TW201525075A - Coloring composition, coloring hardened film, and display element - Google Patents
Coloring composition, coloring hardened film, and display element Download PDFInfo
- Publication number
- TW201525075A TW201525075A TW103141544A TW103141544A TW201525075A TW 201525075 A TW201525075 A TW 201525075A TW 103141544 A TW103141544 A TW 103141544A TW 103141544 A TW103141544 A TW 103141544A TW 201525075 A TW201525075 A TW 201525075A
- Authority
- TW
- Taiwan
- Prior art keywords
- compound
- ring
- formula
- structure represented
- group
- Prior art date
Links
Classifications
-
- 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
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- 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
-
- 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
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials For Photolithography (AREA)
- Optical Filters (AREA)
- Liquid Crystal (AREA)
- Electroluminescent Light Sources (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
Description
本發明係關於著色組成物、著色硬化膜和顯示元件,更詳言之,係關於用於形成在穿透式或反射式的彩色液晶顯示元件、固態攝影元件、有機EL顯示元件、電子紙等中使用的著色硬化膜的著色組成物,使用該著色組成物形成的著色硬化膜以及具備該著色硬化膜的顯示元件。 The present invention relates to a coloring composition, a colored cured film, and a display element, and more particularly to a color liquid crystal display element, a solid-state imaging element, an organic EL display element, an electronic paper, etc. for forming in a transmissive or reflective type. The colored composition of the colored cured film used in the coloring cured film formed using the colored composition and a display element including the colored cured film.
在使用著色放射線敏感性組成物製造彩色濾光片時,已知有在基板上塗布顏料分散型的著色放射線敏感性組成物並乾燥之後,對乾燥塗膜照射放射線以成為所希望的圖案形狀(以下,稱為「曝光」),進行顯影,從而得到各色的像素的方法(例如,參照專利文獻1~2)。另外,還已知有利用分散有碳黑的光聚合性組成物形成黑色矩陣的方法(例如,參照專利文獻3)。此外,也已知有使用顏料分散型的著色樹脂組成物而利用噴墨方式得到各色的像素的方法(例如,參照專利文獻4)。 When a color filter is produced using a colored radiation-sensitive composition, it is known that a pigment-dispersed colored radiation-sensitive composition is applied onto a substrate and dried, and then the dried coating film is irradiated with radiation to have a desired pattern shape ( Hereinafter, a method of performing development to obtain pixels of respective colors (for example, refer to Patent Documents 1 and 2). Further, a method of forming a black matrix by using a photopolymerizable composition in which carbon black is dispersed is known (for example, refer to Patent Document 3). Further, a method of obtaining a pixel of each color by an inkjet method using a pigment-dispersed colored resin composition is known (for example, see Patent Document 4).
對於用於形成著色硬化膜的著色組成物而言,出於形成更高亮度的著色硬化膜的目的,研究了使用染料作為著色劑。例如專利文獻5中,報告了通過使用花青染料作為著色劑,從而得到具有優異的亮度的塗膜。 For the coloring composition for forming a colored cured film, the use of a dye as a colorant has been studied for the purpose of forming a brighter film of higher brightness. For example, in Patent Document 5, it is reported that a coating film having excellent brightness is obtained by using a cyanine dye as a coloring agent.
[專利文獻1]日本特開平2-144502號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2-144502
[專利文獻2]日本特開平3-53201號公報 [Patent Document 2] Japanese Patent Laid-Open No. 3-53201
[專利文獻3]日本特開平6-35188號公報 [Patent Document 3] Japanese Patent Laid-Open No. Hei 6-35188
[專利文獻4]日本特開2000-310706號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2000-310706
[專利文獻5]日本特開2009-235392號公報 [Patent Document 5] Japanese Patent Laid-Open Publication No. 2009-235392
然而,根據本發明人等的研究,知道了對於含有花青染料作為著色劑的著色組成物而言,著色組成物的保存穩定性有時不充分。 However, according to studies by the present inventors, it has been found that the coloring composition containing a cyanine dye as a coloring agent may have insufficient storage stability of the coloring composition.
因此,本發明的課題在於提供含有花青染料作為著色劑、保存穩定性良好且能夠形成高亮度的著色硬化膜的著色組成物。另外,本發明的課題在於提供使用該著色組成物形成的著色硬化膜和具備該著色硬化膜的顯示元件。 Therefore, an object of the present invention is to provide a coloring composition containing a cyanine dye as a coloring agent and having a coloring cured film which is excellent in storage stability and capable of forming high brightness. Further, an object of the present invention is to provide a colored cured film formed using the colored composition and a display element including the colored cured film.
本發明人等進行了深入研究,結果發現通過使用至少2種花青化合物作為著色劑,並控制它們的含有比例,能夠解決上述課題。 As a result of intensive studies, the present inventors have found that the above problems can be solved by using at least two kinds of cyanine compounds as colorants and controlling the content ratio thereof.
即,本發明提供一種著色組成物,其係含有(A)著色劑、(B)黏結劑樹脂和(C)聚合性化合物的著色組成物,(A)著色劑含有具有下述式(1)表示的結構的化合物和具有下述式(2)表示的結構的化合物,具有下述式(2) 表示的結構的化合物的含量相對於具有下述式(1)表示的結構的化合物和具有下述式(2)表示的結構的化合物的合計含量為0.001質量%以上。 That is, the present invention provides a coloring composition comprising (A) a coloring agent, (B) a binder resin, and (C) a coloring composition of a polymerizable compound, and (A) the coloring agent contains the following formula (1) The compound of the structure shown and the compound having the structure represented by the following formula (2) have the following formula (2) The total content of the compound having a structure represented by the following formula (1) and the compound having a structure represented by the following formula (2) is 0.001% by mass or more.
另外,本發明提供一種著色劑,其含有具有下述式(1)表示的結構的化合物和具有下述式(2)表示的結構的化合物,具有下述式(2)表示的結構的化合物的含量相對於具有下述式(1)表示的結構的化合物和具有下述式(2)表示的結構的化合物的合計含量為0.001質量%以上。 Furthermore, the present invention provides a coloring agent containing a compound having a structure represented by the following formula (1) and a compound having a structure represented by the following formula (2), and a compound having a structure represented by the following formula (2) The total content of the compound with respect to the compound represented by the following formula (1) and the compound represented by the following formula (2) is 0.001% by mass or more.
[式(1)中,環Z1和環Z2相互獨立地表示經取代或未經取代的雜環。 [In the formula (1), the ring Z 1 and the ring Z 2 independently of each other represent a substituted or unsubstituted heterocyclic ring.
p表示1或2。其中,p為2時,多個存在的R1和R2可以相同也可以不同。 p represents 1 or 2. Wherein, when p is 2, a plurality of R 1 and R 2 present may be the same or different.
R1~R3相互獨立地表示氫原子、鹵素原子、或者經取代或未經取代的烴基。] R 1 to R 3 independently of each other represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted hydrocarbon group. ]
[式(2)中,環Z3和環Z4相互獨立地表示經取代或未經取代的雜環。 [In the formula (2), the ring Z 3 and the ring Z 4 independently of each other represent a substituted or unsubstituted heterocyclic ring.
p為1時q表示2以上的整數,p為2時q表示3以上的整數。 When p is 1, q represents an integer of 2 or more, and when p is 2, q represents an integer of 3 or more.
R4~R6相互獨立地表示氫原子、鹵素原子、或者經取代或未經取代的烴基。其中,多個存在的R4和R5可以相同也可以不同。] R 4 to R 6 independently of each other represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted hydrocarbon group. Among them, a plurality of R 4 and R 5 present may be the same or different. ]
另外,本發明提供使用上述著色組成物形成的著色硬化膜和具備該著色硬化膜的顯示元件。在此,「著色硬化膜」是指在顯示元件、固態攝影元件中使用的各色像素、黑色矩陣、黑色隔離件等。 Further, the present invention provides a colored cured film formed using the above colored composition and a display element comprising the colored cured film. Here, the "coloring cured film" means a pixel of each color used in a display element or a solid-state image sensor, a black matrix, a black spacer, or the like.
本發明的著色組成物的保存穩定性良好。另外,若使用本發明的著色組成物,能夠形成高亮度的著色硬化膜。 The coloring composition of the present invention has good storage stability. Further, when the colored composition of the present invention is used, a high-color colored cured film can be formed.
因此,本發明的著色組成物極其適用於製作彩色液晶顯示元件、有機EL顯示元件、電子紙等顯示元件、CMOS圖像感應器等固態攝影元件。 Therefore, the coloring composition of the present invention is extremely suitable for producing a solid-state imaging element such as a color liquid crystal display element, an organic EL display element, a display element such as an electronic paper, or a CMOS image sensor.
以下,對本發明進行詳細說明。 Hereinafter, the present invention will be described in detail.
著色組成物Coloring composition
以下,對本發明的著色組成物的構成成分進行詳細說明。 Hereinafter, the constituent components of the colored composition of the present invention will be described in detail.
-(A)著色劑- - (A) colorant -
本發明的著色組成物含有具有下述式(1)表示的結構的化合物(以下,也稱為「化合物(1)」)和具有下述式 (2)表示的結構的化合物(以下,也稱為「化合物(2)」)作為(A)著色劑。 The colored composition of the present invention contains a compound having a structure represented by the following formula (1) (hereinafter also referred to as "compound (1)") and has the following formula The compound of the structure shown in (2) (hereinafter, also referred to as "compound (2)") is (A) a coloring agent.
[式(1)中,環Z1和環Z2相互獨立地表示經取代或未經取代的雜環。 [In the formula (1), the ring Z 1 and the ring Z 2 independently of each other represent a substituted or unsubstituted heterocyclic ring.
p表示1或2。其中,p為2時,多個存在的R1和R2可以相同也可以不同。 p represents 1 or 2. Wherein, when p is 2, a plurality of R 1 and R 2 present may be the same or different.
R1~R3相互獨立地表示氫原子、鹵素原子、或者經取代或未經取代的烴基。] R 1 to R 3 independently of each other represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted hydrocarbon group. ]
[式(2)中,環Z3和環Z4相互獨立地表示經取代或未經取代的雜環。 [In the formula (2), the ring Z 3 and the ring Z 4 independently of each other represent a substituted or unsubstituted heterocyclic ring.
p為1時q表示2以上的整數,p為2時q表示3以上的整數。 When p is 1, q represents an integer of 2 or more, and when p is 2, q represents an integer of 3 or more.
R4~R6相互獨立地表示氫原子、鹵素原子、或者經取代或未經取代的烴基。多個存在的R4和R5可以相同也可以不同。] R 4 to R 6 independently of each other represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted hydrocarbon group. The plurality of R 4 and R 5 present may be the same or different. ]
環Z1~環Z4中的雜環可以是單環式雜環,也可以是多環式雜環。雜環可以是不飽和環也可以是飽和環,另外環內可以具有同種或者不同種類的2個以上的雜 原子(例如,氮原子、氧原子、硫原子)。例如可舉出吡咯啶環、吡唑啉環、啉環、硫代啉環、哌啶環、哌環、高哌環、四氫嘧啶環等含氮脂環式雜環;吡啶環、吡環、嘧啶環、嗒環、喹啉環、異喹啉環、酞環、喹啉環、咪唑環、吡唑環、三唑環、四唑環、噻唑環、苯并噻唑環、唑環、吲哚環、吲唑環、苯并咪唑環、苯并唑、鄰苯二甲醯亞胺環等含氮芳香族雜環;噻吩環、呋喃環、嘌呤環等其它的芳香族雜環。其中,較佳為含氮芳香族雜環,更佳為吲哚環、苯并唑環、苯并噻唑環,進一步更佳為吲哚環。 The heterocyclic ring in the ring Z 1 to the ring Z 4 may be a monocyclic hetero ring or a polycyclic hetero ring. The heterocyclic ring may be an unsaturated ring or a saturated ring, and may have two or more kinds of hetero atoms (for example, a nitrogen atom, an oxygen atom or a sulfur atom) of the same kind or different types in the ring. For example, a pyrrolidine ring, a pyrazoline ring, Porphyrin ring, thio Phenanthene ring, piperidine ring, piperazine Ring, high piper a nitrogen-containing alicyclic heterocyclic ring such as a ring or a tetrahydropyrimidine ring; a pyridine ring or a pyridyl group Ring, pyrimidine ring, anthracene Ring, quinoline ring, isoquinoline ring, anthracene Ring, quin a porphyrin ring, an imidazole ring, a pyrazole ring, a triazole ring, a tetrazole ring, a thiazole ring, a benzothiazole ring, Oxazole ring, anthracene ring, indazole ring, benzimidazole ring, benzo a nitrogen-containing aromatic heterocyclic ring such as an azole or a phthalic acid imine ring; or an aromatic heterocyclic ring such as a thiophene ring, a furan ring or an anthracene ring. Among them, a nitrogen-containing aromatic heterocyclic ring is preferred, and an anthracene ring and a benzo ring are more preferred. The azole ring and the benzothiazole ring are further more preferably an anthracene ring.
p表示1或2,p較佳為1。 p represents 1 or 2, and p is preferably 1.
p為1時,q表示2以上的整數,但較佳為2或3,更佳為2。另外,p為2時,q表示3以上的整數,但較佳為3。 When p is 1, q represents an integer of 2 or more, but is preferably 2 or 3, more preferably 2. Further, when p is 2, q represents an integer of 3 or more, but is preferably 3.
作為p和q的組合,較佳為p為1,且q為2以上,更佳為p為1,且q為2。 As a combination of p and q, p is preferably 1, and q is 2 or more, more preferably p is 1, and q is 2.
作為R1~R6中的鹵素原子,例如可舉出氟原子、氯原子、溴原子。 Examples of the halogen atom in R 1 to R 6 include a fluorine atom, a chlorine atom, and a bromine atom.
作為R1~R6中的烴基,例如可舉出脂肪族烴基、脂環式烴基、芳香族烴基。 Examples of the hydrocarbon group in R 1 to R 6 include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
脂肪族烴基可以是飽和也可以是不飽和,例如可舉出烷基、烯基、炔基。這些脂肪族烴基的碳原子數較佳為1~30,更佳為1~24,特佳為1~20。另外,這些脂肪族烴基可以是直鏈狀也可以是支鏈狀。具體而言,作為烷基,例如可舉出甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基、己基、庚基、辛 基、壬基、癸基、十一烷基、1-甲基癸基、十二烷基、1-甲基十二烷基、1-乙基癸基、十三烷基、十四烷基、第三十二烷基、十五烷基、1-庚基辛基、十六烷基、十八烷基、二十一烷-1-基、二十二烷-1-基、二十三烷-1-基、二十四烷-1-基等。作為烯基,例如可舉出乙烯基、1-丙烯基、2-丙烯基、1-丁烯基、2-丁烯基、1,3-丁二烯基、1-戊烯基、2-戊烯基、1-己烯基、2-乙基-2-丁烯基、2-辛烯基、(4-乙烯基)-5-己烯基、2-癸烯基等。另外,作為炔基,例如可舉出乙炔基、1-丙炔基、1-丁炔基、1-戊炔基、3-戊炔基、1-己炔基、2-乙基-2-丁炔基、2-辛炔基、(4-乙炔基)-5-己炔基、2-癸炔基等。 The aliphatic hydrocarbon group may be saturated or unsaturated, and examples thereof include an alkyl group, an alkenyl group, and an alkynyl group. The number of carbon atoms of these aliphatic hydrocarbon groups is preferably from 1 to 30, more preferably from 1 to 24, particularly preferably from 1 to 20. Further, these aliphatic hydrocarbon groups may be linear or branched. Specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a third butyl group, a hexyl group, a heptyl group, and a octyl group. Base, fluorenyl, fluorenyl, undecyl, 1-methylindenyl, dodecyl, 1-methyldodecyl, 1-ethylindenyl, tridecyl, tetradecyl , thirty-dodecyl, pentadecyl, 1-heptyloctyl, hexadecyl, octadecyl, eicosyl-1-yl, docosa-1-yl, twentieth Trialkyl-1-yl, tetracos-1-yl and the like. Examples of the alkenyl group include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 1,3-butadienyl group, a 1-pentenyl group, and a 2- Pentenyl, 1-hexenyl, 2-ethyl-2-butenyl, 2-octenyl, (4-vinyl)-5-hexenyl, 2-decenyl and the like. Further, examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 1-butynyl group, a 1-pentynyl group, a 3-pentynyl group, a 1-hexynyl group, and a 2-ethyl-2- group. Butynyl, 2-octynyl, (4-ethynyl)-5-hexynyl, 2-decynyl and the like.
作為脂環式烴基,較佳為碳原子數3~30的脂環式烴基。脂環式烴基可以是飽和也可以是不飽和,例如可舉出環烷基、環烯基、稠合多環烴基、橋環烴基、螺環烴基、環狀萜烯烴基等。更具體而言,可舉出環丙基、環丁基、環戊基、環己基、第三丁基環己基、環庚基、環辛基等環烷基;1-環己烯基等環烯基;三環癸基、十氫-2-萘基、金剛烷基等稠合多環烴基;三環[5.2.1.02,6]癸烷-8-基、五環十五烷基、異冰片基、二環戊烯基、三環戊烯基等橋環烴基;從螺[3,4]庚烷、螺[3,4]辛烷除去1個氫原子而得的1價基團等螺環烴基;從對薄荷烷、側柏烷、蒈烷等除去1個氫原子而得的1價基團等環狀萜烯烴基等。上述環烷基和環烯基中,更佳為碳原子數為3~12。 The alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 3 to 30 carbon atoms. The alicyclic hydrocarbon group may be saturated or unsaturated, and examples thereof include a cycloalkyl group, a cycloalkenyl group, a condensed polycyclic hydrocarbon group, a bridged cyclic hydrocarbon group, a spirocyclic hydrocarbon group, and a cyclic terpene group. More specifically, a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a t-butylcyclohexyl group, a cycloheptyl group or a cyclooctyl group; a ring such as a 1-cyclohexenyl group; Alkenyl; condensed polycyclic hydrocarbon group such as tricyclodecyl, decahydro-2-naphthyl, adamantyl; tricyclo[5.2.1.0 2,6 ]decane-8-yl, pentacyclopentadecyl, a bridged hydrocarbon group such as isobornyl, dicyclopentenyl or tricyclopentenyl; a monovalent group obtained by removing one hydrogen atom from spiro[3,4]heptane or spiro[3,4]octane The spirocyclic hydrocarbon group; a cyclic terpene group such as a monovalent group obtained by removing one hydrogen atom from menthane, arborane, decane or the like. More preferably, the above cycloalkyl group and cycloalkenyl group have 3 to 12 carbon atoms.
作為芳香族烴基,較佳為碳原子數6~20的芳 香族烴基,更佳為碳原子數6~10的芳香族烴基。作為芳香族烴基,例如可舉出芳基。在此,本說明書中「芳基」是指單環~三環式芳香族烴基,具體而言,可舉出苯基、苄基、鄰甲苯基、間甲苯基、對甲苯基、二甲苯基、萘基、蒽基、菲基、薁基、9-茀基等。 As the aromatic hydrocarbon group, a aryl group having 6 to 20 carbon atoms is preferred. The aromatic hydrocarbon group is more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms. The aromatic hydrocarbon group may, for example, be an aryl group. Here, the "aryl group" in the present specification means a monocyclic to tricyclic aromatic hydrocarbon group, and specific examples thereof include a phenyl group, a benzyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, and a xylyl group. , naphthyl, anthracenyl, phenanthryl, anthracenyl, 9-fluorenyl and the like.
作為環Z1~環Z4的雜環和R1~R6的烴基的取代基,可舉出鹵素原子、羥基、氰基、甲醯基、羧基、硝基、胺基、二烷基胺基、二芳基胺基、烷氧基、芳氧基、烷氧基羰基、烷基硫基、芳基硫基、三烷基甲矽烷基、巰基、烯丙基、烷基磺醯基、烷基胺磺醯基、脂肪族烴基、雜環基、芳香族烴基等。 Examples of the substituent of the hetero ring of the ring Z 1 to the ring Z 4 and the hydrocarbon group of R 1 to R 6 include a halogen atom, a hydroxyl group, a cyano group, a decyl group, a carboxyl group, a nitro group, an amine group, and a dialkylamine. , diarylamino, alkoxy, aryloxy, alkoxycarbonyl, alkylthio, arylthio, trialkylcarbenyl, decyl, allyl, alkylsulfonyl, An alkylamine sulfonyl group, an aliphatic hydrocarbon group, a heterocyclic group, an aromatic hydrocarbon group or the like.
具有式(1)表示的結構的化合物較佳為具有下述式(1A)表示的結構的化合物(以下,也稱為「化合物(1A)」。另外,具有式(2)表示的結構的化合物較佳為具有下述式(2A)表示的結構的化合物(以下,也稱為「化合物(2A)」)。 The compound having a structure represented by the formula (1) is preferably a compound having a structure represented by the following formula (1A) (hereinafter also referred to as "compound (1A)"). Further, a compound having a structure represented by the formula (2) A compound having a structure represented by the following formula (2A) (hereinafter also referred to as "compound (2A)") is preferred.
[式(1A)中,R1~R3與上述含義相同。 In the formula (1A), R 1 to R 3 have the same meanings as described above.
環Z1A和環Z2A相互獨立地表示經取代或未經取代的芳香族烴環。 The ring Z 1A and the ring Z 2A independently of each other represent a substituted or unsubstituted aromatic hydrocarbon ring.
Q1和Q2相互獨立地表示-O-、-S-或者-CR13R14-。 Q 1 and Q 2 independently represent -O-, -S- or -CR 13 R 14 -.
R11~R14相互獨立地表示經取代或未經取代的烴基。] R 11 to R 14 independently of each other represent a substituted or unsubstituted hydrocarbon group. ]
[式(2A)中,q、R4~R6與上述含義相同。 [In the formula (2A), q, R 4 to R 6 have the same meanings as described above.
環Z3A和環Z4A相互獨立地表示經取代或未經取代的芳香族烴環。 The ring Z 3A and the ring Z 4A independently of each other represent a substituted or unsubstituted aromatic hydrocarbon ring.
Q3和Q4相互獨立地表示-O-、-S-或者-CR23R24-。 Q 3 and Q 4 independently represent -O-, -S- or -CR 23 R 24 -.
R21~R24相互獨立地表示經取代或未經取代的烴基。] R 21 to R 24 independently of each other represent a substituted or unsubstituted hydrocarbon group. ]
作為環Z1A~環Z4A中的芳香族烴環,較佳為碳原子數6~20的芳香族烴環,更佳為碳原子數6~10的芳香族烴環,特佳為苯環。 The aromatic hydrocarbon ring in the ring Z 1A to the ring Z 4A is preferably an aromatic hydrocarbon ring having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon ring having 6 to 10 carbon atoms, particularly preferably a benzene ring. .
作為R1~R6,較佳為氫原子。 R 1 to R 6 are preferably a hydrogen atom.
q較佳為2。 q is preferably 2.
Q1和Q2較佳為-O-、-CR13R14-。作為R13和R14中的烴基,較佳為脂肪族烴基,更佳為烷基。作為烷基,較佳為碳原子數1~8的烷基,更佳為碳原子數1~4的烷基,特佳為甲基、乙基。 Q 1 and Q 2 are preferably -O-, -CR 13 R 14 -. As the hydrocarbon group in R 13 and R 14 , an aliphatic hydrocarbon group is preferred, and an alkyl group is more preferred. The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group.
Q3和Q4較佳為-O-、-CR23R24-。作為R23和R24中的烴基,較佳為脂肪族烴基,更佳為烷基。作為烷基,較佳為碳原子數1~8的烷基,更佳為碳原子數1~4的烷基, 特佳為甲基、乙基。 Q 3 and Q 4 are preferably -O-, -CR 23 R 24 -. As the hydrocarbon group in R 23 and R 24 , an aliphatic hydrocarbon group is preferred, and an alkyl group is more preferred. The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably a methyl group or an ethyl group.
作為R11~R14和R21~R24中的烴基,可舉出脂肪族烴基、脂環式烴基、芳香族烴基。作為具體例,可舉出與R1~R6的烴基中例示的化合物相同的例子。其中,作為R11~R12和R21~R22中的烴基,較佳為脂肪族烴基,更佳為烷基。烷基的碳原子數較佳為1~12,更佳為1~8,特佳為1~6。 Examples of the hydrocarbon group in R 11 to R 14 and R 21 to R 24 include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Specific examples thereof are the same as those exemplified as the hydrocarbon groups of R 1 to R 6 . Among them, as the hydrocarbon group in R 11 to R 12 and R 21 to R 22 , an aliphatic hydrocarbon group is preferred, and an alkyl group is more preferred. The alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 6 carbon atoms.
式(1)表示的結構和式(2)表示的結構為陽離子性時,具有該結構的化合物為了成為電中性可以具有陰離子。作為陰離子,例如可舉出鹵素離子、硼陰離子、磷酸陰離子、羧酸陰離子、硫酸陰離子、有機磺酸陰離子、氮陰離子、甲基化物陰離子、配位體中具有偶氮化合物的過渡金屬配合物的陰離子等。 When the structure represented by the formula (1) and the structure represented by the formula (2) are cationic, the compound having such a structure may have an anion in order to be electrically neutral. Examples of the anion include a halogen ion, a boron anion, a phosphate anion, a carboxylic acid anion, a sulfate anion, an organic sulfonate anion, a nitrogen anion, a methide anion, and a transition metal complex having an azo compound in the ligand. Anion, etc.
作為鹵素離子,可舉出氟化物離子、氯化物離子、溴化物離子、碘化物離子。作為硼陰離子、磷酸陰離子、氮陰離子,例如可舉出日本特開2012-173399號公報的[0037]~[0039]段記載的離子。作為羧酸陰離子,例如可舉出日本特開2009-265641號公報和日本特開2008-096680號公報中記載的羧酸陰離子。作為硫酸陰離子,例如可舉出硫酸陰離子、亞硫酸陰離子等。作為有機磺酸陰離子,例如可舉出日本特開2012-173399號公報、國際公開第2011/037195號小冊子、國際公開第2011/162217號小冊子、日本專利第3736221號說明書和日本特開2011-070172號公報中記載的有機磺酸陰離子。作為甲基化物陰離子,例如可舉出日本特開 2011-145540號公報、美國專利第5554664號說明書、日本特開2005-309408號公報、日本特開2004-085657號公報、日本特表2010-505787號公報等中記載的甲基化物陰離子。 Examples of the halogen ion include a fluoride ion, a chloride ion, a bromide ion, and an iodide ion. Examples of the boron anion, the phosphate anion, and the nitrogen anion include the ions described in paragraphs [0037] to [0039] of JP-A-2012-173399. Examples of the carboxylic acid anion include a carboxylic acid anion described in JP-A-2009-265641 and JP-A-2008-096680. Examples of the sulfate anion include a sulfate anion, a sulfite anion, and the like. Examples of the organic sulfonic acid anion include JP-A-2012-173399, International Publication No. 2011/037195, International Publication No. 2011/162217, Japanese Patent No. 3372221, and Japanese Patent Application No. 2011-070172. The organic sulfonic acid anion described in the publication. As the methide anion, for example, JP-A A methide anion described in JP-A-2005-505787, JP-A-2005-309657, JP-A-2004-085657, and JP-A-2010-505787.
作為配位體中具有偶氮化合物的過渡金屬配合物的陰離子,例如可舉出日本特開2009-163226號公報、日本特開2012-212089號公報中記載的陰離子。 The anion of the transition metal complex having an azo compound in the ligand is, for example, an anion described in JP-A-2009-212226 and JP-A-2012-212089.
這些陰離子中,較佳為硼陰離子、氮陰離子、配位體中具有偶氮化合物的過渡金屬配合物的陰離子,進一步更佳為硼陰離子、氮陰離子。 Among these anions, an anion of a boron anion, a nitrogen anion, a transition metal complex having an azo compound in the ligand, and more preferably a boron anion or a nitrogen anion.
作為硼陰離子的具體例,例如可舉出BF4 -、(CF3)4B-、(CF3)3BF-、(CF3)2BF2 -、(CF3)BF3 -、(C2F5)4B-、(C2F5)3BF-、(C2F5)BF3 -、(C2F5)2BF2 -、(CF3)(C2F5)2BF-、(C6F5)4B-、[(CF3)2C6H3]4B-、(CF3C6H4)4B-、(C6F5)2BF2 -、(C6F5)BF3 -、(C6H3F2)4B-、B(CN)4 -、B(CN)F3 -、B(CN)2F2 -、B(CN)3F-、(CF3)3B(CN)-、(CF3)2B(CN)2 -、(C2F5)3B(CN)-、(C2F5)2B(CN)2 -、(n-C3F7)3B(CN)-、(n-C4F9)3B(CN)-、(n-C4F9)2B(CN)2 -、(n-C6F13)3B(CN)-、(CHF2)3B(CN)-、(CHF2)2B(CN)2 -、(CH2CF3)3B(CN)-、(CH2CF3)2B(CN)2 -、(CH2C2F5)3B(CN)-、(CH2C2F5)2B(CN)2 -、(CH2CH2C3F7)2B(CN)2 -、(n-C3F7CH2)2B(CN)2 -、(C6H5)3B(CN)-、四(五氟苯基)硼酸鹽陰離子等。 Specific examples of the boron anion include BF 4 - , (CF 3 ) 4 B - , (CF 3 ) 3 BF - , (CF 3 ) 2 BF 2 - , (CF 3 ) BF 3 - , (C) 2 F 5 ) 4 B - , (C 2 F 5 ) 3 BF - , (C 2 F 5 )BF 3 - , (C 2 F 5 ) 2 BF 2 - , (CF 3 )(C 2 F 5 ) 2 BF - , (C 6 F 5 ) 4 B - , [(CF 3 ) 2 C 6 H 3 ] 4 B - , (CF 3 C 6 H 4 ) 4 B - , (C 6 F 5 ) 2 BF 2 - , (C 6 F 5 )BF 3 - , (C 6 H 3 F 2 ) 4 B - , B(CN) 4 - , B(CN)F 3 - , B(CN) 2 F 2 - , B(CN 3 F - , (CF 3 ) 3 B(CN) - , (CF 3 ) 2 B(CN) 2 - , (C 2 F 5 ) 3 B(CN) - , (C 2 F 5 ) 2 B( CN) 2 - , (nC 3 F 7 ) 3 B(CN) - , (nC 4 F 9 ) 3 B(CN) - , (nC 4 F 9 ) 2 B(CN) 2 - , (nC 6 F 13 3 B(CN) - , (CHF 2 ) 3 B(CN) - , (CHF 2 ) 2 B(CN) 2 - , (CH 2 CF 3 ) 3 B(CN) - , (CH 2 CF 3 ) 2 B(CN) 2 - , (CH 2 C 2 F 5 ) 3 B(CN) - , (CH 2 C 2 F 5 ) 2 B(CN) 2 - , (CH 2 CH 2 C 3 F 7 ) 2 B(CN) 2 - , (nC 3 F 7 CH 2 ) 2 B(CN) 2 - , (C 6 H 5 ) 3 B(CN) - , tetrakis(pentafluorophenyl) borate anion, and the like.
另外,作為氮陰離子的具體例,例如可舉出[(CN)2N]-、[(FSO2)2N]-、[(FSO2)N(CF3SO2)]-、[(FSO2)N(CF3CF2SO2)]-、[(FSO2)N{(CF3)2CFSO2}]-、[(FSO2)N(CF3CF2CF2SO2)]-、 [(FSO2)N(CF3CF2CF2CF2SO2)]-、[(FSO2)N{(CF3)2CFCF2SO2}]-、[(FSO2)N{CF3CF2(CF3)CFSO2}]-、[(FSO2)N{(CF3)3CSO2}]-、[(CF3SO2)2N]-等。 Further, specific examples of the nitrogen anion include [(CN) 2 N] - , [(FSO 2 ) 2 N] - , [(FSO 2 ) N(CF 3 SO 2 )] - , [(FSO 2 ) N(CF 3 CF 2 SO 2 )] - , [(FSO 2 )N{(CF 3 ) 2 CFSO 2 }] - , [(FSO 2 )N(CF 3 CF 2 CF 2 SO 2 )] - , [(FSO 2 )N(CF 3 CF 2 CF 2 CF 2 SO 2 )] - , [(FSO 2 )N{(CF 3 ) 2 CFCF 2 SO 2 }] - , [(FSO 2 )N{CF 3 CF 2 (CF 3 )CFSO 2 }] - , [(FSO 2 )N{(CF 3 ) 3 CSO 2 }] - , [(CF 3 SO 2 ) 2 N] - and the like.
本發明的著色組成物中,化合物(2)的含量相對於化合物(1)和化合物(2)的合計含量需為0.001質量%以上。本發明人等推斷由於化合物(1)在溶劑中的溶解性低,容易結晶化而成為異物,所以著色組成物的保存穩定性差。而且,推測通過與化合物(1)一起含有規定量以上的化合物(2)能防止化合物(1)的結晶化,改善著色組成物的保存穩定性。從進一步改善保存穩定性的觀點考慮,化合物(2)的含量相對於化合物(1)和化合物(2)的合計含量,較佳為0.003質量%以上,更佳為0.005質量%以上,進一步更佳為0.008質量%以上,特佳為0.01質量%以上。另外,從形成亮度更高的著色硬化膜的觀點考慮,較佳為1質量%以下,更佳為0.4質量%以下,進一步較佳為0.1質量%以下,進一步更佳為0.09質量%以下,更進一步較佳為0.08質量%以下,更進一步更佳為0.07質量%以下。化合物(2)的含量相對於化合物(1)和化合物(2)的合計含量,較佳為0.001~1質量%,更佳為0.003~0.4質量%,進一步更佳為0.005~0.1質量%,更進一步更佳為0.01~0.1質量%,特佳為0.01~0.08質量%。 In the colored composition of the present invention, the content of the compound (2) is required to be 0.001% by mass or more based on the total content of the compound (1) and the compound (2). The present inventors have estimated that the solubility of the compound (1) in a solvent is low, and it is easy to crystallize and become a foreign matter. Therefore, the storage stability of the colored composition is poor. In addition, it is presumed that the compound (1) is contained in a predetermined amount or more together with the compound (1), and the crystallization of the compound (1) can be prevented, and the storage stability of the colored composition can be improved. From the viewpoint of further improving the storage stability, the content of the compound (2) is preferably 0.003% by mass or more, more preferably 0.005% by mass or more, and further preferably the total content of the compound (1) and the compound (2). It is 0.008% by mass or more, and particularly preferably 0.01% by mass or more. In addition, from the viewpoint of forming a colored cured film having a higher brightness, it is preferably 1% by mass or less, more preferably 0.4% by mass or less, further preferably 0.1% by mass or less, and still more preferably 0.09% by mass or less. More preferably, it is 0.08 mass% or less, and still more preferably 0.07 mass% or less. The content of the compound (2) is preferably 0.001 to 1% by mass, more preferably 0.003 to 0.4% by mass, still more preferably 0.005 to 0.1% by mass, even more preferably the total content of the compound (1) and the compound (2). Further, it is more preferably 0.01 to 0.1% by mass, particularly preferably 0.01 to 0.08% by mass.
本發明的著色組成物還可以含有化合物(1)和化合物(2)以外的著色劑(以下,也稱為「其它的著色劑」)。作為其它的著色劑,沒有特別限定,可以根據用途適當地選擇色彩、材質,化合物(1)和化合物(2)以外的顏 料和染料均可使用。其中,在得到亮度和顏色純度高的著色硬化膜的意思中,較佳為有機顏料、有機染料。 The coloring composition of the present invention may further contain a coloring agent other than the compound (1) and the compound (2) (hereinafter also referred to as "another coloring agent"). The other coloring agent is not particularly limited, and a color or a material can be appropriately selected depending on the application, and a color other than the compound (1) and the compound (2) can be selected. Both materials and dyes can be used. Among them, in the meaning of obtaining a colored cured film having high brightness and color purity, an organic pigment or an organic dye is preferred.
作為上述有機顏料,例如可舉出顏色索引(C.I.;The Society of Dyers and Colourists公司發行)中被分類成顏料的化合物。其中,較佳為C.I.顏料紅166、C.I.顏料紅177、C.I.顏料紅179、C.I.顏料紅224、C.I.顏料紅242、C.I.顏料紅254、C.I.顏料紅264、C.I.顏料綠7、C.I.顏料綠36、C.I.顏料綠58、C.I.顏料藍15:6、C.I.顏料藍80、C.I.顏料黃83、C.I.顏料黃129、C.I.顏料黃138、C.I.顏料黃139、C.I.顏料黃150、C.I.顏料黃180、C.I.顏料黃185、C.I.顏料黃211、C.I.顏料黃215、C.I.顏料橙38、C.I.顏料紫23等。另外,還較佳為日本特開2001-081348號公報、日本特開2010-026334號公報、日本特開2010-191304號公報、日本特開2010-237384號公報、日本特開2010-237569號公報、日本特開2011-006602號公報、日本特開2011-145346號公報等中記載的色澱顏料、日本特表2011-523433號公報的式(Ic)表示的溴化二酮基吡咯并吡咯顏料。色澱顏料中,較佳為三芳基甲烷系色澱顏料、系色澱顏料、偶氮系色澱顏料,更佳為三芳基甲烷系色澱顏料和系色澱顏料。 As the above-mentioned organic pigment, for example, a compound classified as a pigment in a color index (CI; issued by The Society of Dyers and Colourists) can be cited. Among them, preferred are CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 179, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 264, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Blue 15:6, CI Pigment Blue 80, CI Pigment Yellow 83, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Yellow 211, CI Pigment Yellow 215, CI Pigment Orange 38, CI Pigment Violet 23, and the like. In addition, Japanese Laid-Open Patent Publication No. 2001-081348, JP-A-2010-026334, JP-A-2010-191304, JP-A-2010-237384, JP-A-2010-237569 The brominated diketopyrrolopyrrole pigment represented by the formula (Ic) of JP-A-2011- 523 433, Japanese Laid-Open Patent Publication No. 2011-145346, and the like. . Among the lake pigments, preferred are triarylmethane-based lake pigments, a lake pigment, an azo lake pigment, more preferably a triaryl methane lake pigment and It is a lake pigment.
本發明中,使用顏料作為其它的著色劑時,也可以通過再結晶法、再沉澱法、溶劑洗滌法、昇華法、真空加熱法或者它們的組合對顏料進行精製來使用。另外,顏料可以根據需要用樹脂對其粒子表面進行改性來使用。作為對顏料的粒子表面進行改性的樹脂,例如 可舉出日本特開2001-108817號公報中記載的載色劑樹脂、或者市售的各種顏料分散用的樹脂。作為碳黑表面的樹脂被覆方法,例如,可以採用日本特開平9-71733號公報、日本特開平9-95625號公報、日本特開平9-124969號公報等中記載的方法。另外,有機顏料可以利用所謂的鹽磨使一次粒子微細化來使用。作為鹽磨的方法,例如,可以採用日本特開平8-179111號公報中公開的方法。 In the present invention, when a pigment is used as another coloring agent, the pigment may be purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. Further, the pigment may be used by modifying the surface of the particles with a resin as needed. As a resin that modifies the surface of the particles of the pigment, for example The vehicle resin described in JP-A-2001-108817 or a commercially available resin for dispersing various pigments is exemplified. For the resin coating method of the surface of the carbon black, for example, the method described in JP-A-H09-71733, JP-A-9-95625, and JP-A-9-124969 can be used. Further, the organic pigment can be used by making the primary particles fine by a so-called salt milling. As a method of salt milling, for example, the method disclosed in Japanese Laid-Open Patent Publication No. Hei 8-179111 can be employed.
本發明中,使用顏料作為其它的著色劑時,還可以使其進一步含有周知的分散劑和分散助劑。作為周知的分散劑,例如可舉出聚胺基甲酸酯系分散劑、聚乙烯亞胺系分散劑、聚氧乙烯烷基醚系分散劑、聚氧乙烯烷基苯基醚系分散劑、聚乙二醇二酯系分散劑、山梨糖醇酐脂肪酸酯系分散劑、聚酯系分散劑、丙烯酸系分散劑等,作為分散助劑,可舉出顏料衍生物等。 In the present invention, when a pigment is used as the other coloring agent, it may further contain a well-known dispersing agent and a dispersing aid. Examples of the known dispersant include a polyurethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, and a polyoxyethylene alkylphenyl ether dispersant. A polyethylene glycol diester-based dispersing agent, a sorbitan fatty acid ester-based dispersing agent, a polyester-based dispersing agent, an acrylic dispersing agent, and the like, and examples of the dispersing aid include a pigment derivative.
這樣的分散劑能夠從商業上獲得,例如,作為丙烯酸系分散劑,可舉出Disperbyk-2000、Disperbyk-2001、BYK-LPN6919、BYK-LPN21116、BYK-LPN22102(以上為BYK-Chemie(BYK)公司製),作為聚胺基甲酸酯系分散劑,可舉出Disperbyk-161、Disperbyk-162、Disperbyk-165、Disperbyk-167、Disperbyk-170、Disperbyk-182、Disperbyk-2164(以上為BYK-Chemie(BYK)公司製),Solsperse 76500(Lubrizol(股)製),作為聚乙烯亞胺系分散劑,可舉出Solsperse 24000(Lubrizol(股)製),作為聚酯系分散劑,可舉出 Adisper PB821、Adisper PB822、Adisper PB880、Adisper PB881(以上為Ajinomoto Fine-Techno(股)製),除此之外還有BYK-LPN21324(不揮發成分為40質量%)(BYK-Chemie(BYK)公司製)等。 Such a dispersing agent can be obtained commercially. For example, as an acrylic dispersing agent, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN22102 (above BYK-Chemie (BYK)) As a polyurethane dispersant, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182, Disperbyk-2164 (above BYK-Chemie) (BYK), manufactured by Solsperse 76500 (manufactured by Lubrizol Co., Ltd.), and as a polyethyleneimine-based dispersant, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), and a polyester-based dispersant, Adisper PB821, Adisper PB822, Adisper PB880, Adisper PB881 (above is Ajinomoto Fine-Techno), in addition to BYK-LPN21324 (40% by mass non-volatiles) (BYK-Chemie (BYK)) System) and so on.
另外,作為顏料衍生物,具體而言,可舉出銅酞花青、二酮基吡咯并吡咯、喹酞酮的磺酸衍生物等。 Further, specific examples of the pigment derivative include sulfonium cyanine, diketopyrrolopyrrole, and a sulfonic acid derivative of quinacridone.
本發明中其它的著色劑可以單獨使用或者混合2種以上使用。 The other coloring agents in the present invention may be used singly or in combination of two or more.
本發明的著色組成物較佳為用於形成紅色像素或者綠色像素。 The colored composition of the present invention is preferably used to form a red pixel or a green pixel.
用於形成紅色像素時,作為(A)著色劑,較佳為與化合物(1)一起含有選自化合物(1)以外的紅色顏料、紅色染料、紫色顏料、紫色染料、黃色顏料、黃色染料和橙色顏料中的至少1種作為其它的著色劑。用於形成綠色像素時,作為(A)著色劑,較佳為與化合物(1)一起含有選自化合物(1)以外的綠色顏料、綠色染料、黃色顏料和黃色染料中的至少1種作為其它的著色劑。 When forming a red pixel, as the (A) coloring agent, it is preferable to contain, together with the compound (1), a red pigment, a red dye, a violet pigment, a violet dye, a yellow pigment, a yellow dye, and the like selected from the compound (1). At least one of the orange pigments is used as another coloring agent. When the green pixel is formed, as the (A) coloring agent, at least one selected from the group consisting of a green pigment other than the compound (1), a green dye, a yellow pigment, and a yellow dye is preferably contained as the coloring agent (A). Coloring agent.
作為上述紅色顏料,較佳為C.I.顏料紅177、以及C.I.顏料紅254、C.I.顏料紅264、日本特表2011-523433號公報的如式(Ic)表示的顏料的二酮基吡咯并吡咯顏料。作為上述紫色顏料,較佳為C.I.顏料紫23。作為上述黃色顏料,較佳為C.I.顏料黃129、C.I.顏料黃138、C.I.顏料黃139、C.I.顏料黃150、C.I.顏料黃185。作為上述橙色顏料,較佳為C.I.顏料橙38。作為上述綠色顏料,較佳為C.I.顏 料綠7、C.I.顏料綠36、C.I.顏料綠58等的酞花青顏料。 As the red pigment, a diketopyrrolopyrrole pigment of a pigment represented by the formula (Ic) of C.I. Pigment Red 177, C.I. Pigment Red 254, C.I. Pigment Red 264, and Japanese Patent Publication No. 2011-523433 is preferable. As the above purple pigment, C.I. Pigment Violet 23 is preferred. As the above yellow pigment, C.I. Pigment Yellow 129, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185 are preferable. As the above orange pigment, C.I. Pigment Orange 38 is preferred. As the above green pigment, preferably C.I. Anthocyanine pigments such as green 7, C.I. pigment green 36, C.I. pigment green 58, and the like.
作為上述紅色染料、紫色染料,較佳為系染料。 As the above red dye or purple dye, preferably Is a dye.
從形成即使以低曝光量色度特性也優異且不易產生缺陷的像素或遮光性優異的黑色矩陣、黑色隔離件的觀點考慮,在著色組成物的固體成分中,(A)著色劑的含量通常為5~70質量%,較佳為10~60質量%,更佳為15~40質量%。在此固體成分是後述的溶劑以外的成分。 From the viewpoint of forming a black matrix or a black separator which is excellent in low chromaticity and low in chromaticity characteristics and which is less likely to cause defects, and in the solid content of the colored composition, (A) the content of the colorant is usually It is 5 to 70% by mass, preferably 10 to 60% by mass, more preferably 15 to 40% by mass. Here, the solid component is a component other than the solvent described later.
另外,使用其它的著色劑時,其它的著色劑的含有比例相對於著色劑的合計含量較佳為99質量%以下,更佳為95質量份以下。下限值沒有特別限定,只要為0.01質量%以上即可。 In addition, when other coloring agents are used, the content ratio of the other coloring agent is preferably 99% by mass or less, and more preferably 95 parts by mass or less based on the total content of the coloring agent. The lower limit value is not particularly limited as long as it is 0.01% by mass or more.
-(B)黏結劑樹脂- - (B) Adhesive Resin -
作為本發明中的(B)黏結劑樹脂,沒有特別限定,但較佳為具有羧基、酚性羥基等酸性官能團的樹脂。其中,較佳為具有羧基的聚合物(以下,也稱為「含羧基聚合物」),例如可舉出具有1個以上的羧基的乙烯性不飽和單體(以下,也稱為「不飽和單體(b1)」)與其它的可共聚的乙烯性不飽和單體(以下,也稱為「不飽和單體(b2)」)的共聚物。 The (B) binder resin in the present invention is not particularly limited, but is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. In particular, a polymer having a carboxyl group (hereinafter also referred to as a "carboxyl group-containing polymer") is preferably an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter, also referred to as "unsaturated". A copolymer of a monomer (b1)") and another copolymerizable ethylenically unsaturated monomer (hereinafter also referred to as "unsaturated monomer (b2)").
作為上述不飽和單體(b1),例如可舉出(甲基)丙烯酸、馬來酸、馬來酸酐、琥珀酸單[2-(甲基)丙烯醯氧基乙基]酯、ω-羧基聚己內酯單(甲基)丙烯酸酯、對乙烯基苯甲酸等。 Examples of the unsaturated monomer (b1) include (meth)acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2-(methyl) propylene methoxyethyl] ester, and ω-carboxyl group. Polycaprolactone mono(meth)acrylate, p-vinylbenzoic acid, and the like.
這些不飽和單體(b1)可以單獨使用或者混合2種以上使用。 These unsaturated monomers (b1) can be used individually or in mixture of 2 or more types.
另外,作為上述不飽和單體(b2),例如可舉出:如N-苯基馬來醯亞胺、N-環己基馬來醯亞胺之類的N-位取代馬來醯亞胺;如苯乙烯、α-甲基苯乙烯、乙烯基甲苯、對羥基苯乙烯、對羥基-α-甲基苯乙烯、對乙烯基苄基縮水甘油醚、苊烯之類的芳香族乙烯基化合物;如(甲基)丙烯酸甲酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸苄酯、聚乙二醇(聚合度2~10)甲醚(甲基)丙烯酸酯、聚丙二醇(聚合度2~10)甲醚(甲基)丙烯酸酯、聚乙二醇(聚合度2~10)單(甲基)丙烯酸酯、聚丙二醇(聚合度2~10)單(甲基)丙烯酸酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸三環[5.2.1.02,6]癸烷-8-基酯、(甲基)丙烯酸二環戊烯酯、丙三醇單(甲基)丙烯酸酯、(甲基)丙烯酸4-羥基苯酯、對基苯酚的環氧乙烷改性(甲基)丙烯酸酯、(甲基)丙烯酸縮水甘油酯、3,4-環氧環己基甲基(甲基)丙烯酸酯、(甲基)丙烯酸3,4-環氧三環[5.2.1.02,6]癸烷-8-基酯、(甲基)丙烯酸3,4-環氧三環[5.2.1.02,6]癸烷-9-基酯、3-[(甲基)丙烯醯氧基甲基]氧雜環丁烷、3-[(甲基)丙烯醯氧基甲基]-3-乙基氧雜環丁烷之類的(甲基)丙烯酸酯;如環己基乙烯基醚、異冰片基乙烯基醚、三 環[5.2.1.02,6]癸烷-8-基乙烯基醚、五環十五烷基乙烯基醚、3-(乙烯基氧甲基)-3-乙基氧雜環丁烷之類的乙烯基醚;在如聚苯乙烯、聚(甲基)丙烯酸甲酯、聚(甲基)丙烯酸正丁酯、聚矽氧烷之類的聚合物分子鏈的末端具有單(甲基)丙烯醯基的大分子單體等。 In addition, examples of the unsaturated monomer (b2) include an N-position substituted maleimide such as N-phenylmaleimide or N-cyclohexylmaleimide; An aromatic vinyl compound such as styrene, α-methylstyrene, vinyl toluene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, terpene; For example, methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, Benzyl (meth)acrylate, polyethylene glycol (degree of polymerization 2~10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2~10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, Tricyclo[methyl]acrylic acid [5.2.1.0 2,6 ]decane-8-yl ester, dicyclopentenyl (meth)acrylate, glycerol mono(meth)acrylate, (meth)acrylic acid 4-hydroxyphenyl ester, pair Ethylene oxide modified (meth) acrylate of phenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, (meth) acrylate 3, 4 - epoxy tricyclo [5.2.1.0 2,6 ]decane-8-yl ester, (meth)acrylic acid 3,4-epoxytricyclo[5.2.1.0 2,6 ]decane-9-yl ester, 3-[(Meth)acryloxymethyl]oxetane, 3-[(meth)acryloxymethyl]-3-ethyloxetane (methyl) Acrylate; such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 2,6 ]decane-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, 3- a vinyl ether such as (vinyloxymethyl)-3-ethyloxetane; in, for example, polystyrene, poly(methyl) methacrylate, poly(methyl) acrylate, poly A macromolecular monomer having a mono(meth)acryl fluorenyl group at the end of the polymer molecular chain such as a decane.
這些不飽和單體(b2)可以單獨使用或者混合2種以上使用。 These unsaturated monomers (b2) can be used individually or in mixture of 2 or more types.
這些不飽和單體(b2)中,較佳為包含如具有環氧乙基的乙烯性不飽和單體、具有氧雜環丁基的乙烯性不飽和單體、具有四氫呋喃基的乙烯性不飽和單體之類的具有碳原子數2~4的環狀醚結構的乙烯性不飽和單體,更佳為包含具有環氧乙基的乙烯性不飽和單體。作為具有環氧乙基的乙烯性不飽和單體,較佳為(甲基)丙烯酸3,4-環氧環己基甲酯、(甲基)丙烯酸3,4-環氧三環[5.2.1.02,6]癸烷-8-基酯、(甲基)丙烯酸3,4-環氧三環[5.2.1.02,6]癸烷-9-基酯。 Among these unsaturated monomers (b2), preferred are ethylenically unsaturated monomers having an epoxy group, ethylenically unsaturated monomers having an oxetanyl group, and ethylenic unsaturation having a tetrahydrofuranyl group. The ethylenically unsaturated monomer having a cyclic ether structure having 2 to 4 carbon atoms, such as a monomer, more preferably contains an ethylenically unsaturated monomer having an epoxy group. As the ethylenically unsaturated monomer having an epoxy group, 3,4-epoxycyclohexylmethyl (meth)acrylate and 3,4-epoxytricyclo(meth)acrylate [5.2.1.0] are preferred. 2,6 ]decane-8-yl ester, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decane-9-yl (meth)acrylate.
在不飽和單體(b1)與不飽和單體(b2)的共聚物中,該共聚物中的不飽和單體(b1)的共聚比例較佳為5~50質量%,進一步更佳為10~40質量%。通過以這樣的範圍使不飽和單體(b1)共聚,能夠得到鹼性顯影性和保存穩定性優異的著色組成物。 In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably from 5 to 50% by mass, further preferably 10 ~40% by mass. By copolymerizing the unsaturated monomer (b1) in such a range, a coloring composition excellent in alkali developability and storage stability can be obtained.
作為不飽和單體(b1)與不飽和單體(b2)的共聚物的具體例,例如可舉出日本特開平7-140654號公報、日本特開平8-259876號公報、日本特開平10-31308號 公報、日本特開平10-300922號公報、日本特開平11-174224號公報、日本特開平11-258415號公報、日本特開2000-56118號公報、日本特開2004-101728號公報等中公開的共聚物。 Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include JP-A-7-140654, JP-A-8-259876, and JP-A-10-10. No. 31308 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Copolymer.
另外,本發明中,例如,還可以將日本特開平5-19467號公報、日本特開平6-230212號公報、日本特開平7-207211號公報、日本特開平9-325494號公報、日本特開平11-140144號公報、日本特開2008-181095號公報等中公開的這種在側鏈具有(甲基)丙烯醯基等聚合性不飽和鍵的含羧基聚合物用作黏結劑樹脂。 In the present invention, for example, Japanese Laid-Open Patent Publication No. Hei 5-19467, JP-A-H06-230212, JP-A-H07-207211, JP-A No. Hei 9-325494, and JP-A No. 9-325494 A carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acrylonitrile group in a side chain disclosed in Japanese Laid-Open Patent Publication No. 2008-181095, or the like, is used as a binder resin.
本發明中的黏結劑樹脂用凝膠滲透層析(以下,省略為GPC)(洗脫溶劑:四氫呋喃)測定的聚苯乙烯換算的重量平均分子量(Mw)通常為1,000~100,000,較佳為3,000~50,000。通過成為這種方式,能夠進一步提高被膜的殘膜率、圖案形狀、耐熱性、電特性、分辨率,另外能夠以高水準抑制塗布時的乾燥異物的產生。 The polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (hereinafter referred to as GPC) (elution solvent: tetrahydrofuran) in the present invention is usually 1,000 to 100,000, preferably 3,000. ~50,000. In this manner, the residual film ratio, the pattern shape, the heat resistance, the electrical properties, and the resolution of the film can be further improved, and the generation of dry foreign matter during coating can be suppressed at a high level.
另外,本發明中的黏結劑樹脂的重量平均分子量(Mw)與數量平均分子量(Mn)之比(Mw/Mn)較佳為1.0~5.0,更佳為1.0~3.0。應予說明,在此所說的Mn是指用GPC(洗脫溶劑:四氫呋喃)測定的聚苯乙烯換算的數量平均分子量。 Further, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the binder resin in the present invention is preferably from 1.0 to 5.0, more preferably from 1.0 to 3.0. In addition, the term "Mn" as used herein means a polystyrene-equivalent number average molecular weight measured by GPC (elution solvent: tetrahydrofuran).
本發明中的黏結劑樹脂可以利用周知的方法製造,也可以利用例如日本特開2003-222717號公報、日本特開2006-259680號公報、國際公開第07/029871號小冊子等中公開的方法控制其結構、Mw、Mw/Mn。 The binder resin in the present invention can be produced by a known method, and can be controlled by a method disclosed in, for example, JP-A-2003-222717, JP-A-2006-259680, and International Publication No. 07/029871. Its structure, Mw, Mw / Mn.
本發明中,黏結劑樹脂可以單獨使用或者混合2種以上使用。 In the present invention, the binder resin may be used singly or in combination of two or more.
本發明中,(B)黏結劑樹脂的含量相對於(A)著色劑100質量份,通常為10~1,000質量份,較佳為20~500質量份,更佳為50~200質量份,進一步更佳為80~150質量份。通過成為這種方式,能夠進一步提高鹼性顯影性、著色組成物的保存穩定性、圖案形狀、色度特性。 In the present invention, the content of the (B) binder resin is usually 10 to 1,000 parts by mass, preferably 20 to 500 parts by mass, more preferably 50 to 200 parts by mass, per 100 parts by mass of the (A) coloring agent. More preferably 80 to 150 parts by mass. By doing so, it is possible to further improve the alkali developability, the storage stability of the colored composition, the pattern shape, and the chromaticity characteristics.
-(C)聚合性化合物- - (C) Polymeric Compound -
本發明中聚合性化合物是指具有2個以上的可聚合的基團的化合物。作為可聚合的基團,例如可舉出乙烯性不飽和基團、環氧乙基、氧雜環丁基、N-烷氧基甲基胺基等。本發明中,作為聚合性化合物,較佳為具有2個以上的(甲基)丙烯醯基的化合物或者具有2個以上的N-烷氧基甲基胺基的化合物。 The polymerizable compound in the present invention means a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an epoxy group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, the polymerizable compound is preferably a compound having two or more (meth)acryl fluorenyl groups or a compound having two or more N-alkoxymethylamino groups.
作為具有2個以上的(甲基)丙烯醯基的化合物的具體例,可舉出使脂肪族多羥基化合物與(甲基)丙烯酸反應而得的多官能(甲基)丙烯酸酯、被己內酯改性的多官能(甲基)丙烯酸酯、被環氧烷改性的多官能(甲基)丙烯酸酯、使具有羥基的(甲基)丙烯酸酯與多官能異氰酸酯反應而得的多官能胺基甲酸酯(甲基)丙烯酸酯、使具有羥基的(甲基)丙烯酸酯與酸酐反應而得的具有羧基的多官能(甲基)丙烯酸酯等。 Specific examples of the compound having two or more (meth) acryloyl fluorenyl groups include polyfunctional (meth) acrylates obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid. An ester-modified polyfunctional (meth) acrylate, a polyfunctional (meth) acrylate modified with an alkylene oxide, a polyfunctional amine obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate A carbamic acid ester (meth) acrylate, a polyfunctional (meth) acrylate having a carboxyl group obtained by reacting a (meth) acrylate having a hydroxyl group and an acid anhydride, or the like.
在此,作為脂肪族多羥基化合物,例如可舉出如乙二醇、丙二醇、聚乙二醇、聚丙二醇之類的2元的 脂肪族多羥基化合物;如甘油、三羥甲基丙烷、季戊四醇、二季戊四醇之類的3元以上的脂肪族多羥基化合物。作為上述具有羥基的(甲基)丙烯酸酯,例如可舉出(甲基)丙烯酸2-羥基乙酯、三羥甲基丙烷二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、丙三醇二甲基丙烯酸酯等。作為上述多官能異氰酸酯,例如可舉出甲苯二異氰酸酯、六亞甲基二異氰酸酯、二苯基亞甲基二異氰酸酯、異佛爾酮二異氰酸酯等。作為酸酐,例如可舉出如琥珀酸酐、馬來酸酐、戊二酸酐、衣康酸酐、鄰苯二甲酸酐、六氫鄰苯二甲酸酐之類的二元酸的酸酐,均苯四甲酸二酐、聯苯四甲酸二酐、二苯甲酮四羧酸二酐之類的四元酸二酐。 Here, examples of the aliphatic polyhydroxy compound include a two-membered product such as ethylene glycol, propylene glycol, polyethylene glycol, or polypropylene glycol. An aliphatic polyhydroxy compound; a trihydric or higher aliphatic polyhydroxy compound such as glycerin, trimethylolpropane, pentaerythritol or dipentaerythritol. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and Pentaerythritol penta (meth) acrylate, glycerol dimethacrylate, and the like. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of the acid anhydride include acid anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, and pyromellitic acid II. A tetrabasic acid dianhydride such as an anhydride, a biphenyltetracarboxylic dianhydride, or a benzophenone tetracarboxylic dianhydride.
另外,作為被己內酯改性的多官能(甲基)丙烯酸酯,例如可舉出日本特開平11-44955號公報的[0015]~[0018]段中記載的化合物。作為上述被環氧烷改性的多官能(甲基)丙烯酸酯,可舉出被選自環氧乙烷和環氧丙烷中的至少1種改性的雙酚A二(甲基)丙烯酸酯、被選自環氧乙烷和環氧丙烷中的至少1種改性的異氰脲酸三(甲基)丙烯酸酯、被選自環氧乙烷和環氧丙烷中的至少1種改性的三羥甲基丙烷三(甲基)丙烯酸酯、被選自環氧乙烷和環氧丙烷中的至少1種改性的季戊四醇三(甲基)丙烯酸酯、被選自環氧乙烷和環氧丙烷中的至少1種改性的季戊四醇四(甲基)丙烯酸酯、被選自環氧乙烷和環氧丙烷中的至少1種改性的二季戊四醇五(甲基)丙烯酸酯、被選自環氧乙烷和環氧丙烷中的至少1種改性的二季戊 四醇六(甲基)丙烯酸酯等。 In addition, examples of the polyfunctional (meth) acrylate modified by the caprolactone include the compounds described in paragraphs [0015] to [0018] of JP-A-11-44955. The polyfunctional (meth) acrylate modified with the alkylene oxide may, for example, be bisphenol A di(meth)acrylate modified with at least one selected from the group consisting of ethylene oxide and propylene oxide. And at least one modified isocyanuric acid tri(meth)acrylate selected from the group consisting of ethylene oxide and propylene oxide, modified by at least one selected from the group consisting of ethylene oxide and propylene oxide Trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate modified by at least one selected from the group consisting of ethylene oxide and propylene oxide, selected from ethylene oxide and At least one modified pentaerythritol tetra(meth)acrylate in propylene oxide, dipentaerythritol penta(meth)acrylate modified by at least one selected from the group consisting of ethylene oxide and propylene oxide At least one modified di-pentazone selected from the group consisting of ethylene oxide and propylene oxide Tetraol hexa(meth) acrylate or the like.
另外,作為具有2個以上的N-烷氧基甲基胺基的化合物,例如可舉出具有三聚氰胺結構、苯并胍胺結構、脲結構的化合物等。應予說明,三聚氰胺結構、苯并胍胺結構是指具有1個以上的三環或者苯基取代三環作為基本骨架的化學結構,亦包括三聚氰胺、苯并胍胺或者它們的縮合物的概念。作為具有2個以上的N-烷氧基甲基胺基的化合物的具體例,可舉出N,N,N’,N’,N”,N”-六(烷氧基甲基)三聚氰胺、N,N,N’,N’-四(烷氧基甲基)苯并胍胺、N,N,N’,N’-四(烷氧基甲基)甘脲等。 In addition, examples of the compound having two or more N-alkoxymethylamino groups include a compound having a melamine structure, a benzoguanamine structure, and a urea structure. It should be noted that the melamine structure and the benzoguanamine structure refer to having one or more three Ring or phenyl substituted three The chemical structure of the ring as a basic skeleton also includes the concept of melamine, benzoguanamine or their condensates. Specific examples of the compound having two or more N-alkoxymethylamino groups include N,N,N',N',N",N"-hexa(alkoxymethyl)melamine, N,N,N',N'-tetrakis(alkoxymethyl)benzoguanamine, N,N,N',N'-tetrakis(alkoxymethyl)glycolil and the like.
這些聚合性化合物中,較佳為使3元以上的脂肪族多羥基化合物與(甲基)丙烯酸反應而得的多官能(甲基)丙烯酸酯、被己內酯改性的多官能(甲基)丙烯酸酯、多官能胺基甲酸酯(甲基)丙烯酸酯、具有羧基的多官能(甲基)丙烯酸酯、N,N,N’,N’,N”,N”-六(烷氧基甲基)三聚氰胺、N,N,N’,N’-四(烷氧基甲基)苯并胍胺。從著色層的強度高、著色層的表面平滑性優異、且在未曝光部的基板上和遮光層上不易產生污垢、膜殘留等的觀點考慮,在使3元以上的脂肪族多羥基化合物與(甲基)丙烯酸反應而得的多官能(甲基)丙烯酸酯中,特佳為三羥甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯,在具有羧基的多官能(甲基)丙烯酸酯中,特佳為使季戊四醇三丙烯酸酯與琥珀酸酐反應而得的化合物、使二季戊四醇五丙烯酸酯與琥 珀酸酐反應而得的化合物。 Among these polymerizable compounds, a polyfunctional (meth) acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid or a polyfunctional (methyl group) modified with caprolactone is preferred. Acrylate, polyfunctional urethane (meth) acrylate, polyfunctional (meth) acrylate having carboxyl group, N, N, N', N', N", N"-hexa (alkoxy) Methyl) melamine, N, N, N', N'-tetrakis(alkoxymethyl)benzoguanamine. From the viewpoint of high strength of the colored layer, excellent surface smoothness of the colored layer, and difficulty in generation of dirt and film residue on the substrate of the unexposed portion and the light shielding layer, the aliphatic polyhydroxy compound having three or more members is used. Among the polyfunctional (meth) acrylates obtained by the reaction of (meth)acrylic acid, particularly preferred are trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, Among the polyfunctional (meth) acrylates of a carboxyl group, a compound obtained by reacting pentaerythritol triacrylate with succinic anhydride, and dipentaerythritol pentaacrylate and a A compound obtained by reacting phenolic anhydride.
本發明中,(C)聚合性化合物可以單獨使用或者混合2種以上使用。 In the present invention, the (C) polymerizable compound may be used singly or in combination of two or more.
本發明中的(C)聚合性化合物的含量相對於(A)著色劑100質量份,較佳為10~1,000質量份,更佳為20~700質量份,進一步更佳為50~500質量份,更進一步更佳為80~250質量份。另外(C)聚合性化合物的含量相對於(B)黏結劑樹脂100質量份,較佳為50~300質量份,更佳為70~200質量份,進一步更佳為100~150質量份。通過成為這種方式,能夠進一步提高硬化性、鹼性顯影性,以高水準抑制在未曝光部的基板上或遮光層上產生污垢、膜殘留等。 The content of the (C) polymerizable compound in the present invention is preferably 10 to 1,000 parts by mass, more preferably 20 to 700 parts by mass, still more preferably 50 to 500 parts by mass, per 100 parts by mass of the (A) coloring agent. Further, it is more preferably 80 to 250 parts by mass. Further, the content of the (C) polymerizable compound is preferably 50 to 300 parts by mass, more preferably 70 to 200 parts by mass, still more preferably 100 to 150 parts by mass, per 100 parts by mass of the (B) binder resin. In this manner, it is possible to further improve the curability and the alkali developability, and to suppress the generation of dirt, film residue, and the like on the substrate of the unexposed portion or the light shielding layer at a high level.
-(D)光聚合引發劑- -(D) Photopolymerization Initiator -
可以使本發明的著色組成物中含有光聚合引發劑。由此,能夠對著色組成物賦予放射線敏感性。本發明中使用的光聚合引發劑是通過可見光線、紫外線、遠紫外線、電子束、X射線等放射線的曝光產生可引發上述聚合性化合物的聚合的活性種的化合物。 The coloring composition of the present invention may contain a photopolymerization initiator. Thereby, it is possible to impart radiation sensitivity to the colored composition. The photopolymerization initiator used in the present invention is a compound which generates an active species which can initiate polymerization of the above polymerizable compound by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam or X-ray.
作為這樣的光聚合引發劑,例如可舉出噻噸酮化合物、苯乙酮化合物、聯咪唑化合物、三化合物、O-醯肟化合物、鎓鹽化合物、苯偶姻化合物、二苯甲酮化合物、α-二酮化合物、多環醌化合物、重氮化合物、醯亞胺磺酸酯化合物等。 Examples of such a photopolymerization initiator include a thioxanthone compound, an acetophenone compound, a biimidazole compound, and the like. a compound, an O-antimony compound, an onium salt compound, a benzoin compound, a benzophenone compound, an α-diketone compound, a polycyclic anthracene compound, a diazo compound, a quinone sulfinate compound, or the like.
本發明中,光聚合引發劑可以單獨使用或者混合2種以上使用。作為光聚合引發劑,較佳為選自噻噸 酮化合物、苯乙酮化合物、聯咪唑化合物、三化合物、O-醯肟化合物中的至少1種。 In the present invention, the photopolymerization initiator may be used singly or in combination of two or more. As the photopolymerization initiator, it is preferably selected from the group consisting of a thioxanthone compound, an acetophenone compound, a biimidazole compound, and three At least one of a compound and an O-tellurium compound.
本發明中較佳的光聚合引發劑中,作為噻噸酮化合物的具體例,可舉出噻噸酮、2-氯噻噸酮、2-甲基噻噸酮、2-異丙基噻噸酮、4-異丙基噻噸酮、2,4-二氯噻噸酮、2,4-二甲基噻噸酮、2,4-二乙基噻噸酮、2,4-二異丙基噻噸酮等。 In a preferred photopolymerization initiator of the present invention, specific examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and 2-isopropylthioxene. Ketone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropyl Ketyl ketone and the like.
另外,作為上述苯乙酮化合物的具體例,可舉出2-甲基-1-[4-(甲硫基)苯基]-2-啉代丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-啉并苯基)丁烷-1-酮、2-(4-甲基苄基)-2-(二甲基胺基)-1-(4-啉并苯基)丁烷-1-酮等。 Further, specific examples of the acetophenone compound include 2-methyl-1-[4-(methylthio)phenyl]-2- Olinone propan-1-one, 2-benzyl-2-dimethylamino-1-(4- Phenyl-phenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4- Phenidophenyl)butan-1-one and the like.
另外,作為上述聯咪唑化合物的具體例,可舉出2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基-1,2’-聯咪唑、2,2’-雙(2,4-二氯苯基)-4,4’,5,5’-四苯基-1,2’-聯咪唑、2,2’-雙(2,4,6-三氯苯基)-4,4’,5,5’-四苯基-1,2’-聯咪唑等。 Further, specific examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole. 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4, 6-Trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole.
應予說明,使用聯咪唑化合物作為光聚合引發劑時,從能夠改善靈敏度的觀點考慮較佳為併用供氫體。在此所說的「供氫體」是指能夠對通過曝光由聯咪唑化合物產生的自由基供給氫原子的化合物。作為供氫體,例如可舉出2-巰基苯并噻唑、2-巰基苯并唑等硫醇供氫體,4,4’-雙(二甲基胺基)二苯甲酮、4,4’-雙(二乙基胺基)二苯甲酮等胺供氫體。本發明中,供氫體可以單獨使用或者混合2種以上使用,但從能夠進一步改善靈敏 度的觀點考慮,較佳為將1種以上的硫醇供氫體和1種以上的胺供氫體組合使用。 In the case where a biimidazole compound is used as the photopolymerization initiator, it is preferred to use a hydrogen donor in combination from the viewpoint of improving sensitivity. The term "hydrogen donor" as used herein refers to a compound capable of supplying a hydrogen atom to a radical generated by a biimidazole compound by exposure. Examples of the hydrogen donor include 2-mercaptobenzothiazole and 2-mercaptobenzoene. An amine hydrogen donor such as a thiol donor hydrogen donor, 4,4'-bis(dimethylamino)benzophenone or 4,4'-bis(diethylamino)benzophenone. In the present invention, the hydrogen donor may be used singly or in combination of two or more. However, from the viewpoint of further improving the sensitivity, it is preferred to combine one or more kinds of thiol hydrogen donors and one or more amine hydrogen donors. use.
另外,作為上述三化合物的具體例,可舉出2,4,6-三(三氯甲基)-s-三、2-甲基-4,6-雙(三氯甲基)-s-三、2-[2-(5-甲基呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)-s-三、2-[2-(呋喃-2-基)乙烯基]-4,6-雙(三氯甲基)-s-三、2-[2-(4-二乙基胺基-2-甲基苯基)乙烯基]-4,6-雙(三氯甲基)-s-三、2-[2-(3,4-二甲氧基苯基)乙烯基]-4,6-雙(三氯甲基)-s-三、2-(4-甲氧基苯基)-4,6-雙(三氯甲基)-s-三、2-(4-乙氧基苯乙烯基)-4,6-雙(三氯甲基)-s-三、2-(4-正丁氧基苯基)-4,6-雙(三氯甲基)-s-三等具有鹵代甲基的三化合物。 In addition, as the above three Specific examples of the compound include 2,4,6-tris(trichloromethyl)-s-three. 2-methyl-4,6-bis(trichloromethyl)-s-three ,2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three 2-[2-(4-Diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-three , 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-three ,2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-three Three with a halogenated methyl group Compound.
另外,作為O-醯肟化合物的具體例,可舉出1-[4-(苯硫基)苯基]-1,2-辛烷二酮2-(O-苯甲醯肟)、1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-乙酮1-(O-乙醯肟)、1-[9-乙基-6-(2-甲基-4-四氫呋喃基甲氧基苯甲醯基)-9H-咔唑-3-基]-乙酮1-(O-乙醯肟)、1-[9-乙基-6-{2-甲基-4-(2,2-二甲基-1,3-二氧戊環基)甲氧基苯甲醯基}-9H-咔唑-3-基]-乙酮1-(O-乙醯肟)等。作為O-醯肟化合物的市售品,還可以使用NCI-831、NCI-930(以上為ADEKA股份有限公司製),DFI-020、DFI-091(以上為Daitochemix股份有限公司製)等。 Further, specific examples of the O-tellurium compound include 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzamide), 1- [9-Ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-ethanone 1-(O-acetamidine), 1-[9-ethyl-6 -(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9H-indazol-3-yl]-ethanone 1-(O-acetamidine), 1-[9-ethyl- 6-{2-Methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzylidene}-9H-indazol-3-yl]-ethanone 1-(O-acetamidine) and the like. As a commercial item of the O-oxime compound, NCI-831, NCI-930 (above, ADEKA Co., Ltd.), DFI-020, DFI-091 (manufactured by Daitochemix Co., Ltd.), or the like can be used.
本發明中,使用苯乙酮化合物等聯咪唑化合物以外的光聚合引發劑時,還可以併用敏化劑。作為這樣的敏化劑,例如可舉出4,4’-雙(二甲基胺基)二苯甲酮 、4,4’-雙(二乙基胺基)二苯甲酮、4-二乙基胺基苯乙酮、4-二甲基胺基苯丙酮、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸2-乙基己酯、2,5-雙(4-二乙基胺基亞苄基)環己酮、7-二乙基胺基-3-(4-二乙基胺基苯甲醯基)香豆素、4-(二乙基胺基)查耳酮等。 In the present invention, when a photopolymerization initiator other than the biimidazole compound such as an acetophenone compound is used, a sensitizer may be used in combination. As such a sensitizer, for example, 4,4'-bis(dimethylamino)benzophenone can be mentioned. , 4,4'-bis(diethylamino)benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 4-dimethylaminobenzoic acid Ester, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3- 4-Diethylaminobenzimidyl)coumarin, 4-(diethylamino)chalcone, and the like.
本發明中,(D)光聚合引發劑的含量相對於(C)聚合性化合物100質量份,較佳為0.01~120質量份,更佳為1~100質量份,進一步更佳為5~50質量份,特佳為10~30質量份。通過成為這種方式,能夠進一步提高硬化性、被膜特性。 In the present invention, the content of the (D) photopolymerization initiator is preferably 0.01 to 120 parts by mass, more preferably 1 to 100 parts by mass, still more preferably 5 to 50 parts by mass based on 100 parts by mass of the (C) polymerizable compound. The mass fraction is particularly preferably 10 to 30 parts by mass. By adopting such an aspect, the curability and the film properties can be further improved.
-(E)溶劑- - (E) Solvent -
本發明的著色組成物含有上述(A)~(C)成分和任意添加的其它成分,通常配合溶劑製備成液態組成物。 The colored composition of the present invention contains the above components (A) to (C) and optionally added other components, and is usually prepared as a liquid composition in combination with a solvent.
作為(E)溶劑,只要分散或者溶解構成著色組成物的(A)~(C)成分、其它的成分,且不與這些成分反應,具有適當的揮發性,就可以適當地選擇使用。 The (E) solvent is appropriately selected and used as long as it disperses or dissolves the components (A) to (C) constituting the colored composition and other components, and does not react with these components, and has appropriate volatility.
這樣溶劑中,例如可舉出:乙二醇單甲醚、乙二醇單乙醚、乙二醇單正丙醚、乙二醇單正丁醚、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單正丙醚、二乙二醇單正丁醚、三乙二醇單甲醚、三乙二醇單乙醚、丙二醇單甲醚、丙二醇單乙醚、丙二醇單正丙醚、丙二醇單正丁醚、二丙二醇單甲醚、二丙二醇單乙醚、二丙二醇單正丙醚、二丙二醇單正丁醚、三丙二醇單甲醚、三丙二醇單乙醚等(聚)伸烷基二醇單烷基醚類; 乳酸甲酯、乳酸乙酯等乳酸烷基酯類;甲醇、乙醇、丙醇、丁醇、異丙醇、異丁醇、第三丁醇、辛醇、2-乙基己醇、環己醇等(環)烷基醇類;二丙酮醇等酮醇類;乙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、二乙二醇單甲醚乙酸酯、二乙二醇單乙醚乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、二丙二醇單甲醚乙酸酯、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯等(聚)伸烷基二醇單烷基醚乙酸酯類;二乙二醇二甲醚、二乙二醇甲乙醚、二乙二醇二乙醚、四氫呋喃等其它的醚類;甲乙酮、環己酮、2-庚酮、3-庚酮等酮類;丙二醇二乙酸酯、1,3-丁二醇二乙酸酯、1,6-己二醇二乙酸酯等二乙酸酯類;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、乙氧基乙酸乙酯、3-甲基-3-甲氧基丁基丙酸酯等烷氧基羧酸酯類;乙酸乙酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯、乙酸異丁酯、甲酸正戊酯、乙酸異戊酯、丙酸正丁酯、丁酸乙酯、丁酸正丙酯、丁酸異丙酯、丁酸正丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸正丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2-氧代丁酸乙酯等其它的酯類;甲苯、二甲苯等芳香族烴類;N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基吡咯啶酮等醯胺或者內醯胺類等。 Examples of such a solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, and diethylene glycol. Monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether , propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, etc. Alcohol monoalkyl ethers; Methyl lactate such as methyl lactate or ethyl lactate; methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tert-butanol, octanol, 2-ethylhexanol, cyclohexanol Ketone alcohols such as (cyclo)alkyl alcohols; diacetone alcohols; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol Alcohol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methyl Alkyl diol monoalkyl ether acetates such as oxybutyl acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc. Ethers; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; propylene glycol diacetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetic acid Diacetate such as ester; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethoxylate Alkoxycarboxylates such as ethyl acetate and 3-methyl-3-methoxybutylpropionate; acetic acid Ester, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, butyl Isopropyl acrylate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxobutyrate, etc. Esters; aromatic hydrocarbons such as toluene and xylene; decylamines such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or indoleamines Wait.
這些溶劑中,從溶解性、顏料分散性、塗布性等觀點考慮,較佳為(聚)伸烷基二醇單烷基醚類、乳酸烷基酯類、(聚)伸烷基二醇單烷基醚乙酸酯類、其它的醚類、酮類、二乙酸酯類、烷氧基羧酸酯類、其它的酯類,特佳為丙二醇單甲醚、丙二醇單乙醚、乙二醇單甲醚乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、3-甲氧基丁基乙酸酯、二乙二醇二甲醚、二乙二醇甲乙醚、環己酮、2-庚酮、3-庚酮、1,3-丁二醇二乙酸酯、1,6-己二醇二乙酸酯、乳酸乙酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、3-甲基-3-甲氧基丁基丙酸酯、乙酸正丁酯、乙酸異丁酯、甲酸正戊酯、乙酸異戊酯、丙酸正丁酯、丁酸乙酯、丁酸異丙酯、丁酸正丁酯、丙酮酸乙酯等。 Among these solvents, from the viewpoints of solubility, pigment dispersibility, coatability, and the like, (poly)alkylene glycol monoalkyl ethers, alkyl lactates, and (poly)alkylene glycols are preferred. Alkyl ether acetates, other ethers, ketones, diacetates, alkoxycarboxylates, other esters, particularly preferably propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl Ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, 3- Methyl ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, isobutyl acetate, n-amyl formate, acetic acid Isoamyl ester, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate, and the like.
本發明中,溶劑可以單獨使用或者混合2種以上使用。 In the present invention, the solvent may be used singly or in combination of two or more.
(E)溶劑的含量沒有特別限定,除著色組成物的溶劑以外的各成分的合計濃度較佳為成為5~50質量%的量,更佳為成為10~40質量%的量。通過成為這種方式,能夠得到分散性、穩定性良好的著色劑分散液以及塗布性、穩定性良好的著色組成物。 The content of the solvent (E) is not particularly limited, and the total concentration of each component other than the solvent of the coloring composition is preferably from 5 to 50% by mass, more preferably from 10 to 40% by mass. In this manner, a colorant dispersion having good dispersibility and stability, and a coloring composition having good coatability and stability can be obtained.
-添加劑- -additive-
本發明的著色組成物根據需要還可以含有各種添加劑。 The colored composition of the present invention may further contain various additives as needed.
作為添加劑,例如可舉出玻璃、氧化鋁等填充劑;聚乙烯醇、聚(丙烯酸氟烷基酯)類等高分子化合物;氟 界面活性劑、矽酮界面活性劑等界面活性劑;乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三(2-甲氧基乙氧基)矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-氯丙基甲基二甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷等密合促進劑;2,2-硫代雙(4-甲基-6-第三丁基苯酚)、2,6-二第三丁基苯酚、季戊四醇四[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯]、3,9-雙[2-[3-(3-第三丁基-4-羥基-5-甲基苯基)-丙醯氧基]-1,1-二甲基乙基]-2,4,8,10-四氧雜-螺[5.5]十一烷、硫代二伸乙基雙[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯]等抗氧化劑;2-(3-第三丁基-5-甲基-2-羥基苯基)-5-氯苯并三唑、烷氧基二苯甲酮類等紫外線吸收劑;聚丙烯酸鈉等抗絮凝劑;丙二酸、己二酸、衣康酸、檸康酸、富馬酸、中康酸、2-胺基乙醇、3-胺基-1-丙醇、5-胺基-1-戊醇、3-胺基-1,2-丙二醇、2-胺基-1,3-丙二醇、4-胺基-1,2-丁烷二醇等殘渣改善劑;琥珀酸單[2-(甲基)丙烯醯氧基乙基]酯、鄰苯二甲酸單[2-(甲基)丙烯醯氧基乙基]酯、ω-羧基聚己內酯單(甲基)丙烯酸酯等顯影性改善劑等。 Examples of the additive include a filler such as glass or alumina; a polymer compound such as polyvinyl alcohol or poly(fluoroalkyl acrylate); and fluorine. Surfactant, surfactant such as surfactant, ketone surfactant; vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, N-(2-amine Benzyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxylate Baseline, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy Baseline, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane Equal adhesion promoter; 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-t-butylphenol, pentaerythritol tetra[3-(3,5-di Third butyl-4-hydroxyphenyl)propionate], 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)-propanoxime 1,1-dimethylethyl]-2,4,8,10-tetraoxa-spiro[5.5]undecane, thiodiethylidene bis[3-(3,5-di Antioxidant such as third butyl-4-hydroxyphenyl)propionate; 2-(3-third Ultraviolet absorbers such as 5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole and alkoxybenzophenone; antiflocculating agents such as sodium polyacrylate; malonic acid and adipic acid , itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1, Residue improver such as 2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol; succinic acid mono[2-(methyl)acryloxyethyl] A developer improving agent such as an ester, a mono[2-(methyl)acryloxyethyl) phthalate, or an ω-carboxypolycaprolactone mono(meth)acrylate.
另外,本發明的著色組成物使用染料和顏料這兩者作為著色劑時,像日本特開2010-132874號公報中公開的那樣,可以採用如下製備方法:使染料溶液通過 第1過濾器後,將通過第1過濾器的染料溶液與另外製備的顏料分散液等混合,使得到的著色組成物通過第2過濾器進行製備。另外,可以採用如下製備方法:將染料、上述(B)~(C)成分以及根據需要使用的其它的成分溶解於溶劑,使得到的溶液通過第1過濾器後,將通過第1過濾器的溶液與另外製備的顏料分散液混合,使得到的著色組成物通過第2過濾器進行製備。另外,也可以採用如下製備方法:使染料溶液通過第1過濾器後,將通過第1過濾器的染料溶液與上述(B)~(C)成分以及根據需要使用的其它的成分混合.溶解,使得到的溶液通過第2過濾器,再將通過第2過濾器的溶液與另外製備的顏料分散液混合,使得到的著色組成物通過第3過濾器進行製備。 Further, when the coloring composition of the present invention uses both a dye and a pigment as a coloring agent, as disclosed in Japanese Laid-Open Patent Publication No. 2010-132874, a preparation method may be employed in which a dye solution is passed. After the first filter, the dye solution passing through the first filter is mixed with a separately prepared pigment dispersion or the like, and the resulting colored composition is prepared by a second filter. In addition, a preparation method may be employed in which a dye, the above components (B) to (C), and other components used as needed are dissolved in a solvent, so that the obtained solution passes through the first filter and passes through the first filter. The solution was mixed with a separately prepared pigment dispersion such that the resulting colored composition was prepared through a second filter. Alternatively, a preparation method may be employed in which the dye solution passing through the first filter is mixed with the components (B) to (C) and other components used as needed after passing the dye solution through the first filter. The solution was dissolved, the resulting solution was passed through a second filter, and the solution passing through the second filter was mixed with the separately prepared pigment dispersion, so that the obtained colored composition was prepared through the third filter.
著色硬化膜和其形成方法Colored hardening film and method of forming same
本發明的著色硬化膜是使用本發明的著色組成物形成的,具體而言,是指構成彩色濾光片的各色像素、黑色矩陣、黑色隔離件等。 The colored cured film of the present invention is formed using the colored composition of the present invention, and specifically refers to each color pixel, black matrix, black spacer, and the like constituting the color filter.
以下,對構成顯示元件、固態攝影元件的彩色濾光片中使用的著色硬化膜和其形成方法進行說明。 Hereinafter, a colored cured film used in a color filter constituting a display element or a solid-state imaging element and a method of forming the same will be described.
作為製造彩色濾光片的方法,第一,可舉出如下的方法。首先,在基板的表面上根據需要以劃分出形成像素的部分的方式形成遮光層(黑色矩陣)。接著,在該基板上塗布例如紅色的本發明的放射線敏感性著色組成物的液狀組成物之後,進行預烘使溶劑蒸發,形成塗膜。接著,藉由光罩對該塗膜進行曝光之後,使用鹼性顯影液進行顯影,溶解除去塗膜的未曝光部。其後,通過後 烘,形成以規定的排列配置有紅色的像素圖案(著色硬化膜)的像素陣列。 As a method of manufacturing a color filter, the first method is as follows. First, a light shielding layer (black matrix) is formed on the surface of the substrate in such a manner as to divide a portion where pixels are formed. Next, a liquid composition of, for example, a red radiation-sensitive coloring composition of the present invention is applied onto the substrate, and then pre-baked to evaporate the solvent to form a coating film. Next, the coating film was exposed by a photomask, and then developed with an alkali developing solution to dissolve and remove the unexposed portion of the coating film. After that, after passing After baking, a pixel array in which red pixel patterns (colored cured films) are arranged in a predetermined arrangement is formed.
接著,使用綠色或者藍色的各放射線敏感性著色組成物,與上述同樣地進行各放射線敏感性著色組成物的塗布、預烘、曝光、顯影和後烘,在同一基板上依次形成綠色的像素陣列和藍色的像素陣列。由此,得到在基板上配置有紅色、綠色和藍色這三原色的像素陣列的彩色濾光片。其中,本發明中,形成各色像素的順序不限於上述順序。 Next, using each of the radiation-sensitive coloring compositions of green or blue, the coating, prebaking, exposure, development, and post-baking of each of the radiation-sensitive coloring compositions are performed in the same manner as described above, and green pixels are sequentially formed on the same substrate. Array and blue pixel array. Thereby, a color filter in which a pixel array of three primary colors of red, green, and blue is disposed on the substrate is obtained. However, in the present invention, the order in which the pixels of the respective colors are formed is not limited to the above order.
上述黑色矩陣可以利用光刻法使通過濺射、蒸鍍而成膜的鉻等金屬薄膜成為所希望的圖案來形成,也可以使用分散有黑色著色劑的放射線敏感性著色組成物與形成上述像素的情況同樣地形成。 The black matrix may be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern by photolithography, or a radiation-sensitive coloring composition in which a black colorant is dispersed and a pixel may be formed. The situation is similarly formed.
作為形成彩色濾光片時使用的基板,例如可舉出玻璃、矽、聚碳酸酯、聚酯、芳香族聚醯胺、聚醯胺醯亞胺、聚醯亞胺等。 Examples of the substrate used for forming the color filter include glass, ruthenium, polycarbonate, polyester, aromatic polyamide, polyamidimide, and polyimide.
另外,還可以根據需要對這些基板實施利用矽烷偶聯劑等的試劑處理、電漿處理、離子鍍、濺射、氣相反應法、真空蒸鍍等適當的前處理。 Further, as appropriate, these substrates may be subjected to an appropriate pretreatment such as reagent treatment such as a decane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, or vacuum vapor deposition.
在基板上塗布放射線敏感性著色組成物時,可以採用噴塗法、輥塗法、旋塗法(spin coat method)、狹縫式模塗法(狹縫式塗布法)、棒塗法等適當的塗布法,特佳為採用旋塗法、狹縫式模塗法。 When a radiation-sensitive coloring composition is applied onto a substrate, a spray coating method, a roll coating method, a spin coating method, a slit die coating method (slit coating method), a bar coating method, or the like may be employed. The coating method is particularly preferably a spin coating method or a slit die coating method.
預烘通常是組合減壓乾燥和加熱乾燥進行。減壓乾燥通常進行到50~200Pa。另外,加熱乾燥的條件 通常為70~110℃、1~10分鐘左右。 The pre-baking is usually carried out by combining dry-pressure drying and heat drying. Drying under reduced pressure usually proceeds to 50 to 200 Pa. In addition, the conditions of heat drying Usually 70~110 °C, 1~10 minutes or so.
塗布厚度以乾燥後的膜厚計,通常為0.6~8μm,較佳為1.2~5μm。 The coating thickness is usually 0.6 to 8 μm, preferably 1.2 to 5 μm, in terms of the film thickness after drying.
作為形成選自像素和黑色矩陣中的至少1種時使用的放射線的光源,例如可舉出氙燈、鹵素燈、鎢燈、高壓汞燈、超高壓汞燈、金屬鹵化物燈、中壓汞燈、低壓汞燈等燈光源,氬離子雷射、YAG雷射、XeCl準分子雷射、氮雷射等雷射光源等。作為曝光用光源,也可以使用紫外線LED。較佳為波長在190~450nm的範圍的放射線。 Examples of the light source for forming radiation to be used in at least one selected from the group consisting of a pixel and a black matrix include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, and a medium pressure mercury lamp. Light source such as low-pressure mercury lamp, argon ion laser, YAG laser, XeCl excimer laser, nitrogen laser and other laser light sources. As the light source for exposure, an ultraviolet LED can also be used. Radiation having a wavelength in the range of 190 to 450 nm is preferred.
放射線的曝光量一般較佳為10~10,000J/m2。 The exposure amount of the radiation is generally preferably from 10 to 10,000 J/m 2 .
另外,作為上述鹼性顯影液,例如,較佳為碳酸鈉、碳酸氫鈉、氫氧化鈉、氫氧化鉀、四甲基氫氧化銨、膽鹼、1,8-二氮雜雙環-[5.4.0]-7-十一碳烯、1,5-二氮雜雙環-[4.3.0]-5-壬烯等的水溶液。 Further, as the above alkaline developing solution, for example, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline or 1,8-diazabicyclo-[5.4 is preferred. .0] an aqueous solution of 7-undecene, 1,5-diazabicyclo-[4.3.0]-5-decene.
也可以向鹼性顯影液中適量添加例如甲醇、乙醇等水溶性有機溶劑或界面活性劑等。應予說明,在鹼性顯影後,通常進行水洗。 A water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the alkaline developer in an appropriate amount. Incidentally, after alkaline development, water washing is usually performed.
作為顯影處理法,可以應用噴淋顯影法、噴霧顯影法、浸漬(dip)顯影法、攪煉(puddle)顯影法等。顯影條件較佳為常溫5~300秒。 As the development treatment method, a shower development method, a spray development method, a dip development method, a puddle development method, or the like can be applied. The developing conditions are preferably from normal temperature to 5 to 300 seconds.
後烘的條件通常是180~280℃、10~60分鐘左右。 The post-baking conditions are usually 180 to 280 ° C for about 10 to 60 minutes.
這樣形成的像素的膜厚通常為0.5~5μm,較佳為1 ~3μm。 The film thickness of the pixel thus formed is usually 0.5 to 5 μm, preferably 1 ~3μm.
另外,作為製造彩色濾光片的第二方法,可以採用日本特開平7-318723號公報、日本特開2000-310706號公報等中公開的利用噴墨方式得到各色的像素的方法。該方法中,首先,在基板的表面上形成也兼具遮光功能的隔壁。接著,在形成的隔壁內將例如紅色的熱硬化性著色組成物的液狀組成物利用噴射裝置噴出後,進行預烘使溶劑蒸發。接著,根據需要對該塗膜進行曝光之後,通過後烘使其硬化,形成藍色的像素圖案。 In addition, as a second method of producing a color filter, a method of obtaining pixels of respective colors by an inkjet method disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2000-310706, and the like. In this method, first, a partition wall which also has a light blocking function is formed on the surface of the substrate. Next, a liquid composition such as a red thermosetting coloring composition is ejected by a spraying device in the formed partition wall, and then pre-baked to evaporate the solvent. Next, the coating film is exposed as needed, and then cured by post-baking to form a blue pixel pattern.
接著,使用綠色或者藍色的各熱硬化性著色組成物與上述同樣地在同一基板上依次形成綠色的像素圖案和藍色的像素圖案。由此,得到在基板上配置有紅色、綠色和藍色這三原色的像素圖案的彩色濾光片。其中,本發明中,形成各色的像素的順序不限定於上述的順序。 Next, a green pixel pattern and a blue pixel pattern are sequentially formed on the same substrate in the same manner as described above using each of the green or blue thermosetting coloring composition. Thereby, a color filter in which pixel patterns of three primary colors of red, green, and blue are arranged on the substrate is obtained. However, in the present invention, the order in which the pixels of the respective colors are formed is not limited to the above-described order.
應予說明,隔壁不僅起到遮光功能,還起到使噴出到隔區內的各色的熱硬化性著色組成物不混色的功能,所以與上述第一方法中使用的黑色矩陣相比,膜厚為厚的。因此,隔壁通常使用黑色放射線敏感性組成物形成。 In addition, since the partition wall not only functions as a light-shielding function but also functions to prevent color mixing of the thermosetting coloring compositions of the respective colors discharged into the compartments, the film thickness is thinner than that of the black matrix used in the first method. It is thick. Therefore, the partition walls are usually formed using a black radiation sensitive composition.
形成彩色濾光片時使用的基板、放射線的光源以及預烘、後烘的方法、條件與上述的第一方法相同。這樣通過噴墨方式形成的像素的膜厚與隔壁的高度為同等程度。 The substrate used for forming the color filter, the light source of the radiation, and the method and conditions for prebaking and post-baking are the same as those of the first method described above. The film thickness of the pixel formed by the inkjet method in this manner is equivalent to the height of the partition wall.
在這樣得到的像素圖案上根據需要形成保護膜後,通過濺射形成透明導電膜。形成透明導電膜後,還可以進一步形成隔離件製成彩色濾光片。隔離件通常使用放射線敏感性組成物形成,但也可以形成具有遮光性的隔離件(黑色隔離件)。該情況下,使用分散有黑色的著色劑的放射線敏感性著色組成物,但本發明的著色組成物也適用於形成該黑色隔離件。 After forming a protective film as needed on the pixel pattern thus obtained, a transparent conductive film is formed by sputtering. After the transparent conductive film is formed, a spacer may be further formed to form a color filter. The spacer is usually formed using a radiation-sensitive composition, but a spacer having a light-shielding property (black spacer) may also be formed. In this case, a radiation-sensitive coloring composition in which a black coloring agent is dispersed is used, but the coloring composition of the present invention is also suitable for forming the black spacer.
本發明的放射線敏感性著色組成物可適用於形成上述彩色濾光片中使用的各色像素、黑色矩陣、黑色隔離件等任一種的著色硬化膜。 The radiation-sensitive coloring composition of the present invention can be suitably used for forming a colored cured film of any of the color pixels, the black matrix, and the black spacer used in the color filter.
這樣形成的包含本發明的著色硬化膜的彩色濾光片的亮度和顏色純度極高,因此在彩色液晶顯示元件、彩色攝像管元件、色彩感測器、有機EL顯示元件、電子紙等中極其有用。應予說明,後述的顯示元件只要具備至少1個以上的使用本發明的放射線敏感性著色組成物形成的著色硬化膜即可。 The color filter including the colored cured film of the present invention thus formed has extremely high brightness and color purity, and thus is extremely excellent in a color liquid crystal display element, a color image pickup element, a color sensor, an organic EL display element, an electronic paper, or the like. it works. In addition, the display element which will be described later may be provided with at least one or more colored cured films formed using the radiation-sensitive coloring composition of the present invention.
顯示元件Display component
本發明的顯示元件具備本發明的著色硬化膜。作為顯示元件,可舉出彩色液晶顯示元件、有機EL顯示元件、電子紙等。 The display element of the present invention comprises the colored cured film of the present invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper.
具備本發明的著色硬化膜的彩色液晶顯示元件可以是穿透式也可以是反射式,可以採用適當的結構。例如,可以採用在與配置有薄膜電晶體(TFT)的驅動用基板不同的基板上形成彩色濾光片,驅動用基板和形成有彩色濾光片的基板隔著液晶層對置的結構。另外,還可以採 用在配置有薄膜電晶體(TFT)的驅動用基板的表面上形成有彩色濾光片的基板與形成有ITO(摻雜有錫的氧化銦)電極的基板隔著液晶層對置的結構。後者的結構具有能夠顯著提高開口率、得到明亮且高精細的液晶顯示元件這樣的優點。應予說明,採用後者的結構時,黑色矩陣、黑色隔離件可以在形成有彩色濾光片的基板側以及形成有ITO電極的基板側中的任一方形成。 The color liquid crystal display element having the colored cured film of the present invention may be of a transmissive type or a reflective type, and an appropriate structure may be employed. For example, a color filter may be formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is disposed, and the substrate for driving and the substrate on which the color filter is formed may be opposed to each other via the liquid crystal layer. In addition, you can also take A substrate on which a color filter is formed on a surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate on which an ITO (tin-doped indium oxide) electrode is formed are opposed to each other via a liquid crystal layer. The latter structure has an advantage of being able to remarkably increase the aperture ratio and obtain a bright and high-definition liquid crystal display element. In the latter configuration, the black matrix and the black spacer may be formed on one of the substrate side on which the color filter is formed and the substrate side on which the ITO electrode is formed.
具備本發明的著色硬化膜的彩色液晶顯示元件除具備冷陰極螢光管(CCFL:Cold Cathode Fluorescent Lamp)之外,還具備以白色LED為光源的背光燈單元。作為白色LED,例如可舉出組合紅色LED、綠色LED和藍色LED通過混色得到白色光的白色LED,組合藍色LED、紅色LED和綠色螢光體通過混色得到白色光的白色LED,組合藍色LED、紅色發光螢光體和綠色發光螢光體通過混色得到白色光的白色LED,通過藍色LED和YAG系螢光體的混色得到白色光的白色LED,組合藍色LED、橙色發光螢光體和綠色發光螢光體通過混色得到白色光的白色LED,組合紫外線LED、紅色發光螢光體、綠色發光螢光體和藍色發光螢光體通過混色得到白色光的白色LED等。 The color liquid crystal display device including the colored cured film of the present invention includes a cold cathode fluorescent tube (CCFL: Cold Cathode Fluorescent Lamp) and a backlight unit using a white LED as a light source. Examples of the white LED include a white LED in which a combination of a red LED, a green LED, and a blue LED obtains white light by color mixing, and a combination of a blue LED, a red LED, and a green phosphor to obtain white light by color mixing, combined blue The color LED, the red illuminating phosphor and the green illuminating phosphor obtain a white LED of white light by color mixing, and a white LED of white light is obtained by color mixing of the blue LED and the YAG-based phosphor, and the combination of the blue LED and the orange illuminating illuminating The light body and the green light-emitting phosphor obtain a white light white LED by color mixing, and a white LED or the like which combines the ultraviolet light LED, the red light-emitting phosphor, the green light-emitting phosphor, and the blue light-emitting phosphor to obtain white light by color mixing.
具備本發明的著色硬化膜的彩色液晶顯示元件可以採用TN(Twisted Nematic,扭曲向列)型、STN(Super Twisted Nematic,超扭曲向列)型、IPS(In-Planes Switching,面內切換)型、VA(Vertical Alignment,垂直配向)型、OCB(Optically Compensated Birefringence,光 學補償彎曲排列)型等適當的液晶模式。 The color liquid crystal display element having the colored cured film of the present invention can be TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, or IPS (In-Planes Switching) type. , VA (Vertical Alignment) type, OCB (Optically Compensated Birefringence, light) Appropriate liquid crystal mode such as compensation and bending arrangement.
另外,具備本發明的著色硬化膜的有機EL顯示元件可以採用適當的結構,例如可舉出日本特開平11-307242號公報中公開的結構。 In addition, the organic EL display element having the colored cured film of the present invention may have a suitable structure, and for example, a structure disclosed in Japanese Laid-Open Patent Publication No. Hei 11-307242.
另外,具備本發明的著色硬化膜的電子紙可以採用適當的結構,例如可舉出日本特開2007-41169號公報中公開的結構。 In addition, the electronic paper provided with the colored cured film of the present invention may have a suitable structure, and for example, the structure disclosed in JP-A-2007-41169 can be cited.
以下,舉出實施例對本發明的實施方式進一步進行具體說明。但本發明不限於下述實施例。 Hereinafter, embodiments of the present invention will be further specifically described by way of examples. However, the invention is not limited to the following embodiments.
<著色劑的合成> <Synthesis of Colorants>
合成例1 Synthesis Example 1
於裝有攪拌子的300mL的茄形燒瓶中加入2,3,3-三甲基吲哚啉9.7g、1-碘代甲烷25.9g和乙腈85mL,邊加熱回流邊攪拌10小時。冷卻至室溫後,將反應溶液加到二異丙基醚425mL中,進行冰冷,靜置30分鐘。其後,通過吸濾濾出析出物,對得到的固體進行減壓乾燥得到16.1g淡粉色的固體。通過1H-NMR和MS譜的分析,確認了得到的固體是上述式表示的化合物(A1)。 To a 300 mL eggplant-shaped flask equipped with a stirrer, 9.7 g of 2,3,3-trimethylporphyrin, 25.9 g of 1-iodomethane, and 85 mL of acetonitrile were placed, and the mixture was stirred for 10 hours while heating under reflux. After cooling to room temperature, the reaction solution was added to 425 mL of diisopropyl ether, ice-cooled, and allowed to stand for 30 minutes. Thereafter, the precipitate was filtered by suction filtration, and the obtained solid was dried under reduced pressure to yield 16.1 g of pale pink solid. It was confirmed by 1 H-NMR and MS spectrum analysis that the obtained solid was the compound (A1) represented by the above formula.
合成例2 Synthesis Example 2
於裝有攪拌子的100mL的茄形燒瓶中加入合成例1中得到的化合物(A1)8.1g和原甲酸乙酯12.0g和吡啶24mL,在120℃攪拌5小時。冷卻至室溫後,用旋轉蒸發儀對反應溶液進行減壓濃縮。其後,加入20mL丙酮,在40℃攪拌30分鐘。其後,加到二異丙基醚200mL中,進行冰冷,靜置30分鐘。其後,通過吸濾濾出析出物,對得到的固體進行減壓乾燥而得到6.3g紅紫色的固體。通過1H-NMR和LC-MS的分析,確認了得到的固體是上述式(A2-1)表示的化合物和上述式(A2-2)表示的化合物的混合物。將該化合物作為著色劑(A-2)。 8.1 g of the compound (A1) obtained in Synthesis Example 1 and 12.0 g of ethyl orthoformate and 24 mL of pyridine were added to a 100 mL eggplant-shaped flask equipped with a stirrer, and the mixture was stirred at 120 ° C for 5 hours. After cooling to room temperature, the reaction solution was concentrated under reduced pressure using a rotary evaporator. Thereafter, 20 mL of acetone was added, and the mixture was stirred at 40 ° C for 30 minutes. Thereafter, it was added to 200 mL of diisopropyl ether, ice-cooled, and allowed to stand for 30 minutes. Then, the precipitate was filtered off with suction filtration, and the obtained solid was dried under reduced pressure to give 6.3 g of a red-purpur solid. It was confirmed by 1 H-NMR and LC-MS that the obtained solid was a mixture of the compound represented by the above formula (A2-1) and the compound represented by the above formula (A2-2). This compound was used as a coloring agent (A-2).
合成例3 Synthesis Example 3
利用以下的方法使著色劑(A-2)再結晶。即,於裝有攪拌子的300mL的茄形燒瓶中加入合成例2中得到的著色劑(A-2)5.0g、含有10質量%的乙醇的離子交換水100g,在80℃攪拌2小時。其後,將溶液冷卻,在5℃靜置一晚。通過吸濾濾出析出物,對得到的固體進行減壓乾燥而得到4.6g紅紫色的固體。將該化合物作為著色劑(A-3)。 The coloring agent (A-2) was recrystallized by the following method. Specifically, 5.0 g of the color former (A-2) obtained in Synthesis Example 2 and 100 g of ion-exchanged water containing 10% by mass of ethanol were placed in a 300 mL eggplant-shaped flask equipped with a stirrer, and the mixture was stirred at 80 ° C for 2 hours. Thereafter, the solution was cooled and allowed to stand at 5 ° C overnight. The precipitate was filtered by suction filtration, and the obtained solid was dried under reduced pressure to yield 4.6 g of a reddish solid. This compound was used as a coloring agent (A-3).
合成例4 Synthesis Example 4
利用以下的方法使著色劑(A-3)再結晶。即,於裝有 攪拌子的300mL的茄形燒瓶中加入合成例3中得到的著色劑(A-3)5.0g、含有10質量%的乙醇的離子交換水100g,在80℃攪拌2小時。其後,將溶液冷卻,在5℃靜置一晚。通過吸濾濾出析出物,對得到的固體進行減壓乾燥而得到4.3g紅紫色的固體。將該化合物作為著色劑(A-4)。 The coloring agent (A-3) was recrystallized by the following method. That is, in the To a 300 mL eggplant-shaped flask of the stirrer, 5.0 g of the color former (A-3) obtained in Synthesis Example 3 and 100 g of ion-exchanged water containing 10% by mass of ethanol were placed, and the mixture was stirred at 80 ° C for 2 hours. Thereafter, the solution was cooled and allowed to stand at 5 ° C overnight. The precipitate was filtered by suction filtration, and the obtained solid was dried under reduced pressure to yield 4.3 g. This compound was used as a coloring agent (A-4).
合成例5 Synthesis Example 5
於裝有攪拌子的300mL的茄形燒瓶中加入合成例2中得到的著色劑(A-2)3.0g、雙三氟甲烷磺醯亞胺鋰2.7g、乙腈24mL、乙酸乙酯36mL和離子交換水30mL,攪拌2小時。其後,分離除去水層,用離子交換水30mL對有機層清洗3次。接著用旋轉蒸發儀對有機層進行減壓濃縮,在50℃真空乾燥一晚,得到4.0g暗紅色的固體。通過1H-NMR和LC-MS的分析,確認了得到的固體是上述式(A5-1)表示的化合物和上述式(A5-2)表示的化合物的混合物。將該化合物作為著色劑(A-5)。 3.0 g of the color former (A-2) obtained in Synthesis Example 2, 2.7 g of lithium bistrifluoromethanesulfonimide, 24 mL of acetonitrile, 36 mL of ethyl acetate, and ions were placed in a 300 mL eggplant-shaped flask equipped with a stir bar. 30 mL of water was exchanged and stirred for 2 hours. Thereafter, the aqueous layer was separated and removed, and the organic layer was washed three times with 30 mL of ion-exchanged water. Then, the organic layer was concentrated under reduced pressure using a rotary evaporator, and dried under vacuum at 50 ° C overnight to give 4.0 g of dark red solid. The solid obtained was confirmed to be a mixture of the compound represented by the above formula (A5-1) and the compound represented by the above formula (A5-2) by analysis of 1 H-NMR and LC-MS. This compound was used as a coloring agent (A-5).
合成例6 Synthesis Example 6
合成例5中,使用著色劑(A-3)代替著色劑(A-2),除此之外,進行與合成例5同樣的反應操作,得到上述式(A5-1)表示的化合物和上述式(A5-2)表示的化合物的混合物。將得到的化合物作為著色劑(A-6)。 In the synthesis example 5, the same reaction operation as in the synthesis example 5 was carried out except that the colorant (A-3) was used instead of the colorant (A-2), and the compound represented by the above formula (A5-1) and the above were obtained. A mixture of compounds represented by the formula (A5-2). The obtained compound was used as a coloring agent (A-6).
合成例7 Synthesis Example 7
合成例5中,使用著色劑(A-4)代替著色劑(A-2),除此之外,進行與合成例5同樣的反應操作,得到上述式(A5-1)表示的化合物和上述式(A5-2)表示的化合物的混合物。將得到的化合物作為著色劑(A-7)。 In the synthesis example 5, the same reaction operation as in the synthesis example 5 was carried out except that the coloring agent (A-4) was used instead of the coloring agent (A-2), and the compound represented by the above formula (A5-1) and the above were obtained. A mixture of compounds represented by the formula (A5-2). The obtained compound was used as a coloring agent (A-7).
合成例8 Synthesis Example 8
合成例5中,使用對(乙烯基苯基)三氟甲烷磺醯亞胺酸三乙胺鹽2.4g代替雙三氟甲烷磺醯亞胺鋰2.7g,除此之外,進行與合成例5同樣的反應操作。通過1H-NMR和LC-MS的分析,確認了得到的固體是上述式(A8-1)表示的化合物和上述式(A8-2)表示的化合物的混合物。將得到的化合物作為著色劑(A-8)。 In Synthesis Example 5, except that 2.4 g of (vinylphenyl)trifluoromethanesulfonimide triethylamine salt was used instead of 2.7 g of lithium bistrifluoromethanesulfonimide, and Synthesis Example 5 was used. The same reaction operation. The solid obtained was confirmed to be a mixture of the compound represented by the above formula (A8-1) and the compound represented by the above formula (A8-2) by analysis of 1 H-NMR and LC-MS. The obtained compound was used as a coloring agent (A-8).
合成例9 Synthesis Example 9
合成例8中,使用著色劑(A-3)代替著色劑(A-2),除此之外,進行與合成例8同樣的反應操作,得到上述式(A8-1)表示的化合物和上述式(A8-2)表示的化合物的混合物。將得到的化合物作為著色劑(A-9)。 In the synthesis example 8, the same reaction operation as in Synthesis Example 8 was carried out except that the colorant (A-3) was used instead of the colorant (A-2), and the compound represented by the above formula (A8-1) and the above were obtained. A mixture of compounds represented by the formula (A8-2). The obtained compound was used as a coloring agent (A-9).
合成例10 Synthesis Example 10
合成例8中,使用著色劑(A-4)代替著色劑(A-2),除此之外,進行與合成例8同樣的反應操作,得到上述式(A8-1)表示的化合物和上述式(A8-2)表示的化合物的混合物。將得到的化合物作為著色劑(A-10)。 In the synthesis example 8, the same reaction operation as in Synthesis Example 8 was carried out except that the colorant (A-4) was used instead of the colorant (A-2), and the compound represented by the above formula (A8-1) and the above were obtained. A mixture of compounds represented by the formula (A8-2). The obtained compound was used as a coloring agent (A-10).
合成例11 Synthesis Example 11
合成例1中,使用1-碘代丙烷30.9g代替1-碘代甲烷25.9g,除此之外,進行與合成例1同樣的反應操作,得到上述式表示的化合物(A11)。 In the same manner as in Synthesis Example 1, except that 30.9 g of 1-iodopropane was used instead of 25.9 g of 1-iodomethane, the compound (A11) represented by the above formula was obtained.
合成例12 Synthesis Example 12
合成例2中,使用合成例11中得到的化合物(A11)8.8g代替化合物(A1)8.1g,除此之外,進行與合成例2同樣的反應操作。通過1H-NMR和LC-MS的分析,確認了得到的化合物是上述式(A12-1)表示的化合物和上述式(A12-2)表示的化合物的混合物。將該化合物作為著色劑(A-12)。 In the synthesis example 2, the same reaction operation as in Synthesis Example 2 was carried out, except that 8.8 g of the compound (A11) obtained in Synthesis Example 11 was used instead of 8.1 g of the compound (A1). The obtained compound was confirmed to be a mixture of the compound represented by the above formula (A12-1) and the compound represented by the above formula (A12-2) by analysis of 1 H-NMR and LC-MS. This compound was used as a coloring agent (A-12).
合成例13 Synthesis Example 13
合成例3中,使用著色劑(A-12)5g代替著色劑(A-2)5g,除此之外,進行與合成例3同樣的再結晶操作。將得到的化合物作為著色劑(A-13)。 In the synthesis example 3, the same recrystallization operation as in the synthesis example 3 was carried out except that 5 g of the colorant (A-12) was used instead of 5 g of the colorant (A-2). The obtained compound was used as a coloring agent (A-13).
合成例14 Synthesis Example 14
合成例4中,使用著色劑(A-13)5g代替著色劑(A-3)5g,除此之外,進行與合成例4同樣的再結晶操作。將得到的化合物作為著色劑(A-14)。 In the synthesis example 4, the same recrystallization operation as in the synthesis example 4 was carried out, except that 5 g of the colorant (A-13) was used instead of 5 g of the colorant (A-3). The obtained compound was used as a coloring agent (A-14).
合成例15 Synthesis Example 15
合成例5中,使用著色劑(A-12)3.3g代替著色劑(A-2)3.0g,除此之外,進行與合成例5同樣的反應操作 ,得到上述式(A15-1)表示的化合物和上述式(A15-2)表示的化合物的混合物。將得到的化合物作為著色劑(A-15)。 In the synthesis example 5, the same reaction operation as in the synthesis example 5 was carried out, except that 3.3 g of the colorant (A-12) was used instead of 3.0 g of the colorant (A-2). A mixture of the compound represented by the above formula (A15-1) and the compound represented by the above formula (A15-2) is obtained. The obtained compound was used as a coloring agent (A-15).
合成例16 Synthesis Example 16
合成例5中,使用著色劑(A-13)3.3g代替著色劑(A-2)3.0g,除此之外,進行與合成例5同樣的反應操作,得到上述式(A15-1)表示的化合物和上述式(A15-2)表示的化合物的混合物。將得到的化合物作為著色劑(A-16)。 In the synthesis example 5, the same reaction operation as in the synthesis example 5 was carried out except that 3.3 g of the colorant (A-13) was used instead of 3.0 g of the colorant (A-2), and the above formula (A15-1) was obtained. A mixture of a compound and a compound represented by the above formula (A15-2). The obtained compound was used as a coloring agent (A-16).
合成例17 Synthesis Example 17
合成例5中,使用著色劑(A-14)3.3g代替著色劑(A-2)3.0g,除此之外,進行與合成例5同樣的反應操作,得到上述式(A15-1)表示的化合物和上述式(A15-2)表示的化合物的混合物。將得到的化合物作為著色劑(A-17)。 In the synthesis example 5, the same reaction operation as in the synthesis example 5 was carried out except that 3.3 g of the colorant (A-14) was used instead of 3.0 g of the colorant (A-2), and the above formula (A15-1) was obtained. A mixture of a compound and a compound represented by the above formula (A15-2). The obtained compound was used as a coloring agent (A-17).
純度確認 Purity confirmation
分別製備著色劑(A-5)~(A-10)和(A-15)~(A-17)的乙腈溶液(著色劑濃度1000ppm),按照以下的分析條件利用高效液相色譜進行純度的定量。測定各著色劑中的化合物(2)、即具有式(2)表示的結構的化合物的濃度,計算相對於化合物(1)和化合物(2)的合計含量的化合物(2)的含量。將結果示於表1。 The acetonitrile solutions (colorant concentration: 1000 ppm) of the colorants (A-5) to (A-10) and (A-15) to (A-17) were separately prepared, and the purity was determined by high performance liquid chromatography according to the following analysis conditions. Quantitative. The concentration of the compound (2) in each coloring agent, that is, the compound having the structure represented by the formula (2), was measured, and the content of the compound (2) relative to the total content of the compound (1) and the compound (2) was calculated. The results are shown in Table 1.
[分析條件] [Analysis conditions]
‧裝置:高效液相色譜[Smartline(PDA SYSTEM)LC SYSTEM,KNAUER公司製] ‧Device: High Performance Liquid Chromatography [Smartline (PDA SYSTEM) LC SYSTEM, manufactured by KNAUER)
‧檢測器:Smartline PDA Detector 2850 ‧Detector: Smartline PDA Detector 2850
‧溶劑:乙腈/0.1%三氟乙酸水溶液=7/3(v/v)混合溶劑 ‧ Solvent: acetonitrile / 0.1% aqueous solution of trifluoroacetic acid = 7 / 3 (v / v) mixed solvent
‧管柱:CAPCELLPAK C18 MG(5μ150x4.6mm,資生堂公司製) ‧Tube: CAPCELLPAK C18 MG (5μ150x4.6mm, manufactured by Shiseido Co., Ltd.)
‧管柱烘箱設定溫度:40℃ ‧column oven set temperature: 40 ° C
‧樣品注入量:10μL ‧ Sample injection amount: 10μL
‧流量:0.5mL/分鐘 ‧Flow: 0.5mL/min
表1中呈示著色劑(A-7)、(A-10)和(A-17)中的化合物(2)的濃度低於高效液相色譜中的檢測限度。 The concentrations of the compounds (2) in the colorants (A-7), (A-10) and (A-17) are shown in Table 1 to be lower than the detection limits in the high performance liquid chromatography.
<顏料分散液的製備> <Preparation of Pigment Dispersion>
製備例1 Preparation Example 1
作為著色劑使用15質量份的C.I.顏料紅254,作為分散劑使用12.5質量份(固體成分濃度40質量%)的BYK-LPN21116(BYK-Chemie(BYK)公司製),作為溶劑使用72.5質量份的丙二醇單甲醚乙酸酯,利用珠磨機進行處理,而製備顏料分散液(a-1)。 15 parts by mass of CI Pigment Red 254 was used as a coloring agent, and 12.5 parts by mass (solid content concentration: 40% by mass) of BYK-LPN21116 (BYK-Chemie (BYK)) was used as a dispersing agent, and 72.5 parts by mass was used as a solvent. Propylene glycol monomethyl ether acetate was treated with a bead mill to prepare a pigment dispersion liquid (a-1).
<著色劑溶液的製備> <Preparation of colorant solution>
製備例2 Preparation Example 2
將著色劑(A-5)10質量份和丙二醇單甲醚90質量份混合,而製備著色劑溶液(A-5)。 A colorant solution (A-5) was prepared by mixing 10 parts by mass of the colorant (A-5) and 90 parts by mass of propylene glycol monomethyl ether.
製備例3~10 Preparation Example 3~10
製備例2中,如表2所示改變著色劑的種類,除此之外,與製備例2同樣地製備著色劑溶液(A-6)~(A-10)和(A-15)~(A-17)。 In the preparation example 2, the colorant solutions (A-6) to (A-10) and (A-15)~ were prepared in the same manner as in Production Example 2 except that the type of the colorant was changed as shown in Table 2. A-17).
<(B)黏結劑樹脂的合成> <(B) Synthesis of binder resin>
合成例18 Synthesis Example 18
於具備冷卻管和攪拌機的燒瓶中投入丙二醇單甲醚乙酸酯100質量份並進行氮置換。加熱到80℃,在該溫度下,歷經1小時滴加丙二醇單甲醚乙酸酯100質量份、甲基丙烯酸20質量份、苯乙烯10質量份、甲基丙烯酸苄酯5質量份、甲基丙烯酸2-羥基乙酯15質量份、甲基丙烯酸2-乙基己酯23質量份、N-苯基馬來醯亞胺12質量份、琥珀酸單(2-丙烯醯氧基乙基)酯15質量份和2,2’-偶氮雙(2,4-二甲基戊腈)6質量份的混合溶液,保持該溫度進行2小時聚合。其後,將反應溶液的溫度升溫至100℃,再進行1小時聚合,由此得到黏結劑樹脂溶液(B1)(固體成分濃度33質量%)。得到的黏結劑樹脂的Mw為12,200,Mn為6,500。 100 parts by mass of propylene glycol monomethyl ether acetate was placed in a flask equipped with a cooling tube and a stirrer, and nitrogen substitution was performed. Heating to 80 ° C, at this temperature, 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, methyl group were added dropwise over 1 hour. 15 parts by mass of 2-hydroxyethyl acrylate, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, and mono(2-propenyloxyethyl) succinate A mixed solution of 15 parts by mass and 6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) was maintained at this temperature for 2 hours. Thereafter, the temperature of the reaction solution was raised to 100 ° C, and polymerization was further carried out for 1 hour to obtain a binder resin solution (B1) (solid content concentration: 33% by mass). The obtained binder resin had a Mw of 12,200 and an Mn of 6,500.
合成例19 Synthesis Example 19
根據日本特開2013-203955號公報的合成例6中記載的方法,得到含有具有下述結構單元的樹脂的溶液。接著,加入丙二醇單甲醚乙酸酯將固體成分濃度調整到33質量%,得到黏結劑樹脂溶液(B2)(固體成分濃度33質量%)。 A solution containing a resin having the following structural unit was obtained by the method described in Synthesis Example 6 of JP-A-2013-203955. Then, propylene glycol monomethyl ether acetate was added to adjust the solid content concentration to 33% by mass to obtain a binder resin solution (B2) (solid content concentration: 33% by mass).
著色組成物的製備Preparation of coloring composition
實施例1 Example 1
將作為(A)著色劑的顏料分散液(a-1)30.5質量份、著色劑溶液(A-5)23.0質量份、作為(B)黏結劑樹脂的黏結劑樹脂溶液(B1)26.3質量份、作為(C)聚合性化合物的二季戊四醇六丙烯酸酯和二季戊四醇五丙烯酸酯的混合物(日本化藥股份有限公司製,商品名KAYARAD DPHA)9.9質量份、作為光聚合引發劑的2-苄基-2-二甲基胺基-1-(4-啉并苯基)丁烷-1-酮(商品名IRGACURE 369,Ciba Specialty Chemicals公司製)1.8質量份和NCI-930(ADEKA股份有限公司製)0.1質量份、作為氟系界面活性劑的MEGAFAC F-554(DIC股份有限公司製)0.05質量份以及作為溶劑的丙二醇單甲醚乙酸酯混合,製備固體成分濃度為20質量%的著色組成物(S-1)。 30.5 parts by mass of the pigment dispersion liquid (a-1) as the coloring agent (A), 23.0 parts by mass of the colorant solution (A-5), and 26.3 parts by mass of the binder resin solution (B1) as the (B) binder resin. 9.9 parts by mass of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) as a (C) polymerizable compound, 2-benzyl group as a photopolymerization initiator -2-dimethylamino-1-(4- 1.8 parts by mass of phenyl phenyl)butane-1-one (trade name: IRGACURE 369, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 0.1 parts by mass of NCI-930 (manufactured by ADEKA CORPORATION), MEGAFAC F as a fluorine-based surfactant 0.05 parts by mass of 554 (manufactured by DIC Corporation) and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a colored composition (S-1) having a solid content concentration of 20% by mass.
色度特性的評價Evaluation of chromaticity characteristics
使用旋塗機在玻璃基板上塗布得到的著色組成物後,用80℃的熱板進行10分鐘預烘形成塗膜。改變旋塗機的轉速通過同樣的操作形成膜厚不同的3片塗膜。 The obtained coloring composition was applied onto a glass substrate using a spin coater, and then pre-baked by a hot plate at 80 ° C for 10 minutes to form a coating film. The three rotation speeds of the spin coater were changed to form three coating films having different film thicknesses by the same operation.
接著,將這些基板冷卻至室溫後,使用高壓汞燈,不用光罩,以2,000J/m2的曝光量對各塗膜曝光包含365nm、405nm和436nm各波長的放射線。其後,以顯影壓力1kgf/cm2(噴嘴直徑1mm)向這些基板噴出23℃的由0.04質量%氫氧化鉀水溶液構成的顯影液,進行90秒噴淋顯影。其後,用超純水清洗該基板,風乾後,進一步在200℃的無塵烘箱內進行30分鐘後烘,形成評價用的著色硬化膜。 Next, after the substrates were cooled to room temperature, radiation of respective wavelengths of 365 nm, 405 nm, and 436 nm was exposed to each of the coating films at a exposure amount of 2,000 J/m 2 using a high pressure mercury lamp without using a photomask. Thereafter, a developing solution composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C was sprayed onto the substrates at a developing pressure of 1 kgf/cm 2 (nozzle diameter: 1 mm), and spray development was performed for 90 seconds. Thereafter, the substrate was washed with ultrapure water, air-dried, and further baked in a dust-free oven at 200 ° C for 30 minutes to form a colored cured film for evaluation.
對得到的3片著色硬化膜使用彩色分析儀(大塚電子(股)製MCPD2000),在C光源、2度視野中,測定CIE顏色系統中的色度座標值(x,y)和刺激值(Y)。根據測定結果,求出色度座標值y=0.329時的色度座標值x和刺激值(Y)。將評價結果示於表3。應予說明,可以說刺激值(Y)越高亮度越高。 The color coordinate analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.) was used for the obtained three colored cured films, and the chromaticity coordinate values (x, y) and the stimulation values in the CIE color system were measured in a C light source and a 2 degree field of view ( Y). Based on the measurement results, the chromaticity coordinate value x and the stimulus value (Y) at the chromaticity coordinate value y=0.329 are obtained. The evaluation results are shown in Table 3. It should be noted that it can be said that the higher the stimulation value (Y), the higher the brightness.
異物評價Foreign body evaluation
使用旋塗機在表面形成有防止鈉離子溶出的SiO2膜的10cm×10cm的鈉鈣玻璃基板上塗布5℃下靜置3天的著色組成物(S-1)後,用90℃的熱板進行4分鐘預烘,形成預烘後的膜厚成為2.5μm的塗膜。用光學顯微鏡觀察得到的基板,若在塗膜上沒有觀察到異物的產生則記為「○」,若塗膜上的異物的產生個數為1個~10個則記為「△ 」,若觀察到塗膜上的異物的產生個數為11個以上則記為「×」。將評價結果示於表3。應予說明,異物越少表示著色組成物的保存穩定性越優異。 After applying a coloring composition (S-1) which was allowed to stand on a 10 cm × 10 cm soda lime glass substrate having a SiO 2 film for preventing elution of sodium ions on the surface by a spin coater and allowed to stand at 5 ° C for 3 days, heat of 90 ° C was used. The plate was prebaked for 4 minutes to form a coating film having a film thickness of 2.5 μm after prebaking. When the substrate was observed by an optical microscope, if no foreign matter was observed on the coating film, it was marked as "○", and if the number of foreign matter on the coating film was 1 to 10, it was recorded as "△". When it is observed that the number of foreign matter on the coating film is 11 or more, it is indicated as "x". The evaluation results are shown in Table 3. Incidentally, the smaller the foreign matter, the more excellent the storage stability of the colored composition.
實施例2~4和比較例1、2 Examples 2 to 4 and Comparative Examples 1, 2
實施例1中,如表3所示改變著色劑溶液的種類,除此之外,與實施例1同樣地製備著色組成物。然後與實施例1同樣地進行評價。將結果示於表3。 In the same manner as in Example 1, except that the type of the colorant solution was changed as shown in Table 3, a colored composition was prepared. Then, evaluation was performed in the same manner as in Example 1. The results are shown in Table 3.
實施例5、6和比較例3 Examples 5, 6 and Comparative Example 3
實施例1中,如表3所示改變著色劑溶液和黏結劑樹脂的種類,除此之外,與實施例1同樣地製備著色組成物。然後與實施例1同樣地進行評價。將結果示於表3。 In the same manner as in Example 1, except that the types of the colorant solution and the binder resin were changed as shown in Table 3, a coloring composition was prepared. Then, evaluation was performed in the same manner as in Example 1. The results are shown in Table 3.
Claims (7)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013249723 | 2013-12-03 | ||
JP2013-249723 | 2013-12-03 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201525075A true TW201525075A (en) | 2015-07-01 |
TWI676657B TWI676657B (en) | 2019-11-11 |
Family
ID=53346024
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW103141544A TWI676657B (en) | 2013-12-03 | 2014-12-01 | Coloring composition, coloring cured film, and display element |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP6398650B2 (en) |
KR (1) | KR102373077B1 (en) |
CN (1) | CN104698748B (en) |
TW (1) | TWI676657B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6295636B2 (en) * | 2013-12-18 | 2018-03-20 | 東洋インキScホールディングス株式会社 | Coloring composition for color filter, and color filter |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0812292B2 (en) | 1989-07-20 | 1996-02-07 | 凸版印刷株式会社 | Heat resistant color filter and manufacturing method thereof |
JP2891418B2 (en) | 1988-11-26 | 1999-05-17 | 凸版印刷株式会社 | Color filter and manufacturing method thereof |
JP2686841B2 (en) * | 1990-03-30 | 1997-12-08 | 富士写真フイルム株式会社 | Information recording medium and optical information recording method |
JPH0635188A (en) | 1992-07-15 | 1994-02-10 | Nippon Kayaku Co Ltd | Photopolymerizable composition for color filter and color filter |
JP3428492B2 (en) * | 1999-04-26 | 2003-07-22 | 富士電機株式会社 | Blue color filter and organic electroluminescent plate |
JP3940523B2 (en) | 1999-04-27 | 2007-07-04 | セイコーエプソン株式会社 | Resin composition for inkjet color filter, color filter, and method for producing color filter |
JP3491158B2 (en) * | 2002-03-01 | 2004-01-26 | 富士電機ホールディングス株式会社 | Blue color filter and organic electroluminescent device using the same |
JP3893391B2 (en) * | 2003-08-05 | 2007-03-14 | キヤノン株式会社 | Manufacturing method of ND filter |
JP2008242324A (en) * | 2007-03-28 | 2008-10-09 | Sumitomo Chemical Co Ltd | Color photosensitive resin composition and color filter array, solid-state image sensor and camera system using the same |
TWI643909B (en) * | 2007-06-21 | 2018-12-11 | 日商三菱化學股份有限公司 | Colored composition for color filter, color filter, liquid crystal display and organic electroluminescence display |
JP5439860B2 (en) | 2008-03-06 | 2014-03-12 | 住友化学株式会社 | Colored photosensitive resin composition |
US8034538B2 (en) * | 2009-02-13 | 2011-10-11 | Eastman Kodak Company | Negative-working imageable elements |
JP6064411B2 (en) * | 2011-09-28 | 2017-01-25 | Jsr株式会社 | Coloring composition, color filter and display element |
CN103034056A (en) * | 2011-10-07 | 2013-04-10 | 住友化学株式会社 | Colored photosensitive resin composition |
JP6028478B2 (en) * | 2011-10-14 | 2016-11-16 | Jsr株式会社 | Colorant, coloring composition, color filter and display element |
JP5482878B2 (en) * | 2012-01-30 | 2014-05-07 | Jsr株式会社 | Colorant, coloring composition, color filter and display element |
JP5999704B2 (en) * | 2013-02-06 | 2016-09-28 | 日本化薬株式会社 | Colored resin composition |
-
2014
- 2014-11-26 JP JP2014238352A patent/JP6398650B2/en active Active
- 2014-11-28 KR KR1020140168186A patent/KR102373077B1/en active IP Right Grant
- 2014-12-01 TW TW103141544A patent/TWI676657B/en active
- 2014-12-02 CN CN201410721122.XA patent/CN104698748B/en active Active
Also Published As
Publication number | Publication date |
---|---|
CN104698748B (en) | 2019-10-29 |
TWI676657B (en) | 2019-11-11 |
JP6398650B2 (en) | 2018-10-03 |
KR102373077B1 (en) | 2022-03-11 |
JP2015129263A (en) | 2015-07-16 |
CN104698748A (en) | 2015-06-10 |
KR20150064679A (en) | 2015-06-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI494380B (en) | Coloring composition, color filter and display device | |
TWI627233B (en) | Colored composition, colored cured film and display element | |
TWI624505B (en) | Colored composition, color filter and color liquid crystal display element | |
TWI704413B (en) | Colored composition, colored cured film and display element | |
TWI628240B (en) | Coloring agent, coloring composition, color filter and display element | |
TWI650380B (en) | Coloring composition, coloring cured film, and display element | |
KR20130088058A (en) | Colorant, coloring composition, color filter and display device | |
TW201700627A (en) | Coloring composition, cured coloring film, color filter, display element, and solid-state imaging element which can form a cured coloring film capable of well-balancing and realizing in high standard heat tolerance, solvent resistance, and image-developing | |
TW201437293A (en) | Coloring composition, coloring cured film and display element | |
JP6248838B2 (en) | Colored composition, colored cured film, display element and solid-state image sensor | |
TW201406801A (en) | Curable composition, curable film and display element | |
TW201434997A (en) | Coloring composition, coloring cured film, display device, and solid-state imaging device | |
JP6303936B2 (en) | Colored composition, colored cured film, and display element | |
TW201738281A (en) | Coloring composition, colored cured film, display element, and solid-state imaging element | |
JP2015161715A (en) | Coloring composition, cured coloring film, and display element | |
TWI594076B (en) | Coloring composition, color filter, and display element | |
TWI603151B (en) | Colored composition, color filter and display element | |
TW201502700A (en) | Coloring composition, coloring cured film, and display element | |
TW201527444A (en) | Coloring composition, colored cured film and display device | |
TWI635142B (en) | Coloring composition, coloring cured film, and display element | |
TW201300464A (en) | Coloring agent, coloring composition, color filter, and display component | |
TW201533169A (en) | Coloring composition, coloring cured film and display device | |
JP2017066377A (en) | Coloring composition, colored cured film, display element and solid state image sensor | |
JP2013227495A (en) | Coloring composition, color filter and display element | |
TW201446887A (en) | Coloring composition, colored cured film and display element |