TWI679499B - Colored curable resin composition, color filter and liquid crystal display device - Google Patents

Colored curable resin composition, color filter and liquid crystal display device Download PDF

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TWI679499B
TWI679499B TW105108526A TW105108526A TWI679499B TW I679499 B TWI679499 B TW I679499B TW 105108526 A TW105108526 A TW 105108526A TW 105108526 A TW105108526 A TW 105108526A TW I679499 B TWI679499 B TW I679499B
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hydrocarbon group
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dye
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TW201642036A (en
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中野駿
Suguru NAKANO
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南韓商東友精細化工有限公司
Dongwoo Fine-Chem Co., Ltd.
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Abstract

本發明以得到圖案形狀優異的濾色器為課題。本發明的著色固化性樹脂組合物含有著色劑、樹脂、聚合性化合物和聚合引發劑，其特徵在於，上述著色劑包含染料，上述染料的含量在著色劑100質量份中為90質量份以上，上述聚合引發劑包含由下述式(d1)表示的化合物。 An object of the present invention is to obtain a color filter having an excellent pattern shape. The colored curable resin composition of the present invention contains a colorant, a resin, a polymerizable compound, and a polymerization initiator. The colorant contains a dye, and the content of the dye is 90 parts by mass or more in 100 parts by mass of the colorant. The polymerization initiator includes a compound represented by the following formula (d1).

Figure TWI679499B_A0001
Figure TWI679499B_A0001

Description

著色固化性樹脂組合物、濾色器及液晶顯示裝置 Colored curable resin composition, color filter and liquid crystal display device 技術領域 Technical field

本發明涉及著色固化性樹脂組合物。 The present invention relates to a colored curable resin composition.

背景技術 Background technique

著色固化性樹脂組合物用於在液晶顯示裝置、電致發光顯示裝置及等離子體顯示器等顯示裝置中使用的濾色器的製造。專利文獻1中記載了包含由三芳基甲烷系鹼性染料和抗衡化合物組成的造鹽化合物、和肟酯系光聚合引發劑的感光性著色組合物(專利文獻1)。 The colored curable resin composition is used for producing a color filter used in a display device such as a liquid crystal display device, an electroluminescent display device, and a plasma display. Patent Document 1 describes a photosensitive coloring composition containing a salt-forming compound composed of a triarylmethane-based basic dye and a counter compound, and an oxime ester-based photopolymerization initiator (Patent Document 1).

另外，作為光聚合性的組合物中的高感度的光引發劑，提出了苯并咔唑化合物的肟酯衍生物(專利文獻2)。 In addition, as a highly sensitive photoinitiator in a photopolymerizable composition, an oxime ester derivative of a benzocarbazole compound has been proposed (Patent Document 2).

現有技術文獻 Prior art literature 專利文獻 Patent literature

專利文獻1：日本特開2014-170098號公報 Patent Document 1: Japanese Patent Application Laid-Open No. 2014-170098

專利文獻2：日本特表2014-500852號公報 Patent Document 2: Japanese Patent Publication No. 2014-500852

對於以往已知的上述的感光性著色組合物，得到的著色圖案、即濾色器的形狀不能充分地滿足需要。因此， 本發明中以得到圖案形狀優異的濾色器作為課題。 With the conventionally known photosensitive coloring composition, the coloring pattern obtained, that is, the shape of the color filter, cannot sufficiently meet the needs. therefore, The object of the present invention is to obtain a color filter having an excellent pattern shape.

專利文獻2教導了使用苯并咔唑化合物的肟酯衍生物作為光聚合性組合物中的光引發劑，但對於該組合物含有著色劑時的圖案形狀的變化沒有任何教導。 Patent Document 2 teaches the use of an oxime ester derivative of a benzocarbazole compound as a photoinitiator in a photopolymerizable composition, but does not teach any change in the shape of the pattern when the composition contains a colorant.

本發明包含以下的發明。 The present invention includes the following inventions.

[1]著色固化性樹脂組合物，其含有著色劑、樹脂、聚合性化合物和聚合引發劑，作為上述著色劑，包含染料，上述染料的含量在著色劑100質量份中為90質量份以上，上述聚合引發劑包含由下述式(d1)表示的化合物。 [1] A colored curable resin composition containing a colorant, a resin, a polymerizable compound, and a polymerization initiator. The colorant contains a dye, and the content of the dye is 90 parts by mass or more in 100 parts by mass of the colorant. The polymerization initiator includes a compound represented by the following formula (d1).

Figure TWI679499B_D0001
[式(d1)中，Rd1表示可具有取代基的碳數6~18的芳香族烴基、可具有取代基的碳數3~36的雜環基、可具有取代基的碳數1~15的烷基、或者可具有取代基的碳數7~33的芳烷基，上述烷基或芳烷基中所含的亞甲基(-CH2-)可替換為-O-、-CO-、-S-、-SO2-或-N(Rd5)-。
Figure TWI679499B_D0001
 [In formula (d1), R d1 represents an aromatic hydrocarbon group having 6 to 18 carbons which may have a substituent, a heterocyclic group having 3 to 36 carbons which may have a substituent, and 1 to 15 carbons which may have a substituent Alkyl group or an aralkyl group having 7 to 33 carbon atoms which may have a substituent, the methylene group (-CH 2- ) contained in the alkyl group or aralkyl group may be replaced with -O-, -CO- , -S-, -SO 2 -or -N (R d5 )-.

Rd2表示碳數6~18的芳香族烴基、碳數3~36的雜環基、或碳數1~10的烷基。 R d2 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, a heterocyclic group having 3 to 36 carbon atoms, or an alkyl group having 1 to 10 carbon atoms.

Rd3表示可具有取代基的碳數6~18的芳香族烴基、可具有取代基的碳數3~36的雜環基。 R d3 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, and a heterocyclic group having 3 to 36 carbon atoms which may have a substituent.

Rd4表示可具有取代基的碳數6~18的芳香族烴基、或可具有取代基的碳數1~15的脂肪族烴基，上述脂肪族烴基中所含的亞甲基(-CH2-)可替換為-O-、-CO-或-S-，上述脂肪族烴基中所含的次甲基(-CH<)可替換為-PO3<，上述脂肪族烴基中所含的氫原子可被OH基取代。 R d4 represents an aromatic hydrocarbon group having 6 to 18 carbons which may have a substituent, or an aliphatic hydrocarbon group having 1 to 15 carbons which may have a substituent, and the methylene group (-CH 2- ) Can be replaced with -O-, -CO- or -S-, and the methine group (-CH <) contained in the aliphatic hydrocarbon group can be replaced with -PO 3 <, the hydrogen atom contained in the aliphatic hydrocarbon group It may be substituted by an OH group.

Rd5表示碳數1~10的烷基，該烷基中所含的亞甲基(-CH2-)可替換為-O-或-CO-。] R d5 represents an alkyl group having 1 to 10 carbon atoms, and the methylene group (-CH 2- ) contained in the alkyl group may be replaced with -O- or -CO-. ]

[2][1]所述的著色固化性樹脂組合物，其中，作為上述著色劑，不含顏料。 [2] The colored curable resin composition according to [1], wherein the colorant contains no pigment.

[3][1]或[2]所述的著色固化性樹脂組合物，其中，上述染料包含選自二苯并哌喃染料、三芳基甲烷染料、由式(Ab2)表示的化合物、香豆素染料、蒽醌染料和四氮雜卟啉染料中的至少一種的染料。 [3] The colored curable resin composition according to [1] or [2], wherein the dye contains a compound selected from the group consisting of a dibenzopiperan dye, a triarylmethane dye, a compound represented by the formula (Ab2), and coumarin A dye of at least one of a pigment dye, an anthraquinone dye, and a tetraazaporphyrin dye.

Figure TWI679499B_D0002
[式(Ab2)中，R41~R44各自獨立地表示氫原子、碳數1~20的飽和烴基、可具有取代基的碳數6~20的芳香族烴基或可具有取代基的碳數7~30的芳烷基，該碳數1~20的飽和烴基中， 該飽和烴基中所含的氫原子可被取代或未取代的氨基或鹵素原子取代，該飽和烴基的碳數為2~20的情況下，該飽和烴基中所含的亞甲基可替換為氧原子或-CO-。不過，該碳數2~20的飽和烴基中，鄰接的亞甲基不會同時被替換為氧原子，末端的亞甲基不會被替換為氧原子或-CO-。R41與R42可結合並與它們結合的氮原子一起形成環，R43與R44可結合並與它們結合的氮原子一起形成環。
Figure TWI679499B_D0002
 [In the formula (Ab2), R 41 to R 44 each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a carbon number which may have a substituent. An aralkyl group of 7 to 30. In the saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a substituted or unsubstituted amino or halogen atom. The carbon number of the saturated hydrocarbon group is 2 to In the case of 20, the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or -CO-. However, in this saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent methylene group will not be replaced with an oxygen atom at the same time, and the terminal methylene group will not be replaced with an oxygen atom or -CO-. R 41 and R 42 may be combined and form a ring with the nitrogen atom to which they are bonded, and R 43 and R 44 may be combined and form a ring with the nitrogen atom to which they are bonded.

R47~R54各自獨立地表示氫原子、鹵素原子、硝基、羥基、或碳數1~8的烷基，該烷基的碳數為2~8的情況下，構成該烷基的亞甲基可被氧原子或-CO-替換，R48與R52可相互結合而形成-NH-、-S-或-SO2-。不過，該烷基中，鄰接的亞甲基不會同時被氧原子替換，末端的亞甲基不會被氧原子或-CO-替換。 R 47 to R 54 each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms. When the alkyl group has 2 to 8 carbon atoms, the alkyl group constituting the alkyl group is The methyl group may be replaced by an oxygen atom or -CO-, and R 48 and R 52 may be combined with each other to form -NH-, -S-, or -SO 2- . However, in this alkyl group, adjacent methylene groups are not replaced by oxygen atoms at the same time, and terminal methylene groups are not replaced by oxygen atoms or -CO-.

環T1表示可具有取代基的碳數3~10的芳香族雜環。 Ring T 1 represents an aromatic heterocyclic ring having 3 to 10 carbon atoms which may have a substituent.

[Y]m-表示任意的m價的陰離子。] [Y] m- represents an arbitrary m-valent anion. ]

[4][1]~[3]的任一項所述的著色固化性樹脂組合物，其中，作為上述染料，包含二苯并哌喃染料和由上述式(Ab2)表示的化合物。 [4] The colored curable resin composition according to any one of [1] to [3], wherein the dye includes a dibenzopiperan dye and a compound represented by the formula (Ab2).

[5]由[1]~[4]的任一項所述的著色固化性樹脂組合物形成的濾色器。 [5] A color filter formed from the colored curable resin composition according to any one of [1] to [4].

[6]液晶顯示裝置，其包含[5]所述的濾色器。 [6] A liquid crystal display device including the color filter according to [5].

根據本發明的著色固化性樹脂組合物，能夠形成形狀優異的濾色器。 According to the colored curable resin composition of the present invention, a color filter having an excellent shape can be formed.

圖1為說明著色圖案的斷面形狀的概略圖。 FIG. 1 is a schematic diagram illustrating a cross-sectional shape of a colored pattern.

具體實施方式 detailed description

本發明的著色固化性樹脂組合物包含著色劑(A)、樹脂(B)、聚合性化合物(C)和聚合引發劑(D)。 The colored curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D).

本說明書中，作為各成分例示的化合物只要無特別說明，可以單獨或將多種組合使用。 In the present specification, the compounds exemplified as respective components may be used alone or in combination of a plurality of types unless otherwise specified.

<著色劑(A)> <Colorant (A)>

本發明的著色固化性樹脂組合物中，作為著色劑(A)，包含染料。 The colored curable resin composition of the present invention contains a dye as a colorant (A).

作為上述染料，可列舉例如色指數(The Society of Dyers and Colourists出版)中在顏料以外分類為具有色調的物質的化合物、染色筆記(色染社)中記載的公知的染料。另外，根據化學結構，可列舉偶氮染料、菁染料、酞菁染料、蒽醌染料、萘醌染料、醌亞胺染料、次甲基染料、偶氮甲鹼染料、方酸(

Figure TWI679499B_D0003
)染料、吖啶染料、苯乙烯基染料、喹啉染料及硝基染料等。這些中，優選在有機溶劑中溶解的染料。 Examples of the dye include a compound classified as a substance having a color tone other than a pigment in the color index (published by The Society of Dyers and Colourists), and a publicly-known dye described in Dyeing Notes (Seiransha). In addition, according to the chemical structure, azo dyes, cyanine dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, azomethine dyes, and squaric acid (
Figure TWI679499B_D0003
) Dyes, acridine dyes, styryl dyes, quinoline dyes and nitro dyes. Among these, a dye dissolved in an organic solvent is preferable.

具體地，可列舉C.I.溶劑黃4、14、15、23、24、25、38、62、63、68、79、81、82、83、89、94、98、99、162；C.I.溶劑橙2、7、11、15、26、41、54、56、99；C.I.溶劑紅24、49、90、91、111、118、119、122、124、 125、127、130、132、143、145、146、150、151、155、160、168、169、172、175、181、207、222、227、230、245、247；C.I.溶劑紫11、13、14、26、31、36、37、38、45、47、48、51、59、60；C.I.溶劑藍14、18、35、36、45、58、59、59：1、63、68、69、78、79、83、94、97、98、100、101、102、104、105、111、112、122、128、132、136、139；C.I.溶劑綠1、3、5、28、29、32、33；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.酸性橙6、7、8、10、12、26、50、51、52、56、62、63、64、74、75、94、95、107、108、149、162、169、173；C.I.酸性紅73、80、91、97、138、151、211、274；C.I.酸性綠3、5、9、25、27、28、41；C.I.酸性紫34、120；C.I.酸性藍25、27、40、45、78、80、112；等C.I.酸性染料、 C.I.鹼性綠1；等C.I.鹼性染料、C.I.活性黃2、76、116；C.I.活性橙16；等C.I.活性染料、C.I.直接黃2、4、28、33、34、35、38、39、43、44、47、50、54、58、68、69、70、71、86、93、94、95、98、102、108、109、129、132、136、138、141；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.直接藍40；等C.I.直接染料、C.I.分散黃51、54、76；C.I.分散紫26、27；C.I.分散藍1、14、56、60；等C.I.分散染料、作為C.I.媒染染料，C.I.媒染黃5、8、10、16、20、26、30、31、33、42、43、45、56、61、62、65；C.I.媒染橙3、4、5、8、12、13、14、20、21、23、24、28、29、32、34、35、36、37、42、43、47、48；等C.I.媒染染料、C.I.還原綠1等C.I.還原染料等。 Specific examples include CI solvent yellow 4, 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162; CI solvent orange 2 , 7, 11, 15, 26, 41, 54, 56, 99; CI Solvent Red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247; CI solvent violet 11, 13 , 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; CI Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139; CI Solvent Green 1, 3, 5, 28, 29 , 32, 33; CI solvent dyes, CI acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76 , 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169 , 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240 , 242, 243, 251; CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173; CI Acid Red 73, 80, 91, 97, 138, 151, 211, 274; CI Acid Green 3, 5, 9, 25, 27, 28, 41; CI Acid Violet 34, 120; CI Acid Blue 25, 27, 40, 45, 78, 80, 112; etc. CI acid dyes, CI basic green 1; other CI basic dyes, CI active yellow 2, 76, 116; CI active orange 16; other CI reactive dyes, CI direct yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141; CI Direct Orange 26 , 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI Direct Blue 40; CI Direct Dye, CI Disperse Yellow 51, 54, 76; CI disperse violet 26, 27; CI disperse blue 1, 14, 56, 60; CI disperse dyes, etc., as CI mordant dyes, CI mordant yellow 5, 8, 10, 16, 20, 26, 30, 31 , 33, 42, 43, 45, 56, 61, 62, 65; CI Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; etc. CI mordant dyes, CI reducing green 1 and other CI reducing dyes.

其中，上述染料優選包含選自二苯并哌喃染料(Aa)、三芳基甲烷染料(Ab)、由式(Ab2)表示的化合物、香豆素染料(Ac)、蒽醌染料(Ad)、和四氮雜卟啉染料(Ae)中的至少一種的染料(以下有時稱為“染料(A1)”)，更優選包含選自二苯并哌喃染料(Aa)、三芳基甲烷染料(Ab)、和由式(Ab2)表示的化合物中的至少一種的染料，進一步優選包含二苯 并哌喃染料(Aa)、和三芳基甲烷染料(Ab)或由式(Ab2)表示的化合物，特別優選包含二苯并哌喃染料及由式(Ab2)表示的化合物。 Among them, the dye preferably contains a compound selected from the group consisting of a dibenzopiperan dye (Aa), a triarylmethane dye (Ab), a compound represented by the formula (Ab2), a coumarin dye (Ac), an anthraquinone dye (Ad), And at least one of a tetraazaporphyrin dye (Ae) (hereinafter sometimes referred to as "dye (A1)"), more preferably a dye selected from a dibenzopiperan dye (Aa), a triarylmethane dye ( Ab) and a dye of at least one of the compounds represented by the formula (Ab2), further preferably containing diphenyl The piperane dye (Aa), the triarylmethane dye (Ab), or a compound represented by the formula (Ab2), particularly preferably a dibenzopiperan dye and a compound represented by the formula (Ab2).

本說明書中，所謂染料，是指在溶劑中可溶的色素。 In this specification, a dye means a pigment which is soluble in a solvent.

二苯并哌喃染料(Aa)是包含在分子內具有二苯并哌喃骨架的化合物的染料。作為二苯并哌喃染料(Aa)，例如可列舉C.I.酸性紅51(以下省略C.I.酸性紅的記載，只記載編號。其他也同樣。)、52、87、92、94、289、388等C.I.酸性紅染料；C.I.酸性紫9、30、102等C.I.酸性紫染料；C.I.鹼性紅1(若丹明6G)、2、3、4、8、10(若丹明B)、11等C.I.鹼性紅染料；C.I.鹼性紫10、11、25等C.I.鹼性紫染料；C.I.溶劑紅218等C.I.溶劑紅染料；C.I.媒染紅27等C.I.媒染紅染料；C.I.活性紅36(玫瑰紅B)等C.I.活性紅染料；磺基若丹明G；特開2010-32999號公報中記載的二苯并哌喃染料；以及專利第4492760號公報中記載的二苯并哌喃染料；等。作為二苯并哌喃染料(Aa)，優選在有機溶劑中溶解的染料。 The dibenzopiperan dye (Aa) is a dye containing a compound having a dibenzopiperan skeleton in the molecule. Examples of the dibenzopiperan dye (Aa) include CI acid red 51 (hereinafter, the description of CI acid red is omitted, and only the number is described. The same applies to others), CIs such as 52, 87, 92, 94, 289, and 388 Acid red dyes; CI acid violet dyes such as CI acid violet 9, 30, 102; CI basic red 1 (rhodamine 6G), 2, 3, 4, 8, 10 (rhodamine B), 11 and other CI bases Red dyes; CI basic violet dyes such as CI Basic Violet 10, 11, 25; CI solvent red dyes such as CI Solvent Red 218; CI mordant red dyes such as CI Mordant Red 27; CI reactive red 36 (Rose Red B), etc. CI reactive red dye; sulforhodamine G; dibenzopiperan dye described in JP-A-2010-32999; dibenzopiperan dye described in Patent No. 4492760; and the like. The dibenzopiperan dye (Aa) is preferably a dye dissolved in an organic solvent.

這些中，作為二苯并哌喃染料(Aa)，優選包含由式(1a)表示的化合物(以下有時稱為“化合物(1a)”。)的染料。化合物(1a)可以是其互變異構體。使用化合物(1a)的情況下，二苯并哌喃染料(Aa)中的化合物(1a)的含量優選為50質量%以上，更優選為70質量%以上，進一步優選為90質量%以上。特別地，作為二苯并哌喃染料(Aa)，優選只使用化合物(1a)。 Among these, as the dibenzopiperan dye (Aa), a dye containing a compound represented by formula (1a) (hereinafter sometimes referred to as “compound (1a)”) is preferred. The compound (1a) may be a tautomer thereof. When using the compound (1a), the content of the compound (1a) in the dibenzopiperan dye (Aa) is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more. In particular, as the dibenzopiperan dye (Aa), it is preferable to use only the compound (1a).

Figure TWI679499B_D0004
Figure TWI679499B_D0004

[式(1a)中，R1~R4相互獨立地表示氫原子、可以具有取代基的碳數1~20的1價的飽和烴基、或者、可以具有取代基的碳數6~10的1價的芳香族烴基，該飽和烴基中所含的亞甲基(-CH2-)可以被-O-、-CO-或-NR11-替代。R1和R2可一起形成含氮原子的環，R3和R4可一起形成含氮原子的環。 [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 which may have a substituent, or a 1 to 6 carbon atom which may have a substituent. A valent aromatic hydrocarbon group, and the methylene group (-CH 2- ) contained in the saturated hydrocarbon group may be replaced by -O-, -CO-, or -NR 11- . R 1 and R 2 may together form a nitrogen atom-containing ring, and R 3 and R 4 may together form a nitrogen atom-containing ring.

R5表示-OH、-SO3 -、-SO3H、-SO3 -Z+、-CO2H、-CO2 -Z+、-CO2R8、-SO3R8或-SO2NR9R10。 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 .

R6和R7相互獨立地表示氫原子或碳數1~6的烷基。 R 6 and R 7 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

m表示0~5的整數。m為2以上時，多個R5可以相同，也可不同。 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表示0或1的整數。 a represents an integer of 0 or 1.

X表示鹵素原子。 X represents a halogen atom.

Z+表示+N(R11)4、Na+或K+，4個R11可以相同，也可不同。 Z + represents + N (R 11 ) 4 , Na + or K + . The four R 11 may be the same or different.

R8表示碳數1~20的1價的飽和烴基，該飽和烴基中所含的氫原子可以被鹵素原子取代。 R 8 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.

R9及R10相互獨立地表示氫原子或可具有取代基的碳數1~20的1價的飽和烴基，該飽和烴基中所含的-CH2-可以 被-O-、-CO-、-NH-或-NR8-替代，R9和R10可相互結合以形成含氮原子的3~10元環的雜環。 R 9 and R 10 independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH 2 -contained in the saturated hydrocarbon group may be replaced by -O-, -CO-, Instead of -NH- or -NR 8- , R 9 and R 10 may be combined with each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom.

R11表示氫原子、碳數1~20的1價的飽和烴基或碳數7~10的芳烷基。] R 11 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. ]

式(1a)中，-SO3 -存在的情況下，其個數為1個。 In formula (1a), when -SO 3 -is present, the number is one.

作為R1~R4中的碳數6~10的1價的芳香族烴基，例如可列舉苯基、甲苯基、二甲苯基、均三甲苯基、丙基苯基及丁基苯基等。 Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R 1 to R 4 include phenyl, tolyl, xylyl, mesityl, propylphenyl, and butylphenyl.

作為該芳香族烴基可具有的取代基，可列舉鹵素原子、-R8、-OH、-OR8、-SO3 -、-SO3H、-SO3 -Z+、-CO2H、-CO2R8、-SR8、-SO2R8、-SO3R8或-SO2NR9R10，優選這些取代基將芳香族烴基中所含的氫原子取代。這些中，作為取代基，優選-SO3 -、-SO3H、-SO3 -Z+、-SO3R8及-SO2NR9R10，更優選-SO3 -Z+及-SO2NR9R10。作為這種情況下的-SO3 -Z+，優選-SO3 - +N(R11)4。另外，作為-SO2NR9R10，優選-SO2NHR9。如果R1~R4為這些基團，由包含化合物(1a)的本發明的著色固化性樹脂組合物能夠形成異物的產生少並且耐熱性優異的濾色器。 Examples of the aromatic hydrocarbon group may have a substituent group, 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. These substituents preferably substitute a hydrogen atom contained in an aromatic hydrocarbon group. Among these, as a substituent group, preferably -SO 3 -, -SO 3 H, -SO 3 - Z +, -SO 3 R 8 and -SO 2 NR 9 R 10, more preferably -SO 3 - Z + and -SO 2 NR 9 R 10 . As -SO 3 - Z + in this case, -SO 3- + N (R 11 ) 4 is preferred. Further, -SO 2 NR 9 R 10, preferably -SO 2 NHR 9. When R 1 to R 4 are these groups, the colored curable resin composition of the present invention containing the compound (1a) can form a color filter with little generation of foreign matter and excellent heat resistance.

作為R1~R4及R8~R11中的碳數1~20的1價的飽和烴基，例如可列舉甲基、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-乙基己基等分支鏈狀烷基；環丙基、環戊基、環己基、環庚基、環辛基、三環癸基等碳數3~20的環狀烷基。 Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R 1 to R 4 and R 8 to R 11 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl. Straight-chain alkyl groups such as methyl, nonyl, decyl, dodecyl, cetyl, eicosyl; isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl And other branched chain alkyl groups; cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl and other cyclic alkyl groups with 3 to 20 carbon atoms.

R1~R4中的該飽和烴基中所含的氫原子可以被例如作為取代基的碳數6~10的芳香族烴基或鹵素原子取代。作為可以取代R1~R4的飽和烴基的氫原子的碳數6~10的芳香族烴基，可列舉與作為R1~R4中的碳數6~10的芳香族烴基例示的基團同樣的基團。 The hydrogen atom contained in the saturated hydrocarbon group in R 1 to R 4 may be substituted with, for example, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom as a substituent. As the number of carbon atoms can be substituted saturated hydrocarbon group R 1 ~ R 4 are hydrogen atoms, aromatic hydrocarbon group having 6 to 10 include the same groups as R 1 ~ R 4 carbon atoms in the aromatic hydrocarbon group having 6 to 10 illustrate Examples of Group.

R9及R10中的該飽和烴基中所含的氫原子可以被例如作為取代基的羥基或鹵素原子取代。 The hydrogen atom contained in the saturated hydrocarbon group in R 9 and R 10 may be substituted with, for example, a hydroxyl group or a halogen atom as a substituent.

作為R1及R2一起形成的環、以及R3及R4一起形成的環，例如可列舉以下的環，更優選不含雙鍵的環。 Examples of the ring formed together by R 1 and R 2 and the ring formed together by R 3 and R 4 include the following rings, and more preferably a ring not containing a double bond.

Figure TWI679499B_D0005
Figure TWI679499B_D0005

作為-OR8，例如可列舉甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基、庚氧基、辛氧基、2-乙基己氧基及二十烷氧基等烷氧基等。 Examples of -OR 8 include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, and icosyl. Alkoxy and the like.

作為-CO2R8，例如可列舉甲氧基羰基、乙氧基羰基、丙氧基羰基、叔丁氧基羰基、己氧基羰基及二十烷氧基羰基等烷氧基羰基等。 Examples of -CO 2 R 8 include alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tert-butoxycarbonyl, hexyloxycarbonyl, and eicosyloxycarbonyl.

作為-SR8，例如可列舉甲基硫烷基、乙基硫烷基、丁基硫烷基、己基硫烷基、癸基硫烷基及二十烷基硫烷基等烷基硫烷基等。 Examples of -SR 8 include alkylsulfanyl groups such as methylsulfanyl, ethylsulfanyl, butylsulfanyl, hexylsulfanyl, decylsulfanyl, and eicosylsulfanyl. Wait.

作為-SO2R8，例如可列舉甲基磺醯基、乙基磺醯基、丁基磺醯基、己基磺醯基、癸基磺醯基及二十烷基磺醯基等烷基磺醯基等。 Examples of -SO 2 R 8 include alkylsulfonyl, methylsulfonyl, ethylsulfonyl, butylsulfonyl, hexylsulfonyl, decylsulfonyl, and eicosylsulfonyl.醯 基 et al.

作為-SO3R8，例如可列舉甲氧基磺醯基、乙氧基磺醯基、丙氧基磺醯基、叔丁氧基磺醯基、己氧基磺醯基及二十烷氧基磺醯基等烷氧基磺醯基等。作為-SO3R8的R8，優選碳數3~20的分支鏈狀烷基，更優選碳數6~12的分支鏈狀烷基，進一步優選2-乙基己基。可以形成異物的產生少的濾色器。 Examples of -SO 3 R 8 include methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tert-butoxysulfonyl, hexylsulfonyl, and eicosyloxy. Alkoxysulfonyl and the like. As R -SO 3 R 8 8 carbon atoms, branched chain alkyl group preferably having 3 to 20 carbon atoms, more preferably branched chain alkyl group having 6 to 12, more preferably 2-ethylhexyl. It is possible to form a color filter with little foreign matter.

作為-SO2NR9R10，例如可列舉氨磺醯基；N-甲基氨磺醯基、N-乙基氨磺醯基、N-丙基氨磺醯基、N-異丙基氨磺醯基、N-丁基氨磺醯基、N-異丁基氨磺醯基、N-仲-丁基氨磺醯基、N-叔-丁基氨磺醯基、N-戊基氨磺醯基、N-(1-乙基丙基)氨磺醯基、N-(1,1-二甲基丙基)氨磺醯基、N-(1,2-二甲基丙基)氨磺醯基、N-(2,2-二甲基丙基)氨磺醯基、N-(1-甲基丁基)氨磺醯基、N-(2-甲基丁基)氨磺醯基、N-(3-甲基丁基)氨磺醯基、N-環戊基氨磺醯基、N-己基氨磺醯基、N-(1,3-二甲基丁基)氨磺醯基、N-(3,3-二甲基丁基)氨磺醯基、N-庚基氨磺醯基、N-(1-甲基己基)氨磺醯基、N-(1,4-二甲基戊基)氨磺醯基、N-辛基氨磺醯基、N-(2-乙基己基)氨磺醯基、N-(1,5-二甲基己基)氨磺醯基、N-(1,1,2,2-四甲基丁基)氨磺醯基等的N-1取代氨磺醯基；N,N-二甲基氨磺醯基、N,N-乙基甲基氨磺醯基、N,N-二乙基氨磺醯基、N,N-丙基甲基氨磺醯基、N,N-異丙基甲基氨磺醯基、N,N-叔丁基甲基氨磺醯基、N,N-丁基乙基氨磺醯基、N,N-雙(1-甲基丙基)氨磺醯基、N,N-庚基甲基氨磺醯基等的N,N-2取代氨磺醯基等。 Examples of -SO 2 NR 9 R 10 include sulfamoyl groups; N-methylsulfamomethyl, N-ethylsulfamomethyl, N-propylsulfamomethyl, and N-isopropylamino Sulfonyl, N-butylsulfamoyl, N-isobutylsulfamoyl, N-sec-butylsulfamoyl, N-tert-butylsulfamoyl, N-pentylamino Sulfonyl, N- (1-ethylpropyl) sulfamoyl, N- (1,1-dimethylpropyl) sulfamoyl, N- (1,2-dimethylpropyl) Sulfamoyl, N- (2,2-dimethylpropyl) sulfamoyl, N- (1-methylbutyl) sulfamoyl, N- (2-methylbutyl) sulfamo Fluorenyl, N- (3-methylbutyl) sulfamofluorenyl, N-cyclopentylsulfamofluorenyl, N-hexylsulfamofluorenyl, N- (1,3-dimethylbutyl) amino Sulfofluorenyl, N- (3,3-dimethylbutyl) sulfamofluorenyl, N-heptylsulfamofluorenyl, N- (1-methylhexyl) sulfamofluorenyl, N- (1, 4-dimethylpentyl) sulfamoyl, N-octylsulfamoyl, N- (2-ethylhexyl) sulfamoyl, N- (1,5-dimethylhexyl) sulfamo N-1 substituted sulfamoyl groups such as fluorenyl, N- (1,1,2,2-tetramethylbutyl) sulfamomethyl; N, N-dimethylsulfamomethyl, N, N -Ethyl methylsulfamoyl, N, N-diethylsulfamoyl, N, N-propyl Methylsulfamoyl, N, N-isopropylmethylsulfamomethyl, N, N-tert-butylmethylsulfamomethyl, N, N-butylethylsulfamomethyl, N, N- N, N-2 substituted sulfamoyl groups such as bis (1-methylpropyl) sulfamoyl, N, N-heptylmethylsulfamomethyl and the like.

上述N-1取代氨磺醯基中，作為R8，優選碳數3~20的分支鏈狀烷基，更優選碳數6~12的分支鏈狀烷基，進一步優選2-乙基己基。可以形成異物的產生少的濾色器。 Among the N-1 substituted sulfamoyl groups, R 8 is preferably a branched alkyl group having 3 to 20 carbon atoms, more preferably a branched alkyl group having 6 to 12 carbon atoms, and even more preferably 2-ethylhexyl. It is possible to form a color filter with little foreign matter.

作為R5，優選-CO2H、-CO2 -Z+、-CO2R8、-SO3 -、-SO3 -Z+、-SO3H或-SO2NHR9，更優選-SO3 -、-SO3 -Z+、-SO3H或-SO2NHR9。 As R 5, preferably -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 -, -SO 3 - Z +, -SO 3 H or -SO 2 NHR 9, and more preferably -SO 3 -, -SO 3 - Z + , -SO 3 H or -SO 2 NHR 9.

m優選1~4，更優選1或2。 m is preferably 1 to 4, and more preferably 1 or 2.

作為R6及R7中的碳數1~6的烷基，可列舉上述列舉的烷基中碳數1~6的烷基。其中，作為R6、R7，優選氫原子。 Examples of the alkyl group having 1 to 6 carbon atoms in R 6 and R 7 include alkyl groups having 1 to 6 carbon atoms in the alkyl groups listed above. Among them, R 6 and R 7 are preferably a hydrogen atom.

作為R11中的碳數7~10的芳烷基，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 11 include benzyl, phenylethyl, and phenylbutyl.

作為R11，優選碳數1~20的飽和烴基或苄基。 R 11 is preferably a saturated hydrocarbon group or a benzyl group having 1 to 20 carbon atoms.

Z+為+N(R11)4、Na+或K+，優選為+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，優選4個R11中至少2個為碳數5~20的1價的飽和烴基。另外，4個R11的合計碳數優選20~80，更優選20~60。在化合物(1a)中+N(R11)4存在的情況下，如果R11為這些基團，則由包含化合物(1a)的本發明的著色固化性樹脂組合物能夠形成異物少的濾色器。 As the + N (R 11 ) 4 , at least two of the four R 11 are preferably 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 these groups, the colored curable resin composition of the present invention containing the compound (1a) can form a color filter with little foreign matter. Device.

作為R1~R4的組合，優選R1及R3為氫原子、R2及R4為碳數6~10的1價的具有取代基的芳香族烴基的組合。作為上述芳香族烴基的取代基，優選-SO3 -、-SO3H、-SO3 -Z+、-SO3R8或-SO2NHR9，更優選-SO3 -Z+或-SO2NHR9。這些取代基將芳香族烴基中所含的氫原子取代。 The combination of R 1 to R 4 is preferably a combination of R 1 and R 3 being a hydrogen atom and R 2 and R 4 being a monovalent aromatic hydrocarbon group having a substituent having 6 to 10 carbon atoms. Examples of the substituted aromatic hydrocarbon group, preferably -SO 3 -, -SO 3 H, -SO 3 - Z +, -SO 3 R 8 or -SO 2 NHR 9, and more preferably -SO 3 - Z + or -SO 2 NHR 9 . These substituents substitute hydrogen atoms contained in the aromatic hydrocarbon group.

作為R1~R4的組合，也優選R1~R4全部為1價的飽和烴基的組合。這種情況下，作為該飽和烴基，優選為甲基或乙基。 The combination of R 1 to R 4 is also preferably a combination in which all of R 1 to R 4 are monovalent saturated hydrocarbon groups. In this case, the saturated hydrocarbon group is preferably a methyl group or an ethyl group.

另外，作為R1~R4的組合，也優選R1及R3為可具有取代基的碳數1~10的飽和烴基、R2及R4為可具有取代基的苯基的組合。 In addition, as the combination of R 1 to R 4, a combination of R 1 and R 3 being a saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and a combination of R 2 and R 4 being a phenyl group which may have a substituent are also preferable.

這種情況下，R1可以與取代R2的苯基的取代基形成環，R3可以與取代R4的苯基的取代基形成環。 In this case, R 1 may form a ring with a substituent of a phenyl group substituted for R 2 , and R 3 may form a ring with a substituent of a phenyl group substituted for R 4 .

另外，R1及R3的碳數相互獨立地優選為1~3。作為R1、R3的飽和烴基中所含的氫原子的取代基，優選可被碳數1~3的烷氧基取代的碳數6~10的芳香族烴基、或鹵素原子。 The carbon numbers of R 1 and R 3 are preferably 1 to 3 independently of each other. As a substituent of a hydrogen atom contained in a saturated hydrocarbon group of R 1 and R 3 , an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom which may be substituted with an alkoxy group having 1 to 3 carbon atoms is preferred.

另外，作為R2及R4的苯基可具有的取代基，優選碳數1~4的烷基、碳數1~4的烷基硫烷基或碳數1~4的烷基磺醯基，更優選碳數1~4的烷基，進一步優選甲基。將R2及R4的苯基取代的取代基的個數為0~5，優選0~2，更優選0或1。 In addition, as the substituent which the phenyl group of R 2 and R 4 may have, an alkyl group having 1 to 4 carbons, an alkylsulfan group having 1 to 4 carbons, or an alkylsulfonyl group having 1 to 4 carbons is preferable. An alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group is more preferable. The number of the phenyl-substituted substituents of R 2 and R 4 is 0 to 5, preferably 0 to 2, and more preferably 0 or 1.

作為可取代上述R2及R4的苯基的碳數1~4的烷基，可列舉甲基、乙基、丙基、丁基、異丙基、異丁基、仲-丁基、叔-丁基等。 Examples of the alkyl group having 1 to 4 carbon atoms which can replace the phenyl groups of R 2 and R 4 include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, and tertiary. -Butyl and the like.

另外，作為可取代上述R2及R4的苯基的碳數1~4的烷基硫烷基，可列舉甲基硫烷基、乙基硫烷基、丙基硫烷基、丁基硫烷基及異丙基硫烷基等。 Examples of the alkylsulfanyl group having 1 to 4 carbon atoms which can replace the phenyl groups of R 2 and R 4 include methylsulfanyl group, ethylsulfanyl group, propylsulfanyl group, and butylsulfanyl group. Alkyl and isopropylsulfanyl.

進而，作為可取代上述R2及R4的苯基的碳數1~4的烷基磺醯基，可列舉甲基磺醯基、乙基磺醯基、丙基磺醯基、丁基磺醯基及異丙基磺醯基等。 Furthermore, examples of the alkylsulfonyl group having 1 to 4 carbon atoms that can replace the phenyl groups of R 2 and R 4 include methylsulfonyl, ethylsulfonyl, propylsulfonyl, and butylsulfonyl. Fluorenyl and isopropylsulfonyl.

作為化合物(1a)，可列舉例如由式(1-1)~式(1-43)表示的化合物。應予說明，式中，R40表示碳數1~20的1價的飽和烴基，優選為碳數6~12的分支鏈狀烷基，更優選為2-乙基己基。 Examples of the compound (1a) include compounds represented by the formulae (1-1) to (1-43). 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.

Figure TWI679499B_D0006
Figure TWI679499B_D0006

Figure TWI679499B_D0007
Figure TWI679499B_D0007

Figure TWI679499B_D0008
Figure TWI679499B_D0008

Figure TWI679499B_D0009
Figure TWI679499B_D0009

Figure TWI679499B_D0010
Figure TWI679499B_D0010

Figure TWI679499B_D0011
Figure TWI679499B_D0011

Figure TWI679499B_D0012
Figure TWI679499B_D0012

Figure TWI679499B_D0013
Figure TWI679499B_D0013

進而，後述的式(Ab2)中，R48與R52相互結合形成了-O-的化合物也作為二苯并哌喃染料(Aa)列舉。 Furthermore, in the formula (Ab2) described later, compounds in which R 48 and R 52 are bonded to each other to form -O- are also listed as dibenzopiperan dyes (Aa).

這些中，優選C.I.酸性紅289的磺醯胺化物、C.I.酸性紅289的季銨鹽、C.I.酸性紫102的磺醯胺化物或C.I.酸性紫102的季銨鹽。作為這樣的化合物，例如可列舉式(1-1)~式(1-8)、式(1-11)或式(1-12)所示的化合物等。 Among these, C.I. acid red 289 sulfonamidate, C.I. acid red 289 quaternary ammonium salt, C.I. acid violet 102 sulfonamide and C.I. acid violet 102 quaternary ammonium salt are preferred. Examples of such a compound include compounds represented by the formulae (1-1) to (1-8), (1-11), or (1-12).

另外，在有機溶劑中的溶解性優異的方面，也優選由式(1-24)~式(1-33)的任一個表示的化合物。 In addition, in terms of excellent solubility in an organic solvent, a compound represented by any one of formulas (1-24) to (1-33) is also preferable.

二苯并哌喃染料(Aa)能夠使用已市售的二苯并哌喃染料(例如，中外化成(株)製造的“Chugai Aminol Fast Pink R-H/C”、田岡化學工業(株)製造的“Rhodamin 6G”)。另外，也可以將已市售的二苯并哌喃染料作為起始原料，參考特開2010-32999號公報合成。 As the dibenzopiperan dye (Aa), a commercially available dibenzopiperan dye (for example, "Chugai Aminol Fast Pink RH / C" manufactured by Chugai Kasei Co., Ltd., "Tagawa Chemical Industry Co., Ltd." Rhodamin 6G "). Alternatively, a commercially available dibenzopiperan dye may be used as a starting material and synthesized by referring to Japanese Patent Application Laid-Open No. 2010-32999.

包含二苯并哌喃染料(Aa)的情況下，其含量在染料(A1)100質量份中優選為5質量份以上，更優選為10質量份以上，進一步優選為15質量份以上，特別優選為18質量 份以上，優選為50質量份以下，更優選為40質量份以下，進一步優選為35質量份以下。 When the dibenzopiperan dye (Aa) is contained, its content is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, and particularly preferably 100 parts by mass of the dye (A1). For 18 quality It is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and still more preferably 35 parts by mass or less.

三芳基甲烷染料(Ab)為包含具有3個芳香族基團結合於一個碳原子的結構的化合物的染料。該芳香族基團可以是芳香族烴基，也可以是芳香族雜環基。作為三芳基甲烷染料(Ab)，例如可列舉C.I.溶劑藍2、4、5、43、124；C.I.鹼性紫3、14、25；C.I.鹼性藍1、5、7、11、26及專利第4492760號公報中記載的三芳基甲烷染料等。優選在有機溶劑中溶解的染料。 The triarylmethane dye (Ab) is a dye containing a compound having a structure in which three aromatic groups are bonded to one carbon atom. The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group. Examples of the triarylmethane dye (Ab) include CI solvent blue 2, 4, 5, 43, 124; CI basic violet 3, 14, 25; CI basic blue 1, 5, 7, 11, 26, and patents Triarylmethane dyes and the like described in Gazette No. 4492760. Dyes dissolved in organic solvents are preferred.

這些中，作為三芳基甲烷染料(Ab)，優選包含由式(Ab1)表示的化合物(以下有時稱為“化合物(Ab1)”。)。 Among these, the triarylmethane dye (Ab) preferably contains a compound represented by the formula (Ab1) (hereinafter sometimes referred to as "compound (Ab1)").

Figure TWI679499B_D0014
Figure TWI679499B_D0014

[式(Ab1)中，R1A~R8A各自獨立地表示氫原子、鹵素原子、硝基、羥基、或碳數1~20的飽和烴基，該飽和烴基的碳數為2~20的情況下，構成該飽和烴基的亞甲基可以被置換為氧原子或-CO-。不過，該碳數2~20的飽和烴基中，鄰接的亞甲基不會同時被置換為氧原子，末端的亞甲基不會置換為氧原子或-CO-。 [In the formula (Ab1), R 1A to R 8A each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or a saturated hydrocarbon group having 1 to 20 carbon atoms, and when the saturated hydrocarbon group has 2 to 20 carbon atoms The methylene group constituting the saturated hydrocarbon group may be replaced with an oxygen atom or -CO-. However, in this saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent methylene groups are not replaced with oxygen atoms at the same time, and terminal methylene groups are not replaced with oxygen atoms or -CO-.

R9A~R12A各自獨立地表示氫原子、碳數1~20的飽和烴 基、可具有取代基的碳數6~20的芳香族烴基或可具有取代基的碳數7~30的芳烷基，該飽和烴基中所含的氫原子可以被取代或未取代的氨基或鹵素原子取代，該飽和烴基的碳數為2~20的情況下，該飽和烴基中所含的亞甲基可以被置換為氧原子或-CO-。不過，該碳數2~20的飽和烴基中，鄰接的亞甲基不會同時被置換為氧原子，末端的亞甲基不會被置換為氧原子或-CO-。R9A與R10A可結合並與它們結合的氮原子一起形成環，R11A與R12A可結合並與它們結合的氮原子一起形成環。 R 9A to R 12A each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent The hydrogen atom contained in the saturated hydrocarbon group may be substituted with a substituted or unsubstituted amino or halogen atom. When the carbon number of the saturated hydrocarbon group is 2 to 20, the methylene group contained in the saturated hydrocarbon group may be replaced. Is an oxygen atom or -CO-. However, in this saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent methylene groups are not replaced with oxygen atoms at the same time, and terminal methylene groups are not replaced with oxygen atoms or -CO-. R 9A and R 10A may bind and form a ring with the nitrogen atom to which they are bound, and R 11A and R 12A may bind and form a ring with the nitrogen atom to which they are bound.

A表示可被取代的碳數6~20的芳香族烴基。 A represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may be substituted.

[G]g-表示任意的g價的陰離子。g表示0或任意的自然數。] [G] g- represents an arbitrary g-valent anion. g represents 0 or any natural number. ]

應予說明，式(Ab1)中，在1分子中包含多個由下述式表示的陽離子的情況下，它們可以為相同的結構，也可以為不同的結構。 In addition, in the formula (Ab1), when a plurality of cations represented by the following formula are contained in one molecule, they may have the same structure or different structures.

Figure TWI679499B_D0015
[式中，A及R1A~R12A分別與上述同義。]
Figure TWI679499B_D0015
 [In the formula, A and R 1A to R 12A are synonymous with the above. ]

由R1A~R12A表示的碳數1~20的飽和烴基可以為直鏈狀、分支鏈狀及環狀的任一種，優選為鏈狀。R1A~R12A的飽和烴基的碳數更優選為1~10，進一步優選為1~8。作為 直鏈狀或分支鏈狀的飽和烴基(烷基)，可列舉甲基、乙基、丙基、丁基、戊基、己基、辛基、壬基、癸基等。該鏈狀飽和烴基(烷基)的碳數優選為1~10，更優選為1~8，進一步優選為1~6。 The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R 1A to R 12A may be any of linear, branched, and cyclic, and is preferably chain. The carbon number of the saturated hydrocarbon group of R 1A to R 12A is more preferably 1 to 10, and still more preferably 1 to 8. Examples of the linear or branched saturated hydrocarbon group (alkyl group) include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, and decyl. The carbon number of this chain-like saturated hydrocarbon group (alkyl group) is preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 6.

由R1A~R12A表示的環狀的飽和烴基(脂環式飽和烴基)可以為單環，也可以為多環。作為該環狀的飽和烴基(脂環式飽和烴基)，可列舉環丙基、環丁基、環戊基、環己基、金剛烷基等。該環狀的飽和烴(脂環式飽和烴基)基的碳數優選為碳數3~10，更優選為碳數6~10。 The cyclic saturated hydrocarbon group (alicyclic saturated hydrocarbon group) represented by R 1A to R 12A may be monocyclic or polycyclic. Examples of the cyclic saturated hydrocarbon group (alicyclic saturated hydrocarbon group) include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl. The carbon number of the cyclic saturated hydrocarbon (alicyclic saturated hydrocarbon group) group is preferably 3 to 10 carbon atoms, and more preferably 6 to 10 carbon atoms.

作為由R1A~R12A表示的飽和烴基的具體例，可列舉由下述式表示的基團。下述式中，＊表示鍵合端。 Specific examples of the saturated hydrocarbon group represented by R 1A to R 12A include a group represented by the following formula. In the following formula, * represents a bonding end.

Figure TWI679499B_D0016
Figure TWI679499B_D0016

由R1A~R12A表示的飽和烴基的碳數為2~20的情況下，該飽和烴基中所含的亞甲基可以被置換為氧原子或-CO-，優選地可以被置換為氧原子。另外，可以在構成該飽和烴基的亞甲基間***氧原子。不過，該碳數2~20的飽和烴基中，鄰接的亞甲基不會同時被置換為氧原子，末端的亞甲基不會被置換為氧原子或-CO-。亞甲基可以被置換為氧原子或-CO-的飽和烴基的優選的碳數為2~10，更優選 為2~8，進一步優選為2~6。作為亞甲基可被置換為氧原子的飽和烴基，優選直鏈狀或分支鏈狀的飽和烴基(即直鏈狀或分支鏈狀烷基)，更優選直鏈狀的飽和烴基(即直鏈狀烷基)。作為該基團，例如可列舉由下述式表示的基團。下述式中，＊表示鍵合端。 When the carbon number of the saturated hydrocarbon group represented by R 1A to R 12A is 2 to 20, the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or -CO-, and may preferably be replaced with an oxygen atom. . An oxygen atom may be inserted between the methylene groups constituting the saturated hydrocarbon group. However, in this saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent methylene groups are not replaced with oxygen atoms at the same time, and terminal methylene groups are not replaced with oxygen atoms or -CO-. The saturated carbon group in which the methylene group may be replaced with an oxygen atom or -CO- has a preferable carbon number of 2 to 10, more preferably 2 to 8, and still more preferably 2 to 6. As the saturated hydrocarbon group in which the methylene group can be replaced with an oxygen atom, a linear or branched saturated hydrocarbon group (that is, a linear or branched alkyl group) is preferred, and a linear saturated hydrocarbon group (that is, a linear chain) is more preferred. Like alkyl). Examples of the group include a group represented by the following formula. In the following formula, * represents a bonding end.

Figure TWI679499B_D0017
Figure TWI679499B_D0017

另外，亞甲基被置換為氧原子或-CO-時，末端與氧原子或-CO-之間、或者氧原子或-CO-與氧原子或-CO-之間的碳數優選1~4個，更優選2~3個。 When the methylene group is replaced with an oxygen atom or -CO-, the number of carbon atoms between the terminal and the oxygen atom or -CO- or between the oxygen atom or -CO- and the oxygen atom or -CO- is preferably 1 to 4. , More preferably 2 to 3.

作為R9A~R12A的飽和烴基可具有的取代或未取代的氨基，可列舉氨基；N-甲基氨基、N-乙基氨基、N-苯基氨基、N,N-二甲基氨基、N,N-二乙基氨基等。另外，作為R9A~R12A的飽和烴基可具有的鹵素原子，可列舉氟原子、氯原子、溴原子、碘原子。 Examples of the substituted or unsubstituted amino group that the saturated hydrocarbon group of R 9A to R 12A may have include amino group; N-methylamino group, N-ethylamino group, N-phenylamino group, N, N-dimethylamino group, N, N-diethylamino and the like. Examples of the halogen atom that the saturated hydrocarbon group of R 9A to R 12A may have include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

另外，由R9A~R12A表示的芳香族烴基的碳數優選為6~20，更優選為6~15，進一步優選為6~12。作為該芳香族烴基，可列舉苯基、甲苯基、乙基苯基、丙基苯基、二甲苯基、萘基、蒽基、菲基、聯苯基、三聯苯基等。優選苯基、萘基等。另外，該芳香族烴基可具有1或2個以上的 取代基，作為該取代基，可列舉氟原子、氯原子、碘原子、溴原子等鹵素原子；氯甲基、三氟甲基等碳數1~6的鹵代烷基；甲氧基、乙氧基等碳數1~6的烷氧基；羥基；氨磺醯基；甲基磺醯基等碳數1~6的烷基磺醯基；甲氧基羰基、乙氧基羰基等碳數1~6的烷氧基羰基；等。 The carbon number of the aromatic hydrocarbon group represented by R 9A to R 12A is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 12. Examples of the aromatic hydrocarbon group include phenyl, tolyl, ethylphenyl, propylphenyl, xylyl, naphthyl, anthryl, phenanthryl, biphenyl, terphenyl, and the like. Phenyl, naphthyl and the like are preferred. The aromatic hydrocarbon group may have one or two or more substituents. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom; and carbon numbers such as a chloromethyl group and a trifluoromethyl group. 1 to 6 halogenated alkyl groups; alkoxy groups having 1 to 6 carbon atoms, such as methoxy and ethoxy groups; hydroxyl groups; amidosulfonyl groups; 1 to 6 carbon alkoxycarbonyl groups such as methoxycarbonyl and ethoxycarbonyl; etc.

進而，由R9A~R12A表示的芳烷基的碳數為7~30，更優選為7~20，進一步優選為7~17。作為由R9A~R12A表示的芳烷基，可列舉在作為R9A~R12A的芳香族烴基說明的基團上結合了亞甲基、亞乙基、亞丙基等碳數1~5的亞烷基的基團等。 The carbon number of the aralkyl group represented by R 9A to R 12A is 7 to 30, more preferably 7 to 20, and even more preferably 7 to 17. Examples of the aralkyl group represented by R 9A to R 12A include a carbon group having 1 to 5 carbon atoms such as a methylene group, an ethylene group, and a propylene group bonded to the group described as the aromatic hydrocarbon group of R 9A to R 12A . Alkylene groups and the like.

其中，作為R1A~R8A，優選氫原子或碳數1~20的飽和烴基(優選為烷基)，更優選為氫原子、或甲基，特別優選氫原子。 Among them, R 1A to R 8A are preferably a hydrogen atom or a saturated hydrocarbon group (preferably an alkyl group) having 1 to 20 carbon atoms, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

R9A~R12A，從合成的容易性的方面出發，優選各自獨立地為碳數1~10的飽和烴基(優選為烷基)、可具有取代基的碳數6~20的芳香族烴基或可具有取代基的碳數7~30的芳烷基，更優選各自獨立地為碳數1~8的飽和烴基(優選為烷基)、苯基、萘基、具有甲基的苯基、具有甲基的萘基；未取代的芳烷基、或被選自鹵素原子、甲氧基、乙氧基、氨磺醯基、甲基磺醯基、甲氧基羰基、和乙氧基羰基中的1種以上、特別地1種取代的芳烷基，進一步優選各自獨立地為碳數1~4的直鏈狀烷基。 From the viewpoint of ease of synthesis, R 9A to R 12A are each preferably a saturated hydrocarbon group (preferably an alkyl group) having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or An aralkyl group having 7 to 30 carbon atoms which may have a substituent, more preferably a saturated hydrocarbon group (preferably an alkyl group) having 1 to 8 carbon atoms, a phenyl group, a naphthyl group, a phenyl group having a methyl group, Methyl naphthyl; unsubstituted aralkyl, or selected from the group consisting of a halogen atom, methoxy, ethoxy, sulfamoyl, methylsulfonyl, methoxycarbonyl, and ethoxycarbonyl One or more substituted aralkyl groups are particularly preferably a linear alkyl group each independently having 1 to 4 carbon atoms.

作為由A表示的芳香族烴基，可列舉苯基、甲苯基、乙基苯基、二甲苯基、萘基、蒽基、菲基、聯苯基、 三聯苯基等碳數6~20的芳香族烴基。 Examples of the aromatic hydrocarbon group represented by A include phenyl, tolyl, ethylphenyl, xylyl, naphthyl, anthryl, phenanthryl, biphenyl, An aromatic hydrocarbon group having 6 to 20 carbon atoms such as terphenyl.

作為由A表示的芳香族烴基可具有的取代基，可列舉例如氟原子、氯原子、碘原子等鹵素原子；甲氧基、乙氧基等碳數1~6的烷氧基；羥基；氨磺醯基；甲基磺醯基等碳數1~6的烷基磺醯基；甲氧基羰基、乙氧基羰基等碳數1~6的烷氧基羰基等；可被取代的氨基；磺基；-SO3 -；-SO3J等。作為可取代上述氨基的取代基，可列舉可被氨基或鹵素原子取代的甲基等碳數1~20的烷基；可被碳數1~4的烷基、羥基、SO3 -基、甲基磺醯基、二烷基氨基或碳數1~10的烷氧基取代的苯基等芳基；等。 Examples of the substituent which the aromatic hydrocarbon group represented by A may have include a halogen atom such as a fluorine atom, a chlorine atom, and an iodine atom; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; and ammonia Sulfonyl groups; alkylsulfonyl groups with 1 to 6 carbons such as methylsulfonyl; alkoxycarbonyl groups with 1 to 6 carbons such as methoxycarbonyl and ethoxycarbonyl; substituted amino groups; sulfo group; -SO 3 -; -SO 3 J and the like. As described above may be substituted with an amino substituent group, or an amino group which may be substituted include a halogen atom such as a methyl alkyl group having 1 to 20 carbon atoms; the alkyl group may be 1 to 4 carbon atoms, a hydroxyl group, SO 3 - group, A Aryl groups such as sulfofluorenyl, dialkylamino, or alkoxy substituted with 1 to 10 carbon atoms; etc.

其中，作為A，優選可具有取代基的芳香族烴基。 Among these, A is preferably an aromatic hydrocarbon group which may have a substituent.

作為J，可列舉無機陽離子或有機陽離子。具體地，可列舉與上述的化合物(1a)中的Z+同樣的陽離子及下述式的陽離子等。 Examples of J include inorganic cations and organic cations. Specific examples include the same cations as Z + in the above-mentioned compound (1a), and cations of the following formula.

Figure TWI679499B_D0018
Figure TWI679499B_D0018

作為可具有取代基的芳香族烴基的具體例，可列舉由下述式表示的基團。下述式中，＊表示鍵合端。 Specific examples of the aromatic hydrocarbon group which may have a substituent include a group represented by the following formula. In the following formula, * represents a bonding end.

作為可具有取代基的芳烷基的具體例，可列舉在下述芳香族烴基的各具體例的鍵合端結合了亞甲基的基團。 Specific examples of the aralkyl group which may have a substituent include a group in which a methylene group is bonded to the bonding end of each specific example of the following aromatic hydrocarbon group.

Figure TWI679499B_D0019
Figure TWI679499B_D0019

Figure TWI679499B_D0020
Figure TWI679499B_D0020

A中，作為可具有取代基的芳香族烴基，可列舉由下述式表示的基團。＊表示鍵合端。 In A, examples of the aromatic hydrocarbon group which may have a substituent include a group represented by the following formula. * Indicates a bonding end.

Figure TWI679499B_D0021
Figure TWI679499B_D0021

其中，優選由式(A1-1)及式(A1-3)表示的基團。 Among them, groups represented by the formula (A1-1) and the formula (A1-3) are preferred.

[G]g-表示g價的陰離子。g可以為0，通常為1~14，優選為1~12，更優選為1~10，進一步優選為1~6，特別優選為1~4。作為[G]g-，可列舉公知的陰離子，可以是F-、Cl-、 Br-等的鹵化物離子，從耐熱性的方面出發，優選含硼陰離子、含鋁陰離子、含氟陰離子。 [G] g- represents a g-valent anion. g may be 0, usually 1 to 14, preferably 1 to 12, more preferably 1 to 10, even more preferably 1 to 6, and particularly preferably 1 to 4. As [G] g-, include well-known anionic, may be F -, Cl -, Br - and other halide ions, from the viewpoint of heat resistance, preferably boron-containing anions, aluminum-containing anion, fluorine anion.

作為含硼陰離子及含鋁陰離子，可列舉例如由下述式(y4)表示的陰離子。 Examples of the boron-containing anion and the aluminum-containing anion include anions represented by the following formula (y4).

Figure TWI679499B_D0022
Figure TWI679499B_D0022

[式(y4)中，W1、W2各自獨立地表示具有從1價的質子給予性取代基放出質子而成的取代基2個的基團。M3表示硼或鋁。] [In the formula (y4), W 1 and W 2 each independently represent a group having two substituents in which a proton is released from a monovalent proton donating substituent. M3 represents boron or aluminum. ]

作為具有從1價的質子給予性取代基放出質子而成的取代基2個的基團，可列舉從具有至少2個1價的質子給予性取代基(例如羥基、羧酸基等)的化合物從2個質子給予性取代基分別放出質子而成的基團。作為該化合物，優選為可具有取代基的兒茶酚、可具有取代基的2,3-二羥基萘、可具有取代基的2,2’-聯苯酚、可具有取代基的3-羥基-2-萘甲酸、可具有取代基的2-羥基-1-萘甲酸、可具有取代基的1-羥基-2-萘甲酸、可具有取代基的聯萘酚、可具有取代基的水楊酸、可具有取代基的苄基酸或可具有取代基的扁桃酸。 Examples of the group having two substituents derived from a monovalent proton donating substituent include compounds having at least two monovalent proton donating substituents (for example, a hydroxyl group and a carboxylic acid group). A group in which protons are released from two proton donating substituents, respectively. The compound is preferably catechol which may have a substituent, 2,3-dihydroxynaphthalene which may have a substituent, 2,2'-biphenol which may have a substituent, and 3-hydroxy- which may have a substituent. 2-naphthoic acid, 2-hydroxy-1-naphthoic acid that may have a substituent, 1-hydroxy-2-naphthoic acid that may have a substituent, binaphthol that may have a substituent, salicylic acid that may have a substituent , Benzyl acid which may have a substituent or mandelic acid which may have a substituent.

在上述例示的化合物中，作為取代基，可列舉飽和烴基(例如，烷基、環烷基等)、鹵素原子、鹵代烷基、羥基、氨基、硝基、烷氧基等。 Among the compounds exemplified above, examples of the substituent include a saturated hydrocarbon group (for example, an alkyl group, a cycloalkyl group, etc.), a halogen atom, a halogenated alkyl group, a hydroxyl group, an amino group, a nitro group, and an alkoxy group.

作為可具有取代基的水楊酸，可列舉水楊酸、3- 甲基水楊酸、3-叔-丁基水楊酸、3-甲氧基水楊酸、3-硝基水楊酸、4-三氟甲基水楊酸、3,5-二-叔-丁基水楊酸、3-氨基水楊酸、4-氨基水楊酸、5-氨基水楊酸、6-氨基水楊酸等單氨基水楊酸；3-羥基水楊酸(2,3-二羥基苯甲酸)、4-羥基水楊酸(2,4-二羥基苯甲酸)、5-羥基水楊酸(2,5-二羥基苯甲酸)、6-羥基水楊酸(2,6-二羥基苯甲酸)等單羥基水楊酸；4,5-二羥基水楊酸、4,6-二羥基水楊酸等二羥基水楊酸；3-氯水楊酸、4-氯水楊酸、5-氯水楊酸、6-氯水楊酸、3-溴水楊酸、4-溴水楊酸、5-溴水楊酸、6-溴水楊酸等單鹵代水楊酸；3,5-二氯水楊酸、3,5-二溴水楊酸、3,5-二碘水楊酸等二鹵代水楊酸；3,5,6-三氯水楊酸等三鹵代水楊酸；等。 Examples of the salicylic acid that may have a substituent include salicylic acid, 3- Methylsalicylic acid, 3-tert-butylsalicylic acid, 3-methoxysalicylic acid, 3-nitrosalicylic acid, 4-trifluoromethylsalicylic acid, 3,5-di-tert-salicylic acid -Monosalicylic acid such as butylsalicylic acid, 3-aminosalicylic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid; 3-hydroxysalicylic acid (2, 3-dihydroxybenzoic acid), 4-hydroxysalicylic acid (2,4-dihydroxybenzoic acid), 5-hydroxysalicylic acid (2,5-dihydroxybenzoic acid), 6-hydroxysalicylic acid (2 , 6-dihydroxybenzoic acid) and other monohydroxysalicylic acid; 4,5-dihydroxysalicylic acid, 4,6-dihydroxysalicylic acid and other dihydroxysalicylic acid; 3-chlorosalicylic acid, 4- Monohalo, such as chlorosalicylic acid, 5-chlorosalicylic acid, 6-chlorosalicylic acid, 3-bromosalicylic acid, 4-bromosalicylic acid, 5-bromosalicylic acid, 6-bromosalicylic acid, etc. Salicylic acid; 3,5-dichlorosalicylic acid, 3,5-dibromosalicylic acid, 3,5-diiodosalicylic acid, and other dihalosalicylic acids; 3,5,6-trichlorowater Salicylic acid and other trihalosalicylic acid; etc.

作為可具有取代基的苄基酸，可列舉

Figure TWI679499B_D0023
Examples of the benzyl acid which may have a substituent include
Figure TWI679499B_D0023

作為可具有取代基的扁桃酸，可列舉

Figure TWI679499B_D0024
Examples of the mandelic acid which may have a substituent include
Figure TWI679499B_D0024

等。 Wait.

作為由式(y4)表示的陰離子中優選的陰離子，為由下述式表示的陰離子，可列舉具有表1中記載的取代基的陰離子(BC-1)~陰離子(BC-24)、以及、分別由式(BC-25)、式(BC-26)、式(BC-27)及式(BC-28)表示的陰離子(BC-25)~陰離子(BC-28)等。 Preferred anions among the anions represented by the formula (y4) are anions represented by the following formulas, and examples thereof include anions (BC-1) to anions (BC-24) having a substituent described in Table 1, and, Anions (BC-25) to anions (BC-28) represented by formula (BC-25), formula (BC-26), formula (BC-27), and formula (BC-28), respectively.

Figure TWI679499B_D0025
Figure TWI679499B_D0025

Figure TWI679499B_D0027
Figure TWI679499B_D0027

作為由式(y4)表示的陰離子，優選陰離子(BC-1)、陰離子(BC-2)、陰離子(BC-3)、陰離子(BC-25)、陰離子(BC-26)、陰離子(BC-27)，更優選陰離子(BC-1)、陰離子(BC-2)、陰離子(BC-25)，進一步優選陰離子(BC-1)、陰離 子(BC-2)。通過使用這些陰離子作為[G]g-，存在由式(Ab2)表示的染料在有機溶劑中的溶解性優異的傾向。 As the anion represented by the formula (y4), an anion (BC-1), an anion (BC-2), an anion (BC-3), an anion (BC-25), an anion (BC-26), and an anion (BC- 27), more preferably anion (BC-1), anion (BC-2), and anion (BC-25), and still more preferably anion (BC-1) and anion (BC-2). By using these anions as [G] g- , there is a tendency that the dye represented by the formula (Ab2) has excellent solubility in an organic solvent.

作為含氟陰離子，例如可列舉由下述式(y6)、(y7)、(y8)、(y9)表示的陰離子。 Examples of the fluorine-containing anion include anions represented by the following formulae (y6), (y7), (y8), and (y9).

Figure TWI679499B_D0028
Figure TWI679499B_D0028

[式(y6)中，W3及W4各自獨立地表示氟原子或碳數1~4的氟化烷基，或者，W3與W4可一起形成碳數1~4的氟化亞烷基。] [In formula (y6), W 3 and W 4 each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms, or W 3 and W 4 may form a fluorinated alkylene group having 1 to 4 carbon atoms together. base. ]

Figure TWI679499B_D0029
Figure TWI679499B_D0029

[式(y7)中，W5~W7各自獨立地表示氟原子或碳數1~4的氟化烷基。] [In the formula (y7), W 5 to W 7 each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms. ]

Figure TWI679499B_D0030
Figure TWI679499B_D0030

[式(y8)中，Y1表示碳數1~4的氟化亞烷基。] [In the formula (y8), Y 1 represents a fluorinated alkylene group having 1 to 4 carbon atoms. ]

Figure TWI679499B_D0031
Figure TWI679499B_D0031

[式(y9)中，Y2表示碳數1~4的氟化烷基。] [In the formula (y9), Y 2 represents a fluorinated alkyl group having 1 to 4 carbon atoms. ]

式(y6)及(y7)中，作為碳數1~4的氟化烷基，優選 全氟烷基。作為該全氟烷基，可列舉-CF3、-CF2CF3、-CF2CF2CF3、-CF(CF3)2、-CF2CF2CF2CF3、-CF2CF(CF3)2、-C(CF3)3等。 In the formulae (y6) and (y7), the fluorinated alkyl group having 1 to 4 carbon atoms is preferably a perfluoroalkyl group. Examples of the perfluoroalkyl group include -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF (CF 3 ) 2 , -CF 2 CF 2 CF 2 CF 3 , -CF 2 CF ( CF 3 ) 2 , -C (CF 3 ) 3 and the like.

式(y6)中，作為碳數1~4的氟化亞烷基，優選全氟亞烷基，可列舉-CF2-、-CF2CF2-、-CF2CF2CF2-、-C(CF3)2-、-CF2CF2CF2CF2-等。 In the formula (y6), the fluorinated alkylene group having 1 to 4 carbon atoms is preferably a perfluoroalkylene group, and examples thereof include -CF 2- , -CF 2 CF 2- , -CF 2 CF 2 CF 2 -,- C (CF 3 ) 2- , -CF 2 CF 2 CF 2 CF 2- , and the like.

式(y8)中，作為碳數1~4的氟化亞烷基，優選全氟亞烷基。作為全氟亞烷基，可列舉-CF2-、-CF2CF2-、-CF2CF2CF2-、-C(CF3)2-、-CF2CF2CF2CF2-等。 In the formula (y8), the fluorinated alkylene group having 1 to 4 carbon atoms is preferably a perfluoroalkylene group. Examples of the perfluoroalkylene group include -CF 2- , -CF 2 CF 2- , -CF 2 CF 2 CF 2- , -C (CF 3 ) 2- , -CF 2 CF 2 CF 2 CF 2- , etc. .

式(y9)中，作為碳數1~4的氟化烷基，優選全氟烷基。作為全氟烷基，可列舉-CF3、-CF2CF3、-CF2CF2CF3、-CF(CF3)2、-CF2CF2CF2CF3、-CF2CF(CF3)2、-C(CF3)3等。 In the formula (y9), the fluorinated alkyl group having 1 to 4 carbon atoms is preferably a perfluoroalkyl group. Examples of the perfluoroalkyl group include -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF (CF 3 ) 2 , -CF 2 CF 2 CF 2 CF 3 , -CF 2 CF (CF 3 ) 2 , -C (CF 3 ) 3 and the like.

作為由式(y6)表示的陰離子(以下有時稱為“陰離子(6)”)，可列舉分別由式(6-1)~式(6-6)所示的陰離子(以下有時稱為“陰離子(6-1)”~“陰離子(6-6)”)。 Examples of the anion represented by the formula (y6) (hereinafter sometimes referred to as "anion (6)") include anions represented by the formulas (6-1) to (6-6) (hereinafter sometimes referred to as "anions (6)"). "Anion (6-1)" to "anion (6-6)").

Figure TWI679499B_D0032
Figure TWI679499B_D0032

作為由式(y7)表示的陰離子(以下有時稱為“陰離子(7)”)，可列舉由下述式表示的陰離子(7-1)。 Examples of the anion represented by the formula (y7) (hereinafter sometimes referred to as "anion (7)") include the anion (7-1) represented by the following formula.

Figure TWI679499B_D0033
Figure TWI679499B_D0033

作為由式(y8)表示的陰離子(以下有時稱為“陰離子(8)”)，可列舉分別由式(8-1)~式(8-4)表示的陰離子(以下有時稱為“陰離子(8-1)”~“陰離子(8-4)”)。 Examples of the anion represented by the formula (y8) (hereinafter sometimes referred to as "anion (8)") include anions represented by the formulas (8-1) to (8-4) (hereinafter sometimes referred to as "" Anion (8-1) "to" anion (8-4) ").

Figure TWI679499B_D0034
Figure TWI679499B_D0034

作為由式(y9)表示的陰離子(以下有時稱為“陰離子(9)”)，可列舉分別由式(9-1)~式(9-4)表示的陰離子(以下有時稱為“陰離子(9-1)”~“陰離子(9-4)”)。 Examples of the anion represented by the formula (y9) (hereinafter sometimes referred to as "anion (9)") include anions represented by the formulas (9-1) to (9-4) (hereinafter sometimes referred to as "" Anion (9-1) "to" anion (9-4) ").

Figure TWI679499B_D0035
Figure TWI679499B_D0035

通過含有選自陰離子(6)、陰離子(7)、陰離子(8)及陰離子(9)中的至少1個的陰離子(即含氟陰離子。以下有時稱為“陰離子(6)~(9)”)，能夠提高由式(Ab2)表示的染料在有機溶劑中的溶解性提高。其中，優選陰離子(6)、(7)，更優選陰離子(6-1)、陰離子(6-2)、陰離子(7-1)，特別優選陰離子(6-2)。 An anion (that is, a fluorine-containing anion) containing at least one selected from the group consisting of anion (6), anion (7), anion (8) and anion (9) "), The solubility of the dye represented by the formula (Ab2) in an organic solvent can be improved. Among these, anions (6) and (7) are preferred, anions (6-1), anions (6-2), and anions (7-1) are more preferred, and anions (6-2) are particularly preferred.

由式(6)、式(7)、式(8)或式(9)表示的陰離子的鹼 金屬鹽可以使用市售的產品，可以採用國際公開第2008/075672號、特開2010-280586號公報中記載的方法等製造。 Base of anion represented by formula (6), formula (7), formula (8) or formula (9) As the metal salt, a commercially available product can be used, and it can be produced by a method described in International Publication No. 2008/075672 and Japanese Patent Application Laid-Open No. 2010-280586.

作為由式(Ab1)表示的化合物，例如可列舉由下述式表示的化合物。下述式中J與上述同義。 Examples of the compound represented by the formula (Ab1) include compounds represented by the following formula. In the following formula, J is synonymous with the above.

Figure TWI679499B_D0036
Figure TWI679499B_D0036

Figure TWI679499B_D0037
Figure TWI679499B_D0037

Figure TWI679499B_D0038
Figure TWI679499B_D0038

包含三芳基甲烷染料(Ab)的情況下，其含量在染料(A1)100質量份中優選為1質量份以上，更優選為50質量份以上，進一步優選為60質量份以上，進一步優選為65質量份以上，優選為99質量份以下，更優選為95質量份以下，進一步優選為90質量份以下，進一步優選為85質量份以下，特別優選為82質量份以下。 When triarylmethane dye (Ab) is contained, its content is preferably 1 part by mass or more, more preferably 50 parts by mass or more, still more preferably 60 parts by mass or more, and still more preferably 65 parts by mass of 100 parts by mass of the dye (A1). It is preferably 99 parts by mass or less, more preferably 95 parts by mass or less, still more preferably 90 parts by mass or less, still more preferably 85 parts by mass or less, and particularly preferably 82 parts by mass or less.

在由式(Ab2)表示的化合物(以下有時稱為化合物(Ab2)。)中也包含其互變異構體。 A compound represented by the formula (Ab2) (hereinafter sometimes referred to as a compound (Ab2).) Also includes its tautomer.

Figure TWI679499B_D0039
Figure TWI679499B_D0039

[式(Ab2)中，R41~R44各自獨立地表示氫原子、碳數1~20的飽和烴基、可具有取代基的碳數6~20的芳香族烴基或可具有取代基的碳數7~30的芳烷基，該碳數1~20的飽和烴基中，該飽和烴基中所含的氫原子可以被取代或未取代的氨基或鹵素原子取代，該飽和烴基的碳數為2~20的情況下，該飽和烴基中所含的亞甲基可以被置換為氧原子或-CO-。不過，該碳數2~20的飽和烴基中，鄰接的亞甲基不會同時被置換為氧原子，末端的亞甲基不會被置換為氧原子或-CO-。R41與R42可結合並與它們結合的氮原子一起形成環，R43與R44可結合並與它們結合的氮原子一起形成環。 [In the formula (Ab2), R 41 to R 44 each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a carbon number which may have a substituent. An aralkyl group of 7 to 30. In the saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a substituted or unsubstituted amino or halogen atom. The carbon number of the saturated hydrocarbon group is 2 to In the case of 20, the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or -CO-. However, in this saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent methylene groups are not replaced with oxygen atoms at the same time, and terminal methylene groups are not replaced with oxygen atoms or -CO-. R 41 and R 42 may be combined and form a ring with the nitrogen atom to which they are bonded, and R 43 and R 44 may be combined and form a ring with the nitrogen atom to which they are bonded.

R47~R54相互獨立地表示氫原子、鹵素原子、硝基、羥基、或碳數1~8的烷基，該烷基的碳數為2~8的情況下，該烷基中所含的亞甲基可以被置換為氧原子或-CO-，R48與R52可相互結合而形成-NH-、-S-或-SO2-。不過，該烷基中，鄰接的亞甲基不會同時被置換為氧原子，末端的亞甲基不會被置換為氧原子或-CO-。 R 47 to R 54 each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms. When the alkyl group has 2 to 8 carbon atoms, the alkyl group contains The methylene group may be replaced with an oxygen atom or -CO-, and R 48 and R 52 may be combined with each other to form -NH-, -S-, or -SO 2- . However, in this alkyl group, the adjacent methylene group is not replaced with an oxygen atom at the same time, and the terminal methylene group is not replaced with an oxygen atom or -CO-.

環T1表示可具有取代基的碳數3~10的芳香族雜環。 Ring T 1 represents an aromatic heterocyclic ring having 3 to 10 carbon atoms which may have a substituent.

[Y]m-表示任意的m價的陰離子。 [Y] m- represents an arbitrary m-valent anion.

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

應予說明，1分子中包含多個由下述式表示的陽離子的情況下，它們可以為相同的結構，也可以為不同的結構。 When a plurality of cations represented by the following formula are contained in one molecule, they may have the same structure or different structures.

Figure TWI679499B_D0040
Figure TWI679499B_D0040

[式中，環T1、R41~R44及R47~R54分別與上述同義。] [In the formula, the rings T 1 , R 41 to R 44 and R 47 to R 54 have the same meanings as described above. ]

上述環T1的芳香族雜環可以是單環，也可以是稠合環。由環T1表示的芳香族雜環的碳數為3~10，優選為3~8。另外，芳香族雜環優選為5~10元環，更優選為5~9元環。作為單環的芳香族雜環，例如可列舉吡咯環、噁唑環、吡唑環、咪唑環、噻唑環等含有氮原子的5元環；呋喃環、色烯環、噻吩環等不含氮原子的5元環；吡啶環、嘧啶環、噠嗪環、吡嗪環等含有氮原子的6元環；等，作為稠合環的芳香族雜環，可列舉吲哚環、苯并咪唑環、苯并噻唑環、喹啉環等含有氮原子的稠合環；苯并呋喃環等不含氮原子的環；等。 The aromatic heterocyclic ring of the ring T 1 may be a monocyclic ring or a fused ring. The carbon number of the aromatic heterocyclic ring represented by the ring T 1 is 3 to 10, and preferably 3 to 8. The aromatic heterocyclic ring is preferably a 5- to 10-membered ring, and more preferably a 5- to 9-membered ring. Examples of the monocyclic aromatic heterocyclic ring include a 5-membered ring containing a nitrogen atom, such as a pyrrole ring, an oxazole ring, a pyrazole ring, an imidazole ring, and a thiazole ring; and a nitrogen-free ring such as a furan ring, a chromene ring, and a thiophene ring 5-membered atomic ring; 6-membered ring containing nitrogen atom, such as pyridine ring, pyrimidine ring, pyridazine ring, and pyrazine ring; etc. As the aromatic heterocyclic ring of the fused ring, an indole ring and a benzimidazole ring are listed , Fused rings containing nitrogen atoms, such as benzothiazole ring and quinoline ring; rings containing no nitrogen atom, such as benzofuran ring; etc.

作為環T1的芳香族雜環可具有的取代基，可列舉鹵素原子、氰基、可具有取代基的碳數1~20的飽和烴基(優選地 碳數1~20的烷基)、取代或未取代的氨基、或者可具有取代基的碳數6~20的芳香族烴基等，優選地，可列舉碳數1~20的飽和烴基(優選地碳數1~20的烷基)、取代或未取代的氨基、或者可具有取代基的碳數6~20的芳香族烴基。 Examples of the substituent which the aromatic heterocyclic ring of ring T 1 may have include a halogen atom, a cyano group, a saturated hydrocarbon group having 1 to 20 carbon atoms (preferably an alkyl group having 1 to 20 carbon atoms), and a substituent which may have a substituent. Or an unsubstituted amino group, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and preferably, a saturated hydrocarbon group having 1 to 20 carbon atoms (preferably an alkyl group having 1 to 20 carbon atoms), a substituted Or an unsubstituted amino group or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

其中，作為環T1的芳香族雜環，優選含有氮原子的芳香族雜環，更優選含有氮原子的5元環的芳香族雜環。 Among these, as the aromatic heterocyclic ring of ring T 1, an aromatic heterocyclic ring containing a nitrogen atom is preferable, and a 5-membered aromatic heterocyclic ring containing a nitrogen atom is more preferable.

另外，環T1更優選為由式(Ab2-x1)表示的環。 The ring T 1 is more preferably a ring represented by the formula (Ab2-x1).

Figure TWI679499B_D0041
[式(Ab2-x1)中，環T2表示碳數3~10的芳香族雜環。
Figure TWI679499B_D0041
 [In formula (Ab2-x1), ring T 2 represents an aromatic heterocyclic ring having 3 to 10 carbon atoms.

R45及R46各自獨立地表示氫原子、碳數1~20的飽和烴基、可具有取代基的碳數6~20的芳香族烴基或可具有取代基的碳數7~30的芳烷基，該碳數1~20的飽和烴基中，該飽和烴基中所含的氫原子可以被取代或未取代的氨基或鹵素原子取代，該飽和烴基的碳數為2~20的情況下，該飽和烴基中所含的亞甲基可以被置換為氧原子或-CO-。不過，該碳數2~20的飽和烴基中，鄰接的亞甲基不會同時被置換為氧原子，末端的亞甲基不會被置換為氧原子或-CO-。R45與R46可結合並與它們結合的氮原子一起形成環。 R 45 and R 46 each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent In the saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a substituted or unsubstituted amino or halogen atom. When the saturated hydrocarbon group has 2 to 20 carbon atoms, the saturated hydrocarbon group is saturated. The methylene group contained in the hydrocarbon group may be replaced with an oxygen atom or -CO-. However, in this saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent methylene groups are not replaced with oxygen atoms at the same time, and terminal methylene groups are not replaced with oxygen atoms or -CO-. R 45 and R 46 may be bonded together with the nitrogen atom to which they are bonded to form a ring.

R55表示碳數1~20的飽和烴基、或可具有取代基的碳數 6~20的芳香族烴基。 R 55 represents a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

k1表示0或1。 k1 means 0 or 1.

＊表示與碳陽離子的鍵合端。] * Indicates a bonding end with a carbocation. ]

進而，環T1特別優選為由式(Ab2-y1)表示的環。 Furthermore, the ring T 1 is particularly preferably a ring represented by the formula (Ab2-y1).

Figure TWI679499B_D0042
[式(Ab2-y1)中，R56表示氫原子、碳數1~20的飽和烴基、或可具有取代基的碳數6~20的芳香族烴基。
Figure TWI679499B_D0042
 [In the formula (Ab2-y1), R 56 represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

X2表示氧原子、-NR57-或硫原子。 X2 represents an oxygen atom, -NR 57- , or a sulfur atom.

R57表示氫原子或碳數1~10的烷基。 R 57 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

R45及R46與上述同義。 R 45 and R 46 have the same meanings as described above.

＊表示與碳陽離子的鍵合端。] * Indicates a bonding end with a carbocation. ]

上述式中，環T2的芳香族雜環可列舉與環T1中例示的芳香族雜環同樣的環。 Examples of the aromatic heterocyclic ring of ring T 2 in the above formula include the same ring as the aromatic heterocyclic ring exemplified for ring T 1 .

另外，環T1也優選為由式(Ab2-x2)表示的環。 The ring T 1 is also preferably a ring represented by the formula (Ab2-x2).

Figure TWI679499B_D0043
[式(Ab2-x2)中，環T3表示具有氮原子的碳數3~10的芳香族雜環。
Figure TWI679499B_D0043
 [In formula (Ab2-x2), ring T 3 represents an aromatic heterocyclic ring having 3 to 10 carbon atoms having a nitrogen atom.

R58表示碳數1~20的飽和烴基、或可具有取代基的碳數6~20的芳香族烴基。 R 58 represents a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

R59表示氫原子、可具有取代基的碳數1~20的飽和烴基、可具有取代基的碳數6~20的芳香族烴基或可具有取代基的碳數7~30的芳烷基。 R 59 represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbons which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbons which may have a substituent, or an aralkyl group having 7 to 30 carbons which may have a substituent.

k2表示0或1。 k2 means 0 or 1.

＊表示與碳陽離子的鍵合端。] * Indicates a bonding end with a carbocation. ]

環T1進一步優選為由式(Ab2-y2)表示的環。 The ring T 1 is more preferably a ring represented by the formula (Ab2-y2).

Figure TWI679499B_D0044
[式(Ab2-y2)中， R60表示氫原子、碳數1~20的飽和烴基、或可具有取代基的碳數6~20的芳香族烴基。
Figure TWI679499B_D0044
 [In the formula (Ab2-y2), R 60 represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

R59與上述同義。 R 59 is synonymous with the above.

＊表示與碳陽離子的鍵合端。] * Indicates a bonding end with a carbocation. ]

由R41~R46、R55、R56及R58~R60表示的飽和烴基可以為直鏈狀、分支鏈狀及環狀的任一種。另外，該飽和烴基的碳數優選為1~10，更優選為1~8，進一步優選為1~6，特別優選為1~4。作為由R41~R46、R55、R56及R58~R60表示的碳數1~20的飽和烴基，可列舉與作為由R1表示的飽和烴基例示的基團同樣的基團。另外，鏈狀飽和烴基(烷基)的碳數優選為1~8，更優選為1~6，進一步優選為1~4。另外，環狀 飽和烴基(脂環式烴基)的碳數優選為3~10，更優選為6~10。 The saturated hydrocarbon group represented by R 41 to R 46 , R 55 , R 56, and R 58 to R 60 may be any of linear, branched, and cyclic. The carbon number of the saturated hydrocarbon group is preferably 1 to 10, more preferably 1 to 8, even more preferably 1 to 6, and particularly preferably 1 to 4. Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R 41 to R 46 , R 55 , R 56, and R 58 to R 60 include the same groups as those exemplified as the saturated hydrocarbon group represented by R 1 . The carbon number of the chain-saturated hydrocarbon group (alkyl group) is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 4. The carbon number of the cyclic saturated hydrocarbon group (alicyclic hydrocarbon group) is preferably 3 to 10, and more preferably 6 to 10.

另外，由R41~R46表示的飽和烴基的碳數為2~20的情況下，該飽和烴基中所含的亞甲基可以被置換為氧原子或-CO-，優選地可以被置換為氧原子。另外，在構成該飽和烴基的亞甲基間可***氧原子。不過，該碳數2~20的飽和烴基中，鄰接的亞甲基不會同時被置換為氧原子，末端的亞甲基不會被置換為氧原子或-CO-。這種情況下，作為該飽和烴基，優選直鏈狀或分支鏈狀的飽和烴基(即直鏈狀或分支鏈狀烷基)，更優選直鏈狀的飽和烴基(即直鏈狀烷基)。亞甲基可被置換為氧原子或-CO-的飽和烴基的優選的碳數為2~10，更優選為2~8。另外，亞甲基被置換為氧原子或-CO-時，末端與氧原子或-CO-之間、或者氧原子或-CO-與氧原子或-CO-之間的碳數優選1~4個，更優選2~3個。 In addition, when the carbon number of the saturated hydrocarbon group represented by R 41 to R 46 is 2 to 20, the methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom or -CO-, and may preferably be substituted with Oxygen atom. An oxygen atom may be inserted between the methylene groups constituting the saturated hydrocarbon group. However, in this saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent methylene groups are not replaced with oxygen atoms at the same time, and terminal methylene groups are not replaced with oxygen atoms or -CO-. In this case, the saturated hydrocarbon group is preferably a linear or branched saturated hydrocarbon group (that is, a linear or branched alkyl group), and more preferably a linear saturated hydrocarbon group (that is, a linear alkyl group). . The saturated carbon group in which the methylene group may be replaced with an oxygen atom or -CO- has a preferable carbon number of 2 to 10, and more preferably 2 to 8. When the methylene group is replaced with an oxygen atom or -CO-, the number of carbon atoms between the terminal and the oxygen atom or -CO- or between the oxygen atom or -CO- and the oxygen atom or -CO- is preferably 1 to 4. , More preferably 2 to 3.

由R41~R46、R55、R56及R58~R60表示的飽和烴基可以被取代或未取代的氨基或鹵素原子取代。作為取代氨基，例如可列舉二甲基氨基、二乙基氨基等烷基氨基。另外，作為鹵素原子，可列舉氟、氯、溴、碘。另外，鹵素原子為氟原子的情況下，由R41~R46、R55、R56及R58~R60表示的被鹵素原子(氟原子)取代的飽和烴基優選為三氟甲基、五氟乙基、七氟丙基等全氟烷基。 The saturated hydrocarbon group represented by R 41 to R 46 , R 55 , R 56, and R 58 to R 60 may be substituted with a substituted or unsubstituted amino group or a halogen atom. Examples of the substituted amino group include alkylamino groups such as dimethylamino and diethylamino. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. When the halogen atom is a fluorine atom, the saturated hydrocarbon group substituted with a halogen atom (fluorine atom) represented by R 41 to R 46 , R 55 , R 56, and R 58 to R 60 is preferably a trifluoromethyl group, penta Perfluoroalkyl groups such as fluoroethyl and heptafluoropropyl.

作為由R59表示的烷基可具有的取代基，可列舉鹵素原子、氰基等。 Examples of the substituent which the alkyl group represented by R 59 may have include a halogen atom, a cyano group, and the like.

另外，作為由R41~R46、R55、R56、R58~R60表示的 可被取代的芳香族烴基，可列舉與由R9A表示的可被取代的芳香族烴基同樣的基團。該芳香族烴基的碳數優選為6~20，更優選為6~10。作為該芳香族烴基，優選苯基、甲苯基、二甲苯基、萘基。另外，該芳香族烴基可具有1或2個以上的取代基。 Examples of the substitutable aromatic hydrocarbon group represented by R 41 to R 46 , R 55 , R 56 , and R 58 to R 60 include the same groups as the substitutable aromatic hydrocarbon group represented by R 9A . The carbon number of the aromatic hydrocarbon group is preferably 6 to 20, and more preferably 6 to 10. The aromatic hydrocarbon group is preferably a phenyl group, a tolyl group, a xylyl group, or a naphthyl group. The aromatic hydrocarbon group may have one or two or more substituents.

作為由R41~R46、R59表示的可被取代的芳烷基，可列舉與由R9A表示的可被取代的芳烷基同樣的基團。 Examples of the substitutable aralkyl group represented by R 41 to R 46 and R 59 include the same groups as the substitutable aralkyl group represented by R 9A .

作為由R57表示的碳數1~10的烷基，可列舉R9A中例示的直鏈狀或分支鏈狀烷基中為碳數1~10的基團等。 Examples of the alkyl group having 1 to 10 carbon atoms represented by R 57 include a group having 1 to 10 carbon atoms in the linear or branched alkyl group exemplified in R 9A .

由R41~R46、R55、R56、R58~R60表示的基團中，作為上述芳香族烴基及上述芳烷基中的取代基，可列舉氟原子、氯原子、碘等鹵素原子；甲氧基、乙氧基等碳數1~6的烷氧基；羥基；甲基、乙基等碳數1~6的烷基；氨磺醯基；甲基磺醯基等碳數1~6的烷基磺醯基；甲氧基羰基、乙氧基羰基等碳數1~6的烷氧基羰基等。 Among the groups represented by R 41 to R 46 , R 55 , R 56 , and R 58 to R 60 , examples of the substituents in the aromatic hydrocarbon group and the aralkyl group include halogens such as a fluorine atom, a chlorine atom, and iodine. Atoms; alkoxy groups with 1 to 6 carbons such as methoxy and ethoxy; hydroxyl groups; alkyl groups with 1 to 6 carbons such as methyl and ethyl; sulfamoyl groups; carbon numbers with methylsulfonyl groups 1 to 6 alkylsulfonyl groups; alkoxycarbonyl groups having 1 to 6 carbon atoms such as methoxycarbonyl and ethoxycarbonyl groups.

由R47~R54表示的碳數1~8的烷基可以為直鏈狀、分支鏈狀及環狀的任一種，優選為鏈狀，可列舉R1中例示的直鏈狀、分支鏈狀及環狀烷基中為碳數1~8的基團等。 The alkyl group having 1 to 8 carbon atoms represented by R 47 to R 54 may be any of linear, branched, and cyclic, and is preferably a chain. Examples thereof include the linear and branched chains exemplified in R 1 Examples of the cyclic alkyl group and the cyclic alkyl group include a group having 1 to 8 carbon atoms.

另外，作為由R47~R54表示的構成碳數2~8的烷基的亞甲基被置換為氧原子或-CO-的基團(優選地被置換為氧原子的基團。不過，該烷基中，鄰接的亞甲基不會同時被置換為氧原子，末端的亞甲基不會被置換為氧原子或-CO-)，可列舉從由上述R41~R46表示的構成碳數2~20的烷基的亞甲基被置換為氧原子或-CO-的基團中選擇了碳數8以 下的基團的基團。 In addition, the methylene group constituting the alkyl group having 2 to 8 carbon atoms represented by R 47 to R 54 is a group substituted with an oxygen atom or -CO- (preferably a group substituted with an oxygen atom. However, In this alkyl group, the adjacent methylene group is not replaced with an oxygen atom at the same time, and the terminal methylene group is not replaced with an oxygen atom or -CO-), and examples thereof include the structures represented by R 41 to R 46 described above. Among the groups in which the methylene group of the alkyl group having 2 to 20 carbon atoms is replaced with an oxygen atom or -CO-, a group having a carbon number of 8 or less is selected.

其中，作為R41~R44、R55、R58、R59，優選碳數1~20的飽和烴基(優選地烷基)、可具有取代基的碳數6~20的芳香族烴基。 Among them, R 41 to R 44 , R 55 , R 58 , and R 59 are preferably a saturated hydrocarbon group (preferably an alkyl group) having 1 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

另外，作為R47~R54，各自獨立地優選氫原子、鹵素原子或碳數1~8的烷基，各自獨立地特別優選氫原子、甲基、氟原子或氯原子。 In addition, as R 47 to R 54 , a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms are each independently preferable, and a hydrogen atom, a methyl group, a fluorine atom, or a chlorine atom is particularly preferably independent of each other.

進而，作為R56，優選碳數1~10的飽和烴基(優選地烷基)、或可具有取代基的芳香族烴基，更優選為碳數1~8的飽和烴基(優選地烷基)、或鹵素原子、碳數1~4的鹵代烷基、碳數1~4的烷氧基、羥基、碳數1~4的烷基、或者可被甲基磺醯基取代的芳香族烴基。 Furthermore, as R 56 , a saturated hydrocarbon group (preferably an alkyl group) having 1 to 10 carbon atoms or an aromatic hydrocarbon group which may have a substituent is preferable, and a saturated hydrocarbon group (preferably an alkyl group) having 1 to 8 carbon atoms is more preferred, Or a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an aromatic hydrocarbon group which may be substituted with a methylsulfonyl group.

作為R57，優選氫原子或碳數1~8的烷基。 R 57 is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

作為式(Ab2)的陽離子部分，如下述表2中所示，可列舉由式(Ab2-I)表示的陽離子1~陽離子12等。表中，＊表示鍵合端。 Examples of the cation moiety of the formula (Ab2) include cations 1 to 12 and the like represented by the formula (Ab2-I), as shown in Table 2 below. In the table, * indicates a bonding end.

Figure TWI679499B_D0045
Figure TWI679499B_D0045

表2中，Ph1~Ph9意味著由下述式表示的基團。式中，＊表示鍵合端。 In Table 2, Ph1 to Ph9 represent a group represented by the following formula. In the formula, * represents a bonding end.

Figure TWI679499B_D0047
Figure TWI679499B_D0047

另外，作為式(Ab2)的陽離子部分，如下述表3中所示，也可列舉由式(Ab2-II)表示的陽離子13~陽離子16等。表中，＊表示鍵合端。 In addition, as the cation part of the formula (Ab2), as shown in Table 3 below, cations 13 to 16 and the like represented by the formula (Ab2-II) can also be cited. In the table, * indicates a bonding end.

Figure TWI679499B_D0048
Figure TWI679499B_D0048

表3中，Ph1、Ph10、Ph11意味著由下述式表示的基團。式中，＊表示鍵合端。 In Table 3, Ph1, Ph10, and Ph11 represent groups represented by the following formulas. In the formula, * represents a bonding end.

Figure TWI679499B_D0050
Figure TWI679499B_D0050

其中，作為式(Ab2)的陽離子部分，優選陽離子1~陽離子6、陽離子11、或陽離子12，特別優選陽離子1、陽離子2、或陽離子12。 Among these, as the cation part of the formula (Ab2), cation 1 to cation 6, cation 11, or cation 12 are preferred, and cation 1, cation 2, or cation 12 is particularly preferred.

作為[Y]m-，可列舉上述的公知的陰離子，進而，可列舉式(y10)、式(y11)所示的陰離子。 [Y] m- includes the above-mentioned known anions, and further includes anions represented by the formula (y10) and the formula (y11).

Figure TWI679499B_D0051
[式中，RB6表示2價的有機基團。RB7表示3價的芳香族烴基。n表示自然數。]
Figure TWI679499B_D0051
 [In the formula, R B6 represents a divalent organic group. R B7 represents a trivalent aromatic hydrocarbon group. n represents a natural number. ]

作為由式(y10)表示的陰離子，例如可列舉甲烷二磺酸陰離子、丙烷二磺酸陰離子、甲苯二磺酸陰離子、萘二磺酸陰離子、及由下述式表示的陰離子等。 Examples of the anion represented by the formula (y10) include a methane disulfonic acid anion, a propane disulfonic acid anion, a toluene disulfonic acid anion, a naphthalene disulfonic acid anion, and an anion represented by the following formula.

Figure TWI679499B_D0052
Figure TWI679499B_D0052

作為由式(y11)表示的陰離子，例如可列舉由下述式表示的陰離子等。式中，n表示自然數。 Examples of the anion represented by the formula (y11) include an anion represented by the following formula. In the formula, n represents a natural number.

Figure TWI679499B_D0053
Figure TWI679499B_D0053

從耐熱性的方面出發，優選的陰離子為含硼陰離子、 含鋁陰離子及含氟陰離子。 From the viewpoint of heat resistance, preferred anions are boron-containing anions, Aluminum-containing anions and fluorine-containing anions.

作為化合物(Ab2)，例如可列舉由下述式表示的化合物。 Examples of the compound (Ab2) include compounds represented by the following formula.

Figure TWI679499B_D0054
Figure TWI679499B_D0054

Figure TWI679499B_D0055
Figure TWI679499B_D0055

Figure TWI679499B_D0056
Figure TWI679499B_D0056

Figure TWI679499B_D0057
Figure TWI679499B_D0057

Figure TWI679499B_D0058
Figure TWI679499B_D0058

Figure TWI679499B_D0059
Figure TWI679499B_D0059

Figure TWI679499B_D0060
Figure TWI679499B_D0060

包含由式(Ab2)表示的化合物的情況下，其含量在染料(A1)100質量份中優選為50質量份以上，更優選為60質量份以上，進一步優選為65質量份以上，優選為95質量份以下，更優選為90質量份以下，進一步優選為85質量份以下，特別優選為82質量份以下。 When the compound represented by the formula (Ab2) is included, the content thereof is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, still more preferably 65 parts by mass or more, and preferably 95 parts by mass of 100 parts by mass of the dye (A1). It is more preferably 90 parts by mass or less, still more preferably 85 parts by mass or less, and particularly preferably 82 parts by mass or less.

香豆素染料(Ac)為包含在分子內具有香豆素骨 架的化合物的染料。作為香豆素染料(Ac)，可列舉例如C.I.酸性黃227、250；C.I.分散黃82、184；C.I.溶劑橙112；C.I.溶劑黃160、172；專利第1299948號公報中記載的香豆素染料；等。優選在有機溶劑中溶解的染料。 Coumarin dye (Ac) is contained in the molecule with coumarin bone Frame of compounds for dyes. Examples of the coumarin dye (Ac) include CI acid yellow 227 and 250; CI disperse yellow 82 and 184; CI solvent orange 112; CI solvent yellow 160 and 172; and coumarin dyes described in Patent No. 1299948. ;Wait. Dyes dissolved in organic solvents are preferred.

這些中，作為香豆素染料，優選例如由式(Ac1)表示的化合物(以下有時稱為“化合物(Ac1)”)。 Among these, as the coumarin dye, for example, a compound represented by the formula (Ac1) (hereinafter sometimes referred to as "compound (Ac1)") is preferable.

Figure TWI679499B_D0061
Figure TWI679499B_D0061

[式(Ac1)中，XC表示氧原子或硫原子。 [In the formula (Ac1), X C represents an oxygen atom or a sulfur atom.

R1C各自獨立地表示碳數1~20的飽和烴基，該飽和烴基的碳數為2~20的情況下，構成該飽和烴基的亞甲基可以被置換為氧原子。不過，該碳數2~20的飽和烴基中，鄰接亞甲基不會同時被置換為氧原子，末端的亞甲基不會被置換為氧原子。 R 1C each independently represents a saturated hydrocarbon group having 1 to 20 carbon atoms. When the saturated hydrocarbon group has 2 to 20 carbon atoms, the methylene group constituting the saturated hydrocarbon group may be replaced with an oxygen atom. However, in this saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent methylene groups are not replaced with oxygen atoms at the same time, and terminal methylene groups are not replaced with oxygen atoms.

R2C~R13C各自獨立地表示氫原子、鹵素原子、氰基、硝基、氨基甲醯基、氨磺醯基、-SO3M、-CO2M、羥基、甲醯基、氨基、碳數1~20的1價的烴基，構成該烴基的亞甲基可以被替換為氧原子、硫原子、-N(R14C)-、磺醯基或羰基，該烴基中所含的氫原子可以被鹵素原子、氰基、硝基、氨基甲醯基、氨磺醯基、-SO3M、-CO2M、羥基、甲醯基或氨 基取代。 R 2C to R 13C each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO 3 M, -CO 2 M, a hydroxyl group, a methylamino group, an amino group, and a carbon atom. A monovalent hydrocarbon group of 1 to 20, the methylene group constituting the hydrocarbon group may be replaced with an oxygen atom, a sulfur atom, -N (R 14C )-, a sulfonyl group, or a carbonyl group, and the hydrogen atom contained in the hydrocarbon group may be substituted with a halogen atom, cyano, nitro, acyl carbamoyl, sulfamoyl acyl, -SO 3 M, -CO 2 M , hydroxy, methyl acyl or amino.

R14C表示氫原子或碳數1~20的1價的烴基，存在多個R14C的情況下，它們可以相同，也可以不同。 R 14C represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When a plurality of R 14C are present, they may be the same or different.

M表示氫原子或鹼金屬原子。 M represents a hydrogen atom or an alkali metal atom.

LC表示碳數1~20的2價的烴基或磺醯基。] L C represents a divalent hydrocarbon group or a sulfofluorenyl group having 1 to 20 carbon atoms. ]

R1C的碳數1~20的飽和烴基可以為直鏈狀、分支鏈狀、或環狀的任一種，優選為鏈狀。具體地，可列舉與作為R1的碳數1~20的飽和烴基例示的基團同樣的基團。 The saturated hydrocarbon group having 1 to 20 carbon atoms in R 1C may be linear, branched, or cyclic, and is preferably chain. Specifically, the same groups as those exemplified as the saturated hydrocarbon group having 1 to 20 carbon atoms as R 1 can be mentioned.

另外，由R1C表示的飽和烴基的碳數為2~20的情況下，該飽和烴基中所含的亞甲基可以被置換為氧原子。另外，構成該飽和烴基的亞甲基間可***氧原子。不過，該碳數2~20的飽和烴基中，鄰接亞甲基不會同時被置換為氧原子，末端的亞甲基不會被置換為氧原子。 When the carbon number of the saturated hydrocarbon group represented by R 1C is 2 to 20, the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom. An oxygen atom may be inserted between the methylene groups constituting the saturated hydrocarbon group. However, in this saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent methylene groups are not replaced with oxygen atoms at the same time, and terminal methylene groups are not replaced with oxygen atoms.

作為R2C~R14C的碳數1~20的1價的烴基，可列舉碳數1~20的1價的飽和烴基、碳數1~20的1價的不飽和脂肪族烴基、碳數6~10的1價的芳香族烴基等。作為上述碳數1~20的1價的飽和烴基，可列舉與作為R1中的碳數1~20的1價的飽和烴基例示的基團同樣的基團。另外，作為上述碳數1~20的1價的不飽和烴基，可列舉乙烯基、丙烯基、丁烯基、戊烯基、己烯基、庚烯基、辛烯基、壬烯基、癸烯基、十一碳烯基、十二碳烯基、十六碳烯基、十八碳烯基、二十碳烯基等直鏈狀烯基；環戊烯基、環己烯基、環庚烯基等環烯基；等。另外，作為上述碳數6~10的1價的芳香族烴基，可列舉與作為R1中的碳數6~10的芳香族烴基例示的基團同 樣的基團。 Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms in R 2C to R 14C include a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, a monovalent unsaturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, and carbon number 6 A monovalent aromatic hydrocarbon group of ~ 10 and the like. Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms include the same groups as those exemplified as the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R 1 . Examples of the monovalent unsaturated hydrocarbon group having 1 to 20 carbon atoms include vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, and decyl Linear alkenyl groups such as alkenyl, undecenyl, dodecenyl, hexadecenyl, octadecenyl, eicosenyl; cyclopentenyl, cyclohexenyl, cyclo Cycloalkenyl such as heptenyl; etc. Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms include the same groups as those exemplified as the aromatic hydrocarbon group having 6 to 10 carbon atoms in R 1 .

作為LC的碳數1~20的2價的烴基，可列舉碳數1~20的2價的飽和烴基、碳數1~20的2價的不飽和烴基、碳數6~10的2價的芳香族烴基，可列舉使R2C中的碳數1~20的1價的烴基中所含的1個氫原子作為鍵合端的基團等。 Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms in L C include a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, a divalent unsaturated hydrocarbon group having 1 to 20 carbon atoms, and a divalent hydrocarbon group having 6 to 10 carbon atoms. Examples of the aromatic hydrocarbon group include a group in which one hydrogen atom contained in a monovalent hydrocarbon group having 1 to 20 carbon atoms in R 2C is used as a bonding end.

進而，多個的R1C~R13C優選為彼此相同的基團。 Furthermore, a plurality of R 1C to R 13C are preferably the same groups.

其中，作為R1C，優選碳數1~20的鏈狀烷基，更優選碳數1~10的鏈狀烷基。 Among them, R 1C is preferably a chain alkyl group having 1 to 20 carbon atoms, and more preferably a chain alkyl group having 1 to 10 carbon atoms.

作為R2C~R6C，優選氫原子、或碳數1~20的1價的烴基，更優選氫原子、或碳數1~10的飽和烴基，進一步優選氫原子、或碳數1~5的鏈狀烷基。 As R 2C to R 6C , a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms is preferred, a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms is more preferred, and a hydrogen atom or 1 to 5 carbon atoms is more preferred. Chain alkyl.

作為R7C~R13C，優選氫原子、或碳數1~20的1價的烴基，特別優選氫原子。 As R 7C to R 13C , a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms is preferred, and a hydrogen atom is particularly preferred.

作為LC，優選磺醯基或亞甲基、亞丙基等碳數1~20的飽和烴基。另外，LC的2價的烴基優選為碳數1~10，更優選為碳數1~5。 L C is preferably a saturated hydrocarbon group having 1 to 20 carbon atoms, such as a sulfonyl group, a methylene group, and a propylene group. The divalent hydrocarbon group of L C is preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.

另外，作為XC，特別優選氧原子。 As X C , an oxygen atom is particularly preferred.

作為化合物(Ac1)，例如可列舉由下式表示的化合物。 Examples of the compound (Ac1) include compounds represented by the following formula.

Figure TWI679499B_D0062
Figure TWI679499B_D0062

Figure TWI679499B_D0063
Figure TWI679499B_D0063

包含香豆素染料(Ac)的情況下，其含量在染料(A1)100質量份中優選為1質量份以上，更優選為50質量份以上，進一步優選為80質量份以上，也優選為100質量份，也優選為99質量份以下。 When the coumarin dye (Ac) is contained, the content is preferably 1 part by mass or more, more preferably 50 parts by mass or more, still more preferably 80 parts by mass or more, and also preferably 100 parts by mass of 100 parts by mass of the dye (A1). It is also preferably 99 parts by mass or less.

作為蒽醌染料(Ad)，可使用公知的物質。作為蒽醌染料(Ad)，例如可列舉C.I.溶劑黃117(以下省略C.I.溶劑黃的記載，只記載編 號。)、163、167、189、C.I.溶劑橙77、86、C.I.溶劑紅111、143、145、146、150、151、155、168、169、172、175、181、207、222、227、230、245、247、C.I.溶劑紫11、13、14、26、31、36、37、38、45、47、48、51、59、60、C.I.溶劑藍14、18、35、36、45、58、59、59：1、63、68、69、78、79、83、94、97、98、100、101、102、104、105、111、112、122、128、132、136、139、C.I.溶劑綠3、28、29、32、33、C.I.酸性紅80、C.I.酸性綠25、27、28、41、C.I.酸性紫34、C.I.酸性藍25、27、40、45、78、80、112C.I.分散黃51、C.I.分散紫26、27、C.I.分散藍1、14、56、60、C.I.直接藍40、C.I.媒染紅3、11、C.I.媒染藍8等。蒽醌染料(Ad)優選在有機溶劑中溶解的染料，更優選藍色、紫色或紅色的蒽醌染料。 As the anthraquinone dye (Ad), a known substance can be used. Examples of the anthraquinone dye (Ad) include C.I. Solvent Yellow 117 (hereinafter, the description of C.I. Solvent Yellow is omitted, and only the editor is described) number. ), 163, 167, 189, CI solvent orange 77, 86, CI solvent red 111, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247, CI Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60, CI Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139, CI solvents Green 3, 28, 29, 32, 33, CI Acid Red 80, CI Acid Green 25, 27, 28, 41, CI Acid Violet 34, CI Acid Blue 25, 27, 40, 45, 78, 80, 112C.I . Disperse Yellow 51, CI Disperse Purple 26, 27, CI Disperse Blue 1, 14, 56, 60, CI Direct Blue 40, CI Mordant Red 3, 11, CI Mordant Blue 8, etc. The anthraquinone dye (Ad) is preferably a dye dissolved in an organic solvent, and more preferably a blue, purple or red anthraquinone dye.

這些中，作為蒽醌染料(Ad)，優選由式(1d)表示的化合物(以下有時稱為“化合物(1d)”。)。 Among these, as the anthraquinone dye (Ad), a compound represented by formula (1d) (hereinafter sometimes referred to as "compound (1d)") is preferable.

Figure TWI679499B_D0064
Figure TWI679499B_D0064

[式(1d)中，R91及R92各自獨立地表示氫原子、可具有取代基的碳數1~10的脂肪族烴基、可具有取代基的碳數3~10的脂環式烴基、或、式(1d’) [In formula (1d), R 91 and R 92 each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, an alicyclic hydrocarbon group having 3 to 10 carbon atoms which may have a substituent, Or, (1d ')

Figure TWI679499B_D0065
Figure TWI679499B_D0065

(式(1d’)中，R93表示碳數1~6的烷基、鹵素原子、-SO3H、-CO2H、-CO2R94、-NHCOR94、-SO3R94或-SO2NR94R95。 (In formula (1d '), R 93 represents an alkyl group having 1 to 6 carbon atoms, a halogen atom, -SO 3 H, -CO 2 H, -CO 2 R 94 , -NHCOR 94 , -SO 3 R 94 , or- SO 2 NR 94 R 95 .

R94表示可被鹵素原子、羥基或氨基取代的碳數1~10的脂肪族烴基、或者可被鹵素原子、羥基或氨基取代的碳數3~10的脂環式烴基。 R 94 represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom, a hydroxyl group or an amino group, or an alicyclic hydrocarbon group having 3 to 10 carbon atoms which may be substituted with a halogen atom, a hydroxyl group or an amino group.

R95表示氫原子、碳數1~10的飽和烴基。 R 95 represents a hydrogen atom and a saturated hydrocarbon group having 1 to 10 carbon atoms.

r表示0~5的整數。r為2以上的情況下，多個R93可以相同，也可不同。 r represents an integer from 0 to 5. When r is 2 or more, a plurality of R 93 may be the same or different.

X91表示單鍵或碳數1~6的亞烷基。)所示的基團。] X 91 represents a single bond or an alkylene group having 1 to 6 carbon atoms. ). ]

化合物(1d)具有-SO3H和/或-CO2H的情況下，它 們可以形成鹽(例如Na鹽、K鹽)。 When the compound (1d) has -SO 3 H and / or -CO 2 H, they may form a salt (for example, Na salt, K salt).

R91及R92、R94及R95中，作為碳數1~10的脂肪族烴基，例如可列舉甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、異丙基、異丁基、仲丁基、叔丁基、異戊基、新戊基、2-乙基己基等。 Examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms among R 91 and R 92 , R 94 and R 95 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and the like. Nonyl, decyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, 2-ethylhexyl and the like.

作為這些脂肪族烴基可具有的取代基，可列舉羥基、鹵素原子、或氨基等，優選羥基或鹵素原子。 As a substituent which these aliphatic hydrocarbon groups may have, a hydroxyl group, a halogen atom, or an amino group etc. are mentioned, A hydroxyl group or a halogen atom is preferable.

作為由R91、R92及R94表示的碳數3~10的脂環式烴基，可列舉環丙基、環戊基、環己基、環庚基、環辛基、三環癸基等。 Examples of the alicyclic hydrocarbon group having 3 to 10 carbon atoms represented by R 91 , R 92 and R 94 include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl.

作為這些脂環式烴基可具有的取代基，可列舉羥基、鹵素原子或氨基等，優選羥基或鹵素原子。 As a substituent which these alicyclic hydrocarbon groups may have, a hydroxyl group, a halogen atom, or an amino group etc. are mentioned, A hydroxyl group or a halogen atom is preferable.

作為由R93表示的碳數1~6的烷基，可列舉例如甲基、乙基、丙基、丁基、戊基、己基、異丙基、異丁基、仲丁基、叔丁基、異戊基、新戊基等。 Examples of the alkyl group having 1 to 6 carbon atoms represented by R 93 include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, and tert-butyl. , Isopentyl, neopentyl, etc.

作為-CO2R94，可列舉甲氧基羰基、乙氧基羰基、丙氧基羰基、叔丁氧基羰基、己氧基羰基及二十烷氧基羰基等。 Examples of -CO 2 R 94 include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, and an eicosyloxycarbonyl group.

作為-NHCOR94，可列舉N-乙醯基氨基、N-丙醯基氨基、N-丁醯基氨基、N-異丁醯基氨基及N-新戊醯基氨基等。 Examples of -NHCOR 94 include N-ethylamino, N-propylamino, N-butylamino, N-isobutylamino, N-neopentylamino, and the like.

作為-SO3R94，可列舉甲氧基磺醯基、乙氧基磺醯基、丙氧基磺醯基、叔丁氧基磺醯基、己氧基磺醯基及二十烷氧基磺醯基等。 Examples of -SO 3 R 94 include methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tert-butoxysulfonyl, hexylsulfonyl, and eicosyloxy. Sulfonyl and others.

作為-SO2NR94R95，可列舉N-甲基氨磺醯基、N-乙基氨磺醯基、N-丙基氨磺醯基、N-異丙基氨磺醯基、N-丁基氨磺醯基、N-異丁基氨磺醯基、N-仲-丁基氨磺醯基、N-叔-丁基氨磺醯基、N-戊基氨磺醯基、N-(1-乙基丙基)氨磺醯基、N-(1,1-二甲基丙基)氨磺醯基、N-(1,2-二甲基丙基)氨磺醯基、N-(2,2-二甲基丙基)氨磺醯基、N-(1-甲基丁基)氨磺醯基、N-(2-甲基丁基)氨磺醯基、N-(3-甲基丁基)氨磺醯基、N-環戊基氨磺醯基、N-環己基氨磺醯基、N-己基氨磺醯基、N-(1,3-二甲基丁基)氨磺醯基、N-(3,3-二甲基丁基)氨磺醯基、N-庚基氨磺醯基、N-(1-甲基己基)氨磺醯基、N-(1,4-二甲基戊基)氨磺醯基、N-辛基氨磺醯基、N-(2-乙基己基)氨磺醯基、N-(1,5-二甲基)己基氨磺醯基、N-(1,1,2,2-四甲基丁基)氨磺醯基、N-(5-氨基戊基)氨磺醯基等N-1取代氨磺醯基；N,N-二甲基氨磺醯基、N,N-乙基甲基氨磺醯基、N,N-二乙基氨磺醯基、N,N-丙基甲基氨磺醯基、N,N-異丙基甲基氨磺醯基、N,N-叔-丁基甲基氨磺醯基、N,N-丁基乙基氨磺醯基、N,N-雙(1-甲基丙基)氨磺醯基、N,N-庚基甲基氨磺醯基等N,N-2取代氨磺醯基等。 Examples of -SO 2 NR 94 R 95 include N-methylsulfamominyl, N-ethylsulfamominyl, N-propylsulfamominyl, N-isopropylsulfamominyl, and N- Butylsulfamoyl, N-isobutylsulfamomethyl, N-sec-butylsulfamomethyl, N-tert-butylsulfamomethyl, N-pentylsulfamomethyl, N- (1-ethylpropyl) sulfamoyl, N- (1,1-dimethylpropyl) sulfamoyl, N- (1,2-dimethylpropyl) sulfamoyl, N -(2,2-dimethylpropyl) sulfamoyl, N- (1-methylbutyl) sulfamoyl, N- (2-methylbutyl) sulfamoyl, N- ( 3-methylbutyl) sulfamoyl, N-cyclopentylsulfamoyl, N-cyclohexylsulfamomethyl, N-hexylsulfamomethyl, N- (1,3-dimethylbutyl Sulfamoyl, N- (3,3-dimethylbutyl) sulfamoyl, N-heptylsulfamoyl, N- (1-methylhexyl) sulfamoyl, N- (1,4-dimethylpentyl) sulfamoyl, N-octylsulfamoyl, N- (2-ethylhexyl) sulfamoyl, N- (1,5-dimethyl) Hexylsulfamoyl, N- (1,1,2,2-tetramethylbutyl) sulfamomethyl, N- (5-aminopentyl) sulfamomethyl, and other N-1 substituted sulfamomethyl groups ; N, N-Dimethylsulfamoyl, N, N-ethylmethylsulfamoyl, N , N-Diethylsulfamominyl, N, N-propylmethylsulfamominyl, N, N-isopropylmethylsulfamominyl, N, N-tert-butylmethylsulfamominyl , N, N-butylethylsulfamoyl, N, N-bis (1-methylpropyl) sulfamomethyl, N, N-heptylmethylsulfamoyl, etc.N, N-2 Substituted sulfamoyl and the like.

X91中，作為碳數1~6的亞烷基，可列舉亞甲基、亞乙基、丙烷-1,3-二基、丙烷-1,2-二基、丁烷-1,4-二基、戊烷-1,5-二基、己烷-1,6-二基、乙烷-1,1-二基、丁烷-1,3-二基、2-甲基丙烷-1,3-二基、2-甲基丙烷-1,2-二基、戊烷-1,4-二基、2-甲基丁烷-1,4-二基等。 Examples of the alkylene group having 1 to 6 carbon atoms in X 91 include methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, and butane-1,4-. Diyl, pentane-1,5-diyl, hexane-1,6-diyl, ethane-1,1-diyl, butane-1,3-diyl, 2-methylpropane-1 , 3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, 2-methylbutane-1,4-diyl, and the like.

作為R93，優選可具有羥基的碳數1~5的烷基、 -SO3R94、-SO2NR94R95，更優選-SO2NR94R95，進一步優選-SO2NHR94(各式中，R94及R95與上述定義相同)。 R 93 is preferably an alkyl group having 1 to 5 carbon atoms which may have a hydroxyl group, -SO 3 R 94 , -SO 2 NR 94 R 95 , more preferably -SO 2 NR 94 R 95 , and still more preferably -SO 2 NHR 94 ( In each formula, R 94 and R 95 have the same definitions as above).

作為化合物(1d)，例如可列舉式(3-1)~式(3-11)所示的化合物。 Examples of the compound (1d) include compounds represented by the formulae (3-1) to (3-11).

Figure TWI679499B_D0066
Figure TWI679499B_D0066

作為蒽醌染料(Ad)，為由式(1d)表示的化合物，優選R91及R92為氫原子、碳數1~5的烷基、可具有鹵素原子的苯基、及由式(1d’)表示的基團的化合物，更優選由式(3-4)及式(3-11)表示的化合物。如果為這些蒽醌染料，則能夠形 成高對比度的塗膜、圖案，而且能夠形成異物的產生也少、耐光性優異的塗膜、圖案。 The anthraquinone dye (Ad) is a compound represented by formula (1d). R 91 and R 92 are preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group which may have a halogen atom, and a compound represented by formula (1d). The compound represented by a group represented by ') is more preferably a compound represented by the formula (3-4) or (3-11). With these anthraquinone dyes, it is possible to form a coating film and a pattern with high contrast, and it is possible to form a coating film and a pattern with little generation of foreign matter and excellent light resistance.

包含蒽醌染料(Ad)的情況下，其含量在染料(A1)100質量份中優選為1質量份以上、99質量份以下。 When an anthraquinone dye (Ad) is contained, the content is preferably 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the dye (A1).

四氮雜卟啉染料(Ae)為在分子內具有四氮雜卟啉骨架的化合物。另外，四氮雜卟啉染料(Ae)為酸性染料或鹼性染料的情況下，可以與任意的陽離子或陰離子形成鹽。 A tetraazaporphyrin dye (Ae) is a compound having a tetraazaporphyrin skeleton in the molecule. When the tetraazaporphyrin dye (Ae) is an acid dye or a basic dye, it may form a salt with any cation or anion.

這些中，作為四氮雜卟啉染料(Ae)，優選包含由式(1e)表示的結構(以下有時稱為化合物(1e)。)的染料。 Among these, as the tetraazaporphyrin dye (Ae), a dye containing a structure represented by the formula (1e) (hereinafter sometimes referred to as a compound (1e)) is preferable.

Figure TWI679499B_D0067
Figure TWI679499B_D0067

[式(1e)中，R71~R78各自獨立地表示氫原子、鹵素原子、氰基、硝基、取代或未取代的烷基、取代或未取代的烷氧基、取代或未取代的芳基、取代或未取代的芳氧基、取代或未取代的芳烷氧基、或者取代或未取代的氨基，M4表示2個氫原子、2個1價的金屬原子、2價的金屬原子、3價的取代金屬原子、或氧化金屬。 [In the formula (1e), R 71 to R 78 each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted Aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted aralkoxy, or substituted or unsubstituted amino, M4 represents 2 hydrogen atoms, 2 monovalent metal atoms, divalent metal atoms , Trivalent substituted metal atom, or oxidized metal.

式(1e)中所謂芳基，為苯基、萘基等碳數6~30的芳香族烴基；呋喃基、噻吩基、吡啶基等碳數3~20的雜環 式芳香族基團，優選為芳香族烴基。 The so-called aryl group in formula (1e) is an aromatic hydrocarbon group having 6 to 30 carbon atoms such as phenyl and naphthyl; and a heterocyclic ring having 3 to 20 carbon atoms such as furyl, thienyl, and pyridyl The aromatic group of formula is preferably an aromatic hydrocarbon group.

式(1e)中，R71~R78優選各自獨立地為氫原子、鹵素原子、氰基、硝基、碳數1~24的取代或未取代的烷基、碳數1~24的取代或未取代的烷氧基、碳數6~30的取代或未取代的芳基、碳數4~30的取代或未取代的芳氧基、碳數7~30的取代或未取代的芳烷氧基、或碳數1~30的取代氨基。 In the formula (1e), R 71 to R 78 are preferably each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 24 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 24 carbon atoms. Unsubstituted alkoxy, substituted or unsubstituted aryl having 6 to 30 carbons, substituted or unsubstituted aryloxy having 4 to 30 carbons, substituted or unsubstituted aralkoxy having 7 to 30 carbons Or a substituted amino group having 1 to 30 carbon atoms.

R71~R78更優選地各自獨立地為氫原子、氟原子、氯原子、溴原子、氰基、碳數1~16的取代或未取代的烷基、碳數1~16的取代或未取代的烷氧基、碳數6~24的取代或未取代的芳基、碳數6~24的取代或未取代的芳氧基、碳數7~24的取代或未取代的芳烷氧基、或碳數1~16的取代氨基。 R 71 to R 78 are more preferably each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms, or a substituted or unsubstituted carbon group having 1 to 16 carbon atoms. Substituted alkoxy, substituted or unsubstituted aryl having 6 to 24 carbons, substituted or unsubstituted aryloxy having 6 to 24 carbons, substituted or unsubstituted aralkoxy having 7 to 24 carbons Or a substituted amino group having 1 to 16 carbon atoms.

R71~R78更優選地各自獨立地為氫原子、氟原子、溴原子、氰基、碳數1~10的取代或未取代的烷基、碳數1~10的取代或未取代的烷氧基、碳數6~16的取代或未取代的芳基、碳數6~16的取代或未取代的芳氧基、碳數7~16的取代或未取代的芳烷氧基、或碳數1~12的取代氨基。 R 71 to R 78 are more preferably each independently a hydrogen atom, a fluorine atom, a bromine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms. Oxygen, substituted or unsubstituted aryl having 6 to 16 carbons, substituted or unsubstituted aryloxy having 6 to 16 carbons, substituted or unsubstituted aralkoxy having 7 to 16 carbons, or carbon Substituted amino groups of 1-12.

式(1e)中，以下示出R71~R78的具體例。 In the formula (1e), specific examples of R 71 to R 78 are shown below.

作為鹵素原子，可列舉氟原子、氯原子、溴原子。 Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

作為未取代的烷基，可列舉甲基、乙基、正丙基、異丙基、正丁基、異丁基、仲丁基、叔丁基、正戊基、異戊基、新戊基、叔戊基、正己基、1-甲基戊基、4-甲基-2-戊基、2-乙基丁基、正庚基、1-甲基己基、正辛基、1-甲基庚基、2-乙基己基、2-丙基戊基、正壬基、2,2-二甲基庚基、2,6-二甲基-4-庚基、3,5,5-三甲基己基、正癸基、1-乙基辛 基、正十一烷基、1-甲基癸基、正十二烷基、正十三烷基、1-己基庚基、正十四烷基、正十五烷基、1-庚基辛基、正十六烷基、正十七烷基、1-辛基壬基、正十八烷基、1-壬基癸基、1-癸基十一烷基、正二十烷基、正二十二烷基、正二十四烷基、1-金剛烷基、環戊基、環己基、降冰片基等只包含碳原子和氫原子的直鏈、分支或環狀的烷基。 Examples of the unsubstituted alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, and neopentyl. , Tert-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, 1-methyl Heptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-tri Methylhexyl, n-decyl, 1-ethyloctyl Base, n-undecyl, 1-methyldecyl, n-dodecyl, n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, 1-heptyloctyl , N-hexadecyl, n-heptadecyl, 1-octylnonyl, n-octadecyl, 1-nonyldecyl, 1-decylundecyl, n-icosyl, n-icosyl Dialkyl, n-tetracosyl, 1-adamantyl, cyclopentyl, cyclohexyl, norbornyl and the like are straight-chain, branched, or cyclic alkyl groups containing only carbon and hydrogen atoms.

作為烷基中的取代基，可列舉碳數1~16的烷氧基、烷氧基烷氧基、芳烷氧基、芳氧基、烷硫基、鹵素原子、鹵代烷氧基等。 Examples of the substituent in the alkyl group include an alkoxy group having 1 to 16 carbon atoms, an alkoxyalkoxy group, an aralkyloxy group, an aryloxy group, an alkylthio group, a halogen atom, and a halogenated alkoxy group.

作為具有取代基的烷基的具體例，可列舉甲氧基甲基、乙氧基甲基、正-丁氧基甲基、正-己氧基甲基、(2-乙基丁氧基)甲基、正-辛氧基甲基、正-癸氧基甲基、2-甲氧基乙基、2-乙氧基乙基、2-正-丙氧基乙基、2-異丙氧基乙基、2-正-丁氧基乙基、2-正-戊氧基乙基、2-正-己氧基乙基、2-(2’-乙基丁氧基)乙基、2-正-庚氧基乙基、2-正-辛氧基乙基、2-(2’-乙基己氧基)乙基、2-正-癸氧基乙基、2-正-十二烷氧基乙基、2-正-十四烷氧基乙基、2-環己氧基乙基、2-甲氧基丙基、3-甲氧基丙基、3-乙氧基丙基、3-正-丙氧基丙基、3-異丙氧基丙基、3-(正-丁氧基)丙基、3-(正-戊氧基)丙基、3-(正-己氧基)丙基、3-(2’-乙基丁氧基)丙基、3-(正-辛氧基)丙基、3-(2’-乙基己氧基)丙基、3-(正-癸氧基)丙基、3-(正-十二烷氧基)丙基、3-(正-十四烷氧基)丙基、3-環己氧基丙基、4-甲氧基丁基、4-乙氧基丁基、4-正-丙氧基丁基、4-異丙氧基丁基、4-正-丁氧基丁基、4-正-己氧基丁基、4- 正-辛氧基丁基、4-正-癸氧基丁基、4-正-十二烷氧基丁基、5-甲氧基戊基、5-乙氧基戊基、5-正-丙氧基戊基、6-乙氧基己基、6-異丙氧基己基、6-正-丁氧基己基、6-正-己氧基己基、6-正-癸氧基己基、4-甲氧基環己基、7-乙氧基庚基、7-異丙氧基庚基、8-甲氧基辛基、10-甲氧基癸基、10-正-丁氧基癸基、12-乙氧基十二烷基、12-異丙氧基十二烷基、四氫糠基等的、具有烷氧基的烷基；(2-甲氧基乙氧基)甲基、(2-乙氧基乙氧基)甲基、(2-正-丁氧基乙氧基)甲基、(2-正-己氧基乙氧基)甲基、(3-甲氧基丙氧基)甲基、(3-乙氧基丙氧基)甲基、(3-正-丁氧基丙氧基)甲基、(3-正-戊氧基丙氧基)甲基、(4-甲氧基丁氧基)甲基、(6-甲氧基己氧基)甲基、(10-乙氧基癸氧基)甲基、2-(2’-甲氧基乙氧基)乙基、2-(2’-乙氧基乙氧基)乙基、2-(2’-正-丁氧基乙氧基)乙基、3-(2’-乙氧基乙氧基)丙基、3-(2’-甲氧基丙氧基)丙基、3-(2’-異丙氧基丙氧基)丙基、3-(3’-甲氧基丙氧基)丙基、3-(3’-乙氧基丙氧基)丙基等的、具有烷氧基烷氧基的烷基；例如，苄氧基甲基、2-苄氧基乙基、2-苯乙氧基乙基、2-(4’-甲基苄氧基)乙基、2-(2’-甲基苄氧基)乙基、2-(4’-氟苄氧基)乙基、2-(4’-氯苄氧基)乙基、3-苄氧基丙基、3-(4’-甲氧基苄氧基)丙基、4-苄氧基丁基、2-(苄氧基甲氧基)乙基、2-(4’-甲基苄氧基甲氧基)乙基等的、具有芳烷氧基的烷基；苯氧基甲基、4-甲基苯氧基甲基、3-甲基苯氧基甲基、2-甲基苯氧基甲基、4-甲氧基苯氧基甲基、4-氟苯氧基甲基、 4-氯苯氧基甲基、2-氯苯氧基甲基、2-苯氧基乙基、2-(4’-甲基苯氧基)乙基、2-(4’-乙基苯氧基)乙基、2-(4’-甲氧基苯氧基)乙基、2-(4’-氯苯氧基)乙基、2-(4’-溴苯氧基)乙基、2-(1’-萘氧基)乙基、2-(2’-萘氧基)乙基、3-苯氧基丙基、3-(2’-萘氧基)丙基、4-苯氧基丁基、4-(2’-乙基苯氧基)丁基、5-(4’-叔-丁基苯氧基)戊基、6-(2’-氯苯氧基)己基、8-苯氧基辛基、10-苯氧基癸基、10-(3’-氯苯氧基)癸基、2-(2’-苯氧基乙氧基)乙基、3-(2’-苯氧基乙氧基)丙基、4-(2’-苯氧基乙氧基)丁基等的、具有芳氧基的烷基；正-丁硫基甲基、正-己硫基甲基、2-甲硫基乙基、2-乙硫基乙基、2-正-丁硫基乙基、2-正-己硫基乙基、2-正-辛硫基乙基、2-正-癸硫基乙基、3-甲硫基丙基、3-乙硫基丙基、3-正-丁硫基丙基、4-乙硫基丁基、4-正-丙硫基丁基、4-正-丁硫基丁基、5-乙硫基戊基、6-甲硫基己基、6-乙硫基己基、6-正-丁硫基己基、8-甲硫基辛基等的、具有烷硫基的烷基；氟甲基、3-氟丙基、6-氟己基、8-氟辛基、三氟甲基、1,1-二氫-全氟乙基、1,1-二氫-全氟-正-丙基、1,1,3-三氫-全氟-正-丙基、2-氫-全氟-2-丙基、1,1-二氫-全氟-正-丁基、1,1-二氫-全氟-正-戊基、1,1-二氫-全氟-正-己基、6-氟己基、4-氟環己基、1,1-二氫-全氟-正-辛基、1,1-二氫-全氟-正-癸基、1,1-二氫-全氟-正-十二烷基、1,1-二氫-全氟-正-十四烷基、1,1-二氫-全氟-正-十六烷基、全氟乙基、全氟-正-丙基、全氟-正-戊基、全氟-正-己基、2,2-雙(三氟甲基)丙基、二氯甲基、2-氯乙基、3-氯丙基、4-氯環己基、7-氯庚基、8-氯 辛基、2,2,2-三氯乙基等的具有鹵素原子的烷基；氟甲氧基甲基、3-氟-正-丙氧基甲基、6-氟-正-己氧基甲基、三氟甲氧基甲基、1,1-二氫-全氟乙氧基甲基、1,1-二氫-全氟-正-丙氧基甲基、2-氫-全氟-2-丙氧基甲基、1,1-二氫-全氟-正-丁氧基甲基、1,1-二氫-全氟-正-戊氧基甲基、1,1-二氫-全氟-n-己氧基甲基、1,1-二氫-全氟-正-辛氧基甲基、1,1-二氫-全氟-正-癸氧基甲基、1,1-二氫-全氟-正-十四烷氧基甲基、2,2-雙(三氟甲基)丙氧基甲基、3-氯-正-丙氧基甲基、2-(8-氟-正-辛氧基)乙基、2-(1,1-二氫-全氟乙氧基)乙基、2-(1,1,3-三氫-全氟-正-丙氧基)乙基、2-(1,1-二氫-全氟-正-戊氧基)乙基、2-(6-氟-正-己氧基)乙基、2-(1,1-二氫-全氟-正-辛氧基)乙基、3-(4-氟環己氧基)丙基、3-(1,1-二氫-全氟乙氧基)丙基、3-(1,1-二氫-全氟-正-十二烷氧基)丙基、4-(全氟-正-己氧基)丁基、4-(1,1-二氫-全氟乙氧基)丁基、6-(2-氯乙氧基)己基、6-(1,1-二氫-全氟乙氧基)己基等的、具有鹵代烷氧基的烷基；苯氧基甲基、4-甲基苯氧基甲基、3-甲基苯氧基甲基、2-甲基苯氧基甲基、4-乙基苯氧基甲基、4-正-丙基苯氧基甲基、4-正-丁基苯氧基甲基、4-叔-丁基苯氧基甲基、4-正-己基苯氧基甲基、4-正-辛基苯氧基甲基、4-正-癸基苯氧基甲基、4-甲氧基苯氧基甲基、4-乙氧基苯氧基甲基、4-丁氧基苯氧基甲基、4-正-戊氧基苯氧基甲基、4-氟苯氧基甲基、3-氟苯氧基甲基、2-氟苯氧基甲基、3,4-二氟苯氧基甲基、4-氯苯氧基甲基、2-氯苯氧基甲基、4-苯基苯氧基甲基、1- 萘氧基甲基、2-萘氧基甲基、2-呋喃氧基甲基、1-苯氧基乙基、2-苯氧基乙基、2-(4’-甲基苯氧基)乙基、2-(4’-乙基苯氧基)乙基、2-(4’-正-己基苯氧基)乙基、2-(4’-甲氧基苯氧基)乙基、2-(4’-正-丁氧基苯氧基)乙基、2-(4’-氟苯氧基)乙基、2-(4’-氯苯氧基)乙基、2-(4’-溴苯氧基)乙基、2-(1’-萘氧基)乙基、2-(2’-萘氧基)乙基、2-苯氧基丙基、3-苯氧基丙基、3-(4’-甲基苯氧基)丙基、3-(2’-萘氧基)丙基、4-苯氧基丁基、4-(2’-乙基苯氧基)丁基、4-苯氧基戊基、5-苯氧基戊基、5-(4’-叔-丁基苯氧基)戊基、6-苯氧基己基、6-(2’-氯苯氧基)己基、8-苯氧基辛基、10-苯氧基癸基、10-(3’-甲基苯氧基)癸基等的、具有芳氧基的烷基。 Specific examples of the alkyl group having a substituent include methoxymethyl, ethoxymethyl, n-butoxymethyl, n-hexyloxymethyl, and (2-ethylbutoxy) Methyl, n-octyloxymethyl, n-decyloxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-n-propoxyethyl, 2-isopropoxy Ethyl, 2-n-butoxyethyl, 2-n-pentyloxyethyl, 2-n-hexyloxyethyl, 2- (2'-ethylbutoxy) ethyl, 2 -N-heptyloxyethyl, 2-n-octyloxyethyl, 2- (2'-ethylhexyloxy) ethyl, 2-n-decylethyl, 2-n-dodecyl Alkoxyethyl, 2-n-tetradecyloxyethyl, 2-cyclohexyloxyethyl, 2-methoxypropyl, 3-methoxypropyl, 3-ethoxypropyl , 3-n-propoxypropyl, 3-isopropoxypropyl, 3- (n-butoxy) propyl, 3- (n-pentyloxy) propyl, 3- (n-hexane (Oxy) propyl, 3- (2'-ethylbutoxy) propyl, 3- (n-octyloxy) propyl, 3- (2'-ethylhexyloxy) propyl, 3- (N-decyloxy) propyl, 3- (n-dodecyloxy) propyl, 3- (n-tetradecanyloxy) propyl, 3-cyclohexyloxypropyl, 4-methyl Oxybutyl, 4- Methoxybutyl, 4-n - propoxybutyl, 4-isopropyl-methoxybutyl, 4-n - butoxybutyl, 4-n - hexyl-methoxybutyl, 4- N-octyloxybutyl, 4-n-decyloxybutyl, 4-n-dodecyloxybutyl, 5-methoxypentyl, 5-ethoxypentyl, 5-n- Propoxypentyl, 6-ethoxyhexyl, 6-isopropoxyhexyl, 6-n-butoxyhexyl, 6-n-hexyloxyhexyl, 6-n-decylhexyl, 4- Methoxycyclohexyl, 7-ethoxyheptyl, 7-isopropoxyheptyl, 8-methoxyoctyl, 10-methoxydecyl, 10-n-butoxydecyl, 12 -Alkyl groups having an alkoxy group such as ethoxydodecyl, 12-isopropoxydodecyl, tetrahydrofurfuryl; (2-methoxyethoxy) methyl, (2 -Ethoxyethoxy) methyl, (2-n-butoxyethoxy) methyl, (2-n-hexyloxyethoxy) methyl, (3-methoxypropoxy ) Methyl, (3-ethoxypropoxy) methyl, (3-n-butoxypropoxy) methyl, (3-n-pentoxypropoxy) methyl, (4- (Methoxybutoxy) methyl, (6-methoxyhexyloxy) methyl, (10-ethoxydecoxy) methyl, 2- (2'-methoxyethoxy) ethyl Group, 2- (2'-ethoxyethoxy) ethyl, 2- (2'-n-butoxyethoxy) ethyl, 3- (2'-ethoxyethoxy) propane Base, 3- (2'-methoxypropoxy) propyl, 3- (2'-isopropoxypropoxy) propyl, 3- (3'-methoxypropoxy) propyl, 3- ( An alkyl group having an alkoxyalkoxy group such as 3'-ethoxypropoxy) propyl; for example, benzyloxymethyl, 2-benzyloxyethyl, 2-phenethoxyethyl , 2- (4'-methylbenzyloxy) ethyl, 2- (2'-methylbenzyloxy) ethyl, 2- (4'-fluorobenzyloxy) ethyl, 2- (4 ' -Chlorobenzyloxy) ethyl, 3-benzyloxypropyl, 3- (4'-methoxybenzyloxy) propyl, 4-benzyloxybutyl, 2- (benzyloxymethoxy) ) Alkyl groups having an aralkyloxy group such as ethyl, 2- (4'-methylbenzyloxymethoxy) ethyl; phenoxymethyl, 4-methylphenoxymethyl, 3 -Methylphenoxymethyl, 2-methylphenoxymethyl, 4-methoxyphenoxymethyl, 4-fluorophenoxymethyl, 4-chlorophenoxymethyl, 2-chlorophenoxymethyl, 2-phenoxyethyl, 2- (4'-methylphenoxy) ethyl, 2- (4'-ethylbenzene Oxy) ethyl, 2- (4'-methoxyphenoxy) ethyl, 2- (4'-chlorophenoxy) ethyl, 2- (4'-bromophenoxy) ethyl, 2- (1'-naphthyloxy) ethyl, 2- (2'-naphthyloxy) ethyl, 3-phenoxypropyl, 3- (2'-naphthyloxy) propyl, 4-benzene Oxybutyl, 4- (2'-ethylphenoxy) butyl, 5- (4'-tert-butylphenoxy) pentyl, 6- (2'-chlorophenoxy) hexyl, 8-phenoxyoctyl, 10-phenoxydecyl, 10- (3'-chlorophenoxy) decyl, 2- (2'-phenoxyethoxy) ethyl, 3- (2 Alkyl groups such as' -phenoxyethoxy) propyl and 4- (2'-phenoxyethoxy) butyl; n-butylthiomethyl, n-hexylthio Methyl, 2-methylthioethyl, 2-ethylthioethyl, 2-n-butylthioethyl, 2-n-hexylthioethyl, 2-n-octylthioethyl, 2-n-decylthioethyl, 3-methylthiopropyl, 3-ethylthiopropyl, 3-n-butylthiopropyl, 4-ethylthiobutyl, 4-n-propylthio Butyl, 4-n-butylthiobutyl, 5-ethylthiopentyl, 6-methyl Hexyl, 6-ethylthiohexyl, 6-n-butylthiohexyl, 8-methylthiooctyl, and other alkylthio groups; fluoromethyl, 3-fluoropropyl, 6-fluoro Hexyl, 8-fluorooctyl, trifluoromethyl, 1,1-dihydro-perfluoroethyl, 1,1-dihydro-perfluoro-n-propyl, 1,1,3-trihydro-per Fluoro-n-propyl, 2-hydro-perfluoro-2-propyl, 1,1-dihydro-perfluoro-n-butyl, 1,1-dihydro-perfluoro-n-pentyl, 1 1,1-dihydro-perfluoro-n-hexyl, 6-fluorohexyl, 4-fluorocyclohexyl, 1,1-dihydro-perfluoro-n-octyl, 1,1-dihydro-perfluoro-n -Decyl, 1,1-dihydro-perfluoro-n-dodecyl, 1,1-dihydro-perfluoro-n-tetradecyl, 1,1-dihydro-perfluoro-n- Cetyl, perfluoroethyl, perfluoro-n-propyl, perfluoro-n-pentyl, perfluoro-n-hexyl, 2,2-bis (trifluoromethyl) propyl, dichloromethyl Methyl, 2-chloroethyl, 3-chloropropyl, 4-chlorocyclohexyl, 7-chloroheptyl, 8-chloro Alkyl groups having a halogen atom such as octyl, 2,2,2-trichloroethyl; fluoromethoxymethyl, 3-fluoro-n-propoxymethyl, 6-fluoro-n-hexyloxy Methyl, trifluoromethoxymethyl, 1,1-dihydro-perfluoroethoxymethyl, 1,1-dihydro-perfluoro-n-propoxymethyl, 2-hydro-perfluoro 2-propoxymethyl, 1,1-dihydro-perfluoro-n-butoxymethyl, 1,1-dihydro-perfluoro-n-pentyloxymethyl, 1,1-di Hydrogen-perfluoro-n-hexyloxymethyl, 1,1-dihydro-perfluoro-n-octyloxymethyl, 1,1-dihydro-perfluoro-n-decyloxymethyl, 1 1,1-dihydro-perfluoro-n-tetradecanyloxymethyl, 2,2-bis (trifluoromethyl) propoxymethyl, 3-chloro-n-propoxymethyl, 2- (8-fluoro-n-octyloxy) ethyl, 2- (1,1-dihydro-perfluoroethoxy) ethyl, 2- (1,1,3-trihydro-perfluoro-n- Propoxy) ethyl, 2- (1,1-dihydro-perfluoro-n-pentyloxy) ethyl, 2- (6-fluoro-n-hexyloxy) ethyl, 2- (1, 1-dihydro-perfluoro-n-octyloxy) ethyl, 3- (4-fluorocyclohexyloxy) propyl, 3- (1,1-dihydro-perfluoroethoxy) propyl, 3- (1,1-dihydro-perfluoro-n-dodecyloxy) propyl, 4- (perfluoro-n-hexyloxy) butyl, 4- (1,1-dihydro-perfluoro Fluoroethoxy ) Alkyl groups having a halogenated alkoxy group such as butyl, 6- (2-chloroethoxy) hexyl, 6- (1,1-dihydro-perfluoroethoxy) hexyl; phenoxymethyl, 4-methylphenoxymethyl, 3-methylphenoxymethyl, 2-methylphenoxymethyl, 4-ethylphenoxymethyl, 4-n-propylphenoxymethyl Methyl, 4-n-butylphenoxymethyl, 4-tert-butylphenoxymethyl, 4-n-hexylphenoxymethyl, 4-n-octylphenoxymethyl, 4 -N-decylphenoxymethyl, 4-methoxyphenoxymethyl, 4-ethoxyphenoxymethyl, 4-butoxyphenoxymethyl, 4-n-pentyloxy Methylphenoxymethyl, 4-fluorophenoxymethyl, 3-fluorophenoxymethyl, 2-fluorophenoxymethyl, 3,4-difluorophenoxymethyl, 4-chlorobenzene Oxymethyl, 2-chlorophenoxymethyl, 4-phenylphenoxymethyl, 1- Naphthyloxymethyl, 2-naphthyloxymethyl, 2-furanyloxymethyl, 1-phenoxyethyl, 2-phenoxyethyl, 2- (4'-methylphenoxy) Ethyl, 2- (4'-ethylphenoxy) ethyl, 2- (4'-n-hexylphenoxy) ethyl, 2- (4'-methoxyphenoxy) ethyl, 2- (4'-n-butoxyphenoxy) ethyl, 2- (4'-fluorophenoxy) ethyl, 2- (4'-chlorophenoxy) ethyl, 2- (4 '-Bromophenoxy) ethyl, 2- (1'-naphthyloxy) ethyl, 2- (2'-naphthyloxy) ethyl, 2-phenoxypropyl, 3-phenoxypropyl Group, 3- (4'-methylphenoxy) propyl, 3- (2'-naphthyloxy) propyl, 4-phenoxybutyl, 4- (2'-ethylphenoxy) Butyl, 4-phenoxypentyl, 5-phenoxypentyl, 5- (4'-tert-butylphenoxy) pentyl, 6-phenoxyhexyl, 6- (2'-chloro Alkyl groups having an aryloxy group such as phenoxy) hexyl, 8-phenoxyoctyl, 10-phenoxydecyl, 10- (3'-methylphenoxy) decyl.

作為未取代的烷氧基，可列舉由上述烷基的具體例衍生的烷氧基。作為取代烷氧基中的取代基，可列舉與上述烷基中的取代基同樣的取代基。 As an unsubstituted alkoxy group, the alkoxy group derived from the specific example of the said alkyl group is mentioned. Examples of the substituent in the substituted alkoxy group include the same substituents as those described above for the alkyl group.

作為未取代的芳基，可列舉苯基、1-萘基、2-萘基、2-蒽基、1-菲基、2-菲基、3-菲基、1-芘基、2-芘基、2-苝基、3-苝基、2-熒蒽基、3-熒蒽基、7-熒蒽基、8-熒蒽基。 Examples of the unsubstituted aryl group include phenyl, 1-naphthyl, 2-naphthyl, 2-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 1-fluorenyl, 2-fluorene Base, 2-fluorenyl, 3-fluorenyl, 2-fluoranthenyl, 3-fluoranthenyl, 7-fluoranthenyl, 8-fluoranthenyl.

取代芳基中，作為取代基，可列舉碳數1~10的烷基、烷氧基、芳氧基、芳基、鹵素原子等。 Examples of the substituted aryl group include an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an aryloxy group, an aryl group, and a halogen atom.

作為取代基芳基的具體例，可列舉1-甲基-2-芘基、2-甲基苯基、4-乙基苯基、4-叔-丁基苯基、4-(4’-叔-丁基環己基)苯基、3-環己基苯基、2-環己基苯基、4-乙基-1-萘基、6-正-丁基-2-萘基、2,4-二甲基苯基等的具有烷基的芳基； 4-甲氧基苯基、3-乙氧基苯基、2-乙氧基苯基、4-正-丙氧基苯基、3-正-丙氧基苯基、4-異丙氧基苯基、3-異丙氧基苯基、2-異丙氧基苯基、2-仲-丁氧基苯基、4-正-戊氧基苯基、4-異戊氧基苯基、2-甲基-5-甲氧基苯基、2-苯氧基苯基等的具有烷氧基及芳氧基的芳基；4-苯基苯基、3-苯基苯基、2-苯基苯基、2,6-二苯基苯基、4-(2’-萘基)苯基、2-苯基-1-萘基、1-苯基-2-萘基、7-苯基-1-芘基等的具有芳基的芳基；4-氟苯基、3-氟苯基、2-氟苯基、4-氯苯基、4-溴苯基、2-氯-5-甲基苯基、2-氯-6-甲基苯基、2-甲基-3-氯苯基、2-甲氧基-4-氟苯基、2-氟-4-甲氧基苯基等的具有鹵素原子的芳基；進而，可列舉2-三氟甲基苯基、3-三氟甲基苯基、4-三氟甲基苯基、3,5-雙(三氟甲基)苯基、4-全氟乙基苯基、4-甲硫基苯基、4-乙硫基苯基、4-氰基苯基、3-氰基苯基等。 Specific examples of the substituent aryl include 1-methyl-2-fluorenyl, 2-methylphenyl, 4-ethylphenyl, 4-tert-butylphenyl, and 4- (4'- Tert-butylcyclohexyl) phenyl, 3-cyclohexylphenyl, 2-cyclohexylphenyl, 4-ethyl-1-naphthyl, 6-n-butyl-2-naphthyl, 2,4- Aryl groups with alkyl groups such as dimethylphenyl; 4-methoxyphenyl, 3-ethoxyphenyl, 2-ethoxyphenyl, 4-n-propoxyphenyl, 3-n-propoxyphenyl, 4-isopropoxy Phenyl, 3-isopropoxyphenyl, 2-isopropoxyphenyl, 2-sec-butoxyphenyl, 4-n-pentyloxyphenyl, 4-isopentoxyphenyl, Aryl groups with alkoxy and aryloxy groups such as 2-methyl-5-methoxyphenyl, 2-phenoxyphenyl; 4-phenylphenyl, 3-phenylphenyl, 2- Phenylphenyl, 2,6-diphenylphenyl, 4- (2'-naphthyl) phenyl, 2-phenyl-1-naphthyl, 1-phenyl-2-naphthyl, 7-benzene Aryl groups having an aryl group such as methyl-1-fluorenyl; 4-fluorophenyl, 3-fluorophenyl, 2-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 2-chloro-5 -Methylphenyl, 2-chloro-6-methylphenyl, 2-methyl-3-chlorophenyl, 2-methoxy-4-fluorophenyl, 2-fluoro-4-methoxybenzene Aryl groups having a halogen atom, such as a radical; and further, 2-trifluoromethylphenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl, 3,5-bis (trifluoromethyl) Phenyl), 4-perfluoroethylphenyl, 4-methylthiophenyl, 4-ethylthiophenyl, 4-cyanophenyl, 3-cyanophenyl, and the like.

作為未取代的芳氧基，可列舉由上述芳基的具體例衍生的芳氧基。作為取代芳氧基中的取代基，可列舉與上述芳基中的取代基同樣的取代基。 As an unsubstituted aryloxy group, the aryloxy group derived from the specific example of the said aryl group is mentioned. Examples of the substituent in the substituted aryloxy group include the same substituents as those described above for the aryl group.

作為取代或未取代的芳烷基氧基，可列舉苄氧基、α-甲基苄氧基、苯乙氧基、α-甲基苯乙氧基、α,α-二甲基苄氧基、α,α-二甲基苯乙氧基、4-甲基苯乙氧基、4-甲基苄氧基、4-異丙基苄氧基等的、未取代或具有烷基的芳烷氧基；4-苄基苄氧基、4-苯乙基苄氧基、4-苯基苄氧基等的具有芳基或芳烷基的芳烷氧基；4-甲氧基苄氧基、4-正-十四 烷氧基苄氧基、4-正-十五烷氧基苄氧基、3,4-二甲氧基苄氧基、4-甲氧基甲基苄氧基、4-乙烯氧基甲基苄氧基、4-苄氧基苄氧基、4-苯乙氧基苄氧基等的具有取代氧基的芳烷氧基；4-羥基苄氧基、4-羥基-3-甲氧基苄氧基等具有羥基的芳烷氧基；4-氟苄氧基、3-氯苄氧基、3,4-二氯苄氧基等具有鹵素原子的芳烷氧基；2-糠氧基、二苯基甲氧基、1-萘基甲氧基、2-萘基甲氧基等。 Examples of the substituted or unsubstituted aralkyloxy group include benzyloxy, α-methylbenzyloxy, phenethyloxy, α-methylphenethyloxy, and α, α-dimethylbenzyloxy. Unsubstituted or alkyl-containing arane such as α, α-dimethylphenethoxy, 4-methylphenethoxy, 4-methylbenzyloxy, 4-isopropylbenzyloxy, etc. Aryloxy; 4-benzylbenzyloxy, 4-phenethylbenzyloxy, 4-phenylbenzyloxy and other aralkyloxy groups having an aryl or aralkyl group; 4-methoxybenzyloxy 4-positive-fourteen Alkoxybenzyloxy, 4-n-pentadecyloxybenzyloxy, 3,4-dimethoxybenzyloxy, 4-methoxymethylbenzyloxy, 4-vinyloxymethyl Aryloxy groups with substituted oxy groups such as benzyloxy, 4-benzyloxybenzyloxy, 4-phenethoxybenzyloxy; 4-hydroxybenzyloxy, 4-hydroxy-3-methoxy Aryloxy groups having a hydroxyl group, such as benzyloxy; Aryloxy groups having a halogen atom, such as 4-fluorobenzyloxy, 3-chlorobenzyloxy, 3,4-dichlorobenzyloxy; 2-furfuryloxy , Diphenylmethoxy, 1-naphthylmethoxy, 2-naphthylmethoxy, and the like.

作為具有取代基的氨基的具體例，可列舉N-甲基氨基、N-乙基氨基、N-正-丁基氨基、N-環己基氨基、N-正-辛基氨基、N-正-癸基氨基等具有烷基的氨基；N-苄基氨基、N-苯基氨基、N-(3-甲基苯基)氨基、N-(4-甲基苯基)氨基、N-(4-正-丁基苯基)氨基、N-(4-甲氧基苯基)氨基、N-(3-氟苯基)氨基、N-(4-氯苯基)氨基、N-(1-萘基)氨基、N-(2-萘基)氨基等具有芳烷基或芳基的氨基；N,N-二甲基氨基、N,N-二乙基氨基、N,N-二-正-丁基氨基、N,N-二-正-己基氨基、N,N-二-正-辛基氨基、N,N-二-正-癸基氨基、N,N-二-正-十二烷基氨基、N-甲基-N-乙基氨基、N-乙基-N-正-丁基氨基、N-甲基-N-苯基氨基、N-乙基-N-苯基氨基、N-正-丁基-N-苯基氨基等具有2個烷基或芳烷基作為取代基的氨基；N,N-二苯基氨基、N,N-二(3-甲基苯基)氨基、N,N-二(4-甲基苯基)氨基、N,N-二(4-乙基苯基)氨基、N,N-二(4-叔- 丁基苯基)氨基、N,N-二(4-正-己基苯基)氨基、N,N-二(4-甲氧基苯基)氨基、N,N-二(4-乙氧基苯基)氨基、N,N-二(4-正-丁氧基苯基)氨基、N,N-二(4-正-己氧基苯基)氨基、N,N-二(1-萘基)氨基、N,N-二(2-萘基)氨基、N-苯基-N-(3-甲基苯基)氨基、N-苯基-N-(4-甲基苯基)氨基、N-苯基-N-(4-辛基苯基)氨基、N-苯基-N-(4-甲氧基苯基)氨基、N-苯基-N-(4-乙氧基苯基)氨基、N-苯基-N-(4-正-己氧基苯基)氨基、N-苯基-N-(4-氟苯基)氨基、N-苯基-N-(1-萘基)氨基、N-苯基-N-(2-萘基)氨基、N-苯基-N-(3-苯基苯基)氨基、N-苯基-N-(4-苯基苯基)氨基等具有2個芳基作為取代基的氨基等。 Specific examples of the amino group having a substituent include N-methylamino, N-ethylamino, N-n-butylamino, N-cyclohexylamino, N-n-octylamino, and N-n- An amino group having an alkyl group such as decylamino; N-benzylamino, N-phenylamino, N- (3-methylphenyl) amino, N- (4-methylphenyl) amino, N- (4 -N-butylphenyl) amino, N- (4-methoxyphenyl) amino, N- (3-fluorophenyl) amino, N- (4-chlorophenyl) amino, N- (1- (Napthyl) amino, N- (2-naphthyl) amino and other amino groups having aralkyl or aryl groups; N, N-dimethylamino, N, N-diethylamino, N, N-di-n- -Butylamino, N, N-di-n-hexylamino, N, N-di-n-octylamino, N, N-di-n-decylamino, N, N-di-n-dodecyl Alkylamino, N-methyl-N-ethylamino, N-ethyl-N-n-butylamino, N-methyl-N-phenylamino, N-ethyl-N-phenylamino, Amino groups such as N-n-butyl-N-phenylamino with 2 alkyl or aralkyl groups as substituents; N, N-diphenylamino, N, N-bis (3-methylphenyl) Amino, N, N-bis (4-methylphenyl) amino, N, N-bis (4-ethylphenyl) amino, N, N-bis (4-tert- Butylphenyl) amino, N, N-bis (4-n-hexylphenyl) amino, N, N-bis (4-methoxyphenyl) amino, N, N-bis (4-ethoxy Phenyl) amino, N, N-bis (4-n-butoxyphenyl) amino, N, N-bis (4-n-hexyloxyphenyl) amino, N, N-bis (1-naphthalene ) Amino, N, N-bis (2-naphthyl) amino, N-phenyl-N- (3-methylphenyl) amino, N-phenyl-N- (4-methylphenyl) amino N-phenyl-N- (4-octylphenyl) amino, N-phenyl-N- (4-methoxyphenyl) amino, N-phenyl-N- (4-ethoxybenzene ) Amino, N-phenyl-N- (4-n-hexyloxyphenyl) amino, N-phenyl-N- (4-fluorophenyl) amino, N-phenyl-N- (1- Naphthyl) amino, N-phenyl-N- (2-naphthyl) amino, N-phenyl-N- (3-phenylphenyl) amino, N-phenyl-N- (4-phenylbenzene An amino group, etc. having two aryl groups as a substituent.

式(1e)中，M表示2個氫原子、2個1價的金屬原子、2價的金屬原子、3價的取代金屬原子、或氧化金屬原子，更優選為2個氫原子、2價的金屬原子、或氧化金屬原子，進一步優選為2價的金屬原子、或氧化金屬原子。 In the formula (1e), M represents two hydrogen atoms, two monovalent metal atoms, divalent metal atoms, trivalent substituted metal atoms, or oxidized metal atoms, and more preferably two hydrogen atoms and a divalent The metal atom or the oxidized metal atom is more preferably a divalent metal atom or an oxidized metal atom.

作為由M表示的1價的金屬原子，可列舉Na、K、Li等。 Examples of the monovalent metal atom represented by M include Na, K, and Li.

作為由M表示的2價的金屬原子，可列舉Cu、Zn、Fe、Co、Ni、Ru、Rh、Pd、Pt、Mn、Mg、Ti、Be、Ca、Ba、Cd、Hg、Pb、Sn等。 Examples of the divalent metal atom represented by M include Cu, Zn, Fe, Co, Ni, Ru, Rh, Pd, Pt, Mn, Mg, Ti, Be, Ca, Ba, Cd, Hg, Pb, Sn Wait.

作為由M表示的3價的取代金屬原子，可列舉Al-Cl、Ga-Br、Ga-I、In-Cl、Al-C6H5、In-C6H5、Mn(OH)、Mn[OSi(CH3)3]、Fe-Cl等。 Examples of the trivalent substituted metal atom represented by M include Al-Cl, Ga-Br, Ga-I, In-Cl, Al-C 6 H 5 , In-C 6 H 5 , Mn (OH), and Mn. [OSi (CH 3 ) 3 ], Fe-Cl and the like.

作為由M表示的氧化金屬原子，可以列舉VO、MnO、TiO等。 Examples of the oxidized metal atom represented by M include VO, MnO, and TiO.

式(1e)中，M更優選為Cu、Zn、Fe、Co、Ni、Pd、Mn、Mg、VO及TiO，進一步優選為Cu、Ni、Pd及VO，特別優選為Cu、Pd及VO。 In formula (1e), M is more preferably Cu, Zn, Fe, Co, Ni, Pd, Mn, Mg, VO, and TiO, still more preferably Cu, Ni, Pd, and VO, and particularly preferably Cu, Pd, and VO.

作為化合物(1e)的具體例，可列舉由式(2-1)~式(2-38)表示的化合物。 Specific examples of the compound (1e) include compounds represented by the formulae (2-1) to (2-38).

Figure TWI679499B_D0068
Figure TWI679499B_D0068

Figure TWI679499B_D0069
Figure TWI679499B_D0069

Figure TWI679499B_D0070
Figure TWI679499B_D0070

Figure TWI679499B_D0071
Figure TWI679499B_D0071

Figure TWI679499B_D0072
Figure TWI679499B_D0072

作為四氮雜卟啉染料(Ae)，優選由式(2-29)表示的化合物。 As the tetraazaporphyrin dye (Ae), a compound represented by the formula (2-29) is preferable.

包含四氮雜卟啉染料(Ae)的情況下，其含量在染料(A1)100質量份中優選為1質量份以上、99質量份以下。 When the tetraazaporphyrin dye (Ae) is contained, the content thereof is preferably 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the dye (A1).

染料中，染料(A1)的含量相對於染料的總量，優選為70質量%以上、100質量%以下，更優選為80質量%以上、100質量%以下，進一步優選為85質量%以上、100質量%以下。 The content of the dye (A1) in the dye is preferably 70% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, and still more preferably 85% by mass or more and 100% by mass. Mass% or less.

另外，著色劑(A)中，染料的含量相對於著色劑100質量份，為90質量份以上，優選為93質量份以上，更優選為95質量份以上，進一步優選為99質量份以上，特別優選為100質量份，即不含顏料。 In addition, the content of the dye in the colorant (A) is 90 parts by mass or more, preferably 93 parts by mass or more, more preferably 95 parts by mass or more, and still more preferably 99 parts by mass or more, based on 100 parts by mass of the colorant. It is preferably 100 parts by mass, that is, contains no pigment.

著色劑(A)可還含有顏料(A2)。作為顏料(A2)，能夠無特別限定地使用公知的顏料，例如，可列舉色指數(The Society of Dyers and Colourists出版)中分類為顏料的顏料，可以將這些單獨使用，或者將2種以上組合使用。 The colorant (A) may further contain a pigment (A2). As a pigment (A2), a well-known pigment can be used without a restriction | limiting, For example, the pigment classified as a pigment by the color index (published by The Society of Dyers and Colourists) is mentioned, These can be used individually or in combination of 2 or more types use.

著色劑(A)的含量相對於固體成分的總量，優選為1質量%以上、60質量%以下，更優選為3質量%以上、55質量%以下，進一步優選為5質量%以上、50質量%以下。如果著色劑(A)的含量在上述的範圍內，則製成濾色器時的色濃度充分，並且能夠使組合物中含有必要量的樹脂、聚合性化合物，因此能夠形成機械強度充分的著色圖案。在此，本說明書中的“固體成分的總量”是指從著色固化性樹脂組合物的總量中去除溶劑的含量的量。固體成分的總量及相對於其的各成分的含量例如可以採用液相色譜或氣相色譜等公知的分析手段測定。 The content of the colorant (A) is preferably 1% by mass or more and 60% by mass or less with respect to the total amount of the solid content, more preferably 3% by mass or more and 55% by mass or less, and still more preferably 5% by mass or more and 50% by mass. %the following. When the content of the colorant (A) is within the above-mentioned range, the color density at the time of forming a color filter is sufficient, and the resin and a polymerizable compound can be contained in the composition in a necessary amount, so that a color with sufficient mechanical strength can be formed pattern. Here, the "total amount of solid content" in the present specification means an amount in which the content of the solvent is removed from the total amount of the colored curable resin composition. The total amount of the solid component and the content of each component relative to the solid component can be measured by a known analysis means such as liquid chromatography or gas chromatography.

<樹脂(B)> <Resin (B)>

對樹脂(B)並無特別限定，優選為鹼可溶性樹脂，優選為具有來自從不飽和羧酸及不飽和羧酸酐中選擇的至少1種的結構單元的聚合物。上述單體(a)優選與具有碳數2~4的環狀醚結構和烯屬不飽和鍵的單體(b)、以及可與單體(a)共聚的單體(c)的至少一者共聚而用於樹脂(B)。 The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and is preferably a polymer having a structural unit derived from at least one kind selected from an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. The monomer (a) is preferably at least one of a monomer (b) having a cyclic ether structure with 2 to 4 carbon atoms and an ethylenically unsaturated bond, and a monomer (c) copolymerizable with the monomer (a). The copolymer is used for the resin (B).

對反應順序並無限定，可以將單體(a)、以及單體(b)和(c)的至少一者一次性地共聚。另外，將單體(a)~(c)全部使用的情況下，可在將單體(a)和單體(b)共聚後使單體(c)反應，也可在使單體(a)與單體(c)共聚後使單體(b)反應。另外，還 可以使單體(a)與單體(b)、單體(c)的共聚物反應，進而使羧酸酐反應。 The reaction sequence is not limited, and at least one of the monomers (a) and (b) and (c) may be copolymerized at one time. When all of the monomers (a) to (c) are used, the monomer (c) may be reacted after the monomer (a) and the monomer (b) are copolymerized, or the monomer (a) may be reacted. ) And copolymerize the monomer (c) to react the monomer (b). Also, also The monomer (a) and the copolymer of the monomer (b) and the monomer (c) can be reacted to further react the carboxylic anhydride.

作為(a)，可列舉例如丙烯酸、甲基丙烯酸、巴豆酸、鄰-、間-、對-乙烯基苯甲酸等不飽和單羧酸；馬來酸、富馬酸、檸康酸、中康酸、衣康酸、3-乙烯基鄰苯二甲酸、4-乙烯基鄰苯二甲酸、3,4,5,6-四氫鄰苯二甲酸、1,2,3,6-四氫鄰苯二甲酸、二甲基四氫鄰苯二甲酸、1,4-環己烯二羧酸等不飽和二羧酸；甲基-5-降冰片烯-2,3-二羧酸、5-羧基雙環[2.2.1]庚-2-烯、5,6-二羧基雙環[2.2.1]庚-2-烯、5-羧基甲基雙環[2.2.1]庚-2-烯、5-羧基乙基雙環[2.2.1]庚-2-烯等含有羧基的雙環不飽和化合物；不包括富馬酸及中康酸的上述不飽和二羧酸的酸酐等的羧酸酐；等。 Examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid; maleic acid, fumaric acid, citraconic acid, and Zhongkang Acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid Unsaturated dicarboxylic acids such as phthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid, 5- Carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxymethylbicyclo [2.2.1] hept-2-ene, 5- Carboxyethyl bicyclic [2.2.1] hept-2-ene and other bicyclic unsaturated compounds containing a carboxyl group; carboxylic anhydrides such as the anhydrides of the aforementioned unsaturated dicarboxylic acids excluding fumaric acid and mesaconic acid; and the like.

可列舉琥珀酸單[2-(甲基)丙烯醯氧基乙基]酯、鄰苯二甲酸單[2-(甲基)丙烯醯氧基乙基]酯等2元以上的多元羧酸的不飽和單[(甲基)丙烯醯氧基烷基]酯類；α-(羥基甲基)丙烯酸這樣的在同一分子中含有羥基和羧基的不飽和丙烯酸酯類等。 Examples of the polyvalent or higher polycarboxylic acids such as mono [2- (meth) acryloxyethyl] succinate and mono [2- (meth) acryloxyethyl] phthalate Unsaturated mono [(meth) acryloxyalkyl] esters; unsaturated acrylates such as α- (hydroxymethyl) acrylic acid, which contain a hydroxyl group and a carboxyl group in the same molecule, and the like.

這些中，從共聚反應性的方面、得到的樹脂在鹼水溶液中的溶解性的方面出發，優選丙烯酸、甲基丙烯酸、馬來酸酐等。 Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferred from the viewpoint of copolymerization reactivity and the solubility of the obtained resin in an alkaline aqueous solution.

(b)是指具有碳數2~4的環狀醚結構(例如，選自環氧乙烷環、氧雜環丁烷環和四氫呋喃環中的至少1種)和烯 屬不飽和鍵的聚合性化合物。(b)優選具有碳數2~4的環狀醚和(甲基)丙烯醯氧基的單體。 (b) refers to 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) and an olefin A polymerizable compound that is an unsaturated bond. (b) A monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acrylic fluorenyloxy group is preferred.

作為(b)，可列舉例如具有環氧乙基和烯屬不飽和鍵的單體(b1)(以下有時稱為“(b1)”)、具有氧雜環丁基和烯屬不飽和鍵的單體(b2)(以下有時稱為“(b2)”)、具有四氫呋喃基和烯屬不飽和鍵的單體(b3)(以下有時稱為“(b3)”)等。 Examples of (b) include, for example, a monomer (b1) having an epoxyethyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), an oxetanyl group, and an ethylenically unsaturated bond. Monomer (b2) (hereinafter sometimes referred to as "(b2)"), monomer (b3) (hereinafter sometimes referred to as "(b3)") having a tetrahydrofuryl group and an ethylenically unsaturated bond, and the like.

作為(b1)，可列舉例如具有直鏈狀或分支鏈狀的脂肪族不飽和烴被環氧化的結構的單體(b1-1)(以下有時稱為“(b1-1)”)、具有脂環式不飽和烴被環氧化的結構的單體(b1-2)(以下有時稱為“(b1-2)”)。 Examples of (b1) include, for example, a monomer (b1-1) (hereinafter sometimes referred to as "(b1-1)") having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized, A monomer (b1-2) (hereinafter referred to as "(b1-2)") having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized.

作為(b1-1)，優選具有縮水甘油基和烯屬不飽和鍵的單體。作為(b1-1)，具體地，可列舉(甲基)丙烯酸縮水甘油酯、β-甲基縮水甘油基(甲基)丙烯酸酯、β-乙基縮水甘油基(甲基)丙烯酸酯、縮水甘油基乙烯基醚、乙烯基苄基縮水甘油基醚、α-甲基乙烯基苄基縮水甘油基醚、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。 As (b1-1), a monomer having a glycidyl group and an ethylenically unsaturated bond is preferable. Specific examples of (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, and glycidyl Glyceryl vinyl ether, vinyl benzyl glycidyl ether, α-methyl vinyl benzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis ( Glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris ( Glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4, 5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) styrene, and the like.

作為(b1-2)，可列舉乙烯基環己烯一氧化物、1,2-環氧-4-乙烯基環己烷(例如，

Figure TWI679499B_D0073
(註冊商標)2000；(株)
Figure TWI679499B_D0074
製造)、(甲基)丙烯酸3,4-環氧環己基甲酯(例如，
Figure TWI679499B_D0075
(註冊商標)A400；(株)
Figure TWI679499B_D0076
製造)、(甲基)丙烯酸3,4-環氧環己基甲酯(例如，
Figure TWI679499B_D0077
(註冊商標)M100；(株)
Figure TWI679499B_D0078
製造)、由式(BI)表示的化合物和由式(BII)表示的化合物等。 Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example,
Figure TWI679499B_D0073
(Registered trademark) 2000; Co., Ltd.
Figure TWI679499B_D0074
Manufactured), 3,4-epoxycyclohexyl methyl (meth) acrylate (e.g.,
Figure TWI679499B_D0075
(Registered trademark) A400;
Figure TWI679499B_D0076
Manufactured), 3,4-epoxycyclohexyl methyl (meth) acrylate (e.g.,
Figure TWI679499B_D0077
(Registered trademark) M100;
Figure TWI679499B_D0078
(Manufactured), a compound represented by the formula (BI), a compound represented by the formula (BII), and the like.

Figure TWI679499B_D0079
Figure TWI679499B_D0079

[式(BI)及式(BII)中，Rb1和Rb2各自獨立地表示氫原子、或者碳數1~4的烷基，該烷基中所含的氫原子可被羥基取代。 [In formulae (BI) and (BII), R b1 and R b2 each independently 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.

Xb1和Xb2表示單鍵、＊-Rb3-、＊-Rb3-O-、＊-Rb3-S-或＊-Rb3-NH-。 X b1 and X b2 represents a single bond, * - R b3 -, * - R b3 -O -, * - R b3 -S- or * -R b3 -NH-.

Rb3表示碳數1~6的亞烷基。 R b3 represents an alkylene group having 1 to 6 carbon atoms.

＊表示與O的鍵合端。] * Indicates a bonding end with O. ]

作為Rb1、Rb2的碳數1~4的烷基，可列舉甲基、乙基等。 Examples of the alkyl group having 1 to 4 carbon atoms of R b1 and R b2 include a methyl group and an ethyl group.

作為Rb1、Rb2的氫原子被羥基取代的烷基，可列舉羥基甲基、羥基乙基等。 Examples of the alkyl group in which a hydrogen atom of R b1 and R b2 is substituted with a hydroxyl group include a hydroxymethyl group and a hydroxyethyl group.

作為Rb1和Rb2，優選氫原子、碳數1~4的烷基、或碳數1~4的羥基烷基，更優選為氫原子、或碳數1~4的烷基，進一步優選地，可列舉氫原子、甲基。 R b1 and R b2 are preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and still more preferably Examples include a hydrogen atom and a methyl group.

作為Rb3的亞烷基，可列舉直鏈狀或分支鏈狀的亞烷基，具體地，可列舉亞甲基、亞乙基。 Examples of the R b3 alkylene group include a linear or branched alkylene group, and specific examples include a methylene group and an ethylene group.

作為Xb1及Xb2，優選單鍵、＊-Rb3-、或＊-Rb3-O-，更優選為單鍵、或＊-Rb3-O-，進一步優選地，可列舉單鍵、＊-CH2-O-及＊-CH2CH2-O-，特別優選地，可列舉單鍵、*-CH2CH2-O-(＊表示與O的鍵合端)。 As X b1 and X b2, preferably a single bond, * - R b3 -, or * -R b3 -O-, more preferably a single bond, or * -R b3 -O-, more preferably, examples include a single bond, * -CH 2 -O- and * -CH 2 CH 2 -O-, particularly preferably , a single bond , * -CH 2 CH 2 -O- (* represents a bonding end with O).

作為由式(BI)表示的化合物，可列舉由式(BI-1)~式(BI-15)的任一個表示的化合物等。其中，優選由式(BI-1)、式(BI-3)、式(BI-5)、式(BI-7)、式(BI-9)或式(BI-11)~式(BI-15)表示的化合物，更優選由式(BI-1)、式(BI-7)、式(BI-9)或式(BI-15)表示的化合物。 Examples of the compound represented by the formula (BI) include compounds represented by any one of the formulae (BI-1) to (BI-15). Among them, it is preferable to use formula (BI-1), formula (BI-3), formula (BI-5), formula (BI-7), formula (BI-9), or formula (BI-11) to formula (BI- The compound represented by 15) is more preferably a compound represented by formula (BI-1), formula (BI-7), formula (BI-9) or formula (BI-15).

Figure TWI679499B_D0080
Figure TWI679499B_D0080

Figure TWI679499B_D0081
Figure TWI679499B_D0081

作為由式(BII)表示的化合物，可列舉由式 (BII-1)~式(BII-15)的任一個表示的化合物等。其中，優選由式(BII-1)、式(BII-3)、式(BII-5)、式(BII-7)、式(BII-9)或式(BII-11)~式(BII-15)表示的化合物，更優選由式(BII-1)、式(BII-7)、式(BII-9)或式(BII-15)表示的化合物。 Examples of the compound represented by the formula (BII) include (BII-1) to a compound represented by any one of formulas (BII-15) and the like. Among them, it is preferable to use formula (BII-1), formula (BII-3), formula (BII-5), formula (BII-7), formula (BII-9), or formula (BII-11) to formula (BII- The compound represented by 15) is more preferably a compound represented by formula (BII-1), formula (BII-7), formula (BII-9) or formula (BII-15).

Figure TWI679499B_D0082
Figure TWI679499B_D0082

Figure TWI679499B_D0083
Figure TWI679499B_D0083

由式(BI)表示的化合物及由式(BII)表示的化合物可以各自單獨地使用，也可將2種以上並用。將由式(BI)表示的化合物及由式(BII)表示的化合物並用的情況下，它們的含有比率[由式(BI)表示的化合物：由式(BII)表示的化合物]以摩爾基準計，優選為5：95~95：5，更優選為20：80~80：20。 The compound represented by the formula (BI) and the compound represented by the formula (BII) may be used individually, or two or more kinds may be used in combination. When a compound represented by the formula (BI) and a compound represented by the formula (BII) are used in combination, their content ratio [compound represented by the formula (BI): compound represented by the formula (BII)] is on a molar basis, It is preferably 5:95 to 95: 5, and more preferably 20:80 to 80:20.

作為上述(b2)，更優選具有氧雜環丁基和(甲基)丙烯醯氧基的單體。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-乙基-3-(甲基)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-乙基-3-(甲基)丙烯醯氧基乙基氧雜環丁烷等。 As said (b2), the monomer which has an oxetanyl group and a (meth) acryloxy group is more preferable. Examples of (b2) include 3-methyl-3- (meth) acryloxymethyloxetane and 3-ethyl-3- (meth) acryloxymethyloxane Butane, 3-methyl-3- (meth) propenyloxyethyloxetane, 3-ethyl-3- (meth) propenyloxyethyloxetane, and the like.

作為(c)，可列舉例如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸仲丁酯、(甲基)丙烯酸叔丁酯、(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)丙烯酸三環[5.2.1.02,6]癸烷-8-基酯(在該技術領域中，作為慣用名，稱為“(甲基)丙烯酸雙環戊酯”。此外，有時稱為“(甲基)丙烯酸三環癸酯”。)、(甲基)丙烯酸三環[5.2.1.02,6]癸烷-9-基酯、(甲基)丙烯酸三環[5.2.1.02,6]癸烯-8-基酯(該技術領域中，作為慣用名，稱為“(甲基)丙烯酸雙環戊烯酯”。)、(甲基)丙烯酸三環[5.2.1.02,6]癸烯-9-基酯、(甲基)丙烯酸雙環戊氧基乙酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸金剛烷酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸炔丙酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸萘酯、(甲基)丙烯酸苄酯等(甲基)丙烯酸酯；(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯等含有羥基的(甲基)丙烯酸酯；馬來酸二乙酯、富馬酸二乙酯、衣康酸二乙酯等二羧酸二酯；雙環[2.2.1]庚-2-烯、5-甲基雙環[2.2.1]庚-2-烯、5-乙基 雙環[2.2.1]庚-2-烯、5-羥基雙環[2.2.1]庚-2-烯、5-羥基甲基雙環[2.2.1]庚-2-烯、5-(2’-羥基乙基)雙環[2.2.1]庚-2-烯、5-甲氧基雙環[2.2.1]庚-2-烯、5-乙氧基雙環[2.2.1]庚-2-烯、5,6-二羥基雙環[2.2.1]庚-2-烯、5,6-二(羥基甲基)雙環[2.2.1]庚-2-烯、5,6-二(2’-羥基乙基)雙環[2.2.1]庚-2-烯、5,6-二甲氧基雙環[2.2.1]庚-2-烯、5,6-二乙氧基雙環[2.2.1]庚-2-烯、5-羥基-5-甲基雙環[2.2.1]庚-2-烯、5-羥基-5-乙基雙環[2.2.1]庚-2-烯、5-羥基甲基-5-甲基雙環[2.2.1]庚-2-烯、5-叔-丁氧基羰基雙環[2.2.1]庚-2-烯、5-環己氧基羰基雙環[2.2.1]庚-2-烯、5-苯氧基羰基雙環[2.2.1]庚-2-烯、5,6-雙(叔-丁氧基羰基)雙環[2.2.1]庚-2-烯、5,6-雙(環己氧基羰基)雙環[2.2.1]庚-2-烯等雙環不飽和化合物；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、N-琥珀醯亞氨基-3-馬來醯亞胺苯甲酸鹽、N-琥珀醯亞氨基-4-馬來醯亞胺丁酸鹽、N-琥珀醯亞氨基-6-馬來醯亞胺己酸鹽、N-琥珀醯亞氨基-3-馬來醯亞胺丙酸鹽、N-(9-吖啶基)馬來醯亞胺等二羰基亞胺衍生物；苯乙烯、α-甲基苯乙烯、乙烯基甲苯、對-甲氧基苯乙烯等含有乙烯基的芳香族化合物；(甲基)丙烯腈等含有乙烯基的腈；氯乙烯、偏氯乙烯等鹵化烴；(甲基)丙烯醯胺等含有乙烯基的醯胺；醋酸乙烯酯等酯；1,3-丁二烯、異戊二烯、2,3-二甲基-1,3-丁二烯等二烯；等。 Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, and t-butyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, Tricyclo [5.2.1.0 2,6 ] decane-8-yl (meth) acrylate (In this technical field, as a common name, it is called "dicyclopentyl (meth) acrylate". In addition, sometimes It is called "tricyclodecyl (meth) acrylate".), Tricyclo [5.2.1.0 2,6 ] decane-9-yl (meth) acrylate, 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".), Tricyclic (meth) acrylate [5.2.1.0 2, 6 ) decene-9-yl ester, dicyclopentyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantane (meth) acrylate, allyl (meth) acrylate, ( Propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, (meth) (Meth) acrylates such as benzyl acrylate; hydroxyl-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; diethyl maleate, Dicarboxylic acid diesters such as diethyl fumarate and diethyl itaconic acid; bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5- Ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2 '-Hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene Ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-bis (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (2 ' -Hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1 ] Hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxy Methyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2. 1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bis (tert- (Oxycarbonyl) bicyclic [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, and other bicyclic unsaturated compounds; N-phenyl horse Lyme imine, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimide-3-maleimide benzoate, N-succinimide -4-maleimide iminobutyrate, N-succinimide imino-6-maleimide iminohexanoate, N-succinimide imino-3-maleimide propionate, N- (9-acridyl) dicarbonylimine derivatives such as maleimide; vinyl-containing aromatic compounds such as styrene, α-methylstyrene, vinyl toluene, and p-methoxystyrene; Vinyl-containing nitriles such as (meth) acrylonitrile; halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; vinylamines containing vinyl such as (meth) acrylamide; esters such as vinyl acetate; 1,3-butane Diene such as olefin, isoprene, 2,3-dimethyl-1,3-butadiene; etc.

這些中，從共聚反應性及耐熱性的方面出發，優選苯乙烯、乙烯基甲苯、N-苯基馬來醯亞胺、N-環己基馬來醯 亞胺、N-苄基馬來醯亞胺、雙環[2.2.1]庚-2-烯等。 Among these, styrene, vinyltoluene, N-phenylmaleimide, and N-cyclohexylmaleimide are preferred from the viewpoint of copolymerization reactivity and heat resistance. Imine, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene, etc.

對聚合引發劑及溶劑等並無特別限定，能夠使用本領域中通常使用的物質。例如，作為聚合引發劑，可列舉偶氮化合物(2,2’-偶氮二異丁腈、2,2’-偶氮二(2,4-二甲基戊腈)等)、有機過氧化物(過氧化苯甲醯等)，作為溶劑，只要將各單體溶解即可，可列舉作為本發明的著色固化性樹脂組合物的溶劑(E)後述的溶劑等。 The polymerization initiator, the solvent, and the like are not particularly limited, and those commonly used in the art can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), and the like, and organic peroxides. As the solvent, it is sufficient to dissolve each monomer as a solvent, and examples of the solvent (E) described later as the solvent (E) of the colored curable resin composition of the present invention are mentioned.

應予說明，得到的共聚物可以原樣地使用反應後的溶液，也可使用濃縮或稀釋了的溶液，可使用採用再沉澱等方法作為固體(粉體)取出的產物。特別地，在該聚合時，作為溶劑，通過使用本發明的著色固化性樹脂組合物中所含的溶劑，能夠將反應後的溶液直接地在本發明的著色固化性樹脂組合物的製備中使用，因此能夠使本發明的著色固化性樹脂組合物的製造工序簡化。 In addition, the obtained copolymer may be used as it is after the reaction, or may be a concentrated or diluted solution, and a product obtained as a solid (powder) by a method such as reprecipitation may be used. In particular, during the polymerization, by using the solvent contained in the colored curable resin composition of the present invention as a solvent, the solution after the reaction can be directly used in the preparation of the colored curable resin composition of the present invention. Therefore, the manufacturing process of the colored curable resin composition of this invention can be simplified.

另外，根據需要，可以使用羧酸或羧酸酐與環狀醚的反應催化劑(例如三(二甲基氨基甲基)苯酚等)及阻聚劑(例如氫醌等)等。 In addition, if necessary, a reaction catalyst (for example, tris (dimethylaminomethyl) phenol, etc.), a polymerization inhibitor (for example, hydroquinone, etc.), and the like for the reaction of a carboxylic acid or a carboxylic anhydride with a cyclic ether can be used.

作為羧酸酐，可列舉馬來酸酐、檸康酸酐、衣康酸酐、3-乙烯基鄰苯二甲酸酐、4-乙烯基鄰苯二甲酸酐、3,4,5,6-四氫鄰苯二甲酸酐、1,2,3,6-四氫鄰苯二甲酸酐、二甲基四氫鄰苯二甲酸酐、5,6-二羧基雙環[2.2.1]庚-2-烯酐等。羧酸酐的使用量相對於(a)的使用量1摩爾，優選0.5~1摩爾。 Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride Dicarboxylic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride, etc. . The used amount of the carboxylic acid anhydride is 1 mol, preferably 0.5 to 1 mol, based on the used amount of (a).

作為樹脂(B)，具體地，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、(甲基)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、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)丙烯酸縮水甘油酯加成於(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物而成的樹脂、使(甲基)丙烯酸縮水甘油酯加成於(甲基)丙烯酸三環癸酯/苯乙烯/(甲基)丙烯酸共聚物而成的樹脂、使(甲基)丙烯酸縮水甘油酯加成於(甲基)丙烯酸三環癸酯/(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物而成的樹脂等樹脂[K4]；使(甲基)丙烯酸與(甲基)丙烯酸三環癸酯/(甲基)丙烯酸縮水甘油酯的共聚物反應而成的樹脂、使(甲基)丙烯酸與(甲基)丙烯酸三環癸酯/苯乙烯/(甲基)丙烯酸縮水甘油酯的共聚物反應而成的樹脂等樹脂[K5]；使(甲基)丙烯酸與(甲基)丙烯酸三環癸酯/(甲基)丙烯酸縮水甘油酯的共聚物反應，進而使四氫鄰苯二甲酸酐與得到的樹脂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 acid copolymer, glycidyl (meth) acrylate / Styrene / (meth) acrylic acid copolymer, (meth) acrylic 3,4-epoxytricyclo [5.2.1.0 2.6 ] decyl / (meth) acrylic acid / N-cyclohexylmaleimide copolymer , Such as 3-methyl-3- (meth) acryloxymethyloxetane / (meth) acrylic acid / styrene copolymer [K2]; benzyl (meth) acrylate / (formaldehyde) Base) acrylic resin, styrene / (meth) acrylic copolymer resin [K3]; glycidyl (meth) acrylate is added to benzyl (meth) acrylate / (meth) acrylic copolymer to Resin made by adding glycidyl (meth) acrylate to tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, and glycidyl (meth) acrylate Addition to tricyclodecyl (meth) acrylate / (formaldehyde) ) Resins such as benzyl acrylate / (meth) acrylic copolymer [K4]; Copolymers of (meth) acrylic acid and tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate Resins obtained by reaction, resins such as (meth) acrylic acid and tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate copolymers [K5]; A resin such as a resin obtained by reacting a copolymer of (meth) acrylic acid with tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate, and further reacting tetrahydrophthalic anhydride with the obtained resin [K6 ]Wait.

其中，作為樹脂(B)，優選樹脂[K1]及樹脂[K2]。 Among them, the resin (B) is preferably a resin [K1] and a resin [K2].

樹脂(B)的聚苯乙烯換算的重均分子量優選為3,000~100,000，更優選為5,000~50,000，進一步優選為5,000~30,000。如果分子量在上述的範圍內，則存在濾色器的硬度提高、殘膜率高、未曝光部對於顯影液的溶解性良 好、著色圖案的解析度提高的傾向。 The polystyrene equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000. If the molecular weight is within the above range, there is an increase in the hardness of the color filter, a high residual film rate, and good solubility of the unexposed portion in the developing solution. Good, the resolution of the colored pattern tends to increase.

樹脂(B)的分子量分佈[重均分子量(Mw)/數均分子量(Mn)]優選為1.1~6，更優選為1.2~4。 The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

樹脂(B)的固體成分酸值優選為50~170mg-KOH/g，更優選為60~150mg-KOH/g，進一步優選為70~135mg-KOH/g。在此，固體成分酸值是作為中和樹脂(B)1g所需的氫氧化鉀的量(mg)測定的值，例如，能夠通過使用氫氧化鉀水溶液進行滴定而求出。 The solid content acid value of the resin (B) is preferably 50 to 170 mg-KOH / g, more preferably 60 to 150 mg-KOH / g, and still more preferably 70 to 135 mg-KOH / g. Here, the solid content acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be determined by, for example, titration using an aqueous potassium hydroxide solution.

樹脂(B)的含量，相對於固體成分的總量，優選為7~65質量%，更優選為13~60質量%，進一步優選為17~55質量%。如果樹脂(B)的含量在上述的範圍內，能夠形成著色圖案，而且存在著色圖案的解析度和殘膜率提高的傾向。 The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass with respect to the total amount of the solid content. When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution and the residual film rate of the colored pattern tend to be improved.

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

聚合性化合物(C)是能夠利用由聚合引發劑(D)產生的活性自由基和/或酸聚合的化合物，可列舉例如具有聚合性的烯屬不飽和鍵的化合物等，優選為(甲基)丙烯酸酯化合物。 The polymerizable compound (C) is a compound that can be polymerized using living radicals and / or acids generated by the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, and are preferably (methyl ) Acrylate compounds.

其中，聚合性化合物(C)優選為具有3個以上烯屬不飽和鍵的聚合性化合物。作為這樣的聚合性化合物，可列舉例如壬基苯基卡必醇丙烯酸酯、2-羥基-3-苯氧基丙基丙烯酸酯、2-乙基己基卡必醇丙烯酸酯、丙烯酸2-羥基乙酯、N-乙烯基吡咯烷酮、上述的作為(a)、(b)和(c)例示的化合物等具有1個烯屬不飽和鍵的化合物； 1,6-己二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三甘醇二(甲基)丙烯酸酯、雙酚A的雙(丙烯醯氧基乙基)醚和3-甲基戊二醇二(甲基)丙烯酸酯等具有2個烯屬不飽和鍵的化合物；三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、、三(2-(甲基)丙烯醯氧基乙基)異氰脲酸酯等具有3個烯屬不飽和鍵的化合物；季戊四醇四(甲基)丙烯酸酯、乙二醇改性季戊四醇四(甲基)丙烯酸酯、丙二醇改性季戊四醇四(甲基)丙烯酸酯、己內酯改性季戊四醇四(甲基)丙烯酸酯等具有4個烯屬不飽和鍵的化合物；二季戊四醇五(甲基)丙烯酸酯等具有5個烯屬不飽和鍵的化合物；二季戊四醇六(甲基)丙烯酸酯、乙二醇改性二季戊四醇六(甲基)丙烯酸酯、丙二醇改性二季戊四醇六(甲基)丙烯酸酯、己內酯改性二季戊四醇六(甲基)丙烯酸酯等具有6個烯屬不飽和鍵的化合物；三季戊四醇七(甲基)丙烯酸酯、三季戊四醇八(甲基)丙烯酸酯、四季戊四醇九(甲基)丙烯酸酯、四季戊四醇十(甲基)丙烯酸酯等具有7個以上烯屬不飽和鍵的化合物；等。 Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such a polymerizable compound include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropylacrylate, 2-ethylhexylcarbitol acrylate, and 2-hydroxyethyl acrylate Compounds having one ethylenically unsaturated bond such as esters, N-vinylpyrrolidone, the compounds exemplified as (a), (b), and (c) above; 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis Compounds with 2 ethylenically unsaturated bonds, such as bis (propylene ethoxyethyl) ether of phenol A and 3-methylpentanediol di (meth) acrylate; trimethylolpropane tri (methyl) Compounds with three ethylenically unsaturated bonds, such as acrylate, pentaerythritol tri (meth) acrylate, and tris (2- (meth) acryloxyethyl) isocyanurate; pentaerythritol tetra (methyl) ) Acrylate, ethylene glycol-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, etc. Compounds with saturated bonds; compounds with five ethylenically unsaturated bonds such as dipentaerythritol penta (meth) acrylate; dipentaerythritol hexa (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate , Propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. have 6 Ethylenically unsaturated compounds; tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tetrapentaerythritol dec (meth) acrylate, etc. have 7 Compounds with more than one ethylenically unsaturated bond; etc.

其中，聚合性化合物(C)優選為具有3個以上烯屬不飽和鍵的聚合性化合物，更優選為具有5個~6個烯屬不飽和鍵的聚合性化合物。特別優選二季戊四醇五(甲基)丙烯酸酯及二季戊四醇六(甲基)丙烯酸酯。 Among these, the polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds, and more preferably a polymerizable compound having 5 to 6 ethylenically unsaturated bonds. Particularly preferred are dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

聚合性化合物(C)的重均分子量優選為150以上2,900以下，更優選為250以上1,500以下。 The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, and more preferably 250 or more and 1,500 or less.

聚合性化合物(C)的含量，相對於固體成分的總量，優選為7~65質量%，更優選為13~60質量%，進一步優選為17~55質量%。如果聚合性化合物(C)的含量在上述的範圍內，則存在著色圖案形成時的殘膜率及濾色器的耐化學品性提高的傾向。 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 content. When content of a polymerizable compound (C) exists in the said range, there exists a tendency for the residual film rate at the time of formation of a coloring pattern, and the chemical resistance of a color filter to improve.

另外，樹脂(B)與聚合性化合物(C)的含量比[樹脂(B)：聚合性化合物(C)]以質量基準計，優選為20：80~80：20，更優選為35：65~80：20。 The content ratio of the resin (B) to the polymerizable compound (C) [resin (B): polymerizable compound (C)] is preferably 20:80 to 80:20 on a mass basis, and more preferably 35:65. ~ 80: 20.

<聚合引發劑(D)> <Polymerization Initiator (D)>

聚合引發劑(D)是利用光、熱的作用產生活性自由基、可引發聚合的化合物。本發明的著色固化性樹脂組合物作為聚合引發劑包含由下述式(d1)表示的化合物(以下有時稱為“化合物(d1)”。)。 The polymerization initiator (D) is a compound that generates living radicals by the action of light and heat and can initiate polymerization. The colored curable resin composition of the present invention contains a compound represented by the following formula (d1) as a polymerization initiator (hereinafter sometimes referred to as "compound (d1)").

Figure TWI679499B_D0084
Figure TWI679499B_D0084

[式(d1)中，Rd1表示可具有取代基的碳數6~18的芳香族烴基、可具有取代基的碳數3~36的雜環基、可具有取代基的碳數1~15 的烷基、或者可具有取代基的碳數7~33的芳烷基，上述烷基或芳烷基中所含的亞甲基(-CH2-)可替換為-O-、-CO-、-S-、-SO2-或-N(Rd5)-。 [In formula (d1), R d1 represents an aromatic hydrocarbon group having 6 to 18 carbons which may have a substituent, a heterocyclic group having 3 to 36 carbons which may have a substituent, and 1 to 15 carbons which may have a substituent Alkyl group or an aralkyl group having 7 to 33 carbon atoms which may have a substituent, the methylene group (-CH 2- ) contained in the alkyl group or aralkyl group may be replaced with -O-, -CO- , -S-, -SO 2 -or -N (R d5 )-.

Rd2表示碳數6~18的芳香族烴基、碳數3~36的雜環基、或碳數1~10的烷基。 R d2 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, a heterocyclic group having 3 to 36 carbon atoms, or an alkyl group having 1 to 10 carbon atoms.

Rd3表示可具有取代基的碳數6~18的芳香族烴基、可具有取代基的碳數3~36的雜環基。 R d3 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, and a heterocyclic group having 3 to 36 carbon atoms which may have a substituent.

Rd4表示可具有取代基的碳數6~18的芳香族烴基、或可具有取代基的碳數1~15的脂肪族烴基，上述脂肪族烴基中所含的亞甲基(-CH2-)可替換為-O-、-CO-或-S-，上述脂肪族烴基中所含的次甲基(-CH<)可替換為-PO3<，上述脂肪族烴基中所含的氫原子可被OH基取代。 R d4 represents an aromatic hydrocarbon group having 6 to 18 carbons which may have a substituent, or an aliphatic hydrocarbon group having 1 to 15 carbons which may have a substituent, and the methylene group (-CH 2- ) Can be replaced with -O-, -CO- or -S-, and the methine group (-CH <) contained in the aliphatic hydrocarbon group can be replaced with -PO 3 <, the hydrogen atom contained in the aliphatic hydrocarbon group It may be substituted by an OH group.

Rd5表示碳數1~10的烷基，該烷基中所含的亞甲基(-CH2-)可替換為-O-或-CO-。] R d5 represents an alkyl group having 1 to 10 carbon atoms, and the methylene group (-CH 2- ) contained in the alkyl group may be replaced with -O- or -CO-. ]

由Rd1表示的芳香族烴基的碳數優選為6~15，更優選為6~12，進一步優選為6~10。作為該芳香族烴基，例如可列舉苯基、萘基、蒽基、菲基、聯苯基、三聯苯基等，更優選苯基、萘基，特別優選苯基。 The carbon number of the aromatic hydrocarbon group represented by R d1 is preferably from 6 to 15, more preferably from 6 to 12, and even more preferably from 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group. A phenyl group and a naphthyl group are more preferable, and a phenyl group is particularly preferable.

另外，由Rd1表示的芳香族烴基可具有1或2個以上的取代基。取代基優選取代於芳香族烴基的α位、γ位，更優選取代於γ位。作為該取代基，可列舉甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基等碳數1~15的烷基；氟原子、氯原子、碘原子、溴原子等鹵素原子；等。 The aromatic hydrocarbon group represented by R d1 may have one or two or more substituents. The substituent is preferably substituted at the α and γ positions of the aromatic hydrocarbon group, and more preferably at the γ position. Examples of the substituent include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and tridecyl , Tetradecyl, pentadecyl, and other alkyl groups having 1 to 15 carbon atoms; halogen atoms such as fluorine atom, chlorine atom, iodine atom, and bromine atom; etc.

作為上述取代基的烷基的碳數優選為1~10，更優選為1~7。作為該取代基的烷基可以是直鏈狀、分支鏈狀、及環狀的任一種，可以是將鏈狀的基團和環狀的基團組合而成的基團。作為該取代基的烷基中所含的亞甲基(-CH2-)可以被替換為-O-或-S-。另外，該烷基中所含的氫原子可以被氟原子、氯原子、碘原子、溴原子等鹵素原子取代，優選被氟原子取代。 The carbon number of the alkyl group as the substituent is preferably 1 to 10, and more preferably 1 to 7. The alkyl group as the substituent may be any of linear, branched, and cyclic groups, and may be a group obtained by combining a chain group and a cyclic group. The methylene group (-CH 2- ) contained in the alkyl group as the substituent may be replaced with -O- or -S-. The hydrogen atom contained in the alkyl group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom, or a bromine atom, and is preferably substituted with a fluorine atom.

作為由Rd1表示的芳香族烴基的取代基的烷基，例如可列舉由下述式表示的基團等。式中＊表示鍵合端。 Examples of the alkyl group as a substituent of the aromatic hydrocarbon group represented by R d1 include a group represented by the following formula. In the formula, * indicates a bonding end.

Figure TWI679499B_D0085
Figure TWI679499B_D0085

Figure TWI679499B_D0086
Figure TWI679499B_D0086

作為由Rd1表示的可具有取代基的芳香族烴基，可列舉由下述式表示的基團等。式中，＊表示鍵合端。 Examples of the aromatic hydrocarbon group which may have a substituent represented by R d1 include a group represented by the following formula. In the formula, * represents a bonding end.

Figure TWI679499B_D0087
Figure TWI679499B_D0087

Figure TWI679499B_D0088
Figure TWI679499B_D0088

作為由Rd1表示的可具有取代基的芳香族烴基，優選由下述式表示的基團。 The aromatic hydrocarbon group which may have a substituent represented by R d1 is preferably a group represented by the following formula.

Figure TWI679499B_D0089
Figure TWI679499B_D0089

[式中，Rd6表示可被鹵素原子取代的碳數1以上、10以下的烷基，Rd6中所含的氫原子可被鹵素原子取代。m2表示1~5的整數。] [In the formula, R d6 represents an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, and a hydrogen atom contained in R d6 may be substituted with a halogen atom. m2 represents an integer from 1 to 5. ]

作為由Rd6表示的烷基，可列舉與作為由Rd1表示的芳香族烴基的取代基例示的烷基同樣的基團。由Rd6表示的烷基的碳數優選為2以上、7以下，更優選為2以上、5以下。另外，Rd6的烷基可以是直鏈狀、分支鏈狀、及環狀的任一種，優選為鏈狀。 Examples of the alkyl group represented by R d6 include the same groups as those exemplified as the substituent of the aromatic hydrocarbon group represented by R d1 . The carbon number of the alkyl group represented by R d6 is preferably 2 or more and 7 or less, and more preferably 2 or more and 5 or less. The alkyl group of R d6 may be any of linear, branched, and cyclic, and is preferably chain.

作為可取代Rd6中所含的氫原子的鹵素原子，可列舉氟原子、氯原子、碘原子、溴原子，特別優選氟原子。另外，優選Rd6中所含的氫原子的2個以上、10個以下被鹵素原子取代，優選3個以上、6個以下被鹵素原子取代。Rd6O-基的取代位置優選鄰位、對位，特別優選對位。 Examples of the halogen atom that can replace a hydrogen atom contained in R d6 include a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom, and a fluorine atom is particularly preferred. Moreover, it is preferable that two or more and ten or less of the hydrogen atoms contained in R d6 are substituted with a halogen atom, and it is preferred that three or more and six or less be substituted with a halogen atom. The substitution position of the R d6 O- group is preferably ortho and para, and particularly preferably para.

另外，m2優選為1~2，特別優選為1。 In addition, m2 is preferably 1 to 2, and particularly preferably 1.

由Rd1表示的雜環基的碳數優選為3~20，更優選為3~10，進一步優選為3~5。作為該雜環基，可列舉吡咯基、呋喃基、噻吩基、吲哚基、苯并呋喃基、咔唑基等。 The carbon number of the heterocyclic group represented by R d1 is preferably 3 to 20, more preferably 3 to 10, and even more preferably 3 to 5. Examples of the heterocyclic group include pyrrolyl, furyl, thienyl, indolyl, benzofuryl, and carbazolyl.

另外，Rd1的雜環基可具有1或2個以上的取代基。作為該取代基，可列舉與作為Rd1的芳香族烴基可具有的取代基例示的基團同樣的基團。 The heterocyclic group of R d1 may have one or two or more substituents. Examples of the substituent include the same groups as those exemplified as the substituent which the aromatic hydrocarbon group of R d1 may have.

由Rd1表示的烷基的碳數優選為1~12。作為由Rd1 表示的烷基，可列舉甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基等。這些烷基可以是直鏈狀、分支鏈狀、及環狀的任一種，也可以是將鏈狀的基團和環狀的基團組合的基團。另外，Rd1的烷基中，亞甲基(-CH2-)可被替換為-O-、-CO-、-S-、-SO2-或-NRd5-，氫原子可被OH基、或SH基取代。 The carbon number of the alkyl group represented by R d1 is preferably 1 to 12. Examples of the alkyl group represented by R d1 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, Tridecyl, tetradecyl, pentadecyl and the like. These alkyl groups may be any of linear, branched, and cyclic groups, and may be a group combining a chain group and a cyclic group. In the alkyl group of R d1 , the methylene group (-CH 2- ) may be replaced with -O-, -CO-, -S-, -SO 2- , or -NR d5- , and the hydrogen atom may be replaced by an OH group. , Or SH group substitution.

Rd5表示碳數1~10的烷基，優選為碳數1~5的烷基，更優選為碳數1~3的烷基。該烷基可以為鏈狀(直鏈狀或分支鏈狀)，也可為環狀，可以是直鏈狀、分支鏈狀、及環狀的任一種，也可以是將鏈狀的基團與環狀的基團組合的基團。另外，Rd5的烷基中，亞甲基(-CH2-)可被替換為-O-、-CO-。 R d5 represents an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group may be linear (straight or branched) or cyclic, and may be any of linear, branched, and cyclic, or a chain-like group and A group of cyclic groups. In the alkyl group of R d5 , methylene (-CH 2- ) may be replaced with -O- or -CO-.

作為由Rd1表示的可具有取代基的烷基，具體地，可列舉由下述式表示的基團等。＊表示鍵合端。 Specific examples of the alkyl group which may have a substituent represented by R d1 include a group represented by the following formula. * Indicates a bonding end.

Figure TWI679499B_D0090
Figure TWI679499B_D0090

進而，由Rd1表示的可具有取代基的芳烷基優選為將Rd1所示的芳香族烴基與由上述Rd1所示的烷基導出的亞烷基組合而成的基團。上述芳烷基的碳數優選為7~33，更優選為7~18，進一步優選為7~12。該芳烷基可具有1或2個以上的取代基，作為該取代基，可列舉與作為上述Rd1所示的芳香族烴基、及Rd1所示的烷基可具有的取代基例示的基團同樣的基團。作為將該Rd1所示的芳香族烴基與由上述Rd1所示的烷基導出的2價的基團組合而成的基團，具體地，可列舉由下述式表示的基團。式中＊表示鍵合端。 Further, R d1 represents the substituent may have an aryl group is preferably an aromatic hydrocarbon group represented by R d1 combination derived from alkylene group represented by the above R d1. The carbon number of the aralkyl group is preferably 7 to 33, more preferably 7 to 18, and even more preferably 7 to 12. The aralkyl group may have one or two or more substituents. Examples of the substituent include the groups exemplified as the aromatic hydrocarbon group represented by the aforementioned R d1 and the substituents which the alkyl group represented by the R d1 may have. The same group. The combination of the aromatic hydrocarbon group represented by R d1 and a divalent group derived from the above-described alkyl groups represented by R d1 from a group specifically include groups represented by the following formula. In the formula, * indicates a bonding end.

Figure TWI679499B_D0091
Figure TWI679499B_D0091

其中，作為Rd1，優選可具有取代基的芳香族烴基、或、可具有取代基的烷基，更優選可具有取代基的芳香族烴基。 Among them, R d1 is preferably an aromatic hydrocarbon group which may have a substituent or an alkyl group which may have a substituent, and more preferably an aromatic hydrocarbon group which may have a substituent.

由Rd2表示的芳香族烴基的碳數優選為6~15，更優選為6~12，進一步優選為6~10。作為該芳香族烴基，例如可列舉苯基、萘基、蒽基、菲基、聯苯基、三聯苯基等。 The carbon number of the aromatic hydrocarbon group represented by R d2 is preferably from 6 to 15, more preferably from 6 to 12, and even more preferably from 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a biphenyl group, and a terphenyl group.

由Rd2表示的雜環基的碳數優選為3~20，更優選為3~10，進一步優選為3~5。作為該雜環基，例如可列舉吡咯基、呋喃基、噻吩基、吲哚基、苯并呋喃基、咔唑基等。 The carbon number of the heterocyclic group represented by R d2 is preferably 3 to 20, more preferably 3 to 10, and even more preferably 3 to 5. Examples of the heterocyclic group include pyrrolyl, furyl, thienyl, indolyl, benzofuryl, and carbazolyl.

由Rd2表示的烷基的碳數優選為1~7，更優選為1~5，特別優選為1~3。作為該烷基，可列舉甲基、乙基、丙基、丁 基、戊基、己基、庚基、辛基、壬基、癸基等。該烷基可以是直鏈狀、分支鏈狀、及環狀的任一種，也可以是將鏈狀的基團與環狀的基團組合而成的基團。 The carbon number of the alkyl group represented by R d2 is preferably 1 to 7, more preferably 1 to 5, and particularly preferably 1 to 3. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. The alkyl group may be any of linear, branched, and cyclic groups, and may be a group obtained by combining a chain group and a cyclic group.

其中，作為Rd2，優選鏈狀烷基，更優選為碳數1~5的鏈狀烷基，進一步優選為碳數1~3的鏈狀烷基，特別優選為甲基。 Among them, R d2 is preferably a chain alkyl group, more preferably a chain alkyl group having 1 to 5 carbon atoms, still more preferably a chain alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.

由Rd3表示的芳香族烴基的碳數優選為6~15，更優選為6~12，進一步優選為6~10。作為該芳香族烴基，例如可列舉苯基、萘基、蒽基、菲基、聯苯基、三聯苯基等，更優選苯基、萘基。 The carbon number of the aromatic hydrocarbon group represented by R d3 is preferably from 6 to 15, more preferably from 6 to 12, and even more preferably from 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, a terphenyl group, and the like, and a phenyl group and a naphthyl group are more preferable.

另外，由Rd3表示的芳香族烴基可具有1或2個以上的取代基。取代基優選取代於芳香族烴基的α位、γ位。作為該取代基，優選碳數1~15的脂肪族烴基，具體地，可列舉甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基等碳數1~15的烷基；乙烯基、丙烯基、丁烯基、戊烯基、己烯基、庚烯基、壬烯基、癸烯基等的碳數1~15的烯基；等。 The aromatic hydrocarbon group represented by R d3 may have one or two or more substituents. The substituent is preferably substituted at the α and γ positions of the aromatic hydrocarbon group. The substituent is preferably an aliphatic hydrocarbon group having 1 to 15 carbon atoms. Specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and the like. Alkyl groups having 1 to 15 carbons; vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, nonenyl, decenyl and other alkenyl groups having 1 to 15 carbons; etc. .

作為上述取代基的脂肪族烴基的碳數更優選為1~7。另外，作為該取代基的脂肪族烴基可以是直鏈狀、分支鏈狀、及環狀的任一種，也可以是將鏈狀的基團和環狀的基團組合而成的基團。另外，作為該取代基的脂肪族烴基中，亞甲基(-CH2-)可以被替換為-O-、-CO-或-S-，次甲基(-CH<)可以被替換為-N<。 The carbon number of the aliphatic hydrocarbon group as the substituent is more preferably 1 to 7. The aliphatic hydrocarbon group as the substituent may be any of linear, branched, and cyclic groups, and may be a combination of a chain group and a cyclic group. In the aliphatic hydrocarbon group as the substituent, the methylene group (-CH 2- ) may be replaced with -O-, -CO-, or -S-, and the methine group (-CH <) may be replaced with- N <.

作為由Rd3表示的芳香族烴基的取代基的脂肪族烴基，例如可列舉由下述式表示的基團等。式中＊表示鍵合端。 Examples of the aliphatic hydrocarbon group as a substituent of the aromatic hydrocarbon group represented by R d3 include a group represented by the following formula. In the formula, * indicates a bonding end.

Figure TWI679499B_D0092
Figure TWI679499B_D0092

作為由Rd3表示的可具有取代基的芳香族烴基，例如可列舉由下述式表示的基團等。式中＊表示鍵合端。 Examples of the aromatic hydrocarbon group which may have a substituent represented by R d3 include a group represented by the following formula. In the formula, * indicates a bonding end.

Figure TWI679499B_D0093
Figure TWI679499B_D0093

由Rd3表示的雜環基的碳數優選為3~20，更優選為3~10，進一步優選為3~5。作為該雜環基，例如可列舉吡咯基、呋喃基、噻吩基、吲哚基、苯并呋喃基、咔唑基等。 The carbon number of the heterocyclic group represented by R d3 is preferably 3 to 20, more preferably 3 to 10, and even more preferably 3 to 5. Examples of the heterocyclic group include pyrrolyl, furyl, thienyl, indolyl, benzofuryl, and carbazolyl.

另外，由Rd3表示的雜環基可具有1或2個以上的取代基， 作為該取代基，可列舉與作為由Rd1表示的芳香族烴基可具有的取代基例示的基團同樣的基團。 The heterocyclic group represented by R d3 may have one or two or more substituents. Examples of the substituent include the same groups as those exemplified as the substituent which the aromatic hydrocarbon group represented by R d1 may have. group.

其中，作為Rd3，優選為具有取代基的芳香族烴基，作為該取代基，優選碳數1~7(更優選地碳數1~3)的鏈狀烷基，取代基的個數優選為2個以上、5個以下。 Among them, R d3 is preferably an aromatic hydrocarbon group having a substituent. The substituent is preferably a chain alkyl group having 1 to 7 carbon atoms (more preferably 1 to 3 carbon atoms). The number of substituents is preferably 2 or more and 5 or less.

由Rd4表示的芳香族烴基的碳數優選為6~15，更優選為6~12，進一步優選為6~10。作為該芳香族烴基，例如可列舉苯基、萘基、蒽基、菲基、聯苯基、三聯苯基等，更優選苯基、萘基，特別優選苯基。 The carbon number of the aromatic hydrocarbon group represented by R d4 is preferably from 6 to 15, more preferably from 6 to 12, and even more preferably from 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group. A phenyl group and a naphthyl group are more preferable, and a phenyl group is particularly preferable.

另外，由Rd4表示的芳香族烴基可具有1或2個以上的取代基。作為該取代基，可列舉與作為Rd1的芳香族烴基可具有的取代基同樣的基團。 The aromatic hydrocarbon group represented by R d4 may have one or two or more substituents. Examples of the substituent include the same groups as those which the aromatic hydrocarbon group of R d1 may have.

由Rd4表示的脂肪族烴基的碳數優選為1~13，更優選為2~10，進一步優選為4~9。作為Rd4的脂肪族烴基，可列舉甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基等烷基；乙烯基、丙烯基、丁烯基、戊烯基、己烯基、庚烯基、辛烯基、壬烯基、癸烯基、十一碳烯基、十二碳烯基、十三碳烯基、十四碳烯基、十五碳烯基等烯基；等。這些脂肪族烴基可以是鏈狀(直鏈狀或分支鏈狀)，也可以是環狀，還可以是將鏈狀的基團與環狀的基團組合而成的基團。另外，由Rd4表示的脂肪族烴基中，亞甲基(-CH2-)可以被替換為-O-、-CO-或-S-，次甲基(-CH<)可以被替換為-PO3<。上述脂肪族烴基中所含的氫原子可以被OH基取代。 The carbon number of the aliphatic hydrocarbon group represented by R d4 is preferably 1 to 13, more preferably 2 to 10, and even more preferably 4 to 9. Examples of the aliphatic hydrocarbon group of R d4 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and deca Trialkyl, tetradecyl, pentadecyl and other alkyl groups; vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl , Undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl and other alkenyl groups; etc. These aliphatic hydrocarbon groups may be chain-shaped (straight-chain or branched-chain), may be cyclic, and may be a group obtained by combining a chain-shaped group and a cyclic group. In the aliphatic hydrocarbon group represented by R d4 , the methylene group (-CH 2- ) may be replaced with -O-, -CO-, or -S-, and the methine group (-CH <) may be replaced with- PO 3 <. The hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with an OH group.

作為由Rd4表示的可具有取代基的脂肪族烴基， 例如可列舉由下述式表示的基團等。式中＊表示鍵合端。 Examples of the aliphatic hydrocarbon group which may have a substituent represented by R d4 include a group represented by the following formula. In the formula, * indicates a bonding end.

Figure TWI679499B_D0094
Figure TWI679499B_D0094

作為Rd4，優選為可具有取代基的鏈狀脂肪族烴基，更優選為不具有取代基的鏈狀烷基，進一步優選為不具有取代基的分支鏈狀烷基。 R d4 is preferably a chain aliphatic hydrocarbon group which may have a substituent, more preferably a chain alkyl group having no substituent, and still more preferably a branched chain alkyl group having no substituent.

作為化合物(d1)，如下述表4~10中所示，可列舉由式(d1)表示的化合物(d1-1)~(d1-67)。表中＊表示鍵合端。 Examples of the compound (d1) include compounds (d1-1) to (d1-67) represented by the formula (d1), as shown in Tables 4 to 10 below. In the table, * indicates a bonding end.

Figure TWI679499B_D0095
Figure TWI679499B_D0095

其中，優選化合物(d1-3)~(d1-6)、(d1-18)~(d1-52)、(d1-55)、(d1-56)、(d1-60)、(d1-61)，更優選為化合物(d1-3)~(d1-6)、(d1-18)~(d1-41)，進一步優選為化合物(d1-24)、(d1-36)~(d1-40)，特別優選為化合物(d1-24)。 Among them, preferred compounds (d1-3) to (d1-6), (d1-18) to (d1-52), (d1-55), (d1-56), (d1-60), (d1-61) ), More preferably compounds (d1-3) to (d1-6), (d1-18) to (d1-41), and still more preferably compounds (d1-24), (d1-36) to (d1-40) ), Particularly preferably compound (d1-24).

化合物(d1)的含量在聚合引發劑(D)100質量份中優選為2質量份以上、100質量份以下，更優選為30質量份 以上，進一步優選為40質量份以上，特別優選為50質量份以上，優選為90質量份以下，更優選為70質量份以下，進一步優選為60質量份以下。 The content of the compound (d1) is preferably 2 parts by mass or more and 100 parts by mass or less, and more preferably 30 parts by mass in 100 parts by mass of the polymerization initiator (D). The above is more preferably 40 parts by mass or more, particularly preferably 50 parts by mass or more, preferably 90 parts by mass or less, more preferably 70 parts by mass or less, and still more preferably 60 parts by mass or less.

化合物(d1)可以採用特表2014-500852號公報中記載的製造方法製造。 Compound (d1) can be produced by the production method described in Japanese Patent Application Publication No. 2014-500852.

此外，聚合引發劑(D)可進一步含有上述化合物(d1)以外的聚合引發劑。對它們並無特別限定，可以使用公知的聚合引發劑。 The polymerization initiator (D) may further contain a polymerization initiator other than the compound (d1). They are not particularly limited, and known polymerization initiators can be used.

作為產生活性自由基的聚合引發劑，可列舉上述化合物(d1)以外的O-醯基肟化合物、聯咪唑化合物、烷基苯基酮化合物、三嗪化合物及醯基氧化膦化合物。其中，作為聚合引發劑(D)，除了化合物(d1)以外，優選包含聯咪唑化合物、或烷基苯基酮化合物，更優選包含聯咪唑化合物。 Examples of the polymerization initiator that generates living radicals include O-fluorenyl oxime compounds, biimidazole compounds, alkylphenyl ketone compounds, triazine compounds, and fluorenyl phosphine oxide compounds other than the compound (d1). Among these, as the polymerization initiator (D), in addition to the compound (d1), a biimidazole compound or an alkylphenyl ketone compound is preferably contained, and a biimidazole compound is more preferably contained.

作為上述O-醯基肟化合物，可列舉N-苯甲醯氧基-1-(4-苯基硫烷基苯基)丁烷-1-酮-2-亞胺、N-苯甲醯氧基-1-(4-苯基硫烷基苯基)辛烷-1-酮-2-亞胺、N-苯甲醯氧基-1-(4-苯基硫烷基苯基)-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-2,4-二氧雜環戊基甲氧基)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

Figure TWI679499B_D0103
(註冊商標)OXE01、OXE02(以上 為BASF社製造)、N-1919(ADEKA社製造)等市售品。其中，O-醯基肟化合物優選選自N-苯甲醯氧基-1-(4-苯基硫烷基苯基)丁烷-1-酮-2-亞胺、N-苯甲醯氧基-1-(4-苯基硫烷基苯基)辛烷-1-酮-2-亞胺、N-苯甲醯氧基-1-(4-苯基硫烷基苯基)-3-環戊基丙烷-1-酮-2-亞胺和N-乙醯氧基-1-[4-{4-(2-羥基乙氧基)苯基}硫烷基苯基]-丙烷-1-酮-2-亞胺中的至少1種，更優選選自N-苯甲醯氧基-1-(4-苯基硫烷基苯基)辛烷-1-酮-2-亞胺和N-乙醯氧基-1-[4-{4-(2-羥基乙氧基)苯基}硫烷基苯基]-丙烷-1-酮-2-亞胺中的至少1種。如果為這些O-醯基肟化合物，傾向於得到高明度的濾色器。 Examples of the O-fluorenyl oxime compound include N-benzyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine and N-benzyloxy 1- (4-phenylsulfanylphenyl) octane-1-one-2-imine, N-benzyloxy-1- (4-phenylsulfanylphenyl) -3 -Cyclopentylpropane-1-one-2-imine, N-ethoxyl-1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazole-3- Alkyl] ethane-1-imine, N-ethoxy-1--1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxy Heterocyclopentylmethoxy) benzylidene} -9H-carbazol-3-yl] ethane-1-imine, N-ethoxyl-1- [9-ethyl-6- (2 -Methylbenzyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzyloxy-1- [9-ethyl-6- ( 2-methylbenzylidene) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-one-2-imine and the like. be usable
Figure TWI679499B_D0103
(Registered trademark) OXE01, OXE02 (above manufactured by BASF), N-1919 (made by ADEKA) and other commercially available products. Among these, the O-fluorenyl oxime compound is preferably selected from the group consisting of N-benzyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine, and N-benzyloxy 1- (4-phenylsulfanylphenyl) octane-1-one-2-imine, N-benzyloxy-1- (4-phenylsulfanylphenyl) -3 -Cyclopentylpropane-1-one-2-imine and N-ethoxyl-1- [4- {4- (2-hydroxyethoxy) phenyl} sulfanylphenyl] -propane- At least one kind of 1-keto-2-imine, more preferably selected from N-benzyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine And at least one of N-ethoxyl-1- [4- {4- (2-hydroxyethoxy) phenyl} sulfanylphenyl] -propane-1-one-2-imine. In the case of these O-fluorenyl oxime compounds, color filters with high brightness tend to be obtained.

作為聯咪唑化合物，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，參照特開平6-75372號公報、特開平6-75373號公報等。)、2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基聯咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四(烷氧基苯基)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，參照特公昭48-38403號公報、特開昭62-174204號公報等。)、4,4’,5,5’-位的苯基被烷氧羰基取代的咪唑化合物(例如，參照特開平7-10913號公報等)等。 Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichloro (Phenyl) -4,4'5,5'-tetraphenylbiimidazole (for example, refer to Japanese Patent Application Laid-Open No. 6-75372, Japanese Patent Application Laid-Open No. 6-75373, etc.), 2,2'-bis (2- (Chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxy) Phenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (dialkoxyphenyl) biimidazole, 2,2'-bis (2 -Chlorophenyl) -4,4 ', 5,5'-tetrakis (trialkoxyphenyl) biimidazole (for example, refer to JP 48-38403, JP 62-174204, etc.) , An imidazole compound in which a phenyl group at the 4,4 ′, 5,5′-position is substituted with an alkoxycarbonyl group (for example, refer to Japanese Patent Application Laid-Open No. 7-10913).

其中，優選由式(d4)表示的化合物。 Among them, a compound represented by the formula (d4) is preferred.

Figure TWI679499B_D0104
Figure TWI679499B_D0104

[式(d4)中，Rd13~Rd16各自獨立地表示氫原子或烷氧基(優選地碳數1~4的烷氧基、更優選地甲氧基)。Rd17及Rd18各自獨立地表示氫原子或鹵素原子(優選地氯原子)。] [In formula (d4), R d13 to R d16 each independently represent a hydrogen atom or an alkoxy group (preferably an alkoxy group having 1 to 4 carbon atoms, and more preferably a methoxy group). R d17 and R d18 each independently represent a hydrogen atom or a halogen atom (preferably a chlorine atom). ]

作為由上述式(d4)表示的化合物，具體地，可列舉下述式所示的化合物，優選這些的混合物。 Specific examples of the compound represented by the formula (d4) include compounds represented by the following formula, and a mixture of these is preferred.

Figure TWI679499B_D0105
Figure TWI679499B_D0105

上述烷基苯基酮化合物是具有由式(d5)表示的部分結構或由式(d6)表示的部分結構的化合物。這些部分結構中，苯環可具有取代基。 The alkyl phenyl ketone compound is a compound having a partial structure represented by the formula (d5) or a partial structure represented by the formula (d6). In these partial structures, the benzene ring may have a substituent.

Figure TWI679499B_D0106
Figure TWI679499B_D0106

作為具有由式(d5)表示的部分結構的化合物，可 列舉例如2-甲基-2-嗎啉代-1-(4-甲基硫烷基苯基)丙烷-1-酮、2-二甲基氨基-1-(4-嗎啉代苯基)-2-苄基丁烷-1-酮、2-(二甲基氨基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎啉基)苯基]丁烷-1-酮等。可使用

Figure TWI679499B_D0107
369、907、379(以上為BASF社製造)等的市售品。 Examples of the compound having a partial structure represented by the formula (d5) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propane-1-one, and 2-di Methylamino-1- (4-morpholinophenyl) -2-benzylbutane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane-1-one and the like. be usable
Figure TWI679499B_D0107
Commercial products such as 369, 907, and 379 (above manufactured by BASF).

作為具有由式(d6)表示的部分結構的化合物，可列舉例如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-酮的低聚物、α,α-二乙氧基苯乙酮、苯偶醯二甲基縮酮等。 Examples of the compound having a partial structure represented by the formula (d6) 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, benzophenone dimethyl ketal, etc.

在感度的方面，作為烷基苯基酮化合物，優選具有由式(d5)表示的部分結構的化合物。 In terms of sensitivity, as the alkylphenyl ketone compound, a compound having a partial structure represented by formula (d5) is preferred.

作為上述三嗪化合物，可列舉例如2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-(4-甲氧基萘基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-胡椒基-1,3,5-三嗪、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(5-甲基呋喃-2-基)乙烯基]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(4-二乙基氨基-2-甲基苯基)乙烯基]-1,3,5-三嗪、2,4-雙(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三嗪等。 Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloro) (Methyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperyl-1,3,5-triazine , 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [ 2- (5-methylfuran-2-yl) vinyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) Vinyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl] -1 , 3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) vinyl] -1,3,5-triazine, etc. .

作為上述醯基氧化膦化合物，可列舉2,4,6-三甲基苯甲醯基二苯基氧化膦等。可使用

Figure TWI679499B_D0108
(註册商标)819(BASF社製)等的市售品。 Examples of the fluorenylphosphine oxide compound include 2,4,6-trimethylbenzylidenediphenylphosphine oxide and the like. be usable
Figure TWI679499B_D0108
(Registered trademark) 819 (manufactured by BASF) and other commercially available products.

進而，作為聚合引發劑(D)，可列舉苯偶姻、苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻異丙基醚、苯偶姻異丁基醚等苯偶姻化合物；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’-甲基二苯基硫醚、3,3’,4,4’-四(叔-丁基過氧羰基)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、苯偶醯、苯基乙醛酸甲酯、二茂鈦化合物等。這些優選與後述的聚合引發助劑(D1)(特別是胺類)組合使用。 Furthermore, 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, methyl o-benzylidene benzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3 ', 4 , 4'-tetra (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone and other benzophenone compounds; 9,10-phenanthrenequinone, 2-ethyl Anthraquinones, camphorquinones and other quinone compounds; 10-butyl-2-chloroacridone, benzoin, methyl phenylglyoxylate, titanocene compounds, etc. These are preferably used in combination with a polymerization initiation aid (D1) (particularly, amines) described later.

其中，使用2種以上的聚合引發劑的情況下，優選化合物(d1)與聯咪唑化合物的組合、化合物(d1)和聯咪唑化合物和後述的硫醇化合物的組合、或者、化合物(d1)與烷基苯基酮化合物的組合等。 Among these, when two or more polymerization initiators are used, a combination of the compound (d1) and a biimidazole compound, a compound (d1) and a combination of a biimidazole compound and a thiol compound described later, or a compound (d1) and Combinations of alkyl phenyl ketone compounds and the like.

聚合引發劑(D)的含量相對於樹脂(B)和聚合性化合物(C)的合計100質量份，優選為0.1~30質量份，更優選為1~20質量份，進一步優選為2~15質量份。如果聚合引發劑(D)的含量在上述的範圍內，由於存在高感度化、使曝光時間縮短的傾向，因此濾色器的生產率提高。 The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and still more preferably 2 to 15 parts by mass based on 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). Parts by mass. When the content of the polymerization initiator (D) is within the above-mentioned range, the sensitivity tends to be high and the exposure time tends to be shortened, so that the productivity of the color filter is improved.

<聚合引發助劑(D1)> <Polymerization Initiation Auxiliary (D1)>

聚合引發助劑(D1)是用於促進用聚合引發劑引發了聚合的聚合性化合物的聚合的化合物、或增感劑。包含聚合引發助劑(D1)的情況下，通常與聚合引發劑(D)組合使用。 The polymerization initiation aid (D1) is a compound or a sensitizer for promoting the polymerization of a polymerizable compound in which the polymerization is initiated by the polymerization initiator. When a polymerization initiator (D1) is contained, it is usually used in combination with a polymerization initiator (D).

作為聚合引發助劑(D1)，可列舉胺化合物、烷氧基蒽化合物、噻噸酮化合物和羧酸化合物等。 Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

作為上述胺化合物，可列舉三乙醇胺、甲基二乙醇胺、三異丙醇胺等鏈烷醇胺；4-二甲基氨基苯甲酸甲酯、4-二甲基氨基苯甲酸乙酯、4-二甲基氨基苯甲酸異戊酯、苯甲酸2-二甲基氨基乙酯、4-二甲基氨基苯甲酸2-乙基己酯等氨基苯甲酸酯；N,N-二甲基對甲苯胺、4,4’-雙(二甲基氨基)二苯甲酮(通稱米蚩酮)、4,4’-雙(二乙基氨基)二苯甲酮、4,4’-雙(乙基甲基氨基)二苯甲酮等烷基氨基二苯甲酮等；其中，優選烷基氨基二苯甲酮，優選4,4’-雙(二乙基氨基)二苯甲酮。可使用EAB-F(保土谷化學工業(株)製造)等的市售品。 Examples of the amine compound include alkanolamines such as triethanolamine, methyldiethanolamine, and triisopropanolamine; methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Aminobenzoates such as dimethylaminobenzoic acid isoamyl, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate; N, N-dimethyl para Toluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as stilbone), 4,4'-bis (diethylamino) benzophenone, 4,4'-bis ( Alkylaminobenzophenones, such as ethylmethylamino) benzophenone; Among these, alkylaminobenzophenones are preferable, and 4,4'-bis (diethylamino) benzophenone is preferable. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can be used.

作為上述烷氧基蒽化合物，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.

作為上述噻噸酮化合物，可列舉2-異丙基噻噸酮、4-異丙基噻噸酮、2,4-二乙基噻噸酮、2,4-二氯噻噸酮、1-氯-4-丙氧基噻噸酮等。 Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Chloro-4-propoxythioxanthone and the like.

包含上述噻噸酮化合物的情況下，其含量在聚合引發助劑100質量份中，優選為50質量份以上、100質量份以下，更優選為70質量份以上、99質量份以下。 When the thioxanthone compound is contained, the content thereof is preferably 100 parts by mass or more and 100 parts by mass or less, and more preferably 70 parts by mass or more and 99 parts by mass or less in 100 parts by mass of the polymerization initiation aid.

作為上述羧酸化合物，可列舉苯基硫烷基醋酸、甲基苯基硫烷基醋酸、乙基苯基硫烷基醋酸、甲基乙基苯基硫烷基醋酸、二甲基苯基硫烷基醋酸、甲氧基苯基硫烷基醋酸、二甲氧基苯基硫烷基醋酸、氯苯基硫烷基醋酸、 二氯苯基硫烷基醋酸、N-苯基甘氨酸、苯氧基醋酸、萘硫基醋酸、N-萘基甘氨酸、萘氧基醋酸等。 Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, and dimethylphenylsulfanyl. Alkylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, Dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, and the like.

作為聚合引發助劑(D1)，優選噻噸酮化合物。 As the polymerization initiation aid (D1), a thioxanthone compound is preferable.

使用這些聚合引發助劑(D1)的情形下，其含量相對於樹脂(B)和聚合性化合物(C)的合計量100質量份，優選為0.1~30質量份，更優選為1~20質量份。 When using these polymerization initiation aids (D1), the content is preferably 0.1 to 30 parts by mass, 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). Serving.

另外，使用聚合引發助劑(D1)的情況下，其含量相對於聚合引發劑(D)的合計量100質量份，優選為5~500質量份，更優選為10~300質量份，進一步優選為15~250質量份。如果聚合引發助劑(D1)的量在該範圍內，則能夠進一步以高感度形成著色圖案，濾色器的生產率傾向於提高。 When the polymerization initiation aid (D1) is used, the content is preferably 5 to 500 parts by mass, more preferably 10 to 300 parts by mass, and more preferably 100 parts by mass with respect to the total amount of the polymerization initiator (D). It is 15 to 250 parts by mass. When the amount of the polymerization initiation aid (D1) is within this range, a colored pattern can be further formed with high sensitivity, and the productivity of the color filter tends to increase.

<硫醇化合物(T)> <Thiol compound (T)>

本發明的著色固化性樹脂組合物優選還包含硫醇化合物(T)。 The colored curable resin composition of the present invention preferably further contains a thiol compound (T).

上述硫醇化合物為在分子內具有硫烷基(-SH)的化合物。 The thiol compound is a compound having a sulfanyl group (-SH) in the molecule.

作為在分子內具有1個硫烷基的化合物，可列舉例如2-硫烷基噁唑、2-硫烷基噻唑、2-硫烷基苯并咪唑、2-硫烷基苯并噻唑、2-硫烷基苯并噁唑、2-硫烷基烴酸、2-硫烷基吡啶、2-硫烷基吡啶-3-硫醇、2-硫烷基吡啶-N-氧化物、4-氨基-6-羥基-2-硫烷基嘧啶、4-氨基-6-羥基-2-硫烷基嘧啶、4-氨基-2-硫烷基嘧啶、6-氨基-5-亞硝基-2-硫尿嘧啶、4,5-二氨基-6-羥基-2-硫烷基嘧啶、4,6-二氨基-2-硫烷基嘧啶、2,4-二氨基-6-硫烷基嘧啶、4,6-二羥基-2-硫烷基嘧啶、4,6-二甲 基-2-硫烷基嘧啶、4-羥基-2-硫烷基-6-甲基嘧啶、4-羥基-2-硫烷基-6-丙基嘧啶、2-硫烷基-4-甲基嘧啶、2-硫烷基嘧啶、2-硫尿嘧啶、3,4,5,6-四氫嘧啶-2-硫醇、4,5-二苯基咪唑-2-硫醇、2-硫烷基咪唑、2-硫烷基-1-甲基咪唑、4-氨基-3-肼基-5-硫烷基-1,2,4-***、3-氨基-5-硫烷基-1,2,4-***、2-甲基-4H-1,2,4-***-3-硫醇、4-甲基-4H-1,2,4-***-3-硫醇、3-硫烷基1H-1,2,4-***-3-硫醇、2-氨基-5-硫烷基-1,3,4-噻二唑、5-氨基-1,3,4-噻二唑-2-硫醇、2,5-二硫烷基-1,3,4-噻二唑、(呋喃-2-基)甲烷硫醇、2-硫烷基-5-噻唑烷酮、2-硫烷基噻唑啉、2-硫烷基-4(3H)-喹唑啉酮、1-苯基-1H-四唑-5-硫醇、2-喹啉硫醇、2-硫烷基-5-甲基苯并咪唑、2-硫烷基-5-硝基苯并咪唑、6-氨基-2-硫烷基苯并噻唑、5-氯-2-硫烷基苯并噻唑、6-乙氧基-2-硫烷基苯并噻唑、6-硝基-2-硫烷基苯并噻唑、2-硫烷基萘并咪唑、2-硫烷基萘并噁唑、3-硫烷基-1,2,4-***、4-氨基-6-硫烷基吡唑并[2,4-d]吡啶、2-氨基-6-嘌呤硫醇、6-硫烷基嘌呤、4-硫烷基-1H-吡唑并[2,4-d]嘧啶等。 Examples of the compound having one sulfanyl group in the molecule include 2-sulfanyloxazole, 2-sulfanylthiazole, 2-sulfanyl benzimidazole, 2-sulfanylbenzothiazole, and 2 -Sulfanylbenzoxazole, 2-sulfanyl hydrocarbon acid, 2-sulfanylpyridine, 2-sulfanylpyridine-3-thiol, 2-sulfanylpyridine-N-oxide, 4- Amino-6-hydroxy-2-sulfanylpyrimidine, 4-amino-6-hydroxy-2-sulfanylpyrimidine, 4-amino-2-sulfanylpyrimidine, 6-amino-5-nitroso-2 -Thiouracil, 4,5-diamino-6-hydroxy-2-sulfanylpyrimidine, 4,6-diamino-2-sulfanylpyrimidine, 2,4-diamino-6-sulfanylpyrimidine , 4,6-dihydroxy-2-sulfanylpyrimidine, 4,6-dimethyl Methyl-2-sulfanylpyrimidine, 4-hydroxy-2-sulfanyl-6-methylpyrimidine, 4-hydroxy-2-sulfanyl-6-propylpyrimidine, 2-sulfan-4-methyl Pyrimidine, 2-thioalkylpyrimidine, 2-thiouracil, 3,4,5,6-tetrahydropyrimidine-2-thiol, 4,5-diphenylimidazole-2-thiol, 2-thio Alkyl imidazole, 2-sulfanyl-1-methylimidazole, 4-amino-3-hydrazino-5-sulfanyl-1,2,4-triazole, 3-amino-5-sulfanyl- 1,2,4-triazole, 2-methyl-4H-1,2,4-triazole-3-thiol, 4-methyl-4H-1,2,4-triazole-3-thiol , 3-sulfanyl 1H-1,2,4-triazole-3-thiol, 2-amino-5-sulfanyl-1,3,4-thiadiazole, 5-amino-1,3, 4-thiadiazole-2-thiol, 2,5-dithioalkyl-1,3,4-thiadiazole, (furan-2-yl) methanethiol, 2-thioalkyl-5-thiazole Alkanone, 2-sulfanylthiazoline, 2-sulfanyl-4 (3H) -quinazolinone, 1-phenyl-1H-tetrazol-5-thiol, 2-quinolinethiol, 2 -Sulfanyl-5-methylbenzimidazole, 2-sulfan-5-nitrobenzimidazole, 6-amino-2-sulfanylbenzothiazole, 5-chloro-2-sulfanylbenzene Benzothiazole, 6-ethoxy-2-sulfanylbenzothiazole, 6-nitro-2-sulfanylbenzothiazole, 2-sulfanylnaphthoimidazole, 2-sulfanylnaphthoxazole 3-sulfanyl-1,2,4-triazole, 4-amino-6-sulfanylpyrazolo [2,4-d] pyridine, 2-amino-6-purinethiol, 6-sulfan Purines, 4-sulfanyl-1H-pyrazolo [2,4-d] pyrimidines and the like.

作為在分子內具有2個以上硫烷基的化合物，可列舉己二硫醇、癸二硫醇、1,4-雙(甲基硫烷基)苯、丁二醇雙(3-硫烷基丙酸酯)、丁二醇雙(3-硫烷基乙酸酯)、乙二醇雙(3-硫烷基乙酸酯)、三羥甲基丙烷三(3-硫烷基乙酸酯)、丁二醇雙(3-硫烷基丙酸酯)、三羥甲基丙烷三(3-硫烷基丙酸酯)、三羥甲基丙烷三(3-硫烷基乙酸酯)、季戊四醇四(3-硫烷基丙酸酯)、季戊四醇四(3-硫烷基乙酸酯)、三羥基乙基 三(3-硫烷基丙酸酯)、季戊四醇四(3-硫烷基丁酸酯)、1,4-雙(3-硫烷基丁氧基)丁烷等。 Examples of the compound having two or more sulfanyl groups in the molecule include hexanedithiol, decanedithiol, 1,4-bis (methylsulfanyl) benzene, and butanediol bis (3-sulfanyl) Propionate), butanediol bis (3-sulfanyl acetate), ethylene glycol bis (3-sulfanyl acetate), trimethylolpropane tri (3-sulfanyl acetate) ), Butanediol bis (3-thioalkylpropionate), trimethylolpropane tri (3-thioalkylpropionate), trimethylolpropane tri (3-thioalkylacetate) , Pentaerythritol tetra (3-sulfanylpropionate), pentaerythritol tetra (3-sulfanylacetate), trihydroxyethyl Tris (3-sulfanylpropionate), pentaerythritol tetra (3-sulfanylbutyrate), 1,4-bis (3-sulfanylbutoxy) butane, and the like.

作為硫醇化合物，優選在分子內具有1個硫烷基的化合物，特別優選2-硫烷基苯并噻唑。 As the thiol compound, a compound having one sulfanyl group in the molecule is preferred, and 2-thioalkylbenzothiazole is particularly preferred.

硫醇化合物的含量，在聚合引發助劑100質量份中，優選為0.5質量份~20質量份，更優選為1質量份~15質量份。如果硫醇化合物的含量在該範圍內，則存在感度提高、而且顯影性變得良好的傾向。 The content of the thiol compound is preferably 0.5 to 20 parts by mass, and more preferably 1 to 15 parts by mass in 100 parts by mass of the polymerization initiation aid. When content of a thiol compound exists in this range, there exists a tendency for sensitivity to improve and developability to become favorable.

<溶劑(E)> <Solvent (E)>

本發明的著色固化性樹脂組合物優選還包含溶劑(E)。 The colored curable resin composition of the present invention preferably further contains a solvent (E).

對溶劑(E)並無特別限定，能夠使用該領域中通常使用的溶劑。例如，可列舉酯溶劑(在分子內包含-COO-、不含-O-的溶劑)、醚溶劑(在分子內包含-O-、不含-COO-的溶劑)、醚酯溶劑(在分子內包含-COO-和-O-的溶劑)、酮溶劑(在分子內包含-CO-、不含-COO-的溶劑)、醇溶劑(在分子內包含OH、不含-O-、-CO-和-COO-的溶劑)、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. For example, ester solvents (solvents containing -COO- and -O-free in the molecule), ether solvents (solvents containing -O- and -COO-free in the molecule), ether ester solvents (solvent in the molecule Solvents containing -COO- and -O-), ketone solvents (solvents containing -CO-, -COO-free), alcohol solvents (containing OH in the molecule, -O-, -CO free) -And -COO- solvents), aromatic hydrocarbon solvents, amidine solvents, dimethyl sulfene, and the like.

作為酯溶劑，可列舉乳酸甲酯、乳酸乙酯、乳酸丁酯、2-羥基異丁酸甲酯、醋酸乙酯、醋酸正丁酯、醋酸異丁酯、甲酸戊酯、醋酸異戊酯、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、環己醇乙酸酯和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, amyl formate, isoamyl acetate, Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, cyclohexane Alcohol acetate and γ-butyrolactone, etc.

作為醚溶劑，可列舉乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丙基醚、乙二醇單丁基醚、二甘醇單甲基醚、二甘醇單乙基醚、二甘醇單丁基醚、丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單丙基醚、丙二醇單丁基醚、3-甲氧基-1-丁醇、3-甲氧基-3-甲基丁醇、四氫呋喃、四氫吡喃、1,4-二噁烷、二甘醇二甲基醚、二甘醇二乙基醚、二甘醇甲基乙基醚、二甘醇二丙基醚、二甘醇二丁基醚、茴香醚、苯***和甲基茴香醚等。 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, and diethylene glycol monoethyl ether. Ethyl 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-methyl Oxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, Diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyl ether and methyl anisole.

作為醚酯溶劑，可列舉甲氧基醋酸甲酯、甲氧基醋酸乙酯、甲氧基醋酸丁酯、乙氧基醋酸甲酯、乙氧基醋酸乙酯、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、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、丙二醇單丙基醚乙酸酯、乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、二甘醇單乙基醚乙酸酯、二甘醇單丁基醚乙酸酯和二丙二醇甲基醚乙酸酯等。 Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-methoxypropionate. Ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate Esters, 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 mono Ethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, two Glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, and the like.

作為酮溶劑，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、雙丙酮醇、環戊酮、環己酮和異佛爾酮等。 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-pentan Ketones, diacetone alcohol, cyclopentanone, cyclohexanone and isophorone.

作為醇溶劑，可列舉甲醇、乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、丙二醇和甘油等。 Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerol.

作為芳香族烴溶劑，可列舉苯、甲苯、二甲苯和1,3,5-三甲基苯等。 Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and 1,3,5-trimethylbenzene.

作為醯胺溶劑，可列舉N,N-二甲基甲醯胺、N,N-二甲基乙醯胺和N-甲基吡咯烷酮等。 Examples of the amidine solvent include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

上述的溶劑中，從塗布性、乾燥性的方面出發，優選1atm下的沸點為120℃以上180℃以下的有機溶劑。作為溶劑，優選丙二醇單甲基醚乙酸酯、乳酸乙酯、丙二醇單甲基醚、3-乙氧基丙酸乙酯、乙二醇單甲基醚、二甘醇單甲基醚、二甘醇單乙基醚、雙丙酮醇、4-羥基-4-甲基-2-戊酮和N,N-二甲基甲醯胺，更優選丙二醇單甲基醚乙酸酯、丙二醇單甲基醚、乳酸乙酯、雙丙酮醇和3-乙氧基丙酸乙酯。 Among the solvents described above, an organic solvent having a boiling point of 1 to 120 ° C. or higher and 180 ° C. or lower at 1 atm is preferred from the viewpoints of coating properties and drying properties. As the solvent, 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. Glycol monoethyl ether, diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone and N, N-dimethylformamide, more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether Ether, ethyl lactate, diacetone alcohol, and ethyl 3-ethoxypropionate.

溶劑(E)的含量，相對於本發明的著色固化性樹脂組合物的總量，優選為35~95質量%，更優選為40~92質量%。換言之，著色固化性樹脂組合物的固體成分的總量優選為5~65質量%，更優選為8~60質量%。如果溶劑(E)的含量在上述的範圍內，塗布時的平坦性變得良好，而且在形成了濾色器時由於色濃度沒有不足，因此存在顯示特性變得良好的傾向。 The content of the solvent (E) is preferably 35 to 95% by mass, and more preferably 40 to 92% by mass based on the total amount of the colored curable resin composition of the present invention. In other words, the total amount of the solid content of the colored curable resin composition is preferably 5 to 65% by mass, and more preferably 8 to 60% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating becomes good, and since the color density is not insufficient when the color filter is formed, the display characteristics tend to be good.

<流平劑(F)> <Leveling agent (F)>

本發明的著色固化性樹脂組合物可含有流平劑(F)。 The colored curable resin composition of the present invention may contain a leveling agent (F).

作為流平劑(F)，可列舉有機矽系表面活性劑、氟系表面活性劑和具有氟原子的有機矽系表面活性劑等。這些可在側鏈具有聚合性基團。 Examples of the leveling agent (F) include a silicone-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom. These may have a polymerizable group in a side chain.

作為有機矽系表面活性劑，可列舉在分子內具有矽氧烷鍵的表面活性劑等。具體地，可列舉

Figure TWI679499B_D0109
DC3PA、同SH7PA、同DC11PA、同SH21PA、同SH28PA、同SH29PA、同SH30PA、同SH8400(商品名：東麗-道康寧(株)製造)、KP321、KP322、KP323、KP324、KP326、KP340、KP341(信越化學工業(株)製造)、TSF400、TSF401、TSF410、TSF4300、TSF4440、TSF4445、TSF-4446、TSF4452和TSF4460(
Figure TWI679499B_D0110
Figure TWI679499B_D0111
合同會社製造)等。 Examples of the silicone-based surfactant include a surfactant having a siloxane bond in the molecule. Specifically, it can be enumerated
Figure TWI679499B_D0109
DC3PA, the same as SH7PA, the same as DC11PA, the same as SH21PA, the same as SH28PA, the same as SH29PA, the same as SH30PA, and the same as SH8400 (trade names: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 ( (Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 (
Figure TWI679499B_D0110
Figure TWI679499B_D0111
Contract company)).

作為上述的氟系表面活性劑，可列舉在分子內具有氟碳鏈的表面活性劑等。具體地，可列舉

Figure TWI679499B_D0112
(註冊商標)FC430、同FC431(住友
Figure TWI679499B_D0113
(株)製造)、
Figure TWI679499B_D0114
Figure TWI679499B_D0115
(註冊商標)F142D、同F171、同F172、同F173、同F177、同F183、同F554、同R30、同RS-718-K(DIC(株)製造)、
Figure TWI679499B_D0116
(註冊商標)EF301、同EF303、同EF351、同EF352(三菱
Figure TWI679499B_D0117
電子化成(株)製造)、
Figure TWI679499B_D0118
(註冊商標)S381、同S382、同SC101、同SC105(旭硝子(株)製造)和E5844((株)
Figure TWI679499B_D0119
研究所製造)等。 Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Specifically, it can be enumerated
Figure TWI679499B_D0112
(Registered trademark) FC430, same as FC431 (Sumitomo
Figure TWI679499B_D0113
Co., Ltd.),
Figure TWI679499B_D0114
Figure TWI679499B_D0115
(Registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K (manufactured by DIC Corporation),
Figure TWI679499B_D0116
(Registered trademark) EF301, same EF303, same EF351, same EF352 (Mitsubishi
Figure TWI679499B_D0117
(Manufactured by Electrochemical Corporation),
Figure TWI679499B_D0118
(Registered trademark) S381, same S382, same SC101, same SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured company)
Figure TWI679499B_D0119
Research Institute)).

作為上述的具有氟原子的有機矽系表面活性劑，可列舉在分子內具有矽氧烷鍵和氟碳鏈的表面活性劑等。具體地，可列舉

Figure TWI679499B_D0120
(註冊商標)R08、同BL20、同F475、同F477和同F443(DIC(株)製造)等。 Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, it can be enumerated
Figure TWI679499B_D0120
(Registered trademark) R08, same BL20, same F475, same F477 and same F443 (manufactured by DIC Corporation), etc.

流平劑(F)的含量，相對於著色固化性樹脂組合 物的總量，優選為0.001質量%以上0.2質量%以下，更優選為0.002質量%以上0.1質量%以下，進一步優選為0.01質量%以上0.05質量%以下。應予說明，在該含量中不含上述顏料分散劑的含量。如果流平劑(F)的含量在上述的範圍內，則能夠使濾色器的平坦性變得良好。 Content of leveling agent (F) with respect to coloring curable resin combination The total amount of the substance is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass or less, and still more preferably 0.01% by mass or more and 0.05% by mass or less. The content of the pigment dispersant is not included in the content. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be made good.

<其他成分> <Other ingredients>

本發明的著色固化性樹脂組合物，根據需要，可包含填充劑、其他的高分子化合物、密合促進劑、抗氧化劑、光穩定劑、鏈轉移劑等該技術領域中公知的添加劑。 The colored curable resin composition of the present invention may contain additives known in the technical field such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, and chain transfer agents, as necessary.

作為上述的密合促進劑，可列舉例如乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三(2-甲氧基乙氧基)矽烷、N-(2-氨基乙基)-3-氨基丙基甲基二甲氧基矽烷、N-(2-氨基乙基)-3-氨基丙基三甲氧基矽烷、3-氨基丙基三乙氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基甲基二甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-氯丙基甲基二甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷等。 Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (2-methoxyethoxy) silane, and N- (2-aminoethyl). -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidyloxy Propyltrimethoxysilane, 3-glycidyloxymethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethyl Oxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and the like.

<著色固化性樹脂組合物的製造方法> <Manufacturing method of colored curable resin composition>

本發明的著色固化性樹脂組合物，能夠通過將例如著色劑(A)、樹脂(B)、聚合性化合物(C)、聚合引發劑(D)、以及根據需要使用的溶劑(E)、流平劑(F)、聚合引發助劑(D1)和其他成分混合而製備。 The colored curable resin composition of the present invention can be prepared by, for example, coloring agent (A), resin (B), polymerizable compound (C), polymerization initiator (D), and solvent (E) used as needed, and The leveling agent (F), the polymerization initiation aid (D1), and other components are prepared by mixing.

對於染料，可預先分別溶解於溶劑(E)的一部分或全部 中而製備溶液。優選用孔徑0.01~1μm左右的過濾器將該溶液過濾。 The dye can be separately dissolved in part or all of the solvent (E) in advance Medium to prepare a solution. This solution is preferably filtered with a filter having a pore size of about 0.01 to 1 μm.

優選用孔徑0.01~10μm左右的過濾器將混合後的著色固化性樹脂組合物過濾。 It is preferable to filter the colored curable resin composition after mixing with a filter having a pore size of about 0.01 to 10 μm.

<濾色器和液晶顯示裝置的製造方法> <Manufacturing Method of Color Filter and Liquid Crystal Display Device>

作為由本發明的著色固化性樹脂組合物形成濾色器的方法，可列舉光刻法及使用噴墨設備的方法等。光刻法是例如將本發明的著色固化性樹脂組合物塗布於基板上，將溶劑等揮發成分除去等，使其乾燥而形成著色組合物層，經由光掩模將該著色組合物層曝光而顯影的方法。顯影後，根據需要通過進行加熱，能夠形成著色圖案。上述著色圖案的形成方法中，通過在曝光時不使用光掩模和/或不顯影，從而能夠形成作為上述著色組合物層的固化物的著色塗膜。能夠使這樣得到的著色圖案和著色塗膜作為濾色器。 Examples of a method for forming a color filter from the colored curable resin composition of the present invention include a photolithography method and a method using an inkjet device. The photolithography method is, for example, applying the colored curable resin composition of the present invention to a substrate, removing a volatile component such as a solvent, etc., and drying it to form a colored composition layer, and exposing the colored composition layer through a photomask to Development method. After development, if necessary, a colored pattern can be formed by heating. In the method for forming a colored pattern, a colored coating film that is a cured product of the colored composition layer can be formed by using no photomask and / or no development during exposure. The coloring pattern and colored coating film obtained in this way can be used as a color filter.

作為基板，可使用樹脂板、矽、在上述基板上形成了鋁、銀、銀/銅/鈀合金薄膜等的產物。在這些基板上可形成另外的濾色器層、樹脂層、電晶體、電路等。 As the substrate, a resin plate, silicon, or a product obtained by forming an aluminum, silver, silver / copper / palladium alloy film, or the like on the substrate can be used. Additional color filter layers, resin layers, transistors, circuits, etc. can be formed on these substrates.

對製作的濾色器的膜厚並無特別限定，能夠根據目的的用途等適當調整，例如，為0.1~30μm，優選為1~20μm，更優選為1~6μm。 The thickness of the produced color filter is not particularly limited, and can be appropriately adjusted according to the intended use and the like, and is, for example, 0.1 to 30 μm, preferably 1 to 20 μm, and more preferably 1 to 6 μm.

採用光刻法的各色圖元的形成能夠在公知或慣用的裝置、條件下進行。例如，能夠如下所述製作。 The formation of each color element using the photolithography method can be performed under a known or conventional apparatus and conditions. For example, it can be produced as follows.

首先，將著色固化性樹脂組合物塗布在基板上，通過加熱乾燥(預烘焙)和/或減壓乾燥，從而將溶劑等揮發成分 除去而乾燥，得到平滑的著色組合物層。 First, a colored curable resin composition is coated on a substrate, and volatile components such as solvents are dried by heating (pre-baking) and / or drying under reduced pressure. It was removed and dried to obtain a smooth coloring composition layer.

作為塗布方法，可列舉旋塗法、狹縫塗布法、狹縫和旋轉塗布法等。 Examples of the coating method include a spin coating method, a slit coating method, a slit and a spin coating method, and the like.

接下來，對於著色組合物層，經由用於形成目標的著色圖案的光掩模而曝光。 Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern.

由於能夠對曝光面全體均勻地照射平行光線，進行光掩模和形成了著色組合物層的基板的正確的對位，因此優選使用掩模對準器和步進器等曝光裝置。 Since the entire exposure surface can be uniformly irradiated with parallel light rays, and accurate alignment of the photomask and the substrate on which the coloring composition layer is formed, an exposure device such as a mask aligner and a stepper is preferably used.

通過使曝光後的著色組合物層與顯影液接觸而顯影，從而在基板上形成著色圖案。通過顯影，著色組合物層的未曝光部在顯影液中溶解而被除去。作為顯影液，優選例如氫氧化鉀、碳酸氫鈉、碳酸鈉、氫氧化四甲基銨等鹼性化合物的水溶液。 The coloring composition layer after exposure is developed by contacting with the developing solution, thereby forming a coloring pattern on the substrate. By the development, the unexposed part of the coloring composition layer is dissolved in the developing solution and removed. As the developing solution, for example, an aqueous solution of a basic compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide is preferable.

顯影方法可以是浸沒式(

Figure TWI679499B_D0121
)法、浸漬法和噴霧法等的任一種。進而，在顯影時可使基板傾斜任意的角度。 The development method can be immersion (
Figure TWI679499B_D0121
) Method, dipping method and spray method. Furthermore, the substrate can be tilted at an arbitrary angle during development.

顯影後優選進行水洗。 After development, washing with water is preferred.

進而，優選對得到的著色圖案進行後烘焙。 Furthermore, it is preferable to post-bake the obtained coloring pattern.

根據本發明的著色固化性樹脂組合物，能夠製作形狀特別優異的濾色器。該濾色器可用作用於顯示裝置(例如，液晶顯示裝置、有機EL裝置、電子紙等)和固體攝像元件的濾色器。 According to the colored curable resin composition of the present invention, a color filter having a particularly excellent shape can be produced. This color filter can be used as a color filter for a display device (for example, a liquid crystal display device, an organic EL device, an electronic paper, etc.) and a solid-state imaging element.

[實施例] [Example]

以下列舉實施例對本發明更具體地說明，但本發明當然並不受下述實施例限制，當然也可以在可適合前述 後述的主旨的範圍內適當地加以改變而實施，這些都包含在本發明的技術範圍內。應予說明，以下中只要無特別說明，“份”意味著“質量份”，“%”意味著“質量%”。 The following examples are given to explain the present invention more specifically, but the present invention is not limited to the following examples. The scope of the subject matter described later is appropriately changed and implemented, and these are included in the technical scope of the present invention. It should be noted that "part" means "mass part" and "%" means "mass%" unless otherwise specified.

以下的合成例中，化合物採用質量品質分析(LC；Agilent製1200型、MASS；Agilent製LC/MSD型)或元素分析(VARIO-EL；(

Figure TWI679499B_D0122
(株)製))鑒定。 In the following synthesis examples, compounds were analyzed by mass spectrometry (LC; Agilent 1200 type, MASS; Agilent LC / MSD type) or elemental analysis (VARIO-EL; (
Figure TWI679499B_D0122
Co., Ltd.)) identification.

[合成例1] [Synthesis example 1]

在具備回流冷凝器、滴液漏斗和攪拌器的燒瓶內使氮以0.02L/分流入而成為氮氣氛，裝入3-甲氧基-1-丁醇200質量份及3-甲氧基丁基乙酸酯105質量份，邊攪拌邊加熱到70℃。接下來，將甲基丙烯酸60質量份、丙烯酸3,4-環氧三環[5.2.1.02,6]癸酯(由式(I-1)表示的化合物及由式(II-1)表示的化合物的摩爾比50：50的混合物。)240質量份溶解於3-甲氧基丁基乙酸酯140質量份中而調製溶液，使用滴液漏斗、歷時4小時將該溶解液滴入保溫於70℃的燒瓶內。另一方面，將聚合引發劑2,2’-偶氮雙(2,4-二甲基戊腈)30質量份溶解於3-甲氧基丁基乙酸酯225質量份的溶液使用另外的滴液漏斗歷時4小時滴入燒瓶內。聚合引發劑的溶液的滴入結束後，在70℃保持4小時，然後冷卻到室溫，得到了固體成分32.6質量%、酸值110mg-KOH/g(固體成分換算)的樹脂B’1溶液。得到的樹脂B’1的重均分子量Mw為13,400，分子量分佈為2.50。 In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen was introduced at 0.02 L / min to form a nitrogen atmosphere, and 200 parts by mass of 3-methoxy-1-butanol and 3-methoxybutane were charged. 105 parts by mass of ethyl acetate was heated to 70 ° C while stirring. Next, 60 parts by mass of methacrylic acid and 3,4-epoxytricyclo [5.2.1.0 2,6 ] decyl acrylate (a compound represented by the formula (I-1) and a compound represented by the formula (II-1) A mixture of 50:50 molar ratio of the compound.) 240 parts by mass was dissolved in 140 parts by mass of 3-methoxybutyl acetate to prepare a solution, and the dissolving solution was dropped into the heat preservation solution using a dropping funnel over 4 hours. Inside a 70 ° C flask. On the other hand, a solution in which 30 parts by mass of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in 225 parts by mass of 3-methoxybutyl acetate was used separately. The dropping funnel was dripped into the flask over 4 hours. 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 resin B'1 solution having a solid content of 32.6% by mass and an acid value of 110 mg-KOH / g (solid content conversion) was obtained . The weight average molecular weight Mw of the obtained resin B'1 was 13,400, and the molecular weight distribution was 2.50.

合成例1中得到的樹脂的重均分子量(Mw)及數均分子量(Mn)的測定使用GPC法，在以下的條件下進行。 The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin obtained in Synthesis Example 1 were measured using the GPC method under the following conditions.

裝置；K2479((株)島津製作所製) Installation; K2479 (manufactured by Shimadzu Corporation)

柱；SHIMADZU Shim-pack GPC-80M Column; SHIMADZU Shim-pack GPC-80M

柱溫度；40℃ Column temperature; 40 ° C

溶劑；THF(四氫呋喃) Solvent; THF (tetrahydrofuran)

流速；1.0mL/min Flow rate; 1.0mL / min

檢測器；RI Detector; RI

校正用標準物質；TSK STANDARD POLYSTYRENE F-40、F-4、F-288、A-2500、A-500(東曹(株)製) Calibration Standards; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

將上述得到的聚苯乙烯換算的重均分子量及數均分子量之比(Mw/Mn)作為分子量分佈。 The ratio of the weight-average molecular weight and the number-average molecular weight (Mw / Mn) in terms of polystyrene obtained as described above was used as the molecular weight distribution.

[實施例1~3及比較例1~4] [Examples 1 to 3 and Comparative Examples 1 to 4]

以成為表11中所示的組成的方式將各成分混合，得到了著色固化性樹脂組合物。 Each component was mixed so that it might become a composition shown in Table 11, and the colored curable resin composition was obtained.

表11中，各成分如以下所述。 In Table 11, each component is as follows.

著色劑(A-1)：由式(1)表示的化合物

Figure TWI679499B_D0125
Colorant (A-1): a compound represented by formula (1)
Figure TWI679499B_D0125

著色劑(A-2)：由式(2)表示的化合物

Figure TWI679499B_D0126
Colorant (A-2): Compound represented by formula (2)
Figure TWI679499B_D0126

著色劑(A-3)：鹼性藍7(東京化成工業(株)製造)

Figure TWI679499B_D0127
Colorant (A-3): Basic Blue 7 (manufactured by Tokyo Chemical Industry Co., Ltd.)
Figure TWI679499B_D0127

著色劑(A-4)：由式(Ac1-1)表示的化合物

Figure TWI679499B_D0128
Colorant (A-4): a compound represented by the formula (Ac1-1)
Figure TWI679499B_D0128

樹脂(B)：合成例1中得到的樹脂B’1 Resin (B): Resin B'1 obtained in Synthesis Example 1

聚合性化合物(C)：(商品名：A-TMM-3LM-N，新中村化學工業(株)製造) Polymerizable compound (C): (trade name: A-TMM-3LM-N, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)

聚合引發劑(D-1)：由式(d1-40)表示的化合物 Polymerization initiator (D-1): a compound represented by the formula (d1-40)

Figure TWI679499B_D0129
Figure TWI679499B_D0129

聚合引發劑(D-2)：1,2-辛二酮，1-[4-(苯硫基)-2-(O-苯 甲醯基肟)](商品名

Figure TWI679499B_D0130
OXE01、BASF社製造) Polymerization initiator (D-2): 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzylideneoxime)] (trade name
Figure TWI679499B_D0130
(OXE01, BASF company)

聚合引發劑(D-3)：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(商品名

Figure TWI679499B_D0131
OXE02、BASF社製造) Polymerization initiator (D-3): N-ethoxyl-1- [9-ethyl-6- (2-methylbenzyl) -9H-carbazol-3-yl] ethane-1 -Imine (trade name
Figure TWI679499B_D0131
(OXE02, BASF company)

聚合引發助劑(D-4)：2,4-二乙基噻噸酮(KAYACURE(註冊商標)DETX-2：日本化藥(株)製造) Polymerization initiation aid (D-4): 2,4-diethylthioxanthone (KAYACURE (registered trademark) DETX-2: manufactured by Nippon Kayaku Co., Ltd.)

聚合引發劑(D-5)：2,2’,4-三(2-氯苯基)-5-(3,4-二甲氧基苯基)-4,5-二苯基-1,1’-聯咪唑(商品名：TCDM、CHEMBRIDGE INTERNATIONAL CORPORATION製造) Polymerization initiator (D-5): 2,2 ', 4-tris (2-chlorophenyl) -5- (3,4-dimethoxyphenyl) -4,5-diphenyl-1, 1'-biimidazole (trade name: TCDM, manufactured by CHEMBRIDGE INTERNATIONAL CORPORATION)

硫醇化合物(T-1)：2-巰基苯并噻唑(商品名

Figure TWI679499B_D0132
M、三新化學工業(株)製造) Thiol compound (T-1): 2-mercaptobenzothiazole (trade name
Figure TWI679499B_D0132
M, Sanxin Chemical Industry Co., Ltd.)

流平劑(F)：聚醚改性矽油(

Figure TWI679499B_D0133
SH8400：東麗-道康寧(株)製造) Leveling agent (F): polyether modified silicone oil (
Figure TWI679499B_D0133
SH8400: manufactured by Toray Dow Corning Co., Ltd.)

添加劑(G)：3-甲基丙烯醯氧基丙基三甲氧基矽烷(KBM-503：信越化學工業(株)製造) Additive (G): 3-methacryloxypropyltrimethoxysilane (KBM-503: manufactured by Shin-Etsu Chemical Co., Ltd.)

溶劑(E)：丙二醇單甲基醚乙酸酯 Solvent (E): propylene glycol monomethyl ether acetate

由上述式(d1-40)表示的化合物按照特表2014-500852號公報中記載的方法製備。 The compound represented by the above formula (d1-40) is prepared according to the method described in Japanese Patent Application Publication No. 2014-500852.

[塗膜的形成] [Formation of coating film]

將2英寸見方的玻璃基板(

Figure TWI679499B_D0134
XG；道康寧社製造)用中性洗劑、水及醇依次清洗後乾燥。在該玻璃基板上將上述得到的著色固化性樹脂組合物旋塗以使後烘焙後的膜厚成為3.0μm，接下來在清潔烘箱中、90℃下預烘焙3分鐘。 然後，在230℃下加熱20分鐘，得到了塗膜。 Place a 2-inch square glass substrate (
Figure TWI679499B_D0134
XG; manufactured by Dow Corning Corporation). Wash with a neutral lotion, water, and alcohol in this order and then dry. The colored curable resin composition obtained above was spin-coated on this glass substrate so that the film thickness after post-baking became 3.0 μm, and then pre-baked in a clean oven at 90 ° C. for 3 minutes. Then, it heated at 230 degreeC for 20 minutes, and obtained the coating film.

[圖案的製作] [Making of patterns]

在2英寸見方的玻璃基板(

Figure TWI679499B_D0135
2000；道康寧社製造)上將著色固化性樹脂組合物採用旋塗法塗布以使後烘焙後的膜厚成為2.0μm後，在100℃下預烘焙3分鐘，形成了組合物層。冷卻後，使形成了組合物層的基板與石英玻璃製光掩模的間隔為80μm，使用曝光機(TME-150RSK；
Figure TWI679499B_D0136
Figure TWI679499B_D0137
(株)製造)，在大氣氣氛下、40mJ/cm2的曝光量(365nm基準)下進行光照射。應予說明，作為光掩模，使用形成50μm的線和間隙圖案的光掩模。使光照射後的組合物層在包含非離子系表面活性劑0.12%和氫氧化鉀0.04%的水溶液中在25℃下浸漬60秒而顯影，水洗後，在烘箱中、230℃下進行20分鐘後烘焙，從而得到了圖案。對於得到的圖案，使用膜厚測定裝置(DEKTAK3；日本真空技術(株)製造)測定了膜厚，結果確認為2.0μm。 On a 2-inch square glass substrate (
Figure TWI679499B_D0135
2000; manufactured by Dow Corning) was applied on the colored curable resin composition by a spin coating method so that the film thickness after post-baking was 2.0 μm, and then pre-baked at 100 ° C. for 3 minutes to form a composition layer. After cooling, the distance between the substrate on which the composition layer was formed and the photomask made of quartz glass was 80 μm, and an exposure machine (TME-150RSK;
Figure TWI679499B_D0136
Figure TWI679499B_D0137
(Manufactured by Co., Ltd.), and light irradiation was performed at an exposure amount (based on 365 nm) of 40 mJ / cm 2 in an atmospheric atmosphere. In addition, as a photomask, the photomask which formed a 50 micrometer line and gap pattern was used. The composition layer after light irradiation was immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ° C for 60 seconds for development. After washing with water, the composition layer was subjected to an oven at 230 ° C for 20 minutes. After baking, the pattern is obtained. The obtained pattern was measured for film thickness using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.), and it was confirmed to be 2.0 μm.

對於實施例1~3及比較例1~4中得到的著色圖案，使用掃描型電子顯微鏡(S-4000；(株)日立

Figure TWI679499B_D0138
Figure TWI679499B_D0139
製造)，分別觀察形狀。圖1中，如果為由(p1)表示的形狀(所謂的正錐形形狀)，則記為○，如果為由(p2)表示的形狀，則記為×。如果為由(p1)表示的形狀，在著色圖案上層疊無機膜時存在在無機膜不易產生龜裂、剝離的傾向，為良好。將結果示於表12。 For the colored patterns obtained in Examples 1 to 3 and Comparative Examples 1 to 4, a scanning electron microscope (S-4000; Hitachi, Ltd.) was used.
Figure TWI679499B_D0138
Figure TWI679499B_D0139
(Manufacturing), and observe the shape separately. In FIG. 1, a shape represented by (p1) (so-called forward tapered shape) is denoted by ○, and a shape represented by (p2) is denoted by ×. If it is a shape represented by (p1), when an inorganic film is laminated | stacked on a colored pattern, there exists a tendency for the inorganic film not to generate | occur | produce cracks and peeling easily, and it is favorable. The results are shown in Table 12.

產業上的利用可能性 Industrial availability

根據本發明，可以提供能夠形成良好的著色圖案的著色固化性樹脂組合物。 According to this invention, the coloring curable resin composition which can form a favorable coloring pattern can be provided.

由本發明的著色固化性樹脂組合物得到的圖案及塗膜可用作構成濾色器基板和/或陣列基板的一部分的透明膜、圖案、光間隔物、外敷層、絕緣膜、液晶取向控制用突起、微透鏡、塗層等，可以在具備這些塗膜或圖案作為其構成部件的一部分的濾色器基板、陣列基板等、進而具備這些濾色器基板和/或陣列基板的顯示裝置、例如液晶顯示裝置、有機EL裝置、電子紙等中優選地利用。 The pattern and coating film obtained from the colored curable resin composition of the present invention can be used as a transparent film, a pattern, a photo spacer, an overcoat layer, an insulating film, and a liquid crystal alignment control constituting a part of a color filter substrate and / or an array substrate. The protrusions, microlenses, coatings, and the like may be provided in a color filter substrate, an array substrate, or the like that includes these coating films or patterns as part of its constituent members, or a display device that includes these color filter substrates and / or array substrates, for example, It is preferably used in a liquid crystal display device, an organic EL device, an electronic paper, and the like.

Claims (5)

一種著色固化性樹脂組合物，其含有著色劑、樹脂、聚合性化合物和聚合引發劑；其中，作為上述著色劑，包含染料；上述染料的含量在著色劑100質量份中為90質量份以上，上述聚合引發劑包含由下述式(d1)表示的化合物及聯咪唑化合物，上述染料包含選自由二苯并哌喃染料、三芳基甲烷染料、由式(Ab2)表示的化合物、香豆素染料、蒽醌染料、和四氮雜卟啉染料所組成之群組中的至少一種染料；式(d1)中，Rd1表示可具有取代基的碳數6~18的芳香族烴基、可具有取代基的碳數3~36的雜環基、可具有取代基的碳數1~15的烷基、或可具有取代基的碳數7~33的芳烷基，上述烷基或芳烷基中所含的亞甲基(-CH2-)可被替換為-O-、-CO-、-S-、-SO2-或-N(Rd5)-，Rd2表示碳數6~18的芳香族烴基、碳數3~36的雜環基、或碳數1~10的烷基，Rd3表示可具有取代基的碳數6~18的芳香族烴基、可具有取代基的碳數3~36的雜環基，Rd4表示可具有取代基的碳數6~18的芳香族烴基、或可具有取代基的碳數1~15的脂肪族烴基，上述脂肪族烴基中所含的亞甲基(-CH2-)可被替換為-O-、-CO-或-S-，上述脂肪族烴基中所含的次甲基(-CH<)可被替換為-PO3<，上述脂肪族烴基中所含的氫原子可被OH基取代，Rd5表示碳數1~10的烷基，該烷基中所含的亞甲基(-CH2-)可被替換為-O-或-CO-；式(Ab2)中，R41~R44各自獨立地表示氫原子、碳數1~20的飽和烴基、可具有取代基的碳數6~20的芳香族烴基或可具有取代基的碳數7~30的芳烷基，該碳數1~20的飽和烴基中，該飽和烴基中所含的氫原子可被取代或未取代的氨基或鹵素原子取代，該飽和烴基的碳數為2~20的情況下，該飽和烴基中所含的亞甲基可被氧原子或-CO-置換，不過，該碳數2~20的飽和烴基中鄰接的亞甲基不會同時地被氧原子置換，末端的亞甲基不會被氧原子或-CO-置換，R41與R42可結合並與它們結合的氮原子一起形成環，R43與R44可結合並與它們結合的氮原子一起形成環，R47~R54各自獨立地表示氫原子、鹵素原子、硝基、羥基、或碳數1~8的烷基，該烷基的碳數為2~8的情況下，構成該烷基的亞甲基可以被氧原子或-CO-置換，R48與R52可相互結合而形成-NH-、-S-或-SO2-，不過，該烷基中，鄰接的亞甲基不會同時被氧原子置換，末端的亞甲基不會被氧原子或-CO-置換，環T1表示可具有取代基的碳數3~10的芳香族雜環，[Y]m-表示任意的m價的陰離子。A colored curable resin composition comprising a colorant, a resin, a polymerizable compound, and a polymerization initiator; wherein the colorant includes a dye; and the content of the dye is 90 parts by mass or more in 100 parts by mass of the colorant, The polymerization initiator includes a compound represented by the following formula (d1) and a biimidazole compound, and the dye includes a compound selected from a dibenzopiperan dye, a triarylmethane dye, a compound represented by the formula (Ab2), and a coumarin dye. At least one dye from the group consisting of anthraquinone dye, and tetraazaporphyrin dye; In the formula (d1), R d1 represents an aromatic hydrocarbon group having 6 to 18 carbons which may have a substituent, a heterocyclic group having 3 to 36 carbons which may have a substituent, and 1 to 15 carbons which may have a substituent. An alkyl group or an aralkyl group having 7 to 33 carbon atoms which may have a substituent, and the methylene group (-CH 2- ) contained in the alkyl group or the aralkyl group may be replaced with -O-, -CO- , -S-, -SO 2 -or -N (R d5 )-, R d2 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, a heterocyclic group having 3 to 36 carbon atoms, or an alkyl group having 1 to 10 carbon atoms R d3 represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, and heterocyclic group having 3 to 36 carbon atoms which may have a substituent, and R d4 represents an aromatic group having 6 to 18 carbon atoms which may have a substituent. A hydrocarbon group or an aliphatic hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, and the methylene group (-CH 2- ) contained in the aliphatic hydrocarbon group may be replaced with -O-, -CO-, or -S- The methine group (-CH <) contained in the aliphatic hydrocarbon group may be replaced with -PO 3 <, and the hydrogen atom contained in the aliphatic hydrocarbon group may be substituted by an OH group. R d5 represents a carbon number of 1 to 10 Alkyl group, the methylene group (-CH 2- ) contained in the alkyl group may be replaced with -O- or -CO-; In the formula (Ab2), R 41 to R 44 each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or 7 carbon atoms which may have a substituent. An aralkyl group of ~ 30, in the saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a substituted or unsubstituted amino or halogen atom, and the carbon number of the saturated hydrocarbon group is 2 to 20 In the case, the methylene group contained in the saturated hydrocarbon group may be replaced by an oxygen atom or -CO-, but the adjacent methylene groups in the saturated hydrocarbon group having 2 to 20 carbon atoms will not be replaced by an oxygen atom at the same time. The terminal methylene group will not be replaced by an oxygen atom or -CO-. R 41 and R 42 can be combined to form a ring with the nitrogen atom to which they are bonded. R 43 and R 44 can be combined to form a nitrogen atom with them. A ring, and R 47 to R 54 each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms. When the alkyl group has 2 to 8 carbon atoms, the alkyl group is constituted. methylene may be replaced with an oxygen atom or a -CO-, R 48 and R 52 may be bonded to each other to form a -NH -, - S- or -SO 2 -, however, the alkyl, alkylene adjacent Groups do not simultaneously replaced with an oxygen atom, a methylene group end is not replaced with an oxygen atom or a -CO-, T 1 represents the ring carbon atoms may have a substituent aromatic heterocyclic group having 3 to 10, [Y] m- Represents an arbitrary m-valent anion. 如請求項1所述的著色固化性樹脂組合物，其中，作為上述著色劑，不含顏料。The colored curable resin composition according to claim 1, wherein the colorant does not contain a pigment. 如請求項1所述的著色固化性樹脂組合物，其中，作為上述染料，包含二苯并哌喃染料、和由上述式(Ab2)表示的化合物。The colored curable resin composition according to claim 1, wherein the dye includes a dibenzopiperan dye and a compound represented by the formula (Ab2) as the dye. 一種濾色器，其係由如請求項1所述的著色固化性樹脂組合物所形成者。A color filter formed by the colored curable resin composition according to claim 1. 一種液晶顯示裝置，其包含如請求項4所述的濾色器。A liquid crystal display device includes the color filter according to claim 4.
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