TWI491599B - Compounds and coloring compositions - Google Patents
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- TWI491599B TWI491599B TW100120256A TW100120256A TWI491599B TW I491599 B TWI491599 B TW I491599B TW 100120256 A TW100120256 A TW 100120256A TW 100120256 A TW100120256 A TW 100120256A TW I491599 B TWI491599 B TW I491599B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
- C07D407/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
- C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
- C07D311/82—Xanthenes
- C07D311/84—Xanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
- C07D311/88—Nitrogen atoms
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- C07—ORGANIC CHEMISTRY
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- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
- C07D407/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a carbon chain containing aromatic rings
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- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/12—Amino derivatives of triarylmethanes without any OH group bound to an aryl nucleus
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/28—Pyronines ; Xanthon, thioxanthon, selenoxanthan, telluroxanthon dyes
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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Description
本發明係關於一種有效用作染料之化合物及包含該化合物之著色組合物。The present invention relates to a compound useful as a dye and a colored composition comprising the same.
於液晶顯示面板、電致發光面板及電漿顯示面板等中所使用之顯示裝置用彩色濾光片中,一直使用染料作為著色劑。作為此種染料,例如已知有如C.I.鹼性紅1這樣的二苯并哌喃化合物(專利文獻1)。In a color filter for a display device used in a liquid crystal display panel, an electroluminescence panel, a plasma display panel, or the like, a dye is always used as a colorant. As such a dye, for example, a dibenzopyran compound such as C.I. Basic Red 1 is known (Patent Document 1).
專利文獻1:日本專利特開2001-106712號Patent Document 1: Japanese Patent Laid-Open No. 2001-106712
作為顯示裝置用彩色濾光片之著色劑,若使用移染性高之染料,則該染料會向其他顏色之彩色濾光片或保護層等不含著色劑之樹脂膜移動,從而導致顯示裝置之顯示特性降低。此處,所謂移染性,是指於目標材料中所含之染料以空氣或水蒸氣為介質而附著於其他材料或者被吸收,但上述之二苯并哌喃化合物,存在未必能夠充分滿足移染性之情形。When a dye having a high color shifting property is used as a coloring agent for a color filter for a display device, the dye moves to a resin film containing no coloring agent such as a color filter or a protective layer of another color, thereby causing a display device. The display characteristics are reduced. Here, the term "transferability" means that the dye contained in the target material adheres to other materials or is absorbed by air or water vapor as a medium, but the above-mentioned dibenzopyran compound may not be sufficiently satisfied. The situation of dyeing.
亦即,本發明係提供以下[1]~[6]者。That is, the present invention provides the following [1] to [6].
[1] 一種化合物,其以式(I)而表示,[1] A compound represented by formula (I),
[式(I)中,L表示碳數為1~20之2價飽和烴基,該飽和烴基中所含之氫原子亦可經鹵素原子取代,該飽和烴基中所含之-CH2 -亦可經-CO-或-O-取代;R1 及R2 分別獨立地表示氫原子、亦可具有取代基之碳數為1~16之1價脂肪族烴基或亦可具有取代基之碳數為2~18之醯基;R3 ~R10 分別獨立地表示氫原子、亦可具有取代基之碳數為1~8之1價脂肪族烴基或亦可具有取代基之碳數為6~10之1價芳香族烴基,該脂肪族烴基中所含之-CH2 -亦可經-O-取代;R11 ~R14 分別獨立地表示氫原子或甲基。[In the formula (I), L represents a divalent saturated hydrocarbon group having a carbon number of 1 to 20, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom, and -CH 2 - contained in the saturated hydrocarbon group may also be Substituting -CO- or -O-; R 1 and R 2 each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent, or a carbon number which may have a substituent a thiol group of 2 to 18; R 3 to R 10 each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, or a carbon number which may have a substituent of 6 to 10 The monovalent aromatic hydrocarbon group, -CH 2 - contained in the aliphatic hydrocarbon group may be substituted by -O-; and R 11 to R 14 each independently represent a hydrogen atom or a methyl group.
X1- 及X2- 表示無機陰離子或有機陰離子]。X 1- and X 2- represent an inorganic anion or an organic anion].
[2] 如[1]之化合物,其中L係碳數為5~15之烷二基,該烷二基中所含之-CH2 -亦可經-O-取代。[2] The compound of [1], wherein the L-based carbon number is 5 to 15 alkanediyl, and the -CH 2 - contained in the alkanediyl group may be substituted by -O-.
[3] 一種染料,其以如[1]或[2]之化合物為主成分。[3] A dye containing a compound such as [1] or [2] as a main component.
[4] 一種著色組合物,其包含:選自由樹脂、光聚合性化合物、光聚合起始劑及溶劑所組成之群中之至少1種,及含有如[3]之染料之著色劑。[4] A coloring composition comprising: at least one selected from the group consisting of a resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, and a coloring agent containing the dye of [3].
[5] 一種彩色濾光片,其係使用如[4]之著色組合物而形成。[5] A color filter formed using the coloring composition of [4].
[6] 一種顯示裝置,其包含如[5]之彩色濾光片。[6] A display device comprising the color filter of [5].
本發明之化合物係式(I)所表示之化合物(以下有時稱為「化合物(I)」)。The compound of the present invention is a compound represented by the formula (I) (hereinafter sometimes referred to as "compound (I)").
[式(I)中,L表示碳數為1~20之2價飽和烴基,該飽和烴基中所含之氫原子亦可經鹵素原子取代,該飽和烴基中所含之-CH2 -亦可經-CO-或-O-取代。[In the formula (I), L represents a divalent saturated hydrocarbon group having a carbon number of 1 to 20, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom, and -CH 2 - contained in the saturated hydrocarbon group may also be Substituted by -CO- or -O-.
R1 及R2 分別獨立地表示氫原子、亦可具有取代基之碳數為1~16之1價脂肪族烴基或亦可具有取代基之碳數為2~18之醯基。R 1 and R 2 each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent, or a fluorenyl group having 2 to 18 carbon atoms which may have a substituent.
R3 ~R10 分別獨立地表示氫原子、亦可具有取代基之碳數為1~8之1價脂肪族烴基或亦可具有取代基之碳數為6~10之1價芳香族烴基,該脂肪族烴基中所含之-CH2 -亦可經-O-取代。R 3 to R 10 each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. The -CH 2 - contained in the aliphatic hydrocarbon group may also be substituted by -O-.
R11 ~R14 分別獨立地表示氫原子或甲基。R 11 to R 14 each independently represent a hydrogen atom or a methyl group.
X1- 及X2- 表示無機陰離子或有機陰離子]。X 1- and X 2- represent an inorganic anion or an organic anion].
L表示碳數為1~20之2價直鏈狀飽和烴基,該飽和烴基中所含之氫原子亦可經鹵素原子取代,該飽和烴基中所含之-CH2 -亦可經-CO-或-O-取代。L represents a divalent linear saturated hydrocarbon group having a carbon number of 1 to 20, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom, and -CH 2 - contained in the saturated hydrocarbon group may also be subjected to -CO- Or -O- substituted.
該飽和烴基可為碳數為1~20之烷二基、碳數為3~20之環烷二基及該等基組合而成之碳數為4~20之基中的任意基。The saturated hydrocarbon group may be an alkanediyl group having 1 to 20 carbon atoms, a cycloalkanediyl group having 3 to 20 carbon atoms, and any of the groups having a carbon number of 4 to 20 in combination.
作為上述烷二基,可列舉:亞甲基、伸乙基、丙二基、丙二基、丁二基、戊二基、己二基、庚二基、辛二基、癸二基、十四烷二基及二十烷二基等。Examples of the alkanediyl group include a methylene group, an ethylidene group, a propylenediyl group, a propylenediyl group, a butyldiyl group, a pentanediyl group, a hexyldiyl group, a hexyldiyl group, a octyldiyl group, a fluorenyl group, and a decyl group. Tetralinediyl and eicosanediyl and the like.
作為-CH2 -經-O-取代之烷二基,可列舉:-(CH2 )3 -O-(CH2 )3 -、-(CH2 )3 -O-(CH2 )4 -O-(CH2 )3 -及-(CH2 )3 -O-(CH2 )2 -O-(CH2 )2 -O-(CH2 )3 -等。As the -CH 2 -O-substituted alkanediyl group, -(CH 2 ) 3 -O-(CH 2 ) 3 -, -(CH 2 ) 3 -O-(CH 2 ) 4 -O -(CH 2 ) 3 - and -(CH 2 ) 3 -O-(CH 2 ) 2 -O-(CH 2 ) 2 -O-(CH 2 ) 3 -.
作為上述環烷二基,可列舉:環戊二基、環己二基、環辛二基等。Examples of the cycloalkanediyl group include a cyclopentadienyl group, a cyclohexanediyl group, and a cyclooctyldiyl group.
作為烷二基與環烷二基組合而成之基,可列舉如下所示之基等。Examples of the group in which the alkanediyl group and the cycloalkanediyl group are combined include the groups shown below.
作為L,較佳的是-CH2 -亦可經-O-取代之碳數為5~15之烷二基,且較佳的是-CH2 -亦可經-O-取代之5~15之直鏈狀烷二基,更佳的是CH2 -亦可經-O-取代之碳數為6~10之直鏈狀烷二基。作為較佳之基,例如可列舉:-(CH2 )6 -、-(CH2 )10 -、-(CH2 )3 -O-(CH2 )3 -、-(CH2 )3 -O-(CH2 )4 -O-(CH2 )3 -或-(CH2 )3 -O-(CH2 )2 -O-(CH2 )2 -O-(CH2 )3 -。As L, it is preferred that -CH 2 - may also be substituted with -O-, and the alkyl group having 5 to 15 carbon atoms, and preferably -CH 2 - may be substituted by -O- 5 to 15 the linear alkyl group, more preferably is CH 2 - may be substituted -O- carbon atoms of straight-chain alkanediyl group of 6 to 10. Preferred examples of the group include -(CH 2 ) 6 -, -(CH 2 ) 10 -, -(CH 2 ) 3 -O-(CH 2 ) 3 -, -(CH 2 ) 3 -O- (CH 2 ) 4 -O-(CH 2 ) 3 - or -(CH 2 ) 3 -O-(CH 2 ) 2 -O-(CH 2 ) 2 -O-(CH 2 ) 3 -.
R1 及R2 分別獨立地表示氫原子、亦可具有取代基之碳數為1~16之1價脂肪族烴基或亦可具有取代基之碳數為2~18之醯基。R 1 and R 2 each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent, or a fluorenyl group having 2 to 18 carbon atoms which may have a substituent.
碳數為1~16之1價脂肪族烴基可為直鏈狀、分枝鏈狀或環狀之任意者。脂肪族烴基之碳數不包含取代基之碳數,該數較佳的是6~10,更佳的是1~4。The monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms may be any of a linear chain, a branched chain or a cyclic group. The carbon number of the aliphatic hydrocarbon group does not include the carbon number of the substituent, and the number is preferably from 6 to 10, more preferably from 1 to 4.
作為上述之1價脂肪族烴基,例如可列舉:甲基、乙基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、甲基丁基(1,1,3,3-四甲基丁基等)、甲基己基(1,5-二甲基己基等)、乙基己基(2-乙基己基等)、環戊基、環己基、甲基環己基(2-甲基環己基等)及環己基烷基等。Examples of the above monovalent aliphatic hydrocarbon group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a second butyl group, a third butyl group, and a methyl butyl group (for example). 1,1,3,3-tetramethylbutyl or the like), methylhexyl (1,5-dimethylhexyl, etc.), ethylhexyl (2-ethylhexyl, etc.), cyclopentyl, cyclohexyl, Methylcyclohexyl (2-methylcyclohexyl, etc.) and cyclohexylalkyl.
上述之1價脂肪族烴基中所含之氫原子亦可經碳數為1~8之烷氧基或羧基取代。作為經碳數為1~8之烷氧基取代之1價脂肪族烴基,可列舉:丙氧基丙基(3-(異丙氧基)丙基等)及烷氧基丙基(3-(2-乙基己氧基)丙基等)。作為經羧基取代之C1-16 脂肪族烴基,可列舉:2-羧基乙基、3-羧基乙基丙基及4-羧基丁基等。The hydrogen atom contained in the above monovalent aliphatic hydrocarbon group may be substituted with an alkoxy group having 1 to 8 carbon atoms or a carboxyl group. Examples of the monovalent aliphatic hydrocarbon group substituted with an alkoxy group having 1 to 8 carbon atoms include a propoxypropyl group (3-(isopropoxy)propyl group, etc.) and an alkoxypropyl group (3- (2-ethylhexyloxy)propyl, etc.). Examples of the C 1-16 aliphatic hydrocarbon group substituted by a carboxyl group include a 2-carboxyethyl group, a 3-carboxyethylpropyl group, and a 4-carboxybutyl group.
碳數為2~18之醯基中所含之氫原子亦可經碳數為1~8之烷氧基取代。亦可具有取代基之碳數為2~18之醯基的碳數包括取代基之碳數而計數,該數較佳的是6~10。作為亦可具有取代基之醯基,例如可列舉:乙醯基、苯甲醯基、甲氧基苯甲醯基(對甲氧基苯甲醯基等)等。The hydrogen atom contained in the fluorenyl group having 2 to 18 carbon atoms may be substituted by an alkoxy group having 1 to 8 carbon atoms. The carbon number of the fluorenyl group having a carbon number of 2 to 18 which may have a substituent includes the number of carbon atoms of the substituent, and the number is preferably 6 to 10. Examples of the mercapto group which may have a substituent include an ethyl fluorenyl group, a benzamidine group, a methoxybenzylidene group (p-methoxybenzylidene group, etc.).
R1 及R2 較佳的是氫原子、碳數為1~4之1價脂肪族烴基或碳數為2~5之醯基。作為較佳之基,可列舉:氫原子、乙醯基及丙醯基,更佳的是氫原子。R 1 and R 2 are preferably a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 4 carbon atoms or a mercapto group having 2 to 5 carbon atoms. Preferred examples of the group include a hydrogen atom, an ethenyl group and a propyl group, and more preferably a hydrogen atom.
R3 ~R10 分別獨立地表示氫原子、亦可經取代之碳數為1~8之1價脂肪族烴基或亦可經取代之碳數為6~10之1價芳香族烴基。碳數為1~8之1價脂肪族烴基之碳數不包括取代基之碳數,該數為1~8,較佳的是1~4。碳數為6~10之1價芳香族烴基之碳數不包括取代基之碳數,該數為6~10,較佳的是6~8。R 3 to R 10 each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms which may be substituted, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted. The carbon number of the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms does not include the carbon number of the substituent, and the number is 1 to 8, preferably 1 to 4. The carbon number of the monovalent aromatic hydrocarbon group having a carbon number of 6 to 10 does not include the carbon number of the substituent, and the number is 6 to 10, preferably 6 to 8.
碳數為1~8之1價脂肪族烴基可為直鏈狀、分枝鏈狀或環狀之任意者。作為該脂肪族烴基,可列舉:作為表示R1 及R2 之1價脂肪族烴基而列舉之基中的碳數為1~8者。The monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms may be any of a linear chain, a branched chain or a cyclic group. Examples of the aliphatic hydrocarbon group include those having 1 to 8 carbon atoms in the group represented by the monovalent aliphatic hydrocarbon group of R 1 and R 2 .
碳數為1~8之1價脂肪族烴基中所含之-CH2 -亦可經-O-取代。碳數為1~8之1價脂肪族烴基中所含之氫原子亦可經氟原子等鹵素原子取代。The -CH 2 - contained in the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms may also be substituted by -O-. The hydrogen atom contained in the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms may be substituted with a halogen atom such as a fluorine atom.
R3 ~R10 較佳的是氫原子、-CH2 -亦可經-O-取代之碳數為1~6之烷基。作為較佳之基,可列舉:氫原子、甲基、乙基、-(CH2 )2 CH(CH3 )2 、-(CH2 )2 -O-CH3 、或-(CH2 )3 -O-CH3 ,更佳的是氫原子或乙基。R 3 to R 10 are preferably a hydrogen atom, and -CH 2 - may be an -O-substituted alkyl group having 1 to 6 carbon atoms. Preferred examples thereof include a hydrogen atom, a methyl group, an ethyl group, -(CH 2 ) 2 CH(CH 3 ) 2 , -(CH 2 ) 2 -O-CH 3 , or -(CH 2 ) 3 - O-CH 3 is more preferably a hydrogen atom or an ethyl group.
R11 ~R14 分別獨立地表示氫原子或甲基,較佳的是甲基。R 11 to R 14 each independently represent a hydrogen atom or a methyl group, and preferably a methyl group.
X- 表示無機陰離子或有機陰離子。作為無機陰離子或有機陰離子,可列舉:氟化物離子、氯化物離子、溴化物離子、碘化物離子、過氯酸離子、次氯酸離子、對甲苯鋶離子、CH3 -COO- 、Ph-COO- 、CH3 -SO3 - 、CF3 -SO3 - 等,較佳的是列舉:氯化物離子、過氯酸離子、CH3 -COO- 、對甲苯鋶離子、CF3 -SO3 - 。特別是有機離子於含有於樹脂硬化性化合物中之情形時有用,進而為非金屬鹽,因此於強調絕緣性之領域中亦有用。X - represents an inorganic anion or an organic anion. Examples of the inorganic anion or organic anion include fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, hypochlorous acid ion, p-toluene ion, CH 3 -COO − , and Ph-COO. - , CH 3 -SO 3 - , CF 3 -SO 3 -, etc., preferably include chloride ion, perchloric acid ion, CH 3 -COO - , p-toluene ion, CF 3 -SO 3 - . In particular, since organic ions are useful in the case of being contained in a resin-curable compound, and are also non-metal salts, they are also useful in the field of emphasizing insulation.
作為化合物(I),可列舉式(I-1)~式(I-18)所表示之化合物。表中之L表示右側之結合鍵為與-NR1 -之氮原子之結合鍵。The compound (I) includes a compound represented by the formula (I-1) to the formula (I-18). L in the table indicates that the bond bond on the right side is a bond to the nitrogen atom of -NR 1 -.
化合物(I)較佳的是R3 與R7 、R4 與R8 、R5 與R9 、R6 與R10 、R11 與R13 、R12 與R14 、X1 與X2 分別為相同之基之化合物,亦即式(I-0)所表示之化合物,更佳的是進而R1 與R2 為相同之基之化合物。若為該等化合物,則可容易地製造化合物(I)。The compound (I) is preferably R 3 and R 7 , R 4 and R 8 , R 5 and R 9 , R 6 and R 10 , R 11 and R 13 , R 12 and R 14 , X 1 and X 2 respectively. The compound of the same group, that is, the compound represented by the formula (I-0), more preferably a compound wherein R 1 and R 2 are the same. In the case of these compounds, the compound (I) can be easily produced.
[式(I-0)中,L、R1 ~R6 、R11 、R12 及X1 表示與上述相同之含意。]In the formula (I-0), L, R 1 to R 6 , R 11 , R 12 and X 1 have the same meanings as described above. ]
化合物(I)可藉由如下方法製造:於溶劑中,使式(I-A)所表示之化合物及式(I-A')所表示之化合物The compound (I) can be produced by subjecting a compound represented by the formula (I-A) and a compound represented by the formula (I-A') to a solvent.
[式(I-A)及式(I-A')中,R3 ~R14 、X1 及X2 表示與上述相同之含意。Y1 及Y2 表示羥基、-OR20 或鹵素原子。R20 表示碳數為1~8之脂肪族烴基。]In the formula (IA) and the formula (I-A'), R 3 to R 14 , X 1 and X 2 have the same meanings as described above. Y 1 and Y 2 represent a hydroxyl group, -OR 20 or a halogen atom. R 20 represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms. ]
與式(I-B)所表示之化合物And the compound represented by formula (I-B)
[式(I-B)中,L、R1 及R2 表示與上述相同之含意。]In the formula (IB), L, R 1 and R 2 represent the same meanings as described above. ]
於0~250℃下進行反應。The reaction was carried out at 0 to 250 °C.
作為式(I-B)所表示之化合物,可列舉:乙二胺、丁二胺、己二胺、環己二胺、1,12-二胺基十二烷、4,4-亞甲基雙(2-甲基環己胺)、異佛爾酮二胺、1,4-丁二醇雙(3-胺基丙基)醚、二乙二醇雙(3-胺基丙基)醚等。Examples of the compound represented by the formula (IB) include ethylenediamine, butylenediamine, hexamethylenediamine, cyclohexanediamine, 1,12-diaminododecane, and 4,4-methylenebis ( 2-methylcyclohexylamine), isophorone diamine, 1,4-butanediol bis(3-aminopropyl)ether, diethylene glycol bis(3-aminopropyl)ether, and the like.
式(I-B)所表示之化合物可單獨使用,亦可併用2種以上。相對於式(I-A)所表示之化合物及式(I-A')所表示之化合物之合計量1莫耳而言,式(I-B)所表示之化合物之使用量較佳的是0.5~3莫耳。The compound represented by the formula (I-B) may be used singly or in combination of two or more. With respect to the total amount of the compound represented by the formula (IA) and the compound represented by the formula (I-A'), the compound represented by the formula (IB) is preferably used in an amount of 0.5 to 3 mol. ear.
於Y1 及Y2 為羥基之情形時,較佳的是使用式(I-B)所表示之化合物之鹽酸鹽。In the case where Y 1 and Y 2 are a hydroxyl group, it is preferred to use the hydrochloride of the compound represented by the formula (IB).
又,於Y1 及Y2 為羥基之情形時,較佳的是使用公知之縮合劑。作為縮合劑,可列舉:(PhO)3 P、(PhO)PCl2 、PhPOCl2 、(C3 H7 )3 P(O)O、POCl3 、SOCl2 -Et3 N、Ph3 P-C2 Cl6 等,更佳的是與烷基醯胺類溶劑中之吡啶組合而使用。相對於式(I-A)所表示之化合物及式(I-A')所表示之化合物之合計量1莫耳而言,縮合劑之使用量較佳的是2~10莫耳。相對於式(I-A)所表示之化合物及式(I-A')所表示之化合物之合計量1莫耳而言,吡啶之使用量較佳的是20~80莫耳。Further, in the case where Y 1 and Y 2 are a hydroxyl group, it is preferred to use a known condensing agent. Examples of the condensing agent include (PhO) 3 P, (PhO)PCl 2 , PhPOCl 2 , (C 3 H 7 ) 3 P(O)O, POCl 3 , SOCl 2 -Et 3 N, and Ph 3 PC 2 Cl. 6 or the like is more preferably used in combination with pyridine in a alkylguanamine solvent. The amount of the condensing agent to be used is preferably from 2 to 10 mols, based on the total amount of the compound represented by the formula (IA) and the compound represented by the formula (I-A'). The pyridine is preferably used in an amount of from 20 to 80 mols per mol of the compound represented by the formula (IA) and the compound represented by the formula (I-A').
於Y1 及Y2 為-OR20 之情形時,較佳的是添加公知之鹼觸媒。作為鹼觸媒,可列舉乙醇鈉、氫化鈉等。相對於式(I-A)所表示之化合物及式(I-A')所表示之化合物之合計量1莫耳而言,鹼觸媒之使用量較佳的是0.01~2莫耳。In the case where Y 1 and Y 2 are -OR 20, it is preferred to add a known alkali catalyst. Examples of the base catalyst include sodium ethoxide and sodium hydride. The amount of the base catalyst to be used is preferably 0.01 to 2 moles based on the total amount of the compound represented by the formula (IA) and the compound represented by the formula (I-A').
上述反應係於溶劑中進行。作為溶劑,例如較佳的是:水;1,4-二噁烷等醚類(特別是環狀醚類);氯仿、二氯甲烷、四氯化碳、1,2-二氯乙烷、二氯乙烯、三氯乙烯、全氯乙烯、二氯丙烷、氯戊烷、1,2-二溴乙烷等鹵化烴類;丙酮、甲基異丁基酮、環己酮等酮類;苯、甲苯、二甲苯等碳系芳香族類;N,N-二甲基甲醯胺、N,N-二丁基甲醯胺、N,N-二甲基乙醯胺、N-甲基吡咯啶酮等烷基醯胺類等。溶劑可單獨使用,亦可併用2種以上。相對於式(I-A)所表示之化合物及式(I-A')所表示之化合物之合計量1質量份而言,溶劑之使用量較佳的是1~20質量份,更佳的是2~10質量份。The above reaction is carried out in a solvent. As the solvent, for example, water; ethers such as 1,4-dioxane (especially cyclic ethers); chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane, and the like are preferable. Halogenated hydrocarbons such as dichloroethylene, trichloroethylene, perchloroethylene, dichloropropane, chloropentane, 1,2-dibromoethane; ketones such as acetone, methyl isobutyl ketone and cyclohexanone; benzene Carbonaceous aromatics such as toluene and xylene; N,N-dimethylformamide, N,N-dibutylformamide, N,N-dimethylacetamide, N-methylpyrrolidone Equivalent alkyl amides and the like. The solvent may be used singly or in combination of two or more. The solvent is preferably used in an amount of from 1 to 20 parts by mass, more preferably 2 parts by mass based on 1 part by mass of the total of the compound represented by the formula (IA) and the compound represented by the formula (I-A'). ~10 parts by mass.
上述反應較佳的是於氮氣環境下或氬氣環境下進行。亦可於利用氯化鈣等而乾燥之空氣下進行。The above reaction is preferably carried out under a nitrogen atmosphere or an argon atmosphere. It can also be carried out in air which is dried by using calcium chloride or the like.
反應溫度較佳的是0~250℃,更佳的是10~200℃。反應時間較佳的是1~25小時,更佳的是3~15小時。The reaction temperature is preferably 0 to 250 ° C, more preferably 10 to 200 ° C. The reaction time is preferably from 1 to 25 hours, more preferably from 3 to 15 hours.
式(I-A)所表示之化合物、式(I-A')所表示之化合物、式(I-B)所表示之化合物及溶劑之添加順序並無特別限定,較佳的是於包含式(I-A)所表示之化合物、式(I-A')所表示之化合物及溶劑之溶液中,添加(滴加)式(I-B)所表示之化合物。於使用縮合劑之情形時,較佳的是於包含式(I-A)所表示之化合物、式(I-A')所表示之化合物、縮合劑及溶劑之溶液中,添加(滴加)式(I-B)所表示之化合物。於使用鹼觸媒之情形時,較佳的是於包含式(I-A)所表示之化合物、式(I-A')所表示之化合物、鹼觸媒及溶劑之溶液中,添加(滴加)式(I-B)所表示之化合物。The order of addition of the compound represented by the formula (IA), the compound represented by the formula (I-A'), the compound represented by the formula (IB) and the solvent is not particularly limited, and it is preferred to include the formula (IA). The compound represented by the formula (IB) is added (dropwise) to the solution of the compound represented by the formula (I-A') and the solvent. In the case of using a condensing agent, it is preferred to add (drop) a solution containing a compound represented by the formula (IA), a compound represented by the formula (I-A'), a condensing agent, and a solvent. Compound represented by IB). In the case of using an alkali catalyst, it is preferred to add (drop) to a solution containing a compound represented by the formula (IA), a compound represented by the formula (I-A'), a base catalyst, and a solvent. a compound represented by the formula (IB).
自以上述方式而獲得之反應混合物中得到作為目標化合物之化合物(I)的方法並無特別限定,可採用公知之各種方法(酸析或鹽析等)。濾取之晶體通常利用水等進行清洗,繼而加以乾燥。又,亦可視需要利用再結晶等公知之方法進一步純化。The method of obtaining the compound (I) as the target compound from the reaction mixture obtained in the above manner is not particularly limited, and various known methods (such as acid precipitation or salting out) can be employed. The crystals collected by filtration are usually washed with water or the like and then dried. Further, it may be further purified by a known method such as recrystallization as needed.
本發明之化合物顯示出高溶解性、低移染性及高分光濃度,因此可用作利用反射光或穿透光而進行彩色顯示之纖維材料、液晶顯示裝置等中之染料。又,本發明之化合物於測定吸收光譜時在500~600 nm之波段中具有最大吸收,因此可用作紅色或紫色染料。Since the compound of the present invention exhibits high solubility, low transferability, and high spectroscopic concentration, it can be used as a dye in a fiber material, a liquid crystal display device or the like which performs color display by reflected light or transmitted light. Further, the compound of the present invention has a maximum absorption in a wavelength band of 500 to 600 nm when measuring an absorption spectrum, and thus can be used as a red or violet dye.
本發明之染料係以本發明之化合物為主成分之染料,且為含有50質量%以上之本發明之化合物之染料。The dye of the present invention is a dye containing a compound of the present invention as a main component, and is a dye containing 50% by mass or more of the compound of the present invention.
本發明之染料可單獨為化合物(I),較佳的是混合2種以上之化合物(I)之染料。其中,更佳的是混合2種以上之僅L不同之化合物(I)而成之染料。藉由組合該等化合物,從而於溶劑中之溶解性優異。作為較佳之化合物(I)之組合,例如為式(I-1)所表示之化合物與式(I-2)所表示之化合物。The dye of the present invention may be the compound (I) alone, and it is preferred to mix two or more kinds of the dye of the compound (I). Among them, a dye obtained by mixing two or more kinds of compounds (I) different in L is more preferable. By combining these compounds, the solubility in a solvent is excellent. As a preferable combination of the compound (I), for example, a compound represented by the formula (I-1) and a compound represented by the formula (I-2).
混合2種以上之化合物(I)而成之染料可單獨製造各個化合物(I)然後加以混合而獲得,亦可於製造時製成混合物而獲得。後者例如可於式(I-A)所表示之化合物及式(I-A')與式(I-B)所表示之化合物之反應中,使用2種以上之式(I-B)所表示之化合物,藉此製成混合物而獲得。A dye obtained by mixing two or more kinds of the compound (I) can be obtained by separately producing each compound (I) and then mixing them, or by preparing a mixture at the time of production. The latter can be produced, for example, by using two or more compounds represented by the formula (IB) in the reaction of the compound represented by the formula (IA) and the compound represented by the formula (I-A') and the formula (IB). Obtained as a mixture.
本發明之著色組合物包含:選自由樹脂(以下有時稱為「樹脂(B)」)、光聚合性化合物(以下有時稱為「光聚合性化合物(C)」)、光聚合起始劑(以下有時稱為「光聚合起始劑(D)」)及溶劑(以下有時稱為「溶劑(E)」)所組成之群中之至少1種、及含有本發明之染料的著色劑(以下有時稱為「著色劑(A)」)。The coloring composition of the present invention is selected from the group consisting of a resin (hereinafter sometimes referred to as "resin (B)"), a photopolymerizable compound (hereinafter sometimes referred to as "photopolymerizable compound (C)"), and photopolymerization initiation. At least one of a group consisting of a reagent (hereinafter sometimes referred to as "photopolymerization initiator (D)") and a solvent (hereinafter sometimes referred to as "solvent (E)"), and a dye containing the dye of the present invention A coloring agent (hereinafter sometimes referred to as "coloring agent (A)").
著色劑(A)可進而包含與本發明之染料不同之染料、顏料(A-2)。The colorant (A) may further contain a dye (A-2) different from the dye of the present invention.
作為與本發明之染料不同之染料,可列舉於染料索引(Colour Index)(The Society of Dyers and Colourists出版)中,分類為溶劑(Solvent)、酸性(Acid)、鹼性(Basic)、反應(reactive)、直接(Direct)、分散(Disperse)、或還原(Vat)之化合物等。更具體而言,可列舉如以下之染料索引(C.I.)編號之染料,但並不限定於該等。As the dye different from the dye of the present invention, it can be exemplified by the Colour Index (published by The Society of Dyers and Colourists), and classified into a solvent (Solvent), an acid (Acid), a basic (Basic), and a reaction ( Reactive), direct, disperse, or reduced (Vat) compounds. More specifically, the dyes of the following dye index (C.I.) number are mentioned, but it is not limited to these.
C.I. 溶劑黃25、79、81、82、83、89;C.I. Solvent yellow 25, 79, 81, 82, 83, 89;
C.I. 酸性黃7、23、25、42、65、76;C.I. Acid yellow 7, 23, 25, 42, 65, 76;
C.I. 反應黃2、76、116;C.I. Reaction yellow 2, 76, 116;
C.I. 直接黃4、28、44、86、132;C.I. Direct yellow 4, 28, 44, 86, 132;
C.I. 分散黃54、76;C.I. Disperse yellow 54, 56;
C.I. 溶劑橙41、54、56、99;C.I. Solvent Orange 41, 54, 56, 99;
C.I. 酸性橙56、74、95、108、149、162;C.I. Acidic oranges 56, 74, 95, 108, 149, 162;
C.I. 反應橙16;C.I. Reaction orange 16;
C.I. 直接橙26;C.I. Direct orange 26;
C.I. 溶劑紅24、49、90、91、118、119、122、124、125、127、130、132、160、218;C.I. Solvent Red 24, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 160, 218;
C.I. 酸性紅73、91、92、97、138、151、211、274、289;C.I. Acid red 73, 91, 92, 97, 138, 151, 211, 274, 289;
C.I. 酸性紫102;C.I. Acid Violet 102;
C.I. 溶劑藍35、37、38、44、59、64、67、70;C.I. Solvent Blue 35, 37, 38, 44, 59, 64, 67, 70;
C.I. 酸性藍40、45、78、80、83、90、100、171、185;C.I. Acid blue 40, 45, 78, 80, 83, 90, 100, 171, 185;
C.I. 鹼性藍65、140;C.I. Basic blue 65, 140;
C.I. 反應藍15、38;C.I. Reaction Blue 15, 38;
C.I. 分散藍143;C.I. Disperse blue 143;
C.I. 直接藍86、87;C.I. Direct Blue 86, 87;
C.I. 溶劑綠1、5;C.I. Solvent Green 1, 5;
C.I. 酸性綠3、5、9、25、28;C.I. Acidic green 3, 5, 9, 25, 28;
C.I. 鹼性綠1;C.I. Alkaline green 1;
C.I. 還原綠1;C.I. Restore green 1;
C.I. 酸性黑58、60、107;C.I. Acid black 58, 60, 107;
C.I. 溶劑黑27等。C.I. Solvent black 27 and the like.
作為顏料(A-2),可列舉於顏料分散抗蝕劑中所通常使用之有機顏料或無機顏料。作為無機顏料,可列舉如金屬氧化物或金屬錯鹽這樣的金屬化合物,具體可列舉:鐵、鈷、鋁、鎘、鉛、銅、鈦、鎂、鉻、鋅、銻等之金屬氧化物或複合金屬氧化物。又,作為有機顏料及無機顏料,具體而言,可列舉於染料索引(Colour Index)(The Society of Dyers and Colourists出版)中,分類為顏料(Pigment)之化合物。更具體而言,可列舉如下之染料索引(C.I.)編號之顏料,但並不限定於該等。The pigment (A-2) is exemplified by an organic pigment or an inorganic pigment which is usually used in a pigment dispersion resist. Examples of the inorganic pigment include a metal compound such as a metal oxide or a metal salt, and specific examples thereof include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. Composite metal oxide. Further, specific examples of the organic pigment and the inorganic pigment include a compound classified as a pigment in a Colour Index (published by The Society of Dyers and Colourists). More specifically, the following dye index (C.I.) number of pigments may be mentioned, but it is not limited thereto.
C.I. 顏料黃20、24、31、53、83、86、93、94、109、110、117、125、137、138、139、147、148、150、153、154、166、173及180;C.I. Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173 and 180;
C.I. 顏料橙13、31、36、38、40、42、43、51、55、59、61、64、65及71;C.I. Pigment oranges 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71;
C.I. 顏料紅9、97、105、122、123、144、149、166、168、176、177、180、192、215、216、224、242、254、255及264;C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255 and 264;
C.I. 顏料紫14、19、23、29、32、33、36、37及38;C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38;
C.I. 顏料藍15(15:3、15:4、15:6等)、21、28、60、64及76;C.I. Pigment Blue 15 (15:3, 15:4, 15:6, etc.), 21, 28, 60, 64 and 76;
C.I. 顏料綠7、10、15、25、36及47;C.I. Pigment Green 7, 10, 15, 25, 36 and 47;
C.I. 顏料棕28;C.I. Pigment Brown 28;
C.I. 顏料黑1及7等。C.I. Pigment black 1 and 7, etc.
相對於著色組合物中之固形物成分而言,著色劑(A)之含量較佳的是5~60質量%,更佳的是8~55質量%,進而更佳的是10~50質量%。此處,所謂固形物成分,是指著色組合物中之除溶劑以外成分之合計。The content of the colorant (A) is preferably from 5 to 60% by mass, more preferably from 8 to 55% by mass, even more preferably from 10 to 50% by mass, based on the solid content of the coloring composition. . Here, the solid content component means a total of components other than the solvent in the coloring composition.
於著色劑(A)進而包含與本發明之染料不同之染料、顏料(A-2)之情形時,著色劑(A)中之本發明之染料之含量較佳的是3~80質量%,更佳的是3~70質量%,進而更佳的是3~50質量%。In the case where the colorant (A) further contains a dye or pigment (A-2) different from the dye of the present invention, the content of the dye of the present invention in the colorant (A) is preferably from 3 to 80% by mass. More preferably, it is 3 to 70% by mass, and more preferably 3 to 50% by mass.
著色劑(A)中之顏料(A-2)之含量為20~97質量%,較佳的是30~97質量%,更佳的是50~97質量%。The content of the pigment (A-2) in the colorant (A) is 20 to 97% by mass, preferably 30 to 97% by mass, more preferably 50 to 97% by mass.
作為樹脂(B),並無特別限定,可使用任意樹脂。例如,樹脂(B)含有由(甲基)丙烯酸所得到之結構單元。此處,(甲基)丙烯酸係表示丙烯酸及/或甲基丙烯酸。The resin (B) is not particularly limited, and any resin can be used. For example, the resin (B) contains a structural unit derived from (meth)acrylic acid. Here, (meth)acrylic acid means acrylic acid and/or methacrylic acid.
作為樹脂(B),具體而言較佳的是:甲基丙烯酸/甲基丙烯酸苄酯共聚物、甲基丙烯酸/甲基丙烯酸苄酯/苯乙烯共聚物、甲基丙烯酸/甲基丙烯酸苄酯/甲基丙烯酸異冰片基酯共聚物、甲基丙烯酸/苯乙烯/甲基丙烯酸苄酯/N-苯基馬來醯亞胺共聚物、甲基丙烯酸與選自由式(B-1-1)所表示之化合物及式(B-1-2)所表示之化合物所組成之群中之至少1種之共聚物等。As the resin (B), specifically, preferred are: methacrylic acid/benzyl methacrylate copolymer, methacrylic acid/benzyl methacrylate/styrene copolymer, methacrylic acid/benzyl methacrylate /Isobornyl methacrylate copolymer, methacrylic acid / styrene / benzyl methacrylate / N-phenyl maleimide copolymer, methacrylic acid and selected from the formula (B-1-1) A copolymer of at least one of the compound represented by the compound represented by the formula (B-1-2) and the like.
樹脂(B)之聚苯乙烯換算之重量平均分子量較佳的是5,000~35,000,更佳的是6,000~30,000,特佳的是7,000~28,000。The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably 5,000 to 35,000, more preferably 6,000 to 30,000, and particularly preferably 7,000 to 28,000.
樹脂(B)之酸值較佳的是50~150,更佳的是60~135,特佳的是70~135。The acid value of the resin (B) is preferably from 50 to 150, more preferably from 60 to 135, and particularly preferably from 70 to 135.
相對於著色組合物之固形物成分而言,樹脂(B)之含量較佳的是7~65質量%,更佳的是13~60質量%,特佳的是17~55質量%。The content of the resin (B) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, particularly preferably from 17 to 55% by mass, based on the solid content of the coloring composition.
光聚合性化合物(C)若為可藉由利用照射光而自光聚合起始劑(D)所產生之活性自由基、酸等而聚合之化合物,則無特別限定。例如可列舉具有聚合性之碳-碳不飽和鍵之化合物等。The photopolymerizable compound (C) is not particularly limited as long as it is a compound which can be polymerized by an active radical, an acid or the like generated from the photopolymerization initiator (D) by irradiation with light. For example, a compound having a polymerizable carbon-carbon unsaturated bond or the like can be given.
作為上述光聚合性化合物(C),較佳的是具有3個以上聚合性基之光聚合性化合物。作為具有3個以上聚合性基之光聚合性化合物,例如可列舉:季戊四醇四丙烯酸酯、季戊四醇四甲基丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇五甲基丙烯酸酯、二季戊四醇六丙烯酸酯、二季戊四醇六甲基丙烯酸酯等。上述光聚合性化合物(C)可單獨使用,亦可組合2種以上而使用。The photopolymerizable compound (C) is preferably a photopolymerizable compound having three or more polymerizable groups. Examples of the photopolymerizable compound having three or more polymerizable groups include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol hexaacrylate, and the like. Dipentaerythritol hexamethacrylate or the like. The photopolymerizable compound (C) may be used singly or in combination of two or more.
相對於著色組合物之固形物成分而言,光聚合性化合物(C)之含量較佳的是5~65質量%,更佳的是10~60質量%。The content of the photopolymerizable compound (C) is preferably from 5 to 65% by mass, and more preferably from 10 to 60% by mass, based on the solid content of the coloring composition.
作為上述光聚合起始劑(D),可列舉活性自由基產生劑、酸產生劑等。活性自由基產生劑係藉由照射光而產生活性自由基之化合物。作為上述活性自由基產生劑,可列舉:苯乙酮化合物、安息香化合物、二苯甲酮化合物、噻噸酮化合物、三化合物、肟化合物等。Examples of the photopolymerization initiator (D) include a living radical generator, an acid generator, and the like. The living radical generating agent is a compound which generates an active radical by irradiating light. Examples of the living radical generating agent include an acetophenone compound, a benzoin compound, a benzophenone compound, a thioxanthone compound, and the like. Compounds, hydrazine compounds, and the like.
作為上述苯乙酮化合物,例如可列舉:二乙氧基苯乙酮、2-N-嗎啉基-1-(4-甲基硫烷基苯基)-2-甲基丙烷-1-酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、苯偶醯二甲基縮酮、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-(1-甲基乙烯基)苯基]丙烷-1-酮之寡聚物等,較佳的是列舉2-嗎啉基-1-(4-甲基硫烷基苯基)-2-甲基丙烷-1-酮等。Examples of the acetophenone compound include diethoxyacetophenone and 2-N-morpholinyl-1-(4-methylsulfanylphenyl)-2-methylpropan-1-one. , 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzoin dimethyl ketal, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy) Phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one As the oligomer or the like, 2-morpholinyl-1-(4-methylsulfanylphenyl)-2-methylpropan-1-one or the like is preferably exemplified.
作為上述安息香化合物,例如可列舉:安息香、安息香甲醚、安息香乙醚、安息香異丙醚、安息香異丁醚等。Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.
作為上述二苯甲酮化合物,例如可列舉:二苯甲酮、鄰苯甲醯基苯甲酸甲酯、4-苯基二苯甲酮、4-苯甲醯基-4'-甲基二苯硫醚、3,3',4,4'-四(第三丁基過氧羧基)二苯甲酮、2,4,6-三甲基二苯甲酮等。Examples of the benzophenone compound include benzophenone, methyl ortho-benzoylbenzoate, 4-phenylbenzophenone, and 4-benzylidene-4'-methyldiphenyl. Thioether, 3,3',4,4'-tetrakis(t-butylperoxycarboxy)benzophenone, 2,4,6-trimethylbenzophenone, and the like.
作為上述噻噸酮化合物,例如可列舉: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, and 2,4-dichlorothioxanthone. 1-Chloro-4-propoxythioxanthone and the like.
作為上述三化合物,例如可列舉:2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三、2,4-雙(三氯甲基)-6-(4-甲氧基萘基)-1,3,5三、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三、2,4-雙(三氯甲基)-6-[2-(5-甲基呋喃-2-基)乙烯基]-1,3,5-三、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-1,3,5-三、2,4-雙(三氯甲基)-6-[2-(4-二乙基胺基-2-甲基苯基)乙烯基]-1,3,5-三、2,4-雙(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三等。As the above three The compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tri , 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-three Wait.
作為上述肟化合物,例如可列舉O-醯基肟系化合物,作為其具體例,可列舉:N-苯甲醯基氧基-1-(4-苯基硫烷基苯基)丁烷-1-酮-2-亞胺、N-苯甲醯基氧基-1-(4-苯基硫烷基苯基)辛烷-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-亞胺等。Examples of the ruthenium compound include an O-fluorenyl fluorene-based compound, and specific examples thereof include N-benzimidyloxy-1-(4-phenylsulfanylphenyl)butane-1. -keto-2-imine, N-benzylideneoxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-acetoxy-1 -[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethane-1-imine, N-ethyloxy-1-[9-B -6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolylmethoxy)benzylidenyl}-9H-indazol-3-yl] Ethane-1-imine and the like.
又,作為活性自由基產生劑,例如亦可使用:2,4,6-三甲基苯甲醯基二苯基氧化膦、2,2'-雙(鄰氯苯基)-4,4',5,5'-四苯基-1,2'-聯咪唑、10-丁基-2-氯吖啶酮、2-乙基蒽醌、二苯基乙二酮、9,10-菲醌、樟腦醌、苯基乙醛酸甲酯、二茂鈦化合物等。Further, as the living radical generating agent, for example, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide or 2,2'-bis(o-chlorophenyl)-4,4' may also be used. ,5,5'-tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylhydrazine, diphenylethylenedione, 9,10-phenanthrenequinone , camphorquinone, methyl phenylglyoxylate, titanium titanate compound, and the like.
酸產生劑係藉由照射光而產生酸之化合物。An acid generator is a compound which generates an acid by irradiating light.
作為酸產生劑,例如可列舉:4-羥基苯基二甲基鋶對甲苯磺酸鹽、4-羥基苯基二甲基鋶六氟銻酸鹽、4-乙醯氧基苯基二甲基鋶對甲苯磺酸鹽、4-乙醯氧基苯基-甲基-苄基鋶六氟銻酸鹽、三苯基鋶對甲苯磺酸鹽、三苯基鋶六氟銻酸鹽、二苯基錪對甲苯磺酸鹽、二苯基錪六氟銻酸鹽等鎓鹽類或硝基苄基甲苯磺酸鹽類、安息香甲苯磺酸鹽類等。Examples of the acid generator include 4-hydroxyphenyldimethylhydrazine p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-ethenoxyphenyldimethylate.鋶p-toluenesulfonate, 4-acetoxyphenyl-methyl-benzyl hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyl An anthracene salt such as p-toluenesulfonate or diphenylphosphonium hexafluoroantimonate or a nitrobenzyl tosylate or a benzoin tosylate.
又,作為上述活性自由基產生劑之上述化合物中,亦存在與產生活性自由基之同時產生酸之化合物,例如三系光聚合起始劑亦可用作酸產生劑。Further, among the above-mentioned compounds which are active radical generating agents, there are also compounds which generate an acid simultaneously with the generation of active radicals, for example, three A photopolymerization initiator can also be used as the acid generator.
相對於樹脂(B)及光聚合性化合物(C)之合計量而言,光聚合起始劑(D)之含量較佳的是0.1~30質量%,更佳的是1~20質量%。若光聚合起始劑之含量於上述之範圍內,則高感光度化而縮短曝光時間,從而使生產性提高。The content of the photopolymerization initiator (D) is preferably from 0.1 to 30% by mass, and more preferably from 1 to 20% by mass, based on the total amount of the resin (B) and the photopolymerizable compound (C). When the content of the photopolymerization initiator is within the above range, the sensitivity is increased and the exposure time is shortened, thereby improving productivity.
作為溶劑(E),例如可列舉:醚類、芳香族烴類、除上述以外之酮類、醇類、酯類、醯胺類等。Examples of the solvent (E) include ethers, aromatic hydrocarbons, ketones other than the above, alcohols, esters, and guanamines.
作為上述醚類,例如可列舉:四氫呋喃、四氫吡喃、1,4-二噁烷、乙二醇單甲醚、乙二醇單乙醚、乙二醇單丙醚、乙二醇單丁醚、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丁醚、二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇甲基乙基醚、二乙二醇二丙醚、二乙二醇二丁醚、丙二醇單甲醚、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、丙二醇單丙醚乙酸酯、乙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、二乙二醇單乙醚乙酸酯、二乙二醇單丁醚乙酸酯、苯甲醚、苯乙醚、甲基苯甲醚等。Examples of the ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether. , diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, two Ethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether Acid ester, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, anisole, phenethyl ether, methyl anisole, and the like.
作為上述芳香族烴類,例如可列舉:苯、甲苯、二甲苯、均三甲苯等。Examples of the aromatic hydrocarbons include benzene, toluene, xylene, and mesitylene.
作為上述酮類,例如可列舉:丙酮、2-丁酮、2-庚酮、3-庚酮、4-庚酮、4-甲基-2-戊酮、4-羥基-4-甲基-2-戊酮、環戊酮、環己酮等。Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, and 4-hydroxy-4-methyl- 2-pentanone, cyclopentanone, cyclohexanone, and the like.
作為上述醇類,例如可列舉:甲醇、乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、甘油等。Examples of the alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin.
作為上述酯類,例如可列舉:乙酸乙酯、乙酸正丁酯、乙酸異丁酯、甲酸戊酯、乙酸異戊酯、乙酸異丁酯、丙酸丁酯、丁酸異丙酯、丁酸乙酯、丁酸丁酯、烷基酯類、乳酸甲酯、乳酸乙酯、乳酸丁酯、甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯、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、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、γ-丁內酯等。Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, and butyric acid. Ethyl ester, butyl butyrate, alkyl ester, methyl lactate, ethyl lactate, butyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxy acetic acid Methyl ester, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, Methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, Methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate Ethyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, γ-butyrolactone, and the like.
作為上述醯胺類,例如可列舉:N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基吡咯啶酮等。Examples of the above guanamines include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.
作為溶劑(E),較佳的是丙二醇單甲醚及丙二醇單甲醚乙酸酯。As the solvent (E), preferred are propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate.
該等溶劑可單獨使用,亦可組合2種以上使用。These solvents may be used singly or in combination of two or more.
相對於著色組合物而言,著色組合物中溶劑(E)之含量較佳的是70~95質量%,更佳的是75~90質量%。The content of the solvent (E) in the coloring composition is preferably 70 to 95% by mass, and more preferably 75 to 90% by mass based on the coloring composition.
本發明之著色組合物亦可進而包含界面活性劑(G)。作為界面活性劑(G),可列舉:聚矽氧系界面活性劑、氟系界面活性劑及具有氟原子之聚矽氧系界面活性劑。The coloring composition of the present invention may further comprise a surfactant (G). Examples of the surfactant (G) include a polyfluorene-based surfactant, a fluorine-based surfactant, and a polyfluorene-based surfactant having a fluorine atom.
作為上述聚矽氧系界面活性劑,可列舉具有矽氧烷鍵之界面活性劑等。具體而言,可列舉:Toray Silicone DC3PA、Toray Silicone SH7PA、Toray Silicone DC11PA、Toray Silicone SH21PA、Toray Silicone SH28PA、Toray Silicone SH29PA、Toray Silicone SH30PA、聚醚改性矽油SH8400(商品名:Dow Corning Toray股份有限公司製造)、KP321、KP322、KP323、KP324、KP326、KP340、KP341(信越化學工業股份有限公司製造)、TSF400、TSF401、TSF410、TSF4300、TSF4440、TSF4445、TSF-4446、TSF4452、TSF4460(Momentive Performance Materials Japan合同會社製造)等。Examples of the polyfluorene-based surfactant include a surfactant having a decane bond. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Polyether Modified Emu Oil SH8400 (trade name: Dow Corning Toray Limited Co., Ltd.) Manufactured by the company), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momentive Performance Materials) Japan contract company manufacturing) and so on.
作為上述氟系界面活性劑,可列舉具有氟碳鏈之界面活性劑等。具體可列舉:Fluorad(商品名)FC430、Fluorad FC431(Sumitomo 3M股份有限公司製造)、Megafac(商品名)F142D、Megafac F171、Megafac F172、Megafac F173、Megafac F177、Megafac F183、Megafac R30(DIC股份有限公司製造)、Eftop(商品名)EF301、Eftop EF303、Eftop EF351、Eftop EF352(Mitsubishi Materials Electronic Chemicals股份有限公司製造)、Surflon(商品名)S381、Surflon S382、Surflon SC101、Surflon SC105(旭硝子股份有限公司製造)、E5844(大金精密化學研究所股份有限公司製造)等。The fluorine-based surfactant may, for example, be a surfactant having a fluorocarbon chain. Specific examples include Fluorad (trade name) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (trade name) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac R30 (limited in DIC shares) Manufactured by the company, Eftop (trade name) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (trade name) S381, Surflon S382, Surflon SC101, Surflon SC105 (Asahi Glass Co., Ltd. Manufacturing), E5844 (manufactured by Daikin Precision Chemical Research Co., Ltd.), etc.
作為具有上述氟原子之聚矽氧系界面活性劑,可列舉具有矽氧烷鍵及氟碳鏈之界面活性劑等。具體可列舉:Megafac(註冊商標)R08、Megafac BL20、Megafac F475、Megafac F477、Megafac F443(DIC股份有限公司製造)等。Examples of the polyfluorene-based surfactant having the above fluorine atom include a surfactant having a decane bond and a fluorocarbon chain. Specific examples include Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, Megafac F443 (manufactured by DIC Corporation), and the like.
相對於著色組合物而言,界面活性劑(G)之含量較佳的是0.00001~0.2質量%,更佳的是0.001~0.1質量%。若界面活性劑(G)之含量於上述範圍內,則存在平坦性變得良好之傾向而較佳。The content of the surfactant (G) is preferably 0.00001 to 0.2% by mass, and more preferably 0.001 to 0.1% by mass based on the coloring composition. When the content of the surfactant (G) is within the above range, flatness tends to be good, and it is preferred.
該等界面活性劑可單獨使用,亦可組合2種以上使用。These surfactants may be used singly or in combination of two or more.
作為使用本發明之著色組合物而形成彩色濾光片或其圖案之方法,例如可列舉如下方法:將本發明之著色組合物塗佈於基板或其他樹脂層(例如預先形成於基板上之其他著色組合物層等)上,將溶劑等揮發成分去除/乾燥而形成著色層,並經由光罩對該著色層進行曝光而顯影之方法;無須光微影法之使用噴墨機器之方法等。As a method of forming a color filter or a pattern thereof using the coloring composition of the present invention, for example, a method of applying the coloring composition of the present invention to a substrate or another resin layer (for example, other previously formed on a substrate) may be mentioned. In the coloring composition layer or the like, a method of removing and drying a volatile component such as a solvent to form a colored layer, and developing the colored layer through a photomask, and developing the inkjet device without using a photolithography method.
該情形時之塗膜之膜厚並無特別限定,可根據所使用之材料、用途等而適當調整,較佳的是0.1~30 μm,更佳的是1~20 μm,進而更佳的是1~6 μm。The film thickness of the coating film in this case is not particularly limited, and may be appropriately adjusted depending on the material to be used, the use, and the like, and is preferably 0.1 to 30 μm, more preferably 1 to 20 μm, and even more preferably 1~6 μm.
著色組合物之塗佈方法例如可列舉:擠壓塗佈法、直接凹板印刷式塗佈法、反向凹版印刷塗佈法、CAP塗佈法、模塗法等。又,亦可使用浸漬塗佈機、棒式塗佈機、旋轉塗佈機、狹縫&旋轉塗佈機、刮刀式塗佈機(有時亦稱為擠壓式塗佈機、幕式淋塗機、非旋轉塗佈機)等塗佈機進行塗佈。Examples of the coating method of the coloring composition include an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method, and a die coating method. Further, a dip coater, a bar coater, a spin coater, a slit & spin coater, or a knife coater (sometimes referred to as a squeeze coater or a curtain spray) may be used. Coating by a coater such as a coater or a non-rotating coater.
至於溶劑之去除或乾燥,例如可列舉:自然乾燥、通風乾燥、減壓乾燥等。具體之乾燥溫度較佳的是10~120℃,更佳的是25~100℃。As for the removal or drying of the solvent, for example, natural drying, air drying, and reduced-pressure drying can be mentioned. The specific drying temperature is preferably from 10 to 120 ° C, more preferably from 25 to 100 ° C.
乾燥時間較佳的是10秒~60分鐘,更佳的是30秒~30分鐘。於進行減壓乾燥之情形時,較佳的是於50~150 Pa之壓力下、20~25℃之溫度範圍內進行。The drying time is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes. In the case of drying under reduced pressure, it is preferably carried out at a temperature of from 50 to 150 Pa at a temperature ranging from 20 to 25 °C.
對乾燥後之塗膜,經由用以形成目標圖案之光罩而進行曝光。此時之光罩上的圖案形狀並無特別限定,可使用與目標用途對應之圖案形狀。The dried coating film is exposed through a photomask for forming a target pattern. The shape of the pattern on the mask at this time is not particularly limited, and a pattern shape corresponding to the intended use can be used.
作為用於曝光之光源,較佳的是產生250~450 nm波長之光之光源。具體可列舉:水銀燈、發光二極體、金屬鹵素燈、鹵素燈等,亦可使用截止特定波段之濾光片進行截止,或使用抽出特定波段之帶通濾波器而選擇性地抽出,並進行曝光。As the light source for exposure, a light source which generates light of a wavelength of 250 to 450 nm is preferable. Specific examples thereof include a mercury lamp, a light-emitting diode, a metal halide lamp, a halogen lamp, etc., and may be cut off using a filter that cuts off a specific band, or selectively extracted by using a band pass filter that extracts a specific band, and performs exposure.
為了能夠對整個曝光面均勻的照射平行光線,或進行遮罩與基材之精確之位置對準,較佳的是使用遮罩對準器、步進機等裝置。In order to be able to uniformly illuminate the entire exposed surface with parallel rays or to precisely position the mask with the substrate, it is preferred to use a mask aligner, a stepper or the like.
於曝光後,可藉由與顯影液接觸而使特定部分,例如未曝光部溶解而進行顯影,從而獲得圖案。作為顯影液,可列舉亦可包含界面活性劑之鹼性化合物(氫氧化鉀、碳酸鈉、四甲基氫氧化銨等)之水溶液等。After the exposure, development can be carried out by bringing a specific portion, for example, an unexposed portion, into contact with the developer to obtain a pattern. The developing solution may, for example, be an aqueous solution of a basic compound (potassium hydroxide, sodium carbonate, tetramethylammonium hydroxide or the like) which may contain a surfactant.
顯影方法可為覆液法、浸漬法、噴霧法等之任意者。進而於顯影時亦可將基板傾斜任意角度。較佳的是於顯影後進行水洗。The development method may be any of a liquid coating method, a dipping method, a spray method, and the like. Further, the substrate can be tilted at an arbitrary angle during development. It is preferred to carry out water washing after development.
進而,亦可視需要進行後烘烤處理。作為後烘烤處理,較佳的是例如150~230℃、10~240分鐘之範圍。Further, post-baking treatment may be performed as needed. The post-baking treatment is preferably in the range of, for example, 150 to 230 ° C for 10 to 240 minutes.
本發明之著色組合物可適宜地用於形成彩色濾光片或著色圖案。藉由本發明之著色組合物,能夠獲得色濃度、亮度、對比度、感光度、解像度、耐熱性等優異之著色圖案及彩色濾光片。又,該等彩色濾光片或著色圖案可用作光學膜、陣列基板、彩色濾光片基板等構成零件之一部分。進而,選自由該等光學膜、陣列基板及彩色濾光片基板所組成之群的至少1種等可以公知之型態利用於液晶顯示裝置、有機EL(Electroluminescence,電致發光)裝置等顯示裝置中;固體攝像元件等與著色影像相關之機器中。The coloring composition of the present invention can be suitably used to form a color filter or a colored pattern. According to the coloring composition of the present invention, a coloring pattern and a color filter excellent in color density, brightness, contrast, sensitivity, resolution, heat resistance, and the like can be obtained. Further, the color filters or colored patterns may be used as part of components such as an optical film, an array substrate, and a color filter substrate. Further, at least one type selected from the group consisting of the optical film, the array substrate, and the color filter substrate can be used in a display device such as a liquid crystal display device or an organic EL (Electroluminescence) device. Medium; solid-state imaging device and the like in a machine related to coloring images.
本發明化合物之移染性低,因此亦可由包含以本發明之化合物為主成分之染料之著色組合物而製作顯示特性優異之顯示裝置用彩色濾光片。Since the compound of the present invention has low transferability, a color filter for a display device having excellent display characteristics can be produced from a coloring composition containing a dye containing a compound of the present invention as a main component.
以下,列舉實施例對本發明加以更具體之說明。再者,實施例及比較例中之「%」及「份」,只要無特別標記,則為質量%及質量份。Hereinafter, the present invention will be more specifically described by way of examples. In addition, "%" and "part" in the examples and comparative examples are mass% and mass parts unless otherwise specified.
以下反應係於氮氣環境下進行。於具備回流管之四口燒瓶中向C.I.鹼性紅15.0份中添加N-甲基吡咯啶酮20.0份後,攪拌30分鐘而製備反應溶液。於室溫下一面攪拌反應溶液,一面滴加1,12-二胺基十二烷1.05份。於滴加結束後,一面將反應容器保溫為140度一面攪拌3小時。進而將1,12-二胺基十二烷0.53份添加至反應溶液中,然後一面將反應容器保溫為140度一面攪拌3小時。進而將1,12-二胺基十二烷0.53份添加至反應溶液中,然後一面將反應容器保溫為140度一面攪拌3小時。將冷卻至室溫之反應溶液注入至10%鹽酸水0.2升中而獲得紅色懸濁液。將過濾所獲得之紅色固體於減壓、60℃下進行乾燥,獲得式(I-1)所表示之化合物1.3份(產率23%)。The following reaction was carried out under a nitrogen atmosphere. After adding 20.0 parts of N-methylpyrrolidone to 15.0 parts of C.I. basic red in a four-necked flask equipped with a reflux tube, the mixture was stirred for 30 minutes to prepare a reaction solution. The reaction solution was stirred while stirring at room temperature, and 1.05 part of 1,12-diaminododecane was added dropwise. After the completion of the dropwise addition, the reaction vessel was kept at 140 degrees while stirring for 3 hours. Further, 0.53 parts of 1,12-diaminododecane was added to the reaction solution, and the mixture was stirred while maintaining the reaction vessel at 140 degrees for 3 hours. Further, 0.53 parts of 1,12-diaminododecane was added to the reaction solution, and the mixture was stirred while maintaining the reaction vessel at 140 degrees for 3 hours. The reaction solution cooled to room temperature was poured into 0.2 liter of 10% hydrochloric acid water to obtain a red suspension. The red solid obtained by filtration was dried under reduced pressure at 60 ° C to obtain 1.3 parts of the compound represented by the formula (I-1) (yield 23%).
化合物(I-2)之結構係根據質譜分析而決定。質譜儀使用JMS-700(日本電子股份有限公司製造)。The structure of the compound (I-2) is determined by mass spectrometry. The mass spectrometer was JMS-700 (manufactured by JEOL Ltd.).
質譜分析:離子化模式=FD+:m/z=1065Mass spectrometry: ionization mode = FD +: m / z = 1065
將化合物(I-2)0.35 g溶解於乳酸乙酯中而使體積為250 cm3 ,並將其中之2 cm3 利用離子交換水進行稀釋而使體積為100 cm3 (濃度:0.028 g/L),使用紫外可見近紅外分光光度計(V-650;日本分光股份有限公司製造)(石英槽,光徑長度:1 cm)測定吸收光譜。該化合物於λmax=529 nm顯示為吸光度1.6(任意單位)。0.35 g of the compound (I-2) was dissolved in ethyl lactate to have a volume of 250 cm 3 , and 2 cm 3 of the solution was diluted with ion-exchanged water to have a volume of 100 cm 3 (concentration: 0.028 g/L). The absorption spectrum was measured using an ultraviolet-visible near-infrared spectrophotometer (V-650; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 1.6 (arbitrary unit) at λmax = 529 nm.
以下反應係於氮氣環境下進行。於具備回流管之四口燒瓶中向C.I.鹼性紅15.0份中添加N-甲基吡咯啶酮20.0份後,攪拌30分鐘而製備反應溶液。於室溫下一面攪拌反應溶液,一面滴加1,4-丁二醇雙(3-胺基丙基)醚1.07份。於滴加結束後,一面將反應容器保溫為140度一面攪拌3小時。進而將1,4-丁二醇雙(3-胺基丙基)醚0.54份添加至反應溶液中,然後一面將反應容器保溫為140度一面攪拌3小時。進而將1,4-丁二醇雙(3-胺基丙基)醚0.54份添加至反應溶液中,然後一面將反應容器保溫為140度一面攪拌3小時。將冷卻至室溫之反應溶液注入至10%鹽酸水0.2升中而獲得紅色懸濁液。將過濾所獲得之紅色固體於減壓、60℃下進行乾燥,獲得式(I-3)所表示之化合物1.6份(產率29%)。The following reaction was carried out under a nitrogen atmosphere. After adding 20.0 parts of N-methylpyrrolidone to 15.0 parts of C.I. basic red in a four-necked flask equipped with a reflux tube, the mixture was stirred for 30 minutes to prepare a reaction solution. The reaction solution was stirred while stirring at room temperature, and 1.07 parts of 1,4-butanediol bis(3-aminopropyl)ether was added dropwise. After the completion of the dropwise addition, the reaction vessel was kept at 140 degrees while stirring for 3 hours. Further, 0.54 parts of 1,4-butanediol bis(3-aminopropyl)ether was added to the reaction solution, and the mixture was stirred while maintaining the reaction vessel at 140 degrees for 3 hours. Further, 0.54 parts of 1,4-butanediol bis(3-aminopropyl)ether was added to the reaction solution, and the mixture was stirred while maintaining the reaction vessel at 140 degrees for 3 hours. The reaction solution cooled to room temperature was poured into 0.2 liter of 10% hydrochloric acid water to obtain a red suspension. The red solid obtained by filtration was dried under reduced pressure at 60 ° C to obtain 1.6 parts of the compound represented by the formula (I-3) (yield 29%).
化合物(I-3)之結構係根據質譜分析而決定。質譜儀使用JMS-700(日本電子股份有限公司製造)。The structure of the compound (I-3) is determined by mass spectrometry. The mass spectrometer was JMS-700 (manufactured by JEOL Ltd.).
質譜分析:離子化模式=FD+:m/z=1068Mass spectrometry: ionization mode = FD +: m / z = 1068
將化合物(I-2)0.35 g溶解於乳酸乙酯中而使體積為250 cm3 ,並將其中之2 cm3 利用離子交換水進行稀釋而使體積為100 cm3 (濃度:0.028 g/L),使用紫外可見近紅外分光光度計(石英槽,光徑長度:1 cm)測定吸收光譜。該化合物於λmax=530 nm顯示為吸光度2.0(任意單位)。0.35 g of the compound (I-2) was dissolved in ethyl lactate to have a volume of 250 cm 3 , and 2 cm 3 of the solution was diluted with ion-exchanged water to have a volume of 100 cm 3 (concentration: 0.028 g/L). The absorption spectrum was measured using an ultraviolet visible near-infrared spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.0 (arbitrary unit) at λmax = 530 nm.
於具備回流冷凝器、滴液漏斗及攪拌機之燒瓶內以0.02 L/min流入氮其而成為氮氣環境,加入3-甲氧基-1-丁醇200質量份及3-甲氧基丁基乙酸酯100質量份,一面攪拌一面加熱至70℃。繼而,將甲基丙烯酸98質量份、丙烯酸-3,4-環氧三環[5.2.1.02,6 ]癸酯(以莫耳比50:50混合式(B-1-1)所表示之化合物及式(B-1-2)所表示之化合物)394質量份溶解於3-甲氧基-1-丁醇140質量份中而製備溶液,使用滴液泵將該溶解液以4小時滴加至保溫為70℃至燒瓶內。另一方面,使用其他滴液泵,將3-甲氧基丁基乙酸酯240質量份中溶解有聚合起始劑2,2'-偶氮雙(2,4-二甲基戊腈)27質量份之溶液,以4小時滴加至燒瓶內。於聚合起始劑溶液之滴加結束後,於70℃下保持4小時,其後冷卻至室溫,獲得固形物成分為44.3質量%之共聚物(樹脂B1)之溶液。所獲得之樹脂B1之重量平均分子量Mw為7500,分子量分佈為1.7,酸值為111 mgKOH/g。Into 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-methoxybutyl B were added. 100 parts by mass of the acid ester was heated to 70 ° C while stirring. Then, 98 parts by mass of methacrylic acid and 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl acrylate (expressed in a molar ratio of 50:50 (B-1-1)) 394 parts by mass of the compound and the compound represented by the formula (B-1-2) were dissolved in 140 parts by mass of 3-methoxy-1-butanol to prepare a solution, and the solution was dropped in 4 hours using a drip pump. Add to 70 ° C to the flask. On the other hand, using another drip pump, 240 parts by mass of 3-methoxybutyl acetate was dissolved with a polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile). 27 parts by mass of the solution was added dropwise to the flask over 4 hours. After completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin B1) having a solid content of 44.3 mass%. The obtained resin B1 had a weight average molecular weight Mw of 7,500, a molecular weight distribution of 1.7, and an acid value of 111 mgKOH/g.
以下之實施例中所使用之成分,有時如下述那樣進行省略記載。The components used in the following examples may be omitted as described below.
(I-2) 著色劑:實施例1中所合成之偶氮化合物(I-2) Colorant: The azo compound synthesized in Example 1
(I-3) 著色劑:實施例2中所合成之偶氮化合物(I-3) Colorant: the azo compound synthesized in Example 2
(II-1) 著色劑:鹼性紅1(II-1) Colorant: Alkaline Red 1
(B-1) 樹脂:樹脂B1溶液(B-1) Resin: Resin B1 solution
(B-2) 樹脂:甲基丙烯酸/甲基丙烯酸苄酯(莫耳比:30/70)共聚物(田岡化學工業股份有限公司製造,平均分子量10700、酸值70 mgKOH/g)之33.8%丙二醇單甲醚乙酸酯溶液(B-2) Resin: 33.8% of methacrylic acid/benzyl methacrylate (Morby: 30/70) copolymer (manufactured by Tajika Chemical Industry Co., Ltd., average molecular weight 10700, acid value 70 mgKOH/g) Propylene glycol monomethyl ether acetate solution
(C-1) 聚合性化合物:二季戊四醇六丙烯酸酯(KAYARAD DPHA;日本化藥股份有限公司製造)(C-1) Polymerizable compound: dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
(D-1) 光聚合起始劑:N-苯甲醯基氧基-1-(4-苯基硫烷基苯基)辛烷-1-酮-2-亞胺(Irgacure OXE01;BASF Japan公司製造)(D-1) Photopolymerization initiator: N-benzylideneoxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine (Irgacure OXE01; BASF Japan Made by the company)
(G-1) 界面活性劑:聚醚改性矽油(Toray Silicone SH8400;Dow Corning Toray股份有限公司製造)(G-1) Surfactant: Polyether modified eucalyptus oil (Toray Silicone SH8400; manufactured by Dow Corning Toray Co., Ltd.)
(E-1) 溶劑:丙二醇單甲醚(E-1) Solvent: propylene glycol monomethyl ether
(E-2) 溶劑:丙二醇單甲醚乙酸酯(E-2) Solvent: propylene glycol monomethyl ether acetate
(E-3) 溶劑:N,N-二甲基甲醯胺(E-3) Solvent: N,N-dimethylformamide
將(I-2) 0.30質量份(I-2) 0.30 parts by mass
(B-1) 1.67質量份(B-1) 1.67 parts by mass
(C-1) 0.74質量份(C-1) 0.74 parts by mass
(D-1) 0.22質量份(D-1) 0.22 parts by mass
(G-1) 0.001質量份(G-1) 0.001 parts by mass
(E-1) 6.23質量份(E-1) 6.23 parts by mass
(E-2) 0.84質量份(E-2) 0.84 parts by mass
混合而獲得著色組合物。Mixing to obtain a coloring composition.
將(B-2) 40.2質量份(B-2) 40.2 parts by mass
(C-1) 5.8質量份(C-1) 5.8 parts by mass
(D-1) 0.58質量份(D-1) 0.58 parts by mass
(G-1) 0.01質量份(G-1) 0.01 parts by mass
(E-1) 46.6質量份(E-1) 46.6 parts by mass
(E-2) 6.8質量份(E-2) 6.8 parts by mass
混合而獲得樹脂組合物。The resin composition was obtained by mixing.
利用旋轉塗佈法將上述所獲得之著色組合物塗佈於玻璃(#1737;Corning)上,以100℃、3分鐘使揮發成分揮發。於冷卻後,使用曝光機(TME-150RSK;Topcon股份有限公司製造),於大氣環境下以150 mJ/cm2 之曝光量(365 nm基準)進行光照射,形成著色組合物之塗佈膜(膜厚2.2 μm)。The coloring composition obtained above was applied onto glass (#1737; Corning) by a spin coating method, and the volatile component was volatilized at 100 ° C for 3 minutes. After cooling, an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used to irradiate light at an exposure amount of 150 mJ/cm 2 (365 nm basis) in an atmosphere to form a coating film of the colored composition ( The film thickness is 2.2 μm).
利用旋轉塗佈法將上述所獲得之著色組合物塗佈於玻璃(#1737;Corning)上,以100℃、3分鐘使揮發成分揮發。於冷卻後,使用曝光機(TME-150RSK;Topcon股份有限公司製造),於大氣環境下以150 mJ/cm2 之曝光量(365 nm為基準)進行光照射。於烘箱中,以220℃加熱2小時,形成樹脂組合物之塗佈膜(膜厚2.2 μm)。The coloring composition obtained above was applied onto glass (#1737; Corning) by a spin coating method, and the volatile component was volatilized at 100 ° C for 3 minutes. After cooling, an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used, and light irradiation was performed under an atmospheric environment at an exposure amount of 150 mJ/cm 2 (365 nm). The film was heated at 220 ° C for 2 hours in an oven to form a coating film of a resin composition (film thickness: 2.2 μm).
使著色組合物之塗佈膜及樹脂組合物之塗佈膜於空開70 μm之間隔的狀態下對向,於230℃下加熱120分鐘,使用比色計(OSP-SP-200;OLYMPUS公司製造)測定樹脂組合物之塗佈膜加熱前後之色差(ΔEab*)。對所獲得之塗佈膜實施以上之移染性評價,結果是樹脂組合物之色差(ΔEab*)為2.2。The coating film of the coloring composition and the coating film of the resin composition were opposed to each other at a space of 70 μm, and heated at 230 ° C for 120 minutes, using a colorimeter (OSP-SP-200; OLYMPUS Co., Ltd. Manufacture) The color difference (ΔEab*) before and after heating of the coating film of the resin composition was measured. The coating film obtained was subjected to the above evaluation of the transferability, and as a result, the color difference (ΔEab*) of the resin composition was 2.2.
除將(I-2)著色劑:實施例1中所合成之偶氮化合物變更為(I-3)著色劑:實施例2中所合成之偶氮化合物以外,以與實施例3相同之方式,製作著色組合物之塗佈膜及樹脂組合物之塗佈膜,實施移染性評價,結果是樹脂組合物之色差(ΔEab*)為1.8。The same procedure as in Example 3 was carried out except that the (I-2) colorant: the azo compound synthesized in Example 1 was changed to the (I-3) colorant: the azo compound synthesized in Example 2, in the same manner as in Example 3. The coating film of the coloring composition and the coating film of the resin composition were prepared, and the transfer property was evaluated. As a result, the color difference (ΔEab*) of the resin composition was 1.8.
將(II-1) 0.30質量份(II-1) 0.30 parts by mass
(B-1) 1.67質量份(B-1) 1.67 parts by mass
(C-1) 0.74質量份(C-1) 0.74 parts by mass
(D-1) 0.22質量份(D-1) 0.22 parts by mass
(G-1) 0.001質量份(G-1) 0.001 parts by mass
(E-2) 0.84質量份(E-2) 0.84 parts by mass
(E-3) 6.23質量份(E-3) 6.23 parts by mass
混合而獲得著色組合物。Mixing to obtain a coloring composition.
以與實施例4相同之方式,製作著色組合物之塗佈膜及樹脂組合物之塗佈膜,實施移染性評價,結果是樹脂組合物之色差(ΔEab*)為57.2。In the same manner as in Example 4, the coating film of the coloring composition and the coating film of the resin composition were prepared, and the transfer property was evaluated. As a result, the color difference (ΔEab*) of the resin composition was 57.2.
自上述結果可知,與比較例之化合物相比而言,實施例之化合物可使移染性非常低。From the above results, it was found that the compound of the example had a very low transferability as compared with the compound of the comparative example.
本發明之化合物移染性低,因此可藉由使用包含以本發明之化合物為主成分之染料之著色組合物而製作顯示特性優異之顯示裝置用彩色濾光片。Since the compound of the present invention has low transferability, a color filter for a display device having excellent display characteristics can be produced by using a coloring composition containing a dye containing a compound of the present invention as a main component.
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JP5715380B2 (en) * | 2010-06-30 | 2015-05-07 | 富士フイルム株式会社 | Colored curable composition, color filter, production method thereof, solid-state imaging device, liquid crystal display device, and dye multimer |
JP5223980B2 (en) * | 2011-04-21 | 2013-06-26 | 大日本印刷株式会社 | Color material dispersion, colored resin composition for color filter, color filter, liquid crystal display device and organic light emitting display device |
JP5221787B2 (en) * | 2011-04-21 | 2013-06-26 | 大日本印刷株式会社 | Color material and method for producing the same |
EP2821444A4 (en) * | 2012-02-29 | 2015-03-11 | Fujifilm Corp | Colored composition, inkjet recording ink, and inkjet recording method |
JP5816576B2 (en) * | 2012-02-29 | 2015-11-18 | 富士フイルム株式会社 | Colored composition, method for producing colored composition, ink for ink jet recording, and ink jet recording method |
JP5816575B2 (en) * | 2012-02-29 | 2015-11-18 | 富士フイルム株式会社 | Colored composition, method for producing colored composition, ink for ink jet recording, and ink jet recording method |
JP5816574B2 (en) * | 2012-02-29 | 2015-11-18 | 富士フイルム株式会社 | Colored composition, method for producing colored composition, ink for ink jet recording, and ink jet recording method |
JP2014071320A (en) * | 2012-09-28 | 2014-04-21 | Dainippon Printing Co Ltd | Manufacturing method for color filter and transparent-protective-film forming resin composition |
WO2014061143A1 (en) | 2012-10-18 | 2014-04-24 | 大日本印刷株式会社 | Coloring material and method for producing same |
WO2015046083A1 (en) * | 2013-09-30 | 2015-04-02 | 富士フイルム株式会社 | Compound having xanthene skeleton, colorant composition, ink for inkjet recording, inkjet recording method, inkjet printer cartridge, and inkjet recording material |
JP6295600B2 (en) * | 2013-10-23 | 2018-03-20 | 大日本印刷株式会社 | Color material, color material dispersion, colored resin composition for color filter, color filter, liquid crystal display device, and organic light emitting display device |
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JP7052206B2 (en) * | 2017-03-24 | 2022-04-12 | 三菱ケミカル株式会社 | Colored resin composition, color filter and image display device |
JPWO2019044872A1 (en) * | 2017-08-31 | 2020-10-08 | 富士フイルム和光純薬株式会社 | Rhodamine-linked compound |
JP2022056354A (en) * | 2020-09-29 | 2022-04-08 | 保土谷化学工業株式会社 | Xanthene dye, coloring composition containing the dye, colorant for color filters, and color filter |
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JP2000017183A (en) * | 1998-04-30 | 2000-01-18 | Bunshi Bio Photonics Kenkyusho:Kk | Coloring matter having rotaxane structure, labeling agent and method therefor |
CN1653531A (en) * | 2002-05-17 | 2005-08-10 | 西巴特殊化学品控股有限公司 | Optical storage media comprising pentacyclic xanthylium dyes |
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