以下的發明。 The present invention includes the following inventions.

[1]一種化合物,係式(A-VI)所示之化合物。 [1] A compound which is a compound represented by the formula (A-VI).

[式(A-VI)中,R1A至R8A各自獨立地表示氫原子、鹵原子、硝基、羥基,或碳數1至20的烷基(在構成該烷基的碳原子間可插入氧 原子)。 [In the formula (A-VI), R 1A to R 8A each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 20 carbon atoms (can be inserted between the carbon atoms constituting the alkyl group) Oxygen atom).

R9A至R12A各自獨立地表示氫原子、可具有取代基之碳數1至20的烷基(在構成該烷基的碳原子間可插入氧原子)或可具有取代基之芳基。但是,R9A至R12A中的至少一者係包含矽原子。 R 9A to R 12A each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbons which may have a substituent (an oxygen atom may be inserted between carbon atoms constituting the alkyl group), or an aryl group which may have a substituent. However, at least one of R 9A to R 12A includes a silicon atom.

Gg-表示相對陰離子。 G g- represents a relative anion.

g表示任意的自然數。 g represents an arbitrary natural number.

D表示可具有取代基之芳基,或可具有取代基之雜芳基。] D represents an aryl group which may have a substituent, or a heteroaryl group which may have a substituent. ]

[2]如[1]所述的化合物,其中,R9A至R12A中的至少一者係式(iia)所示之基。 [2] The compound according to [1], wherein at least one of R 9A to R 12A is a group represented by formula (iia).

*-L 1 -Si(R 144 ) 3 (iia)[式(iia)中,L1表示碳數1至12的烷二基,該烷二基所含的-CH2-可經-O-、-CO-或-NR111-取代。 * -L 1 -Si (R 144) in 3 (iia) [formula (iia), L 1 represents a C alkyl group two 1 to 12, -CH alkanediyl group which contains 2 - may be -O- , -CO- or -NR 111- .

R111表示氫原子或碳數1至20的1價飽和烴基。 R 111 represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.

3個R144各自獨立地表示氫原子、羥基、碳數1至12的烷基或碳數1至12的烷氧基。 The three R 144 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.

*表示與氮原子之鍵結。] * Indicates a bond with a nitrogen atom. ]

[3]如[2]所述的化合物,其中,R9A至R12A中的至少一者係式(ii)所示之基。 [3] The compound according to [2], wherein at least one of R 9A to R 12A is a group represented by formula (ii).

[式(ii)中,n表示1至8的整數,3個R14各自獨立地表示氫原子、羥基、碳數1至4的烷基或碳數1至4的烷氧基,*表示與氮原子之鍵結。] [In formula (ii), n represents an integer of 1 to 8, and three R 14 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and * represents an Bonding of nitrogen atoms. ]

[4]如[1]所述的化合物,其中,式(A-VI)所示之化合物係式(A-II)所示之化合物。 [4] The compound according to [1], wherein the compound represented by the formula (A-VI) is a compound represented by the formula (A-II).

[式(A-II)中,X表示氧原子或硫原子。 [In the formula (A-II), X represents an oxygen atom or a sulfur atom.

R41至R46各自獨立地表示氫原子、可具有取代基之碳數1至20的烷基(在構成該烷基的碳原子間可插入氧原子)或可具有取代基之芳基。但是,R41至R44中的至少一者係式(iia)所示之基。 R 41 to R 46 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbons which may have a substituent (an oxygen atom may be inserted between carbon atoms constituting the alkyl group), or an aryl group which may have a substituent. However, at least one of R 41 to R 44 is a group represented by formula (iia).

*-L 1 -Si(R 144 ) 3 (iia)[式(iia)中,L1表示碳數1至12的烷二基,該烷二基所含的-CH2-可經-O-、-CO-或-NR111-取代。 * -L 1 -Si (R 144) in 3 (iia) [formula (iia), L 1 represents a C alkyl group two 1 to 12, -CH alkanediyl group which contains 2 - may be -O- , -CO- or -NR 111- .

R111表示氫原子或碳數1至20的1價飽和烴基。 R 111 represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.

3個R144各自獨立地表示氫原子,羥基,碳數1至12的烷基或碳數1至12的烷氧基。 The three R 144 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbons or an alkoxy group having 1 to 12 carbons.

*表示與氮原子之鍵結。] * Indicates a bond with a nitrogen atom. ]

R47至R54各自獨立地表示氫原子、鹵原子、硝基、羥基,或碳數1至8的烷基(在構成該烷基的碳原子間可插入氧原子)。 R 47 to R 54 each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms (an oxygen atom may be inserted between the carbon atoms constituting the alkyl group).

R55表示氫原子、碳數1至20的烷基、或可具有取代 基之芳基。 R 55 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group which may have a substituent.

Gg-表示相對陰離子。 G g- represents a relative anion.

g表示任意的自然數。] g represents an arbitrary natural number. ]

[5]如[4]所述的化合物,其中,R41至R44中的至少一者係式(ii)所示之基。 [5] The compound according to [4], wherein at least one of R 41 to R 44 is a group represented by formula (ii).

(式(ii)中,n表示1至8的整數,3個R14各自獨立地表示氫原子、羥基、碳數1至4的烷基或碳數1至4的烷氧基,*表示與氮原子之鍵結。) (In formula (ii), n represents an integer of 1 to 8, three R 14 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and * represents an Bonding of nitrogen atoms.)

[6]一種著色劑,係含有如[1]至[5]中任一項所述之化合物。 [6] A coloring agent containing the compound according to any one of [1] to [5].

[7]如[6]所述的著色劑,其再含有藍色顏料。 [7] The coloring agent according to [6], which further contains a blue pigment.

[8]如[7]所述的著色劑,其中,藍色顏料係C.I.顏料藍15:6。 [8] The coloring agent according to [7], wherein the blue pigment is C.I. Pigment Blue 15: 6.

[9]一種著色硬化性樹脂組成物,係含有[6]至[8]中任一項所述的著色劑、樹脂、聚合性化合物及聚合起始劑。 [9] A coloring curable resin composition containing the coloring agent according to any one of [6] to [8], a resin, a polymerizable compound, and a polymerization initiator.

[10]一種塗膜,係由如[9]所述的著色硬化性樹脂組成物所形成者。 [10] A coating film formed from the colored hardening resin composition according to [9].

[11]一種彩色濾光片,係由如[9]所述的著色硬化性樹脂組成物所形成者。 [11] A color filter formed of the color hardening resin composition according to [9].

[12]一種顯示裝置,係含有如[11]所述的彩色濾光片者。 [12] A display device comprising the color filter according to [11].

本發明的化合物係對有機溶媒的溶解性優異。 The compound system of the present invention is excellent in solubility in an organic solvent.

本發明的化合物係式(A-VI)所示之化合物(以下有時稱為「化合物(A-VI)」。),化合物(A-VI)中,亦包含其互變異構物。 The compound of the present invention is a compound represented by formula (A-VI) (hereinafter sometimes referred to as "compound (A-VI)"), and compound (A-VI) also includes tautomers thereof.

式(A-VI)中,R1A至R8A各自獨立地表示氫原子、鹵原子、硝基、羥基、或碳數1至20的烷基(在構成該烷基的碳原子間可插入氧原子)。 In the formula (A-VI), R 1A to R 8A each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 20 carbon atoms (oxygen may be inserted between the carbon atoms constituting the alkyl group atom).

R9A至R12A各自獨立地表示氫原子、可具有取代基之碳數1至20的烷基(在構成該烷基的碳原子間可插入氧原子)或可具有取代基之芳基。但是,R9A至R12A中的至少一者係包含矽原子。 R 9A to R 12A each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbons which may have a substituent (an oxygen atom may be inserted between carbon atoms constituting the alkyl group), or an aryl group which may have a substituent. However, at least one of R 9A to R 12A includes a silicon atom.

Gg-表示相對陰離子。 G g- represents a relative anion.

g表示任意的自然數。 g represents an arbitrary natural number.

D表示可具有取代基之芳基,或可具有取代基之雜芳基。 D represents an aryl group which may have a substituent, or a heteroaryl group which may have a substituent.

式(A-VI)所示化合物係以式(A-II)所示化合物(以下有時稱為「化合物(A-II)」。)為佳。 The compound represented by the formula (A-VI) is preferably a compound represented by the formula (A-II) (hereinafter sometimes referred to as "compound (A-II)").

化合物(A-II)中亦包含其互變異構物。 The compound (A-II) also includes its tautomer.

式(A-II)中,X表示氧原子或硫原子。 In the formula (A-II), X represents an oxygen atom or a sulfur atom.

R41至R46各自獨立地表示氫原子、可具有取代基之碳數1至20的烷基(在構成該烷基的碳原子間可插入氧原子)或可具有取代基之芳基。但是,R41至R44中的至少一者係式(iia)所示之基。 R 41 to R 46 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbons which may have a substituent (an oxygen atom may be inserted between carbon atoms constituting the alkyl group), or an aryl group which may have a substituent. However, at least one of R 41 to R 44 is a group represented by formula (iia).

*-L 1 -Si(R 144 ) 3 (iia)[式(iia)中,L1表示碳數1至12的烷二基,該烷二基所含的-CH2-可經-O-、-CO-或-NR111-取代。 * -L 1 -Si (R 144) in 3 (iia) [formula (iia), L 1 represents a C alkyl group two 1 to 12, -CH alkanediyl group which contains 2 - may be -O- , -CO- or -NR 111- .

R111表示氫原子或碳數1至20的1價飽和烴基。 R 111 represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.

3個R144各自獨立地表示氫原子、羥基、碳數1至12的烷基或碳數1至12的烷氧基。 The three R 144 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.

*表示與氮原子之鍵結。] * Indicates a bond with a nitrogen atom. ]

R55表示氫原子、碳數1至20的烷基,或可具有取代基之芳基。 R 55 represents a hydrogen atom, an alkyl group having 1 to 20 carbons, or an aryl group which may have a substituent.

Gg-表示相對陰離子。 G g- represents a relative anion.

g表示任意的自然數。 g represents an arbitrary natural number.

式(A-VI)及式(A-II)中,R1A至R12A,R41至R46及R55所示之碳數1至20的烷基可為鏈狀、支鏈狀及環狀之任一者,作為該烷基的具體例,可列舉如:下述式所示之基。其中,該烷基係以碳數1至8的烷基為佳,碳數1至6的烷基更佳,碳數1至4的烷基又更佳。 In the formula (A-VI) and the formula (A-II), the alkyl group having 1 to 20 carbon atoms represented by R 1A to R 12A , R 41 to R 46, and R 55 may be a chain, branched chain, or ring As a specific example of any one of these states, a group represented by the following formula is mentioned. Among them, the alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable.

(*表示與碳原子或與氮原子之鍵結。) (* Indicates a bond with a carbon atom or a nitrogen atom.)

在構成該烷基的碳原子之間插入有氧原子的基係可列舉下述式所示之基。其中,以構成碳數1至10的烷基的碳原子之間插入有氧原子的基為佳,以構成碳數1至6的烷基的碳原子之間插入有氧原子的基更佳。 Examples of the group in which an oxygen atom is inserted between the carbon atoms constituting the alkyl group include a group represented by the following formula. Among them, a group having an oxygen atom inserted between carbon atoms constituting an alkyl group having 1 to 10 carbon atoms is more preferable, and a group having an oxygen atom inserted between carbon atoms constituting an alkyl group having 1 to 6 carbon atoms is more preferable.

(*表示與碳原子或與氮原子之鍵結。) (* Indicates a bond with a carbon atom or a nitrogen atom.)

R9A至R12A及R41至R46所示之烷基具有的取代基係可列舉如:含有矽原子之基、胺基、烷胺基及鹵原子等。 Examples of the substituents of the alkyl group represented by R 9A to R 12A and R 41 to R 46 include a group containing a silicon atom, an amino group, an alkylamino group, and a halogen atom.

含有矽原子之基係可列舉如:三甲基矽氧基、三乙基矽氧基等的矽氧基;三甲氧基矽基、三乙氧基矽基等的三(烷氧基)矽基等。作為含有矽原子之基的具體例係可列舉式(iia)所示之基。 Examples of the silicon atom-containing radicals include: trimethylsilyl, triethylsilyl, and the like; trimethoxysilyl, triethoxysilyl, and other tri (alkoxy) silyl Base etc. Specific examples of the group containing a silicon atom include a group represented by formula (iia).

烷胺基係可列舉如:具有碳數1至12的烷基的烷胺基。 Examples of the alkylamino group include alkylamino groups having an alkyl group having 1 to 12 carbon atoms.

鹵原子係可列舉如:氟原子、氯原子、溴原子及碘。 Examples of the halogen atom system include a fluorine atom, a chlorine atom, a bromine atom, and iodine.

具有該等取代基的碳數1至20的烷基之例可列舉下述式所示之基。下述式中,*表示與氮原子之鍵結。 Examples of the alkyl group having 1 to 20 carbon atoms having such a substituent include a group represented by the following formula. In the following formula, * represents a bond with a nitrogen atom.

R9A至R12A,R41至R46及R55所示之芳基中,取代基係可列舉如:氟原子、氯原子、溴原子、碘等鹵原子;氯甲基、三氟甲基等碳數1至6的鹵烷基;甲氧基、乙氧基等碳數1至6的烷氧基;羥基;胺磺醯基;甲磺醯基等碳數1至6的烷磺醯基等。 Among the aryl groups represented by R 9A to R 12A , R 41 to R 46 and R 55 , examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine; chloromethyl, trifluoromethyl Haloalkyl groups having 1 to 6 carbon atoms; alkoxy groups having 1 to 6 carbon atoms such as methoxy and ethoxy groups; hydroxyl groups; sulfamoyl groups; Base etc.

該芳基係可列舉如:苯基、萘基等碳數6至10的芳基。 Examples of the aryl system include aryl groups having 6 to 10 carbon atoms such as phenyl and naphthyl.

可具有取代基之芳基的具體例係可列舉下述式所示之基。 Specific examples of the aryl group which may have a substituent include a group represented by the following formula.

(式中,*表示與氮原子之鍵結。) (In the formula, * represents a bond with a nitrogen atom.)

R1A至R8A及R47至R54由合成的容易度之點,係以各自獨立地為氫原子、鹵原子,或碳數1至8的烷基為佳,以各自獨立地為氫原子、甲基、氟原子或氯原子更佳。 In terms of ease of synthesis, R 1A to R 8A and R 47 to R 54 are each preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms, and each independently a hydrogen atom. A methyl, fluorine, or chlorine atom is more preferred.

R9A、R10A、R11A及R12A中的至少一者係包含矽原子。「含有矽原子」係指在R9A、R10A、R11A及R12A表示的烷基或芳基所有的取代基中含有矽原子之意。也就是說,R9A、R10A、R11A及R12A中的至少一者係具有取代基之 烷基或具有取代基之芳基,而在該烷基及芳基中的取代基含有矽原子。 At least one of R 9A , R 10A , R 11A and R 12A includes a silicon atom. "Containing a silicon atom" means that a silicon atom is included in all the substituents of the alkyl group or aryl group represented by R 9A , R 10A , R 11A and R 12A . That is, at least one of R 9A , R 10A , R 11A and R 12A is an alkyl group having a substituent or an aryl group having a substituent, and the substituent in the alkyl group and the aryl group contains a silicon atom .

R9A、R10A、R11A及R12A中的至少一者係以具有包含矽原子之基作為取代基的基為佳。 At least one of R 9A , R 10A , R 11A and R 12A is preferably a group having a group containing a silicon atom as a substituent.

R9A至R12A中的至少一者係以式(iia)所示之基為佳,R9A至R12A中的至少一者係以式(ii)所示之基更佳。 R 9A to R 12A are system to at least one of formula (IIa) as shown in the preferred group, R 9A to R 12A in at least one line in formula (ii) the group shown better.

*-L 1 -Si(R 144 ) 3 (iia)[式中,L1表示碳數1至12的烷二基,該烷二基所含的-CH2-可經-O-、-CO-或-NR111-取代。 * -L 1 -Si (R 144 ) 3 (iia) [wherein L 1 represents an alkanediyl group having 1 to 12 carbon atoms, and -CH 2 -which is contained in the alkanediyl group may be passed through -O-, -CO -Or -NR 111 -substituted.

R111表示氫原子或碳數1至20的1價飽和烴基。 R 111 represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.

3個R144各自獨立地表示氫原子、羥基、碳數1至12的烷基或碳數1至12的烷氧基。 The three R 144 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.

*表示與氮原子之鍵結。] * Indicates a bond with a nitrogen atom. ]

式(ii)中,n表示1至8的整數,3個R14各自獨立地表示氫原子、羥基、碳數1至4的烷基或碳數1至4的烷氧基,*表示與氮原子之鍵結。 In formula (ii), n represents an integer of 1 to 8, and three R 14 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and * represents a nitrogen atom. Atomic bond.

R9A至R12A中之2者係以式(iia)所示之基為佳,由R9A及R10A所選出的1個,及由R11A及R12A所選出的1個係以式(iia)所示之基更佳。 Two of R 9A to R 12A are preferably based on the formula (iia), one selected by R 9A and R 10A , and one selected by R 11A and R 12A are expressed by the formula ( The base shown by iia) is better.

R9A及R12A係以各自獨立地為式(iia)所示之基為佳,各自獨立地為式(ii)所示之基更佳。 R 9A and R 12A are each preferably a group represented by the formula (iia), and more preferably each independently represented by the formula (ii).

L1所示之烷二基係可列舉如:亞甲基、伸乙基、丙烷-1,3-二基、丁烷-1,4-二基、戊烷-1,5-二基、己烷-1,6-二基、庚烷-1,7-二基、辛烷-1,8-二基、壬烷-1,9-二基、癸烷-1,10-二基、十一烷-1,11-二基、十二烷-1,12-二基、十三烷-1,13-二基、十四烷-1,14-二基、十五烷-1,15-二基、十六烷-1,16-二基及十七烷-1,17-二基、乙烷-1,1-二基、丙烷-1,1-二基、丙烷-1,2-二基、丙烷-2,2-二基、戊烷-2,4-二基、2-甲基丙烷-1,3-二基、2-甲基丙烷-1,2-二基、戊烷-1,4-二基、2-甲基丁烷-1,4-二基、環丁烷-1,3-二基、環戊烷-1,3-二基、環己烷-1,4-二基、環辛烷-1,5-二基等的環烷二基、降莰烷-1,4-二基、降莰烷-2,5-二基、金剛烷-1,5-二基、金剛烷-2,6-二基等。 Examples of the alkanediyl system represented by L 1 include methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, Hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, Undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl, pentadecane-1, 15-diyl, hexadecane-1,16-diyl and heptadecane-1,17-diyl, ethane-1,1-diyl, propane-1,1-diyl, propane-1, 2-diyl, propane-2,2-diyl, pentane-2,4-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, Pentane-1,4-diyl, 2-methylbutane-1,4-diyl, cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane- 1,4-Diyl, cyclooctane-1,5-diyl and other cycloalkanediyl, norbornane-1,4-diyl, norbornane-2,5-diyl, adamantane-1 , 5-diyl, adamantane-2,6-diyl, etc.

L1係以碳數1至8的烷二基為佳。 L 1 is preferably an alkyldiyl group having 1 to 8 carbon atoms.

R111所示之飽和烴基係可列舉如:甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十二烷基、十六烷基、二十烷基、異丙基、異丁基、二級丁基、三級丁基、異戊基、新戊基及2-乙基己基、環丙基、環戊基、環己基、環庚基、環辛基及三環癸基等。 Examples of the saturated hydrocarbon group represented by R 111 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and hexadecyl , Eicosyl, isopropyl, isobutyl, secondary butyl, tertiary butyl, isopentyl, neopentyl and 2-ethylhexyl, cyclopropyl, cyclopentyl, cyclohexyl, cyclo Heptyl, cyclooctyl and tricyclodecyl.

R144所示之烷基係可列舉如:甲基、乙基、丙基、異丙基、丁基、異丁基、二級丁基、三級丁基、正戊基、異戊基、新戊基、正己基、2-乙基己基、正庚基、正辛基、正壬基、正癸基、正十二烷基、正十六烷基,以碳數1至4的烷基為佳。 Examples of the alkyl system represented by R 144 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, isopentyl, Neopentyl, n-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-hexadecyl, alkyl having 1 to 4 carbon atoms Better.

R144所示之烷氧基係可列舉如:甲氧基、乙 氧基、正丙氧基、異丙氧基、正丁氧基、二級丁氧基、三級丁氧基、正戊氧基、正己氧基、正庚氧基、正辛氧基、2-乙基己氧基、正壬氧基、正癸氧基、正十一烷氧基及正十二烷氧基,以碳數1至4的烷氧基為佳。 Examples of the alkoxy system represented by R 144 include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, secondary butoxy, tertiary butoxy, and n-pentyl. Oxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 2-ethylhexyloxy, n-nonoxy, n-decoxy, n-undecyloxy and n-dodecyloxy Alkoxy having 1 to 4 carbon atoms is preferred.

式(ii)中,R14所示之烷基係可列舉如:甲基、乙基、丙基及丁基。 Examples of the alkyl system represented by R 14 in formula (ii) include methyl, ethyl, propyl, and butyl.

R14所示之烷氧基係可列舉如:甲氧基、乙氧基、丙氧基及丁氧基。 Examples of the alkoxy system represented by R 14 include methoxy, ethoxy, propoxy, and butoxy.

R14係以氫原子、甲基、乙基、丙基、甲氧基、乙氧基或丙氧基為佳,以氫原子、甲基、乙基、甲氧基或乙氧基更佳,以甲氧基或乙氧基又更佳。 R 14 is preferably a hydrogen atom, methyl, ethyl, propyl, methoxy, ethoxy or propoxy, more preferably a hydrogen atom, methyl, ethyl, methoxy or ethoxy, Methoxy or ethoxy is more preferred.

3個R14係以相同者為佳。 The three R 14 series are preferably the same.

n係以1至6的整數為佳,以1至4的整數更佳。 n is preferably an integer of 1 to 6, and more preferably an integer of 1 to 4.

R41至R44中的至少一者係以式(iia)所示之基為佳,以式(ii)所示之基更佳。R41及R44以各自獨立地為式(iia)所示之基為佳,以各自獨立地為式(ii)所示之基更佳。 At least one of R 41 to R 44 is preferably a base represented by formula (iia), and more preferably a base represented by formula (ii). R 41 and R 44 are preferably each independently a base represented by formula (iia), and more preferably each independently a base represented by formula (ii).

式(iia)所示之基係可列舉下述所示之基。其中,以式(ii-1)至式(ii-6)所示之基為佳。 Examples of the group represented by the formula (iia) include the groups shown below. Among them, the bases represented by the formulae (ii-1) to (ii-6) are preferred.

(各化學式中,*表示與氮原子或與碳原子之鍵結。) (In each chemical formula, * represents a bond with a nitrogen atom or a carbon atom.)

R9A至R12A及R41至R44不為式(iia)所示之基時,以各自獨立地為氫原子、碳數1至20之烷基或可具有取代基之芳基為佳,以各自獨立地為氫原子、碳數1至8的烷基,或具有鹵原子、碳數1至4的氟甲基、碳數1至4的烷氧基或碳數1至4的烷基作為取代基的芳基(例如,下述式所示之芳基)更佳。 When R 9A to R 12A and R 41 to R 44 are not a group represented by formula (iia), an alkyl group having 1 to 20 carbon atoms or an aryl group which may have a substituent, which is each independently a hydrogen atom, is preferred. Each is independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a halogen atom, a fluoromethyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms An aryl group (for example, an aryl group represented by the following formula) as a substituent is more preferred.

(各式中,*表示與氮原子之鍵結。) (In each formula, * represents a bond with a nitrogen atom.)

R47至R54所示之烷基(在構成該烷基的碳原子之間可插入氧原子)之例可列舉下述式所示之基。 Examples of the alkyl group represented by R 47 to R 54 (an oxygen atom may be inserted between the carbon atoms constituting the alkyl group) include a group represented by the following formula.

(各式中,*表示與碳原子之鍵結。) (In each formula, * represents a bond with a carbon atom.)

由合成的容易度之點,R45、R46及R55係以各自獨立地為碳數1至20的烷基或可具有取代基之芳基為佳,以各自獨立地為碳數1至8的烷基或下述式所示之芳基更佳。 From the viewpoint of the ease of synthesis, R 45 , R 46 and R 55 are each preferably an alkyl group having 1 to 20 carbon atoms or an aryl group which may have a substituent, and each independently having a carbon number of 1 to An alkyl group of 8 or an aryl group represented by the following formula is more preferred.

(各式中,*表示與氮原子之鍵結。) (In each formula, * represents a bond with a nitrogen atom.)

式(A-VI)及式(A-II)中,Gg-所示之相對陰離子係可列舉如:F-、Cl-、Br-、I-等鹵離子,及式(y1)、式(y2)及式(y3)所示之陰離子。 Of formula (A-VI) and of formula (A-II), the relative anionic shown as the G g- include: F -, Cl -, Br -, I - and other halides, and the formula (Y1), formula (y2) and an anion represented by formula (y3).

式(y1)中,RB1表示鹵烴基。鹵烴基係以經氟原子取代的基為佳,其例可列舉如:-CF3、-CF2CF3、-CF2CF2CF3、-CF(CF3)2、-CF2CF2CF2CF3、-CF2CF(CF3)2、-C(CF3)3In the formula (y1), R B1 represents a halogenated hydrocarbon group. The halogenated hydrocarbon group is preferably a group substituted with a fluorine atom, and examples thereof include -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF (CF 3 ) 2 , -CF 2 CF 2 CF 2 CF 3 , -CF 2 CF (CF 3 ) 2 , and -C (CF 3 ) 3 .

式(y2)中,RB2及RB3表示鹵原子或鹵烴基。 In formula (y2), R B2 and R B3 represent a halogen atom or a halogenated hydrocarbon group.

鹵原子係可列舉如:氟原子、氯原子、溴原子及碘原子,而以氟原子為佳。 Examples of the halogen atom system include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred.

鹵烴基係以經氟原子取代的基為佳,可列舉如:-CF3、-CF2CF3、-CF2CF2CF3、-CF(CF3)2、-CF2CF2CF2CF3、-CF2CF(CF3)。 The halogenated hydrocarbon group is preferably a group substituted with a fluorine atom, and examples thereof include -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF (CF 3 ) 2 , -CF 2 CF 2 CF 2 CF 3 , -CF 2 CF (CF 3 ).

RB2及RB3可互相鍵結而形成包含-SO2-N--SO2-之環。 R B2 and R B3 may be bonded to each other to form a ring including -SO 2 -N -- SO 2- .

式(y3)中,RB4及RB5表示具有2價芳環之基。2價芳環係以伸苯基、伸萘基等碳數6至10的芳烴環為佳。RB4及RB5所示之基係以具有乙烯基、烯丙基等碳數2至4的烯基(alkenyl)為佳。RB4及RB5之例可列舉下述的基。 In formula (y3), R B4 and R B5 represent a group having a divalent aromatic ring. The divalent aromatic ring system is preferably an aromatic hydrocarbon ring having 6 to 10 carbon atoms such as phenylene and naphthyl. The group represented by R B4 and R B5 is preferably an alkenyl group having 2 to 4 carbon atoms such as a vinyl group and an allyl group. Examples of R B4 and R B5 include the following groups.

式(y3)中,M表示鋁原子或硼原子。 In formula (y3), M represents an aluminum atom or a boron atom.

Gg-係以鹵離子或式(y2)所示之陰離子為佳, 以式(y2)所示之陰離子更佳。 G g- is preferably a halide ion or an anion represented by the formula (y2), and more preferably an anion represented by the formula (y2).

Gg-中的g係以1為佳。 The g in G g- is preferably 1.

式(A-VI)之D中,可具有取代基之芳基係可列舉如:下述式所示之基等可具有取代基之苯基,或可具有取代基之萘基。作為該苯基或萘基的取代基係可列舉如:鹵原子、碳數1至4的烷胺基、碳數2至8的二烷胺基及可具有碳數1至4的烷基或碳數1至4的烷氧基之苯基。 Examples of the aryl group which may have a substituent in D of the formula (A-VI) include a phenyl group which may have a substituent such as a group represented by the following formula, or a naphthyl group which may have a substituent. Examples of the substituent of the phenyl or naphthyl group include a halogen atom, an alkylamino group having 1 to 4 carbon atoms, a dialkylamino group having 2 to 8 carbon atoms, and an alkyl group having 1 to 4 carbon atoms or A phenyl group having 1 to 4 carbon atoms.

(各式中,*表示與碳原子之鍵結。) (In each formula, * represents a bond with a carbon atom.)

該芳基中,以式(A1-2)及式(A1-6)所示之基為佳。 Among the aryl groups, those represented by the formula (A1-2) and the formula (A1-6) are preferred.

式(A-VI)的D中,可具有取代基之雜芳基之例可列舉如:下述式所示之基等具有苯基及RX1RX2N(RX1及RX2各自獨立地表示碳數1至4的烷基,或可具有碳數1至4的烷基作為取代基之苯基)的噻唑基。 Examples of the heteroaryl group which may have a substituent in D of the formula (A-VI) include a group represented by the following formula having a phenyl group and R X1 R X2 N (R X1 and R X2 are each independently A thiazolyl group representing an alkyl group having 1 to 4 carbons or a phenyl group which may have an alkyl group having 1 to 4 carbons as a substituent.

(各式中,*表示與碳原子之鍵結。) (In each formula, * represents a bond with a carbon atom.)

該雜芳基中,以式(A1-12)及式(A1-13)所示之基為佳。 Among the heteroaryl groups, those represented by the formula (A1-12) and the formula (A1-13) are preferred.

式(A-VI)中,D係以可具有取代基之苯基、可具有取代基之萘基或可具有取代基之5員環的雜芳基為佳,以可具有取代基之萘基或可具有取代基之噻唑基更佳。 In the formula (A-VI), D is preferably a phenyl group which may have a substituent, a naphthyl group which may have a substituent, or a 5-membered heteroaryl group which may have a substituent, and a naphthyl group which may have a substituent. Or a thiazolyl group which may have a substituent is more preferable.

化合物(A-VI)中的陽離子係可列舉如:式(A-VI-1)至(A-VI-28)所示之陽離子。 Examples of the cation system in the compound (A-VI) include cations represented by the formulae (A-VI-1) to (A-VI-28).

其中,以式(A-VI-1)、式(A-VI-2)、式(A-VI-5)、式(A-VI-6)、式(A-VI-9)及式(A-VI-10)所示之陽離子為佳。 Among them, the formulas (A-VI-1), (A-VI-2), (A-VI-5), (A-VI-6), (A-VI-9), and ( A-VI-10) is preferably a cation.

化合物(A-VI)係可列舉如:式(A-VI-1a)至(A-VI-28a)及式(A-VI-1b)至(A-VI-28b)所示之化合物。其中 尤以式(A-VI-1b)、式(A-VI-2b)、式(A-VI-5b)、式(A-VI-6b)、式(A-VI-9b)及式(A-VI-10b)所示之化合物為佳。 Examples of the compound (A-VI) include compounds represented by the formulae (A-VI-1a) to (A-VI-28a) and the formulae (A-VI-1b) to (A-VI-28b). among them In particular, formula (A-VI-1b), formula (A-VI-2b), formula (A-VI-5b), formula (A-VI-6b), formula (A-VI-9b), and formula (A -VI-10b) is preferably a compound.

化合物(A-II)中的陽離子係可列舉如:式(A-I-a1)至(A-I-a24)所示之陽離子。其中尤以式(A-I-a1)至式(A-I-a6)所示之陽離子為佳。 Examples of the cation system in the compound (A-II) include cations represented by the formulae (A-I-a1) to (A-I-a24). Among them, the cations represented by the formula (A-I-a1) to (A-I-a6) are particularly preferable.

化合物(A-II)係可列舉如:式(A-I-a1a)至(A-I-a24a)及式(A-I-a1b)至(A-I-a24b)所示之化合物。其中尤 以式(A-I-a1a)至式(A-I-a6a)及式(A-I-a1b)至式(A-I-a6b)所示之化合物為佳。 Examples of the compound (A-II) include compounds represented by the formulae (A-I-a1a) to (A-I-a24a) and the formulae (A-I-a1b) to (A-I-a24b). Where especially The compounds represented by the formulae (A-I-a1a) to (A-I-a6a) and the formulae (A-I-a1b) to (A-I-a6b) are preferred.

化合物(A-VI)係例如可藉由使式D-H(D與上述定義相同。)所示之化合物與式(C-II)所示之化合物反應而製造。 The compound (A-VI) can be produced, for example, by reacting a compound represented by the formula D-H (D is the same as defined above) with a compound represented by the formula (C-II).

這種反應可在有機溶媒的存在下進行亦可在無溶媒下進行。 This reaction can be performed in the presence of an organic solvent or without a solvent.

式(C-II)中,R1A至R12A各自表示與前述相同之意。 In the formula (C-II), R 1A to R 12A each have the same meaning as described above.

式(C-II)所示化合物的使用量,相對於D-H 所示化合物1莫耳,係以各為0.5莫耳以上8莫耳以下為佳,以1莫耳以上3莫耳以下更佳。 The amount of the compound represented by formula (C-II) relative to D-H The compounds shown are 1 mole, preferably 0.5 moles to 8 moles, more preferably 1 mole to 3 moles.

反應溫度係以30℃至180℃為佳,以80℃至130℃更佳。反應時間係以1小時至12小時為佳,以3小時至8小時更佳。 The reaction temperature is preferably 30 ° C to 180 ° C, and more preferably 80 ° C to 130 ° C. The reaction time is preferably 1 hour to 12 hours, and more preferably 3 hours to 8 hours.

任一種反應,由收率的觀點,以在有機溶媒中進行為佳。有機溶媒係可列舉如:甲苯、二甲苯等的烴溶媒;氯苯、二氯苯、三氯甲烷等鹵烴溶媒;甲醇、乙醇、異丙醇、丁醇等醇溶媒;硝苯等硝烴溶媒;甲基異丁基酮等酮溶媒;1-甲基-2-吡咯啶酮等醯胺溶媒等。有機溶媒的使用量,相對於式D-H所示之化合物1質量份,係以1質量份以上20質量份以下為佳,以2質量份以上10質量份以下更佳。 Either reaction is preferably carried out in an organic solvent from the viewpoint of yield. Examples of organic solvents include: hydrocarbon solvents such as toluene and xylene; halogen hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform; alcohol solvents such as methanol, ethanol, isopropanol, and butanol; and nitrocarbons such as nitrobenzene Solvents; ketone solvents such as methyl isobutyl ketone; ammonium solvents such as 1-methyl-2-pyrrolidone. The amount of the organic solvent used is preferably 1 part by mass or more and 20 parts by mass or less with respect to 1 part by mass of the compound represented by Formula D-H, and more preferably 2 parts by mass or more and 10 parts by mass or less.

上述反應,由收率的觀點,係以在縮合劑的存在下實施為佳。縮合劑係可列舉如:磷酸、多磷酸、三氯一氧化磷、硫酸及亞硫醯氯等。 The above reaction is preferably carried out in the presence of a condensing agent from the viewpoint of yield. Examples of the condensing agent include phosphoric acid, polyphosphoric acid, phosphorous trichloride, sulfuric acid, and thionyl chloride.

縮合劑的使用量,相對於式D-H所示之化合物1質量份,係以0.1質量份以上20質量份以下為佳,以0.2質量份以上5質量份以下更佳。 The amount of the condensing agent used is preferably 0.1 parts by mass or more and 20 parts by mass or less, and more preferably 0.2 parts by mass or more and 5 parts by mass or less based on 1 part by mass of the compound represented by Formula D-H.

由反應混合物取得目的化合物之化合物(A-VI)的方法並無特別限定,可採用習知的各種手法。其例可列舉如:將反應混合物與醇(例如,甲醇等)混合,濾取析出的結晶的方法。反應混合物以添加於前述醇為佳。添加反應混合物的溫度係以-100℃以上50℃以下為佳,以 -80℃以上0℃以下更佳。又,之後,以在同溫度下攪拌0.5至2小時左右為佳。濾取的結晶係以使用水等進行清洗,繼而加以乾燥者為佳。亦可依所需以再結晶等的習知手法進一步精製。 The method for obtaining the target compound (A-VI) from the reaction mixture is not particularly limited, and various known methods can be used. Examples thereof include a method of mixing a reaction mixture with an alcohol (for example, methanol), and filtering the precipitated crystals. The reaction mixture is preferably added to the aforementioned alcohol. The temperature at which the reaction mixture is added is preferably -100 ° C to 50 ° C. -80 ° C to 0 ° C is more preferred. After that, it is preferably stirred at the same temperature for about 0.5 to 2 hours. The crystals collected by filtration are preferably washed with water or the like and then dried. It can also be further refined by conventional methods such as recrystallization.

D-H所示化合物可列舉下述的化合物,以式(A1-2D)、式(A1-6D)、式(A1-12D)、式(A1-13D)為佳。該化合物以式(A1-2D)至式(A1-6D)所示之化合物可由市售的試藥取得,式(A1-12D)至式(A1-17D)所示之化合物可經習知的各種手法,例如,西德專利申請案P3928243.0號所述的手法而調製。 Examples of the compound represented by D-H include the following compounds, and the formula (A1-2D), the formula (A1-6D), the formula (A1-12D), and the formula (A1-13D) are preferable. The compounds represented by the formulae (A1-2D) to (A1-6D) can be obtained from commercially available reagents. The compounds represented by the formulae (A1-12D) to (A1-17D) can be obtained by conventional methods. Various methods are prepared, for example, the method described in West German Patent Application No. P3928243.0.

本發明的著色劑(以下,有時將該著色劑稱為「著色劑(A)」)係包含化合物(A-VI)。著色劑(A)可再包含其他的染料(亦即,化合物(A-VI)以外的染料)、顏料或該等的混合物。 The coloring agent of the present invention (hereinafter, this colorant may be referred to as "colorant (A)") contains the compound (A-VI). The colorant (A) may further contain other dyes (that is, dyes other than the compound (A-VI)), pigments, or a mixture of these.

本發明的著色硬化性樹脂組成物係包含化合物(A-II)等含化合物(A-VI)的著色劑(A)、樹脂(B)、聚合性化合物(C)及聚合起始劑(D)。可再含有溶劑(E)。 The coloring curable resin composition of the present invention contains a coloring agent (A) containing a compound (A-VI) such as a compound (A-II), a resin (B), a polymerizable compound (C), and a polymerization initiator (D ). It may further contain a solvent (E).

本說明書中,各成分之例示化合物如無特別的註明,可單獨或多種組合使用。 In the present specification, the exemplified compounds of each component may be used alone or in combination unless otherwise specified.

<著色劑(A)> <Colorant (A)>

著色劑(A)係除了本發明的化合物之外,為了調色之目的,亦即為了調整分光特性,而可再含有其他的染料(A2)、顏料(P)或該等的混合物。 In addition to the compound of the present invention, the colorant (A) may further contain other dyes (A2), pigments (P), or a mixture thereof for the purpose of toning, that is, to adjust the spectral characteristics.

染料(A2)係可列舉如:油溶性染料、酸性染料、酸性染料的胺鹽及酸性染料的磺醯胺衍生物等的染料,其例可列舉如:以色指數(Color Index,The Society of Dyers and Colourists出版)染料所分類的化合物,及在染色筆記(色染社)所述的習知染料。 The dyes (A2) are dyes such as oil-soluble dyes, acid dyes, amine salts of acid dyes, and sulfonamide derivatives of acid dyes, and examples thereof include: Color Index, The Society of Dyers and Colourists publishes) compounds classified by dyes, and the conventional dyes described in Dyeing Notes (Color Dye Co.).

依據化學構造,可列舉如:香豆素染料、含金屬的偶氮染料、吡啶酮偶氮染料、巴比妥偶氮染料、喹啉黃(quinophthalone)染料,次甲基染料、花青染料、蒽醌染料、三苯基甲烷染料、二苯并哌喃(xanthene)染料及酞花青染料等。該等的染料可單獨使用或將2種以上併用。 According to the chemical structure, examples include: coumarin dyes, metal-containing azo dyes, pyridone azo dyes, barbitur azo dyes, quinophthalone dyes, methine dyes, cyanine dyes, Anthraquinone dyes, triphenylmethane dyes, xanthene dyes and phthalocyanine dyes. These dyes can be used alone or in combination of two or more.

染料(A2)之具體例係可列舉如:C.I.溶劑黃4(以下,省略C.I.溶劑黃的記述,只記述編號。)、14、15、23、24、38、62、63、68、82、94、98、99、162;C.I.溶劑橙2、7、11、15、26、56等的C.I.溶劑染料,C.I.酸性黃1、3、7、9、11、17、23、25、29、34、36、38、40、42、54、65、72、73、76、79、98、99、111、112、113、114、116、119、123、128、134、135、138、139、140、144、150、155、157、160、161、163、168、169、172、177、178、179、184、190、193、196、197、199、202、203、204、205、207、212、214、220、221、228、230、232、235、238、240、242、243、251;C.I.酸性橙6、7、8、10、12、26、50、51、52、56、62、63、64、74、75、94、95、107、108、169、173;C.I.酸性紅52等的C.I.酸性染料,C.I.直接黃2、33、34、35、38、39、43、47、 50、54、58、68、69、70、71、86、93、94、95、98、102、108、109、129、136、138、141;C.I.直接橙34、39、41、46、50、52、56、57、61、64、65、68、70、96、97、106、107等的C.I.直接染料,C.I.媒染黃(mordant yellow)5、8、10、16、20、26、30、31、33、42、43、45、56、61、62、65;C.I.媒染橙3、4、5、8、12、13、14、20、21、23、24、28、29、32、34、35、36、37、42、43、47、48等的C.I.媒染染料。 Specific examples of the dye (A2) include CI solvent yellow 4 (hereinafter, the description of CI solvent yellow is omitted, and only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, and 94, 98, 99, 162; CI solvent dyes such as CI solvent orange 2, 7, 11, 15, 26, 56, etc., CI acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34 , 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140 , 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212 , 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; CI acid dyes such as CI Acid Red 52, CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141; CI Direct Orange 34, 39, 41, 46, 50 , 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107, etc. CI direct dyes, CI mordant yellow 5, 8, 10, 16, 20, 26, 30 , 31, 33, 42, 43, 45, 56, 61, 62, 65; CI mordant orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, CI mordant dyes such as 34, 35, 36, 37, 42, 43, 47, 48 and so on.

在著色劑(A)中的化合物(A-II)等的化合物(A-VI)的含有量,相對於著色劑的總量,係以3至99.9質量%為佳,以4至80質量%更佳,以5至30質量%又更佳。化合物(A-VI)的含有量在前述的範圍內時,由於製成彩色濾光片時的亮度高,因而為佳。 The content of the compound (A-VI) such as the compound (A-II) in the colorant (A) is preferably 3 to 99.9% by mass, and 4 to 80% by mass relative to the total amount of the colorant. More preferably, 5 to 30% by mass is more preferable. When the content of the compound (A-VI) is within the aforementioned range, it is preferable because the brightness when the color filter is made is high.

顏料(P)並無特別限定而可使用習知的顏料,其例可列舉如:以色指數(The Society of Dyers and Colourists出版)顏料所分類的顏料。 The pigment (P) is not particularly limited, and conventional pigments can be used, and examples thereof include pigments classified by color index (published by The Society of Dyers and Colourists) pigments.

例如,C.I.顏料黃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等的黄色顏料;C.I.顏料橙13、31、36、38、40、42、43、51、55、59、61、64、65、71、73等的橙色的顏料;C.I.顏料綠7、36、58等的綠色顏料; C.I.顏料紅9、97、105、122、123、144、149、166、168、176、177、180、192、209、215、216、224、242、254、255、264、265等的紅色顏料;C.I.顏料藍15、15:3、15:4、15:6、60等的藍色顏料;C.I.顏料紫1、19、23、29、32、36、38等的紫色顏料。 For example, CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138 , 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and other yellow pigments; CI pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; CI Pigment Green 7, 36, 58 and other green pigments; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. ; CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments; CI Pigment Purple 1, 19, 23, 29, 32, 36, 38 and other purple pigments.

顏料(P)係以C.I.顏料黃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等的黄色顏料;C.I.顏料綠7、36、58等的綠色顏料;C.I.顏料藍15、15:3、15:4、15:6等的藍色顏料為佳,以C.I.顏料黃150、185;C.I.顏料綠58及C.I.顏料藍15:6更佳,以C.I.顏料藍15:6為特佳。由於著色劑(A)包含前述顏料,使透過光譜容易最佳化,彩色濾光片的耐熱性及耐藥品性會變佳。 Pigment (P) is CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and other yellow pigments; CI Pigment Green 7, 36, 58 and other green pigments; CI Pigment Blue 15, 15: 3 Blue pigments such as 15: 4, 15: 6, etc. are preferred, with CI Pigment Yellow 150, 185; CI Pigment Green 58 and CI Pigment Blue 15: 6 are more preferred, and CI Pigment Blue 15: 6 is particularly preferred. Since the colorant (A) contains the aforementioned pigment, the transmission spectrum is easily optimized, and the heat resistance and chemical resistance of the color filter are improved.

著色劑(A)中,顏料(P)的含有量相對於著色劑(A)的總量,以0.1至60質量%為佳,以8至55質量%更佳。以上述比率含有該顏料時,使透過光譜容易最佳化,彩色濾光片的耐熱性及耐藥品性變佳。 The content of the pigment (P) in the colorant (A) is preferably 0.1 to 60% by mass, and more preferably 8 to 55% by mass, with respect to the total amount of the colorant (A). When the pigment is contained in the above ratio, the transmission spectrum is easily optimized, and the heat resistance and chemical resistance of the color filter are improved.

著色硬化性樹脂組成物中,著色劑(A)的含有量相對於固形分的總量,係以5至60質量%為佳,以8至55質量%更佳,以10至50質量%又更佳。著色劑(A)的含有量在前述的範圍內時,製成彩色濾光片時的色濃度足夠,並且可使組成物中含有必要量的樹脂(B)及聚合性化 合物(C),可形成機械強度充分的圖案。 The content of the colorant (A) in the colored curable resin composition is preferably 5 to 60% by mass, more preferably 8 to 55% by mass, and 10 to 50% by mass based on the total solid content. Better. When the content of the colorant (A) is within the aforementioned range, the color density when the color filter is made is sufficient, and the resin (B) and the polymerizable amount can be contained in the composition in a necessary amount. Compound (C) can form a pattern with sufficient mechanical strength.

在這裏,本說明書中的「固形分總量」係指著色硬化性樹脂組成物的總量減去溶劑的含有量之量者。固形分的總量及各成分對該總量的含有量可由例如液相層析法或氣相層析法等的習知的分析手段測定。 Here, the "total solid content" in this specification means the total amount of the colored curable resin composition minus the content of the solvent. The total amount of the solid content and the content of each component with respect to the total amount can be measured by a conventional analysis means such as liquid chromatography or gas chromatography.

<樹脂(B)> <Resin (B)>

樹脂(B)並無特別限定,惟以鹼可溶性樹脂為佳。樹脂(B)係可列舉以下的樹脂[K1]至[K6]等。 The resin (B) is not particularly limited, but is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6].

樹脂[K1];由不飽和羧酸及不飽和羧酸酐所成群組中選出的至少1種(Ba)(以下有時稱為「(Ba)」),與具有碳數2至4的環狀醚構造及乙烯性不飽和鍵的單體(Bb)(以下有時稱為「(Bb)」)的共聚物;樹脂[K2];(Ba)、(Bb)及可與(Ba)共聚的單體(Bc)(但是,與(Ba)及(Bb)不同。)(以下有時稱為「(Bc)」)的共聚物;樹脂[K3];(Ba)及(Bc)的共聚物;樹脂[K4];將(Ba)及(Bc)的共聚物與(Bb)反應的樹脂;樹脂[K5];將(Bb)及(Bc)的共聚物與(Ba)反應的樹脂;樹脂[K6];將(Bb)及(Bc)的共聚物與(Ba)反應,再與羧酸酐反應的樹脂。 Resin [K1]; at least one (Ba) (hereinafter sometimes referred to as "(Ba)") selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and a ring having 2 to 4 carbon atoms Copolymer of monomers (Bb) (hereinafter sometimes referred to as "(Bb)"), which are ether-like structures and ethylenically unsaturated bonds; resins [K2]; (Ba), (Bb), and copolymerizable with (Ba) (Bc) (but different from (Ba) and (Bb).) (Hereinafter sometimes referred to as "(Bc)"); copolymer of resin [K3]; (Ba) and (Bc) Resin [K4]; resin that reacts the copolymer of (Ba) and (Bc) with (Bb); resin [K5]; resin that reacts the copolymer of (Bb) and (Bc) with (Ba); Resin [K6]; A resin in which a copolymer of (Bb) and (Bc) is reacted with (Ba) and then reacted with a carboxylic anhydride.

(Ba)在具體上可列舉如:丙烯酸、甲基丙烯酸、巴豆酸、鄰-、間-、對-乙烯安息香酸等的不飽和單羧酸;順丁烯二酸、反丁烯二酸、焦檸檬酸、甲基反丁烯二酸、亞甲基丁二酸(itaconic acid)、3-乙烯酞 酸、4-乙烯酞酸、3,4,5,6-四氫酞酸、1,2,3,6-四氫酞酸、二甲基四氫酞酸、1,4-環己烯二羧酸等的不飽和二羧酸;甲基-5-降莰烯-2,3-二羧酸、5-羧基雙環[2.2.1]庚-2-烯、5,6-二羧基雙環[2.2.1]庚-2-烯、5-羧基-5-甲基雙環[2.2.1]庚-2-烯、5-羧基-5-乙基雙環[2.2.1]庚-2-烯、5-羧基-6-甲基雙環[2.2.1]庚-2-烯、5-羧基-6-乙基雙環[2.2.1]庚-2-烯等含有羧基的雙環不飽和化合物;順丁烯二酸酐、焦檸檬酸酐、亞甲基丁二酸酐、3-乙烯酞酸酐、4-乙烯酞酸酐、3,4,5,6-四氫酞酸酐、1,2,3,6-四氫酞酸酐、二甲基四氫酞酸酐、5,6-二羧基雙環[2.2.1]庚-2-烯酐等不飽和二羧酸酐;琥珀酸單[2-(甲基)丙烯醯氧基乙基]酯、酞酸單[2-(甲基)丙烯醯氧基乙基]酯等的2價以上多羧酸的不飽和單[(甲基)丙烯醯氧基烷基]酯;如α-(羥甲基)丙烯酸的同一分子中含有羥基及羧基的不飽和丙烯酸酯等。 (Ba) Specific examples include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-ethylene benzoic acid; maleic acid, fumaric acid, Pyrocitric acid, methyl fumaric acid, itaconic acid, 3-vinylphthalein Acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene di Unsaturated dicarboxylic acids such as carboxylic acids; methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclic [ 2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, and other bicyclic unsaturated compounds containing carboxyl groups; Diene anhydride, pyrocitric anhydride, methylene succinic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydro Unsaturated dicarboxylic anhydrides such as phthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] heptan-2-ene anhydride; succinate mono [2- (meth) acrylic acid Unsaturated mono [(meth) acryloxyalkyl] esters of polyvalent polycarboxylic acids such as ethyl] esters, phthalic acid mono [2- (meth) acryloxyethyl] esters; such as The α- (hydroxymethyl) acrylic acid contains unsaturated acrylates such as a hydroxyl group and a carboxyl group in the same molecule.

該等中,由可得共聚合反應性之點及所得樹脂對鹼水溶液的溶解性之點,以丙烯酸、甲基丙烯酸、順丁烯二酸酐等為佳。 Among them, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the point that copolymerization reactivity is obtained and the solubility of the obtained resin to an alkali aqueous solution.

(Bb)係可列舉如:具有碳數2至4的環狀醚構造(例如,由環氧乙烷環(oxirane ring)、氧環丁烷環(oxetane ring)與四氫呋喃環所成群組中選出的至少1種)與乙烯性不飽和鍵的聚合性化合物。(Bb)係以具有碳數2至4的環狀醚與(甲基)丙烯醯氧基的單體為佳。 Examples of the (Bb) system include a cyclic ether structure having 2 to 4 carbon atoms (for example, a group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring). At least one selected) a polymerizable compound having an ethylenically unsaturated bond. The (Bb) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acrylic fluorenyloxy group.

本說明書中,「(甲基)丙烯酸」就表示丙烯酸及甲基丙烯酸所成群組中選出的至少1種。「(甲基)丙烯醯基」及「(甲基)丙烯酸酯」等的標示亦為同義。 In this specification, "(meth) acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The designations of "(meth) acrylfluorenyl" and "(meth) acrylate" are also synonymous.

(Bb)之例可列舉如:具有環氧乙基與乙烯性不飽和鍵的單體、具有環氧丁基及乙烯性不飽和鍵的單體及具有四氫呋喃基與乙烯性不飽和鍵的單體等。 Examples of (Bb) include a monomer having an epoxy ethyl group and an ethylenically unsaturated bond, a monomer having an epoxy butyl group and an ethylenically unsaturated bond, and a monomer having a tetrahydrofuran group and an ethylenically unsaturated bond.体 等。 Body and so on.

(Bb)而言,由可更提高所得彩色濾光片的耐熱性、耐藥性等的信頼性之點,以具有環氧乙基及乙烯性不飽和鍵的單體為佳。 (Bb) From the viewpoint of further improving the reliability of the obtained color filter, such as heat resistance and chemical resistance, a monomer having an epoxyethyl group and an ethylenically unsaturated bond is preferred.

(Bc)之例可列舉如:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸二級丁酯、(甲基)丙烯酸三級丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸十二烷酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸環戊酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸2-甲基環己酯、(甲基)丙烯酸三環[5.2.1.02,6]癸烷-8-基酯(在本行業技術領域,以「(甲基)丙烯酸二環戊酯」的慣用名稱呼。又,有時稱為「(甲基)丙烯酸三環癸酯」。)、(甲基)丙烯酸三環[5.2.1.02,6]癸烯-8-基酯(在本行業技術領域,以「(甲基)丙烯酸二環戊烯酯」的慣用名稱呼。)、(甲基)丙烯酸二環戊氧基乙酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸金剛烷酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸炔丙酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸萘酯、(甲基)丙烯酸苄酯等(甲基)丙烯酸酯;(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥 丙酯等含有羥基的(甲基)丙烯酸酯類;順丁烯二酸二乙酯、反丁烯二酸二乙酯、亞甲基丁二酸二乙酯等二羧酸二酯;雙環[2.2.1]庚-2-烯、5-甲基雙環[2.2.1]庚-2-烯、5-乙基雙環[2.2.1]庚-2-烯、5-羥基雙環[2.2.1]庚-2-烯、5-羥甲基雙環[2.2.1]庚-2-烯、5-(2’-羥乙基)雙環[2.2.1]庚-2-烯、5-甲氧基雙環[2.2.1]庚-2-烯、5-乙氧基雙環[2.2.1]庚-2-烯、5,6-二羥基雙環[2.2.1]庚-2-烯、5,6-二(羥甲基)雙環[2.2.1]庚-2-烯、5,6-二(2’-羥乙基)雙環[2.2.1]庚-2-烯、5,6-二甲氧基雙環[2.2.1]庚-2-烯、5,6-二乙氧基雙環[2.2.1]庚-2-烯、5-羥基-5-甲基雙環[2.2.1]庚-2-烯、5-羥基-5-乙基雙環[2.2.1]庚-2-烯、5-羥甲基-5-甲基雙環[2.2.1]庚-2-烯、5-三級丁氧基羰基雙環[2.2.1]庚-2-烯、5-環己氧基羰基雙環[2.2.1]庚-2-烯、5-苯氧基羰基雙環[2.2.1]庚-2-烯、5,6-雙(三級丁氧基羰基)雙環[2.2.1]庚-2-烯、5,6-雙(環己氧基羰基)雙環[2.2.1]庚-2-烯等的雙環不飽和化合物;N-苯基順丁烯二亞醯胺、N-環己基順丁烯二亞醯胺、N-苄基順丁烯二亞醯胺、N-琥珀醯亞胺基-3-順丁烯二亞醯胺苯甲酸酯、N-琥珀醯亞胺基-4-順丁烯二亞醯胺丁酸酯、N-琥珀醯亞胺基-6-順丁烯二亞醯胺己酸酯、N-琥珀醯亞胺基-3-順丁烯二亞醯胺丙酸酯、N-(9-吖啶基)順丁烯二亞醯胺等的二羰基醯亞胺衍生物;苯乙烯、α-甲基苯乙烯、間-甲基苯乙烯、對-甲基苯乙烯、乙烯甲苯、對-甲氧基苯乙烯、丙烯腈、 甲基丙烯腈、氯乙烯、二氯亞乙烯、丙烯醯胺、甲基丙烯醯胺、乙酸乙烯酯、1,3-丁二烯、異戊二烯、2,3-二甲基-1,3-丁二烯等。 Examples of (Bc) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, secondary butyl (meth) acrylate, and trimethyl (meth) acrylate. Butyl, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate Ester, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6 ] decane-8-yl ester (in this industry In the technical field, it is called by the common name of "dicyclopentyl (meth) acrylate." It is also sometimes called "tricyclodecyl (meth) acrylate."), Tricyclic (meth) acrylate [5.2. 1.0 2,6 ] decene-8-yl ester (in the technical field of this industry, it is called by the common name of "dicyclopentenyl (meth) acrylate."), Dicyclopentyloxyethyl (meth) acrylate Ester, isoamyl (meth) acrylate, adamantane (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, (meth) (Meth) acrylates such as naphthyl acrylate, benzyl (meth) acrylate, etc .; ) Hydroxy-containing (meth) acrylates such as 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate; diethyl maleate, diethyl fumarate, methylene Dicarboxylic acid diesters such as diethyl succinate; bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2. 1] hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) Bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6- Dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-bis (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene , 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methyl Bicyclo [2.2.1] hept-2-ene, 5-tertiary butoxycarbonyl bicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonyl bicyclo [2.2.1] hept-2-ene Ene, 5-phenoxycarbonyl bicyclo [2.2.1] hept-2-ene, 5,6-bis (tertiary butoxycarbonyl) bicyclo [2.2.1] hept-2-ene Bicyclic unsaturated compounds such as 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene; N-phenyl-cis-butenediimidine, N-cyclohexyl-cis-butenedi Sulfenimide, N-benzylcis butylenediimide, N-succinimidylimide-3-cis butylenediimideamine benzoate, N-succinimidylimide-4-cisbutyl Arylene diimide butyrate, N-succinimide imino-6-cis butylene diimide hexanoate, N-succinimide 3-maleimide dipropionate , N- (9-acridyl) maleimide derivatives such as maleimide, styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene , Vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, dichloroethylene, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, Isoprene, 2,3-dimethyl-1,3-butadiene, etc.

該等中,由共聚合反應性及耐熱性的點,以苯乙烯、乙烯甲苯、N-苯基順丁烯二亞醯胺、N-環己基順丁烯二亞醯胺、N-苄基順丁烯二亞醯胺、雙環[2.2.1]庚-2-烯等為佳。 Among these, from the point of copolymerization reactivity and heat resistance, styrene, vinyltoluene, N-phenylcis butylenediimide, N-cyclohexylcis butylenediimide, and N-benzyl Preference is given to maleimide and bicyclo [2.2.1] hept-2-ene.

樹脂(B)而言,具體上可列舉如:3,4-環氧環己基甲基(甲基)丙烯酸酯/(甲基)丙烯酸共聚物、3,4-環氧三環[5.2.1.02,6]癸基丙烯酸酯/(甲基)丙烯酸共聚物等的樹脂[K1];(甲基)丙烯酸環氧丙酯/(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物、(甲基)丙烯酸環氧丙酯/苯乙烯/(甲基)丙烯酸共聚物、3,4-環氧三環[5.2.1.02,6]癸基丙烯酸酯/(甲基)丙烯酸/N-環己基順丁烯二亞醯胺共聚物、3-甲基-3-(甲基)丙烯醯基氧甲基氧環丁烷/(甲基)丙烯酸/苯乙烯共聚物等的樹脂[K2];(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物、苯乙烯/(甲基)丙烯酸共聚物等的樹脂[K3];在(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物加成(甲基)丙烯酸環氧丙酯的樹脂、在(甲基)丙烯酸酯三環癸酯/苯乙烯/(甲基)丙烯酸共聚物加成(甲基)丙烯酸環氧丙酯的樹脂、在(甲基)丙烯酸酯三環癸酯/(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物加成(甲基)丙烯酸環氧丙酯樹脂等的樹脂[K4];將(甲基)丙烯酸酯三環癸酯/(甲基)丙烯酸環氧丙酯的共聚物與(甲基)丙烯酸反應的樹脂、將(甲基)丙烯酸酯三環癸酯/苯乙烯/(甲基)丙烯酸 環氧丙酯的共聚物與(甲基)丙烯酸反應的樹脂等的樹脂[K5];將(甲基)丙烯酸酯三環癸酯/(甲基)丙烯酸環氧丙酯的共聚物與(甲基)丙烯酸反應的樹脂再與四氫酞酸酐反應的樹脂等的樹脂[K6]等。 Specific examples of the resin (B) include: 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic copolymer, 3,4-epoxy tricyclic [5.2.1.0 2,6 ] resins such as decyl acrylate / (meth) acrylic copolymer [K1]; propylene oxide (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic copolymer, ( Glycidyl acrylate / styrene / (meth) acrylic copolymer, 3,4-epoxy tricyclic [5.2.1.0 2,6 ] decyl acrylate / (meth) acrylic acid / N-ring Resin such as hexyl cis butene diimide copolymer, 3-methyl-3- (meth) acryl fluorenyloxymethyloxycyclobutane / (meth) acrylic acid / styrene copolymer, etc. [K2]; Resin [K3] such as benzyl (meth) acrylate / (meth) acrylic copolymer, styrene / (meth) acrylic copolymer; add benzyl (meth) acrylate / (meth) acrylic copolymer (Meth) acrylic acid propylene oxide resin, (meth) acrylic acid tricyclodecyl ester / styrene / (meth) acrylic acid copolymer addition (meth) acrylic acid propylene oxide resin, (Meth) acrylate tricyclodecyl ester / benzyl (meth) acrylate / (meth) acrylic acid copolymer Resin [K4] into (meth) acrylic acid propylene resin; etc .; a resin obtained by reacting (meth) acrylic acid tricyclodecyl / (meth) acrylic acid propylene copolymer with (meth) acrylic acid Resins, resins such as (meth) acrylic acid tricyclodecyl ester / styrene / (meth) acrylic acid propylene copolymers and (meth) acrylic acid-reacted resins [K5]; (meth) Resin [K6] and the like, such as a resin in which a copolymer of acrylate tricyclodecyl / glycidyl (meth) acrylate reacts with (meth) acrylic acid, and a resin with tetrahydrophthalic anhydride.

其中,樹脂(B)而言,尤以樹脂[K1]及樹脂[K2]為佳。 Among them, the resin (B) is particularly preferably the resin [K1] and the resin [K2].

樹脂[K1]可參考文獻「高分子合成的實験法」(大津隆行著 發行所(股)化學同人 第1版第1刷1972年3月1日發行)所述的方法及該文獻所述的引用文獻而製造。 Resin [K1] can be referred to the method described in the document "The Practical Method of Polymer Synthesis" (Otsu Takayuki Publishing Co., Ltd., the first edition of the first edition of the Chemical Doctrine, March 1, 1972) and the method described in the document It is manufactured by citations.

所得的共聚物,可將反應後的溶液直接使用,或使用經濃縮或稀釋的溶液,亦可使用以再沈殿等的方法作成固體(粉體)所取出者。該聚合時之溶劑,由於可藉由使用本發明的著色硬化性樹脂組成物中所含的溶劑,而可將反應後的溶液直接使用於本發明的著色硬化性樹脂組成物的調製,因此可簡化本發明的著色硬化性樹脂組成物的製程。 The obtained copolymer can be used as it is after the reaction, or it can be used as a concentrated or diluted solution, or it can be used as a solid (powder) by a method such as re-sinking. The solvent at the time of polymerization can be used directly for the preparation of the colored curable resin composition of the present invention by using the solvent contained in the colored curable resin composition of the present invention. The manufacturing process of the coloring curable resin composition of this invention is simplified.

樹脂(B)的聚苯乙烯換算的重量平均分子量係以3,000至100,000為佳,以5,000至50,000更佳,以5,000至30,000又更佳。分子量在前述的範圍內時,彩色濾光片的硬度提高,殘膜率高,未曝光部對顯影液的溶解性良好,著色圖案的解析度有提高的傾向。 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. When the molecular weight is within the above range, the hardness of the color filter is increased, the residual film ratio is high, the solubility of the unexposed portion in the developing solution is good, and the resolution of the colored pattern tends to be improved.

樹脂(B)的分子量分佈[重量平均分子量(Mw)/數平均分子量(Mn)]係以1.1至6為佳,以1.2至4 更佳。 The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably from 1.1 to 6, and from 1.2 to 4 Better.

樹脂(B)的酸值係以50至170mg-KOH/g為佳,以60至150mg-KOH/g更佳,以70至135mg-KOH/g又更佳。其中之酸值係作為中和樹脂(B)1g所需要的氫氧化鉀的量(mg)而測定的值,例如可使用氫氧化鉀水溶液滴定而求得。 The acid value of the resin (B) is preferably 50 to 170 mg-KOH / g, more preferably 60 to 150 mg-KOH / g, and even more preferably 70 to 135 mg-KOH / g. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B). For example, the acid value can be determined by titration with an aqueous potassium hydroxide solution.

樹脂(B)的含有量,相對於固形分的總量,以7至65質量%為佳,以13至60質量%更佳,以17至55質量%又更佳。樹脂(B)的含有量如在前述的範圍內時,可形成著色圖案,且著色圖案的解析度及殘膜率有提高的傾向。 The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and even more preferably 17 to 55% by mass with respect to the total solid content. When the content of the resin (B) is within the aforementioned range, a colored pattern can be formed, and the resolution and the residual film rate of the colored pattern tend to increase.

<聚合性化合物(C)> <Polymerizable compound (C)>

聚合性化合物(C)係可由聚合起始劑(D)產生的活性自由基及/或酸而聚合的化合物,其例可列舉如:具有聚合性的乙烯性不飽和鍵的化合物等,以(甲基)丙烯酸酯化合物為佳。 The polymerizable compound (C) is a compound that can be polymerized from living radicals and / or acids generated by the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, and ( A meth) acrylate compound is preferred.

聚合性化合物(C)係以具有3個以上的乙烯性不飽和鍵的聚合性化合物為佳。如此聚合性化合物係可列舉如:三(甲基)丙烯酸三羥甲基丙烷酯、新戊四醇三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、三新戊四醇八(甲基)丙烯酸酯、三新戊四醇七(甲基)丙烯酸酯、四新戊四醇十(甲基)丙烯酸酯、四新戊四醇九(甲基)丙烯酸酯、三聚異氰酸三(2-(甲基)丙烯醯氧基乙基)酯、乙二醇改質新 戊四醇四(甲基)丙烯酸酯、乙二醇改質二新戊四醇六(甲基)丙烯酸酯、丙二醇改質新戊四醇四(甲基)丙烯酸酯、丙二醇改質二新戊四醇六(甲基)丙烯酸酯、γ-己內酯改質新戊四醇四(甲基)丙烯酸酯、γ-己內酯改質二新戊四醇六(甲基)丙烯酸酯等。 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, neopentaerythritol tri (meth) acrylate, neopentaerythritol tetra (meth) acrylate, and dipentaerythritol. Alcohol penta (meth) acrylate, dinepentaerythritol hexa (meth) acrylate, trinepentaerythritol octa (meth) acrylate, trinepentaerythritol hepta (meth) acrylate, tetraxin Pentaerythritol deca (meth) acrylate, tetranepentaerythritol nona (meth) acrylate, tris (2- (meth) acryloxyethyl) isocyanate, ethylene glycol modification Quality new Pentaerythritol tetra (meth) acrylate, ethylene glycol modified dinepentaerythritol hexa (meth) acrylate, propylene glycol modified neopentaerythritol tetra (meth) acrylate, propylene glycol modified dipentyl Tetraol hexa (meth) acrylate, γ-caprolactone modified neopentaerythritol tetra (meth) acrylate, γ-caprolactone modified dipentaerythritol hexa (meth) acrylate, and the like.

其中尤以二新戊四醇五(甲基)丙烯酸酯及二新戊四醇六(甲基)丙烯酸酯為佳。 Among them, dipentaerythritol penta (meth) acrylate and dinepentaerythritol hexa (meth) acrylate are preferred.

聚合性化合物(C)的重量平均分子量係以150至2,900為佳,以250至1,500更佳。 The weight-average molecular weight of the polymerizable compound (C) is preferably 150 to 2,900, and more preferably 250 to 1,500.

著色硬化性樹脂組成物中,聚合性化合物(C)的含有量相對於固形分的總量,係以7至65質量%為佳,以13至60質量%更佳,以17至55質量%又更佳。聚合性化合物(C)的含有量在前述的範圍內時,著色圖案形成時的殘膜率及彩色濾光片的耐藥品性有提高的傾向。 The content of the polymerizable compound (C) in the colored curable resin composition is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and 17 to 55% by mass with respect to the total solid content. Even better. When the content of the polymerizable compound (C) is within the above range, the residual film rate at the time of forming a colored pattern and the chemical resistance of the color filter tend to be improved.

<聚合起始劑(D)> <Polymerization initiator (D)>

聚合起始劑(D)如為經由光或熱的作用而產生活性自由基、酸等而能開始聚合的化合物,則無特別限定,可使用習知的聚合起始劑。 The polymerization initiator (D) is not particularly limited as long as it is a compound capable of starting polymerization by generating active radicals, acids, and the like through the action of light or heat, and a conventional polymerization initiator can be used.

產生活性自由基的聚合起始劑之例可列舉如:O-醯基肟(o-acyl oxime)化合物、苯烷基酮化合物、三嗪化合物、醯基膦氧化物(acylphosphine oxide)及聯咪唑化合物。 Examples of polymerization initiators that generate living radicals include: O-acyl oxime compounds, benzoyl ketone compounds, triazine compounds, acylphosphine oxide, and biimidazole Compound.

前述O-醯基肟化合物係可列舉如:N-苄醯氧基-1-(4-苯基硫苯基)丁烷-1-酮-2-亞胺、N-苄醯氧基-1-(4- 苯基硫苯基)辛烷-1-酮-2-亞胺、N-苄醯氧基-1-(4-苯基硫苯基)-3-環戊基丙烷-1-酮-2-亞胺、N-乙醯氧基-1-[9-乙基-6-(2-甲基苄醯基)-9H-咔唑-3-基]乙烷-1-亞胺、N-乙醯氧基-1-[9-乙基-6-{2-甲基-4-(3,3-二甲基-2,4-二氧雜環戊基甲氧基)苄醯基}-9H-咔唑-3-基]乙烷-1-亞胺、N-乙醯氧基-1-[9-乙基-6-(2-甲基苄醯基)-9H-咔唑-3-基]-3-環戊基丙烷-1-亞胺、N-苄醯氧基-1-[9-乙基-6-(2-甲基苄醯基)-9H-咔唑-3-基]-3-環戊基丙烷-1-酮-2-亞胺等。可使用Irgacure(註冊商標)OXE01、OXE02(以上均為BASF公司製)、N-1919(ADEKA公司製)等的市售品。其中,O-醯基肟化合物係以由N-苄醯氧基-1-(4-苯基硫苯基)丁烷-1-酮-2-亞胺、N-苄醯氧基-1-(4-苯基硫苯基)辛烷-1-酮-2-亞胺及N-苄醯氧基-1-(4-苯基硫苯基)-3-環戊基丙烷-1-酮-2-亞胺所成群組中選出的至少1種為佳,以N-苄醯氧基-1-(4-苯基硫苯基)辛烷-1-酮-2-亞胺更佳。如為該等的O-醯基肟化合物,則有可得高亮度的彩色濾光片的傾向。 Examples of the O-fluorenyl oxime compound system include: N-benzyloxy-1- (4-phenylthiophenyl) butane-1-one-2-imine, and N-benzyloxy-1 -(4- Phenylthiophenyl) octane-1-one-2-imine, N-benzyloxy-1- (4-phenylthiophenyl) -3-cyclopentylpropane-1-one-2- Imine, N-Ethyloxy-1- [9-ethyl-6- (2-methylbenzylfluorenyl) -9H-carbazol-3-yl] ethane-1-imine, N-ethyl Methoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxolylmethoxy) benzylfluorenyl}- 9H-carbazol-3-yl] ethane-1-imine, N-ethoxyl-1--1- [9-ethyl-6- (2-methylbenzylfluorenyl) -9H-carbazole-3 -Yl] -3-cyclopentylpropane-1-imine, N-benzyloxy-1- [9-ethyl-6- (2-methylbenzylfluorenyl) -9H-carbazole-3- Group] -3-cyclopentylpropane-1-one-2-imine and the like. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (all of which are manufactured by BASF), and N-1919 (made by ADEKA) can be used. Among them, O-fluorenyl oxime compounds are composed of N-benzyloxy-1- (4-phenylthiophenyl) butane-1-one-2-imine, N-benzyloxy-1- (4-phenylthiophenyl) octane-1-one-2-imine and N-benzyloxy-1- (4-phenylthiophenyl) -3-cyclopentylpropane-1-one Preferably at least one selected from the group consisting of -2-imines, more preferably N-benzyloxy-1- (4-phenylthiophenyl) octan-1-one-2-imine . Such an O-fluorenyl oxime compound tends to obtain a color filter with high brightness.

前述苯烷基酮化合物係可列舉如:2-甲基-2-N-嗎啉基-1-(4-甲基硫烷基苯基)丙烷-1-酮、2-二甲胺基-1-(4-N-嗎啉基苯基)-2-苄基丁烷-1-酮、2-(二甲基胺)-2-[(4-甲基苯基)甲基]-1-[4-(4-N-嗎啉基)苯基]丁烷-1-酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、2-羥基-2-甲基-1-[4-(2-羥乙氧基)苯基]丙烷-1-酮、1-羥基環己基苯基酮、2-羥基-2-甲基-1-(4-異丙烯基苯基)丙烷-1-酮的寡聚物、α,α-二乙氧基苯乙酮、苄基二甲基縮酮等。可使用Irgacure(註冊商標)369、 907、379(以上均為BASF公司製)等的市售品。 Examples of the benzoyl ketone compound system include 2-methyl-2-N-morpholinyl-1- (4-methylsulfanylphenyl) propane-1-one and 2-dimethylamino- 1- (4-N-morpholinylphenyl) -2-benzylbutane-1-one, 2- (dimethylamine) -2-[(4-methylphenyl) methyl] -1 -[4- (4-N-morpholinyl) phenyl] butane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl -1- [4- (2-hydroxyethoxy) phenyl] propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- (4-isopropenylbenzene Oligomers of propane-1-one, α, α-diethoxyacetophenone, benzyldimethylketal, and the like. Irgacure (registered trademark) 369, Commercial products such as 907, 379 (all of which are manufactured by BASF).

前述三嗪化合物係可列舉如:2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-(4-甲氧基萘基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-向日葵基(piperonyl)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(5-甲基呋喃-2-基)乙烯基]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(4-二乙胺基-2-甲基苯基)乙烯基]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三嗪等。 Examples of the triazine compound system are: 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloro (Methyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5 -Triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl)- 6- [2- (5-methylfuran-2-yl) vinyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2 -Yl) vinyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl ] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) vinyl] -1,3,5- Triazine and so on.

前述醯基膦氧化合物係可列舉如:2,4,6-三甲基苄醯基二苯基膦氧化合物等。可使用Irgacure(註冊商標)819(BASF公司製)等的市售品。 Examples of the aforementioned fluorenylphosphine compound system include 2,4,6-trimethylbenzylfluorenyldiphenylphosphine compound and the like. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) can be used.

前述聯咪唑化合物係可列舉如:2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基聯咪唑、2,2’-雙(2,3-二氯苯基)-4,4’,5,5’-四苯基聯咪唑(參照日本特開平6-75372號公報,日本特開平6-75373號公報等。)、2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基聯咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四(烷氧苯基)聯咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四(二烷氧苯基)聯咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四(三烷氧苯基)聯咪唑(參照日本特公昭48-38403號公報,日本特開昭62-174204號公報等。)、4,4’,5,5’-位的苯基經烷氧羰基(carboalkoxy)取代的咪唑化合物(參照日本特開平7-10913號公報等)等。 Examples of the aforementioned biimidazole compound system are: 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (see Japanese Patent Application Laid-Open No. 6-75372, Japanese Patent Application Laid-Open No. 6-75373, etc.), 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra ( Alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (dialkoxyphenyl) biimidazole, 2,2'-bis ( 2-chlorophenyl) -4,4 ', 5,5'-tetrakis (trialkoxyphenyl) biimidazole (see Japanese Patent Application Publication No. 48-38403, Japanese Patent Application Publication No. 62-174204, etc.) , Imidazole compounds in which the phenyl group at the 4,4 ', 5,5'-position is substituted with a carboalkoxy group (see Japanese Patent Application Laid-Open No. 7-10913, etc.).

聚合起始劑(D)係可列舉如:安息香、安息香甲醚、安息香乙醚、安息香異丙醚、安息香異丁醚等的安息香化合物;二苯基酮、鄰-苄醯基安息香酸甲酯、4-苯基二苯基酮、4-苄醯基-4’-甲基二苯基硫、3,3’,4,4’-四(三級丁基過氧羰基)二苯基酮、2,4,6-三甲基二苯基酮等的二苯基酮化合物;9,10-菲醌、2-乙基蒽醌、樟腦醌等的醌化合物;10-丁基-2-氯吖啶酮、二苯乙二酮、苯基乙醛酸甲酯、二茂鈦(titanocene)化合物等。 Examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; diphenyl ketone, o-benzylidene benzoate methyl ester, 4-phenyldiphenylketone, 4-benzylfluorenyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetrakis (tertiarybutylperoxycarbonyl) diphenylketone, Diphenyl ketone compounds such as 2,4,6-trimethyldiphenyl ketone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone; 10-butyl-2-chloro Acridinone, diphenylethylene dione, methyl phenylglyoxylate, titanocene compound, and the like.

產生酸的聚合起始劑係可列舉如:4-羥苯基二甲基鋶對-甲苯磺酸鹽、4-羥苯基二甲基鋶六氟銻酸鹽、4-乙醯氧基苯基二甲基鋶對-甲苯磺酸鹽、4-乙醯氧基苯基甲基苄基鋶六氟銻酸鹽、三苯基鋶對-甲苯磺酸鹽、三苯基鋶六氟銻酸鹽、二苯基錪對-甲苯磺酸鹽、二苯基錪六氟銻酸鹽等的鎓鹽、及硝苄基甲苯磺酸鹽、安息香甲苯磺酸鹽等。 Examples of the acid-generating polymerization initiator are: 4-hydroxyphenyldimethylfluorene p-toluenesulfonate, 4-hydroxyphenyldimethylfluorene hexafluoroantimonate, 4-ethoxyfluorenylbenzene Dimethylpyridine p-toluenesulfonate, 4-Ethyloxyphenylmethylbenzylpyrene hexafluoroantimonate, triphenylpyrene p-toluenesulfonate, triphenylpyrene hexafluoroantimonate Salts, onium salts such as diphenylsulfonium p-toluenesulfonate, diphenylsulfonium hexafluoroantimonate, and the like, as well as nitrobenzyltoluenesulfonate, benzoin tosylate, and the like.

聚合起始劑(D)係以包含至少1種由O-醯基肟化合物、苯烷基酮化合物、三嗪化合物、醯基膦氧化合物、及聯咪唑化合物所成群組中選出的聚合起始劑為佳,以包含O-醯基肟化合物的聚合起始劑更佳。 The polymerization initiator (D) is obtained by polymerizing at least one selected from the group consisting of an O-fluorenyl oxime compound, an phenalkyl ketone compound, a triazine compound, a fluorenyl phosphino compound, and a biimidazole compound. The initiator is preferred, and a polymerization initiator containing an O-fluorenyl oxime compound is more preferred.

著色硬化性樹脂組成物中,聚合起始劑(D)的含有量,相對於樹脂(B)及聚合性化合物(C)的合計量100質量份,以0.1至30質量份為佳,以1至20質量份更佳。聚合起始劑(D)的含有量如在前述的範圍內時,經高靈敏化而有曝光時間縮短的傾向,因此彩色濾光片的生產性會提 高。 The content of the polymerization initiator (D) in the colored curable resin composition is preferably from 0.1 to 30 parts by mass relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C), and is preferably 1 to 30 parts by mass. It is more preferably 20 parts by mass. When the content of the polymerization initiator (D) is within the aforementioned range, the high sensitivity will tend to shorten the exposure time, so the productivity of the color filter will be improved. high.

<溶劑(E)> <Solvent (E)>

溶劑(E)而言,沒有特別的限定,可使用在該領域通常使用的溶劑。其例可列舉如:酯溶劑(在分子內含有-COO-而不含-O-的溶劑)、醚溶劑(分子內含有-O-而不含-COO-的溶劑)、醚酯溶劑(分子內含有-COO-及-O-的溶劑)、酮溶劑(分子內含有-CO-而不含-COO-的溶劑)、醇溶劑(分子內含有OH而不含-O-、-CO-及-COO-的溶劑)、芳烴溶劑、醯胺溶劑及二甲基亞碸等。 The solvent (E) is not particularly limited, and solvents commonly used in this field can be used. Examples include ester solvents (solvents containing -COO- but not -O- in the molecule), ether solvents (solvents containing -O- but -COO- not in the molecule), and ether ester solvents (molecule Solvents containing -COO- and -O-), ketone solvents (solvents containing -CO- but not -COO- in the molecule), alcohol solvents (containing OH in the molecule but -O-, -CO- and -COO- solvents), aromatic hydrocarbon solvents, amidine solvents and dimethyl sulfene.

酯溶劑係可列舉如:乳酸甲酯、乳酸乙酯、乳酸丁酯、2-羥基異丁酸甲酯、乙酸乙酯、乙酸正丁酯、乙酸異丁酯、甲酸戊酯、乙酸異戊酯、丙酸丁酯、丁酸異丙酯、丁酸乙酯、丁酸丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、乙酸環己醇酯及γ-丁內酯等。 Examples of the ester solvent system include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and isoamyl acetate. , Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, acetic acid Cyclohexanol ester and γ-butyrolactone.

醚溶劑係可列舉如:乙二醇單甲醚、乙二醇單乙醚、乙二醇單丙醚、乙二醇單丁醚、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丁醚、丙二醇單甲醚、丙二醇單乙醚、丙二醇單丙醚、丙二醇單丁醚、3-甲氧基-1-丁醇、3-甲氧基-3-甲基丁醇、四氫呋喃、四氫吡喃、1,4-二噁烷、二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇甲基乙醚、二乙二醇二丙醚、二乙二醇二丁醚、苯甲醚、苯基乙醚及甲基苯甲醚等。 Examples of the ether solvent system include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and two Ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, Tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol dipropyl ether, diethylene glycol Dibutyl ether, anisole, phenyl ether and methyl anisole.

醚酯溶劑係可列舉如:甲氧基乙酸甲酯、 甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯、乙酸3-甲氧基丁酯、乙酸3-甲基-3-甲氧基丁酯、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、丙二醇單丙醚乙酸酯、乙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、二乙二醇單乙醚乙酸酯及二乙二醇單丁醚乙酸酯等。 Examples of the ether ester solvent system include: methyl methoxyacetate, Ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Methyl ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2- Methyl ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, acetic acid 3 -Methoxybutyl, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether Acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like.

酮溶劑係可列舉如:4-羥基-4-甲基-2-戊酮、丙酮、2-丁酮、2-庚酮、3-庚酮、4-庚酮、4-甲基-2-戊酮、環戊酮、環己酮及異佛爾酮(isophorone)等。 Examples of the ketone solvent system include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, and 4-methyl-2- Pentanone, cyclopentanone, cyclohexanone and isophorone.

醇溶劑係可列舉如:甲醇、乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、丙二醇及甘油等。 Examples of the alcohol solvent system include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerol.

芳烴溶劑係可列舉如:苯、甲苯、二甲苯及1,3,5-三甲苯等。 Examples of the aromatic solvent system include benzene, toluene, xylene, and 1,3,5-trimethylbenzene.

醯胺溶劑係可列舉如:N,N-二甲基甲醯胺、N,N-二甲基乙醯胺及N-甲基吡咯啶酮等。 Examples of the amidine solvent system include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

上述的溶劑中,由塗佈性,乾燥性之觀點,以1氣壓下的沸點為120℃以上210℃以下的有機溶劑為佳。溶劑係可列舉如:丙二醇單甲醚乙酸酯、乳酸乙酯、丙二醇單甲醚、3-乙氧基丙酸乙酯、乙二醇單甲醚、二乙二醇單甲醚、二乙二醇單乙醚、4-羥基-4-甲基-2-戊酮及 N,N-二甲基甲醯胺為佳,丙二醇單甲醚乙酸酯、丙二醇單甲醚、N,N-二甲基甲醯胺、N-甲基吡咯啶酮及3-乙氧基丙酸乙酯更佳。 Among the solvents mentioned above, organic solvents having a boiling point of 1 ° C or higher and 210 ° C or lower at 1 atmosphere are preferred from the viewpoints of coating properties and drying properties. Examples of the solvent system include propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diethyl ether. Glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone and N, N-dimethylformamide is preferred, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, N, N-dimethylformamide, N-methylpyrrolidone and 3-ethoxy Ethyl propionate is more preferred.

溶劑(E)的含有量,相對於本發明的著色硬化性樹脂組成物的總量,以70至95質量%為佳,以75至92質量%更佳是。換言之,著色硬化性樹脂組成物的固形分的總量,以5至30質量%為佳,以8至25質量%更佳。溶劑(E)的含有量在前述的範圍內時,塗佈時的平坦性變佳,且在形成彩色濾光片時之色濃度不會不足,故顯示特性會有變佳的傾向。 The content of the solvent (E) is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass based on the total amount of the colored curable resin composition of the present invention. In other words, the total solid content of the colored curable resin composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. When the content of the solvent (E) is within the aforementioned range, the flatness at the time of coating is improved, and the color density is not insufficient when forming a color filter, so the display characteristics tend to be improved.

<其他的成分> <Other ingredients>

本發明的著色硬化性樹脂組成物可依所需而含有聚合起始助劑、調平劑、填充劑、其他的高分子化合物、密著促進劑、抗氧化劑、光安定劑及鏈轉移劑等在本行業技術領域中之習知的添加劑。 The colored curable resin composition of the present invention may contain a polymerization initiation aid, a leveling agent, a filler, other polymer compounds, an adhesion promoter, an antioxidant, a light stabilizer, a chain transfer agent, and the like, as required. Conventional additives in the technical field of the industry.

<著色硬化性樹脂組成物的製造方法> <Manufacturing method of colored curable resin composition>

本發明的著色硬化性樹脂組成物係可藉由混合著色劑(A)、樹脂(B)、聚合性化合物(C)、聚合起始劑(D)、溶劑(E),以及依所需而使用的調平劑、聚合起始助劑及其他成分而調製。 The colored curable resin composition of the present invention can be mixed with a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a solvent (E), and as needed. It is prepared by using a leveling agent, a polymerization initiator, and other ingredients.

顏料(P)係以預先與溶劑(E)的一部分或全部混合,使顏料的平均粒徑成為0.2μm以下左右之方式,使用珠磨機等加以分散者為佳。這時,可依所需而調配前述顏料分散劑、樹脂(B)的一部分或全部。在如此所得的顏 料分散液中,可藉由混合其餘的成分使成為預定的濃度,即可調製目的之著色硬化性樹脂組成物。 The pigment (P) is preferably mixed with a part or all of the solvent (E) in advance so that the average particle diameter of the pigment is about 0.2 μm or less. It is preferably dispersed using a bead mill or the like. In this case, a part or all of the pigment dispersant and the resin (B) may be blended as necessary. In this way In the material dispersion, the intended coloring curable resin composition can be prepared by mixing the remaining components to a predetermined concentration.

著色劑(A)中,作為染料,可添加包含預先在溶劑(E)的一部分或全部溶解所得的染料的溶液。該溶液在與其他成分混合之前,以通過孔徑0.01至1μm左右的過濾器過濾為佳。 To the colorant (A), as the dye, a solution containing a dye obtained by dissolving a part or all of the solvent (E) in advance may be added. This solution is preferably filtered through a filter with a pore size of about 0.01 to 1 μm before being mixed with other ingredients.

上述經混合所得的著色硬化性樹脂組成物係以通過孔徑0.1至10μm左右的過濾器過濾為佳。 The coloring curable resin composition obtained by the above-mentioned mixing is preferably filtered through a filter having a pore size of about 0.1 to 10 μm.

<塗膜的製造方法> <Manufacturing method of coating film>

本發明的塗膜係由本發明的著色硬化性樹脂組成物形成。該塗膜係可藉由使該著色硬化性樹脂組成物硬化而形成。本發明的塗膜可含有後述的著色圖案。將該著色硬化性樹脂組成物硬化的方法係如後述。 The coating film of the present invention is formed of the colored curable resin composition of the present invention. The coating film can be formed by curing the colored curable resin composition. The coating film of this invention may contain the coloring pattern mentioned later. A method for curing the colored curable resin composition is described later.

<彩色濾光片的製造方法> <Manufacturing Method of Color Filter>

本發明的彩色濾光片係由本發明的著色硬化性樹脂組成物形成。該彩色濾光片係可藉由使該著色硬化性樹脂組成物硬化而形成。 The color filter of the present invention is formed of the coloring curable resin composition of the present invention. The color filter can be formed by curing the colored curable resin composition.

該彩色濾光片係例如可將該著色硬化性樹脂組成物塗佈在基板上,再使其乾燥而形成著色組成物層,再隔著光罩使該著色組成物層曝光而得。本發明的彩色濾光片通常在塗膜上具有著色圖案。 The color filter is obtained by, for example, coating the colored curable resin composition on a substrate, and drying the colored curable resin composition to form a colored composition layer, and exposing the colored composition layer through a photomask. The color filter of the present invention usually has a colored pattern on a coating film.

由本發明的著色硬化性樹脂組成物製造著色圖案的方法係可列舉如:光刻法,噴墨法,印刷法等。其中尤以光刻法為佳。光刻法係將前述硬化性樹脂組成物 塗佈在基板上,使其乾燥而形成著色組成物層,再隔著光罩使該組成物層曝光而顯影的方法。 Examples of a method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithography method, an inkjet method, and a printing method. Among them, photolithography is particularly preferred. The photolithography method is based on the aforementioned curable resin composition. A method of coating on a substrate and drying it to form a colored composition layer, and then exposing and developing the composition layer through a photomask.

光刻法中,在曝光時不用光罩,及/或不顯影,即可形成上述著色組成物層的硬化物的塗膜。如此形成的著色圖案及著色塗膜即為本發明的彩色濾光片。 In the photolithography method, a coating film of the cured product of the coloring composition layer described above can be formed without using a mask and / or without development during exposure. The coloring pattern and the coloring coating film thus formed are the color filters of the present invention.

上述彩色濾光片的膜厚並無特別限定,可視目的及用途等而適當地調整,例如為0.1至30μm,以0.1至20μm為佳,以0.5至6μm更佳。 The film thickness of the color filter is not particularly limited and may be appropriately adjusted depending on the purpose and application, and is, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

基板係可使用石英玻璃、硼矽酸玻璃、鋁矽酸鹽玻璃、表面經氧化矽塗覆的鈉鈣玻璃等的玻璃板;聚碳酸酯、聚甲基丙烯酸甲酯、聚對苯二甲酸乙二酯等的樹脂板;矽;在前述基板上形成有鋁、銀、銀/銅/鈀合金薄膜等者。在該等的基板上,可形成其它的彩色濾光片層、樹脂層、電晶體、電路等。 The substrate can be glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, and soda-lime glass coated with silicon oxide; polycarbonate, polymethyl methacrylate, and polyethylene terephthalate Resin plates such as diesters; silicon; aluminum, silver, silver / copper / palladium alloy films, and the like are formed on the substrate. On such substrates, other color filter layers, resin layers, transistors, and circuits can be formed.

以光刻法的各色像素之形成係可使用習知或慣用的裝置及條件實施。例如,可如下述的方式製作。 The formation of pixels of various colors by photolithography can be performed using known or customary devices and conditions. For example, it can be produced as follows.

首先,將著色硬化性樹脂組成物塗佈在基板上,藉由加熱乾燥(預焙)及/或減壓乾燥而將溶劑等的揮發成分去除並乾燥,得到平滑的著色組成物層。 First, a colored curable resin composition is coated on a substrate, and volatile components such as solvents are removed and dried by heating (pre-baking) and / or drying under reduced pressure to obtain a smooth colored composition layer.

塗佈方法係可列舉如:旋轉塗佈法,狹縫塗佈法,狹縫-旋轉塗佈法等。 Examples of the coating method include a spin coating method, a slit coating method, and a slit-spin coating method.

進行加熱乾燥時的溫度係以30至120℃為佳,50至110℃更佳。又加熱時間係以10秒鐘至60分鐘為佳,以30秒鐘至30分鐘更佳。 The temperature for heating and drying is preferably 30 to 120 ° C, and more preferably 50 to 110 ° C. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.

進行減壓乾燥時,以在50至150Pa的壓力下,20至25℃的溫度範圍進行為佳。 When drying under reduced pressure, it is preferably performed at a temperature in the range of 20 to 25 ° C under a pressure of 50 to 150 Pa.

著色組成物層的膜厚並無特別限定,可視目的之彩色濾光片的膜厚而適當地選擇。 The film thickness of the colored composition layer is not particularly limited, and may be appropriately selected depending on the film thickness of the intended color filter.

其次,著色組成物層係隔著用以形成目的之著色圖案的光罩而曝光。該光罩上的圖案並無特別限定,可使用因應目的之用途的圖案。 Next, the colored composition layer is exposed through a photomask for forming a desired colored pattern. The pattern on the photomask is not particularly limited, and a pattern according to the purpose of use can be used.

曝光所用的光源係以產生250至450nm的波長的光之光源為佳。例如,可將未達350nm的光,使用將此波長區域割除的濾光片割除,或將436nm附近,408nm附近,365nm附近的光,以取出該等的波長區域的帶通濾光片選擇取出。具體上可列舉如:水銀燈,發光二極體,金屬鹵素燈,鹵素燈等。 The light source used for the exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, you can remove the light below 350nm by using a filter cut out of this wavelength range, or you can select the bandpass filter in the wavelength range of 436nm, 408nm, and 365nm. . Specific examples include: mercury lamps, light-emitting diodes, metal halogen lamps, halogen lamps, and the like.

由於可在曝光面全面均勻照射平行光線,或在形成有光罩及著色組成物層的基板的正確對準位置,故以使用光罩對準器及步進器等的曝光裝置為佳。 Since the parallel light can be irradiated uniformly on the entire exposure surface or at the correct alignment position of the substrate on which the photomask and the coloring composition layer are formed, an exposure device using a photomask aligner and a stepper is preferred.

藉由使曝光後的著色組成物層與顯影液接觸而顯影,而可在基板上形成著色圖案。經由顯影,著色組成物層的未曝光部會被顯影液溶解而去除。 A colored pattern is formed on the substrate by developing the colored composition layer after exposure by contacting with a developing solution. The unexposed portion of the colored composition layer is dissolved and removed by the developing solution through development.

顯影液係以氫氧化鉀、碳酸氫鈉、碳酸鈉、氫氧化四甲基銨等鹼性化合物的水溶液為佳。該等鹼性化合物的水溶液中的濃度係以0.01至10質量%為佳,以0.03至5質量%更佳。再者,顯影液可含有界面活性劑。 The developing solution is preferably an aqueous solution of a basic compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide. The concentration of the basic compound in the aqueous solution is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. Furthermore, the developing solution may contain a surfactant.

顯影方法可為漿法(paddle method),浸漬法 及噴霧法等的任一種。再者,在顯影時可將基板以任意的角度傾斜。 The developing method may be a paddle method or a dipping method. And spray method. Furthermore, the substrate can be tilted at an arbitrary angle during development.

顯影後以進行水洗為佳。 After development, washing with water is preferred.

再者,以所得著色圖案進行後焙為佳。後焙溫度係以150至250℃為佳,以160至235℃更佳。後焙時間係以1至120分鐘為佳,以10至60分鐘更佳。 Furthermore, post-baking is preferably performed with the obtained colored pattern. The post-baking temperature is preferably 150 to 250 ° C, and more preferably 160 to 235 ° C. The post-baking time is preferably 1 to 120 minutes, and more preferably 10 to 60 minutes.

[實施例] [Example]

以下,以實施例更詳細說明本發明,但本發明不受該等的實施例所限定。例中,代表含有量乃至使用量%及份如無特別註明時均為質量基準。 Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited to these examples. In the examples, the representative content and even the usage% and parts are based on quality unless otherwise specified.

在以下的合成例中,化合物的構造係以質量分析(LC;Agilent製1200型,MASS;Agilent製LC/MSD型)確認。 In the following synthesis examples, the structure of the compound was confirmed by mass analysis (LC; Model 1200 manufactured by Agilent, MASS; Model LC / MSD manufactured by Agilent).

實施例1:式(A-I-a6a)所示之化合物的合成 Example 1: Synthesis of a compound represented by formula (A-I-a6a)

投入硫氰酸鉀36.3份及丙酮160份之後,在室溫下攪拌30分鐘。繼而,將苯甲醯氯(東京化成(股)公司製)50份以10分鐘滴入。滴入終了後,再在室溫下攪拌2小時。繼而,將反應混合物冰冷後,滴入N-乙基-鄰-甲苯胺(東京化成(股)公司製)45.7份。滴入終了後,再在室溫下攪拌30分鐘。繼而,將反應混合物冰冷後,滴入30%氫氧化鈉水溶液34.2份。滴入終了後,再在室溫下攪拌30分鐘。繼而,在室溫下滴入氯乙酸35.3份。滴入終了後,加熱回流下攪拌7小時。繼而,將反應混合物放冷至室溫後,將反應溶液注入於自來水120份中之後添加甲苯200份攪拌30 分鐘。接著停止攪拌,靜置30分鐘後,分離為有機層及水層。將水層以分液操作廢棄後,將有機層以1當量鹽酸200份清洗,繼而以自來水200份清洗,最後以飽和食鹽水200份清洗。 After adding 36.3 parts of potassium thiocyanate and 160 parts of acetone, the mixture was stirred at room temperature for 30 minutes. Then, 50 parts of benzamidine chloride (manufactured by Tokyo Kasei Co., Ltd.) was dropped over 10 minutes. After the addition was completed, the mixture was stirred at room temperature for another 2 hours. Then, after cooling the reaction mixture under ice, 45.7 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After the addition was completed, the mixture was stirred at room temperature for another 30 minutes. Then, after the reaction mixture was ice-cooled, 34.2 parts of a 30% sodium hydroxide aqueous solution was added dropwise. After the addition was completed, the mixture was stirred at room temperature for another 30 minutes. Then, 35.3 parts of chloroacetic acid was added dropwise at room temperature. After the dropping was completed, the mixture was stirred under reflux for 7 hours. Next, after the reaction mixture was allowed to cool to room temperature, the reaction solution was poured into 120 parts of tap water, and then 200 parts of toluene was added and stirred for 30 minutes. minute. Then, the stirring was stopped, and after standing for 30 minutes, it was separated into an organic layer and an aqueous layer. After the aqueous layer was discarded in a liquid separation operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, then 200 parts of tap water, and finally 200 parts of saturated saline.

在有機層添加適當量的芒硝並攪拌30分鐘後,過濾而得到除去水分的有機層。將所得的有機層以蒸發器餾除溶媒,得到淡黄色液體。將所得的淡黄色液體以管柱層析法精製。將精製的淡黄色液體減壓乾燥,得到式(B-I-1)所示之化合物52份。 An appropriate amount of thenardite was added to the organic layer and stirred for 30 minutes, and then filtered to obtain an organic layer from which water was removed. The solvent was distilled off from the obtained organic layer by an evaporator to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried under reduced pressure to obtain 52 parts of a compound represented by the formula (B-I-1).

將4,4-二胺基二苯基酮(東京化成工業(股)製)21.2份、三乙氧基矽烷(東京化成工業(股)製)38.6份及乙酸10份,在四氫呋喃200份中,回流8小時。反應終了後,將四氫呋喃餾除,得到式(A-I-a6-1)所示之化合物60份。 21.2 parts of 4,4-diaminodiphenyl ketone (manufactured by Tokyo Chemical Industry Co., Ltd.), 38.6 parts of triethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 10 parts of acetic acid are added to 200 parts of tetrahydrofuran , Reflux for 8 hours. After the reaction was completed, tetrahydrofuran was distilled off to obtain 60 parts of a compound represented by the formula (A-I-a6-1).

將上述所得的式(A-I-a6-1)所示之化合物 29.6份、式(B-I-1)所示之化合物14.7份及甲苯20份投入後,繼而,添加三氯一氧化磷23份而在95至100℃下攪拌3小時。繼而,將反應混合物冷卻至室溫後,以異丙醇170份稀釋。繼而,將稀釋的反應溶液注入飽和食鹽水300份中之後,添加甲苯100份而攪拌30分鐘。停止攪拌,靜置30分鐘,分離為有機層及水層。將水層以分液操作廢棄後,將有機層以飽和食鹽水300份清洗。在有機層添加適當量的硫酸鈉而攪拌30分鐘後,過濾而得除去水分的有機層。將所得的有機層以蒸發器餾除溶媒,得到青紫色固體。再將青紫色固體減壓乾燥,得到式(A-I-a6a)所示之化合物42.1份。 The compound represented by the formula (A-I-a6-1) obtained above After 29.6 parts, 14.7 parts of the compound represented by the formula (B-I-1) and 20 parts of toluene were added, 23 parts of phosphorus trichloride was added, and the mixture was stirred at 95 to 100 ° C for 3 hours. Then, the reaction mixture was cooled to room temperature, and then diluted with 170 parts of isopropanol. Next, after pouring the diluted reaction solution into 300 parts of saturated saline, 100 parts of toluene was added and stirred for 30 minutes. The stirring was stopped, and the mixture was allowed to stand for 30 minutes, and separated into an organic layer and an aqueous layer. After the aqueous layer was discarded in a liquid separation operation, the organic layer was washed with 300 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer and stirred for 30 minutes, and then filtered to obtain an organic layer from which water was removed. The solvent was distilled off from the obtained organic layer by an evaporator to obtain a blue-violet solid. The blue-violet solid was dried under reduced pressure to obtain 42.1 parts of a compound represented by the formula (A-I-a6a).

式(A-I-a6a)所示之化合物的鑑定 Identification of the compound represented by formula (A-I-a6a)

(質量分析)離子化模式=ESI+:m/z=855.4[M-Cl]+精確質量:890.4 (Mass analysis) Ionization mode = ESI +: m / z = 855.4 [M-Cl] + Exact mass: 890.4

實施例2:式(A-I-a6b)所示之化合物的合成 Example 2: Synthesis of a compound represented by formula (A-I-a6b)

將式(A-I-a6-2)所示之化合物4.2份、雙(三氟甲磺醯基)亞胺鋰(東京化成(股)公司製)2.8份及N,N-二甲基甲醯胺30份投入後,在40℃攪拌3小時。繼而,將反應混合物冷卻 至室溫後,以1小時一邊攪拌一邊滴入自來水500份,得到暗藍色懸浮液。將所得懸浮液過濾,得到青綠色固體。再將青綠色固體減壓乾燥,得到式(A-I-a6b)所示之化合物11.2份。 4.2 parts of a compound represented by formula (AI-a6-2), 2.8 parts of lithium bis (trifluoromethanesulfonyl) imide (manufactured by Tokyo Chemical Industry Co., Ltd.), and N, N-dimethylformamide After 30 parts were added, the mixture was stirred at 40 ° C for 3 hours. The reaction mixture is then cooled After reaching room temperature, 500 parts of tap water was added dropwise with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to give a turquoise solid. The blue-green solid was dried under reduced pressure to obtain 11.2 parts of a compound represented by the formula (A-I-a6b).

將式(A-I-a6a)及式(A-I-a6b)所示之化合物0.35份溶解於三氯甲烷使體積成為250cm3,將其中的2cm3以離子交換水稀釋使體積成為100cm3(濃度:0.028g/L),使用分光光度計(石英槽,光徑長度;1cm)測定吸收光譜。該化合物的極大吸收波長:λ max分別為638nm及639nm。 The compound of formula (AI-a6a) and formula (AI-a6b) 0.35 parts of FIG was dissolved in chloroform so that the volume becomes 250cm 3, 2cm 3 wherein the ion exchanged water so that the volume becomes 100cm 3 (concentration: 0.028 g / L), and the absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length; 1 cm). The maximum absorption wavelength of this compound: λ max is 638 nm and 639 nm, respectively.

實施例3:式(A-VI-2a)所示之化合物的合成 Example 3: Synthesis of a compound represented by formula (A-VI-2a)

實施例1中,除了使用N-1-乙基-萘基胺(東京化成(股)公司製)取代式(B-I-1)以外,與實施例1進行同樣合成,得到式(A-VI-2a)所示之化合物。 In Example 1, except that N-1-ethyl-naphthylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of formula (BI-1), the same synthesis was performed as in Example 1 to obtain formula (A-VI- 2a).

式(A-VI-2a)所示之化合物的鑑定 Identification of the compound represented by formula (A-VI-2a)

(質量分析)離子化模式=ESI+:m/z=719.0[M-Cl]+精確質量:754.5 (Mass analysis) ionization mode = ESI +: m / z = 719.0 [M-Cl] + exact mass: 754.5

實施例4:式(A-VI-2b)所示之化合物的合成 Example 4: Synthesis of a compound represented by formula (A-VI-2b)

實施例2中,除了使用式(A-VI-2a)表示的化合物取代式(A-I-a6a)以外,與實施例2進行同樣合成,得到式(A-VI-2b)所示之化合物。 In Example 2, a compound represented by the formula (A-VI-2b) was obtained in the same manner as in Example 2 except that the compound represented by the formula (A-VI-2a) was used instead of the formula (A-I-a6a).

將式(A-VI-2a)及式(A-VI-2b)所示之化合物0.35份溶解於三氯甲烷使體積成為250cm3,將其中的2cm3以離子交換水稀釋使體積成為100cm3(濃度:0.028g/L),使用分光光度計(石英槽,光徑長度;1cm)測定吸收光譜。該化合物的極大吸收波長:λ max分別為615nm及617nm。 The compound of formula (A-VI-2a) and of formula (A-VI-2b) 0.35 parts of FIG dissolved in chloroform so that the volume becomes 250cm 3, 2cm 3 wherein the ion exchanged water so that the volume becomes 100cm 3 (Concentration: 0.028 g / L), and an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length; 1 cm). The maximum absorption wavelength of this compound: λ max is 615 nm and 617 nm, respectively.

〈溶解度的測定〉 <Measurement of solubility>

對實施例1至4所得的化合物與式(II-0)所示之化合物,在丙二醇單甲醚(以下,簡稱為PGME)、乳酸乙酯(以下,簡稱為EL)、丙二醇單甲醚乙酸酯(以下,簡稱為PGMEA)的溶解度,如以下的方式求得。 For the compounds obtained in Examples 1 to 4 and the compound represented by formula (II-0), propylene glycol monomethyl ether (hereinafter, referred to as PGME), ethyl lactate (hereinafter, referred to as EL), and propylene glycol monomethyl ether The solubility of an acid ester (hereinafter, simply referred to as PGMEA) was determined as follows.

在50mL試樣管中,以下述比率將化合物與上述溶媒混合,之後,將試樣管密封,在30℃以超音波振動機振動3分鐘。繼而在室溫放置30分鐘後,抽吸過濾, 以目視觀察其殘渣。無法確認有不溶物時,判斷溶解性良好而記錄為○,確認有不溶物時判斷為溶解性不佳而記錄為×。結果示於表1。 The compound was mixed with the solvent in a 50 mL sample tube at the following ratio, and then the sample tube was sealed and shaken at 30 ° C. for 3 minutes with an ultrasonic vibration machine. After 30 minutes at room temperature, suction filtration was performed. Visually observe the residue. When insoluble matter cannot be confirmed, the solubility is judged to be good and recorded as ○, and when insoluble matter is confirmed, it is judged to be poor in solubility and recorded as x. The results are shown in Table 1.

[樹脂的合成] [Synthesis of resin]

具備有回流冷凝器、滴液漏斗及攪拌機的燒瓶內注入適量的氮氣而成為氮氣環境,饋入丙二醇單甲醚乙酸酯100份,在攪拌中加熱至85℃。繼而,在該燒瓶內,將甲基丙烯酸19份、3,4-環氧三環[5.2.1.02,6]癸烷-8-基丙烯酸酯及3,4-環氧三環[5.2.1.02,6]癸烷-9-基丙烯酸酯的混合物(含有比例以莫耳比為50:50)(商品名「E-DCPA」,股份公司DAICEL製)171份溶解於丙二醇單甲醚乙酸酯40份的溶 液,使用滴液幫浦約以5小時滴入。另一方面,將聚合起始劑2,2’-偶氮雙(2,4-二甲基戊腈)26份溶解於丙二醇單甲醚乙酸酯120份的溶液使用另外的滴液幫浦約以5小時滴入燒瓶內。聚合起始劑的滴入終了後,保持同溫度約3小時,之後冷卻至室溫,得到固形分43.5%的共聚物(樹脂(B-1))的溶液。 A flask equipped with a reflux condenser, a dropping funnel, and a stirrer was filled with an appropriate amount of nitrogen to create a nitrogen atmosphere. 100 parts of propylene glycol monomethyl ether acetate was fed, and heated to 85 ° C. while stirring. Then, 19 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 2,6 ] decane-8-yl acrylate and 3,4-epoxytricyclo [5.2. 1.0 2,6 ] A mixture of decane-9-yl acrylate (containing a molar ratio of 50:50) (trade name "E-DCPA", manufactured by Daicel Co., Ltd.) was dissolved in propylene glycol monomethyl ether ethyl A solution of 40 parts of the acid ester was dripped in for about 5 hours using a dripping pump. On the other hand, a solution in which 26 parts of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in 120 parts of propylene glycol monomethyl ether acetate was used with another dropping pump. It was dropped into the flask in about 5 hours. After the dripping of the polymerization initiator was completed, the temperature was kept at the same temperature for about 3 hours, and then cooled to room temperature to obtain a solution of the copolymer (resin (B-1)) having a solid content of 43.5%.

所得的樹脂(B-1)的重量平均分子量為8000,分子量分佈為1.98,固形分換算的酸值為53mg-KOH/g。 The weight average molecular weight of the obtained resin (B-1) was 8000, the molecular weight distribution was 1.98, and the acid value in terms of solid content was 53 mg-KOH / g.

[著色硬化性樹脂組成物的調製] [Preparation of colored curable resin composition]

實施例5 Example 5

將:著色劑(A):式(A-I-a6a)所示之染料 2.5份;樹脂(B):樹脂(B-1)(固形分換算) 50份;聚合性化合物(C):二新戊四醇六丙烯酸酯(KAYARAD(註冊商標)DPHA;日本化藥(股)製) 16份;聚合起始劑(D):N-苄醯氧基-1-(4-苯基硫苯基)辛烷-1-酮-2-亞胺(Irgacure(註冊商標)OXE-01;BASF公司製;O-醯基肟化合物) 4.1份;溶劑(E):丙二醇單甲醚乙酸酯 120份;及4-羥-4-甲基-2-戊酮 380份; 調平劑(H):聚醚改質聚矽氧油(TORAY SILICONE SH8400;東麗道康寧(股)製) 0.12份;混合而得著色硬化性樹脂組成物。 Colorant (A): 2.5 parts of dye represented by formula (AI-a6a); Resin (B): Resin (B-1) (solid content conversion) 50 parts; Polymerizable compound (C): dioxin Tetraol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 16 parts; polymerization initiator (D): N-benzyloxy-1- (4-phenylthiophenyl) Octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Corporation; O-fluorenyl oxime compound) 4.1 parts; solvent (E): propylene glycol monomethyl ether acetate 120 parts; And 380 parts of 4-hydroxy-4-methyl-2-pentanone; Leveling agent (H): 0.12 part of polyether modified silicone oil (TORAY SILICONE SH8400; manufactured by Toray Dow Corning Co., Ltd.); mixed to obtain a colored hardening resin composition.

實施例6 Example 6

將:著色劑(A):式(A-I-a6b)所示之染料 2.5份;樹脂(B):樹脂(B-1)(固形分換算) 50份;聚合性化合物(C):二新戊四醇六丙烯酸酯(KAYARAD(註冊商標)DPHA;日本化藥(股)製) 16份;聚合起始劑(D):N-苄醯氧基-1-(4-苯基硫苯基)辛烷-1-酮-2-亞胺(Irgacure(註冊商標)OXE-01;BASF公司製;O-醯基肟化合物) 4.1份;溶劑(E):丙二醇單甲醚乙酸酯 120份;及4-羥基-4-甲基-2-戊酮 380份;調平劑(H):聚醚改質聚矽氧油(TORAY SILICONE SH8400;東麗道康寧(股)製) 0.12份;混合而得著色硬化性樹脂組成物。 Colorant (A): 2.5 parts of dye represented by formula (AI-a6b); Resin (B): Resin (B-1) (solid content conversion) 50 parts; Polymerizable compound (C): dioxin Tetraol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 16 parts; polymerization initiator (D): N-benzyloxy-1- (4-phenylthiophenyl) Octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Corporation; O-fluorenyl oxime compound) 4.1 parts; solvent (E): propylene glycol monomethyl ether acetate 120 parts; And 380 parts of 4-hydroxy-4-methyl-2-pentanone; leveling agent (H): 0.12 parts of polyether modified silicone oil (TORAY SILICONE SH8400; manufactured by Toray Dow Corning Co., Ltd.); A colored curable resin composition was obtained.

實施例7 Example 7

將:著色劑(A):式(A-VI-2a)所示之染料 2.5份;樹脂(B):樹脂(B-1)(固形分換算) 50份;聚合性化合物(C):二新戊四醇六丙烯酸酯(KAYARAD(註冊商標)DPHA;日本化藥(股)製) 16份;聚合起始劑(D):N-苄醯氧基-1-(4-苯基硫 苯基)辛烷-1-酮-2-亞胺(Irgacure(註冊商標)OXE-01;BASF公司製;O-醯基肟化合物) 4.1份;溶劑(E):丙二醇單甲醚乙酸酯 120份;及4-羥基-4-甲基-2-戊酮 380份;調平劑(H):聚醚改質聚矽氧油(TORAY SILICONE SH8400;東麗道康寧(股)製) 0.12份;混合而得著色硬化性樹脂組成物。 The colorant (A): 2.5 parts of the dye represented by the formula (A-VI-2a); the resin (B): the resin (B-1) (solid content conversion) 50 parts; the polymerizable compound (C): two 16 parts of neopentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.); polymerization initiator (D): N-benzyloxy-1- (4-phenylsulfide) Phenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Corporation; O-fluorenyl oxime compound) 4.1 parts; solvent (E): propylene glycol monomethyl ether acetate 120 parts; and 380 parts of 4-hydroxy-4-methyl-2-pentanone; Leveling agent (H): Polyether modified polysiloxane (TORAY SILICONE SH8400; Toray Dow Corning Co., Ltd.) 0.12 parts ; Mixed to obtain a colored curable resin composition.

實施例8 Example 8

將:著色劑(A):式(A-VI-2b)所示之染料 2.5份;樹脂(B):樹脂(B-1)(固形分換算) 50份;聚合性化合物(C):二新戊四醇六丙烯酸酯(KAYARAD(註冊商標)DPHA;日本化藥(股)製) 16份;聚合起始劑(D):N-苄醯氧基-1-(4-苯基硫苯基)辛烷-1-酮-2-亞胺(Irgacure(註冊商標)OXE-01;BASF公司製;O-醯基肟化合物) 4.1份;溶劑(E):丙二醇單甲醚乙酸酯 120份;及4-羥基-4-甲基-2-戊酮 380份;調平劑(H):聚醚改質聚矽氧油(TORAY SILICONE SH8400;東麗道康寧(股)製) 0.12份;混合而得著色硬化性樹脂組成物。 Colorant (A): 2.5 parts of the dye represented by the formula (A-VI-2b); Resin (B): Resin (B-1) (solid content conversion) 50 parts; Polymerizable compound (C): 2 16 parts of neopentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.); polymerization initiator (D): N-benzyloxy-1- (4-phenylthiobenzene) Octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Corporation; O-fluorenyl oxime compound) 4.1 parts; solvent (E): propylene glycol monomethyl ether acetate 120 380 parts of 4-hydroxy-4-methyl-2-pentanone; leveling agent (H): 0.12 parts of polyether modified polysiloxane (TORAY SILICONE SH8400; manufactured by Toray Dow Corning Co., Ltd.); They were mixed to obtain a colored curable resin composition.

實施例9 Example 9

將:C.I.顏料藍15:6(顏料) 4.48份 丙烯酸系顏料分散劑 1.76份丙二醇單甲醚乙酸酯 29.8份混合,使用珠磨機將顏料充分分散,繼而,將著色劑(A):式(A-I-a6a)所示之染料 2.5份;樹脂(B):樹脂(B-1)(固形分換算) 50份;聚合性化合物(C):二新戊四醇六丙烯酸酯(KAYARAD(註冊商標)DPHA;日本化藥(股)製) 16份;聚合起始劑(D):N-苄醯氧基-1-(4-苯基硫苯基)辛烷-1-酮-2-亞胺(Irgacure(註冊商標)OXE-01;BASF公司製;O-醯基肟化合物) 4.1份;溶劑(E):丙二醇單甲醚乙酸酯 100份;及4-羥基-4-甲基-2-戊酮 450份;調平劑(H):聚醚改質聚矽氧油(TORAY SILICONE SH8400;東麗道康寧(股)製) 0.12份;混合而得著色硬化性樹脂組成物。 Will: C.I. Pigment Blue 15: 6 (Pigment) 4.48 parts Acrylic pigment dispersant 1.76 parts of propylene glycol monomethyl ether acetate 29.8 parts were mixed, the pigment was sufficiently dispersed using a bead mill, and then, the colorant (A): 2.5 parts of the dye represented by the formula (AI-a6a); resin (B): 50 parts of resin (B-1) (converted by solid content); polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 16 Parts; polymerization initiator (D): N-benzyloxy-1- (4-phenylthiophenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE-01; BASF Made by the company; 4.1 parts of O-fluorenyl oxime compound); solvent (E): 100 parts of propylene glycol monomethyl ether acetate; and 450 parts of 4-hydroxy-4-methyl-2-pentanone; leveling agent (H ): 0.12 parts of polyether modified silicone oil (TORAY SILICONE SH8400; manufactured by Toray Dow Corning Co., Ltd.); mixed to obtain a colored hardening resin composition.

實施例10 Example 10

將C.I.顏料藍15:6(顏料) 2.2份丙烯酸系顏料分散劑 1.0份丙二醇單甲醚乙酸酯 14.1份混合,使用珠磨機將顏料充分分散,繼而,將著色劑(A):式(A-I-a6a)所示之染料 8.4份;C.I.酸性紅52 0.1份;樹脂(B):樹脂(B-1)(固形分換算) 50份; 聚合性化合物(C):二新戊四醇六丙烯酸酯(KAYARAD(註冊商標)DPHA;日本化藥(股)製) 16份;聚合起始劑(D):N-苄醯氧基-1-(4-苯基硫苯基)辛烷-1-酮-2-亞胺(Irgacure(註冊商標)OXE-01;BASF公司製;O-醯基肟化合物) 4.1份;溶劑(E):丙二醇單甲醚乙酸酯 100份;及4-羥基-4-甲基-2-戊酮 50份;調平劑(H):聚醚改質聚矽氧油(TORAY SILICONE SH8400;東麗道康寧(股)製) 0.12份;混合而得著色硬化性樹脂組成物。 CI Pigment Blue 15: 6 (pigment) 2.2 parts of acrylic pigment dispersant 1.0 part of propylene glycol monomethyl ether acetate 14.1 parts were mixed, the pigment was sufficiently dispersed using a bead mill, and then the colorant (A): Formula ( 8.4 parts of the dye shown by AI-a6a); CI acid red 52 0.1 parts; resin (B): resin (B-1) (solid content conversion) 50 parts; Polymerizable compound (C): 16 parts of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.); polymerization initiator (D): N-benzyloxy-1 -(4-phenylthiophenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Corporation; O-fluorenyl oxime compound) 4.1 parts; solvent (E): 100 parts of propylene glycol monomethyl ether acetate; and 50 parts of 4-hydroxy-4-methyl-2-pentanone; leveling agent (H): polyether modified silicone oil (TORAY SILICONE SH8400; Toray Dow Corning (Manufactured by the company) 0.12 parts; mixed to obtain a colored curable resin composition.

比較例2 Comparative Example 2

將:染料:式(II-0)所示之染料 2.5份;樹脂(B):樹脂(B-1)(固形分換算) 50份;聚合性化合物(C):二新戊四醇六丙烯酸酯(KAYARAD(註冊商標)DPHA;日本化藥(股)製) 16份;聚合起始劑(D):N-苄醯氧基-1-(4-苯基硫苯基)辛烷-1-酮-2-亞胺(Irgacure(註冊商標)OXE-01;BASF公司製;O-醯基肟化合物) 4.1份;溶劑(E):丙二醇單甲醚乙酸酯 100份;及4-羥基-4-甲基-2-戊酮 450份;調平劑(H):聚醚改質聚矽氧油(TORAY SILICONE SH8400;東麗道康寧(股)製) 0.12份;混合而得著色硬化性樹脂組成物。 Dye: 2.5 parts of the dye represented by the formula (II-0); Resin (B): 50 parts of the resin (B-1) (in terms of solid content); polymerizable compound (C): dipentaerythritol hexaacrylic acid Esters (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 16 parts; polymerization initiator (D): N-benzyloxy-1- (4-phenylthiophenyl) octane-1 -Keto-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Corporation; O-fluorenyl oxime compound) 4.1 parts; solvent (E): 100 parts of propylene glycol monomethyl ether acetate; and 4-hydroxyl 450 parts of 4-methyl-2-pentanone; leveling agent (H): 0.12 parts of polyether modified polysiloxane (TORAY SILICONE SH8400; manufactured by Toray Dow Corning Co., Ltd.); coloring and hardening Resin composition.

[圖案的形成] [Formation of pattern]

在2吋見方的玻璃基板(Eagle XG;康寧公司製)上,將著色硬化性樹脂組成物以旋轉塗佈法塗佈後,在100℃預焙3分鐘而得組成物層。冷卻後,將形成有組成物層的玻璃基板與石英玻璃製光罩之間隔設定為100μm,使用曝光機(TME-150RSK;Topcon(股)製),在大氣環境下,以150mJ/cm2的曝光量(365nm基準)光照射。光罩係使用形成有100μm線與間隔圖案的光罩。光照射後,將上述塗膜(膜厚2.8μm),使用含有非離子系界面活性劑0.12%及氫氧化鉀0.04%的水系顯影液在23℃浸漬顯影80秒鐘,水洗後,在烤箱中,在220℃實施後焙20分鐘,得到圖案。 The colored curable resin composition was applied on a 2-inch square glass substrate (Eagle XG; manufactured by Corning Corporation) by a spin coating method, and then prebaked at 100 ° C for 3 minutes to obtain a composition layer. After cooling, the distance between the glass substrate on which the composition layer was formed and the mask made of quartz glass was set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon) was used at 150 mJ / cm 2 in an atmospheric environment. Exposure (365 nm reference) light irradiation. The photomask is a photomask in which 100 μm line and space patterns are formed. After light irradiation, the coating film (thickness: 2.8 μm) was immersed and developed at 23 ° C. for 80 seconds using an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide. After washing with water, it was placed in an oven. After 20 minutes at 220 ° C, a pattern was obtained.

[耐熱性評定] [Heat resistance evaluation]

將著色感光性樹脂組成物的塗佈膜在200℃加熱20分鐘,將塗佈膜的加熱前後的色差(△Eab *)使用測色機(OSP-SP-200;OLYMPUS公司製)測定。將各實施例所得的塗佈膜,各分別實施以上的耐熱性評定的結果,色差(△Eab *)為10.0(實施例5)、10.1(實施例6)、11.2(實施例7)、12.0(實施例8)、7.3(實施例9)及8.5(實施例10)。對比較例2也同樣實施耐熱性評定的結果,色差(△Eab *)為40.1。 The coating film of the colored photosensitive resin composition was heated at 200 ° C. for 20 minutes, and the color difference (ΔEab *) before and after heating of the coating film was measured using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS). The coating film obtained in each example was subjected to the above-mentioned heat resistance evaluation results. The color difference (ΔEab *) was 10.0 (Example 5), 10.1 (Example 6), 11.2 (Example 7), 12.0. (Example 8), 7.3 (Example 9), and 8.5 (Example 10). The heat resistance evaluation was performed in the same manner as in Comparative Example 2. The color difference (ΔEab *) was 40.1.

包含式(A-IV)的化合物的著色硬化性樹脂組成物係可製造具有良好耐熱性的彩色濾光片。 The colored curable resin composition containing the compound of the formula (A-IV) can produce a color filter having good heat resistance.

[產業上的可利用性] [Industrial availability]

本發明的化合物對有機溶媒的溶解性優異。本發明的著色硬化性樹脂組成物含有本發明的化合物,故可由該著色硬化性樹脂組成物製作異物的產生少且品質高的彩色濾光片。 The compound of the present invention is excellent in solubility in an organic solvent. Since the colored curable resin composition of the present invention contains the compound of the present invention, a high-quality color filter with less generation of foreign matter can be produced from the colored curable resin composition.

Claims (11)

一種化合物,係以式(A-VI)所示者,式(A-VI)中,R1A至R8A各自獨立地表示氫原子、鹵原子、硝基、羥基,或碳數1至20的烷基(在構成該烷基的碳原子間可插入氧原子),R9A至R12A各自獨立地表示氫原子、可具有取代基之碳數1至20的烷基(在構成該烷基的碳原子間可插入氧原子)或可具有取代基之芳基,但是,R9A至R12A中的至少一者係下述式(iia)所示之基,Gg-表示相對陰離子,g表示任意的自然數,D表示可具有取代基之芳基,或可具有取代基之雜芳基,*-L1-Si(R144)3 (iia)式(iia)中,L1表示碳數1至12的烷二基,該烷二基所含的-CH2-可經-O-、-CO-或-NR111-取代,R111表示氫原子或碳數1至20的飽和烴基,3個R144各自獨立地表示碳數1至12的烷氧基,*表示與氮原子之鍵結。A compound represented by the formula (A-VI), In the formula (A-VI), R 1A to R 8A each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 20 carbon atoms (an oxygen may be inserted between the carbon atoms constituting the alkyl group Atom), R 9A to R 12A each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbons which may have a substituent (an oxygen atom may be inserted between carbon atoms constituting the alkyl group), or an aromatic group which may have a substituent However, at least one of R 9A to R 12A is a group represented by the following formula (iia), G g- represents a relative anion, g represents an arbitrary natural number, and D represents an aryl group which may have a substituent, Or a heteroaryl group which may have a substituent, * -L 1 -Si (R 144 ) 3 (iia) In the formula (iia), L 1 represents an alkanediyl group having 1 to 12 carbon atoms, and the alkanediyl group contains -CH 2 -may be substituted by -O-, -CO-, or -NR 111- , R 111 represents a hydrogen atom or a saturated hydrocarbon group having 1 to 20 carbon atoms, and three R 144 each independently represent an alkyl group having 1 to 12 carbon atoms Oxygen, * represents a bond with a nitrogen atom. 如申請專利範圍第1項所述之化合物,其中,R9A至R12A中的至少一者係式(ii)所示之基,式(ii)中,n表示1至8的整數,3個R14各自獨立地表示碳數1至4的烷氧基,*表示與氮原子之鍵結。The compound according to item 1 of the scope of patent application, wherein at least one of R 9A to R 12A is a base represented by formula (ii), In formula (ii), n represents an integer of 1 to 8, three R 14 each independently represent an alkoxy group having 1 to 4 carbon atoms, and * represents a bond with a nitrogen atom. 如申請專利範圍第1項所述之化合物,其中,式(A-VI)所示之化合物係式(A-II)所示之化合物,式(A-II)中,X表示氧原子或硫原子,R41至R46各自獨立地表示氫原子、可具有取代基之碳數1至20的烷基(在構成該烷基的碳原子間可插入氧原子)或可具有取代基之芳基,但是,R41至R44中的至少一者係式(iia)所示之基,*-L1-Si(R144)3 (iia)式(iia)中,L1表示碳數1至12的烷二基,該烷二基所含的-CH2-可經-O-、-CO-或-NR111-取代,R111表示氫原子或碳數1至20的1價飽和烴基,3個R144各自獨立地表示碳數1至12的烷氧基,*表示與氮原子之鍵結,R47至R54各自獨立地表示氫原子、鹵原子、硝基、羥基,或碳數1至8的烷基(在構成該烷基的碳原子間可插入氧原子),R55表示氫原子、碳數1至20的烷基,或可具有取代基之芳基,Gg-表示相對陰離子,g表示任意的自然數。The compound described in item 1 of the scope of patent application, wherein the compound represented by the formula (A-VI) is a compound represented by the formula (A-II), In the formula (A-II), X represents an oxygen atom or a sulfur atom, and R 41 to R 46 each independently represent a hydrogen atom and an alkyl group having 1 to 20 carbon atoms which may have a substituent (at the carbon atom constituting the alkyl group) An oxygen atom may be inserted in between) or an aryl group which may have a substituent. However, at least one of R 41 to R 44 is a group represented by formula (iia), * -L 1 -Si (R 144 ) 3 (iia ) In the formula (iia), L 1 represents an alkanediyl group having 1 to 12 carbon atoms, and -CH 2 -contained in the alkanediyl group may be substituted with -O-, -CO-, or -NR 111- , and R 111 represents A hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, three R 144 each independently represent an alkoxy group having 1 to 12 carbon atoms, * represents a bond with a nitrogen atom, and R 47 to R 54 each independently represent A hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms (an oxygen atom can be inserted between the carbon atoms constituting the alkyl group), and R 55 represents a hydrogen atom and an alkyl group having 1 to 20 carbon atoms Or an aryl group which may have a substituent, G g- represents a relative anion, and g represents an arbitrary natural number. 如申請專利範圍第3項所述之化合物,其中,R41至R44中的至少一者係式(ii)所示之基,式(ii)中,n表示1至8的整數,3個R14各自獨立地表示碳數1至4的烷氧基,*表示與氮原子之鍵結。The compound according to item 3 of the scope of patent application, wherein at least one of R 41 to R 44 is a group represented by formula (ii), In formula (ii), n represents an integer of 1 to 8, three R 14 each independently represent an alkoxy group having 1 to 4 carbon atoms, and * represents a bond with a nitrogen atom. 一種著色劑,係含有如申請專利範圍第1項所述之化合物。A coloring agent, which contains the compound as described in item 1 of the scope of patent application. 如申請專利範圍第5項所述之著色劑,其再含有藍色顏料。The coloring agent according to item 5 of the patent application scope, which further contains a blue pigment. 如申請專利範圍第6項所述之著色劑,其中,藍色顏料係C.I.顏料藍15:6。The coloring agent according to item 6 of the scope of patent application, wherein the blue pigment is C.I. Pigment Blue 15: 6. 一種著色硬化性樹脂組成物,係含有如申請專利範圍第5項所述之著色劑、樹脂、聚合性化合物及聚合起始劑。A coloring curable resin composition containing a coloring agent, a resin, a polymerizable compound, and a polymerization initiator as described in item 5 of the scope of patent application. 一種塗膜,係由如申請專利範圍第8項所述之著色硬化性樹脂組成物所形成者。A coating film is formed by the colored hardening resin composition as described in item 8 of the scope of patent application. 一種彩色濾光片,係由如申請專利範圍第8項所述之著色硬化性樹脂組成物所形成者。A color filter is formed of a color-hardening resin composition as described in item 8 of the scope of patent application. 一種顯示裝置,係含有如申請專利範圍第10項所述之彩色濾光片。A display device includes a color filter as described in item 10 of the scope of patent application.
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