TWI675068B - Dye and colored curable resin composition - Google Patents
Dye and colored curable resin composition Download PDFInfo
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Abstract
本發明為一種具有含矽原子之基,且具有方酸菁骨架的染料。 The present invention is a dye having a group containing a silicon atom and a squaraine skeleton.
Description
本發明,係有關於染料及著色硬化性樹脂組成物。 The present invention relates to a dye and a coloring curable resin composition.
方酸菁染料係使用於照相感光體等領域。在日本特開昭60-248652號公報中,所載方酸菁(squarylium)染料係如式(II-0)所示之化合物。 Squaric acid dyes are used in fields such as photoreceptors. In Japanese Patent Application Laid-Open No. 60-248652, the squarylium dye is a compound represented by the formula (II-0).
本發明,係包含以下之發明。 The present invention includes the following inventions.
[1]一種染料,其係含有含矽原子之基,且含方酸菁骨架。 [1] A dye comprising a group containing a silicon atom and a squarocyanine skeleton.
[2]如[1]項所述之染料,其中,含矽原子之基,為含有-Si(R14)3之基 [2] The dye as described in [1], wherein the group containing a silicon atom is a group containing -Si (R 14 ) 3
[R14表示氫原子、羥基、碳數1至4之烷基或碳數1至4之烷氧基,3個R14可分別相同亦可不同]。 [R 14 represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and three R 14 may be the same or different, respectively].
[3]如[1]或[2]項所述之染料,其中,含矽原子之基為式(iia)所示之基
[4]如[1]至[3]之任1項所述之染料,其係式(IIa)所示之化合物
R3、R4、R113及R114分別獨立地表示氫原子或羥基。 R 3 , R 4 , R 113 and R 114 each independently represent a hydrogen atom or a hydroxyl group.
R5、R6、R15及R16分別獨立地表示氫原子、含矽原子之基、可具有取代基的碳數1至20之1價飽和烴基(構成該飽和烴基的碳原子間,亦可插入氧原子或硫原子)或可具有取代基的苯基。惟,R5、R6、R15及R16之至少1個為含矽原子之基]。 R 5 , R 6 , R 15 and R 16 each independently represent a hydrogen atom, a silicon atom-containing group, and a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (between the carbon atoms constituting the saturated hydrocarbon group, also An oxygen atom or a sulfur atom may be inserted) or a phenyl group which may have a substituent. However, at least one of R 5 , R 6 , R 15 and R 16 is a group containing a silicon atom].
[5]如[4]項所述之染料,其中,含矽原子之基為式(iia)所示之基
[6]如[4]或[5]之任1項所述之染料,其中,可具有取代基的苯基為式(i)所示之基:
[7]如[1]至[6]之任1項所述之染料,其係式(II)所示之化合物:
R3a及R4a分別獨立地表示氫原子或羥基。 R 3a and R 4a each independently represent a hydrogen atom or a hydroxyl group.
R5a及R6a中,一者為式(ii)所示之基,另一者則為氫原子、可具有取代基的碳數1至20之1價飽和烴基(構成飽和烴基的碳原子間,亦可插入氧原子或硫原子)或式(i)所示之基。 One of R 5a and R 6a is a group represented by formula (ii), and the other is a hydrogen atom, and a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (between carbon atoms constituting a saturated hydrocarbon group) (You can also insert an oxygen atom or a sulfur atom) or a group represented by formula (i).
[8]一種著色劑,其係含有[1]至[7]之任1項所述之染料。 [8] A coloring agent containing the dye according to any one of [1] to [7].
[9]如[8]項所述之著色劑,其再含有黃色顏料。 [9] The coloring agent according to item [8], which further contains a yellow pigment.
[10]如[9]項所述之著色劑,其中,黃色顏料為選自:C.I.顏料黃138號、C.I.顏料黃150號及C.I.顏料黃185號所成群組之至少1種顏料。 [10] The coloring agent according to item [9], wherein the yellow pigment is at least one pigment selected from the group consisting of C.I. Pigment Yellow 138, C.I. Pigment Yellow 150, and C.I. Pigment Yellow 185.
[11]一種著色硬化性樹脂組成物,其係含有[8]至[10]之任1項所述之著色劑、樹脂、聚合性化合物及聚合起始劑。 [11] A coloring curable resin composition containing the coloring agent according to any one of [8] to [10], a resin, a polymerizable compound, and a polymerization initiator.
[12]一種塗膜,其係由[11]項所述之著色硬化性樹脂組成物所形成。 [12] A coating film formed from the colored curable resin composition according to [11].
[13]一種濾色器,其係由[11]項所述之著色硬化性樹脂組成物所形成。 [13] A color filter formed of the color-hardening resin composition according to [11].
[14]一種顯示裝置,其係含有[13]項所述之濾色器。 [14] A display device comprising the color filter described in [13].
本發明之染料,對有機溶劑之溶解性優異,且以含該染料的著色硬化性樹脂組成物形成之濾色器,就耐熱性之點而言亦優異。 The dye of the present invention is excellent in solubility in an organic solvent, and a color filter formed of a coloring curable resin composition containing the dye is also excellent in heat resistance.
本發明係具有含矽原子之基,且具有方酸菁骨架的染料。 The present invention is a dye having a group containing a silicon atom and a squaraine skeleton.
含矽原子之基,可列舉:三烷基矽氧基、三烷氧基矽基等具有矽氧基之取代基。 Examples of the group containing a silicon atom include a substituent having a siloxy group such as a trialkylsiloxy group and a trialkoxysilyl group.
三烷基矽氧基可列舉:三甲基矽氧基、三乙基矽氧基等,具有碳數1至8(以1至4為較佳)之烷基的三烷基矽氧基。 Examples of the trialkylsiloxy group include trimethylsiloxy group, triethylsiloxy group, and the like, and trialkylsiloxy groups having an alkyl group having 1 to 8 carbon atoms (preferably 1 to 4 are preferred).
三烷氧基矽基,可列舉:三甲氧基矽基、三乙氧基矽基等,具有碳數1至8(以1至4為較佳)之烷氧基的三烷基矽基。 Trialkoxysilyl groups include trimethoxysilyl groups, triethoxysilyl groups, and the like, and trialkylsilyl groups having an alkoxy group having 1 to 8 carbon atoms (preferably 1 to 4 are preferred).
具有矽氧基之基,可再舉如:具有碳數3至10的脂環 烴及矽氧基之基、及具有在後述之碳數1至20的飽和烴基中插入氧原子及硫原子之基及矽氧基之基,此類基,亦可再含鹵素原子、烷基胺基及二烷基胺基(以下,總稱此類取代胺基為「(二)烷基胺基」)等。 It has a siloxy group, for example: an alicyclic ring having 3 to 10 carbon atoms A group of a hydrocarbon and a siloxy group, and a group having an oxygen atom and a sulfur atom and a group of a siloxy group inserted into a saturated hydrocarbon group having a carbon number of 1 to 20 to be described later. Such a group may further include a halogen atom and an alkyl group. Amino groups and dialkylamino groups (hereinafter, such substituted amine groups are collectively referred to as "(di) alkylamino groups") and the like.
本發明之染料中,含矽原子之基,以含-Si(R14)3之基為較佳,含式(iia)所示之基為更佳:
-Si(R14)3中,R14表示氫原子、羥基、碳數1至4之烷基或碳數1至4之烷氧基。3個R14可分別相同亦可不同。 In -Si (R 14 ) 3 , R 14 represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. The three R 14 may be the same or different.
R14所示之烷基,可列舉:甲基、乙基、丙基、丁基。 Examples of the alkyl group represented by R 14 include methyl, ethyl, propyl, and butyl.
R14所示之烷氧基,可列舉:甲氧基、乙氧基、丙氧基、丁氧基。 Examples of the alkoxy group represented by R 14 include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
R14,以碳數1至4之烷基或碳數1至4之烷氧基為佳,氫原子、甲基、乙基、丙基、甲氧基、乙氧基或丙氧基為更佳,氫原子、甲基、乙基、甲氧基或乙氧基為又更佳。 R 14 is preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and more preferably a hydrogen atom, methyl, ethyl, propyl, methoxy, ethoxy, or propoxy Preferably, a hydrogen atom, methyl, ethyl, methoxy or ethoxy is more preferred.
3個R14以相同為較佳。 The three R 14 are preferably the same.
式(iia)中,R144表示氫原子、羥基、碳數1至4之烷基或碳數1至4之烷氧基。 In formula (iia), R 144 represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
L1表示碳數1至8之烷二基。該烷二基中所含之-CH2-亦可經氧原子取代。*表示與氮原子之鍵結基。 L 1 represents an alkanediyl group having 1 to 8 carbon atoms. -CH 2 -contained in the alkanediyl group may be substituted by an oxygen atom. * Indicates a bonding group with a nitrogen atom.
R144表示的烷基,可列舉:甲基、乙基、丙基、丁基。 Examples of the alkyl group represented by R 144 include methyl, ethyl, propyl, and butyl.
R144表示的烷氧基,可列舉:甲氧基、乙氧基、丙氧基、丁氧基。 Examples of the alkoxy group represented by R 144 include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
R144,以氫原子、甲基、乙基、丙基、甲氧基、乙氧基或丙氧基為佳,氫原子、甲基、乙基、甲氧基或乙氧基為更佳。3個R144以相同為佳。 R 144 is preferably a hydrogen atom, methyl, ethyl, propyl, methoxy, ethoxy or propoxy, and more preferably a hydrogen atom, methyl, ethyl, methoxy or ethoxy. The three R 144 are preferably the same.
L1表示之烷二基,可列舉:亞甲基、伸乙基、丙烷-1,3-二基、丙烷-1,2-二基、丁烷-1,4-二基、丁烷-1,3-二基、戊烷-1,5-二基、己烷-1,6-二基、庚烷-1,7-二基、辛烷-1,8-二基等。 Examples of the alkanediyl group represented by L 1 include methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, and butane- 1,3-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, and the like.
L1以碳數1至4之烷二基為較佳。 L 1 is preferably an alkanediyl group having 1 to 4 carbon atoms.
式(iia)所示之基,可列舉下述所示之基。其中,以式(ii-1)所示之基至式(ii-6)所示之基為較佳。 Examples of the group represented by the formula (iia) include the groups shown below. Among them, the base represented by the formula (ii-1) to the base represented by the formula (ii-6) is preferable.
本發明之染料,可列舉例如:具有三甲基 矽氧基、三乙基矽氧基、三甲氧基矽基、三乙氧基矽基等矽氧基之具有方酸菁骨架的染料。 Examples of the dye of the present invention include trimethyl Siloxane, triethylsilyl, trimethoxysilyl, triethoxysilyl, and other siloxy dyes with a squarylium skeleton.
本發明之染料,以含式(IIa)所示之化合物 (以下,亦記載為化合物(IIa))為佳,含式(II)所示之化合物(以下,亦記載為化合物(II))為更佳。化合物(IIa)及化合物(II)亦分別包含其互變異構物。 The dye of the present invention contains a compound represented by formula (IIa) (Hereinafter, it is also described as a compound (IIa)), and it is more preferable that it contains the compound represented by Formula (II) (henceforth, also described as a compound (II)). Compound (IIa) and compound (II) also include their tautomers, respectively.
R3、R4、R113及R114分別獨立地表示氫原子或羥基。 R 3 , R 4 , R 113 and R 114 each independently represent a hydrogen atom or a hydroxyl group.
R5、R6、R15及R16分別獨立地表示氫原子、含矽原子之基、可具有取代基的碳數1至20之1價飽和烴基(構成該飽和烴基的碳原子間,亦可插入氧原子或硫原子)或可具有取代基的苯基。惟,R5、R6、R15及R16之至少1個為含矽原子之基。] R 5 , R 6 , R 15 and R 16 each independently represent a hydrogen atom, a silicon atom-containing group, and a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (between the carbon atoms constituting the saturated hydrocarbon group, also An oxygen atom or a sulfur atom may be inserted) or a phenyl group which may have a substituent. However, at least one of R 5 , R 6 , R 15 and R 16 is a group containing a silicon atom. ]
R3a及R4a分別獨立地表示氫原子或羥基。 R 3a and R 4a each independently represent a hydrogen atom or a hydroxyl group.
R5a及R6a中,一者係式(ii)所示之基,另一者為氫原子、可具有取代基的碳數1至20之1價飽和烴基(構成飽和烴基的碳原子間,亦可插入氧原子或硫原子)或式(i)所示之基。 One of R 5a and R 6a is a group represented by formula (ii), and the other is a hydrogen atom and a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (between carbon atoms constituting a saturated hydrocarbon group, An oxygen atom or a sulfur atom may be inserted) or a group represented by formula (i).
本說明書中,2♁表示環係帶2價之正電荷。 In the present specification, 2 ♁ represents a bivalent positive charge of a ring system.
式(IIa)及式(II)之鹵素原子,可列舉:氟原子、氯原子、溴原子及碘原子。 Examples of the halogen atom of the formula (IIa) and the formula (II) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
式(IIa)及式(II)中1價飽和烴基,可列舉:甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十二碳烷基、十六碳烷基及二十碳烷基等碳數1至20之直鏈狀烷基;異丙基、異丁基、第二丁基、第三丁基、異戊基、新戊基及2-乙基己基等碳數3至20之分枝鏈狀烷基;環丙基、環戊基、環己基、環庚基、環辛基及三環癸基等碳數3至20之脂環飽和烴基。 Examples of monovalent saturated hydrocarbon groups in formula (IIa) and formula (II) include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and dodecyl Alkyl, hexadecyl and icosyl alkyl linear alkyl groups having 1 to 20 carbons; isopropyl, isobutyl, second butyl, third butyl, isopentyl, neo 3 to 20 carbon chain branches such as pentyl and 2-ethylhexyl; 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and tricyclodecyl 20 alicyclic saturated hydrocarbon group.
式(IIa)及式(II)中1價飽和烴基所具有之取代基,可列舉:鹵素原子、羥基及碳數1至8之(二)烷基胺基。 Examples of the substituent of the monovalent saturated hydrocarbon group in the formula (IIa) and the formula (II) include a halogen atom, a hydroxyl group, and a (di) alkylamino group having 1 to 8 carbon atoms.
該鹵素原子可列舉:氟原子、氯原子、溴原子及碘原子。 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
該(二)烷基胺基可列舉:甲基胺基、乙基胺基、正丙基胺基、正丁基胺基、正戊基胺基、二甲基胺基、二乙基胺基、二丙基胺基、乙基甲基胺基等。 Examples of the (di) alkylamino group include methylamino, ethylamino, n-propylamino, n-butylamino, n-pentylamino, dimethylamino, and diethylamino , Dipropylamino, ethylmethylamino, and the like.
可具有取代基的上述飽和烴基之例,可列舉例如下述式所示之基
式(IIa)及式(II)中,構成上述1價飽和烴基
的碳原子間亦可插入氧原子或硫原子之基,可例舉下述式所示之基:
R1、R2、R1a、R2a、R111及R112各為獨立,以氫原子、羥基及碳數1至4之烷基為佳;氫原子、羥基及甲基為更 佳;氫原子為又更佳。 R 1 , R 2 , R 1a , R 2a , R 111 and R 112 are each independent, preferably a hydrogen atom, a hydroxyl group, and an alkyl group having 1 to 4 carbon atoms; a hydrogen atom, a hydroxyl group, and a methyl group are more preferred; hydrogen Atoms are even better.
化合物(IIa)中,R5、R6、R15及R16之至少1個表示含矽原子之基。以R5、R6、R15及R16之至少1個為式(iia)所示之基為較佳;以R5及R6之至少1個為式(iia)所示之基,R15及R16之至少1個為式(iia)所示之基為更佳。 In the compound (IIa), at least one of R 5 , R 6 , R 15 and R 16 represents a group containing a silicon atom. It is preferable that at least one of R 5 , R 6 , R 15 and R 16 is a base represented by formula (iia); at least one of R 5 and R 6 is a base represented by formula (iia), R It is more preferable that at least one of 15 and R 16 is a base represented by formula (iia).
化合物(IIa)中,含矽原子之基以式(iia)所示之基為較佳,式(ii)所示之基為更佳。 In the compound (IIa), a group containing a silicon atom is preferably a group represented by formula (iia), and a group represented by formula (ii) is more preferred.
化合物(IIa)中,可具有取代基之苯基以式(i)所示之基為較佳。 In the compound (IIa), a phenyl group which may have a substituent is preferably a group represented by formula (i).
化合物(IIa),以含矽原子之基為式(iia)所示之基,且可具有取代基之苯基為式(i)所示之基的式(IIa)化合物(以下,該化合物有時稱為「化合物(IIb)」)為更佳。 Compound (IIa) is a compound of formula (IIa) in which a group containing a silicon atom is a group represented by formula (iia), and a phenyl group which may have a substituent is a group represented by formula (i) (Referred to as "compound (IIb)").
化合物(II)中,以R5a及R6a之中,一者為式 (iia)所示之基、另一者為氫原子、可具有取代基的碳數1至20之1價飽和烴基(構成飽和烴基的碳原子間,亦可插入氧原子或硫原子)或式(i)所示之基為佳; 以R5a及R6a之中,一者為式(ii)所示之基、另一者為氫原子、可具有取代基的碳數1至20之1價飽和烴基(構成飽和烴基的碳原子間,亦可插入氧原子或硫原子)或式(i)所示之基為更佳。 In the compound (II), one of R 5a and R 6a is a group represented by formula (iia), the other is a hydrogen atom, and a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent ( Among carbon atoms constituting a saturated hydrocarbon group, an oxygen atom or a sulfur atom may also be inserted) or a group represented by formula (i); Among R 5a and R 6a , one is a group represented by formula (ii), The other is a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (an oxygen atom or a sulfur atom may be inserted between the carbon atoms constituting the saturated hydrocarbon group) or the group represented by formula (i) is Better.
R5、R6、R5a、R6a、R15及R16中,可具有苯 基之取代基,可列舉:碳數1至20之1價飽和烴基、碳數2至20之1價不飽和烴基。 R 5 , R 6 , R 5a , R 6a , R 15 and R 16 may have a phenyl substituent, and examples thereof include a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a monovalent group having 2 to 20 carbon atoms. Saturated hydrocarbyl.
該取代基中1價飽和烴基以:甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、正戊基、正己基、正庚基、2-乙基己基、正辛基、正壬基、正癸基、正十一碳烷基、正十二碳烷基等碳數1至20之烷基為較佳。 The monovalent saturated hydrocarbon group in this substituent is: methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, third butyl, n-pentyl, n-hexyl, n-heptyl, 2 -Ethylhexyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, and other alkyl groups having 1 to 20 carbon atoms are preferred.
該取代基中1價不飽和烴基之例,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、癸烯基等碳數2至20之烯基。 Examples of the monovalent unsaturated hydrocarbon group in the substituent include carbons such as vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, and decenyl. Alkenyl groups of 2 to 20.
式(i)中,R12所示之1價不飽和烴基之例, 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、癸烯基等碳數2至20之烯基。 Examples of the monovalent unsaturated hydrocarbon group represented by R 12 in formula (i) include vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonene Alkenyl groups having 2 to 20 carbon atoms, such as alkyl, decenyl, and the like.
R12所示之1價飽和烴基之例,可列舉:甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、正戊基、正己基、正庚基、2-乙基己基、正辛基、正壬基、正癸基、正十一碳烷基、正十二碳烷基等碳數1至20之烷基。 Examples of the monovalent saturated hydrocarbon group represented by R 12 include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, third butyl, n-pentyl, n-hexyl, Alkyl groups having 1 to 20 carbons such as n-heptyl, 2-ethylhexyl, n-octyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl.
R12,以氫原子或碳數1至4為較佳,氫原子、甲基或乙基為更佳。 R 12 is preferably a hydrogen atom or a carbon number of 1 to 4, and more preferably a hydrogen atom, a methyl group, or an ethyl group.
式(i)所示之基,可例舉如下之基:
式(II)中,n以1至6的整數為佳,1至4的 整數為更佳。 In formula (II), n is preferably an integer of 1 to 6, and 1 to 4 Integers are better.
R5、R6、R5a及R6a所示之基,在分別表示式 (iia)和式(ii)所示之基以外的基時,以氫原子、碳數1至20之飽和烴基、式(i)所示之基為佳,氫原子為更佳。 When the groups represented by R 5 , R 6 , R 5a and R 6a represent groups other than the groups represented by formula (iia) and formula (ii), respectively, a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, The group represented by formula (i) is preferred, and a hydrogen atom is more preferred.
下式所示之基
含有含矽原子之基,且含方酸菁骨架的染 料,可列舉:式(AII-1)所示之化合物至式(AII-75)所示之化合物。 Dyestuffs containing a group containing silicon atoms and a squarine skeleton Examples of the material include a compound represented by the formula (AII-1) to a compound represented by the formula (AII-75).
本發明中,由原料易於取得之點而言,以 式(AII-4)所示之化合物至式(AII-6)所示之化合物、及式(AII-31)所示之化合物至式(AII-33)所示之化合物較佳。 In the present invention, from the point that raw materials are easily available, The compound represented by the formula (AII-4) to the compound represented by the formula (AII-6), and the compound represented by the formula (AII-31) to the compound represented by the formula (AII-33) are preferable.
化合物(II),可依照日本特開2002-363434 號公報中所載之方法製造,具體地,可藉由式(IV-1)所示之化合物與方酸(3,4-二羥基-3-環丁烯-1,2-二酮)(3,4-dihydroxy-3-cyclobutene-1,2-dione)反應而製造。 Compound (II), according to Japanese Patent Application Laid-Open No. 2002-363434 It can be produced by the method described in the publication No. 1, specifically, by using the compound represented by the formula (IV-1) and a cubic acid (3,4-dihydroxy-3-cyclobutene-1,2-dione) ( 3,4-dihydroxy-3-cyclobutene-1,2-dione).
相對於式(IV-1)所示之化合物1莫耳,方酸 之使用量以0.5莫耳以上0.8莫耳以下為佳,0.55莫耳以上0.6莫耳以下為更佳。 Relative to 1 mole of the compound represented by formula (IV-1) The amount used is preferably from 0.5 mol to 0.8 mol, more preferably from 0.55 mol to 0.6 mol.
反應溫度,以30℃至180℃為佳,80℃至140℃為更佳。反應時間以1小時至12小時為佳,3小時至8小時為更佳。 The reaction temperature is preferably 30 ° C to 180 ° C, and more preferably 80 ° C to 140 ° C. The reaction time is preferably 1 hour to 12 hours, and more preferably 3 hours to 8 hours.
由生產率之點而言,反應以在有機溶劑中 進行較佳。有機溶劑可列舉:甲苯、二甲苯等烴溶劑;氯苯、二氯苯、氯仿等鹵化烴溶劑;甲醇、乙醇、異丙醇、丁醇等醇溶劑;硝基苯等硝基烴溶劑;甲基異丁基酮等酮溶劑;1-甲基-2-吡咯啶酮等醯胺溶劑等,該等亦可混合使用。其中以丁醇與甲苯之混合溶劑為較佳。有機溶劑之使用量,相對於式(IV-1)所示之化合物1質量份,以30質量份以上200質量份以下為佳,50質量份以上150質量份以下為更佳。 In terms of productivity, the reaction is in organic solvents Perform better. Examples of organic solvents include: hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform; alcohol solvents such as methanol, ethanol, isopropanol, and butanol; nitro hydrocarbon solvents such as nitrobenzene; Ketone solvents, such as methyl isobutyl ketone; amine solvents, such as 1-methyl-2-pyrrolidone, etc., may be used in combination. Among them, a mixed solvent of butanol and toluene is preferred. The amount of the organic solvent used is preferably 30 parts by mass or more and 200 parts by mass or less, and more preferably 50 parts by mass or more and 150 parts by mass or less with respect to 1 part by mass of the compound represented by the formula (IV-1).
由反應混合物取得目的化合物之化合物(II)的方法並無特別限定,可採用習知的各種方式。例如可以在冷卻後,濾取析出之結晶的方法。所濾取之結晶,係以以水等清洗,其次加以乾燥為佳。視所需,亦可進一步以再結晶等習知之方式精製。 The method for obtaining the target compound (II) from the reaction mixture is not particularly limited, and various conventional methods can be adopted. For example, after cooling, the precipitated crystals can be collected by filtration. The crystals collected by filtration are preferably washed with water and then dried. If necessary, it can be further refined by conventional methods such as recrystallization.
本發明之著色劑,係包含具有含矽原子之基且具有方酸菁骨架的染料(以下,稱此著色劑為「著色劑(A)」)。 The coloring agent of the present invention contains a dye having a group containing a silicon atom and a squarylium skeleton (hereinafter, this colorant is referred to as "colorant (A)").
著色劑(A),在本發明染料之外,為了調色,即為了調整分光特性,亦可再含其他之染料(A2)、顏料(P)、或該等之混合物。 The colorant (A), in addition to the dye of the present invention, may further contain other dyes (A2), pigments (P), or a mixture thereof in order to adjust the color, that is, to adjust the spectral characteristics.
染料(A2)可列舉:油溶性染料、酸性染料、酸性染料 之胺鹽及酸性染料之磺醯胺衍生物等染料,如色料索引(colour index)(The Society of Dyers and Colourists出版)中分類為染料之化合物、和染色筆記(色染社)中所載之習知的染料。而且,若依化學構造,可列舉:香豆素染料、含金偶氮染料、吡啶酮偶氮染料、巴比妥偶氮染料、喹啉黃染料、次甲基染料、花青素染料、蒽醌染料、三苯基甲烷染料、二苯并吡喃(xanthene)染料、及酞青素染料等。此等染料,可單獨使用亦可以2種以上併用。 Examples of the dye (A2) include oil-soluble dyes, acid dyes, and acid dyes. Dyes such as amine salts and sulfonamide derivatives of acid dyes, such as those classified as dyes in the colour index (published by The Society of Dyers and Colourists), and contained in dyeing notes (color dyeing society) The conventional dye. Furthermore, depending on the chemical structure, coumarin dyes, gold-containing azo dyes, pyridone azo dyes, barbituran azo dyes, quinoline yellow dyes, methine dyes, anthocyanin dyes, and anthracene Quinone dyes, triphenylmethane dyes, xanthene dyes, and phthalocyanin dyes. These dyes may be used alone or in combination of two or more.
具體可例舉如:C.I.溶劑黃4號(以下,省略C.I.溶劑黃之記載,而僅記載號碼)、14號、15號、23號、24號、38號、62號、63號、68號、82號、94號、98號、99號、162號;C.I.溶劑橙2號、7號、11號、15號、26號、56號;等C.I.溶劑染料;C.I.酸性黃1號、3號、7號、9號、11號、17號、23號、25號、29號、34號、36號、38號、40號、42號、54號、65號、72號、73號、76號、79號、98號、99號、111號、112號、113號、114號、116號、119號、123號、128號、134號、135號、138號、139號、140號、144號、150號、155號、157號、160號、161號、163號、168號、169號、172號、177號、178號、179號、184號、190號、193號、196號、197號、199號、202號、203號、204號、205號、207號、212號、214號、220號、221號、228號、230號、232號、235號、238號、240號、242號、243號、251 號;C.I.酸性橙6號、7號、8號、10號、12號、26號、50號、51號、52號、56號、62號、63號、64號、74號、75號、94號、95號、107號、108號、169號、173號;等C.I.酸性染料,C.I.直接黃2號、33號、34號、35號、38號、39號、43號、47號、50號、54號、58號、68號、69號、70號、71號、86號、93號、94號、95號、98號、102號、108號、109號、129號、136號、138號、141號;C.I.直接橙34號、39號、41號、46號、50號、52號、56號、57號、61號、64號、65號、68號、70號、96號、97號、106號、107號;等C.I.直接染料,C.I.媒染黃5號、8號、10號、16號、20號、26號、30號、31號、33號、42號、43號、45號、56號、61號、62號、65號;C.I.媒染橙3號、4號、5號、8號、12號、13號、14號、20號、21號、23號、24號、28號、29號、32號、34號、35號、36號、37號、42號、43號、47號、48號;等C.I.媒染染料等。 Specific examples include: CI Solvent Yellow No. 4 (hereinafter, the description of CI Solvent Yellow is omitted, and only the number is recorded), 14, 15, 23, 24, 38, 62, 63, and 68 No. 82, No. 94, No. 98, No. 99, No. 162; CI Solvent Orange No. 2, No. 7, No. 11, No. 15, No. 26, No. 56; etc. CI solvent dyes; CI Acid Yellow No. 1, No. 3 , 7, 9, 9, 17, 23, 25, 29, 34, 36, 38, 40, 42, 42, 54, 65, 72, 73, 76 No. 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 No. 242, 243, 251 No .; CI Acid Orange No. 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; etc. CI acid dyes, CI Direct Yellow No. 2, 33, 34, 35, 38, 39, 43, 47, Numbers 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136 , 138, 141; CI Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96 No. 97, 106, 107; etc. CI direct dyes, CI mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43 No. 45, 56, No. 61, No. 62, No. 65; CI Mordant Orange No. 3, No. 4, No. 5, No. 8, No. 12, No. 13, No. 14, 20, 21, 23, No. 24, No. 28, No. 29, No. 32, No. 34, No. 35, No. 36, No. 37, No. 42, No. 43, No. 47, No. 48; CI mordant dyes, etc.
染料(A2)方面,以香豆素染料、含金偶氮染料、吡啶酮偶氮染料、巴比妥偶氮染料、喹啉黃染料、次甲基染料、花青素染料等之黃色染料為較佳。 For dyes (A2), yellow dyes such as coumarin dyes, gold-containing azo dyes, pyridone azo dyes, barbituric azo dyes, quinoline yellow dyes, methine dyes, and anthocyanin dyes are used. Better.
本發明之染料的含量,相對於著色劑的總量,通常以3至99.9質量%為佳,4至50質量%為更佳,5 至30質量%為又更佳。在本發明之染料的含量在前述範圍內時,製成濾色器時之亮度高,因此為佳。 The content of the dye of the present invention is generally preferably 3 to 99.9% by mass, and more preferably 4 to 50% by mass relative to the total amount of the colorant. 5 It is more preferable to be 30% by mass. When the content of the dye of the present invention is within the aforementioned range, it is preferable that the brightness is high when the color filter is manufactured.
顏料(P)方面,並無特別限定,可使用習知 之顏料,例如:色料索引(The Society of Dyers and Colourists出版)中分類為顏料(pigment)之顏料。 The pigment (P) is not particularly limited, and it can be used conventionally. Pigments, for example, pigments classified as pigments in The Society of Dyers and Colourists.
顏料(P)之例,可列舉:C.I.顏料黃1號、3號、12號、13號、14號、15號、16號、17號、20號、24號、31號、53號、83號、86號、93號、94號、109號、110號、117號、125號、128號、137號、138號、139號、147號、148號、150號、153號、154號、166號、173號、194號、214號等黃色顏料;C.I.顏料橙13號、31號、36號、38號、40號、42號、43號、51號、55號、59號、61號、64號、65號、71號、73號等橙色顏料;C.I.顏料綠7號、36號、58號等綠色顏料。 Examples of the pigment (P) include CI Pigment Yellow No. 1, No. 3, No. 12, No. 13, No. 14, No. 15, No. 16, No. 17, No. 20, No. 24, No. 31, No. 53, No. 83 No. 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, Yellow pigments such as No. 166, No. 173, No. 194, No. 214; CI Pigment Orange No. 13, No. 31, No. 36, No. 38, No. 40, No. 42, No. 43, No. 51, No. 55, No. 59, No. 61 , 64, 65, 71, 73 and other orange pigments; CI Pigment Green No. 7, 36, 58 and other green pigments.
顏料(P),以C.I.顏料黃1號、3號、12號、13號、14號、15號、16號、17號、20號、24號、31號、53號、83號、86號、93號、94號、109號、110號、117號、125號、128號、137號、138號、139號、147號、148號、150號、153號、154號、166號、173號、194號、214號等黃色顏料;及C.I.顏料綠7號、36號、58號等綠色顏料為較佳,C.I.顏料黃138號、150號、185號及C.I.顏料綠36號、58號為更佳,C.I.顏料黃138號、C.I.顏料黃150號及C.I. 顏料黃185號為又更佳。藉由含前述顏料,可使透射光譜容易最佳化,並使濾色器的耐光性及耐藥品性佳。 Pigment (P): CI Pigment Yellow No. 1, 3, 12, 13, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86 , 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173 Yellow pigments such as No. 194, No. 214, etc .; and green pigments such as CI Pigment Green No. 7, 36, and 58 are preferred, CI Pigment Yellow No. 138, 150, 185, and CI Pigment Green No. 36, 58 For the better, CI Pigment Yellow 138, CI Pigment Yellow 150 and CI Pigment Yellow 185 is even better. By including the pigment, the transmission spectrum can be easily optimized, and the light resistance and chemical resistance of the color filter can be improved.
本發明之著色硬化性樹脂組成物,含有著色劑(A)、樹脂(B)、聚合性化合物(C)、及聚合起始劑(D)。而且,亦可含溶劑(E)。 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). It may also contain a solvent (E).
本說明書中,所例舉各成分之化合物,若無特別限定,即可單獨使用亦可複數種組合使用。 In the present specification, the compounds of the respective components are exemplified, and if not particularly limited, they may be used alone or in combination.
本發明之著色硬化性樹脂組成物中,相對 於固形成分的總量,著色劑(A)之含量以5至60質量%為佳,8至55質量%為更佳,10至50質量%為又更佳。著色劑(A)之含量在前述範圍內時,製成濾色器時之色彩濃度充足,且可使組成物中含有所需量之樹脂(B)、聚合性化合物(C),因此可形成機械強度充分之圖型。其中,本說明書中之「固形成分的總量」,係指由著色硬化性樹脂組成物的總量去除溶劑含量之量。固形成分的總量及相對於固形成分的總量之各成分的含量,可例如以液相層析或氣相層析等習知之分析方式測定。 In the colored curable resin composition of the present invention, The content of the colorant (A) is preferably 5 to 60% by mass, more preferably 8 to 55% by mass, and even more preferably 10 to 50% by mass based on the total solid content. When the content of the colorant (A) is within the foregoing range, the color density when the color filter is made is sufficient, and the required amount of the resin (B) and the polymerizable compound (C) can be contained in the composition. A pattern with sufficient mechanical strength. Here, the "total amount of solid components" in the present specification refers to an amount in which the solvent content is removed from the total amount of the coloring curable resin composition. The total amount of the solid components and the content of each component relative to the total amount of the solid components can be measured by a known analytical method such as liquid chromatography or gas chromatography.
樹脂(B)並無特別限定,以鹼可溶性樹脂為較佳。樹脂(B)之例,可舉以下之樹脂[K1]至樹脂[K6]等。 The resin (B) is not particularly limited, and an alkali-soluble resin is preferred. Examples of the resin (B) include the following resins [K1] to [K6].
樹脂[K1]:選自不飽和羧酸及不飽和羧酸酐所成群組之至少1種(Ba)(以下有時稱為「(Ba)」)與碳數2至4之具有環醚構造及乙烯性不飽和鍵的單體(Bb)(以下有時稱為 「(Bb)」)之共聚物;樹脂[K2]:(Ba)、(Bb)、與可和(Ba)共聚合的單體(Bc)(惟,(Ba)及(Bb)不同)(以下有時稱為「(Bc)」)之共聚物;樹脂[K3]:(Ba)與(Bc)之共聚物;樹脂[K4]:使(Ba)與(Bc)之共聚物與(Bb)反應之樹脂;樹脂[K5]:使(Bb)與(Bc)之共聚物與(Ba)反應之樹脂;樹脂[K6]:使(Bb)與(Bc)之共聚物與(Ba)反應,再與羧酸酐反應之樹脂。 Resin [K1]: at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (Ba) (hereinafter sometimes referred to as "(Ba)") and a cyclic ether structure having 2 to 4 carbon atoms And ethylenically unsaturated bond monomer (Bb) (hereinafter sometimes referred to as "(Bb)") copolymer; resin [K2]: (Ba), (Bb), and monomer (Bc) copolymerizable with (Ba) (however, (Ba) and (Bb) are different) ( (Hereinafter sometimes referred to as "(Bc)") copolymer; resin [K3]: copolymer of (Ba) and (Bc); resin [K4]: copolymer of (Ba) and (Bc) and (Bb) ) Resin; Resin [K5]: Resin that reacts the copolymer of (Bb) and (Bc) with (Ba); Resin [K6]: Reacts the copolymer of (Bb) and (Bc) with (Ba) Resin that reacts with carboxylic anhydride.
(Ba)可列舉例如:如丙烯酸、甲基丙烯酸、巴豆酸、隣-、間-、對-乙烯基苯甲酸等不飽和單羧酸;順丁烯二酸、反丁烯二酸、檸康酸、中康酸、伊康酸、3-乙烯基苯二甲酸、4-乙烯基苯二甲酸、3,4,5,6-四氫苯二甲酸、1,2,3,6-四氫苯二甲酸、二甲基四氫苯二甲酸、1,4-環己烯二羧酸等不飽和二羧酸;甲基-5-降莰烯-2,3-二羧酸、5-羧基二環[2.2.1]庚-2-烯、5,6-二羧基二環[2.2.1]庚-2-烯、5-羧基-5-甲基二環[2.2.1]庚-2-烯、5-羧基-5-乙基二環[2.2.1]庚-2-烯、5-羧基-6-甲基二環[2.2.1]庚-2-烯、5-羧基-6-乙基二環[2.2.1]庚-2-烯等含羧基之二環不飽和化合物;順丁烯二酸酐、檸康酸酐、伊康酸酐、3-乙烯基苯二甲酸酐、4-乙烯基苯二甲酸酐、3,4,5,6-四氫苯二甲酸酐、1,2,3,6-四氫苯二甲酸酐、二甲基四氫苯二甲酸酐、脫水5,6-二羧基二環[2.2.1]庚-2-烯等不飽和二羧酸酐;琥珀酸單[2-(甲基)丙烯醯氧基乙基]酯、苯二甲酸單 [2-(甲基)丙烯醯氧基乙基]酯等2元以上之多元羧酸的不飽和單[(甲基)丙烯醯氧基烷基]酯; α-(羥基甲基)丙烯酸之類,同一分子中含羥基及羧基的不飽和丙烯酸酯等。 (Ba) Examples include, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid; maleic acid, fumaric acid, and citraconic acid Acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydro Unsaturated dicarboxylic acids such as phthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxyl Bicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2 -Ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6 -Ethylbicyclo [2.2.1] hept-2-ene and other bicyclic unsaturated compounds containing carboxyl groups; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4- Vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, dehydrated 5, 6-Dicarboxybicyclo [2.2.1] hept-2-ene and other unsaturated dicarboxylic anhydrides; succinate mono [2- (methyl) propane Acyl oxy ethyl] phthalate, mono Unsaturated mono [(meth) acryloxyalkyl] esters of two- or more-valent polycarboxylic acids, such as [2- (meth) acryloxyethyl] esters; α- (hydroxymethyl) acrylic acid and the like, unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule.
該等之中,由共聚反應性之觀點及所得之樹脂對鹼水溶液的溶解性之點而言,以丙烯酸、甲基丙烯酸、順丁烯二酸酐為較佳。 Among these, acrylic acid, methacrylic acid, and maleic anhydride are preferable from the viewpoint of copolymerization reactivity and the solubility of the obtained resin in an alkaline aqueous solution.
(Bb),係指例如碳數2至4之具有環狀醚構 造(例如選自氧雜環丙烷環、氧雜環丁烷環及四氫呋喃環所成群組的至少1種)及乙烯性不飽和鍵的聚合性化合物。 (Bb) means, for example, a cyclic ether structure having 2 to 4 carbon atoms A polymerizable compound (for example, at least one selected from the group consisting of an oxetane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond.
(Bb)以碳數2至4之具有環狀醚及(甲基)丙烯醯氧基的單體為較佳。 (Bb) A monomer having a cyclic ether and a (meth) acryloxy group having 2 to 4 carbon atoms is preferred.
本說明書中,「(甲基)丙烯酸」表示選自:丙烯酸及甲基丙烯酸所成群組的至少1種。「(甲基)丙烯醯基」及「(甲基)丙烯酸酯」等之表示亦有相同之含意。 In the present specification, "(meth) acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The expressions "(meth) acrylfluorenyl" and "(meth) acrylate" have the same meaning.
(Bb)可列舉:具有氧雜環丙烷基及乙烯性不 飽和鍵之單體、具有氧雜環丁烷基及乙烯性不飽和鍵之單體、具有四氫呋喃基及乙烯性不飽和鍵之單體等。 (Bb) Examples include oxetanyl group and ethylenic property. A monomer having a saturated bond, a monomer having an oxetanyl group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuranyl group and an ethylenically unsaturated bond, and the like.
就可使所得之濾色器的耐熱性、耐藥品性等可靠性更高之點而言,(Bb)以含氧雜環丙烷基及乙烯性不飽和鍵之單體為較佳。 In terms of making the obtained color filter more reliable in terms of heat resistance, chemical resistance, and the like, (Bb) is preferably a monomer containing an oxetanyl group and an ethylenically unsaturated bond.
(Bc)可列舉:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸十 二碳烷酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸環戊酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸-2-甲基環己酯、(甲基)丙烯酸三環[5.2.1.02,6]癸烷-8-酯(其技術領域中,慣用名稱為「(甲基)丙烯酸二環戊酯」。而且,亦有時稱為「(甲基)丙烯酸三環癸酯」)、(甲基)丙烯酸三環[5.2.1.02,6]癸烯-8-酯(其技術領域中,慣用名稱為「(甲基)丙烯酸二環戊烯酯」)、(甲基)丙烯酸二環戊醯氧基乙酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸金剛烷酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸炔丙酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸萘酯、(甲基)丙烯酸苯甲酯等(甲基)丙烯酸酯;(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸-2-羥基丙酯等含羥基之(甲基)丙烯酸酯;順丁烯二酸二乙酯、反丁烯二酸二乙酯、伊康酸二乙酯等二羧酸二酯;二環[2.2.1]庚-2-烯、5-甲基二環[2.2.1]庚-2-烯、5-乙基二環[2.2.1]庚-2-烯、5-羥基二環[2.2.1]庚-2-烯、5-羥基甲基二環[2.2.1]庚-2-烯、5-(2’-羥基乙基)二環[2.2.1]庚-2-烯、5-甲氧基二環[2.2.1]庚-2-烯、5-乙氧基二環[2.2.1]庚-2-烯、5,6-二羥基二環[2.2.1]庚-2-烯、5,6-二(羥基甲基)二環[2.2.1]庚-2-烯、5,6-二(2’-羥基乙基)二環[2.2.1]庚-2-烯、5,6-二甲氧基二環[2.2.1]庚-2-烯、5,6-二乙氧基二環[2.2.1]庚-2-烯、5-羥基-5-甲基二環[2.2.1]庚-2-烯、5-羥基-5-乙基二環[2.2.1]庚-2-烯、5-羥基甲基-5-甲基二環[2.2.1]庚-2-烯、5- 第三丁氧基羰基二環[2.2.1]庚-2-烯、5-環己氧基羰基二環[2.2.1]庚-2-烯、5-苯甲氧基羰基二環[2.2.1]庚-2-烯、5,6-雙(第三丁氧基羰基)二環[2.2.1]庚-2-烯、5,6-雙(環己氧基羰基)二環[2.2.1]庚-2-烯等二環不飽和化合物; N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N-苯甲基順丁烯二醯亞胺、N-琥珀醯亞胺基-3-順丁烯二醯亞胺苯甲酸酯、N-琥珀醯亞胺基-4-順丁烯二醯亞胺丁酸酯、N-琥珀醯亞胺基-6-順丁烯二醯亞胺己酸酯、N-琥珀醯亞胺基-3-順丁烯二醯亞胺丙酸酯、N-(9-丙烯醯基)順丁烯二醯亞胺等二羰基醯亞胺衍生物; 苯乙烯、α-甲基苯乙烯、間甲基苯乙烯、對甲基苯乙烯、乙烯基甲苯、對甲氧基苯乙烯、丙烯腈、甲基丙烯腈、氯化乙烯、氯化亞乙烯、丙烯醯胺、甲基丙烯醯胺、乙酸乙烯酯、1,3-丁二烯、異戊二烯、2,3-二甲基-1,3-丁二烯等。 Examples of (Bc) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, second butyl (meth) acrylate, and third butyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, dodecane (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate , Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6 ] decane-8-ester (meth) , The common name is "dicyclopentyl (meth) acrylate". Also, it is sometimes called "tricyclodecyl (meth) acrylate"), tricyclic (meth) acrylate [5.2.1.0 2,6 ] Decene-8-ester (in its technical field, the common name is "dicyclopentenyl (meth) acrylate"), dicyclopentyloxyethyl (meth) acrylate, isopropyl (meth) acrylate Fluorenyl ester, adamantane (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, (meth) (Meth) acrylates such as benzyl acrylate; 2-hydroxyethyl (meth) acrylate (Meth) acrylic acid esters such as 2-hydroxypropyl (meth) acrylate; dicarboxylic acids such as diethyl maleate, diethyl fumarate, and diethyl iconate Diesters; bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1 ] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxydiene Cyclic [2.2.1] hept-2-ene, 5,6-bis (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2 -Ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl -5-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-benzyloxycarbonyl bicyclo [2.2.1] hept-2-ene, 5,6-bis (third butoxycarbonyl) bicyclo [2.2.1] heptane -2-ene, 5,6-bis (cyclohexyl Carbonyl) bicyclic unsaturated compounds such as bicyclo [2.2.1] hept-2-ene; N-phenylcis-butenedifluoreneimine, N-cyclohexylcisbutenedifluoreneimine, N-benzyl N-succinimide diimide, N-succinimide imido-3-cis butemodiimide benzoate, N-succinimide 4-cis butimide diimide butyric acid Ester, N-succinimide-6-cis-butenediimidehexanoate, N-succinimide-3-cis-butenediimidepropionate, N- (9-propylene Fluorenyl) dicarbonyl fluorenimine derivatives such as cis-butene difluorenimide; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxybenzene Ethylene, acrylonitrile, methacrylonitrile, ethylene chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3- Dimethyl-1,3-butadiene and the like.
該等之中,由共聚反應性及耐熱性之點而言,以苯乙烯、乙烯基甲苯、N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N-苯甲基順丁烯二醯亞胺、二環[2.2.1]庚-2-烯等為較佳。 Among these, in terms of copolymerization reactivity and heat resistance, styrene, vinyltoluene, N-phenylcis butylenediimide, N-cyclohexylcisbutenediimide, N -Benzyl cis butene diamidine, bicyclo [2.2.1] hept-2-ene and the like are preferred.
樹脂(B)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-環氧基三環[5.2.1.02,6]癸酯/(甲基)丙烯酸共聚物等樹脂[K1];(甲基)丙烯酸環氧丙酯/(甲基)丙烯酸苯甲酯/(甲基)丙烯酸共聚物、(甲基)丙烯酸環氧丙酯/苯乙烯/(甲基)丙烯酸共聚物、丙烯酸-3,4-環氧三環[5.2.1.02,6]癸酯/(甲基)丙烯酸/N-環己 基順丁烯二醯亞胺共聚物、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)丙烯酸苯甲酯/(甲基)丙烯酸共聚物、苯乙烯/(甲基)丙烯酸共聚物等樹脂[K3];(甲基)丙烯酸苯甲酯/(甲基)丙烯酸共聚物加成(甲基)丙烯酸環氧丙酯之樹脂、(甲基)丙烯酸三環癸酯/苯乙烯/(甲基)丙烯酸共聚物加成(甲基)丙烯酸環氧丙酯之樹脂、(甲基)丙烯酸三環癸酯/(甲基)丙烯酸苯甲酯/(甲基)丙烯酸共聚物加成(甲基)丙烯酸環氧丙酯之樹脂等樹脂[K4];(甲基)丙烯酸三環癸酯/(甲基)丙烯酸環氧丙酯之共聚物與(甲基)丙烯酸反應之樹脂、(甲基)丙烯酸三環癸酯/苯乙烯/(甲基)丙烯酸環氧丙酯之共聚物與(甲基)丙烯酸反應之樹脂等樹脂[K5];(甲基)丙烯酸三環癸酯/(甲基)丙烯酸環氧丙酯之共聚物與(甲基)丙烯酸反應之樹脂再與四氫苯二甲酸酐反應之樹脂等樹脂[K6]等。 Examples of the resin (B) include (meth) acrylic acid-3,4-epoxycyclohexylmethyl ester / (meth) acrylic acid copolymer, acrylic acid-3,4-epoxy tricyclo [5.2.1.0 2,6 ] Decyl ester / (meth) acrylic copolymer [K1]; Glycidyl (meth) acrylate / Benzyl (meth) acrylate / (meth) acrylic acid copolymer, (meth) acrylic acid ring Oxypropyl ester / styrene / (meth) acrylic acid copolymer, acrylic acid-3,4-epoxytricyclo [5.2.1.0 2,6 ] decyl ester / (meth) acrylic acid / N-cyclohexyl maleic diene Resins such as fluorene imine copolymer, 3-methyl-3- (meth) acryloxymethyloxetane / (meth) acrylic acid / styrene copolymer [K2]; (meth) acrylic acid Resins such as benzyl / (meth) acrylic copolymer, styrene / (meth) acrylic copolymer [K3]; benzyl (meth) acrylate / (meth) acrylic copolymer addition (meth) Glycidyl Acrylate Resin, Tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer addition Glycidyl (meth) acrylate Resin, Tricyclodecyl (meth) acrylate Esters / benzyl (meth) acrylate / (meth) acrylic acid copolymers added with glycidyl (meth) acrylate Resins and other resins [K4]; Tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate copolymer with (meth) acrylic acid, Tricyclodecyl (meth) acrylate / benzene Copolymers of ethylene / glycidyl (meth) acrylic acid copolymer and (meth) acrylic acid-reactive resins [K5]; Tricyclodecyl (meth) acrylic acid / glycidyl (meth) acrylate copolymer Resins reacted with (meth) acrylic acid and resins reacted with tetrahydrophthalic anhydride [K6] and the like.
其中,樹脂(B)以樹脂[K1]及樹脂[K2]為較佳。 Among them, the resin (B) is preferably resin [K1] and resin [K2].
樹脂[K1],可參考文獻「高分子合成之實驗法」(大津隆行著 發行人 化學同人股份有限公司 第1版第1刷1972年3月1日發行)中所載之方法及該文獻中所載之引用文獻而製造。 Resin [K1], refer to the method contained in the document "Experimental Methods for Polymer Synthesis" (Otsu Takayuki, Issuer, Chemical Dojin Co., Ltd., 1st Edition, 1st Issue, March 1, 1972) and the document Manufactured by reference.
製得之共聚物,可直接使用反應後之溶液,亦可使用經濃縮或稀釋之溶液,也可使用以再沉澱等方法取出之固體(粉體)。尤其,就該聚合時之溶劑而言,藉由使用本發明之著色硬化性樹脂組成物中所含之溶劑,可將反應後之溶液直接用於調製本發明之著色硬化性樹脂組成物,因此 可將本發明之著色硬化性樹脂組成物之製造步驟簡化。 The prepared copolymer may be used directly after the reaction, or may be a concentrated or diluted solution, or a solid (powder) removed by a method such as reprecipitation. In particular, as for the solvent at the time of polymerization, by using the solvent contained in the colored curable resin composition of the present invention, the solution after the reaction can be directly used to prepare the colored curable resin composition of the present invention. The manufacturing process of the colored curable resin composition of this invention can be simplified.
樹脂(B)換算聚苯乙烯的重量平均分子量,以3,000至100,000為佳,5,000至50,000為更佳,5,000至30,000為又更佳。在分子量在前述範圍內時,可提昇濾色器之硬度,提高薄膜殘留率,使未曝光部分對顯影液之溶解性佳,並有提昇著色圖型之解析度的傾向。 The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000. When the molecular weight is within the aforementioned range, the hardness of the color filter can be increased, the film residual rate can be increased, the unexposed portion has good solubility in the developing solution, and the resolution of the coloring pattern tends to be improved.
樹脂(B)之分子量分布「重量平均分子量(Mw)/數量平均分子量(Mn)」,以1.1至6為佳,1.2至4為更佳。 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)之酸價,以50至170mg-KOH/g為佳,60至150mg-KOH/g為更佳,70至135mg-KOH/g為又更佳。其中,酸價係中和樹脂(B)1g所需之氫氧化鉀的量(mg)之測定值,可例如使用氫氧化鉀水溶液進行滴定而求得。 The acid value of the resin (B) is preferably from 50 to 170 mg-KOH / g, more preferably from 60 to 150 mg-KOH / g, and even more preferably from 70 to 135 mg-KOH / g. The measured value of the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B) with an acid value can be determined by, for example, titration with an aqueous potassium hydroxide solution.
相對於固形成分的總量,樹脂(B)之含量以7至65質量%為佳,13至60質量%為更佳,17至55質量%為又更佳。 樹脂(B)之含量在前述範圍內時,可形成著色圖型,而且有提高著色圖型之解析度及薄膜殘留率的傾向。 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 solid components. When the content of the resin (B) is within the aforementioned range, a colored pattern can be formed, and the resolution of the colored pattern and the film residual rate tend to be improved.
聚合性化合物(C),為可以由聚合起始劑(D)產生的活性自由基及/或酸聚合之化合物,例如:具有聚合性之乙烯性不飽和鍵的化合物等,而以(甲基)丙烯酸酯化合物較佳。 The polymerizable compound (C) is a compound that can be polymerized by living radicals and / or acids generated from the polymerization initiator (D), for example, a compound having a polymerizable ethylenically unsaturated bond, etc. ) Acrylate compounds are preferred.
其中,聚合性化合物(C),以具有3個以上乙烯性不飽和鍵之聚合性化合物較佳。該類聚合性化合物可列舉例如:三羥甲基丙烷三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲 基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、三新戊四醇八(甲基)丙烯酸酯、三新戊四醇七(甲基)丙烯酸酯、四新戊四醇十(甲基)丙烯酸酯、四新戊四醇九(甲基)丙烯酸酯、三聚異氰酸參(2-(甲基)丙烯醯氧基乙基)酯、乙二醇改質新戊四醇四(甲基)丙烯酸酯、乙二醇改質二新戊四醇六(甲基)丙烯酸酯、丙二醇改質新戊四醇四(甲基)丙烯酸酯、丙二醇改質二新戊四醇六(甲基)丙烯酸酯、己內酯改質新戊四醇四(甲基)丙烯酸酯、己內酯改質二新戊四醇六(甲基)丙烯酸酯等。 Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, neopentaerythritol tri (meth) acrylate, neopentaerythritol tetra (meth) acrylate, and dipentaerythritol. Alcohol five (a Base) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol ten (Meth) acrylate, Tetranepentaerythritol nona (meth) acrylate, Trimeric isocyanate (2- (meth) acryloxyethyl), Ethylene glycol modified neopentyl Alcohol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified neopentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol Hexa (meth) acrylate, caprolactone modified neopentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc.
其中,以二新戊四醇五(甲基)丙烯酸酯及二新戊四醇六(甲基)丙烯酸酯較佳。 Of these, dipentaerythritol penta (meth) acrylate and dinepentaerythritol hexa (meth) acrylate are preferred.
聚合性化合物(C)之重量平均分子量,以150 至2,900為佳,250至1,500為更佳。 Weight average molecular weight of polymerizable compound (C), 150 It is preferably 2,900, and more preferably 250 to 1,500.
相對於固形成分之總量,聚合性化合物(C)之含量以7至65質量%為佳,13至60質量%為更佳,17至55質量%為又更佳。當聚合性化合物(C)之含量在前述範圍內時,有提高著色圖型形成時之薄膜殘留率及濾色器的耐藥品性的傾向。 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 solid components. When the content of the polymerizable compound (C) is within the above-mentioned range, there is a tendency that the film residual rate at the time of forming a colored pattern and the chemical resistance of the color filter are increased.
聚合起始劑(D),只要為可由光及熱之作用產生活性自由基、酸等,使聚合開始的化合物即無特別限定,可使用習知之聚合起始劑。產生活性自由基之聚合起始劑之例,可列舉例如:O-醯基肟化合物、烷基苯酮化合物、三化合物、醯基膦氧化物及聯咪唑化合物。 The polymerization initiator (D) is not particularly limited as long as it is a compound that generates living radicals, acids, and the like by the action of light and heat, and a conventional polymerization initiator can be used. Examples of the polymerization initiator that generates living radicals include, for example, O-fluorenyl oxime compounds, alkyl phenone compounds, Compounds, fluorenylphosphine oxides and biimidazole compounds.
前述O-醯基肟化合物之例,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-2,4-二氧基環戊醯基甲基氧基)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。亦可使用Irgacure(註冊商標)OXE 01、OXE 02(以上,為BASF公司製造)、N-1919(ADEKA公司製造)等市售品。 其中,O-醯基肟化合物,以選自: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-亞胺及N-苯甲醯氧基-1-(4-苯基硫烷基苯基)-3-環戊基丙烷-1-酮-2-亞胺所成群組之至少1種為較佳,N-苯甲醯氧基-1-(4-苯基硫烷基苯基)辛烷-1-酮-2-亞胺為更佳。在為該等O-醯基肟化合物時,有製得高亮度的濾色器之傾向。 Examples of the O-fluorenyl oxime compound include N-benzyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine, and N-benzyl Ethoxy-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-methylbenzyl) -9H-carbazole- 3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4- Dioxycyclopentaminylmethyloxy) benzylidene} -9H-carbazol-3-yl] ethane-1-imine, N-ethoxymethyl-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. Commercial products such as Irgacure (registered trademark) OXE 01, OXE 02 (above, manufactured by BASF), and N-1919 (made by ADEKA) can also be used. Among them, the O-fluorenyl oxime compound is selected from the group consisting of: N-benzyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine, and N-benzyl Ethoxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine and N-benzyloxy-1- (4-phenylsulfanylphenyl) At least one of the groups formed by -3-cyclopentylpropane-1-one-2-imine is preferred, and N-benzyloxy-1- (4-phenylsulfanylphenyl) octyl Alkan-1-one-2-imine is more preferred. In the case of these O-fluorenyl oxime compounds, a color filter with a high brightness tends to be obtained.
前述烷基苯酮化合物之例,可列舉:2-甲基-2-N-嗎啉基-1-(4-甲基硫烷基苯基)丙烷-1-酮、2-二甲基胺基-1-(4-N-嗎啉基苯基)-2-苯甲基丁烷-1-酮、2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎啉基)苯基]丁烷-1-酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、2-羥基-2-甲基-1-[4-(2-羥基乙氧基) 苯基]丙烷-1-酮、1-羥基環己基苯基酮、2-羥基-2-甲基-1-(4-異丙烯基苯基)丙烷-1-酮之寡聚物、α,α-二乙氧基苯乙酮、苯甲基二甲醛等。亦可使用Irgacure(註冊商標)369、907、379(以上為BASF公司製造)等市售品。 Examples of the alkyl phenone compound include 2-methyl-2-N-morpholinyl-1- (4-methylsulfanylphenyl) propane-1-one and 2-dimethylamine 2- (4-N-morpholinylphenyl) -2-benzylbutane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) formyl Group] -1- [4- (4-morpholinyl) phenyl] butane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2- Methyl-1- [4- (2-hydroxyethoxy) Phenyl] propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propane-1-one oligomer, α, α-diethoxyacetophenone, benzylformaldehyde and the like. Commercial products such as Irgacure (registered trademark) 369, 907, and 379 (above manufactured by BASF) can also be used.
前述三化合物之例,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-胡椒基-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。 Aforementioned three Examples of the compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-tris , 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-tri , 2,4-bis (trichloromethyl) -6-piperyl-1,3,5-tri , 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) vinyl] -1,3,5-tris Wait.
前述醯基膦氧化物,亦可使用2,4,6-三甲基苯甲醯基二苯基膦氧化物等。Irgacure(註冊商標)819(BASF公司製造)等市售品。 As the fluorenylphosphine oxide, 2,4,6-trimethylbenzylfluorenyldiphenylphosphine oxide or the like can also be used. Commercial products such as Irgacure (registered trademark) 819 (manufactured by BASF).
前述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(參照日本特開平6-75372號公報、日本特開平6-75373號公報等)、2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基聯咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四(烷氧基苯基)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(參照日本特公昭48-38403號公報、日本特開昭62-174204號公 報等)、4,4’,5,5’-位之苯基經碳烷氧基取代之咪唑化合物(參照日本特開平7-10913號公報等)等。 Examples of the aforementioned biimidazole compound include: 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichloro (Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (see Japanese Patent Application Laid-Open No. 6-75372, Japanese Patent Application Laid-Open No. 6-75373, etc.), 2,2'-bis (2- (Chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (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 (refer to Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62-174204 Etc.), imidazole compounds in which the phenyl group at the 4,4 ', 5,5'-position is substituted with a carboalkoxy group (see Japanese Patent Application Laid-Open No. 7-10913, etc.) and the like.
再者,聚合起始劑(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、隣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(第三丁基過氧化羰基)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、苯甲基、苯乙醛酸甲酯、二茂鈦化合物等。 Examples of the polymerization initiator (D) include benzoin and benzene. Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin compounds; benzophenone, o-benzoyl methyl benzoate, 4 -Phenylbenzophenone, 4-benzylidene-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetrakis (third butylperoxycarbonyl) benzophenone , 2,4,6-trimethylbenzophenone and other benzophenone compounds; 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone and other quinone compounds; 10-butyl-2-chloroacryl Pyridone, benzyl, methyl phenylglyoxylate, titanocene compound, etc.
產生酸之聚合起始劑之例,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-乙醯氧基苯基甲基苯甲基鋶六氟銻酸鹽、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、及甲苯磺酸硝基苯甲酯、苯偶姻甲苯磺酸酯等。 Examples of the acid-generating polymerization initiator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-ethylfluorenylbenzene Dimethylpyridine p-toluenesulfonate, 4-Ethyloxyphenylmethylbenzylpyrene hexafluoroantimonate, triphenylpyrene p-toluenesulfonate, triphenylpyrene hexafluoroantimonate , Onium salts such as diphenylphosphonium p-toluenesulfonate, diphenylphosphonium hexafluoroantimonate, and nitrobenzyl tosylate, benzoin tosylate, and the like.
聚合起始劑(D)以含選自:O-醯基肟化合 物、烷基苯酮化合物、三化合物、醯基膦氧化物、及聯咪唑化合物所成群組之至少1種的聚合起始劑為佳,含O-醯基肟化合物的聚合起始劑為更佳。 The polymerization initiator (D) is selected from the group consisting of: O-fluorenyl oxime compound, alkyl phenone compound, A polymerization initiator of at least one of the group consisting of a compound, a fluorenylphosphine oxide, and a biimidazole compound is preferable, and a polymerization initiator containing an O-fluorenyl oxime compound is more preferable.
相對於樹脂(B)及聚合性化合物(C)之合計 量100質量份,聚合起始劑(D)之含量以0.1至30質量份為佳,1至20質量份為更佳。在聚合起始劑(D)之含量在前 述範圍內時,可高靈敏度化而有使曝光時間縮短之傾向,因此可提高濾色器的生產性。 Relative to the total of resin (B) and polymerizable compound (C) The amount is 100 parts by mass, and the content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass. Prior to the content of the polymerization initiator (D) When it is within the above range, the sensitivity can be increased and the exposure time tends to be shortened, so that the productivity of the color filter can be improved.
溶劑(E)並無特別限定,可使用本技術領域中通常使用之溶劑。可列舉例如:酯溶劑(分子內含-COO-,不含-O-之溶劑)、醚溶劑(分子內含-O-,不含-COO-之溶劑)、醚-酯溶劑(分子內含-COO-及-O-之溶劑)、酮溶劑(分子內含-CO-,不含-COO-之溶劑)、醇溶劑(分子內含OH,不含-O-、-CO-及-COO-之溶劑)、芳族烴溶劑、醯胺溶劑、二甲基亞碸等。 The solvent (E) is not particularly limited, and a solvent generally used in the technical field can be used. Examples include: ester solvents (solvents containing -COO-, -O-free solvents), ether solvents (solvents containing -O-, -COO-free solvents), ether-ester solvents (molecules containing -COO- and -O-solvents), ketone solvents (solvents with -CO- in the molecule, but without -COO-), alcohol solvents (with OH in the molecule, -O-, -CO-, and -COO) -Solvents), aromatic hydrocarbon solvents, amine solvents, dimethyl sulfene and the like.
酯溶劑可列舉:乳酸甲酯、乳酸乙酯、乳酸丁酯、2-羥基異丁烷酸甲酯、乙酸乙酯、乙酸正丁酯、乙酸異丁酯、甲酸戊酯、乙酸異戊酯、丙酸丁酯、丁酸異丙酯、丁酸乙酯、丁酸丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、環己醇乙酸酯及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.
醚溶劑之例,可列舉:乙二醇單甲醚、乙二醇單乙醚、乙二醇單丙醚、乙二醇單丁醚、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丁醚、丙二醇單甲醚、丙二醇單乙醚、丙二醇單丙醚、丙二醇單丁醚、3-甲氧基-1-丁醇、3-甲氧基-3-甲基丁醇、四氫呋喃、四氫吡喃、1,4-二烷、二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇甲基乙醚、二乙二醇二丙醚、二乙二醇二丁醚、苯甲醚、苯乙醚及甲基苯甲醚等。 Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol , Tetrahydrofuran, tetrahydropyran, 1,4-di Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyl ether and methyl Anisole and so on.
醚-酯溶劑可列舉:甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯、乙酸-3-甲氧基丁酯、乙酸-3-甲基-3-甲氧基丁酯、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、丙二醇單丙醚乙酸酯、乙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、二乙二醇單乙醚乙酸酯及二乙二醇單丁醚乙酸酯等。 Examples of the ether-ester solvents 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 Ethyloxy-2-methylpropanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Esters, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate, etc. .
酮溶劑可列舉:4-羥基-4-甲基-2-戊酮、丙酮、2-丁酮、2-庚酮、3-庚酮、4-庚酮、4-甲基-2-戊酮、環戊酮、環己酮及異佛酮等。 Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, and 4-methyl-2-pentanone , Cyclopentanone, cyclohexanone and isophorone.
醇溶劑可列舉:甲醇、乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、丙二醇及丙三醇等。 Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerol.
芳族烴溶劑可列舉:苯、甲苯、二甲苯及1,3,5-三甲苯等。 Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and 1,3,5-trimethylbenzene.
醯胺溶劑可列舉:N,N-二甲基甲醯胺、N,N-二甲基乙醯胺及N-甲基吡咯啶酮等。 Examples of the amidine solvents include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.
上述溶劑中,就塗佈性、乾燥性之點而言,以於1atm之沸點為120℃以上210℃以下的有機溶劑為較佳。溶劑方面,以丙二醇單甲醚乙酸酯、乳酸乙酯、丙二醇單甲醚、3-乙氧基丙酸乙酯、乙二醇單甲醚、二乙二醇單甲醚、二乙二醇單乙醚、4-羥基-4-甲基-2-戊酮及N,N-二甲基甲醯胺 為較佳,丙二醇單甲醚乙酸酯、丙二醇單甲醚、N,N-二甲基甲醯胺、N-甲基吡咯啶酮、及3-乙氧基丙酸乙酯為更佳。 Among the above solvents, an organic solvent having a boiling point of 120 ° C. or higher and 210 ° C. or lower at 1 atm in terms of coatability and drying properties is preferred. In terms of solvents, 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 Monoethyl ether, 4-hydroxy-4-methyl-2-pentanone and N, N-dimethylformamide More preferably, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, N, N-dimethylformamide, N-methylpyrrolidone, and ethyl 3-ethoxypropionate are more preferred.
相對於本發明之著色硬化性樹脂組成物的總量,溶劑(E)之含量以70至95質量%為佳,75至92質量%為更佳。 換言之,著色硬化性樹脂組成物的固形成分的總量,以5至30質量%為佳,8至25質量%為更佳。在溶劑(E)的含量在前述範圍內時,可使塗佈時之平坦性良好,而且在形成濾色器時由於色彩濃度不會不足而有使顯示特性佳的傾向。 The content of the solvent (E) is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass based on the total amount of the coloring curable resin composition of the present invention. In other words, the total solid content of the colored curable resin composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. When the content of the solvent (E) is within the aforementioned range, the flatness at the time of coating can be made good, and since the color density is not insufficient when forming a color filter, the display characteristics tend to be good.
本發明之著色硬化性樹脂組成物,視所需,亦可例如包含聚合起始助劑、調平劑、填充劑、其他高分子化合物、促密合劑、抗氧化劑、光安定劑、鏈轉移劑等該技術領域習知之添加劑。 The coloring curable resin composition of the present invention may optionally include, for example, a polymerization initiation aid, a leveling agent, a filler, other polymer compounds, a tackifier, an antioxidant, a light stabilizer, and a chain transfer agent. Wait for additives known in this technical field.
本發明之著色硬化性樹脂組成物,可例如藉由將著色劑(A)、樹脂(B)、聚合性化合物(C)、聚合起始劑(D)、溶劑(E)、以及視所需使用之調平劑、聚合起始助劑及其他成分混合而調製。 The colored curable resin composition of the present invention can be obtained by, for example, coloring agent (A), resin (B), polymerizable compound (C), polymerization initiator (D), solvent (E), and optionally The leveling agent, polymerization initiation aid and other ingredients used are mixed and prepared.
顏料(P),以預先與溶劑(E)之一部分或全部混合,再使用珠磨機等分散至顏料的平均粒徑為0.2μm以下左右為佳。此時,可視所需調配顏料分散劑、樹脂(B)之一部分或全部。再於如此操作所製得之顏料分散液中,以成為預定濃度之方式混合其餘的成分,即可調製目的之著色硬化性 樹脂組成物。 The pigment (P) is preferably partially or completely mixed with a part of the solvent (E) in advance, and then dispersed with a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. In this case, a part or all of the pigment dispersant and the resin (B) may be prepared as required. Then, in the pigment dispersion liquid prepared in this way, the remaining ingredients are mixed so as to have a predetermined concentration, so that the intended color hardening property can be adjusted. Resin composition.
染料,亦可分別預先溶解於溶劑(E)之一部分或全部而調製成溶液。該溶液,以經孔徑0.01至1μm左右的過濾器過濾為佳。 The dye may be dissolved in part or all of the solvent (E) in advance to prepare a solution. This solution is preferably filtered through a filter having a pore size of about 0.01 to 1 μm.
混合後之著色硬化性樹脂組成物,以經過孔徑0.1至10μm左右的過濾器過濾為佳。 The mixed coloring curable resin composition is preferably filtered through a filter having a pore size of about 0.1 to 10 μm.
本發明之塗膜,係由本發明之著色硬化性樹脂組成物形成。該塗膜,可藉由使該著色硬化性樹脂組成物硬化而形成。本發明之塗膜,亦可含後述之著色圖型。使該著色硬化性樹脂組成物硬化的方法如後所述。 The coating film of the present invention is formed from the colored curable resin composition of the present invention. The coating film can be formed by curing the colored curable resin composition. The coating film of the present invention may include a coloring pattern described later. The method of hardening this coloring curable resin composition is mentioned later.
本發明之濾色器,係由本發明之著色硬化性樹脂組成物所形成。該濾色器,可藉由使該著色硬化性樹脂組成物硬化而形成。該濾色器,可例如藉由將該著色硬化性樹脂組成物塗佈於基板上,再經過乾燥而形成著色組成物層,並經由光罩使該著色組成物層曝光而得。本發明之濾色器,亦可在塗膜上含著色圖型。 The color filter of the present invention is formed of the coloring curable resin composition of the present invention. The color filter can be formed by curing the colored curable resin composition. The color filter can be obtained, for example, by coating the colored curable resin composition on a substrate, and then drying to form a colored composition layer, and exposing the colored composition layer through a photomask. The color filter of the present invention may include a coloring pattern on the coating film.
以本發明之著色硬化性樹脂組成物製造著色圖型的方法,可列舉:光蝕刻法、噴墨法、印刷法等。其中,以光蝕刻法為較佳。光蝕刻法,係將前述著色硬化性樹脂組成物塗佈於基板,使之乾燥形成著色組成物層,之後經由光罩使該著色組成物層曝光、顯影的方法。光蝕刻法中,藉由在曝光時不使用光罩、及/或不加以顯影,可形成上述著 色組成物層硬化物之塗膜。如此操作形成的著色圖型及塗膜即為本發明之濾色器。 Examples of the method for producing a colored pattern using the colored curable resin composition of the present invention include a photoetching method, an inkjet method, and a printing method. Among them, a photoetching method is preferable. The photo-etching method is a method in which the colored curable resin composition is coated on a substrate, dried to form a colored composition layer, and then the colored composition layer is exposed and developed through a photomask. In the photoetching method, the above-mentioned formation can be performed by using no photomask and / or no development during exposure. Coating film of color composition layer hardened material. The coloring pattern and coating film formed in this way are the color filters of the present invention.
濾色器的膜厚並無特別限定,可視目的及用途等適當地調整,以如0.1至30μm為佳,0.1至20μm為更佳,0.5至6μm為又更佳。 The film thickness of the color filter is not particularly limited, and may be appropriately adjusted depending on the purpose and application. For example, it is preferably 0.1 to 30 μm, more preferably 0.1 to 20 μm, and even more preferably 0.5 to 6 μm.
基板方面,可使用:石英玻璃、硼矽酸玻璃、氧化鋁矽酸鹽玻璃、表面塗覆氧化矽的鈉鈣玻璃等玻璃板,以及聚碳酸酯、聚甲基丙烯酸碳酸甲酯、聚乙烯對苯二甲酸酯等樹脂板,矽,在前述基板上形成有鋁、銀、銀/銅/鈀合金薄膜等者。該等基板上,亦可形成其他濾色層、樹脂層、電晶體、電路等。 For the substrate, glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda-lime glass with silica coated on the surface, as well as polycarbonate, polymethyl methacrylate carbonate, and polyethylene pairs can be used. Resin plates such as phthalate, silicon, and the like are formed of aluminum, silver, silver / copper / palladium alloy films, and the like on the substrate. On these substrates, other color filter layers, resin layers, transistors, circuits, etc. may also be formed.
以光蝕刻法形成各色畫素,可以習知或慣用之裝置及條件進行。例如可以下述操作製作。 The formation of pixels of various colors by the photo-etching method can be performed by a conventional or conventional device and conditions. For example, it can be manufactured as follows.
首先,將著色硬化性樹脂組成物塗佈於基板上,再藉由加熱乾燥(預焙)及/或減壓乾燥去除溶劑等之揮發成分並加以乾燥,製得平滑之著色組成物層。 First, a colored curable resin composition is coated on a substrate, and then volatile components such as solvents are removed by drying under heat (pre-baking) and / or reduced pressure drying, and dried to obtain a smooth colored composition layer.
塗佈方法可列舉:旋塗法、狹縫塗佈法、細縫式旋塗法等。 Examples of the coating method include a spin coating method, a slit coating method, and a slit coating method.
進行加熱乾燥時之溫度,以30至120℃為佳,50至110℃為更佳。而且,加熱時間以10秒鐘至60分鐘為佳,30秒鐘至30分鐘為更佳。 The temperature during heating and drying is preferably 30 to 120 ° C, and more preferably 50 to 110 ° C. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.
在進行減壓乾燥時,以在50至150Pa之壓力下、20至25℃的溫度範圍進行為佳。 When performing the drying under reduced pressure, it is preferably performed at a temperature ranging from 20 to 25 ° C under a pressure of 50 to 150 Pa.
著色組成物層之膜厚度並無特別限定,可視目的濾色 器之膜厚而適當選擇。 The film thickness of the coloring composition layer is not particularly limited, and color can be filtered according to the purpose The film thickness of the device is appropriately selected.
其次,使著色組成物層經由用以形成目的之著色圖型之光罩曝光。該光罩上之圖型並無特別限定,可視目的之用途使用圖型。 Next, the colored composition layer is exposed through a mask for forming the intended colored pattern. The pattern on the reticle is not particularly limited, and the pattern may be used depending on the purpose of use.
曝光所使用之光源係以產生250至450nm波長之光的光源為佳。例如,可以使用阻斷未達350nm之波長範圍之光之濾光器,阻斷此等波長範圍之光;亦可使用取出436nm附近、408nm附近、365nm附近之波長範圍之光的帶通濾光器,選擇性地取出此等波長範圍之光。具體而言,可列舉:汞燈、發光二極體、金屬鹵素燈、鹵素燈等。 The light source used for the exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, filters that block light in the wavelength range up to 350 nm can be used to block light in these wavelength ranges; band-pass filters that take out light in the wavelength range near 436 nm, 408 nm, and 365 nm can also be used The device selectively extracts light in these wavelength ranges. Specific examples include a mercury lamp, a light-emitting diode, a metal halide lamp, and a halogen lamp.
為了可以平行光線均勻地照射曝光面整體、使光罩與形成著色組成物層的基板可對準正確位置,較佳為使用光罩對準機及步進機等曝光裝置。 In order to illuminate the entire exposure surface uniformly with parallel rays, and to align the photomask and the substrate on which the colored composition layer is formed, it is preferable to use an exposure device such as a photomask aligner and a stepper.
藉由使曝光後之著色組成物層與顯影液接 觸而顯影,即可在基板上形成著色圖型。藉由顯影,可將著色組成物層未曝光部分溶解於顯影液而去除。顯影液,以使用例如:氫氧化鉀、碳酸氫鈉、碳酸鈉、氫氧化四甲基銨等鹼性化合物之水溶液為較佳。該等鹼性化合物的水溶液中之濃度,以0.01至10質量%為佳,0.03至5質量%為更佳。而且,顯影液亦可含界面活性劑。 By contacting the coloring composition layer after exposure with the developing solution, Touch development, you can form a colored pattern on the substrate. By development, the unexposed part of the coloring composition layer can be dissolved in a developing solution and removed. As the developing solution, an aqueous solution of a basic compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide is preferably used. The concentration of these basic compounds in the aqueous solution is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. Moreover, the developing solution may contain a surfactant.
顯影方法,覆液(puddle)法、浸漬(dipping)法及噴灑(spray)法等之任一者均可。而且在顯影時基板亦可以任意之角度傾斜。 The development method may be any of a puddle method, a dipping method, and a spray method. Moreover, the substrate can be tilted at any angle during development.
顯影後,又以進行水洗為佳。 After development, washing with water is preferred.
再者,製得之著色圖型,以進行後焙為佳。後焙溫度以150至250℃為佳,160至235℃為更佳。後焙時間以1至120分鐘為佳,10至60分鐘為更佳。 Furthermore, the coloring pattern obtained is preferably post-baked. The post-baking temperature is preferably 150 to 250 ° C, and more preferably 160 to 235 ° C. The post-baking time is preferably 1 to 120 minutes, and more preferably 10 to 60 minutes.
以下以實施例更詳細說明本發明,惟本發明並不受此等實施例之限定。例中,表示含量乃至使用量的%及份,若無特別限定即為質量基準。 Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited by these examples. In the examples, the percentages and parts indicating the content and even the usage amount are mass standards unless otherwise specified.
以下之合成例中,化合物之構造係藉由質量分析(LC;Agilent公司製造1200型,MASS;Agilent公司製造LC/MSD型)確認。 In the following synthesis examples, the structure of the compound was confirmed by mass analysis (LC; Model 1200 manufactured by Agilent, MASS; Model LC / MSD manufactured by Agilent).
先在3-胺基酚(東京化成工業公司製造)10.9份中,加入三乙氧基矽烷(東京化成工業公司製造)19份及乙酸5份,並於四氫呋喃200份中回流8小時。該反應結束後,餾除四氫呋喃,製得式(AII-32-1)所示之化合物29.8份。 First, to 10.9 parts of 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.), 19 parts of triethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5 parts of acetic acid were added, and refluxed in 200 parts of tetrahydrofuran for 8 hours. After completion of the reaction, tetrahydrofuran was distilled off to obtain 29.8 parts of a compound represented by the formula (AII-32-1).
將製得之式(AII-32-1)所示之化合物2.9份、3,4-二羥基-3-環丁烯-1,2-二酮(東京化成工業股份有限公司製造)0.6份、1-丁醇90份及甲苯60份混合。將所得之混合物使用迪安-斯塔克(Dean-Stark)管除去生成的水同時在125 ℃下攪拌3小時。反應結束後,在餾除溶劑,並加入乙酸15份之後,再滴入18%食鹽水,濾取析出之固體。再將所濾取之固體以己烷清洗。將所得之固體減壓乾燥,製得式(AII-32)所示之化合物3.4份。 2.9 parts of the compound represented by the formula (AII-32-1), 0.6 part of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Tokyo Chemical Industry Co., Ltd.), 90 parts of 1-butanol and 60 parts of toluene were mixed. The resulting mixture was dewatered using a Dean-Stark tube while at 125 Stir at 3 ° C for 3 hours. After the reaction, the solvent was distilled off, and 15 parts of acetic acid was added, and then 18% saline was added dropwise, and the precipitated solid was collected by filtration. The filtered solid was washed with hexane. The obtained solid was dried under reduced pressure to obtain 3.4 parts of a compound represented by the formula (AII-32).
式(AII-32)所示化合物之鑑別 Identification of the compound represented by formula (AII-32)
(質量分析)離子化模式=ESI+:m/z=680.4[M+1]+ (Mass analysis) Ionization mode = ESI + : m / z = 680.4 [M + 1] +
精確質量(Exact Mass):679.3 Exact Mass: 679.3
除使用苯胺取代實施例1中之3-胺基酚之外,係以與實施例1相同方式合成,製得式(AII-5)所示之化合物。 A compound represented by the formula (AII-5) was prepared in the same manner as in Example 1 except that aniline was used instead of the 3-aminophenol in Example 1.
式(AII-5)所示化合物之鑑別 Identification of compounds represented by formula (AII-5)
(質量分析)離子化模式=ESI+:m/z=650.0[M+1]+精確質量:648.9 (Mass analysis) Ionization mode = ESI + : m / z = 650.0 [M + 1] + exact mass: 648.9
除使用三甲氧基矽烷取代實施例1中之三乙氧基矽烷之外,係以與實施例1相同方式合成,製得式(AII-31)所示 之化合物。 A trimethoxysilane was used in place of the triethoxysilane in Example 1, and was synthesized in the same manner as in Example 1 to obtain the formula (AII-31). Of compounds.
式(AII-31)所示化合物之鑑別 Identification of compounds represented by formula (AII-31)
(質量分析)離子化模式=ESI+:m/z=597.8[M+1]+ (Mass analysis) Ionization mode = ESI + : m / z = 597.8 [M + 1] +
精確質量:596.8 Exact mass: 596.8
將式(AII-32)所示之化合物、式(AII-5)所示之化合物及式(AII-31)所示之化合物0.35份分別溶解於氯仿並使體積成為250cm3,再以其中之2cm3以離子交換水稀釋成體積100cm3(濃度:0.028g/L),並以分光光度計(石英管,透光距離:1cm)測定吸光光譜。該化合物之最大吸收波長:λmax,分別為688nm、680nm、687nm。 0.35 parts of the compound represented by the formula (AII-32), the compound represented by the formula (AII-5) and the compound represented by the formula (AII-31) were each dissolved in chloroform to make the volume 250 cm 3 , and then 2 cm 3 was diluted with ion-exchanged water to a volume of 100 cm 3 (concentration: 0.028 g / L), and the absorption spectrum was measured with a spectrophotometer (quartz tube, light transmission distance: 1 cm). The maximum absorption wavelengths of the compound: λ max are 688 nm, 680 nm, and 687 nm, respectively.
對於實施例1至3中所得之化合物及式(II-0)所示之化合物,係以以下方式求得對丙二醇單甲醚(以下,簡稱為PGME)、乳酸乙酯(以下,簡稱為EL)、丙二醇單甲醚乙酸酯(以下,簡稱為PGMEA)之溶解度。 For the compounds obtained in Examples 1 to 3 and the compound represented by formula (II-0), p-propylene glycol monomethyl ether (hereinafter, simply referred to as PGME), ethyl lactate (hereinafter, simply referred to as EL ), The solubility of propylene glycol monomethyl ether acetate (hereinafter, referred to as PGMEA).
在50mL之樣品管中,以下述比例將化合物與上述溶劑混合,之後,再旋緊樣品管,並在30℃下於超音波振盪機中振盪3分鐘。然後在室溫下放置30分鐘之後,抽氣過濾,以目視觀察其殘渣。在未確認到不溶物時,即判定為溶解性佳而為○,在確認到不溶物時,即判定為溶解性不 良而為×。其結果如表1所示。 In a 50 mL sample tube, the compound was mixed with the above-mentioned solvent in the following ratio, and then the sample tube was screwed tightly and shaken in an ultrasonic shaker at 30 ° C for 3 minutes. After standing at room temperature for 30 minutes, it was suction-filtered, and the residue was visually observed. When insoluble matter is not confirmed, it is judged as good solubility and ○, when insoluble matter is confirmed, it is judged as insoluble matter Good and ×. The results are shown in Table 1.
先在具備循環冷卻器、滴液漏斗及攪拌機之燒瓶中,通入適當量之氮氣,使成為氮氣氣體環境,加入丙二醇單甲醚乙酸酯100份,並於攪拌同時加熱至85℃。其次,將於丙二醇單甲醚乙酸酯40份中溶有甲基丙烯酸19份、丙烯酸-3,4-環氧三環[5.2.1.02,6]癸烷-8-酯及丙烯酸-3,4-環氧三環[5.2.1.02,6]癸烷-9-酯之混合物(所含比例係莫耳比為50:50)(商品名「E-DCPA」,Daicel公司製造)171份之溶液, 使用滴液泵,耗時約5小時滴入該燒瓶中。另一方面,再將於丙二醇單甲醚乙酸酯120份中溶有聚合起始劑2,2’-偶氮雙(2,4-二甲基戊腈)26份之溶液使用另一滴液泵,耗時約5小時滴入該燒瓶中。在聚合起始劑滴入結束後,再於同溫度下保持3小時,之後冷卻至室溫,製得固形成分43.5%之共聚物(樹脂(B-1))之溶液。所得之樹脂(B-1)之重量平均分子量為8000,分子量分布為1.98,換算固形成分之酸價為53mg-KOH/g。 First, in a flask equipped with a circulating cooler, a dropping funnel, and a stirrer, pass an appropriate amount of nitrogen to a nitrogen gas environment, add 100 parts of propylene glycol monomethyl ether acetate, and heat to 85 ° C while stirring. Next, 19 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 2,6 ] decane-8-ester, and acrylic acid-3 will be dissolved in 40 parts of propylene glycol monomethyl ether acetate. , 4-epoxytricyclo [5.2.1.0 2,6 ] decane-9-ester mixture (contains a molar ratio of 50:50) (trade name "E-DCPA", manufactured by Daicel) 171 Part of the solution was dropped into the flask using a drip pump over about 5 hours. On the other hand, another solution was prepared by dissolving 26 parts of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 120 parts of propylene glycol monomethyl ether acetate. The pump was dropped into the flask over a period of about 5 hours. After the addition of the polymerization initiator was completed, the solution was kept at the same temperature for 3 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin (B-1)) having a solid content of 43.5%. The weight average molecular weight of the obtained resin (B-1) was 8000, the molecular weight distribution was 1.98, and the acid value in terms of solid content was 53 mg-KOH / g.
將下述成分混合而製得著色硬化性樹脂組成物:
將下述成分混合而製得著色硬化性樹脂組成物:
調平劑(F):聚醚改質聚矽氧油(Toray Silicone SH8400:Dow Corning Toray股份有限公司製造) Leveling agent (F): polyether modified silicone oil (Toray Silicone SH8400: manufactured by Dow Corning Toray Co., Ltd.)
0.1份。實施例9 0.1 serving. Example 9
將下述成分混合而製得著色硬化性樹脂組成物:
將下述成分混合而製得著色硬化性樹脂組成物:
在2吋見方之玻璃基板(EAGLE XG,CORNING公司製造)上,以旋塗法塗佈著色感光性樹脂組成物後,於100℃下預焙3分鐘以得到組成物層。在冷卻後,使形成有組成物層之玻璃基板與石英玻璃製光罩之間隔為100μm,使用曝光機(TME-150RSK,TOPCON股份有限公司製造),在大氣氣體環境下,以150mJ/cm2之曝光量(365nm之基準)照射 光。光罩方面,係使用形成100μm線/間距圖型者。 A 2 inch square glass substrate (EAGLE XG, manufactured by Corning Corporation) was coated with a colored photosensitive resin composition by a spin coating method, and then prebaked at 100 ° C for 3 minutes to obtain a composition layer. After cooling, the distance between the glass substrate on which the composition layer was formed and the mask made of quartz glass was 100 μm, and an exposure machine (TME-150RSK, manufactured by TOPCON Co., Ltd.) was used in an atmosphere of 150 mJ / cm 2 The exposure amount (based on 365 nm) is irradiated with light. For the photomask, a 100 μm line / space pattern is used.
照射上述光後,再將製得之塗膜,在含非離子系界面活性劑0.12%及氫氧化鉀0.04%的水系顯影液中,在23℃下浸漬80秒鐘而顯影,經水洗後,再於烘箱中,以200℃進行後焙20分鐘,製得圖型。 After the above light was irradiated, the obtained coating film was dipped in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C for 80 seconds for development. After washing with water, It was then post-baked in an oven at 200 ° C for 20 minutes to obtain a pattern.
將著色感光性樹脂組成物之塗佈膜以200℃加熱20分鐘,再使用測色機(OSP-SP-200,OLYMPUS公司製造)測定塗佈膜加熱前後的色差(△Eab*)。對於實施例7、8、9所製得之塗佈膜,分別實施以上之耐熱性評估,結果係色差(△Eab*)為12.6(實施例7)、10.2(實施例8)、11.1(實施例9)。對比較例2亦同樣地實施耐熱性評估,結果係色差(△Eab*)為20.5,可知本案染料之耐熱性優異。 The coating film of the colored photosensitive resin composition was heated at 200 ° C. for 20 minutes, and the color difference (ΔEab *) before and after the coating film was heated was measured using a color measuring machine (OSP-SP-200, manufactured by OLYMPUS). The coating films prepared in Examples 7, 8, and 9 were subjected to the above-mentioned heat resistance evaluation, respectively. As a result, the color difference (ΔEab *) was 12.6 (Example 7), 10.2 (Example 8), and 11.1 (Implementation). Example 9). Comparative Example 2 was also evaluated for heat resistance in the same manner. As a result, the color difference (ΔEab *) was 20.5, and it was found that the heat resistance of the dye in this case was excellent.
本發明之染料對有機溶劑之溶解性優異。所以,本發明之著色硬化性樹脂組成物,由於含本發明之染料,故異物之產生少,而可製成高品質之濾色器,而且可提供耐熱性優異之濾色器。 The dye of the present invention has excellent solubility in an organic solvent. Therefore, since the colored curable resin composition of the present invention contains the dye of the present invention, foreign matter is less generated, and a high-quality color filter can be produced, and a color filter excellent in heat resistance can be provided.
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