TWI635326B - Red colored curable resin composition - Google Patents

Red colored curable resin composition Download PDF

Info

Publication number
TWI635326B
TWI635326B TW101146261A TW101146261A TWI635326B TW I635326 B TWI635326 B TW I635326B TW 101146261 A TW101146261 A TW 101146261A TW 101146261 A TW101146261 A TW 101146261A TW I635326 B TWI635326 B TW I635326B
Authority
TW
Taiwan
Prior art keywords
group
hydrocarbon group
carbon atoms
pigment
formula
Prior art date
Application number
TW101146261A
Other languages
Chinese (zh)
Other versions
TW201331712A (en
Inventor
Soyeon Park
朴昭妍
Original Assignee
Sumitomo Chemical Co., Ltd.
住友化學股份有限公司
Dongwoo Fine-Chem Co., Ltd.
東友精細化工有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Chemical Co., Ltd., 住友化學股份有限公司, Dongwoo Fine-Chem Co., Ltd., 東友精細化工有限公司 filed Critical Sumitomo Chemical Co., Ltd.
Publication of TW201331712A publication Critical patent/TW201331712A/en
Application granted granted Critical
Publication of TWI635326B publication Critical patent/TWI635326B/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0072—Preparations with anionic dyes or reactive dyes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Liquid Crystal (AREA)

Abstract

本發明係一種紅色著色硬化性樹脂組合物，其包含著色劑、樹脂、聚合性化合物及聚合起始劑，且著色劑為包含式(1a)所表示之化合物、及選自由黃色顏料、橙色顏料及紅色顏料所組成之群中之至少一種顏料者； The present invention is a red colored curable resin composition comprising a colorant, a resin, a polymerizable compound, and a polymerization initiator, and the colorant contains a compound represented by formula (1a), and is selected from a yellow pigment and an orange pigment. And at least one pigment in the group consisting of red pigments;

[式(1a)中，R1~R4相互獨立表示氫原子、碳數1~20之一價飽和烴基或可具有取代基之碳數6~10之一價芳香族烴基；R5表示-OH、-SO3 -、-SO3H等；R6及R7分別獨立表示氫原子或碳數1~6之烷基；m表示0~5之整數；a表示0或1之整數；X表示鹵素原子；R8表示碳數1~20之一價飽和烴基；R9及R10相互獨立表示氫原子或可具有取代基之碳數1~20之一價飽和烴基]。 [In formula (1a), R 1 to R 4 each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent; R 5 represents- OH, -SO 3 -, -SO 3 H and the like; and R & lt 6 R 7 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms of; m represents an integer of 0 to 5; A represents an integer of 0 or 1; X Represents a halogen atom; R 8 represents a monovalent saturated hydrocarbon group having 1 to 20 carbons; R 9 and R 10 independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbons which may have a substituent].

Description

紅色著色硬化性樹脂組合物 Red colored curable resin composition

本發明係關於一種紅色著色硬化性樹脂組合物。 The present invention relates to a red colored curable resin composition.

著色硬化性樹脂組合物可用於液晶顯示面板、電致發光面板、電漿顯示器面板等顯示器裝置中所使用之彩色濾光片之製造用途。於該著色硬化性樹脂組合物中，已知使用顏料或染料作為著色劑(鈴木八十二著，「液晶顯示器之製造流程詳解」(液晶 )，初版，日刊工業報社，2005年3月，112頁)。 The colored curable resin composition can be used in the manufacture of color filters used in display devices such as liquid crystal display panels, electroluminescence panels, and plasma display panels. In this colored curable resin composition, it is known to use a pigment or a dye as a colorant (Suzuki No. 82, "Detailed explanation of the manufacturing process of a liquid crystal display" ( liquid crystal ), First edition, Nikkan Kogyo Shimbun, March 2005, 112 pages).

對於紅色著色硬化性樹脂組合物，要求可製造高亮度之紅色彩色濾光片。 The red colored curable resin composition is required to be able to produce a red color filter with high brightness.

本發明包含以下之發明。 The present invention includes the following inventions.

[1]一種紅色著色硬化性樹脂組合物，其包含著色劑、樹脂、聚合性化合物及聚合起始劑，且著色劑為包含式(1a)所表示之化合物、及選自由黃色顏料、橙色顏料及紅色顏料所組成之群中之至少一種顏料者； [1] A red colored curable resin composition comprising a colorant, a resin, a polymerizable compound, and a polymerization initiator, and the colorant includes a compound represented by formula (1a), and is selected from a yellow pigment and an orange pigment And at least one pigment in the group consisting of red pigments;

[式(1a)中，R1~R4相互獨立表示氫原子、碳數1~20之一 價飽和烴基或可具有取代基之碳數6~10之一價芳香族烴基，該飽和烴基所含之氫原子可經碳數6~10之芳香族烴基或鹵素原子取代，該芳香族烴基所含之氫原子可經碳數1~3之烷氧基取代，上述飽和烴基所含之-CH2-可經-O-、-CO-或-NR11-取代；R1及R2可與氮原子一同形成包含氮原子之環，R3及R4可與氮原子一同形成包含氮原子之環；R5表示-OH、-SO3 -、-SO3H、-SO3 -Z+、-CO2H、-CO2 -Z+、-CO2R8、-SO3R8或-SO2NR9R10；R6及R7分別獨立表示氫原子或碳數1~6之烷基；m表示0~5之整數；於m為2以上時，複數個R5可相同亦可不同；a表示0或1之整數；X表示鹵素原子；Z+表示+N(R11)4、Na+或K+；R8表示碳數1~20之一價飽和烴基，該飽和烴基所含之氫原子可經鹵素原子取代；R9及R10相互獨立表示氫原子或可具有取代基之碳數1~20之一價飽和烴基，該飽和脂肪族烴基所含之-CH2-可經-O-、-CO-、-NH-或-NR8-取代，R9及R10亦可相互鍵結而與氮原子一同形成3~10員含氮雜環；R11相互獨立表示氫原子、碳數1~20之一價飽和烴基或碳數7~10之芳烷基]。 [In the formula (1a), R 1 to R 4 each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. The hydrogen atom contained may be substituted by an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom. The hydrogen atom contained in the aromatic hydrocarbon group may be substituted by an alkoxy group having 1 to 3 carbon atoms. The -CH contained in the saturated hydrocarbon group is -CH. 2 -may be substituted by -O-, -CO- or -NR 11- ; R 1 and R 2 may form a ring containing a nitrogen atom together with the nitrogen atom, and R 3 and R 4 may form a ring containing a nitrogen atom together with the nitrogen atom ring; R 5 represents -OH, -SO 3 -, -SO 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or - SO 2 NR 9 R 10 ; R 6 and R 7 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; m represents an integer from 0 to 5; when m is 2 or more, a plurality of R 5 may be the same or different Different; a represents an integer of 0 or 1; X represents a halogen atom; Z + represents + N (R 11 ) 4 , Na + or K + ; R 8 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. containing the hydrogen atom may be substituted with a halogen atom; R 9 and R 10 each independently represent a hydrogen atom or an optionally substituted The one having 1 to 20 carbon atoms, monovalent saturated hydrocarbon group, the saturated aliphatic hydrocarbon contained in the -CH 2 - may be -O -, - - NH- or -NR 8 - substituted, R 9 and R 10 also, - CO It can be bonded to each other to form a 3 to 10 member nitrogen-containing heterocyclic ring together with the nitrogen atom; R 11 independently of each other represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms].

[2]如上述[1]之紅色著色硬化性樹脂組合物，其中顏料係選自由C.I.顏料黃138、139、150、C.I.顏料紅177、242 及254所組成之群中之至少一種。 [2] The red colored hardening resin composition according to the above [1], wherein the pigment is selected from C.I. Pigment Yellow 138, 139, 150, C.I. Pigment Red 177, 242 And at least one of the group consisting of 254.

[3]一種紅色彩色濾光片，其係藉由如上述[1]或[2]之紅色著色硬化性樹脂組合物而形成。 [3] A red color filter formed by the red coloring curable resin composition as described in [1] or [2] above.

[4]一種顯示裝置，其包含如上述[3]之紅色彩色濾光片。 [4] A display device including the red color filter as described in [3] above.

根據本發明之紅色著色硬化性樹脂組合物，可製造高亮度之紅色彩色濾光片。 According to the red colored curable resin composition of the present invention, a red color filter with high brightness can be manufactured.

本發明之紅色著色硬化性樹脂組合物包含著色劑(A)、樹脂(B)、聚合性化合物(C)及聚合起始劑(D)。 The red colored curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D).

著色劑(A)包含式(1a)所表示之化合物(以下稱為「化合物(1a)」)及顏料(A2)。進而，著色劑(A)亦可包含染料(但是，與化合物(1a)不同)(以下有時簡稱為「染料(A3)」)。 The colorant (A) includes a compound represented by the formula (1a) (hereinafter referred to as "compound (1a)") and a pigment (A2). Further, the colorant (A) may contain a dye (however, it is different from the compound (1a)) (hereinafter sometimes referred to simply as "dye (A3)").

本發明之紅色著色硬化性樹脂組合物較佳為進而包含溶劑(E)。 The red colored curable resin composition of the present invention preferably further contains a solvent (E).

又，本發明之紅色著色硬化性樹脂組合物視需要可含有選自由聚合起始助劑(D1)及界面活性劑(F)所組成之群中的至少一種。 The red colored curable resin composition of the present invention may contain at least one selected from the group consisting of a polymerization initiator (D1) and a surfactant (F), if necessary.

再者，於本說明書中，作為各成分而例示之化合物只要無特別說明，則可單獨使用或組合複數種而使用。 In addition, in this specification, the compound exemplified as each component can be used individually or in combination of plural types unless there is particular notice.

<著色劑(A)> <Colorant (A)>

化合物(1a)係以式(1a)表示， Compound (1a) is represented by formula (1a),

[式(1a)中，R1~R4相互獨立表示氫原子、碳數1~20之一價飽和烴基或可具有取代基之碳數6~10之一價芳香族烴基，該飽和烴基所含之氫原子可經碳數6~10之芳香族烴基或鹵素原子取代，該芳香族烴基所含之氫原子可經碳數1~3之烷氧基取代，上述飽和烴基所含之-CH2-可經-O-、-CO-或-NR11-取代；R1及R2可與氮原子一同形成包含氮原子之環，R3及R4可與氮原子一同形成包含氮原子之環；R5表示-OH、-SO3 -、-SO3H、-SO3 -Z+、-CO2H、-CO2 -Z+、-CO2R8、-SO3R8或-SO2NR9R10；R6及R7分別獨立表示氫原子或碳數1~6之烷基；m表示0~5之整數；於m為2以上之時，複數個R5可相同亦可不同；a表示0或1之整數；X表示鹵素原子；Z+表示+N(R11)4、Na+或K+；R8表示碳數1~20之一價飽和烴基，該飽和烴基所含之氫原子可經鹵素原子取代；R9及R10相互獨立表示氫原子或可具有取代基之碳數1~20之一價飽和烴基，該飽和脂肪族烴基所含之-CH2-可 經-O-、-CO-、-NH-或-NR8-取代，R9及R10亦可相互鍵結而與氮原子一同形成3~10員含氮雜環；R11相互獨立表示氫原子、碳數1~20之一價飽和烴基或碳數7~10之芳烷基]。 [In the formula (1a), R 1 to R 4 each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. The hydrogen atom contained may be substituted by an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom. The hydrogen atom contained in the aromatic hydrocarbon group may be substituted by an alkoxy group having 1 to 3 carbon atoms. The -CH contained in the saturated hydrocarbon group is -CH. 2 -may be substituted by -O-, -CO- or -NR 11- ; R 1 and R 2 may form a ring containing a nitrogen atom together with the nitrogen atom, and R 3 and R 4 may form a ring containing a nitrogen atom together with the nitrogen atom ring; R 5 represents -OH, -SO 3 -, -SO 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or - SO 2 NR 9 R 10 ; R 6 and R 7 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; m represents an integer of 0 to 5; when m is 2 or more, a plurality of R 5 may be the same or Can be different; a represents an integer of 0 or 1; X represents a halogen atom; Z + represents + N (R 11 ) 4 , Na + or K + ; R 8 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, the saturated hydrocarbon group hydrogen atoms contained in it may be substituted by a halogen atom; R 9 and R 10 each independently represent a hydrogen atom or may have taken One group having a carbon number of 1 to 20 monovalent saturated hydrocarbon group, the saturated aliphatic hydrocarbon contained in the -CH 2 - may be -O -, - - NH- or -NR 8 - substituted, R 9 and R 10, - CO It may also be bonded to each other to form a 3 to 10 member nitrogen-containing heterocyclic ring with the nitrogen atom; R 11 independently of each other represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms].

作為R1~R4中之碳數6~10之一價芳香族烴基，可列舉：苯基、甲苯甲醯基、二甲苯基、基、丙基苯基、丁基苯基等。 Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R 1 to R 4 include phenyl, tolylmethyl, xylyl, Group, propylphenyl, butylphenyl and the like.

作為該芳香族烴基可具有之取代基，可列舉：鹵素原子、-R8、-OH、-OR8、-SO3 -、-SO3H、-SO3 -Z+、-CO2H、-CO2R8、-SR8、-SO2R8、-SO3R8或-SO2NR9R10。該等之中，作為取代基，較佳為-SO3 -、-SO3H、-SO3 -Z+及-SO2NR9R10，更佳為-SO3 -Z+及-SO2NR9R10。作為該情形時之-SO3 -Z+，較佳為-SO3 -+N(R11)4。若R1~R4為該等基，則可自包含化合物(1a)之本發明之紅色著色硬化性樹脂組合物而形成異物之產生較少且耐熱性優異的彩色濾光片。 Examples of the aromatic hydrocarbon group may have the substituent include: halogen atoms, -R 8, -OH, -OR 8 , -SO 3 -, -SO 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 R 8 , -SR 8 , -SO 2 R 8 , -SO 3 R 8 or -SO 2 NR 9 R 10 . Among these, the substituent is preferably -SO 3 -, -SO 3 H, -SO 3 - Z + and -SO 2 NR 9 R 10, more preferably -SO 3 - Z + and -SO 2 NR 9 R 10 . In this case, -SO 3 - Z + is preferably -SO 3- + N (R 11 ) 4 . When R 1 to R 4 are these groups, a color filter with less generation of foreign matter and excellent heat resistance can be formed from the red colored curable resin composition of the present invention containing the compound (1a).

作為R1及R2相互鍵結而與氮原子一同形成之環、以及R3及R4相互鍵結而與氮原子一同形成之環，例如可列舉如下者。 Examples of the ring in which R 1 and R 2 are bonded to each other to form a nitrogen atom, and the ring in which R 3 and R 4 are bonded to each other to form a nitrogen atom include the following.

作為R8~R11中之碳數1~20之一價飽和烴基，可列舉：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、二十烷基等直鏈狀烷基；異丙基、異丁基、異戊基、新戊基、2-乙基己基等支 鏈狀烷基；環丙基、環戊基、環己基、環庚基、環辛基、三環癸基等碳數3~20之脂環式飽和烴基。 Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R 8 to R 11 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl , Linear alkyl groups such as dodecyl, cetyl, eicosyl; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl; Cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl and other alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms.

作為-OR8，可列舉：甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基、庚氧基、辛氧基、2-乙基己氧基、二十烷基氧基等。 Examples of -OR 8 include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, and twentieth. Alkyloxy and the like.

作為-CO2R8，可列舉：甲氧基羰基、乙氧基羰基、丙氧基羰基、第三丁氧基羰基、己氧基羰基、二十烷基氧基羰基等。 Examples of -CO 2 R 8 include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a third butoxycarbonyl group, a hexyloxycarbonyl group, and an eicosyloxycarbonyl group.

作為-SR8，可列舉：甲基硫基、乙基硫基、丁基硫基、己基硫基、癸基硫基、二十烷基硫基等。 Examples of -SR 8 include methylthio, ethylthio, butylthio, hexylthio, decylthio, eicosylthio, and the like.

作為-SO2R8，可列舉：甲基磺醯基、乙基磺醯基、丁基磺醯基、己基磺醯基、癸基磺醯基、二十烷基磺醯基等。 Examples of -SO 2 R 8 include methylsulfonyl, ethylsulfonyl, butylsulfonyl, hexylsulfonyl, decylsulfonyl, and eicosylsulfonyl.

作為-SO3R8，可列舉：甲氧基磺醯基、乙氧基磺醯基、丙氧基磺醯基、第三丁氧基磺醯基、己氧基磺醯基、二十烷基氧基磺醯基等。 Examples of -SO 3 R 8 include methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, third butoxysulfonyl, hexylsulfonyl, and eicosane Ethoxysulfonyl and the like.

作為-SO2NR9R10，例如可列舉：胺磺醯基；N-甲基胺磺醯基、N-乙基胺磺醯基、N-丙基胺磺醯基、N-異丙基胺磺醯基、N-丁基胺磺醯基、N-異丁基胺磺醯基、N-第二丁基胺磺醯基、N-第三丁基胺磺醯基、N-戊基胺磺醯基、N-(1-乙基丙基)胺磺醯基、N-(1,1-二甲基丙基)胺磺醯基、N-(1,2-二甲基丙基)胺磺醯基、N-(2,2-二甲基丙基)胺磺醯基、N-(1-甲基丁基)胺磺醯基、N-(2-甲基丁基)胺磺醯基、N-(3-甲基丁基)胺磺醯基、N-環戊基胺磺醯基、N-己基胺磺醯基、N-(1,3-二甲基丁基)胺磺醯基、N- (3,3-二甲基丁基)胺磺醯基、N-庚基胺磺醯基、N-(1-甲基己基)胺磺醯基、N-(1,4-二甲基戊基)胺磺醯基、N-辛基胺磺醯基、N-(2-乙基己基)胺磺醯基、N-(1,5-二甲基)己基胺磺醯基、N-(1,1,2,2-四甲基丁基)胺磺醯基等經N-1取代之胺磺醯基；N,N-二甲基胺磺醯基、N,N-乙基甲基胺磺醯基、N,N-二乙基胺磺醯基、N,N-丙基甲基胺磺醯基、N,N-異丙基甲基胺磺醯基、N,N-第三丁基甲基胺磺醯基、N,N-丁基乙基胺磺醯基、N,N-雙(1-甲基丙基)胺磺醯基、N,N-庚基甲基胺磺醯基等經N,N-2取代之胺磺醯基等。 Examples of -SO 2 NR 9 R 10 include: sulfamoyl group; N-methylaminosulfonyl group, N-ethylaminesulfonyl group, N-propylaminesulfonyl group, and N-isopropyl group. Aminosulfonyl, N-butylaminesulfonyl, N-isobutylaminesulfonyl, N-second butylaminesulfonyl, N-thirdbutylaminesulfonyl, N-pentyl Aminosulfonyl, N- (1-ethylpropyl) aminosulfonyl, N- (1,1-dimethylpropyl) aminosulfonyl, N- (1,2-dimethylpropyl ) Aminosulfonyl, N- (2,2-dimethylpropyl) aminosulfonyl, N- (1-methylbutyl) aminesulfonyl, N- (2-methylbutyl) amine Sulfonyl, N- (3-methylbutyl) aminesulfonyl, N-cyclopentylaminesulfonyl, N-hexylaminesulfonyl, N- (1,3-dimethylbutyl) Aminesulfenyl, N- (3,3-dimethylbutyl) sulfamidine, N-heptylaminesulfonyl, N- (1-methylhexyl) sulfamidine, N- (1 , 4-dimethylpentyl) aminosulfonyl, N-octylaminesulfonyl, N- (2-ethylhexyl) aminesulfonyl, N- (1,5-dimethyl) hexylamine Sulfonyl, N- (1,1,2,2-tetramethylbutyl) aminesulfonyl and other aminesulfonyl substituted with N-1; N, N-dimethylaminesulfonyl, N , N-ethylmethylaminesulfonyl, N, N-diethylaminesulfonyl N, N-propylmethylaminesulfonyl, N, N-isopropylmethylaminesulfonyl, N, N-third butylmethylaminesulfonyl, N, N-butylethylaminesulfonyl Amidino, N, N-bis (1-methylpropyl) aminesulfonyl, N, N-heptylmethylaminesulfonyl, and the like are substituted by N, N-2.

R9及R10中之碳數1~20之一價飽和烴基可具有取代基。作為該取代基，可列舉羥基及鹵素原子。 The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R 9 and R 10 may have a substituent. Examples of the substituent include a hydroxyl group and a halogen atom.

R9及R10可相互鍵結而與氮原子一同形成3~10員含氮雜環(環內包含1個以上氮原子之雜環)。作為該雜環，例如可列舉如下者。 R 9 and R 10 may be bonded to each other to form a 3 to 10 member nitrogen-containing heterocyclic ring (a heterocyclic ring containing one or more nitrogen atoms) together with the nitrogen atom. Examples of the heterocyclic ring include the following.

R5較佳為-CO2H、-CO2 -Z+、-CO2R8、-SO3 -、-SO3 -Z+、-SO3H及-SO2NHR9，更佳為-SO3 -、-SO3 -Z+、-SO3H及-SO2NHR9。 R 5 is preferably -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 -, -SO 3 - Z +, -SO 3 H and -SO 2 NHR 9, more preferably - SO 3 -, -SO 3 - Z +, -SO 3 H and -SO 2 NHR 9.

m較佳為1~4，更佳為1及2。 m is preferably 1 to 4, more preferably 1 and 2.

作為R6及R7中之碳數1~6之烷基，上述所列舉之烷基中，可列舉碳數為1~6者。 Examples of the alkyl group having 1 to 6 carbon atoms in R 6 and R 7 include those having 1 to 6 carbon atoms among the alkyl groups listed above.

作為R8及R11中之碳數7~10之芳烷基，可列舉：苄基、苯基乙基、苯基丁基等。 Examples of the aralkyl group having 7 to 10 carbon atoms in R 8 and R 11 include benzyl, phenylethyl, and phenylbutyl.

Z+為+N(R11)4、Na+或K+，較佳為+N(R11)4。 Z + is + N (R 11 ) 4 , Na + or K + , and is preferably + N (R 11 ) 4 .

作為上述+N(R11)4，較佳為4個R11中之至少2個為碳數5~20之一價飽和烴基。又，4個R11之合計碳數較佳為20~80，更佳為20~60。於在化合物(1a)中存在+N(R11)4之情形時，若R11為該等基，則可自包含化合物(1a)之本發明之紅色著色硬化性樹脂組合物而形成異物較少的彩色濾光片。 As the + N (R 11 ) 4 , it is preferable that at least two of the four R 11 are a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. The total carbon number of the four R 11 is preferably 20 to 80, and more preferably 20 to 60. When + N (R 11 ) 4 is present in the compound (1a), if R 11 is such a group, it is possible to form a foreign substance from the red colored curable resin composition of the present invention containing the compound (1a). Fewer color filters.

作為化合物(1a)，更佳為式(2a)所表示之化合物(以下有時簡稱為「化合物(2a)」)。化合物(2a)亦可為其互變異構物。 The compound (1a) is more preferably a compound represented by the formula (2a) (hereinafter sometimes simply referred to as "compound (2a)"). Compound (2a) may also be its tautomer.

[式(2a)中，R21~R24分別獨立表示氫原子、-R26或可具有取代基之碳數6~10之一價芳香族烴基；R21及R22可與氮原子一同形成包含氮原子之環，R23及R24可與氮原子一同形成包含氮原子之環；R25表示-SO3 -、-SO3H、-SO3 -Z1+或-SO2NHR26；m1表示0~5之整數；於m1為2以上時，複數個R25可相同亦可不同；a1表示0或1之整數；X1表示鹵素原子； R26表示碳數1~20之一價飽和烴基；Z1+表示+N(R27)4、Na+或K+；R27分別獨立表示碳數1~20之一價飽和烴基或苄基]。 [In formula (2a), R 21 to R 24 each independently represent a hydrogen atom, -R 26 or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent; R 21 and R 22 may be formed together with a nitrogen atom comprises ring nitrogen atoms, R 23 and R 24 may form together with the nitrogen atom of the ring comprising a nitrogen atom; R 25 represents -SO 3 -, -SO 3 H, -SO 3 - Z1 + , or -SO 2 NHR 26; m1 Represents an integer of 0 to 5; when m1 is 2 or more, a plurality of R 25 may be the same or different; a1 represents an integer of 0 or 1; X1 represents a halogen atom; R 26 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms Z1 + represents + N (R 27 ) 4 , Na + or K + ; R 27 each independently represents a monovalent saturated hydrocarbon group or benzyl group having 1 to 20 carbon atoms].

作為R21~R24中之碳數6~10之一價芳香族烴基，可列舉與於上述R1~R4中作為芳香族烴基而列舉者相同之基。該芳香族烴基所含之氫原子可經-SO3 -、-SO3H、-SO3 -Z1+、-SO3R26或-SO2NHR26取代。 Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R 21 to R 24 include the same groups as those listed as the aromatic hydrocarbon group in R 1 to R 4 . The hydrogen atom contained in the aromatic hydrocarbon group may be -SO 3 -, -SO 3 H, -SO 3 - Z1 +, -SO 3 R 26 or -SO 2 NHR 26 group.

作為R21~R24之組合，較佳為R21及R23為氫原子、R22及R24為碳數6~10之一價芳香族烴基、且該芳香族烴基所含之氫原子經-SO3 -、-SO3H、-SO3 -Z1+、-SO3R26或-SO2NHR26取代者。進而較佳之組合係R21及R23為氫原子、R22及R24為碳數6~10之一價芳香族烴基、且該芳香族烴基所含之氫原子經-SO3 -Z1+或-SO2NHR26取代者。 As a combination of R 21 to R 24 , R 21 and R 23 are preferably hydrogen atoms, R 22 and R 24 are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and hydrogen atoms contained in the aromatic hydrocarbon groups are preferably -SO 3 -, -SO 3 H, -SO 3 - Z1 +, -SO 3 R 26 or -SO 2 NHR 26 are substituted. A further preferred combination is that R 21 and R 23 are hydrogen atoms, R 22 and R 24 are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group is -SO 3 - Z1 + or -SO 2 NHR 26 replacement.

若R21~R24為該等基，則可自包含化合物(2a)之本發明之紅色著色硬化性樹脂組合物而形成耐熱性優異的彩色濾光片。 When R 21 to R 24 are these groups, a color filter excellent in heat resistance can be formed from the red colored curable resin composition of the present invention containing the compound (2a).

作為R21及R22相互鍵結而與氮原子一同形成之包含氮原子之環、以及R23及R24相互鍵結而與氮原子一同形成之包含氮原子之環，可列舉與R1及R2相互鍵結而與氮原子一同形成之環相同者。其中，較佳為脂肪族雜環。作為該脂肪族雜環，例如可列舉下述者。 Examples of the ring containing nitrogen atom formed by bonding R 21 and R 22 together with the nitrogen atom and the ring containing nitrogen atom formed by bonding R 23 and R 24 together with the nitrogen atom include R 1 and R 1 R 2 is bonded to each other to form the same ring as the nitrogen atom. Among them, aliphatic heterocycles are preferred. Examples of the aliphatic heterocyclic ring include the following.

作為R26及R27中之碳數1~20之一價飽和烴基，可列舉與 於R8~R11中作為飽和烴基而列舉者相同之基。 Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R 26 and R 27 include the same groups as those listed as the saturated hydrocarbon group in R 8 to R 11 .

於R21~R24為-R26之情形時，-R26較佳為分別獨立為甲基或乙基。又，作為-SO3R26及-SO2NHR26中之R26，較佳為碳數3~20之支鏈狀烷基，更佳為碳數6~12之支鏈狀烷基，進而較佳為2-乙基己基。若R26為該等基，則可自包含化合物(2a)之本發明之紅色著色硬化性樹脂組合物而形成異物之產生較少的彩色濾光片。 When R 21 to R 24 are -R 26 , -R 26 is preferably independently methyl or ethyl. Further, and as -SO 3 R 26 in the -SO 2 NHR 26 R 26, preferred is a branched alkyl group having a carbon number of 3 to 20, more preferably 6 to 12 carbon atoms of the branched chain alkyl group, and further Preferred is 2-ethylhexyl. If R 26 is such a group, a color filter with less generation of foreign matter can be formed from the red colored curable resin composition of the present invention containing the compound (2a).

Z1+為+N(R27)4、Na+或K+，較佳為+N(R27)4。 Z1 + is + N (R 27 ) 4 , Na + or K + , and is preferably + N (R 27 ) 4 .

作為上述+N(R27)4，較佳為4個R27之中，至少2固為碳數5~20之一價飽和烴基。又，4個R27之合計碳數較佳為20~80，更佳為20~60。於在化合物(2a)中存在+N(R27)4之情形時，包含R27為該等基之化合物(2a)之紅色著色硬化性樹脂組合物可形成異物之產生較少的彩色濾光片。 As the + N (R 27 ) 4 , it is preferable that at least two of the four R 27 be a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms. The total carbon number of the four R 27 is preferably 20 to 80, and more preferably 20 to 60. When + N (R 27 ) 4 is present in the compound (2a), the red colored hardening resin composition containing the compound (2a) in which R 27 is such a group can form foreign matter and generate less color filters. sheet.

m1較佳為1~4，更佳為1或2。 m1 is preferably 1 to 4, and more preferably 1 or 2.

作為化合物(1a)，更佳為式(3a)所表示之化合物(以下有時簡稱為「化合物(3a)」)。化合物(3a)亦可為其互變異構物。 The compound (1a) is more preferably a compound represented by the formula (3a) (hereinafter sometimes simply referred to as "compound (3a)"). Compound (3a) may also be its tautomer.

[式(3a)中，R31及R32相互獨立表示碳數1~10之一價飽和烴基，該飽和烴基所含之氫原子可經碳數6~10之芳香族烴基或鹵素原子取代，該芳香族烴基所含之氫原子可經碳數 1~3之烷氧基取代，上述飽和烴基所含之-CH2-可經-O-、-CO-或-NR11-取代；R33及R34相互獨立表示碳數1~4之烷基、碳數1~4之烷基硫基或碳數1~4之烷基磺醯基；R31及R33可與氮原子一同形成包含氮原子之環，R32及R34可與氮原子一同形成包含氮原子之環；p及q相互獨立表示0~5之整數；於p為2以上之時，複數個R33可相同亦可不同，於q為2以上時，複數個R34可相同亦可不同；R11表示與上述相同之含義]。 [In formula (3a), R 31 and R 32 independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with an aromatic hydrocarbon group or halogen atom having 6 to 10 carbon atoms, The hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 3 carbon atoms, and -CH 2 -contained in the saturated hydrocarbon group may be substituted with -O-, -CO-, or -NR 11- ; R 33 And R 34 each independently represent an alkyl group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms or an alkylsulfonyl group having 1 to 4 carbon atoms; R 31 and R 33 may form together with a nitrogen atom and include Ring of nitrogen atom, R 32 and R 34 may form a ring containing nitrogen atom together with nitrogen atom; p and q are independent of each other and represent an integer of 0 to 5. When p is 2 or more, plural R 33 may be the same or Different, when q is 2 or more, a plurality of R 34 may be the same or different; R 11 represents the same meaning as above].

作為R31及R32中之碳數1~10之一價飽和烴基，可列舉R8中之一價飽和烴基中之碳數1~10之基。 Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R 31 and R 32 include a group having 1 to 10 carbon atoms in the monovalent saturated hydrocarbon group in R 8 .

作為可具有取代基之碳數6~10之芳香族烴基，可列舉與R1中者相同之基。 Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent include the same groups as those of R 1 .

作為碳數1~3之烷氧基，可列舉：甲氧基、乙氧基、丙氧基等。 Examples of the alkoxy group having 1 to 3 carbon atoms include a methoxy group, an ethoxy group, and a propoxy group.

R31及R32較佳為相互獨立為碳數1~3之一價飽和烴基。 R 31 and R 32 are each preferably a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms.

作為R33及R34中之碳數1~4之烷基，可列舉：甲基、乙基、丙基、丁基、異丙基、異丁基、第二丁基、第三丁基等。 Examples of the alkyl group having 1 to 4 carbon atoms in R 33 and R 34 include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, second butyl, and third butyl. .

作為R33及R34中之碳數1~4之烷基硫基，可列舉：甲基硫基、乙基硫基、丙基硫基、丁基硫基、異丙基硫基等。 Examples of the alkylthio group having 1 to 4 carbon atoms in R 33 and R 34 include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, and an isopropylthio group.

作為R33及R34中之碳數1~4之烷基磺醯基，可列舉：甲基磺醯基、乙基磺醯基、丙基磺醯基、丁基磺醯基、異丙 基磺醯基等。 Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in R 33 and R 34 include methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, and isopropyl Sulfonyl and others.

R33及R34較佳為碳數1~4之烷基，更佳為甲基。 R 33 and R 34 are preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

p及q較佳為0~2之整數，更佳為0及1。 p and q are preferably integers of 0 to 2, and more preferably 0 and 1.

作為化合物(1a)，例如可列舉式(1-1)~式(1-42)所表示之化合物。再者，式中，R40表示碳數1~20之一價飽和烴基，較佳為碳數6~12之支鏈狀烷基，進而較佳為2-乙基己基。 Examples of the compound (1a) include compounds represented by the formulae (1-1) to (1-42). In the formula, R 40 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched alkyl group having 6 to 12 carbon atoms, and more preferably 2-ethylhexyl.

化合物(1a)可使用市售之染料(例如，中外化成股份有限公司製造之「Chugai Aminol Fast Pink R-H/C」、田岡化學工業股份有限公司製造之「Rhodamin 6G」)。又，亦可以市售之染料作為起始原料並以JP2010-32999-A作為參考而進行合成。 Compound (1a) can be a commercially available one. Dyes (for example, "Chugai Aminol Fast Pink RH / C" manufactured by Sinochem Chemical Co., Ltd., and "Rhodamin 6G" manufactured by Taoka Chemical Industry Co., Ltd.). It can also be sold commercially The dye was synthesized as a starting material and JP2010-32999-A was used as a reference.

作為顏料(A2)，可列舉藉由色指數(Colour index)(The Society of Dyers and Colourists出版)而分類為顏料之黃色顏料、橙色顏料及紅色顏料。 Examples of the pigment (A2) include yellow pigments, orange pigments, and red pigments classified as pigments by the Colour index (published by The Society of Dyers and Colourists).

例如可列舉：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等黃色顏料； C.I.顏料橙13、31、36、38、40、42、43、51、55、59、61、64、65、71、73等橙色顏料；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等紅色顏料。 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 Red 9, 97, 105, 122, 123, 144 , 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 and other red pigments.

除此以外，亦可包括：C.I.顏料藍15、15：3、15：4、15：6、60等藍色顏料；C.I.顏料紫1、19、23、29、32、36、38等紫色顏料；C.I.顏料綠7、36、58等綠色顏料；C.I.顏料棕23、25等棕色顏料；C.I.顏料黑1、7等黑色顏料等。 In addition, it can also include: 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 ; CI Pigment Green 7, 36, 58 and other green pigments; CI Pigment Brown 23, 25 and other brown pigments; CI Pigment Black 1, 7 and other black pigments.

顏料較佳為選自由C.I.顏料黃138、139、150，C.I.顏料紅177、242及254所組成之群中之至少一種，更佳為選自由C.I.顏料紅177、242及254所組成之群中之至少一種。藉由包含上述顏料，作為紅色彩色濾光片之穿透光譜之最佳化較容易，且彩色濾光片之耐光性及耐藥品性變得良好。 The pigment is preferably at least one selected from the group consisting of CI Pigment Yellow 138, 139, 150 and CI Pigment Red 177, 242, and 254, and more preferably selected from the group consisting of CI Pigment Red 177, 242, and 254. At least one of them. By including the pigment described above, it is easier to optimize the transmission spectrum of the red color filter, and the light resistance and chemical resistance of the color filter become good.

顏料視需要可實施松脂處理、使用導入酸性基或鹼性基之顏料衍生物等之表面處理、利用高分子化合物等之對顏料表面之接枝處理、利用硫酸微粒化法等之微粒化處理、或利用用以去除雜質之有機溶劑或水等之洗淨處理、利用離子性雜質之離子交換法等之去除處理等。 If necessary, the pigment can be subjected to rosin treatment, surface treatment using pigment derivatives introduced with acidic or basic groups, grafting treatment on the pigment surface with polymer compounds, micronization treatment using sulfuric acid micronization method, etc. Or, a cleaning treatment using an organic solvent or water to remove impurities, a removal treatment using an ion exchange method using ionic impurities, and the like.

顏料較佳為粒徑均勻。藉由含有顏料分散劑進行分散處理，可獲得顏料均勻地分散於溶液中之狀態之顏料分散液。 The pigment preferably has a uniform particle size. By performing a dispersion treatment containing a pigment dispersant, a pigment dispersion liquid in a state where the pigment is uniformly dispersed in the solution can be obtained.

作為上述顏料分散劑，例如可列舉：陽離子系、陰離子系、非離子系、兩性、聚酯系、聚胺系、丙烯酸系等之顏料分散劑等。該等顏料分散劑可單獨使用，亦可組合兩種以上而使用。作為顏料分散劑，作為商品名可列舉：KP(信越化學工業股份有限公司製造)、Flowlen(共榮社化學股份有限公司製造)、Solsperse(Zeneca股份有限公司製造)、EFKA(CIBA公司製造)、Ajisper(Ajinomoto Fine-Techno股份有限公司製造)、Disperbyk(BYK-Chemie公司製造)等。 Examples of the pigment dispersant include pigment dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic pigments. These pigment dispersants may be used alone or in combination of two or more. Examples of the pigment dispersant include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by CIBA), Ajisper (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (manufactured by BYK-Chemie), and the like.

於使用顏料分散劑之情形時，其使用量相對於顏料(A2)之總量，較佳為1質量%以上且100質量%以下，更佳為5質量%以上且50質量%以下。若顏料分散劑之使用量處於上述範圍內，則有可獲得均勻之分散狀態之顏料分散液的傾向。 When a pigment dispersant is used, its use amount is preferably 1% by mass or more and 100% by mass or less with respect to the total amount of the pigment (A2), and more preferably 5% by mass or more and 50% by mass or less. When the amount of the pigment dispersant is within the above range, there is a tendency that a pigment dispersion liquid in a uniformly dispersed state can be obtained.

染料(A3)並無特別限定，可使用公知之染料，例如可列舉：溶劑染料、酸性染料、直接染料、媒染染料等，較佳為可溶解於有機溶劑中之染料。 The dye (A3) is not particularly limited, and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, mordant dyes, and the like, and dyes soluble in organic solvents are preferred.

作為染料(A3)，例如可列舉藉由色指數(The Society of Dyers and Colourists出版)而分類為染料之化合物、或染色筆記(色染社)中記載之公知之染料。又，根據化學結構，可列舉：偶氮染料、花青染料、三苯基甲烷染料、酞菁染料、蒽醌染料、萘醌染料、醌亞胺染料、次甲基染料、次甲基偶氮染料、方酸染料、吖啶染料、苯乙烯基染料、香豆素染料、喹啉染料及硝基染料等。該等之中，較佳為有 機溶劑可溶性染料。 Examples of the dye (A3) include compounds classified as dyes by the color index (published by The Society of Dyers and Colourists), and well-known dyes described in Dyeing Notes (Dyeing Society). Further, the chemical structure includes azo dyes, cyanine dyes, triphenylmethane dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, and methine azo Dyes, cubic acid dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes and nitro dyes. Of these, it is preferable to have Organic solvent-soluble dyes.

具體而言，可列舉：C.I.溶劑黃4、14、15、23、24、38、62、63、68、82、94、98、99、117、162、163、167、189，C.I.溶劑紅45、49、111、125、130、143、145、146、150、151、155、168、169、172、175、181、207、222、227、230、245、247，C.I.溶劑橙2、7、11、15、26、56、77、86，C.I.溶劑紫11、13、14、26、31、36、37、38、45、47、48、51、59、60等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.酸性紅1、4、8、14、17、18、26、27、29、31、33、34、35、37、40、42、44、57、66、73、76、80、88、97、103、106、111、114、129、133、134、138、143、145、150、151、155、158、160、172、176、182、183、195、198、206、211、215、216、217、227、228、249、252、257、258、260、261、266、268、270、274、277、280、281、308、312、315、316、339、341、345、 346、349、382、383、394、401、412、417、418、422、426，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.酸性紫6B、7、17、19、34等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.直接紅79、82、83、84、91、92、96、97、98、99、105、106、107、172、173、176、177、179、181、182、184、204、207、211、213、218、220、221、222、232、233、234、241、243、246、250，C.I.直接橙26、34、39、41、46、50、52、56、57、61、64、65、68、70、96、97、106、107，C.I.直接紫47、52、54、59、60、65、66、79、80、81、82、84、89、90、93、95、96、103、104等C.I.直接染料；C.I.分散黃51、54、76，C.I.分散紫26、27等C.I.分散染料；C.I.反應性黃2、76、116，C.I.反應性橙16；等C.I.反應性染料；C.I.媒染黃5、8、10、16、20、26、30、31、33、42、43、45、56、61、62、65，C.I.媒染紅1、2、3、4、9、11、12、14、17、18、19、 22、23、24、25、26、30、32、33、36、37、38、39、41、43、45、46、48、53、56、63、71、74、85、86、88、90、94、95，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，C.I.媒染紫1、2、4、5、7、14、22、24、30、31、32、37、40、41、44、45、47、48、53、58等。 Specific examples include: CI solvent yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 117, 162, 163, 167, 189, CI solvent red 45 , 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247, CI solvent orange 2, 7 ,, 11, 15, 26, 56, 77, 86, CI Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60 and other CI solvent dyes; CI Acid Yellow 1, 3, 7, 9, 11, 11, 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 Red 1, 4 , 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 57, 66, 73, 76, 80, 88, 97, 103, 106, 111 114 , 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249 , 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426, 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 Violet 6B, 7, 17, 19, 34; 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 Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250, CI Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97 , 106, 107, CI Direct Purple 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104 and other CI direct dyes; CI disperse yellow 51, 54, 76, CI disperse violet 26, 27 and other CI disperse dyes; CI reactive yellow 2, 76, 116, CI reactive orange 16; CI reactive dyes; CI Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65, CI mordant red 1, 2, 3, 4, 9, 11, 12 , 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95, CI mordant orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47 , 48, CI mordant purple 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58 and so on.

該等染料只要根據所需之彩色濾光片之分光光譜而適當地選擇即可。 These dyes may be appropriately selected according to the spectral spectrum of the desired color filter.

於著色劑(A)包含染料(A3)之情形時，染料(A3)之含量相對於著色劑(A)之總量，較佳為1~90質量%，更佳為1~50質量%。 When the colorant (A) contains the dye (A3), the content of the dye (A3) is preferably 1 to 90% by mass, and more preferably 1 to 50% by mass, relative to the total amount of the colorant (A).

化合物(1a)與顏料(A2)之含有比率以質量基準計，較佳為1：99~99：1，更佳為2：98~50：50，進而較佳為5：95~30：70。藉由設為此種比率，有穿透光譜之最佳化較容易、且所獲得之彩色濾光片之對比度、亮度、耐熱性及耐藥品性優異之傾向。 The content ratio of the compound (1a) to the pigment (A2) is on a mass basis, preferably 1:99 to 99: 1, more preferably 2:98 to 50:50, and further preferably 5:95 to 30:70. . By setting such a ratio, it is easy to optimize the transmission spectrum, and the obtained color filter tends to be excellent in contrast, brightness, heat resistance, and chemical resistance.

著色劑(A)之含量相對於固形物成分之總量，較佳為5~60質量%，更佳為8~50質量%，進而較佳為10~40質量%。若著色劑(A)之含量處於上述範圍內，則製成彩色濾光片時之色濃度較充分，且可使組合物中含有必需量之樹脂(B)或聚合性化合物(C)，因此可形成機械強度充分之彩色濾光片。 The content of the colorant (A) is preferably 5 to 60% by mass, more preferably 8 to 50% by mass, and still more preferably 10 to 40% by mass with respect to the total amount of the solid components. If the content of the colorant (A) is within the above range, the color density when the color filter is made is sufficient, and the necessary amount of the resin (B) or the polymerizable compound (C) can be contained in the composition. It is possible to form a color filter with sufficient mechanical strength.

此處，所謂本說明書中之「固形物成分之總量」，係指 自紅色著色硬化性樹脂組合物之總量中去除溶劑的含量而得之量。固形物成分之總量及各成分相對於總量之含量例如可藉由液相層析法或液氣相層析法等公知之分析方法而進行測定。 Here, the "total amount of solid components" in this specification means The amount obtained by removing the content of the solvent from the total amount of the red colored curable resin composition. The total amount of the solid components and the content of each component with respect to the total amount can be measured by a known analysis method such as liquid chromatography or liquid gas chromatography.

<樹脂(B)> <Resin (B)>

樹脂(B)並無特別限定，較佳為鹼溶性樹脂。作為樹脂(B)，例如可列舉以下之樹脂[K1]~[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]選自由不飽和羧酸及不飽和羧酸酐所組成之群中之至少一種(a)(以下有時簡稱為「(a)」)與具有碳數2~4之環狀醚結構及乙烯性不飽和鍵之單體(b)(以下有時簡稱為「(b)」)的共聚物；樹脂[K2](a)、(b)及可與(a)進行共聚合之單體(c)(其中，與(a)及(b)不同)(以下有時簡稱為「(c)」)之共聚物；樹脂[K3](a)與(c)之共聚物；樹脂[K4]使(a)與(c)之共聚物與(b)反應而成之樹脂；樹脂[K5]使(b)與(c)之共聚物與(a)反應而成之樹脂；樹脂[K6]使(b)與(c)之共聚物與(a)反應，進而使羧酸酐反應而成之樹脂。 Resin [K1] is at least one selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride (a) (hereinafter sometimes referred to as "(a)") and a cyclic ether structure having 2 to 4 carbon atoms And ethylenically unsaturated monomers (b) (hereinafter sometimes referred to as "(b)") copolymers; resins [K2] (a), (b), and monomers copolymerizable with (a) (C) (which is different from (a) and (b)) (hereinafter sometimes referred to as "(c)"); copolymer [K3] (a) and (c) copolymer; resin [K3] K4] Resin made by reacting (a) and (c) copolymer with (b); Resin [K5] Resin made by reacting (b) and (c) copolymer with (a); Resin [ K6] A resin obtained by reacting the copolymer of (b) and (c) with (a) and further reacting a carboxylic anhydride.

作為(a)，具體而言可列舉：丙烯酸、甲基丙烯酸、丁烯酸、鄰乙烯基苯甲酸、間乙烯基苯甲酸、對乙烯基苯甲酸等不飽和單羧酸類；順丁烯二酸、反丁烯二酸、檸康酸、甲基反丁烯二酸、伊康酸、3-乙烯基苯二甲酸、4-乙烯基苯二甲酸、3,4,5,6-四氫苯二甲酸、1,2,3,6-四氫苯二甲酸、二甲基四氫苯二 甲酸、1,4-環己烯二甲酸等不飽和二羧酸類；甲基-5-降冰片烯-2,3-二甲酸、5-羧基雙環[2.2.1]-2-庚烯、5,6-二羧基雙環[2.2.1]-2-庚烯、5-羧基-5-甲基雙環[2.2.1]-2-庚烯、5-羧基-5-乙基雙環[2.2.1]-2-庚烯、5-羧基-6-甲基雙環[2.2.1]-2-庚烯、5-羧基-6-乙基雙環[2.2.1]-2-庚烯等含羧基之雙環不飽和化合物類；順丁烯二酸酐、檸康酸酐、伊康酸酐、3-乙烯基苯二甲酸酐、4-乙烯基苯二甲酸酐、3,4,5,6-四氫苯二甲酸酐、1,2,3,6-四氫苯二甲酸酐、二甲基四氫苯二甲酸酐、5,6-二羧基雙環[2.2.1]-2-庚烯酸酐等不飽和二羧酸類酸酐；琥珀酸單[2-(甲基)丙烯醯氧基乙基]酯、苯二甲酸單[2-(甲基)丙烯醯氧基乙基]酯等2元以上之多元羧酸之不飽和單[(甲基)丙烯醯氧基烷基]酯類；α-(羥基甲基)丙烯酸之類的於同一分子中含有羥基及羧基之不飽和丙烯酸類等。 Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, butenoic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid; maleic acid , Fumaric acid, citraconic acid, methyl fumaric acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrobenzene Dicarboxylic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrobenzene Unsaturated dicarboxylic acids such as formic acid, 1,4-cyclohexene dicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] -2-heptene, 5 , 6-dicarboxybicyclo [2.2.1] -2-heptene, 5-carboxy-5-methylbicyclo [2.2.1] -2-heptene, 5-carboxy-5-ethylbicyclo [2.2.1 ] -2-heptene, 5-carboxy-6-methylbicyclo [2.2.1] -2-heptene, 5-carboxy-6-ethylbicyclo [2.2.1] -2-heptene, etc. Bicyclic unsaturated compounds; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrobenzene Formic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] -2-heptene anhydride, etc. Carboxylic acid anhydrides; poly [2- (meth) acryloxyethyl] succinate, poly [2- (meth) acryloxyethyl] phthalate, and more Unsaturated mono [(meth) acrylic alkoxyalkyl] esters; unsaturated acrylics such as α- (hydroxymethyl) acrylic acid containing hydroxyl and carboxyl groups in the same molecule.

該等之中，就共聚合反應性之方面或所獲得之樹脂於鹼性水溶液中的溶解性之方面而言，較佳為丙烯酸、甲基丙烯酸、順丁烯二酸酐等。 Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferable in terms of copolymerization reactivity or the solubility of the obtained resin in an alkaline aqueous solution.

再者，於本說明書中，所謂「(甲基)丙烯醯基」，表示選自由丙烯醯基及甲基丙烯醯基所組成之群中之至少一種。「(甲基)丙烯酸」及「(甲基)丙烯酸酯」等表述亦具有同樣之含義。 In addition, in this specification, a "(meth) acrylfluorenyl group" means at least 1 sort (s) chosen from the group which consists of an acrylfluorenyl group and a methacrylfluorenyl group. The expressions "(meth) acrylic acid" and "(meth) acrylate" have the same meaning.

(b)例如為具有碳數2~4之環狀醚結構(例如選自由環氧乙烷環、氧雜環丁烷環及四氫呋喃環所組成之群中之至少一 種)與乙烯性不飽和鍵之聚合性化合物。(b)較佳為具有碳數2~4之環狀醚結構與(甲基)丙烯醯氧基之單體。 (b) For example, a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an ethylene oxide ring, an oxetane ring, and a tetrahydrofuran ring) Species) Polymerizable compounds with ethylenically unsaturated bonds. (b) A monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acrylic fluorenyloxy group is preferred.

作為(b)，例如可列舉：具有環氧乙烷基與乙烯性不飽和鍵之單體(b1)(以下有時簡稱為「(b1)」)、具有氧雜環丁基與乙烯性不飽和鍵之單體(b2)(以下有時簡稱為「(b2)」)、具有四氫呋喃基與乙烯性不飽和鍵之單體(b3)(以下有時簡稱為「(b3)」)等。 Examples of (b) include a monomer (b1) having an ethylene oxide group and an ethylenically unsaturated bond (hereinafter sometimes simply referred to as "(b1)"), an oxetanyl group and an ethylenic unsaturated bond. A monomer (b2) of a saturated bond (hereinafter sometimes referred to as "(b2)"), a monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)"), and the like.

(b1)例如可列舉：具有使直鏈狀或支鏈狀之不飽和脂肪族烴環氧化之結構的單體(b1-1)(以下有時簡稱為「(b1-1)」)、及具有使不飽和脂環式烴環氧化之結構之單體(b1-2)(以下有時簡稱為「(b1-2)」)。 (b1) Examples thereof include a monomer (b1-1) having a structure for epoxidizing a linear or branched unsaturated aliphatic hydrocarbon (hereinafter sometimes referred to as "(b1-1)"), and A monomer (b1-2) having a structure for epoxidizing an unsaturated alicyclic hydrocarbon (hereinafter sometimes referred to as "(b1-2)").

作為(b1-1)，可列舉：(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸β-甲基縮水甘油酯、(甲基)丙烯酸β-乙基縮水甘油酯、乙烯基縮水甘油醚、鄰乙烯基苄基縮水甘油醚、間乙烯基苄基縮水甘油醚、對乙烯基苄基縮水甘油醚、α-甲基-鄰乙烯基苄基縮水甘油醚、α-甲基-間乙烯基苄基縮水甘油醚、α-甲基-對乙烯基苄基縮水甘油醚、2,3-雙(縮水甘油氧基甲基)苯乙烯、2,4-雙(縮水甘油氧基甲基)苯乙烯、2,5-雙(縮水甘油氧基甲基)苯乙烯、2,6-雙(縮水甘油氧基甲基)苯乙烯、2,3,4-三(縮水甘油氧基甲基)苯乙烯、2,3,5-三(縮水甘油氧基甲基)苯乙烯、2,3,6-三(縮水甘油氧基甲基)苯乙烯、3,4,5-三(縮水甘油氧基甲基)苯乙烯、2,4,6-三(縮水甘油氧基甲基)苯乙烯等。 Examples of (b1-1) include glycidyl (meth) acrylate, beta-methyl glycidyl (meth) acrylate, beta-ethyl glycidyl (meth) acrylate, and vinyl glycidyl ether. , O-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinyl Benzyl glycidyl ether, α-methyl-p-vinyl benzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) benzene Ethylene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) benzene Ethylene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxy) (Meth) styrene, 2,4,6-tris (glycidyloxymethyl) styrene, and the like.

作為(b1-2)，可列舉：乙烯基環己烯單氧化物、1,2-環 氧-4-乙烯基環己烷(例如Celloxide2000，Daicel股份有限公司製造)、(甲基)丙烯酸3,4-環氧環己基甲酯(例如Cyclomer A400，Daicel股份有限公司製造)、(甲基)丙烯酸3,4-環氧環己基甲酯(例如Cyclomer M100，Daicel股份有限公司製造)、式(I)所表示之化合物及式(II)所表示之化合物等。 Examples of (b1-2) include vinyl cyclohexene monooxide and 1,2-cyclo Oxy-4-vinylcyclohexane (e.g. Celloxide2000, manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexyl methyl (meth) acrylate (e.g. Cyclomer A400, manufactured by Daicel Co., Ltd.), (methyl ) 3,4-epoxycyclohexyl methyl acrylate (for example, Cyclomer M100, manufactured by Daicel Co., Ltd.), a compound represented by formula (I), a compound represented by formula (II), and the like.

[式(I)及式(II)中，Rb1及Rb2表示氫原子、或碳數1~4之烷基，該烷基所含之氫原子可經羥基取代；Xb1及Xb2表示單鍵、-Rb3-、＊-Rb3-O-、＊-Rb3-S-或＊-Rb3-NH-；Rb3表示碳數1~6之烷二基；＊表示與O之鍵結鍵]。 [In formula (I) and formula (II), R b1 and R b2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group; X b1 and X b2 represent a single bond, -R b3 -, * - R b3 -O -, * - R b3 -S- or * -R b3 -NH-; R b3 represents alkanediyl group having a carbon number of 1 to 6; and O * represents the Knot key].

作為碳數1~4之烷基，可列舉：甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基等。 Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, and third butyl.

作為氫原子經羥基取代之烷基，可列舉：羥基甲基、1-羥基乙基、2-羥基乙基、1-羥基丙基、2-羥基丙基、3-羥基丙基、1-羥基-1-甲基乙基、2-羥基-1-甲基乙基、1-羥基丁基、2-羥基丁基、3-羥基丁基、4-羥基丁基等。 Examples of the hydroxy-substituted alkyl group include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, and 1-hydroxyl. 1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like.

Rb1及Rb2較佳為氫原子、甲基、羥基甲基、1-羥基乙基或2-羥基乙基，更佳為氫原子或甲基。 R b1 and R b2 are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

作為烷二基，可列舉：亞甲基、伸乙基、丙烷-1,2-二 基、丙烷-1,3-二基、丁烷-1,4-二基、戊烷-1,5-二基、己烷-1,6-二基等。 Examples of the alkyldiyl group include methylene, ethylene, and propane-1,2-di Base, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, and the like.

作為Xb1及Xb2，較佳為單鍵、亞甲基、伸乙基、＊-CH2-O-或＊-CH2CH2-O-，更佳為單鍵或＊-CH2CH2-O-(＊表示與O之鍵結鍵)。 X b1 and X b2 are preferably a single bond, methylene, ethylene, * -CH 2 -O- or * -CH 2 CH 2 -O-, more preferably a single bond or * -CH 2 CH 2 -O- (* indicates bonding with O).

作為式(I)所表示之化合物，可列舉式(I-1)~式(I-15)中之任一者所表示之化合物等。其中，較佳為式(I-1)、式(I-3)、式(I-5)、式(I-7)、式(I-9)或式(I-11)~式(I-15)所表示之化合物，更佳為式(I-1)、式(I-7)、式(I-9)或式(I-15)所表示之化合物。 Examples of the compound represented by the formula (I) include compounds represented by any one of the formulae (I-1) to (I-15). Among them, formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), or formula (I-11) to formula (I) are preferred. The compound represented by -15) is more preferably a compound represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15).

作為式(II)所表示之化合物，可列舉式(II-1)~式(II-15)中之任一者所表示之化合物等。其中，較佳為式(II-1)、式(II-3)、式(II-5)、式(II-7)、式(II-9)或式(II-11)~式(II-15)所表示之化合物，更佳為式(II-1)、式(II-7)、式(II-9)或式(II-15)所表示之化合物。 Examples of the compound represented by the formula (II) include compounds represented by any one of the formulae (II-1) to (II-15). Among them, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9), or formula (II-11) to formula (II) are preferred. The compound represented by -15) is more preferably a compound represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15).

式(I)所表示之化合物及式(II)所表示之化合物可分別單獨使用，亦可以任意之比率混合而使用。於混合而使用之情形時，式(I)所表示之化合物及式(II)所表示之化合物的含有比率以莫耳基準計，較佳為5：95~95：5，更佳為10：90~90：10，進而較佳為20：80~80：20。 The compound represented by the formula (I) and the compound represented by the formula (II) may be used individually, or they may be mixed and used at an arbitrary ratio. In the case of mixing and using, the content ratio of the compound represented by formula (I) and the compound represented by formula (II) is on a Moore basis, preferably 5:95 to 95: 5, and more preferably 10: 90 to 90:10, and more preferably 20:80 to 80:20.

作為(b2)，更佳為具有氧雜環丁基與(甲基)丙烯醯氧基之單體。作為(b2)，可列舉：3-甲基-3-甲基丙烯醯氧基甲基氧雜環丁烷、3-甲基-3-丙烯醯氧基甲基氧雜環丁烷、3-乙基-3-甲基丙烯醯氧基甲基氧雜環丁烷、3-乙基-3-丙烯醯氧基甲基氧雜環丁烷、3-甲基-3-甲基丙烯醯氧基乙基氧雜環丁烷、3-甲基-3-丙烯醯氧基乙基氧雜環丁烷、3-乙基-3-甲基丙烯醯氧基乙基氧雜環丁烷、3-乙基-3-丙烯醯氧基乙基氧雜環丁烷等。 As (b2), a monomer having an oxetanyl group and a (meth) acryloxy group is more preferable. Examples of (b2) include 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-propenyloxymethyloxetane, 3- Ethyl-3-methacryloxymethyloxetane, 3-ethyl-3-propenemethyloxetane, 3-methyl-3-methacryloxy Ethylethyloxetane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3-methacryloxyethyloxetane, 3 -Ethyl-3-propenyloxyethyloxetane and the like.

作為(b3)，更佳為具有四氫呋喃基與(甲基)丙烯醯氧基之單體。作為(b3)，具體而言，可列舉丙烯酸四氫糠酯(例如Viscoat V # 150，大阪有機化學工業股份有限公司製造)、甲基丙烯酸四氫糠酯等。 As (b3), a monomer having a tetrahydrofuranyl group and a (meth) acryloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Viscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

就可進一步提高所獲得之彩色濾光片之耐熱性、耐藥品性等可靠性的方面而言，(b)較佳為(b1)。進而，就紅色著色硬化性樹脂組合物之保存穩定性優異之方面而言，更佳為(b1-2)。 In terms of further improving the reliability of the obtained color filter, such as heat resistance and chemical resistance, (b) is preferably (b1). Furthermore, (b1-2) is more preferable at the point which is excellent in the storage stability of a red coloring curable resin composition.

作為(c)，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯 酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸十二烷基酯、(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-8-基酯(於該技術領域中，作為慣用名，稱為「(甲基)丙烯酸二環戊酯」。又，有時簡稱為「(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(於該技術領域中，作為慣用名，稱為「(甲基)丙烯酸二環戊烯酯」)、(甲基)丙烯酸二環戊氧基乙酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸金剛烷基酯、(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)丙烯酸酯類；(甲基)丙烯酸2-羥基乙酯及(甲基)丙烯酸2-羥基丙酯等含羥基之(甲基)丙烯酸酯類；順丁烯二酸二乙酯、反丁烯二酸二乙酯、伊康酸二乙酯等二羧酸二酯；雙環[2.2.1]-2-庚烯、5-甲基雙環[2.2.1]-2-庚烯、5-乙基雙環[2.2.1]-2-庚烯、5-羥基雙環[2.2.1]-2-庚烯、5-羥基甲基雙環[2.2.1]-2-庚烯、5-(2'-羥基乙基)雙環[2.2.1]-2-庚烯、5-甲氧基雙環[2.2.1]-2-庚烯、5-乙氧基雙環[2.2.1]-2-庚烯、5,6-二羥基雙環[2.2.1]-2-庚烯、5,6-二(羥基甲基)雙環[2.2.1]-2-庚烯、5,6-二(2'-羥基乙基)雙環[2.2.1]-2-庚烯、5,6-二甲氧基雙環[2.2.1]-2-庚烯、5,6-二乙氧基雙環 [2.2.1]-2-庚烯、5-羥基-5-甲基雙環[2.2.1]-2-庚烯、5-羥基-5-乙基雙環[2.2.1]-2-庚烯、5-羥基甲基-5-甲基雙環[2.2.1]-2-庚烯、5-第三丁氧基羰基雙環[2.2.1]-2-庚烯、5-環己氧基羰基雙環[2.2.1]-2-庚烯、5-苯氧基羰基雙環[2.2.1]-2-庚烯、5,6-雙(第三丁氧基羰基)雙環[2.2.1]-2-庚烯、5,6-雙(環己氧基羰基)雙環[2.2.1]-2-庚烯等雙環不飽和化合物類；N-苯基馬來醯亞胺、N-環己基馬來醯亞胺、N-苄基馬來醯亞胺、3-馬來醯亞胺苯甲酸N-丁二醯亞胺酯、4-馬來醯亞胺丁酸N-丁二醯亞胺酯、6-馬來醯亞胺己酸N-丁二醯亞胺酯、3-馬來醯亞胺丙酸N-丁二醯亞胺酯、N-(9-吖啶基)馬來醯亞胺等二羰基醯亞胺衍生物類；苯乙烯、α-甲基苯乙烯、間甲基苯乙烯、對甲基苯乙烯、乙烯基甲苯、對甲氧基苯乙烯、丙烯腈、甲基丙烯腈、氯乙烯、偏氯乙烯、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 (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, second butyl (meth) acrylate, and Tributyl, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic ring Amyl ester, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6 ] dec-8-yl ester (in this technology In the field, as a common name, it is called "dicyclopentyl (meth) acrylate." Also, it may be abbreviated as "tricyclodecyl (meth) acrylate.") And tricyclic (meth) acrylate. [5.2. 1.0 2,6 ] decene-8-yl ester (in this technical field, as a common name, it is called "dicyclopentenyl (meth) acrylate"), dicyclopentyloxyethyl (meth) acrylate Ester, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, (meth) () (Meth) acrylates such as naphthyl acrylate, benzyl (meth) acrylate Type; (hydroxy) (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; diethyl maleate, fumarate di Dicarboxylic acid diesters such as ethyl ester, diethyl iconate; bicyclo [2.2.1] -2-heptene, 5-methylbicyclo [2.2.1] -2-heptene, 5-ethylbicyclo [ 2.2.1] -2-heptene, 5-hydroxybicyclo [2.2.1] -2-heptene, 5-hydroxymethylbicyclo [2.2.1] -2-heptene, 5- (2'-hydroxyethyl Group) bicyclo [2.2.1] -2-heptene, 5-methoxybicyclo [2.2.1] -2-heptene, 5-ethoxybicyclo [2.2.1] -2-heptene, 5, 6-dihydroxybicyclo [2.2.1] -2-heptene, 5,6-bis (hydroxymethyl) bicyclo [2.2.1] -2-heptene, 5,6-bis (2'-hydroxyethyl) ) Bicyclo [2.2.1] -2-heptene, 5,6-dimethoxybicyclo [2.2.1] -2-heptene, 5,6-diethoxybicyclo [2.2.1] -2- Heptene, 5-hydroxy-5-methylbicyclo [2.2.1] -2-heptene, 5-hydroxy-5-ethylbicyclo [2.2.1] -2-heptene, 5-hydroxymethyl-5 -Methylbicyclo [2.2.1] -2-heptene, 5-tert-butoxycarbonylbicyclo [2.2.1] -2-heptene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] -2 -Heptene, 5-phenoxycarbonylbicyclo [2.2.1] -2-heptene, 5,6-bis (third butoxycarbonyl) bis [2.2.1] Bicyclic unsaturated compounds such as 2-heptene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] -2-heptene; N-phenylmaleimide N-cyclohexylmaleimide, N-benzylmaleimide, 3-maleimide benzoate N-butanediimide, 4-maleimide butyric acid N- Succinimide, 6-maleimide hexanoic acid N-succinimide hexanoate, 3-maleimide iminopropionate N-succinimide imidate, N- (9-acridine Group) dicarbonylfluorenimine derivatives such as maleimidine; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, Acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl- 1,3-butadiene and the like.

該等之中，就共聚合反應性及耐熱性之方面而言，較佳為苯乙烯、乙烯基甲苯、N-苯基馬來醯亞胺、N-環己基馬來醯亞胺及N-苄基馬來醯亞胺。 Among these, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, and N- are preferable in terms of copolymerization reactivity and heat resistance. Benzylmaleimide.

於樹脂[K1]中，關於源自各成分之結構單元之比率，於構成樹脂[K1]之所有結構單元中，較佳為源自(a)之結構單元：2~60莫耳%源自(b)之結構單元：40~98莫耳%， 更佳為源自(a)之結構單元：10~50莫耳%源自(b)之結構單元：50~90莫耳%。 In the resin [K1], regarding the ratio of the structural unit derived from each component, among all the structural units constituting the resin [K1], the structural unit derived from (a) is preferred: 2 to 60 mol% derived from (b) Structural unit: 40 ~ 98 mole%, More preferably, the structural unit derived from (a): 10-50 mol% Structural unit derived from (b): 50-90 mol%.

若樹脂[K1]之結構單元之比率處於上述範圍內，則有紅色著色硬化性樹脂組合物之保存穩定性、形成著色圖案時之顯影性、及所獲得之著色圖案之耐溶劑性優異的傾向。 When the ratio of the structural unit of the resin [K1] is within the above range, there is a tendency that the storage stability of the red colored curable resin composition, the developability when a colored pattern is formed, and the solvent resistance of the obtained colored pattern are excellent. .

樹脂[K1]例如可以文獻「高分子合成之實驗法」(大津隆行著，化學同人發行所股份有限公司，第1版第1次印刷，1972年3月1日發行)中記載之方法、及該文獻中記載之引用文獻作為參考而製造。 The resin [K1] can be, for example, the method described in the document "Experimental Method of Polymer Synthesis" (by Otsu Takayuki, Chemical Co., Ltd., 1st edition, first printing, March 1, 1972), and The references cited in this document are manufactured as a reference.

具體而言，可列舉如下方法：將特定量之(a)及(b)、聚合起始劑及溶劑等添加至反應容器中，例如藉由利用氮置換氧而形成脫氧環境，一面攪拌，一面進行加熱及保溫。再者，此處使用之聚合起始劑及溶劑等並無特別限定，可使用該領域中通常使用者。例如，作為聚合起始劑，可列舉偶氮化合物(2,2'-偶氮雙異丁腈、2,2'-偶氮雙(2,4-二甲基戊腈)等)或有機過氧化物(過氧化苯甲醯等)，作為溶劑，只要為溶解各單體者即可，作為本發明之紅色著色硬化性樹脂組合物之溶劑(E)，可列舉下述溶劑等。 Specifically, a method may be mentioned in which a specific amount of (a) and (b), a polymerization initiator, a solvent, and the like are added to a reaction vessel, and for example, a deoxidizing environment is formed by replacing oxygen with nitrogen, while stirring, Heating and holding. The polymerization initiator, solvent, and the like used herein are not particularly limited, and ordinary users in the field can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) or organic compounds. The oxide (such as benzamidine peroxide) may be any solvent as long as it dissolves each monomer. Examples of the solvent (E) of the red colored curable resin composition of the present invention include the following solvents.

再者，所獲得之共聚物可直接使用反應後之溶液，可使用經濃縮或稀釋之溶液，亦可使用藉由再沈澱等方法形成為固體(粉體)而提取者。尤其是，藉由於該聚合時使用本發明之紅色著色硬化性樹脂組合物所含之溶劑作為溶劑，可將反應後之溶液直接用於本發明之紅色著色硬化性樹脂 組合物的製備，因此可簡化本發明之紅色著色硬化性樹脂組合物之製造步驟。 In addition, the obtained copolymer may be directly used as a solution after the reaction, a concentrated or diluted solution may be used, or it may be extracted by forming into a solid (powder) by a method such as reprecipitation. In particular, by using the solvent contained in the red colored curable resin composition of the present invention as a solvent during the polymerization, the solution after the reaction can be directly used for the red colored curable resin of the present invention. The preparation of the composition can simplify the manufacturing steps of the red colored curable resin composition of the present invention.

於樹脂[K2]中，關於源自各成分之結構單元之比率，構成樹脂[K2]之所有結構單元中，較佳為源自(a)之結構單元：2~45莫耳%源自(b)之結構單元：2~95莫耳%源自(c)之結構單元：1~65莫耳%，更佳為源自(a)之結構單元：5~40莫耳%源自(b)之結構單元：5~80莫耳%源自(c)之結構單元：5~60莫耳%。 In the resin [K2], regarding the ratio of the structural unit derived from each component, among all the structural units constituting the resin [K2], the structural unit derived from (a) is preferred: 2 to 45 mole% derived from ( b) structural unit: 2 ~ 95 mole% derived from (c) structural unit: 1 ~ 65 mole%, more preferably structural unit derived from (a): 5 ~ 40 mole% derived from (b Structural unit of): 5 ~ 80 mol% Structural unit derived from (c): 5 ~ 60 mol%.

若樹脂[K2]之結構單元之比率處於上述範圍內，則有紅色著色硬化性樹脂組合物之保存穩定性、形成著色圖案時之顯影性、以及所獲得之著色圖案之耐溶劑性、耐熱性及機械強度優異的傾向。 When the ratio of the structural unit of the resin [K2] is within the above range, there are storage stability of the red colored curable resin composition, developability when a colored pattern is formed, and solvent resistance and heat resistance of the obtained colored pattern And it tends to be excellent in mechanical strength.

樹脂[K2]例如可與作為樹脂[K1]之製造方法而記載之方法同樣地製造。 The resin [K2] can be produced in the same manner as the method described as the method for producing the resin [K1], for example.

於樹脂[K3]中，關於源自各成分之結構單元之比率，構成樹脂[K3]之所有結構單元中，較佳為源自(a)之結構單元：2~60莫耳%源自(c)之結構單元：40~98莫耳%，更佳為源自(a)之結構單元：10~50莫耳%源自(c)之結構單元：50~90莫耳%。 In the resin [K3], regarding the ratio of the structural unit derived from each component, among all the structural units constituting the resin [K3], the structural unit derived from (a) is preferred: 2 to 60 mole% derived from ( c) structural unit: 40 ~ 98 mole%, more preferably the structural unit derived from (a): 10 ~ 50 mole% structural unit derived from (c): 50 ~ 90 mole%.

樹脂[K3]例如可與作為樹脂[K1]之製造方法而記載之方法同樣地製造。 The resin [K3] can be produced in the same manner as the method described as the method for producing the resin [K1], for example.

樹脂[K4]可藉由獲得(a)與(c)之共聚物並使(b)所具有之碳數2~4之環狀醚加成於(a)所具有的羧酸及/或羧酸酐上而製造。 The resin [K4] can be obtained by copolymerizing (a) and (c) and adding a cyclic ether having 2 to 4 carbon atoms in (b) to the carboxylic acid and / or carboxylic acid in (a). Manufactured on acid anhydride.

首先，與作為樹脂[K1]之製造方法而記載之方法同樣地製造(a)與(c)的共聚物。於該情形時，源自各成分之結構單元之比率較佳為與於樹脂[K3]中列舉者同樣的比率。 First, a copolymer of (a) and (c) is produced in the same manner as the method described as the production method of the resin [K1]. In this case, the ratio of the structural unit derived from each component is preferably the same as the ratio listed in the resin [K3].

繼而，使上述共聚物中之源自(a)之羧酸及/或羧酸酐之一部分與(b)所具有之碳數2~4的環狀醚反應。 Then, a part of the carboxylic acid and / or carboxylic acid anhydride derived from (a) in the above copolymer is reacted with a cyclic ether having 2 to 4 carbon atoms in (b).

緊接著(a)與(c)之共聚物的製造，將燒瓶內氣體環境自氮氣置換為空氣，並將(b)、羧酸或羧酸酐與環狀醚之反應觸媒(例如三(二甲胺基甲基)苯酚等)及聚合抑制劑(例如對苯二酚等)等添加至燒瓶內，例如於60~130℃下反應1~10小時，藉此可製造樹脂[K4]。 Immediately after the manufacture of (a) and (c) copolymers, the gas environment in the flask was replaced with nitrogen from air, and (b), the reaction catalyst of carboxylic acid or carboxylic anhydride and cyclic ether (such as three (two Methylaminomethyl) phenol, etc.) and polymerization inhibitors (such as hydroquinone, etc.) are added to the flask, and reacted at, for example, 60 to 130 ° C for 1 to 10 hours, thereby producing a resin [K4].

(b)之使用量相對於(a)100莫耳，較佳為5~80莫耳，更佳為10~75莫耳。藉由設為該範圍，有紅色著色硬化性樹脂組合物之保存穩定性、形成圖案時之顯影性、以及所獲得之圖案之耐溶劑性、耐熱性、機械強度與感光度的平衡性變得良好之傾向。由於環狀醚之反應性較高、不易殘存未反應之(b)，因此作為樹脂[K4]所使用之(b)，較佳為(b1)，進而較佳為(b1-1)。 The amount of (b) used is preferably 5 to 80 mols, and more preferably 10 to 75 mols relative to (a) 100 mols. By setting it as this range, the storage stability of the red colored curable resin composition, the developability at the time of pattern formation, and the solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern become balanced. Good tendency. Since the cyclic ether has high reactivity and does not easily leave unreacted (b), (b) used as the resin [K4] is preferably (b1), and more preferably (b1-1).

上述反應觸媒之使用量相對於(a)、(b)及(c)之合計量100質量份，較佳為0.001~5質量份。上述聚合抑制劑之使用 量相對於(a)、(b)及(c)之合計量100質量份，較佳為0.001~5質量份。 The used amount of the reaction catalyst is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b), and (c). Use of the above polymerization inhibitors The amount is preferably 0.001 to 5 parts by mass based on the total amount of (a), (b), and (c).

添加方法、反應溫度及時間等反應條件可考慮製造設備或由聚合引起之發熱量等而適當地調整。再者，與聚合條件同樣地，可考慮製造設備或由聚合引起之發熱量等而適當地調整添加方法或反應溫度。 The reaction conditions such as the addition method, the reaction temperature, and the time can be appropriately adjusted in consideration of manufacturing equipment or the amount of heat generated by polymerization. In addition, as with the polymerization conditions, the addition method or reaction temperature can be appropriately adjusted in consideration of manufacturing equipment, heat generation due to polymerization, and the like.

關於樹脂[K5]，作為第一階段，以與上述樹脂[K1]之製造方法同樣之方式獲得(b)與(c)的共聚物。與上述同樣地，所獲得之共聚物可直接使用反應後之溶液，亦可使用經濃縮或稀釋之溶液，亦可使用藉由再沈澱等方法形成為固體(粉體)而提取者。 Regarding the resin [K5], as the first stage, a copolymer of (b) and (c) was obtained in the same manner as in the method for producing the above-mentioned resin [K1]. In the same manner as described above, the obtained copolymer may be used directly after the reaction, a concentrated or diluted solution may be used, or it may be extracted by forming it into a solid (powder) by a method such as reprecipitation.

源自(b)及(c)之結構單元之比率相對於構成上述共聚物之所有結構單元的合計莫耳數，較佳為處於以下之範圍內。 The ratio of the structural units derived from (b) and (c) is preferably within the following range with respect to the total number of moles of all the structural units constituting the copolymer.

較佳為源自(b)之結構單元：5~95莫耳%源自(c)之結構單元：5~95莫耳%，更佳為源自(b)之結構單元：10~90莫耳%源自(c)之結構單元：10~90莫耳%。 Preferably, the structural unit derived from (b): 5 ~ 95 mole% Structural unit derived from (c): 5 ~ 95 mole%, more preferably structural unit derived from (b): 10 ~ 90 mole Ear% is derived from the structural unit of (c): 10 ~ 90 mole%.

進而，於與樹脂[K4]之製造方法同樣之條件下，使(b)與(c)之共聚物所具有之源自(b)之環狀醚與(a)所具有的羧酸或羧酸酐反應，藉此可獲得樹脂[K5]。 Furthermore, under the same conditions as in the method for producing the resin [K4], the cyclic ether derived from (b) and the carboxylic acid or carboxylic acid possessed from (a) which the copolymer of (b) and (c) have The acid anhydride is reacted to obtain a resin [K5].

使上述共聚物反應之(a)之使用量相對於(b)100莫耳，較 佳為5~80莫耳。由於環狀醚之反應性較高、不易殘存未反應之(b)，因此作為樹脂[K5]所使用之(b)，較佳為(b1)，進而較佳為(b1-1)。 The amount of (a) used to react the above copolymer is 100 moles relative to (b), It is preferably 5 to 80 moles. Since the cyclic ether has high reactivity and does not easily remain unreacted (b), (b) used as the resin [K5] is preferably (b1), and more preferably (b1-1).

樹脂[K6]為使樹脂[K5]進而與羧酸酐反應而成之樹脂。使藉由環狀醚與羧酸或羧酸酐之反應所產生之羥基與羧酸酐反應。 The resin [K6] is a resin obtained by reacting the resin [K5] with a carboxylic anhydride. The hydroxy group produced by the reaction of a cyclic ether with a carboxylic acid or a carboxylic acid anhydride is reacted with a carboxylic acid anhydride.

作為羧酸酐，可列舉：順丁烯二酸酐、檸康酸酐、伊康酸酐、3-乙烯基苯二甲酸酐、4-乙烯基苯二甲酸酐、3,4,5,6-四氫苯二甲酸酐、1,2,3,6-四氫苯二甲酸酐、二甲基四氫苯二甲酸酐、5,6-二羧基雙環[2.2.1]-2-庚烯酸酐(雙環庚烯二甲酸酐)等。羧酸酐之使用量相對於(a)之使用量1莫耳，較佳為0.5~1莫耳。 Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrobenzene Dicarboxylic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] -2-heptenoic anhydride (bicycloheptane Dicarboxylic acid anhydride) and the like. The amount of carboxylic acid anhydride used is 1 mole, preferably 0.5 to 1 mole, relative to the amount of (a).

作為樹脂(B)，具體而言，可列舉：(甲基)丙烯酸3,4-環氧環己基甲酯/(甲基)丙烯酸共聚物、丙烯酸3,4-環氧三環[5.2.1.02.6]癸酯/(甲基)丙烯酸共聚物等樹脂[K1]；(甲基)丙烯酸縮水甘油酯/(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物、(甲基)丙烯酸縮水甘油酯/苯乙烯/(甲基)丙烯酸共聚物、丙烯酸3,4-環氧三環[5.2.1.02.6]癸酯/(甲基)丙烯酸/N-環己基馬來醯亞胺共聚物、丙烯酸3,4-環氧三環[5.2.1.02.6]癸酯/(甲基)丙烯酸/乙烯基甲苯/(甲基)丙烯酸二環戊烯酯共聚物、3-甲基-3-(甲基)丙烯醯氧基甲基氧雜環丁烷/(甲基)丙烯酸/苯乙烯共聚物等樹脂[K2]；(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物、苯乙烯/(甲基)丙烯酸共聚物等樹脂[K3]；使(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物加成(甲 基)丙烯酸縮水甘油酯而成之樹脂、使(甲基)丙烯酸三環癸酯/苯乙烯/(甲基)丙烯酸共聚物加成(甲基)丙烯酸縮水甘油酯而成之樹脂、使(甲基)丙烯酸三環癸酯/(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物加成(甲基)丙烯酸縮水甘油酯而成之樹脂等樹脂[K4]；使(甲基)丙烯酸三環癸酯/(甲基)丙烯酸縮水甘油酯之共聚物與(甲基)丙烯酸反應而成之樹脂、使(甲基)丙烯酸三環癸酯/苯乙烯/(甲基)丙烯酸縮水甘油酯之共聚物與(甲基)丙烯酸反應而成之樹脂等樹脂[K5]；使使(甲基)丙烯酸三環癸酯/(甲基)丙烯酸縮水甘油酯之共聚物與(甲基)丙烯酸反應而成之樹脂進而與四氫苯二甲酸酐反應而成的樹脂等樹脂[K6]等。 Specific examples of the resin (B) include 3,4-epoxycyclohexyl methyl (meth) acrylate / (meth) acrylic acid copolymer, and 3,4-epoxy tricycloacrylic acid [5.2.1.0 2.6 ] Resins such as decyl ester / (meth) acrylic copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic copolymer, glycidyl (meth) acrylate Ester / styrene / (meth) acrylic acid copolymer, acrylic acid 3,4-epoxytricyclo [5.2.1.0 2.6 ] decyl ester / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, acrylic acid 3,4-epoxytricyclo [5.2.1.0 2.6 ] decyl / (meth) acrylic acid / vinyltoluene / (meth) acrylic dicyclopentenyl copolymer, 3-methyl-3- (methyl ) Resins such as propylene methyloxycyclobutane / (meth) acrylic acid / styrene copolymer [K2]; benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (formaldehyde) Resins such as acrylic copolymers [K3]; resins obtained by adding benzyl (meth) acrylate / (meth) acrylic copolymer to glycidyl (meth) acrylate, and tricyclic (meth) acrylic acid Decyl ester / styrene / (meth) acrylic acid copolymer addition (meth) propylene Resin made from glycidyl acid, resin obtained by adding tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer to glycidyl (meth) acrylate, etc. Resin [K4]; a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate and (meth) acrylic acid, and tricyclodecyl (meth) acrylate / Resin [K5], such as a resin obtained by reacting a copolymer of styrene / glycidyl (meth) acrylate with (meth) acrylic acid; Tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate Resin [K6] etc., which is a resin obtained by reacting a copolymer of an ester with (meth) acrylic acid and further reacted with tetrahydrophthalic anhydride.

其中，作為樹脂(B)，較佳為樹脂[K1]、樹脂[K2]及樹脂[K3]。 Among them, the resin (B) is preferably resin [K1], resin [K2], and resin [K3].

樹脂(B)之經聚苯乙烯換算之重量平均分子量較佳為3,000~100,000，更佳為5,000~50,000，進而較佳為5,000~30,000。若分子量處於上述範圍內，則有如下傾向：塗膜硬度增高，殘膜率亦較高，未曝光部於顯影液中之溶解性良好，且解像度增高。 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 coating film hardness is increased, the residual film ratio is also high, the solubility of the unexposed portion in the developing solution is good, and the resolution is increased.

樹脂(B)之分子量分佈[重量平均分子量(Mw，Molecular weight)/數量平均分子量(Mn，Number-average molecular weight)]較佳為1.1~6，更佳為1.2~4。 The molecular weight distribution [weight average molecular weight (Mw, Molecular weight) / number average molecular weight (Mn, Number-average molecular weight)] of the resin (B) is preferably 1.1 to 6, more preferably 1.2 to 4.

樹脂(B)之酸值較佳為50~170mg-KOH/g，更佳為60~150mg-KOH/g，進而較佳為70~135mg-KOH/g。此處，酸值係作為中和樹脂1g所需之氫氧化鉀之量(mg)而測定的值， 例如可藉由使用氫氧化鉀水溶液進行滴定而求出。 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. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, For example, it can be calculated | required by titration using potassium hydroxide aqueous solution.

樹脂(B)之含量相對於紅色著色硬化性樹脂組合物之固形物成分，較佳為7~65質量%，更佳為13~60質量%，進而較佳為17~55質量%。若樹脂(B)之含量處於上述範圍內，則有未曝光部於顯影液中之溶解性較高的傾向。 The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass based on the solid content of the red colored curable resin composition. When the content of the resin (B) is within the above range, the solubility of the unexposed portion in the developing solution tends to be high.

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

聚合性化合物(C)係可藉由利用光或熱之作用自聚合起始劑(D)產生之活性自由基及/或酸等而進行聚合之化合物，例如可列舉具有聚合性之乙烯性不飽和鍵之化合物等，較佳為可列舉(甲基)丙烯酸酯化合物。 The polymerizable compound (C) is a compound that can be polymerized by using active radicals and / or acids generated from the polymerization initiator (D) by the action of light or heat, and examples thereof include polymerizable ethylenic compounds. Examples of the compound having a saturated bond include a (meth) acrylate compound.

作為上述聚合性化合物(C)，較佳為具有3個以上之乙烯性不飽和鍵之聚合性化合物。作為此種聚合性化合物，例如可列舉：三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、三季戊四醇八(甲基)丙烯酸酯、三季戊四醇七(甲基)丙烯酸酯、四季戊四醇十(甲基)丙烯酸酯、四季戊四醇九(甲基)丙烯酸酯、異氰尿酸三(2-(甲基)丙烯醯氧基乙基)酯、乙二醇改性季戊四醇四(甲基)丙烯酸酯、乙二醇改性二季戊四醇六(甲基)丙烯酸酯、丙二醇改性季戊四醇四(甲基)丙烯酸酯、丙二醇改性二季戊四醇六(甲基)丙烯酸酯、己內酯改性季戊四醇四(甲基)丙烯酸酯、己內酯改性二季戊四醇六(甲基)丙烯酸酯等。其中，較佳為二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯。 The polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (methyl). Acrylate, Tripentaerythritol octa (meth) acrylate, Tripentaerythritol octa (meth) acrylate, Tetrapentaerythritol deca (meth) acrylate, Tetrapentaerythritol nine (meth) acrylate, Isocyanuric tris (2- (Meth) acryloxyethyl), ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (methyl) ) Acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and the like. Among them, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferred.

聚合性化合物(C)之含量相對於固形物成分之總量，較佳為7~65質量%，更佳為13~60質量%，進而較佳為17~55質量%。若聚合性化合物(C)之含量處於上述範圍內，則有著色圖案之殘膜率及耐藥品性增高之傾向。 The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass with respect to the total amount of the solid components. When the content of the polymerizable compound (C) is within the above range, the residual film rate of the colored pattern and the chemical resistance tend to increase.

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

聚合起始劑(D)只要為藉由光或熱之作用產生活性自由基、酸等並使聚合開始之化合物，則並無特別限定，可使用公知之聚合起始劑。 The polymerization initiator (D) is not particularly limited as long as it is a compound that generates living radicals, acids, and the like by the action of light or heat to start polymerization, and a known polymerization initiator can be used.

作為聚合起始劑(D)，可列舉：烷基苯酮化合物、三化合物、醯基氧化膦化合物、O-醯基肟化合物及聯咪唑化合物等。 Examples of the polymerization initiator (D) include an alkyl phenone compound, Compounds, fluorenyl phosphine oxide compounds, O-fluorenyl oxime compounds, biimidazole compounds, and the like.

O-醯基肟化合物係具有式(d1)所表示之部分結構之化合物。以下，*表示鍵結鍵。 The O-fluorenyl oxime compound is a compound having a partial structure represented by formula (d1). In the following, * indicates a bond key.

作為O-醯基肟化合物，例如可列舉：N-苯甲醯氧基-1-(4-苯基硫基苯基)丁烷-1-酮-2-亞胺、N-苯甲醯氧基-1-(4-苯基硫基苯基)辛烷-1-酮-2-亞胺、N-苯甲醯氧基-1-(4-苯基硫基苯基)-3-環戊基丙烷-1-酮-2-亞胺、N-乙醯氧基-1-[9-乙基-6-(2-甲基苯甲醯基)-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-2,4-二氧環戊基甲氧基)苯甲醯基}-9H-咔唑-3-基]乙烷-1-亞胺、N-乙醯氧基-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-3-環戊基丙烷-1-亞胺、N-苯甲醯氧基-1-[9-乙基-6-(2-甲基苯 甲醯基)-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，BASF公司製造)、N-1919(ADEKA公司製造)等市售品。 Examples of the O-fluorenyl oxime compound 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-ring Amylpropane-1-one-2-imine, N-ethoxyl-1- [9-ethyl-6- (2-methylbenzyl) -9H-carbazol-3-yl] Ethane-1-imine, N-ethoxyl-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxetane Methoxy) benzamyl} -9H-carbazol-3-yl] ethane-1-imine, N-ethoxyl-1- [9-ethyl-6- (2-methyl Benzamidine) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzyloxy-1- [9-ethyl-6- (2-methyl Phenylbenzene Formamyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-one-2-imine and the like. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF), and N-1919 (made by ADEKA) can be used.

烷基苯酮化合物係具有式(d2)所表示之部分結構或式(d3)所表示之部分結構的化合物。該等部分結構中之苯環可具有取代基。 The alkyl phenone compound is a compound having a partial structure represented by the formula (d2) or a partial structure represented by the formula (d3). The benzene ring in these partial structures may have a substituent.

作為具有式(d2)所表示之部分結構之化合物，例如可列舉：2-甲基-2-嗎啉基-1-(4-甲基硫基苯基)丙烷-1-酮、2-二甲胺基-1-(4-嗎啉基苯基)-2-苄基丁烷-1-酮、2-(二甲胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎啉基)苯基]丁烷-1-酮等。可使用Irgacure(註冊商標)369、907及379(以上，BASF公司製造)等市售品。 Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholinyl-1- (4-methylthiophenyl) propane-1-one, and 2-di Methylamino-1- (4-morpholinylphenyl) -2-benzylbutane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane-1-one and the like. Commercial products such as Irgacure (registered trademark) 369, 907, and 379 (above, manufactured by BASF) can be used.

作為具有式(d3)所表示之部分結構之化合物，例如可列舉：2-羥基-2-甲基-1-苯基丙烷-1-酮、2-羥基-2-甲基-1-[4-(2-羥基乙氧基)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-酮之低聚物、α,α-二乙氧基苯乙酮、苄基二甲基縮酮等。 Examples of the compound having a partial structure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenylpropane-1-one and 2-hydroxy-2-methyl-1- [4 -(2-hydroxyethoxy) phenyl] propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propane-1 -Oligomers of ketones, α, α-diethoxyacetophenone, benzyldimethylketal and the like.

就感光度之方面而言，作為烷基苯酮化合物，較佳為具有式(d2)所表示之部分結構之化合物。 In terms of sensitivity, the alkyl phenone compound is preferably a compound having a partial structure represented by formula (d2).

作為三化合物，例如可列舉：2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三、2,4-雙(三氯甲基)-6-(4-甲氧基萘 基)-1,3,5-三、2,4-雙(三氯甲基)-6-向日葵基-1,3,5-三、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三、2,4-雙(三氯甲基)-6-[2-(5-甲基呋喃-2-基)乙烯基]-1,3,5-三、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-1,3,5-三、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、2,4-雙(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三等。 As three Examples of the compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-tris , 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-tri , 2,4-bis (trichloromethyl) -6-sunfloweryl-1,3,5-tri , 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) vinyl] -1,3,5-tris Wait.

作為醯基氧化膦化合物，可列舉2,4,6-三甲基苯甲醯基二苯基氧化膦等。可使用Irgacure(註冊商標)819(BASF公司製造)等市售品。 Examples of the fluorenylphosphine oxide compound include 2,4,6-trimethylbenzylfluorenyldiphenylphosphine oxide and the like. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) can be used.

作為聯咪唑化合物，例如可列舉：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(例如參照JPH06-75372-A、JPH06-75373-A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(烷氧基苯基)聯咪唑、2,2'-雙(2-氯苯基)-4,4',5,5'-四(二烷氧基苯基)聯咪唑、2,2'-雙(2-氯苯基)-4,4',5,5'-四(三烷氧基苯基)聯咪唑(例如參照JPS48-38403-B、JPS62-174204-A等)、4,4'5,5'-位之苯基經烷氧羰基取代之咪唑化合物(例如參照JPH07-10913-A等)等。 Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3- Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (see, for example, JPH06-75372-A, JPH06-75373-A, etc.), 2,2'-bis (2-chlorophenyl ) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetrakis (alkoxyphenyl) Biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorobenzene) -4,4 ', 5,5'-tetrakis (trialkoxyphenyl) biimidazole (for example, see JPS48-38403-B, JPS62-174204-A, etc.), 4,4'5,5'- An imidazole compound in which the phenyl group is substituted with an alkoxycarbonyl group (for example, refer to JPH07-10913-A).

進而，作為聚合起始劑(D)，可列舉：安息香、安息香甲醚、安息香***、安息香異丙醚、安息香異丁醚等安息香化合物；二苯甲酮、鄰苯甲醯基苯甲酸甲酯、4-苯基二苯甲酮、4-苯甲醯基-4'-甲基二苯硫醚、3,3',4,4'-四(過氧化第三丁基羰基)二苯甲酮、2,4,6-三甲基二苯甲酮等二苯 甲酮化合物；9,10-菲醌、2-乙基蒽醌、樟腦醌等醌化合物；10-丁基-2-氯吖啶酮、苄基乙醛酸甲酯、苯基乙醛酸甲酯、二茂鈦化合物等。該等較佳為與下述聚合起始助劑(D1)(尤其是胺類)組合而使用。 Further, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone and methyl benzophenethylbenzoate , 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetrakis (third butylcarbonyl) dibenzoyl Ketones, 2,4,6-trimethylbenzophenone and other diphenyls Ketone compounds; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone; 10-butyl-2-chloroacridone, methyl benzylglyoxylate, methyl phenylglyoxylate Esters, titanocene compounds, etc. These are preferably used in combination with the polymerization initiator (D1) described below (especially amines).

作為酸產生劑，例如可列舉：4-羥基苯基二甲基鋶對甲苯磺酸鹽、4-羥基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鎓鹽類，或硝基苄基甲苯磺酸酯類，安息香甲苯磺酸酯類等。 Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-ethoxyphenylphenyldimethyl.鋶 P-toluenesulfonate, 4-Ethyloxyphenyl / methyl / benzyl hexafluoroantimonate, triphenyl fluorene p-toluenesulfonate, triphenyl fluorene hexafluoroantimonate, diphenyl Onium salts such as p-toluenesulfonate, diphenylsulfonium hexafluoroantimonate, or nitrobenzyltosylate, benzoin tosylate, and the like.

作為聚合起始劑(D)，較佳為包含選自由烷基苯酮化合物、三化合物、醯基氧化膦化合物、O-醯基肟化合物及聯咪唑化合物所組成之群中之至少一種的聚合起始劑，更佳為包含O-醯基肟化合物之聚合起始劑，進而較佳為包含O-醯基肟化合物及烷基苯酮化合物之聚合起始劑。 As the polymerization initiator (D), it is preferable to include The polymerization initiator of at least one of the group consisting of a compound, a fluorenylphosphine oxide compound, an O-fluorenyl oxime compound, and a biimidazole compound is more preferably a polymerization initiator containing an O-fluorenyl oxime compound, and A polymerization initiator containing an O-fluorenyl oxime compound and an alkyl phenone compound is preferred.

聚合起始劑(D)之含量相對於樹脂(B)及聚合性化合物(C)之合計量100質量份，較佳為0.1~30質量份，更佳為1~20質量份。若聚合起始劑(D)之含量處於上述範圍內，則有高成光度化而使曝光時間縮短之傾向，因此生產性提高。 The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is within the above range, there is a tendency that the photogenicity is increased and the exposure time is shortened, so that productivity is improved.

<聚合起始助劑(D1)> <Polymerization starter (D1)>

聚合起始助劑(D1)係用以促進藉由聚合起始劑而使聚合開始之光聚合性化合物之聚合的化合物或增感劑。於包含聚合起始助劑(D1)之情形時，通常與聚合起始劑(D)組合 而使用。 The polymerization initiation aid (D1) is a compound or a sensitizer for promoting polymerization of a photopolymerizable compound whose polymerization is started by a polymerization initiator. When a polymerization initiator (D1) is included, it is usually combined with a polymerization initiator (D) While using.

作為聚合起始助劑(D1)，可列舉：胺化合物、烷氧基蒽化合物、9-氧硫化合物、羧酸化合物等。 Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, and 9-oxosulfur. Compounds, carboxylic acid compounds, and the like.

作為胺化合物，可列舉：三乙醇胺、甲基二乙醇胺、三異丙醇胺、4-二甲胺基苯甲酸甲酯、4-二甲胺基苯甲酸乙酯、4-二甲胺基苯甲酸異戊酯、苯甲酸2-二甲胺基乙酯、4-二甲胺基苯甲酸2-乙基己酯、N,N-二甲基對甲苯胺、4,4'-雙(二甲胺基)二苯甲酮(通稱米其勒酮)、4,4'-雙(二乙胺基)二苯甲酮、4,4'-雙(乙基甲胺基)二苯甲酮等，其中較佳為4,4'-雙(二乙胺基)二苯甲酮。可使用EAB-F(保土各化學工業股份有限公司製造)等市售品。 Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzene Isoamyl formate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethyl-p-toluidine, 4,4'-bis (di (Methylamino) benzophenone (commonly known as Michelin), 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethylmethylamino) benzophenone Etc. Among them, 4,4′-bis (diethylamino) benzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodog Chemical Industry Co., Ltd.) can be used.

作為烷氧基蒽化合物，可列舉：9,10-二甲氧基蒽、2-乙基-9,10-二甲氧基蒽、9,10-二乙氧基蒽、2-乙基-9,10-二乙氧基蒽、9,10-二丁氧基蒽、2-乙基-9,10-二丁氧基蒽等。 Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl- 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

作為9-氧硫化合物，可列舉：2-異丙基9-氧硫、4-異丙基9-氧硫、2,4-二乙基9-氧硫、2,4-二氯9-氧硫、1-氯-4-丙氧基9-氧硫等。 As 9-oxysulfur Compounds, including: 2-isopropyl 9-oxosulfur , 4-isopropyl 9-oxysulfur , 2,4-diethyl 9-oxysulfur , 2,4-dichloro 9-oxysulfur , 1-chloro-4-propoxy9-oxysulfur Wait.

作為羧酸化合物，可列舉：苯基硫基乙酸、甲基苯基硫基乙酸、乙基苯基硫基乙酸、甲基乙基苯基硫基乙酸、二甲基苯基硫基乙酸、甲氧基苯基硫基乙酸、二甲氧基苯基硫基乙酸、氯苯基硫基乙酸、二氯苯基硫基乙酸、N-苯基甘胺酸、苯氧基乙酸、萘基硫乙酸、N-萘基甘胺酸、萘氧基乙酸等。 Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, and methyl formaldehyde. Oxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioglycolic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid , N-naphthyl glycine, naphthyloxyacetic acid, and the like.

作為聚合起始助劑(D1)，較佳為9-氧硫化合物。 As the polymerization initiation aid (D1), 9-oxysulfur is preferable Compound.

又，於使用聚合起始助劑(D1)之情形時，其使用量相對於樹脂(B)及聚合性化合物(C)之合計量100質量份，較佳為0.1~30質量份，更佳為1~20質量份。又，相對於聚合起始劑(D)之含量100質量份，較佳為20~100質量份，更佳為30~80質量份。若聚合起始助劑(D1)之量處於該範圍內，則有可以高感光度形感圖案，進而可獲得高亮度之彩色濾光片之傾向。 When a polymerization initiation aid (D1) is used, the amount of the polymerization initiation aid (D1) is 100 parts by mass relative to the total amount of the resin (B) and the polymerizable compound (C). It is 1 to 20 parts by mass. The content of the polymerization initiator (D) is preferably 100 to 100 parts by mass, and more preferably 30 to 80 parts by mass. When the amount of the polymerization initiation aid (D1) is within this range, there is a tendency that a high-sensitivity shape pattern can be obtained, and a color filter with high brightness can be obtained.

<溶劑(E)> <Solvent (E)>

溶劑(E)並無特別限定，可使用該領域中通常使用之溶劑。例如可列舉：酯溶劑(於分子內包含-COO-而不含-O-之溶劑)、醚溶劑(於分子內包含-O-而不含-COO-之溶劑)、醚酯溶劑(於分子內包含-COO-與-O-之溶劑)、酮溶劑(於分子內包含-CO-而不含-COO-之溶劑)、醇溶劑(於分子內包含OH而不含-O-、-CO-及-COO-之溶劑)、芳香族烴溶劑、醯胺溶劑、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- without -O- in the molecule), ether solvents (solvents containing -O- without -COO- in the molecule), ether ester solvents (in the molecule Solvents containing -COO- and -O-), ketone solvents (solvents containing -CO- but not -COO- in the molecule), alcohol solvents (containing OH in the molecule without -O-, -CO -And -COO- solvents), aromatic hydrocarbon solvents, amidine solvents, dimethyl sulfene, and the like.

作為上述酯溶劑，可列舉：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、環己醇乙酸酯、γ-丁內酯等。 Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, and isopentyl acetate. Ester, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, Cyclohexanol acetate, γ-butyrolactone and the like.

作為上述醚溶劑，可列舉：乙二醇單甲醚、乙二醇單***、乙二醇單丙醚、乙二醇單丁醚、二乙二醇單甲醚、二乙二醇單***、二乙二醇單丁醚、丙二醇單甲醚、丙二醇 單***、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、1,4-二烷、二乙二醇二甲醚、二乙二醇二***、二乙二醇甲基***、二乙二醇二丙醚、二乙二醇二丁醚、苯甲醚、苯***、甲基苯甲醚等。 Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monobutyl ether, 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-di Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyl ether, methyl Anisole and so on.

作為上述醚酯溶劑，可列舉：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、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單***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***乙酸酯、二乙二醇單***乙酸酯、二乙二醇單丁醚乙酸酯等。 Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxypropionate. Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionate Ethyl acetate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2 -Ethyl ethoxy-2-methylpropanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol Monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether Acetate, etc.

作為上述酮溶劑，可列舉：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、異佛爾酮等。 Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, and 4-methyl-2 -Pentanone, cyclopentanone, cyclohexanone, isophorone and the like.

作為上述醇溶劑，可列舉：甲醇、乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、丙二醇、甘油等。 Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

作為上述芳香族烴溶劑，可列舉：苯、甲苯、二甲苯、均三甲苯等。 Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.

作為上述醯胺溶劑，可列舉：N,N-二甲基甲醯胺、N,N- 二甲基乙醯胺、N-甲基吡咯啶酮等。 Examples of the amidamine solvent include N, N-dimethylformamide, N, N- Dimethylacetamide, N-methylpyrrolidone and the like.

上述溶劑中，就塗佈性、乾燥性之方面而言，較佳為1atm(101.325kPa)下之沸點為120℃以上且180℃以下之有機溶劑。其中，較佳為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***、3-甲氧基丁基乙酸酯、3-甲氧基-1-丁醇、4-羥基-4-甲基-2-戊酮及N,N-二甲基甲醯胺，更佳為丙二醇單甲醚乙酸酯、丙二醇單甲醚、二丙二醇甲醚乙酸酯、乳酸乙酯、3-甲氧基丁基乙酸酯、3-甲氧基-1-丁醇及3-乙氧基丙酸乙酯。 Among the above solvents, an organic solvent having a boiling point of 120 ° C. or higher and 180 ° C. or lower at 1 atm (101.325 kPa) is preferable in terms of coating properties and drying properties. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diethylene glycol are preferred. Alcohol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, and N, N-dimethylformamide , More preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol And ethyl 3-ethoxypropionate.

紅色著色硬化性樹脂組合物中之溶劑(E)之含量相對於紅色著色硬化性樹脂組合物，較佳為70~95質量%，更佳為75~92質量%。換言之，紅色著色硬化性樹脂組合物之固形物成分較佳為5~30質量%，更佳為8~25質量%。若溶劑(E)之含量處於上述範圍內，則有如下傾向：塗佈時之平坦性變良好，且因於形成彩色濾光片時色濃度充分而顯示特性變得良好。 The content of the solvent (E) in the red colored curable resin composition is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass, relative to the red colored curable resin composition. In other words, the solid content of the red 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 above-mentioned range, the flatness at the time of coating tends to be good, and the display characteristics become good because the color density is sufficient when the color filter is formed.

<界面活性劑(F)> <Surfactant (F)>

作為界面活性劑(F)，可列舉：聚矽氧系界面活性劑、氟系界面活性劑及具有氟原子之聚矽氧系界面活性劑等。該等可於側鏈上具有聚合性基。 Examples of the surfactant (F) include a polysiloxane-based surfactant, a fluorine-based surfactant, and a polysiloxane-based surfactant having a fluorine atom. These may have a polymerizable group on a side chain.

作為上述聚矽氧系界面活性劑，可列舉具有矽氧烷鍵之界面活性劑等。具體而言，可列舉：Toray Silicone DC3PA、同系列SH7PA、同系列DC11PA、同系列 SH21PA、同系列SH28PA、同系列SH29PA、同系列SH30PA、同系列SH8400(東麗道康寧股份有限公司製造)，KP321、KP322、KP323、KP324、KP326、KP340、KP341(信越化學工業股份有限公司製造)，TSF400、TSF401、TSF410、TSF4300、TSF4440、TSF4445、TSF-4446、TSF4452、TSF4460(邁圖高新材料日本有限公司製造)等。 Examples of the polysiloxane-based surfactant include a surfactant having a siloxane bond. Specific examples include: Toray Silicone DC3PA, same series SH7PA, same series DC11PA, same series SH21PA, same series SH28PA, same series SH29PA, same series SH30PA, same series SH8400 (made by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (made by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (manufactured by Momentive Advanced Materials Japan Co., Ltd.), etc.

作為上述氟系界面活性劑，可列舉具有氟碳鏈之界面活性劑等。具體而言，可列舉：Fluorad(商品名)FC430、同系列FC431(住友3M股份有限公司製造)，Megafac(註冊商標)F142D、同系列F171、同系列F172、同系列F173、同系列F177、同系列F183、同系列F554、同系列R30、同系列RS-718-K(DIC股份有限公司製造)，Eftop(註冊商標)EF301、同系列EF303、同系列EF351、同系列EF352(三菱綜合材料電子化成股份有限公司製造)，Surflon(註冊商標)S381、同系列S382、同系列SC101、同系列SC105(旭玻璃股份有限公司製造)，E5844(大金精密化學研究所股份有限公司製造)等。 Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain. Specific examples include: Fluorad (trade name) FC430, the same series of FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, the same series F171, the same series F172, the same series F173, the same series F177, the same series Series F183, same series F554, same series R30, same series RS-718-K (manufactured by DIC Corporation), Eftop (registered trademark) EF301, same series EF303, same series EF351, same series EF352 (Mitsubishi Materials Corporation) Co., Ltd.), Surflon (registered trademark) S381, same series S382, same series SC101, same series SC105 (made by Asahi Glass Co., Ltd.), E5844 (made by Daikin Precision Chemical Research Institute Co., Ltd.), etc.

作為上述具有氟原子之聚矽氧系界面活性劑，可列舉具有矽氧烷鍵及氟碳鏈之界面活性劑等。具體而言，可列舉：Megafac(註冊商標)R08、同系列BL20、同系列F475、同系列F477、同系列F443(DIC股份有限公司製造)等。 Examples of the polysiloxane-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain. Specific examples include: Megafac (registered trademark) R08, the same series BL20, the same series F475, the same series F477, the same series F443 (manufactured by DIC Corporation), and the like.

界面活性劑(F)之含量相對於紅色著色硬化性樹脂組合物，較佳為0.001質量%以上且0.2質量%以下，更佳為 0.002質量%以上且0.1質量%以下，進而較佳為0.01質量%以上且0.05質量%以下。其中，於上述界面活性劑(F)之含量中不包括上述顏料分散劑之含量。若界面活性劑(F)之含量處於上述範圍內，則可使塗膜之平坦性變得良好。 The content of the surfactant (F) is preferably 0.001% by mass or more and 0.2% by mass or less with respect to the red colored curable resin composition, and more preferably 0.002 mass% or more and 0.1 mass% or less, and more preferably 0.01 mass% or more and 0.05 mass% or less. Wherein, the content of the above-mentioned surfactant (F) does not include the content of the above-mentioned pigment dispersant. When the content of the surfactant (F) is within the above range, the flatness of the coating film can be made good.

<其他成分> <Other ingredients>

本發明之紅色著色硬化性樹脂組合物視需要可含有填充劑、其他高分子化合物、密接促進劑、抗氧化劑、紫外線吸收劑、光穩定劑、鏈轉移劑等於該技術領域中公知之添加劑。 The red colored curable resin composition of the present invention may contain fillers, other polymer compounds, adhesion promoters, antioxidants, ultraviolet absorbers, light stabilizers, and chain transfer agents, which are equivalent to known additives in the technical field, if necessary.

<紅色著色硬化性樹脂組合物之製造方法> <Manufacturing method of red colored curable resin composition>

本發明之紅色著色硬化性樹脂組合物例如可藉由將化合物(1a)、顏料(A2)、樹脂(B)、聚合性化合物(C)及聚合起始劑(D)、以及視需要使用之染料(A3)、聚合起始助劑(D1)、溶劑(E)、界面活性劑(F)及其他成分混合而製備。 The red colored curable resin composition of the present invention can be used, for example, by compound (1a), pigment (A2), resin (B), polymerizable compound (C), and polymerization initiator (D), The dye (A3), the polymerization initiation aid (D1), the solvent (E), the surfactant (F), and other components are prepared by mixing.

顏料(A2)較佳為預先與溶劑(E)之一部分或全部混合，使用珠磨機等使其分散直至顏料之平均粒徑成為0.2μm以下左右為止。此時，視需要可調配上述顏料分散劑、樹脂(B)之一部分或全部。藉由於所獲得之顏料分散液中，以成為特定之濃度之方式將化合物(1a)、樹脂(B)之剩餘部分、聚合性化合物(C)及聚合起始劑(D)、溶劑(E)之剩餘部分、以及視需要使用之染料(A3)、聚合起始劑(D)、聚合起始助劑(D1)、界面活性劑(F)及其他成分等混合，可製備目標紅色著色硬化性樹脂組合物。 The pigment (A2) is preferably partially or fully mixed with the solvent (E) in advance, and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. In this case, a part or all of the pigment dispersant and the resin (B) may be blended as necessary. In the obtained pigment dispersion liquid, the compound (1a), the remainder of the resin (B), the polymerizable compound (C), the polymerization initiator (D), and the solvent (E) are added so as to have a specific concentration. The remaining part and the dye (A3), the polymerization initiator (D), the polymerization initiator (D1), the surfactant (F), and other components used as necessary can be mixed to prepare the target red coloring and hardening property. Resin composition.

關於包含染料(A3)之情形時之染料(A3)及化合物(1a)， 可預先分別溶解於溶劑(E)之一部分或全部中而製備溶液。較佳為利用孔徑0.01~1μm左右之過濾器將該溶液過濾。 Regarding the dye (A3) and the compound (1a) when the dye (A3) is included, The solution can be prepared by dissolving each of them in part or all of the solvent (E) in advance. The solution is preferably filtered with a filter having a pore size of about 0.01 to 1 μm.

較佳為利用孔徑0.1~10μm左右之過濾器將如上所述般混合而製備之紅色著色硬化性樹脂組合物過濾。 The red colored curable resin composition prepared by mixing as described above with a filter having a pore size of about 0.1 to 10 μm is preferably filtered.

<紅色彩色濾光片之製造方法> <Manufacturing method of red color filter>

作為由本發明之紅色著色硬化性樹脂組合物製造紅色彩色濾光片之著色圖案的方法，可列舉：光微影法、噴墨法、印刷法等。其中，較佳為光微影法。光微影法係將上述紅色著色硬化性樹脂組合物塗佈於基板上，使其乾燥而形成組合物層，經由光罩使該組合物層曝光而顯影之方法。於光微影法中，藉由於曝光時不使用光罩、及/或不顯影，可形成上述組合物層之硬化物之著色塗膜。 Examples of a method for producing a colored pattern of a red color filter from the red colored curable resin composition of the present invention include a photolithography method, an inkjet method, and a printing method. Among them, photolithography is preferred. The photolithography method is a method in which the red colored curable resin composition is coated on a substrate and dried to form a composition layer, and the composition layer is exposed and developed through a photomask. In the photolithography method, a colored coating film of a hardened material of the composition layer can be formed by not using a mask and / or not developing during exposure.

所製作之紅色彩色濾光片之膜厚並無特別限定，可根據目的或用途等而適當地調整，例如為0.1~30μm，較佳為0.1~20μm，進而較佳為0.5~6μm。 The film thickness of the produced red color filter is not particularly limited, and can be appropriately adjusted according to the purpose or application, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

作為基板，可使用石英玻璃、硼矽酸玻璃、氧化鋁矽酸鹽玻璃、表面塗佈有二氧化矽之鈉鈣玻璃等玻璃板，或聚碳酸酯、聚甲基丙烯酸甲酯、聚對苯二甲酸乙二酯等樹脂板，矽，於上述基板上形成鋁、銀、銀/銅/鈀合金薄膜等者。於該等基板上，亦可形成其他彩色濾光片層、樹脂層、電晶體、電路等。 As the substrate, glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda-lime glass coated with silicon dioxide, or polycarbonate, polymethyl methacrylate, and polyparaphenylene can be used. Resin plates such as ethylene diformate, silicon, etc., are formed on the substrate with aluminum, silver, silver / copper / palladium alloy films, and the like. On these substrates, other color filter layers, resin layers, transistors, circuits, etc. can also be formed.

利用光微影法之各色像素之形成可以公知或慣用的裝置或條件進行。例如可以如下方式製作。 The formation of each color pixel by the photolithography method can be performed by a known or conventional device or condition. For example, it can be produced as follows.

首先，將紅色著色硬化性樹脂組合物塗佈於基板上，進行加熱乾燥(預烘烤)及/或減壓乾燥，藉此去除溶劑等揮發成分而使其乾燥，從而獲得平滑之組合物層。 First, a red colored curable resin composition is coated on a substrate, followed by heating drying (pre-baking) and / or drying under reduced pressure, thereby removing volatile components such as solvents and drying them, thereby obtaining a smooth composition layer. .

作為塗佈方法，可列舉：旋轉塗佈法、狹縫式塗佈法、狹縫式與旋轉塗佈法等。 Examples of the coating method include a spin coating method, a slit coating method, a slit coating method, and a spin coating method.

進行加熱乾燥之情形時之溫度較佳為30~120℃，更佳為50~110℃。又，作為加熱時間，較佳為10秒鐘~60分鐘，更佳為30秒鐘~30分鐘。 In the case of heating and drying, the temperature 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.

於進行減壓乾燥之情形時，較佳為於50~150Pa之壓力下在20~25℃之溫度範圍內進行。 In the case of drying under reduced pressure, it is preferably performed at a temperature of 20 to 25 ° C under a pressure of 50 to 150 Pa.

組合物層之膜厚並無特別限定，只要根據目標紅色彩色濾光片之膜厚而適當地選擇即可。 The film thickness of the composition layer is not particularly limited, and may be appropriately selected depending on the film thickness of the target red color filter.

繼而，組合物層係經由用以形成目標著色圖案之光罩而曝光。該光罩上之圖案並無特別限定，可使用根據目標用途之圖案。 Then, the composition layer is exposed through a mask for forming a target colored pattern. The pattern on the mask is not particularly limited, and a pattern according to the intended use can be used.

作為曝光所使用之光源，較佳為產生250~450nm之波長之光的光源。例如可使用截斷該波長區域之濾波器而截斷未達350nm之光，或使用提取該等波長區域之帶通濾波器而選擇性地提取436nm附近、408nm附近、365nm附近之光。具體而言，可列舉：水銀燈、發光二極體、金屬鹵素燈、鹵素燈等。 As a light source used for the exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferred. For example, a filter that cuts the wavelength region can be used to cut light below 350 nm, or a band-pass filter that extracts these wavelength regions can be used to selectively extract light near 436 nm, 408 nm, and 365 nm. Specific examples include a mercury lamp, a light-emitting diode, a metal halide lamp, and a halogen lamp.

為了可對整個曝光面均勻地照射平行光線，或進行光罩與基材之準確之位置對準，較佳為使用光罩對準曝光機及步進機等曝光裝置。 In order to uniformly irradiate parallel light to the entire exposure surface, or to accurately align the mask and the substrate, it is preferable to use an exposure device such as a mask alignment exposure machine and a stepper.

藉由使曝光後之組合物層與顯影液接觸而進行顯影，於基板上形成著色圖案。藉由顯影，組合物層之未曝光部溶解於顯影液中而去除。作為顯影液，例如較佳為氫氧化鉀、碳酸氫鈉、碳酸鈉、氫氧化四甲基銨等鹼性化合物之水溶液。該等鹼性化合物之水溶液中之濃度較佳為0.01~10質量%，更佳為0.03~5質量%。進而，顯影液可含有界面活性劑。 The exposed composition layer is brought into contact with a developing solution and developed to form a colored pattern on the substrate. By development, the unexposed portion of the composition layer is dissolved in the developing solution and removed. The developing solution is preferably an aqueous solution of a basic compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethylammonium hydroxide, and the like. The concentration of the basic compound in an 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.

顯影方法可為覆液法、浸漬法及噴霧法等中之任一種。進而，可於顯影時使基板傾斜為任意之角度。 The development method may be any of a liquid coating method, a dipping method, and a spray method. Furthermore, the substrate can be tilted to an arbitrary angle during development.

顯影後，較佳為進行水洗。 After development, washing with water is preferred.

進而，較佳為對所獲得之著色圖案進行後烘烤。後烘烤溫度較佳為150~250℃，更佳為160~235℃。後烘烤時間較佳為1~120分鐘，更佳為10~60分鐘。 Furthermore, it is preferable to post-bake 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.

如此獲得之著色圖案及著色塗膜可用作紅色彩色濾光片。根據本發明之紅色著色硬化性樹脂組合物，可製作亮度尤其高之紅色彩色濾光片，因此該紅色彩色濾光片可用作顯示裝置(例如液晶顯示裝置、有機EL(Electro Luminescence，電致發光)裝置等)、電子紙、固體攝像元件等所使用之紅色彩色濾光片。 The coloring pattern and the coloring film thus obtained can be used as a red color filter. According to the red colored curable resin composition of the present invention, a red color filter having a particularly high brightness can be produced. Therefore, the red color filter can be used as a display device (for example, a liquid crystal display device, an organic EL (Electro Luminescence, electro (Light-emitting) devices, etc.), electronic paper, solid-state imaging devices, and other red color filters.

實施例 Examples

繼而，列舉實施例而更具體地說明本發明。例中，表示含量或使用量之%及份只要無特別說明，則為質量基準。 Next, the present invention will be described more specifically with reference to examples. In the examples, the percentages and parts indicating the content or the amount used are the basis of quality unless otherwise specified.

以下，化合物之結構係藉由質量分析(LC(Liquid Chromatograph，液相層析儀)，Agilent製造之1200型； MASS(Mass Spectrometer，質譜儀)，Agilent製造之LC/MSD)而進行確認。 Hereinafter, the structure of the compound is determined by mass analysis (LC (Liquid Chromatograph, liquid chromatography), Model 1200 manufactured by Agilent; MASS (Mass Spectrometer, LC / MSD manufactured by Agilent).

[合成例1] [Synthesis example 1]

將式(1x)所表示之化合物12份、N-甲基-2-吡咯啶酮60份及哌啶(東京化成工業股份有限公司製造)12.6份混合，將所獲得之混合物於60℃下攪拌5小時。將上述反應液冷卻至室溫後，添加至水600份、35%鹽酸100份之混合液中並於室溫下攪拌1小時。作為抽氣過濾之殘渣而獲得所析出之結晶後，進行乾燥而獲得式(1-47)所表示之化合物12.4份。產率為83%。 12 parts of a compound represented by formula (1x), 60 parts of N-methyl-2-pyrrolidone, and 12.6 parts of piperidine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, and the obtained mixture was stirred at 60 ° C. 5 hours. The reaction solution was cooled to room temperature, and then added to a mixed solution of 600 parts of water and 100 parts of 35% hydrochloric acid, and stirred at room temperature for 1 hour. The precipitated crystal was obtained as a residue by suction filtration, and then dried to obtain 12.4 parts of a compound represented by formula (1-47). The yield was 83%.

式(1-47)所表示之化合物之鑑定 Identification of the compound represented by formula (1-47)

(質量分析)離子化模式=ESI+：m/z=[M+H]+503.4 (Mass analysis) Ionization mode = ESI +: m / z = [M + H] + 503.4

Exact Mass(準確質量)：502.2 Exact Mass: 502.2

[合成例2] [Synthesis example 2]

將式(1x)所表示之化合物15份、N-甲基-2-吡咯啶酮75份及十氫喹啉(東京化成工業股份有限公司製造)25.8份混合，將所獲得之混合物於110℃下攪拌24小時。將上述反應液冷卻至室溫後，添加至水600份、35%鹽酸100份之混 合液中並於室溫下攪拌1小時。作為抽氣過濾之殘渣而獲得所析出之結晶後，進行乾燥而獲得式(1-49)所表示之化合物19.5份。產率為86%。 15 parts of a compound represented by formula (1x), 75 parts of N-methyl-2-pyrrolidone, and 25.8 parts of decahydroquinoline (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, and the obtained mixture was heated at 110 ° C. Stir for 24 hours. After the above reaction solution was cooled to room temperature, it was added to a mixture of 600 parts of water and 100 parts of 35% hydrochloric acid. The mixture was stirred at room temperature for 1 hour. After obtaining the precipitated crystals as a residue by suction filtration, drying was performed to obtain 19.5 parts of a compound represented by the formula (1-49). The yield was 86%.

式(1-49)所表示之化合物之鑑定 Identification of the compound represented by formula (1-49)

(質量分析)離子化模式=ESI+：m/z=[M+H]+611.4 (Mass analysis) Ionization mode = ESI +: m / z = [M + H] + 611.4

Exact Mass：610.3 Exact Mass: 610.3

[合成例3] [Synthesis example 3]

於遮光條件下將式(1x)所表示之化合物20份、N-乙基-鄰甲苯胺(和光純藥工業股份有限公司製造)200份混合，將所獲得之溶液於110℃下攪拌6小時。將所獲得之反應液冷卻至室溫後，添加至水800份、35%鹽酸50份之混合液中並於室溫下攪拌1小時，結果析出結晶。作為抽氣過濾之殘渣而獲得所析出之結晶後，進行乾燥而獲得式(1-50)所表示之化合物24份。產率為80%。 Under light-shielding conditions, 20 parts of the compound represented by the formula (1x) and 200 parts of N-ethyl-o-toluidine (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed, and the obtained solution was stirred at 110 ° C for 6 hours. . After the obtained reaction solution was cooled to room temperature, it was added to a mixed solution of 800 parts of water and 50 parts of 35% hydrochloric acid and stirred at room temperature for 1 hour. As a result, crystals were precipitated. After obtaining the precipitated crystals as a residue by suction filtration, drying was performed to obtain 24 parts of a compound represented by the formula (1-50). The yield was 80%.

式(1-50)所表示之化合物之鑑定 Identification of the compound represented by formula (1-50)

(質量分析)離子化模式=ESI+：m/z=[M+H]+603.4 (Mass analysis) Ionization mode = ESI +: m / z = [M + H] + 603.4

Exact Mass：602.2 Exact Mass: 602.2

[合成例4] [Synthesis example 4]

將式(1x)所表示之化合物12份、N-甲基-2-吡咯啶酮60份及1-甲基哌啶(東京化成工業股份有限公司製造)14.7份混合，將所獲得之混合物於60℃下攪拌5小時。將上述反應液冷卻至室溫後，添加至水600份、35%鹽酸100份之混合液中並於室溫下攪拌1小時。作為抽氣過濾之殘渣而獲得所析出之結晶後，進行乾燥而獲得式(1-48)所表示之化合物13.8份。產率為88%。 12 parts of a compound represented by formula (1x), 60 parts of N-methyl-2-pyrrolidone and 14.7 parts of 1-methylpiperidine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, and the obtained mixture was mixed in Stir for 5 hours at 60 ° C. The reaction solution was cooled to room temperature, and then added to a mixed solution of 600 parts of water and 100 parts of 35% hydrochloric acid, and stirred at room temperature for 1 hour. After obtaining the precipitated crystals as a residue by suction filtration, drying was performed to obtain 13.8 parts of a compound represented by the formula (1-48). The yield was 88%.

式(1-48)所表示之化合物之鑑定 Identification of the compound represented by formula (1-48)

(質量分析)離子化模式=ESI+：m/z=[M+H]+531.2 (Mass analysis) Ionization mode = ESI +: m / z = [M + H] + 531.2

Exact Mass：530.2 Exact Mass: 530.2

[合成例5] [Synthesis example 5]

向具備冷凝管及攪拌裝置之燒瓶中，投入式(A1-1a)所表示之化合物及式(A1-1b)表示之化合物的混合物(商品名Chugai Aminol Fast Pink R，中外化成製造)15份、氯仿150份及N,N-二甲基甲醯胺8.9份，一面於攪拌下維持20℃以下，一面滴加添加亞硫醯氯10.9份。滴加結束後，升溫 至50℃，於同一溫度下維持5小時而使其反應，其後冷卻至20℃。一面於攪拌下將冷卻後之反應溶液維持於20℃以下，一面滴加添加2-乙基己胺12.5份及三乙胺22.1份之混合液。其後，於同一溫度下攪拌5小時而使其反應。繼而，利用旋轉蒸發器對所獲得之反應混合物進行溶劑餾去後，添加少量甲醇並遽烈地攪拌。於離子交換水375份之混合液中一面攪拌一面添加該混合物而析出結晶。將所析出之結晶過濾分離並利用離子交換水充分地洗淨，於60℃下進行減壓乾燥而獲得染料(甲)(式(A1-1-1)~式(A1-1-8)所表示之化合物之混合物)11.3份。 15 parts of a mixture of a compound represented by the formula (A1-1a) and a compound represented by the formula (A1-1b) (trade name Chugai Aminol Fast Pink R, manufactured by Chugai Chemicals) was put into a flask equipped with a condenser and a stirring device. 150 parts of chloroform and 8.9 parts of N, N-dimethylformamide were added dropwise to 10.9 parts of thionyl chloride while maintaining the temperature below 20 ° C under stirring. After the dropwise addition, the temperature was raised The temperature was reduced to 50 ° C, and the reaction was maintained at the same temperature for 5 hours, followed by cooling to 20 ° C. While maintaining the cooled reaction solution below 20 ° C with stirring, a mixed solution of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise. Then, it stirred at the same temperature for 5 hours, and made it react. Then, the obtained reaction mixture was subjected to solvent distillation using a rotary evaporator, and then a small amount of methanol was added and vigorously stirred. This mixture was added to a mixture of 375 parts of ion-exchanged water while stirring to precipitate crystals. The precipitated crystals were separated by filtration, sufficiently washed with ion-exchanged water, and dried under reduced pressure at 60 ° C. to obtain dyes (A) (formula (A1-1-1) to (A1-1-8) A mixture of the indicated compounds) 11.3 parts.

[合成例6] [Synthesis example 6]

向具備攪拌機、溫度計、回流冷凝器及滴液漏斗之燒瓶內，以0.02L/分鐘使氮流通而形成氮氣環境，添加丙二醇單甲醚乙酸酯305份，一面攪拌一面加熱至70℃。繼而，使丙烯酸60份、3,4-環氧三環[5.2.1.02.6]丙烯酸癸酯(以莫耳比計以50：50將式(I-1)所表示之化合物及式(II-1)所表示之化合物混合)440份溶解於丙二醇單甲醚乙酸酯140份中而製備溶液，使用滴液漏斗花費4小時將該溶解液滴加至保溫於70℃之燒瓶內。 In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, nitrogen was allowed to flow at 0.02 L / min to form a nitrogen atmosphere. 305 parts of propylene glycol monomethyl ether acetate was added, and heated to 70 ° C while stirring. Next, 60 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 2.6 ] decyl acrylate (50:50 in molar ratio, and a compound represented by formula (I-1) and formula (II- 1) Compounds indicated) 440 parts were dissolved in 140 parts of propylene glycol monomethyl ether acetate to prepare a solution, and the solution was added dropwise to a flask held at 70 ° C. using a dropping funnel over 4 hours.

另一方面，使用其他滴液漏斗，花費4小時將於丙二醇單甲醚乙酸酯225份中溶解有聚合起始劑2,2'-偶氮雙(2,4-二甲基戊腈)30份之溶液滴加至燒瓶內。聚合起始劑之溶液之滴加結束後，於70℃下保持4小時，其後冷卻至室溫，而獲得重量平均分子量(Mw)為9.1×103、分子量分佈為2.16、固形物成分為34.8%、固形物成分換算之酸值為81mgKOH/g之樹脂B1溶液。樹脂B1具有下述所示之結構單元。 On the other hand, using another dropping funnel, it took 4 hours to dissolve the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 225 parts of propylene glycol monomethyl ether acetate. 30 parts of the solution was added dropwise to the flask. After the dropwise addition of the solution of the polymerization initiator was maintained at 70 ° C. for 4 hours, and then cooled to room temperature, a weight average molecular weight (Mw) of 9.1 × 10 3 , a molecular weight distribution of 2.16, and a solid content of 34.8% resin B1 solution with an acid value of 81 mgKOH / g in terms of solid content. The resin B1 has a structural unit shown below.

於合成例中獲得之樹脂之重量平均分子量(Mw)及數量平均分子量(Mn)的測定係使用GPC(Gel Permeation Chromatography，凝膠滲透層析)法於以下之條件下進行。 The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in the synthesis example were measured using a GPC (Gel Permeation Chromatography) method under the following conditions.

裝置：K2479(島津製作所股份有限公司製造) Device: K2479 (made by Shimadzu Corporation)

管柱：SHIMADZU Shim-pack GPC-80M Column: SHIMADZU Shim-pack GPC-80M

管柱溫度：40℃ Column temperature: 40 ℃

溶劑：THF(Tetrahydrofuran，四氫呋喃) Solvent: THF (Tetrahydrofuran)

流速：1.0mL/min Flow rate: 1.0mL / min

檢測器：RI(Refractive Index，折射率) Detector: RI (Refractive Index, refractive index)

校正用標準物質：TSK STANDARD POLYSTYRENE F-40、F-4、F-288、A-2500、A-500(東梭股份有限公司製造) Calibration Standards: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosho Corporation)

將於上述中獲得之聚苯乙烯換算之重量平均分子量及數量平均分子量的比(Mw/Mn)設為分子量分佈。 The ratio (Mw / Mn) of the weight average molecular weight and the number average molecular weight of the polystyrene conversion obtained in the above was defined as the molecular weight distribution.

實施例1~8、10~12 Examples 1 to 8, 10 to 12

以成為表1所示之組成之方式將各成分混合而獲得紅色著色硬化性樹脂組合物。 Each component was mixed so that it might become a composition shown in Table 1, and the red coloring curable resin composition was obtained.

1)顏料係將顏料分散劑及E-12)欄記載之量之丙二醇單甲醚乙酸酯混合並預先使其分散。 1) Pigment system A pigment dispersant and propylene glycol monomethyl ether acetate in an amount described in the column 2) were mixed and dispersed in advance.

2)E-12)表示丙二醇單甲醚乙酸酯含量之合計。 2) E-1 2) represents the total content of propylene glycol monomethyl ether acetate.

再者，表1中，各成分係表示如下者。又，樹脂(B)表示固形物成分換算之質量份。 In addition, in Table 1, each component is shown as follows. The resin (B) represents parts by mass in terms of solid content.

化合物(1a)：A1-1：式(1-47)所表示之化合物 Compound (1a): A1-1: Compound represented by formula (1-47)

化合物(1a)：A1-2：式(1-49)所表示之化合物 Compound (1a): A1-2: Compound represented by formula (1-49)

化合物(1a)：A1-3：式(1-50)所表示之化合物 Compound (1a): A1-3: Compound represented by formula (1-50)

化合物(1a)：A1-4：式(1-48)所表示之化合物 Compound (1a): A1-4: Compound represented by formula (1-48)

化合物(1a)：A1-5：式(1-41)所表示之化合物 Compound (1a): A1-5: Compound represented by formula (1-41)

化合物(1a)：A1-6：式(1-37)所表示之化合物 Compound (1a): A1-6: Compound represented by formula (1-37)

顏料(A2)：A2-1：C.I.顏料紅254 Pigment (A2): A2-1: C.I. Pigment Red 254

顏料(A2)：A2-2：C.I.顏料紅242 Pigment (A2): A2-2: C.I. Pigment Red 242

顏料(A2)：A2-3：C.I.顏料紅177 Pigment (A2): A2-3: C.I. Pigment Red 177

樹脂(B)：樹脂B1 Resin (B): Resin B1

聚合性化合物(C)：二季戊四醇六丙烯酸酯(KAYARAD(註冊商標)DPHA(Dipentaerythritol Hexaacrylate)，日本化藥股份有限公司製造) Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA (Dipentaerythritol Hexaacrylate), manufactured by Nippon Kayaku Co., Ltd.)

聚合起始劑(D)：N-1919(ADEKA公司製造，O-醯基肟化合物) Polymerization initiator (D): N-1919 (manufactured by ADEKA, O-fluorenyl oxime compound)

聚合起始助劑(D1)：2,4-二乙基9-氧硫(KAYACURE(註冊商標)DETX-S(Diethylthioxanthone)，日本化藥股份有限公司製造) Polymerization initiation aid (D1): 2,4-diethyl 9-oxosulfur (KAYACURE (registered trademark) DETX-S (Diethylthioxanthone), manufactured by Nippon Kayaku Co., Ltd.)

聚合起始劑(D2)：OXE01(Ciba Specialty Chemicals) Polymerization initiator (D2): OXE01 (Ciba Specialty Chemicals)

溶劑(E)：E-1：丙二醇單甲醚乙酸酯 Solvent (E): E-1: Propylene glycol monomethyl ether acetate

溶劑(E)：E-2：丙二醇單甲醚 Solvent (E): E-2: Propylene glycol monomethyl ether

溶劑(E)：E-3：二丙酮醇 Solvent (E): E-3: Diacetone alcohol

界面活性劑(F)：氟系界面活性劑(Megafac(註冊商標)F554，DIC股份有限公司製造) Surfactant (F): Fluorine surfactant (Megafac (registered trademark) F554, manufactured by DIC Corporation)

[著色圖案之製作] [Making of colored patterns]

於藉由旋轉塗佈法將紅色著色硬化性樹脂組合物塗佈於2英吋見方之玻璃基板(伊格爾XG，康寧公司製造)上之後，於100℃下預烘烤3分鐘而形成組合物層。冷卻後，將基板上之組合物層與具有圖案之石英玻璃製光罩的間隔設為100μm，使用曝光機(TME-150RSK，Topcon股份有限公司製造)，於大氣環境下，以150mJ/cm2之曝光量(365nm基準)進行光照射。再者，使用形成有100μm線與間隙圖 案之光罩作為光罩。光照射後，於23℃下使上述塗膜於包含非離子系界面活性劑0.12%與碳酸鈉2%之水系顯影液中浸漬顯影80秒鐘，水洗後，於烘箱中於230℃下進行20分鐘後烘烤，而獲得著色圖案。 After applying a red colored curable resin composition to a 2 inch square glass substrate (Eger XG, manufactured by Corning) by a spin coating method, pre-baking at 100 ° C for 3 minutes to form a combination Physical layer. After cooling, the interval between the composition layer on the substrate and the patterned quartz glass photomask was set to 100 μm, and an exposure machine (TME-150RSK, manufactured by Topcon Co., Ltd.) was used at 150 mJ / cm 2 in the atmospheric environment. The exposure amount (based on 365 nm) was irradiated with light. Furthermore, a photomask in which a 100 μm line and gap pattern was formed was used. After light irradiation, the coating film was immersed and developed in an aqueous developing solution containing non-ionic surfactant 0.12% and sodium carbonate 2% at 23 ° C for 80 seconds. After washing with water, the coating was performed at 230 ° C for 20 seconds in an oven. Bake in minutes to obtain a colored pattern.

[膜厚測定] [Measurement of film thickness]

對所獲得之著色圖案，使用膜厚測定裝置(DEKTAK3，日本真空技術股份有限公司製造))進行膜厚測定。將結果示於表2中。 The obtained colored pattern was subjected to film thickness measurement using a film thickness measuring device (DEKTAK3, manufactured by Japan Vacuum Technology Co., Ltd.). The results are shown in Table 2.

[色度評價] [Chroma evaluation]

對於所獲得之玻璃基板上之著色圖案，使用測色機(OSP-SP-200，Olympus股份有限公司製造)測定分光，使用C光源之等色函數測定CIE(Commission International Eclairage，國際照明委員會)之XYZ表色系中的xy色度座標(x，y)及三刺激值Y。Y之值越大，表示亮度越高。將結果示於表2中。 The color pattern on the obtained glass substrate was measured using a colorimeter (OSP-SP-200, manufactured by Olympus Co., Ltd.), and the CIE (Commission International Eclairage, International Lighting Commission) The xy chromaticity coordinates (x, y) and tristimulus value Y in the XYZ color system. The larger the value of Y, the higher the brightness. The results are shown in Table 2.

[對比度評價] [Contrast evaluation]

除不使用光罩而進行曝光，且未進行顯影以外，進行與著色圖案之形成同樣之操作而製作玻璃基板上之著色塗膜。對該所獲得之玻璃基板上之著色塗膜，使用對比度測色機(CT-1，Tsubosaka電機公司製造，檢測器，BM-5A，光源：F-10)，將空白值設為30000而測定對比度。將利用偏光膜(POLAX-38S，Luceo公司製造)夾持玻璃基板上之著色塗膜而成者設為測定樣品。將結果示於表2中。 Except that exposure was performed without using a photomask and development was not performed, the same operation as in the formation of a colored pattern was performed to prepare a colored coating film on a glass substrate. The color coating film on the obtained glass substrate was measured using a contrast colorimeter (CT-1, manufactured by Tsubosaka Electric Co., Ltd., detector, BM-5A, light source: F-10), and the blank value was measured at 30,000. Contrast. A coloring film (POLAX-38S, manufactured by Luceo) was used to hold a colored coating film on a glass substrate as a measurement sample. The results are shown in Table 2.

實施例14 Example 14

除將式(1-47)所表示之化合物變更為C.I.酸性紅52以外，以與實施例1同樣之方式製備紅色著色硬化性樹脂組合物。對該紅色著色硬化性樹脂組合物進行與實施例1同樣之操作而獲得高亮度之著色圖案。 A red colored curable resin composition was prepared in the same manner as in Example 1 except that the compound represented by the formula (1-47) was changed to C.I. Acid Red 52. This red colored curable resin composition was subjected to the same operation as in Example 1 to obtain a colored pattern with high brightness.

根據本發明之紅色著色硬化性樹脂組合物，可製造高亮度之紅色彩色濾光片。 According to the red colored curable resin composition of the present invention, a red color filter with high brightness can be manufactured.

Claims (4)

一種紅色著色硬化性樹脂組合物，其包含著色劑、樹脂、聚合性化合物及聚合起始劑，且著色劑為包含式(1a)所表示之化合物、及選自由黃色顏料、橙色顏料及紅色顏料所組成之群中之至少一種顏料者；式(1a)所表示之化合物與該顏料之含有比率以質量基準計為5：95~30：70；
Figure TWI635326B_C0001
[式(1a)中，R1及R3相互獨立表示碳數1~20之一價飽和烴基或可具有取代基之碳數6~10之一價芳香族烴基，R2及R4相互獨立表示可具有取代基之碳數6~10之一價芳香族烴基，該飽和烴基所含之氫原子可經碳數6~10之芳香族烴基或鹵素原子取代，該芳香族烴基所含之氫原子可經碳數1~3之烷氧基取代，上述飽和烴基所含之-CH2-可經-O-、-CO-或-NR11-取代；R1及R2可與氮原子一同形成包含氮原子之環，R3及R4可與氮原子一同形成包含氮原子之環；R5表示-OH、-SO3 -、-SO3H、-SO3 -Z+、-CO2H、-CO2 -Z+、-CO2R8、-SO3R8或-SO2NR9R10；R6及R7分別獨立表示氫原子或碳數1~6之烷基；m表示0~5之整數；於m為2以上之時，複數個R5可相同亦可不同；a表示0或1之整數；X表示鹵素原子；Z+表示+N(R11)4、Na+或K+；R8表示碳數1~20之一價飽和烴基，該飽和烴基所含之氫原子可經鹵素原子取代；R9及R10相互獨立表示氫原子或可具有取代基之碳數1~20之一價飽和烴基，該飽和脂肪族烴基所含之-CH2-可經-O-、-CO-、-NH-或-NR8-取代，R9及R10亦可相互鍵結而與氮原子一同形成3~10員含氮雜環；R11相互獨立表示氫原子、碳數1~20之一價飽和烴基或碳數7~10之芳烷基]。A red colored curable resin composition comprising a colorant, a resin, a polymerizable compound, and a polymerization initiator, and the colorant comprises the compound represented by formula (1a), and is selected from the group consisting of yellow pigment, orange pigment, and red pigment At least one pigment in the group; the content ratio of the compound represented by formula (1a) to the pigment is 5: 95 ~ 30: 70 on a mass basis;
Figure TWI635326B_C0001
[In formula (1a), R 1 and R 3 independently represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, and R 2 and R 4 are independent of each other Represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted by an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom, and the hydrogen contained in the aromatic hydrocarbon group The atoms may be substituted with alkoxy groups having 1 to 3 carbon atoms, -CH 2 -contained in the above saturated hydrocarbon group may be substituted with -O-, -CO- or -NR 11- ; R 1 and R 2 may be together with the nitrogen atom form a ring comprising the nitrogen atom, R 3 and R 4 may form together with the nitrogen atom of the ring comprising a nitrogen atom; R 5 represents -OH, -SO 3 -, -SO 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z + , -CO 2 R 8 , -SO 3 R 8 or -SO 2 NR 9 R 10 ; R 6 and R 7 independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; m Represents an integer from 0 to 5; when m is 2 or more, a plurality of R 5 may be the same or different; a represents an integer of 0 or 1; X represents a halogen atom; Z + represents + N (R 11 ) 4 , Na + or K +; R 8 represents one of 1 to 20 carbon atoms, monovalent saturated hydrocarbon group, the hydrogen atom contained in the hydrocarbon group may be saturated Su atoms; R 9 and R 10 each independently represent a hydrogen atom or a substituent group having a carbon number of one of the monovalent saturated hydrocarbon group having 1 to 20, which contain saturated aliphatic hydrocarbon group of -CH 2 - may be -O -, - CO-, -NH- or -NR 8 -substitution, R 9 and R 10 can also be bonded to each other to form a 3- to 10-membered nitrogen-containing heterocyclic ring with the nitrogen atom; R 11 independently represents a hydrogen atom and a carbon number of 1 ~ 20 monovalent saturated hydrocarbon group or aralkyl group having 7 to 10 carbon atoms]. 如請求項1之紅色著色硬化性樹脂組合物，其中顏料係選自由C.I.顏料黃138、139、150、C.I.顏料紅177、242及254所組成之群中之至少一種。The red colored curable resin composition according to claim 1, wherein the pigment is at least one selected from the group consisting of C.I. Pigment Yellow 138, 139, 150, C.I. Pigment Red 177, 242, and 254. 一種紅色彩色濾光片，其係藉由如請求項1或2之紅色著色硬化性樹脂組合物而形成。A red color filter formed by the red colored curable resin composition according to claim 1 or 2. 一種顯示裝置，其包含如請求項3之紅色彩色濾光片。A display device comprising a red color filter as in claim 3.
TW101146261A 2011-12-09 2012-12-07 Red colored curable resin composition TWI635326B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011269971 2011-12-09
JP2011-269971 2011-12-09

Publications (2)

Publication Number Publication Date
TW201331712A TW201331712A (en) 2013-08-01
TWI635326B true TWI635326B (en) 2018-09-11

Family

ID=48862148

Family Applications (1)

Application Number Title Priority Date Filing Date
TW101146261A TWI635326B (en) 2011-12-09 2012-12-07 Red colored curable resin composition

Country Status (3)

Country Link
JP (2) JP6461453B2 (en)
KR (1) KR102062295B1 (en)
TW (1) TWI635326B (en)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104672198B (en) * 2013-11-26 2018-11-16 东友精细化工有限公司 Compound and colored curable resin composition
TWI664243B (en) * 2014-06-05 2019-07-01 韓商東友精細化工有限公司 Colored curable resin composition
TWI674303B (en) * 2014-10-30 2019-10-11 日商住友化學股份有限公司 Colored curable resin composition
TWI674477B (en) * 2014-12-25 2019-10-11 日商富士軟片股份有限公司 Coloring curable composition, color filter, pattern forming method, method of manufacturing color filter, solid-state imaging element, and image display device
CN105929636A (en) * 2015-02-26 2016-09-07 东友精细化工有限公司 Coloring Curable Resin Composition, Color Filter, And Display
CN106019836B (en) 2015-03-27 2021-08-27 东友精细化工有限公司 Colored curable resin composition
JP6937109B2 (en) * 2016-11-07 2021-09-22 東友ファインケム株式会社Ｄｏｎｇｗｏｏ Ｆｉｎｅ−Ｃｈｅｍ Ｃｏ．， Ｌｔｄ． Colored resin composition
JP7079128B2 (en) * 2017-03-29 2022-06-01 住友化学株式会社 Color curable resin composition
JP7046777B2 (en) * 2017-11-10 2022-04-04 東友ファインケム株式会社 Color curable resin composition, color filter and display device
JP7063663B2 (en) * 2018-03-19 2022-05-09 東友ファインケム株式会社 Color curable resin composition, color filter and display device
JP7366564B2 (en) * 2019-03-28 2023-10-23 株式会社Ｄｎｐファインケミカル Red colored resin composition for color filters, red coloring material dispersion for color filters, cured products, color filters, and display devices

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201042368A (en) * 2009-02-13 2010-12-01 Sumitomo Chemical Co Coloring photo-sensitive resin composition and color filter

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04274410A (en) * 1990-12-13 1992-09-30 Samsung Electron Devices Co Ltd Color filter for liquid crystal display element
JP2008242311A (en) * 2007-03-28 2008-10-09 Sumitomo Chemical Co Ltd Colored photosensitive resin composition, and color filter array using the same, and solid state imaging device
JP2011039317A (en) * 2009-08-12 2011-02-24 Sumitomo Chemical Co Ltd Colored photosensitive resin composition
WO2011018987A1 (en) * 2009-08-12 2011-02-17 住友化学株式会社 Display device
JP2011118369A (en) * 2009-10-28 2011-06-16 Sumitomo Chemical Co Ltd Colored photosensitive resin composition
JP2011118368A (en) * 2009-10-28 2011-06-16 Sumitomo Chemical Co Ltd Colored photosensitive resin composition
JP5772263B2 (en) * 2010-07-30 2015-09-02 Jsr株式会社 Coloring composition, color filter and display element
JP5737078B2 (en) * 2011-02-28 2015-06-17 東洋インキＳｃホールディングス株式会社 Red coloring composition for color filter, and color filter
JP2013041145A (en) * 2011-08-17 2013-02-28 Toyo Ink Sc Holdings Co Ltd Coloring composition for color filter, and color filter
JP5789847B2 (en) * 2011-10-12 2015-10-07 東洋インキＳｃホールディングス株式会社 Coloring composition for color filter, and color filter
JP2013101287A (en) * 2011-11-10 2013-05-23 Toyo Ink Sc Holdings Co Ltd Coloring composition for color filter, and color filter

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201042368A (en) * 2009-02-13 2010-12-01 Sumitomo Chemical Co Coloring photo-sensitive resin composition and color filter

Also Published As

Publication number Publication date
TW201331712A (en) 2013-08-01
JP2013140348A (en) 2013-07-18
KR102062295B1 (en) 2020-01-03
KR20130065617A (en) 2013-06-19
JP6713517B2 (en) 2020-06-24
JP2019053303A (en) 2019-04-04
JP6461453B2 (en) 2019-01-30

Similar Documents

Publication Publication Date Title
JP6713517B2 (en) Red colored curable resin composition
TWI544035B (en) Colored curable resin composition
TWI600968B (en) Colored curable resin composition
TWI550347B (en) Colored photosensitive resin composition
TW201335704A (en) Colored curable resin composition
TWI578105B (en) Coloring the photosensitive resin composition
TWI565759B (en) Colored curable resin composition
TW201823377A (en) Colored curable resin composition, color filter formed from the colored curable resin composition and display device including the color filter
KR102003237B1 (en) Colored photosensitive resin composition
KR101837527B1 (en) Colored photosensitive resin composition
TWI604271B (en) Colored curable resin composition
TW201321893A (en) Colored photosensitive resin composition
KR101632461B1 (en) Colored curable resin composition
TWI615680B (en) Colored photosensitive resin composition
TWI570507B (en) Colored photosensitive resin composition
TWI566043B (en) Coloring the photosensitive resin composition
TWI566045B (en) Coloring the photosensitive resin composition