TW201443164A - Coloring composition, coloring cured film and display element - Google Patents
Coloring composition, coloring cured film and display element Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
- C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
- C07D311/82—Xanthenes
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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Abstract
Description
本發明係關於一種著色組成物、著色硬化膜及顯示元件,更詳細而言,係關於形成用於透射型或反射型的彩色液晶顯示元件、固態攝影元件、有機EL顯示元件、電子紙等之著色硬化膜所使用的著色組成物、使用該著色組成物所形成的著色硬化膜、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 forming a color liquid crystal display element, a solid-state imaging element, an organic EL display element, an electronic paper, or the like for a transmissive or reflective type. A colored composition used for the colored cured film, a colored cured film formed using the colored composition, and a display element including the colored cured film.
已知有一種在使用著色感放射線性組成物製造彩色濾光片時,在基板上塗布顏料分散型的著色感放射線性組成物並進行乾燥之後,藉由照射放射線使乾燥塗膜成為所需的圖案形狀(以下稱為「曝光」),並進行顯影,得到各色之畫素的方法(例如,參照專利文獻1~2)。又,也已知有一種利用使碳黑分散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。)。再者,也已知有一種使用顏料分散型的著色樹脂組成物,利用噴墨方式得到各色之畫素的方法(例如,參照專利文獻4。)。 It is known that when a color filter is produced using a coloring sensitizing radiation composition, a pigment dispersion type color sensitizing radiation composition is applied onto a substrate and dried, and then a dry coating film is required by irradiation with radiation. A pattern shape (hereinafter referred to as "exposure") is developed to obtain a pixel of each color (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, see Patent Document 3). In addition, a method of obtaining a pixel of each color by an inkjet method using a pigment-dispersed coloring resin composition is known (for example, refer to Patent Document 4).
近年來強烈需要液晶顯示元件之高對比化或固態攝影元件之高精細化,且為了實現該等,有人探討作為著色劑之染料的應用。例如,專利文獻5中,有人提出使用特定的二苯并哌喃系染料。 In recent years, there has been a strong demand for high contrast of liquid crystal display elements or high definition of solid-state photographic elements, and in order to achieve this, applications of dyes as colorants have been explored. For example, in Patent Document 5, it has been proposed to use a specific dibenzopyran dye.
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2010-254964號公報 Patent Document 5 Japanese Patent Laid-Open Publication No. 2010-254964
然而,使用專利文獻5所提出的染料時,有畫素之對比變低的問題。另一方面,使用染料時,係產生多種彩色濾光片之電壓保持率或耐熱性惡化的問題。因此,強烈需要開發一種適合製作可兼具良好的電壓保持率、高對比及高耐熱性之彩色濾光片之著色組成物。 However, when the dye proposed in Patent Document 5 is used, there is a problem that the contrast of the pixels becomes low. On the other hand, when a dye is used, there arises a problem that the voltage holding ratio or heat resistance of a plurality of color filters is deteriorated. Therefore, there is a strong need to develop a coloring composition suitable for producing a color filter which can achieve both good voltage holding ratio, high contrast, and high heat resistance.
因此,本發明的課題在於提供一種在使用染料作為著色劑時,可形成可兼具良好的電壓保持率、高對比及高耐熱性之著色硬化膜的著色組成物、以及提供一種可作為該著色組成物之著色劑應用的化合物。又,本發明的課題在於提供一種具備由上述著色組成物形成之著色硬化膜而成的彩色濾光片、以及一種具備該彩色濾光片的顯示元件。 Therefore, an object of the present invention is to provide a coloring composition capable of forming a colored cured film which has both good voltage holding ratio, high contrast and high heat resistance when a dye is used as a coloring agent, and provides a coloring property A compound for use as a coloring agent for a composition. Moreover, an object of the present invention is to provide a color filter including a colored cured film formed of the colored composition, and a display element including the color filter.
有鑑於該實情,本案發明人等進行仔細研究時發現:藉由將具有特定結構的染料作為著色劑使用,可解決上述問題,進而完成本發明。 In view of the facts, the inventors of the present invention have conducted intensive studies and found that the above problems can be solved by using a dye having a specific structure as a coloring agent, and the present invention has been completed.
亦即,本發明係提供一種著色組成物,其係包含(A)含有具有下述式(1)所示之結構的化合物(以下也稱為「本著色劑」。)的著色劑、(B)黏結劑樹脂及(C)聚合性化合物;
[在式(1)中,m表示0~5的整數,m為2以上的整數時,複數個R5可相同亦可不同。 [In the formula (1), m represents an integer of 0 to 5, and when m is an integer of 2 or more, a plurality of R 5 's may be the same or different.
R1~R4相互獨立地表示氫原子、經取代或非經取代之烴基、或是經取代或非經取代之雜環基。但是,烴基亦可在C-C鍵之間具有選自於-CO-、-COO-及-CONH-中的鍵聯基。 R 1 to R 4 each independently represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted heterocyclic group. However, the hydrocarbon group may have a linking group selected from the group consisting of -CO-, -COO-, and -CONH- between the CC bonds.
R5相互獨立地表示一價基。 R 5 independently represents a monovalent group.
但是,R1~R4中之1個以上為選自於下述要件(i)~(v)的基。 However, one or more of R 1 to R 4 are a group selected from the following requirements (i) to (v).
(i)為經取代或非經取代的不飽和脂肪族烴基、或是經取代或非經取代的不飽和脂環式烴基。但是,不飽和脂肪族烴基亦可在C-C鍵之間具有選自於-CO-、-COO-及-CONH-中的鍵聯基。 (i) is a substituted or unsubstituted unsaturated aliphatic hydrocarbon group, or a substituted or unsubstituted unsaturated alicyclic hydrocarbon group. However, the unsaturated aliphatic hydrocarbon group may have a linking group selected from -CO-, -COO-, and -CONH- between C-C bonds.
(ii)為以不飽和脂肪族烴基取代的脂環式烴基、或是以不飽和脂肪族烴基或不飽和脂環式烴基取代的芳香族烴基。 (ii) is an alicyclic hydrocarbon group substituted with an unsaturated aliphatic hydrocarbon group, or an aromatic hydrocarbon group substituted with an unsaturated aliphatic hydrocarbon group or an unsaturated alicyclic hydrocarbon group.
(iii)為經取代或非經取代的雜環基、或是以雜環基取代的烴基。 (iii) is a substituted or unsubstituted heterocyclic group or a hydrocarbon group substituted with a heterocyclic group.
(iv)為以選自於包含-CN、-NO2、-NH2、-SH及-CONH2的群組(以下也稱為「取代基群α」。)中之至少1種取代的烴基。 (iv) is a hydrocarbon group substituted with at least one selected from the group consisting of -CN, -NO 2 , -NH 2 , -SH, and -CONH 2 (hereinafter also referred to as "substituent group α"). .
(v)為碳數11以上之經取代或非經取代的脂肪族烴基。] (v) is a substituted or unsubstituted aliphatic hydrocarbon group having a carbon number of 11 or more. ]
又,本發明係提供一種使用上述著色組成物而形成的著色硬化膜、及具備該著色硬化膜的顯示元件。在此,「著色硬化膜」係指使用於顯示元件或固態攝影元件的各色畫素、黑色矩陣、黑色間隔件等。 Moreover, the present invention provides a colored cured film formed using the above colored composition, and a display element including the colored cured film. Here, the "coloring cured film" means a respective color pixel, a black matrix, a black spacer, or the like used for a display element or a solid-state imaging element.
再者,本發明係提供一種具有上述式(1)所示之結構的化合物。 Furthermore, the present invention provides a compound having the structure represented by the above formula (1).
使用本發明之著色組成物的話,可形成電壓保持率、對比及耐熱性均優異的著色硬化膜。 When the colored composition of the present invention is used, a colored cured film excellent in voltage holding ratio, contrast, and heat resistance can be formed.
因此,本發明的著色組成物,極適合使用於彩色液晶顯示元件、有機EL顯示元件、電子紙等之顯示元件、CMOS圖像感測器等之固態攝影元件之製作。 Therefore, the coloring composition of the present invention is highly suitable for use in the production of solid-state imaging elements such as color liquid crystal display elements, organic EL display elements, display elements such as electronic paper, and CMOS image sensors.
以下對於本發明詳細地進行說明。 The invention will be described in detail below.
以下對於本發明之著色組成物的構成成分詳細地進行說明。 Hereinafter, the constituent components of the coloring composition of the present invention will be described in detail.
本發明的著色組成物含有本著色劑作為(A)著色劑。 The colored composition of the present invention contains the present colorant as (A) a colorant.
作為R1~R4的烴基,可舉出脂肪族烴基、脂環式烴基、芳香族烴基。又,該等烴基亦可在C-C鍵之間具有選自於-CO-、-COO-及-CONH-中的鍵聯基。 The hydrocarbon group of R 1 ~ R 4 include aliphatic hydrocarbon group, alicyclic hydrocarbon group, an aromatic hydrocarbon group. Further, the hydrocarbon groups may have a linking group selected from the group consisting of -CO-, -COO-, and -CONH- between the CC bonds.
脂肪族烴基可為飽和亦可為不飽和,具體而言,可舉出烷基、烯基、炔基。該等脂肪族烴基的碳數較佳為1~30,更佳為1~24,特佳為1~20。又,該等脂肪族烴基可為直鏈狀亦可為分支鏈狀。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、二級丁基、三級丁基、己基、庚基、辛基、壬基、癸基、十一基、1-甲基癸基、十二基、1-甲基十一基、1-乙基癸基、十三基、十四基、三級十二基、十五基、1-庚基辛基、十六基、十八基、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。又,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。又,作為在脂肪族烴基的C-C鍵之間具有選自於-CO-、-COO-及-CONH-之鍵聯基的基,例如,可舉出(甲基)丙烯酸乙酯基、(甲基)丙烯酸丙酯基、(甲基)丙烯醯胺乙基、(甲基)丙烯醯胺丙基等。 The aliphatic hydrocarbon group may be saturated or unsaturated, and specific examples thereof include an alkyl group, an alkenyl group, and an alkynyl group. The carbon number of the aliphatic hydrocarbon group is preferably from 1 to 30, more preferably from 1 to 24, particularly preferably from 1 to 20. Further, the 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 secondary butyl group, a tertiary butyl group, a hexyl group, a heptyl group, and an octyl group. , mercapto, fluorenyl, undecyl, 1-methylindenyl, dodecyl, 1-methylundecyl, 1-ethylindenyl, thirteenyl, tetradecyl, tertiary , fifteen, 1-heptyloctyl, hexadecanyl, octadecyl, eicosyl-1-yl, docosa-1-yl, docosa-1-yl, twenty-four Alkyl-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, and a 1-pentenyl group. -pentenyl, 1-hexenyl, 2-ethyl-2-butenyl, 2-octenyl, (4-vinyl)-5-hexenyl, 2-decenyl and the like. Further, as the alkynyl group, for example, Alkynyl, 1-propynyl, 1-butynyl, 1-pentynyl, 3-pentynyl, 1-hexynyl, 2-ethyl-2-butynyl, 2-octynyl, (4-ethynyl)-5-hexynyl, 2-decynyl and the like. In addition, as a group having a bond group selected from -CO-, -COO-, and -CONH- between the CC bonds of the aliphatic hydrocarbon group, for example, an ethyl (meth)acrylate group (A) may be mentioned. A propyl acrylate group, a (meth) acrylamide ethyl group, a (meth) acrylamide propyl group, or the like.
作為脂環式烴基,碳數3~30的脂環式烴基較為理想。脂環式烴基可為飽和也可為不飽和,具體而言,可舉出環烷基、環烯基、縮合多環烴基、交聯環烴基、螺烴基、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、三級丁基環己基、環庚基、環辛基等之環烷基;1-環己烯基等之環烯基;三環癸基、十氫-2-萘基、金剛烷基等之縮合多環烴基;三環[5.2.1.02,6]癸烷-8-基、五環十五基、異莰基、二環戊烯基、三環戊烯基等之交聯環烴基;自螺[3,4]庚烷、螺[3,4]辛烷除去1個氫原子而成的1價基等之螺烴基;自對薄荷烷、側柏烷、長松針烷等除去1個氫原子而成的1價基等之環狀萜烯烴基等。在前述環烷基及環烯基中,碳數為3~12更為理想。 As the alicyclic hydrocarbon group, an alicyclic hydrocarbon group having 3 to 30 carbon atoms is preferred. The alicyclic hydrocarbon group may be saturated or unsaturated, and specific examples thereof include a cycloalkyl group, a cycloalkenyl group, a condensed polycyclic hydrocarbon group, a crosslinked cyclic hydrocarbon group, a spirohydrocarbyl 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 tert-butylcyclohexyl group, a cycloheptyl group or a cyclooctyl group; a 1-cyclohexenyl group; a cycloalkenyl group; a condensed polycyclic hydrocarbon group such as a tricyclodecanyl group, a decahydro-2-naphthyl group, an adamantyl group or the like; a tricyclo[5.2.1.0 2,6 ]decane-8-yl group, a pentacyclic group a cross-linked cyclic hydrocarbon group such as an isodecyl group, a dicyclopentenyl group or a tricyclopentenyl group; a 1 obtained by removing one hydrogen atom from spiro[3,4]heptane or spiro[3,4]octane A spirohydrocarbyl group such as a valent group; and a cyclic terpene group such as a monovalent group obtained by removing one hydrogen atom from menthane, albino, and long pine. Among the above cycloalkyl groups and cycloalkenyl groups, a carbon number of 3 to 12 is more preferable.
作為芳香族烴基,以碳數為6~20者為佳,6~10者為更佳。作為芳香族烴基,具體而言,可舉出芳基。在此,本發明書中「芳基」,係指單環~3環式芳香族烴基,具體而言,可舉出苯基、苯甲基、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, those having a carbon number of 6 to 20 are preferred, and those having 6 to 10 are more preferred. Specific examples of the aromatic hydrocarbon group include an aryl group. Here, the "aryl group" in the present invention means a monocyclic to 3-ring aromatic hydrocarbon group, and specific examples thereof include a phenyl group, a benzyl group, an o-tolyl group, a m-tolyl group, and a p-tolyl group. Xylyl, naphthyl, anthracenyl, phenanthryl, anthracenyl, 9-fluorenyl and the like.
作為R1~R4的雜環基,只要為1價的雜環則沒有特別限定,但較佳為3員環至10員環的單環式或縮合二環式的雜環基,具體而言,可舉出環氧乙烷基、環氧丙烷基、吡咯啶基、咪唑啶基、吡唑啶基、啉基、硫代啉基(thiomorpholinyl)、哌啶基、N-六氫吡啶基、哌基、高哌基(homopiperazinyl)、1,3-二氧戊環-2-基等之脂環式雜環基、吡啶基、吡基、嘧啶基、嗒基、喹啉基、異喹啉基、呔基、啶基、喹啉基、咪唑基、吡唑基、***基、四唑基、噻唑基、苯并噻唑基、唑基、吲哚基、吲唑基、苯并咪唑基、鄰苯二甲醯亞胺、噻吩基、呋喃基、哌喃基、嘌呤基等之芳香族雜環基。 The heterocyclic group of R 1 to R 4 is not particularly limited as long as it is a monovalent heterocyclic ring, and is preferably a monocyclic or condensed bicyclic heterocyclic group having a ring of 3 to 10 members, specifically Examples thereof include an oxiranyl group, an oxypropylene group, a pyrrolidinyl group, an imidazolidinyl group, and a pyrazolyl group. Olinyl, thio Thiomorpholinyl, piperidinyl, N-hexahydropyridyl, piperazine Base, high piper An alicyclic heterocyclic group such as homopiperazinyl or 1,3-dioxolan-2-yl, pyridyl, pyridyl Base, pyrimidinyl, oxime Base, quinolyl, isoquinolyl, anthracene base, Pyridyl, quin Lolinyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, thiazolyl, benzothiazolyl, An aromatic heterocyclic group such as an azolyl group, a fluorenyl group, a carbazolyl group, a benzimidazolyl group, a phthalimide group, a thienyl group, a furyl group, a piperidyl group or a fluorenyl group.
其中,作為R1~R4,較佳為烴基。作為該烴基,較佳為脂肪族烴基、芳香族烴基,更佳為R1~R4均為芳香族烴基之態樣、R1及R4為芳香族烴基且R2及R3為脂肪族烴基之態樣。 Among them, R 1 to R 4 are preferably a hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group, more preferably R 1 to R 4 are all aromatic hydrocarbon groups, R 1 and R 4 are aromatic hydrocarbon groups, and R 2 and R 3 are aliphatic. The aspect of the hydrocarbon group.
R5若為一價基的話則沒有特別限定,但較佳為包含雜原子的一價基,例如,可舉出-CO2 -、-CO2H、-CO2M、-CO2R6、-SO3 -、-SO3H、-SO3M、-SO3R7、-SO2NHR8、-SO2NR9R10、-SO2-O-N=CR11R12、-SO2NHNHR13、-SO2SR14、-SO2NHSO2R15。在此,R6~R11及R13~R15相互獨立地表示經取代或非經取代的烴基,R12表示氫原子、或經取代或非經取代的烴基,M表示鈉原子或鉀原子。 R 5 is not particularly limited as long as it is a monovalent group, but is preferably a monovalent group containing a hetero atom, and examples thereof include -CO 2 - , -CO 2 H, -CO 2 M, and -CO 2 R 6 . , -SO 3 - , -SO 3 H, -SO 3 M, -SO 3 R 7 , -SO 2 NHR 8 , -SO 2 NR 9 R 10 , -SO 2 -ON=CR 11 R 12 , -SO 2 NHNHR 13 , -SO 2 SR 14 , -SO 2 NHSO 2 R 15 . Here, R 6 to R 11 and R 13 to R 15 each independently represent a substituted or unsubstituted hydrocarbon group, R 12 represents a hydrogen atom, or a substituted or unsubstituted hydrocarbon group, and M represents a sodium atom or a potassium atom. .
作為R6~R11及R13~R14的烴基,較佳為脂肪族烴基、芳香族烴基,更佳為碳數1~30的烷基、碳數6~30的芳基。該烷基的碳數較佳為1~24,更佳為1~18。該芳基的碳數較佳為6~20,更佳為6~10。 The hydrocarbon group of R 6 to R 11 and R 13 to R 14 is preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group, more preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. The alkyl group preferably has 1 to 24 carbon atoms, more preferably 1 to 18 carbon atoms. The carbon number of the aryl group is preferably from 6 to 20, more preferably from 6 to 10.
作為R12,較佳為脂肪族烴基,更佳為碳數1~24的烷基,特佳為碳數1~12的烷基特佳。 R 12 is preferably an aliphatic hydrocarbon group, more preferably an alkyl group having 1 to 24 carbon atoms, particularly preferably an alkyl group having 1 to 12 carbon atoms.
作為R15,較佳為脂肪族烴基、芳香族烴基,更佳為碳數1~20的烷基、碳數6~10的芳基。 R 15 is preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group, more preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 10 carbon atoms.
作為該等烴基的具體例,可舉出與前述相同者。 Specific examples of the hydrocarbon groups include the same as described above.
R1~R4及R6~R15的烴基、及R1~R4的雜環基,在不超出本發明之主旨的範圍內,可進一步具有取代基。取代基的位置及數目為任意,具有2個以上的取代基時,該取代基可為相同亦可為不同。作為這樣的取代基,可舉出鹵原子、羥基、氰基、甲醯基、羧基、硝基、胺基、硫醇基、烷氧基、芳氧基、烷硫基、芳硫基、N取代胺基、醯胺基、烷羰基、烷氧羰基、烷磺醯基、烷基胺磺醯基、三烷基矽基、脂肪族烴基、脂環式烴基、芳香族烴基、雜環基等。該等之取代基,亦可進一步具有取代基。 R 1 ~ R 4 and R 6 ~ R 15 is a hydrocarbon group, and R 1 ~ R 4 is heterocyclyl, without departing the scope of the gist of the present invention may further have a substituent. When the position and the number of the substituent are arbitrary, and when there are two or more substituents, the substituent may be the same or different. Examples of such a substituent include a halogen atom, a hydroxyl group, a cyano group, a decyl group, a carboxyl group, a nitro group, an amine group, a thiol group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, and N. Substituted amine, amidino, alkylcarbonyl, alkoxycarbonyl, alkanesulfonyl, alkylaminesulfonyl, trialkylsulfonyl, aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, heterocyclic, etc. . These substituents may further have a substituent.
作為前述鹵原子,可舉出氟原子、氯原子、溴原子、碘原子。 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
作為烷氧基,可舉出甲氧基、乙氧基、丙氧基、丁氧基、己氧基、2-乙基己氧基、辛氧基、十二烷氧基、三級十二烷氧基等之C1-12烷氧基。作為芳氧基,可舉出苯氧基、苯甲氧基等。 Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, a 2-ethylhexyloxy group, an octyloxy group, a dodecyloxy group, and a tertiary triode. A C 1-12 alkoxy group such as an alkoxy group. Examples of the aryloxy group include a phenoxy group and a benzyloxy group.
作為烷硫基,可舉出甲硫基、乙硫基、丙硫基、異丙硫基、丁硫基、異丁硫基、戊硫基、異戊硫基、新戊硫基、環戊硫基、己硫基、環己硫基、庚硫基、環庚硫基、辛硫基、2-乙基己硫基、環辛硫基、壬硫基、癸硫基、三環癸硫基、甲氧基丙硫基、乙氧基丙硫基、己氧基丙硫基、2-乙基己氧基丙硫基、甲氧己硫基、十一烷硫基、十二烷硫基、十四烷硫基、三級十二烷硫基、十六烷硫基、十八烷硫基等之C1-20烷硫基。作為芳硫基,可舉出苯硫基等。 Examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, an isobutylthio group, a pentylthio group, an isopentylthio group, a neopentylthio group, and a cyclopentyl group. Sulfur, hexylthio, cyclohexylthio, heptylthio, cycloheptylthio, octylthio, 2-ethylhexylthio, cyclooctylthio, sulfonylthio, sulfonylthio, tricyclic sulfonium sulfide Base, methoxypropylthio, ethoxypropylthio, hexyloxypropylthio, 2-ethylhexyloxypropylthio, methoxyhexylthio, undecylthio, dodecyl sulfur A C 1-20 alkylthio group such as a tetradecylthio group, a tertiary dodecylthio group, a hexadecylthio group or an octadecylthio group. Examples of the arylthio group include a phenylthio group and the like.
作為N取代胺基的取代基,可舉出C1-6烷基、C6-10芳基等,作為具體例,可舉出與前述相同者。 Examples of the substituent of the N-substituted amino group include a C 1-6 alkyl group and a C 6-10 aryl group. Specific examples thereof include the same as described above.
作為烷羰基,可舉出甲羰基、乙羰基、丙羰基、丁羰基等之C1-6烷羰基。 The alkylcarbonyl group may, for example, be a C 1-6 alkylcarbonyl group such as a methylcarbonyl group, an ethyl carbonyl group, a propylcarbonyl group or a butylated carbonyl group.
作為烷氧羰基,例如,可舉出甲氧羰基、乙氧羰基、丙氧羰基、丁氧羰基、己氧羰基、環己氧羰基、2-乙基己氧羰基、十二烷羰基、十八烷羰基等之C1-20烷氧羰基。 Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a hexyloxycarbonyl group, a cyclohexyloxycarbonyl group, a 2-ethylhexyloxycarbonyl group, a dodecylcarbonyl group, and an octadecyl group. A C 1-20 alkoxycarbonyl group such as an alkylcarbonyl group.
作為烷磺醯基,例如,可舉出甲磺醯基、乙磺醯基、己磺醯基、癸磺醯基、十一烷磺醯基、十二烷磺醯基、十四烷磺醯基、三級十二烷磺醯基、十六烷磺醯基、十八烷磺醯基等之C1-20烷基磺醯基。 Examples of the alkanesulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, a hexylsulfonyl group, a sulfonyl group, an undecanesulfonyl group, a dodecylsulfonyl group, and a tetradecanesulfonate group. A C 1-20 alkylsulfonyl group such as a benzylidene group, a tridecanesulfonyl group, a hexadecane sulfonyl group or an octadecylsulfonyl group.
作為烷基胺磺醯基,可舉出甲基胺磺醯基、乙基胺磺醯基、二甲基胺磺醯基、丙基胺磺醯基、異丙基胺磺醯基、丁基胺磺醯基、己基胺磺醯基、辛基胺磺醯基、2-乙基己基胺磺醯基、十一烷基胺磺醯基、十二 烷基胺磺醯基、1-庚基辛基胺磺醯基等之C1-20烷基胺磺醯基。 Examples of the alkylamine sulfonyl group include methylamine sulfonyl group, ethylamine sulfonyl group, dimethylamine sulfonyl group, propylamine sulfonyl group, isopropylamine sulfonyl group, and butyl group. Aminesulfonyl, hexylamine sulfonyl, octylamine sulfonyl, 2-ethylhexylamine sulfonyl, undecylamine sulfonyl, dodecylamine sulfonyl, 1-heptyl A C 1-20 alkylamine sulfonyl group such as an octylamine sulfonyl group.
作為三烷基矽基,可舉出三甲基矽基等之三C1-6烷矽基。 The trialkylsulfonyl group may be a tri-C 1-6 alkanofluorenyl group such as a trimethylsulfonyl group.
作為脂肪族烴基、芳香族烴基及雜環基的具體例,可舉出與前述相同者。 Specific examples of the aliphatic hydrocarbon group, the aromatic hydrocarbon group and the heterocyclic group are the same as those described above.
m為0~5的整數,但較佳為0~3,更佳為1或2。 m is an integer of 0 to 5, but is preferably 0 to 3, more preferably 1 or 2.
又,式(1)的R1~R4中之1個以上需要為選自於下述要件(i)~(v)的基。 Further, one or more of R 1 to R 4 in the formula (1) need to be a group selected from the following requirements (i) to (v).
(i)為經取代或非經取代的不飽和脂肪族烴基、或是經取代或非經取代的不飽和脂環式烴基。但是,不飽和脂肪族烴基亦可在C-C鍵之間具有選自於-CO-、-COO-及-CONH-中的鍵聯基。 (i) is a substituted or unsubstituted unsaturated aliphatic hydrocarbon group, or a substituted or unsubstituted unsaturated alicyclic hydrocarbon group. However, the unsaturated aliphatic hydrocarbon group may have a linking group selected from -CO-, -COO-, and -CONH- between C-C bonds.
(ii)為以不飽和脂肪族烴基取代的脂環式烴基、或是以不飽和脂肪族烴基或不飽和脂環式烴基取代的芳香族烴基。 (ii) is an alicyclic hydrocarbon group substituted with an unsaturated aliphatic hydrocarbon group, or an aromatic hydrocarbon group substituted with an unsaturated aliphatic hydrocarbon group or an unsaturated alicyclic hydrocarbon group.
(iii)為經取代或非經取代的雜環基、或是以雜環基取代的烴基。 (iii) is a substituted or unsubstituted heterocyclic group or a hydrocarbon group substituted with a heterocyclic group.
(iv)為以選自於取代基群α之至少1種取代的烴基。 (iv) is a hydrocarbon group substituted with at least one selected from the group of substituents α.
(v)為碳數11以上之經取代或非經取代的脂肪族烴基。 (v) is a substituted or unsubstituted aliphatic hydrocarbon group having a carbon number of 11 or more.
作為要件(i)及(ii)的不飽和脂肪族烴基,可舉出與前述相同者,但其中較佳為烯基。其碳數較佳為2~20,更佳為2~10,特佳為2~6。 The unsaturated aliphatic hydrocarbon group of the requirements (i) and (ii) is the same as the above, but among them, an alkenyl group is preferred. The carbon number is preferably from 2 to 20, more preferably from 2 to 10, and particularly preferably from 2 to 6.
作為要件(i)及(ii)的不飽和脂環式烴基,可舉出與前述相同者,但其中較佳為環烯基。其碳數較佳為4~8,更佳為5或6。 The unsaturated alicyclic hydrocarbon group as the requirements (i) and (ii) is the same as the above, but among them, a cycloalkenyl group is preferred. The carbon number is preferably 4 to 8, more preferably 5 or 6.
作為要件(iii)的雜環基,可舉出與前述相同者,但脂環式雜環基較為理想。又,作為要件(iv)的烴基,較佳為飽和烴基,更佳為飽和脂肪族烴基。飽和脂肪族烴基的碳數較佳為1~20,更佳為1~10,特佳為2~6。 The heterocyclic group of the element (iii) is the same as the above, but an alicyclic heterocyclic group is preferred. Further, as the hydrocarbon group of the element (iv), a saturated hydrocarbon group is preferred, and a saturated aliphatic hydrocarbon group is more preferred. The carbon number of the saturated aliphatic hydrocarbon group is preferably from 1 to 20, more preferably from 1 to 10, particularly preferably from 2 to 6.
作為要件(iv)的取代基群α,更佳為-CN、-NO2。又,作為要件(iv)的烴基,較佳為脂肪族烴基、芳香族烴基。前述脂肪族烴基的碳數較佳為1~20,更佳為1~10,特佳為2~6。 The substituent group α as the element (iv) is more preferably -CN or -NO 2 . Further, the hydrocarbon group of the component (iv) is preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The carbon number of the aliphatic hydrocarbon group is preferably from 1 to 20, more preferably from 1 to 10, particularly preferably from 2 to 6.
要件(v)的碳數11以上之脂肪族烴基可為飽和亦可為不飽和。具體而言,可舉出與前述相同者中之碳數為11以上的飽和脂肪族烴基及不飽和脂肪族烴基。前述脂肪族烴基的碳數較佳為11~20,更佳為11~16。作為要件(v)的取代基,可舉出鹵原子、羥基、氰基、甲醯基、羧基、硝基、胺基、硫醇基、烷氧基、芳氧基、烷硫基、芳硫基、N取代胺基、烷羰基、烷氧羰基、烷磺醯基、烷基胺磺醯基、三烷基矽基、脂環式烴基、芳香族烴基、雜環基等。作為該等取代基的具體例,可舉出與前述相同者。 The aliphatic hydrocarbon group having a carbon number of 11 or more in the element (v) may be saturated or unsaturated. Specifically, a saturated aliphatic hydrocarbon group and an unsaturated aliphatic hydrocarbon group having 11 or more carbon atoms in the same manner as described above are mentioned. The carbon number of the aliphatic hydrocarbon group is preferably from 11 to 20, more preferably from 11 to 16. The substituent of the element (v) may, for example, be a halogen atom, a hydroxyl group, a cyano group, a decyl group, a carboxyl group, a nitro group, an amine group, a thiol group, an alkoxy group, an aryloxy group, an alkylthio group or an aromatic sulfur. A group, an N-substituted amino group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkanesulfonyl group, an alkylaminesulfonyl group, a trialkylsulfonyl group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group or the like. Specific examples of the substituents include the same as described above.
前述要件(i)~(v)之中,R1~R4中之1個以上較佳為經取代或非經取代的不飽和脂肪族烴基、以不飽和脂肪族烴基取代的芳香族烴基、以雜環基取代的烴基、以選自於取代基群α中之至少1種取代的脂肪族烴基或 芳香族烴基、碳數11以上之經取代或非經取代的脂肪族烴基,更佳為經取代或非經取代的不飽和脂肪族烴基、以不飽和脂肪族烴基取代的芳香族烴基、以選自於取代基群α中之至少1種取代的脂肪族烴基或芳香族烴基。 Among the above-mentioned requirements (i) to (v), one or more of R 1 to R 4 are preferably a substituted or unsubstituted unsaturated aliphatic hydrocarbon group, an aromatic hydrocarbon group substituted with an unsaturated aliphatic hydrocarbon group, More preferably, the hydrocarbon group substituted with a heterocyclic group, the aliphatic hydrocarbon group or aromatic hydrocarbon group substituted with at least one selected from the substituent group α, and the substituted or unsubstituted aliphatic hydrocarbon group having a carbon number of 11 or more. A substituted or unsubstituted unsaturated aliphatic hydrocarbon group, an aromatic hydrocarbon group substituted with an unsaturated aliphatic hydrocarbon group, or an aliphatic hydrocarbon group or an aromatic hydrocarbon group substituted with at least one selected from the substituent group α.
作為式(1)所示的結構,例如,可舉出以下的結構。其中較佳為結構式(a1)、(a10)、(a16)、(a17)、(a19)、(a20)、(a22)、(a39)~(a45)。但Ra係表示2-乙基己基。 The structure represented by the formula (1) is, for example, the following structure. Among them, structural formulas (a1), (a10), (a16), (a17), (a19), (a20), (a22), (a39) to (a45) are preferred. However, R a represents 2-ethylhexyl.
式(1)所示的結構為陽離子性時,具有式(1)所示的結構之化合物成為電中性,且具有陰離子。作為該陰離子,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、甲基金屬化合物陰離子等。更具體而言,例如,可舉出日本特表2007-503477號公報所記載的陰離子。 When the structure represented by the formula (1) is cationic, the compound having the structure represented by the formula (1) is electrically neutral and has an anion. 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, and a methyl metal compound anion. More specifically, for example, an anion described in JP-A-2007-503477 can be cited.
式(1)所示的結構為陰離子性時,具有式(1)所示的結構之化合物成為電中性,且具有陽離子。作為該陽離子,例如,可舉出金屬陽離子、鎓陽離子等。作為金屬陽離子,例如,可舉出鋰離子、鈉離子、鉀離子等之1價的金屬陽離子、鎂離子、鈣離子等之2價的金屬陽離子。作為鎓陽離子,可舉出銨陽離子、鋶陽離子等。作為前述銨陽離子,例如,可舉出四甲基銨、四乙基銨、單硬脂基三甲基銨、二硬脂基二甲基銨、三硬脂基單甲基銨、鯨蠟基三甲基銨、三辛基甲基銨、二辛基二甲基銨、單月桂基三甲基銨、二月桂基二甲基銨、三月桂基甲基銨、三戊基苯甲基銨、三己基苯甲基銨、三辛基苯甲基銨、三月桂基苯甲基銨、苯甲基二甲基硬脂基銨、苯甲基二甲基辛基銨、二烷基(烷基為C14~C18)二甲基銨等。作為前述鋶陽離子,例如,可舉出甲基三辛基鋶、辛基三丁基鋶、十二基三丁基鋶、十六基三丁基鋶、二己基二辛基鋶等之四烷基鋶、苯甲基三丁基鋶等之芳基三烷基鋶、二丁基二苯基鋶等之二烷基二芳基鋶、丁基三苯基鋶等之烷基三苯基鋶、苯甲基三苯基鋶等之四芳基鋶等。 When the structure represented by the formula (1) is anionic, the compound having the structure represented by the formula (1) is electrically neutral and has a cation. Examples of the cation include a metal cation, a phosphonium cation, and the like. Examples of the metal cation include a monovalent metal cation such as a lithium ion, a sodium ion, and a potassium ion, and a divalent metal cation such as a magnesium ion or a calcium ion. Examples of the phosphonium cation include an ammonium cation, a phosphonium cation, and the like. Examples of the ammonium cation include tetramethylammonium, tetraethylammonium, monostearyltrimethylammonium, distearyldimethylammonium, tristea monomethylammonium, and cetyl. Trimethylammonium, trioctylmethylammonium, dioctyldimethylammonium, monolauryltrimethylammonium, dilauryldimethylammonium, trilaurylmethylammonium, triamylbenzylammonium , trihexylbenzylammonium, trioctylbenzylammonium, trilaurylbenzylammonium, benzyldimethyldimethylammonium, benzyldimethyloctylammonium, dialkyl (alkane) The base is C14~C18) dimethylammonium and the like. Examples of the phosphonium cation include tetradecane such as methyltrioctylfluorene, octyltributylphosphonium, dodecyltributylphosphonium, hexadecyltributylphosphonium, and dihexyldioctylfluorene. An alkyltriphenylphosphonium such as an aryltrialkylsulfonium such as an aryltrialkylsulfonium such as benzyltributylphosphonium or a dialkyldiarylsulfonium such as dibutyldiphenylphosphonium or a butyltriphenylphosphonium. And tetraaryl fluorene such as benzyltriphenylphosphonium.
本著色劑可利用適當的方法進行製造,例如,可舉出與日本特開2010-254964號公報的實施例、日本特開2013-011869號公報的實施例3同樣的方法。如前述進行而得到的本著色劑,對以環己酮等之酮為例的各種有機溶媒為可溶,而且具有優異的耐熱性。 The coloring agent can be produced by an appropriate method, and examples thereof include the same methods as those in Example 3 of JP-A-2010-254964, and JP-A-2013-011869. The coloring agent obtained as described above is soluble in various organic solvents exemplified by ketones such as cyclohexanone, and has excellent heat resistance.
在本發明中,本著色劑可單獨使用或混合2種以上而使用。 In the present invention, the coloring agent may be used singly or in combination of two or more.
本發明的著色組成物包含本著色劑作為著色劑,同時可進一步包含其他著色劑。作為其他著色劑,並沒有特別限定,可因應用途適當選擇色彩或材質。 The coloring composition of the present invention contains the present colorant as a coloring agent, and may further contain other coloring agents. The other coloring agent is not particularly limited, and the color or material can be appropriately selected depending on the application.
作為其他的著色劑,也可使用任何顏料、本著色劑以外的染料及天然色素,但在得到輝度及色純度高的畫素之意義中,較佳為有機顏料、有機染料,特佳為有機顏料。 As the other coloring agent, any pigment, a dye other than the coloring agent, and a natural coloring matter may be used. However, in the sense of obtaining a pixel having high luminance and high color purity, organic pigments and organic dyes are preferred, and organic pigments are preferred. pigment.
作為有機顏料,例如,可舉出在色指數(C.I.;The Society of Dyers and Colourists公司發行)中分類為顏料的化合物,亦即,附有如下述的色指數(C.I.)號碼者。 As the organic pigment, for example, a compound classified as a pigment in a color index (C.I.; issued by The Society of Dyers and Colourists), that is, a color index (C.I.) number as described below is attached.
C.I.顏料紅166、C.I.顏料紅177、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16、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179、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.顏料橘38;C.I.顏料紫23。 CI Pigment Red 166, CI Pigment Red 177, 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 16, 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 179, CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Yellow 211, CI Pigment Yellow 215; CI Pigment Orange 38; CI Pigment Violet 23.
其他可舉出記載於日本特開2001-081348號公報、日本特開2010-026334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號公報等的色澱顏料。 Others are disclosed in JP-A-2001-081348, JP-A-2010-026334, JP-A-2010-237384, JP-A-2010-237569, and JP-A-. A lake pigment such as Japanese Laid-Open Patent Publication No. 2011-145346.
又,作為前述染料,以三芳基甲烷系染料、蒽醌系染料、偶氮系染料等較為理想。更具體而言,可舉出記載於國際公開第10/123071號公報、日本特開2011-116803號公報、日本特開2011-117995號公報、日本特開2011-133844號公報、日本特開2011-174987號公報等的有機染料。 Further, as the dye, a triarylmethane dye, an anthraquinone dye, an azo dye or the like is preferable. More specifically, Japanese Laid-Open Patent Publication No. 2011-116803, JP-A-2011-117995, JP-A-2011-133844, and JP-A-2011 An organic dye such as No. 174987.
本發明的著色組成物以用於藍色畫素之形成較為理想。該情況中,以包含本著色劑作為(A)著色劑,同時包含選自於含有藍色顏料、藍色染料、紫色顏料及紫色染料之群組中的至少1種作為其他著色劑較為理想。該情況中,本著色劑之含有比例在全著色劑中宜為0.1~80質量%,較佳為1~80質量%,更佳為5~60質量%,特佳為10~40質量%。 The colored composition of the present invention is preferably used for the formation of blue pixels. In this case, it is preferable to contain at least one selected from the group consisting of a blue pigment, a blue dye, a violet pigment, and a violet dye as the other coloring agent, including the coloring agent as the coloring agent (A). In this case, the content ratio of the coloring agent is preferably from 0.1 to 80% by mass, preferably from 1 to 80% by mass, more preferably from 5 to 60% by mass, particularly preferably from 10 to 40% by mass, based on the total coloring agent.
在本發明中,也可將任意混合之其他的顏料,利用再結晶法、再沉澱法、溶劑清洗法、昇華法、真空加熱法或該等之組合進行精製而使用。又,該等顏料,根據所需,亦可將其粒子表面以樹脂進行改質而使用。作為將顏料之粒子表面予以改質的樹脂,例如,可舉出記載於日本特開2001-108817號公報的載體樹脂、或市售之各種的顏料分散用之樹脂。作為碳黑表面的樹脂被覆方法,例如,可採用記載於日本特開平9-71733號公報、日本特開平9-95625號公報、日本特開平9-124969號公報等的方法。又,有機顏料亦可利用所謂 的鹽磨,將一次粒子細微化而使用。作為鹽磨的方法,例如,可採用揭露於日本特開平08-179111號公報的方法。 In the present invention, any other pigment which is optionally mixed may be used by a recrystallization method, a reprecipitation method, a solvent cleaning method, a sublimation method, a vacuum heating method, or a combination thereof. Further, these pigments may be used by modifying the surface of the particles with a resin as needed. Examples of the resin for modifying the surface of the pigment particles include a carrier resin described in JP-A-2001-108817, and various commercially available resins for pigment dispersion. For example, a method of coating the surface of the carbon black, for example, a method disclosed in JP-A-H09-71733, JP-A-9-95625, JP-A-9-124969, and the like can be employed. Also, organic pigments can also use so-called The salt mill uses the primary particles to be fine. As a method of salt milling, for example, a method disclosed in Japanese Laid-Open Patent Publication No. Hei 08-179111 can be employed.
又,在本發明中,含有任意混合之其他的著色劑,同時也可進一步含有周知的分散劑及分散助劑。作為周知的分散劑,例如,可舉出胺基甲酸酯系分散劑、聚乙烯亞胺系分散劑、聚氧乙烯烷酯系分散劑、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,而且作為分散助劑,可舉出顏料衍生物等。 Further, in the present invention, other coloring agents which are arbitrarily mixed may be contained, and a known dispersing agent and dispersing aid may be further contained. Examples of the known dispersant include a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ester dispersant, a polyoxyethylene alkyl phenyl ether dispersant, and a polydispersant. A glycol diester dispersing agent, a sorbitan fatty acid ester dispersing agent, a polyester dispersing agent, an acrylic dispersing agent, etc., and a dispersing auxiliary agent, a pigment derivative etc. are mentioned.
如前述的分散劑,可以商業方式取得,例如,作為丙烯酸系分散劑,可舉出Disperbyk-2000、Disperbyk-2001、BYK-LPN6919、BYK-LPN21116、BYK-LPN21324(以上為BYK公司製)等;作為胺基甲酸酯系分散劑,可舉出Disperbyk-161、Disperbyk-162、Disperbyk-165、Disperbyk-167、Disperbyk-170、Disperbyk-182(以上、BYK公司製)、Solsperse 76500(Lubrizol(股)公司製)等;作為聚乙烯亞胺系分散劑,可舉出Solsperse 24000(Lubrizol(股)公司製)等;作為聚酯系分散劑,可舉出Ajisper PB821、Ajisper PB822、Ajisper PB880、Ajisper PB881(以上為Ajinomoto Fine-Techno(股)公司製)等。 The above-mentioned dispersing agent can be obtained commercially, and examples of the acrylic dispersing agent include Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (above, BYK), and the like; Examples of the urethane-based dispersant include Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, BYK), and Solsperse 76500 (Lubrizol) As a polyethyleneimine-based dispersing agent, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.) or the like; and polyester-based dispersing agent, Ajisper PB821, Ajisper PB822, Ajisper PB880, Ajisper PB881 (above is Ajinomoto Fine-Techno Co., Ltd.) and the like.
又,作為前述顏料衍生物,具體而言,可舉出銅鈦花青、二酮吡咯并吡咯、喹酞酮的磺酸衍生物等。 In addition, specific examples of the pigment derivative include a copper methocyanine, a diketopyrrolopyrrole, and a sulfonic acid derivative of quinacridone.
在本發明中,其他的著色劑可單獨使用或混合2種以上而使用。 In the present invention, other coloring agents may be used singly or in combination of two or more.
含有其他著色劑時,其他著色劑的含有比例,相對於著色劑之合計含量較佳為99.9質量%以下,更佳為99質量%以下,在更佳為95質量%以下,特佳為90質量%以下。下限值並沒有特別限定,只要為0.01質量%以上即可。 When the other coloring agent is contained, the content of the other coloring agent is preferably 99.9% by mass or less, more preferably 99% by mass or less, even more preferably 95% by mass or less, and particularly preferably 90% by mass based on the total amount of the coloring agent. %the following. The lower limit value is not particularly limited as long as it is 0.01% by mass or more.
從形成耐熱性、及輝度高且色純度優異的畫素、或是遮光性優異的黑色矩陣、黑色間隔件的觀點來看,(A)著色劑之含有比例,通常在著色組成物之固體成分中為5~70質量%,較佳為5~60質量%,更佳為10~40質量%。在此之固體成分係為後述溶媒以外的成分。 From the viewpoint of forming a pixel having high heat resistance, high luminance and excellent color purity, or a black matrix or a black spacer excellent in light shielding properties, (A) the content ratio of the coloring agent is usually a solid component of the coloring composition. The amount is 5 to 70% by mass, preferably 5 to 60% by mass, more preferably 10 to 40% by mass. The solid component here is a component other than the solvent described later.
作為本發明的(B)黏結劑樹脂,並沒有特別限定,但以具有羧基、酚性羥基等之酸性官能基的樹脂較為理想。其中,以具有羧基的聚合物(以下也稱為「含有羧基的聚合物」。)較為理想,例如,可舉出具有1個以上之羧基的烯性不飽和單體(以下也稱為「不飽和單體(b1)」。)與其他可共聚合的烯性不飽和單體(以下也稱為「不飽和單體(b2)」。)之共聚合物。 The (B) binder resin of the present invention is not particularly limited, but a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group is preferred. In particular, a polymer having a carboxyl group (hereinafter also referred to as a "carboxyl group-containing polymer") is preferable, and examples thereof include an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter also referred to as "no." Saturated monomer (b1)") a copolymer of a copolymerizable ethylenically unsaturated monomer (hereinafter also referred to as "unsaturated monomer (b2)").
作為前述不飽和單體(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)丙烯醯氧基乙酯]、ω-羧基聚己內酯單(甲基)丙烯酸酯、對乙烯苯甲酸等。 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.
該等之不飽和單體(b1)可單獨使用或混合2種以上而使用。 These unsaturated monomers (b1) can be used individually or in mixture of 2 or more types.
又,作為前述不飽和單體(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N-位取代馬來醯亞胺; 如苯乙烯、α-甲基苯乙烯、對羥基苯乙烯、對羥基-α-甲基苯乙烯、對乙烯基苯甲基環氧丙基醚、苊烯之芳香族乙烯化合物;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-羥乙酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸苯甲酯、聚乙二醇(聚合度2~10)甲基醚(甲基)丙烯酸酯、聚丙二醇(聚合度2~10)甲基醚(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)丙烯酸異莰酯、(甲基)丙烯酸三環[5.2.1.02,6]癸-8-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、對異丙苯酚之環氧乙烷變性(甲基)丙烯酸酯、(甲基)丙烯酸環氧丙酯、(甲基)丙烯酸-3,4-環氧環己基甲酯、3-[(甲基)丙烯醯氧基甲基]氧環丁烷、3-[(甲基)丙烯醯氧基甲基]-3-乙基氧環丁烷之(甲基)丙烯酸酯;如環己基乙烯基醚、異莰基乙烯基醚、三環[5.2.1.02,6]癸烷-8-基乙烯基醚、五環十五基乙烯基醚、3-(乙烯氧基甲基)-3-乙基氧環丁烷之乙烯基醚; 如聚苯乙烯、聚(甲基)丙烯酸甲酯、聚(甲基)丙烯酸正丁酯、聚矽氧烷之在聚合物分子鏈之末端具有單(甲基)丙烯醯基的巨單體等。 Further, examples of the unsaturated monomer (b2) include N-position substituted maleimine such as N-phenylmaleimide and N-cyclohexylmaleimide; Ethylene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyloxypropyl ether, terpene aromatic vinyl compounds; such as (meth)acrylic acid Methyl ester, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, (methyl) Benzyl 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, isodecyl (meth) acrylate, ( Trimethyl [meth) acrylate [5.2.1.0 2,6 ] 癸-8-ester, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, (meth) acrylate-4- Hydroxyphenyl ester, p-isopropylphenol ethylene oxide denatured (meth) acrylate, (methyl) propyl Glycidyl acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-[(methyl)propenyloxymethyl]oxocyclobutane, 3-[(meth)propene a (meth) acrylate of methoxymethyl]-3-ethyloxycyclobutane; such as cyclohexyl vinyl ether, isodecyl vinyl ether, tricyclo [5.2.1.0 2,6 ] decane- 8-vinyl vinyl ether, pentacyclopentadecyl vinyl ether, vinyl ether of 3-(vinyloxymethyl)-3-ethyloxycyclobutane; such as polystyrene, poly(meth)acrylic acid A macromonomer having a mono(meth)acrylinyl group at the end of a polymer molecular chain, such as a methyl ester, n-butyl poly(meth)acrylate, or polyoxyalkylene.
該等之不飽和單體(b2)可單獨使用或混合2種以上而使用。 These unsaturated monomers (b2) can be used individually or in mixture of 2 or more types.
在不飽和單體(b1)與不飽和單體(b2)的共聚合物中,該共聚合物中之不飽和單體(b1)的共聚合比例宜為5~50質量%,更佳為10~40質量%。藉由在如前述的範圍內共聚合不飽和單體(b1),可得到鹼顯影性及保存安定性均優異的著色組成物。 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, more preferably 10~40% by mass. By copolymerizing the unsaturated monomer (b1) within the above range, a coloring composition excellent in both alkali developability and storage stability can be obtained.
作為不飽和單體(b1)與不飽和單體(b2)之共聚合物的具體例,例如,可舉出揭露於日本特開平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號公報等的共聚合物。 Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) are disclosed in Japanese Laid-Open Patent Publication No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A copolymer of the publication or the like.
又,在本發明中,例如,如日本特開平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號公報等所揭露,也可將在側鏈具有(甲基)丙烯醯基等之聚合性不飽和鍵之含有羧基的聚合物作為黏結劑樹脂使用。 In the present invention, for example, Japanese Laid-Open Patent Publication No. Hei 5-19467, Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. A polymer containing a carboxyl group having a polymerizable unsaturated bond such as a (meth) acrylonitrile group in a side chain may be used as a binder resin, as disclosed in JP-A-2008-181095.
本發明的黏結劑樹脂之以膠體滲透層析(以下簡稱為GPC。)(溶出溶媒:四氫呋喃)測定的聚苯乙烯換 算之重量平均分子量(Mw),通常為1,000~100,000,較佳為3,000~50,000。藉由成為如前述的態樣,可進一步提高被膜之殘膜率、圖案形狀、耐熱性、電特性、解析度,而且可以高水準抑制塗布時的乾燥異物之產生。 The polystyrene resin of the binder resin of the present invention is measured by colloidal permeation chromatography (hereinafter referred to as GPC) (dissolving solvent: tetrahydrofuran). The weight average molecular weight (Mw) is usually from 1,000 to 100,000, preferably from 3,000 to 50,000. According to the above aspect, 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 at the time of coating can be suppressed at a high level.
又,本發明的黏結劑樹脂之重量平均分子量(Mw)與數量平均分子量(Mn)之比(Mw/Mn)宜為1.0~5.0,更佳為1.0~3.0。再者,在此指的Mn為以GPC(溶出溶媒:四氫呋喃)測定的聚苯乙烯換算之數量平均分子量。 Further, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the binder resin of the present invention is preferably from 1.0 to 5.0, more preferably from 1.0 to 3.0. In addition, Mn referred to herein is a number average molecular weight in terms of polystyrene measured by GPC (eluent solvent: tetrahydrofuran).
本發明的黏結劑樹脂,可利用周知的方法進行製造,例如,也可利用揭露於日本特開2003-222717號公報、日本特開2006-259680號公報、國際公開第07/029871號公報等的方法,控制其結構或Mw、Mw/Mn。 The binder resin of the present invention can be produced by a known method. For example, it can be disclosed in Japanese Laid-Open Patent Publication No. 2003-222717, JP-A-2006-259680, and International Publication No. 07/029871. Method, control its structure or Mw, Mw / Mn.
在本發明中,黏結劑樹脂可單獨使用或混合2種以上而使用。 In the present invention, the binder resin may be used singly or in combination of two or more.
在本發明中,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50~150質量份。藉由成為如前述的態樣,可進一步提高鹼顯影性、著色組成物之保存安定性、色度特性。 In the present invention, the content of the binder resin is usually 10 to 1,000 parts by mass, preferably 20 to 500 parts by mass, more preferably 50 to 150 parts by mass, per 100 parts by mass of the (A) colorant. By the aspect as described above, the alkali developability, the storage stability of the colored composition, and the chromaticity characteristics can be further improved.
在本發明中,聚合性化合物係指具有2個以上之可聚合的基之化合物。作為可聚合的基,例如,可舉出烯性不飽和基、環氧乙烷基、氧雜環丁烷基、N-烷氧基甲基胺基等。在本發明中,作為聚合性化合物,以 具有2個以上之(甲基)丙烯醯基的化合物、或具有2個以上之N-烷氧基甲基胺基的化合物較為理想。 In the present invention, the polymerizable compound means a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, as a polymerizable compound, A compound having two or more (meth)acrylinyl groups or a compound having two or more N-alkoxymethylamino groups is preferred.
作為具有2個以上之(甲基)丙烯醯基的化合物之具體例,可舉出使脂肪族聚羥基化合物與(甲基)丙烯酸反應而得到的多官能(甲基)丙烯酸酯、經己內酯變性的多官能(甲基)丙烯酸酯、經環氧烷變性的多官能(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到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到之具有羧基的多官能(甲基)丙烯酸酯等。 Specific examples of the compound having two or more (meth)acryl fluorenyl groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid. An ester-denatured polyfunctional (meth) acrylate, an alkylene oxide-denatured polyfunctional (meth) acrylate, a polyfunctional amine group obtained by reacting a hydroxyl group-containing (meth) acrylate with a polyfunctional isocyanate An acid ester (meth) acrylate or a polyfunctional (meth) acrylate having a carboxyl group obtained by reacting a (meth) acrylate having a hydroxyl group with an acid anhydride.
在此,作為脂肪族聚羥基化合物,例如,可舉出如乙二醇、丙二醇、聚乙二醇、聚丙二醇之2價的脂肪族聚羥基化合物;如丙三醇、三羥甲基丙烷、季戊四醇、二季戊四醇之3價以上的脂肪族聚羥基化合物。作為前述具有羥基的(甲基)丙烯酸酯,例如,可舉出(甲基)丙烯酸-2-羥乙酯、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。作為前述多官能異氰酸酯,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二元酸的酐、苯均四酸酐、聯苯四羧酸二酐、二苯甲酮四羧酸二酐之四元酸二酐。 Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; for example, glycerin, trimethylolpropane, An aliphatic polyhydroxy compound having a trivalent or higher valence of pentaerythritol or dipentaerythritol. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, and pentaerythritol tri(meth)acrylate. Dipentaerythritol 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 anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, and pyromellitic anhydride. Tetracarboxylic acid dianhydride of benzenetetracarboxylic dianhydride and benzophenone tetracarboxylic dianhydride.
又,作為經己內酯變性的多官能(甲基)丙烯酸酯,例如,可舉出記載於日本特開平11-44955號公報之段落[0015]~[0018]的化合物。作為前述經環氧烷變性的多官能(甲基)丙烯酸酯,可舉出利用選自於環氧乙烷及環氧丙烷之至少1種進行變性的雙酚A二(甲基)丙烯酸酯、利用選自於環氧乙烷及環氧丙烷之至少1種進行變性的異三聚氰酸三(甲基)丙烯酸酯、利用選自於環氧乙烷及環氧丙烷之至少1種進行變性的三羥甲基丙烷三(甲基)丙烯酸酯、利用選自於環氧乙烷及環氧丙烷之至少1種進行變性的季戊四醇三(甲基)丙烯酸酯、利用選自於環氧乙烷及環氧丙烷之至少1種進行變性的季戊四醇四(甲基)丙烯酸酯、利用選自於環氧乙烷及環氧丙烷之至少1種進行變性的二季戊四醇五(甲基)丙烯酸酯、利用選自於環氧乙烷及環氧丙烷之至少1種進行變性的二季戊四醇六(甲基)丙烯酸酯等。 In addition, as the polyfunctional (meth) acrylate which is denatured by caprolactone, for example, a compound described in paragraphs [0015] to [0018] of JP-A-11-44955 is mentioned. The polyfunctional (meth) acrylate which is denatured with the alkylene oxide, bisphenol A di(meth)acrylate which is denatured by at least one selected from the group consisting of ethylene oxide and propylene oxide, Denaturation by using at least one selected from the group consisting of ethylene oxide and propylene oxide, and tris(meth)acrylate, which is selected from at least one of ethylene oxide and propylene oxide, is used. Trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate modified by at least one selected from the group consisting of ethylene oxide and propylene oxide, and selected from ethylene oxide Pentaerythritol tetra(meth)acrylate which is denatured by at least one of propylene oxide and dipentaerythritol penta (meth) acrylate which is denatured by at least one selected from the group consisting of ethylene oxide and propylene oxide It is selected from dipentaerythritol hexa(meth)acrylate which is denatured by at least one of ethylene oxide and propylene oxide.
又,作為具有2個以上之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。再者,三聚氰胺結構、苯并胍胺結構係指具有1個以上之三環或經苯基取代的三環作為基本骨架的化學結構,為也包含三聚氰胺、苯并胍胺或該等之縮合物的概念。作為具有2個以上之N-烷氧基甲基胺基的化合物之具體例,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)乙炔脲等。 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. Furthermore, the melamine structure and the benzoguanamine structure refer to having more than one of three Ring or three substituted by phenyl The chemical structure of the ring as a basic skeleton is a concept that also contains melamine, benzoguanamine or the like. 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)acetylene urea and the like.
該等聚合性化合物之中,以使3價以上之脂肪族聚羥基化合物與(甲基)丙烯酸反應而得到的多官能(甲基)丙烯酸酯、經己內酯變性的多官能(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)苯并胍胺較為理想。從著色層強度高、著色層之表面平滑性優異,且在未曝光部的基板上及遮光層上難以產生渣滓、膜殘留等之觀點來看,在使3價以上之脂肪族聚羥基化合物與(甲基)丙烯酸反應而得到的多官能(甲基)丙烯酸酯中,以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特為理想,在具有羧基的多官能(甲基)丙烯酸酯中,以使季戊四醇三丙烯酸酯與琥珀酸酐反應而得到的化合物、使二季戊四醇五丙烯酸酯與琥珀酸酐反應而得到的化合物特為理想。 Among these polymerizable compounds, a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound having a trivalent or higher value with (meth)acrylic acid, or a polyfunctional (methyl) modified by caprolactone 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 are preferred. The trivalent or higher aliphatic polyhydroxy compound is obtained from the viewpoint of high strength of the colored layer and excellent surface smoothness of the colored layer, and it is difficult to cause dross or film residue on the substrate of the unexposed portion and the light shielding layer. Among the polyfunctional (meth) acrylates obtained by the reaction of (meth)acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are particularly preferred. Among the polyfunctional (meth) acrylates having a carboxyl group, a compound obtained by reacting pentaerythritol triacrylate with succinic anhydride, and a compound obtained by reacting dipentaerythritol pentaacrylate with succinic anhydride are particularly preferable.
在本發明中,(C)聚合性化合物可單獨使用或混合2種以上而使用。 In the present invention, the (C) polymerizable compound may be used singly or in combination of two or more.
本發明的(C)聚合性化合物之含量,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,特佳為30~500質量份,最佳為50~150質量份。藉由成為如前述的態樣,可進一步提高硬化性、鹼顯影性,且可以高水準抑制在未曝光部的基板上或是遮光層上產生渣滓、膜殘留等。 The content of the (C) polymerizable compound of the present invention is preferably 10 to 1,000 parts by mass, more preferably 20 to 700 parts by mass, even more preferably 30 to 500 parts by mass, based on 100 parts by mass of the (A) coloring agent. Good for 50~150 parts by mass. According to the above aspect, the curability and the alkali developability can be further improved, and the occurrence of dross or film residue on the substrate of the unexposed portion or the light shielding layer can be suppressed at a high level.
在本發明的著色組成物中可含有光聚合起始劑。根據前述,可對著色組成物賦予感放射線性。在本發明使用的光聚合起始劑,係為利用可見光線、紫外線、遠紫外線、電子束、X射線等之放射線的曝光,產生能引發前述聚合性化合物的聚合的活性物種之化合物。 A photopolymerization initiator may be contained in the colored composition of the present invention. According to the foregoing, the coloring composition can be imparted with radiation. The photopolymerization initiator used in the present invention is a compound which emits an active species capable of initiating polymerization of the polymerizable compound by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, or X-ray.
作為如前述的光聚合起始劑,例如,可舉出噻吨酮系化合物、苯乙酮系化合物、聯咪唑系化合物、三系化合物、O-醯基肟系化合物、鎓鹽系化合物、苯偶姻系化合物、二苯甲酮系化合物、α-二酮系化合物、多核醌系化合物、重氮系化合物、醯亞胺磺酸酯系化合物等。 Examples of the photopolymerization initiator as described above include a thioxanthone compound, an acetophenone compound, a biimidazole compound, and the like. Compound, O-mercapto oxime compound, sulfonium salt compound, benzoin compound, benzophenone compound, α-diketone compound, polynuclear oxime compound, diazo compound, sulfimine sulfonate An acid ester compound or the like.
在本發明中,光聚合起始劑可單獨使用或混合2種以上而使用。作為光聚合起始劑,以選自於噻吨酮系化合物、苯乙酮系化合物、聯咪唑系化合物、三系化合物、O-醯基肟系化合物的群組中之至少1種較為理想。 In the present invention, the photopolymerization initiator may be used singly or in combination of two or more. The photopolymerization initiator is selected from the group consisting of a thioxanthone compound, an acetophenone compound, a biimidazole compound, and three At least one of the group of the compound and the O-mercapto lanthanide compound is preferred.
本發明之較理想的光聚合起始劑之中,作為噻吨酮系化合物的具體例,可舉出噻吨酮、2-氯噻吨酮、2-甲基噻吨酮、2-異丙基噻吨酮、4-異丙基噻吨酮、2,4-二氯噻吨酮、2,4-二甲基噻吨酮、2,4-二乙基噻吨酮、2,4-二異丙基噻吨酮等。 Among the preferable photopolymerization initiators of the present invention, specific examples of the thioxanthone-based compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and 2-isopropyl Thiophenone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4- Diisopropyl thioxanthone and the like.
又,作為前述苯乙酮系化合物的具體例,可舉出2-甲基-1-[4-(甲硫基)苯基]-2-N-啉基丙-1-酮、2-苯甲基-2-二甲胺基-1-(4-N-啉基苯基)丁-1-酮、2-(4- 甲基苯甲基)-2-(二甲胺基)-1-(4-N-啉基苯基)丁-1-酮等。 Further, specific examples of the acetophenone-based compound include 2-methyl-1-[4-(methylthio)phenyl]-2-N- Orolinyl propan-1-one, 2-benzyl-2-yldimethylamino-1-(4-N- Polinylphenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-N- Polinylphenyl)butan-1-one and the like.
又,作為前述聯咪唑系化合物的具體例,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-based 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, and the like.
再者,使用聯咪唑系化合物作為光聚合起始劑時,從改良感度的觀點來看,以併用氫予體較為理想。在此所稱的「氫予體」意指可對於利用曝光而自聯咪唑系化合物產生的自由基供予氫原子的化合物。作為氫予體,例如,可舉出2-硫醇基苯并噻唑、2-硫醇基苯并唑等之硫醇系氫予體、4,4'-雙(二甲胺基)二苯甲酮、4,4'-雙(二乙胺基)二苯甲酮等之胺系氫予體。在本發明中,氫予體可單獨使用或混合2種以上而使用,但從進一步改良感度的觀點來看,以組合1種以上的硫醇系氫予體與1種以上的胺系氫予體而使用較為理想。 Further, when a biimidazole-based compound is used as a photopolymerization initiator, it is preferred to use a hydrogen donor in combination from the viewpoint of improving the sensitivity. The term "hydrogen donor" as used herein means a compound which can supply a hydrogen atom to a radical generated from a biimidazole compound by exposure. As the hydrogen donor, for example, 2-thiol benzothiazole or 2-thiol benzo can be mentioned. An amine-based hydrogen donor such as a thiol-based hydrogen donor such as oxazole, 4,4'-bis(dimethylamino)benzophenone or 4,4'-bis(diethylamino)benzophenone . In the present invention, the hydrogen donor may be used alone or in combination of two or more. However, from the viewpoint of further improving the sensitivity, one or more kinds of thiol-based hydrogen donors and one or more amine-based hydrogens may be combined. It is ideal for use.
又,作為前述三系化合物的具體例,可舉出2,4,6-參(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-三等之具有鹵甲基的三系化合物。 Again, as the aforementioned three Specific examples of the compound include 2,4,6-para(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 of the halomethyl groups a compound.
又,作為O-醯基肟系化合物的具體例,可舉出1,2-辛烷二酮,1-[4-(苯硫基)苯基]-,2-(O-苯甲醯基肟)、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯基肟)、乙酮,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]-,1-(O-乙醯基肟)、乙酮,1-[9-乙基-6-{2-甲基-4-(2,2-二甲基-1,3-二氧雜環戊基)甲氧基苯甲醯基}-9H-咔唑-3-基]-,1-(O-乙醯基肟)等。作為O-醯基肟系化合物的市售品,也可使用NCI-831、NCI-930(以上為股份有限公司ADEKA公司製)、DFI-020、DFI-091(以上為DAITO CHEMIX股份有限公司製)等。 Further, specific examples of the O-fluorenyl fluorene-based compound include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzylidene).肟), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-ethylindenyl), B Ketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9H-indazol-3-yl]-, 1-(O-ethenyl)肟), ethyl ketone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzidine }}-9H-carbazol-3-yl]-, 1-(O-ethylindenyl) and the like. As a commercial item of the O-indenyl ruthenium compound, NCI-831, NCI-930 (above, ADEKA Co., Ltd.), DFI-020, and DFI-091 (the above is manufactured by DAITO CHEMIX Co., Ltd.) can also be used. )Wait.
在本發明中,使用苯乙酮系化合物等之聯咪唑系化合物以外的光聚合起始劑時,也可併用增感劑。作為如前述的增感劑,例如,可舉出4,4'-雙(二甲胺基)二苯甲酮、4,4'-雙(二乙胺基)二苯甲酮、4-二乙胺基苯乙酮、4-二甲胺基苯丙酮、4-二甲胺基苯甲酸乙酯、4-二甲胺基苯甲酸-2-乙基己酯、2,5-雙(4-二乙胺基苯亞甲基)環己酮、7-二乙胺基-3-(4-二乙胺基苯甲醯基)香豆素、4-(二乙胺基)查耳酮等。 In the present invention, when a photopolymerization initiator other than the biimidazole compound such as an acetophenone-based compound is used, a sensitizer may be used in combination. Examples of the sensitizer as described above include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 4-di. Ethyl acetophenone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4 -diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzimidyl)coumarin, 4-(diethylamino)chalcone Wait.
在本發明中,光聚合起始劑的含量,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,特佳為10~60質量份。藉由成為如前述的態樣,可進一步提高硬化性、被膜特性。 In the present invention, the content of the photopolymerization initiator is preferably 0.01 to 120 parts by mass, more preferably 1 to 100 parts by mass, even more preferably 10 to 60 parts by mass, per 100 parts by mass of the (C) polymerizable compound. . By the aspect as described above, the curability and film properties can be further improved.
本發明的著色組成物為含有前述(A)~(C)成分、及任意添加之其他的成分者,但通常係摻合溶媒作為液狀組成物進行製備。 The colored composition of the present invention is a component containing the above-mentioned components (A) to (C) and optionally added, but is usually prepared by mixing a solvent as a liquid component.
作為前述溶媒,只要為將構成著色組成物的(A)~(C)成分或其他成分分散或溶解,且不與該等之成分反應,並具有適度的揮發性者,則可適當選擇而使用。 The solvent is appropriately selected and used as long as it disperses or dissolves the components (A) to (C) constituting the colored composition or other components, and does not react with the components. .
如前述的溶媒之中,例如,可舉出乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單正丙基醚、乙二醇單正丁基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單正丙基醚、二乙二醇單正丁基醚、三乙二醇單甲基醚、三乙二醇單乙基醚、丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單正丙基醚、丙二醇單正丁基醚、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單正丙基醚、二丙二醇單正丁基醚、三丙二醇單甲基醚、三丙二醇單乙基醚等之(聚)烯烴基二醇單烷酯類;乳酸甲酯、乳酸乙酯等之乳酸烷酯類;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、環己醇等之(環)烷醇類;二丙酮醇等之酮醇類;乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、二乙二醇單甲基醚乙酸酯、二乙二醇單乙基醚乙酸酯、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、二丙二醇單甲基醚乙酸酯、乙酸-3-甲氧丁酯、乙酸-3- 甲基-3-甲氧丁酯等之(聚)烯烴基二醇單烷基醚乙酸酯類;二乙二醇二甲基醚、二乙二醇甲基乙基醚、二乙二醇二乙基醚、四氫呋喃等之其他的醚類;甲乙酮、環己酮、2-庚酮、3-庚酮等之酮類;丙二醇二乙酸酯、1,3-丁二醇二乙酸酯、1,6-己二醇二乙酸酯等之二乙酸酯類;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、丙酸-3-甲基-3-甲氧基丁酯等之烷氧基羧酸酯類;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-側氧丁酸乙酯等之其他的酯類;甲苯、二甲苯等之芳香族烴類;N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基吡咯啶酮等之醯胺或內醯胺類等。 Examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, and diethylene glycol. Monomethyl ether, 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, (poly)alkylene glycol monoalkyl esters such as dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; alkyl lactate such as methyl lactate or ethyl lactate; methanol , (cyclo)alkanols such as ethanol, propanol, butanol, isopropanol, isobutanol, tert-butanol, octanol, 2-ethylhexanol, cyclohexanol; ketones such as diacetone alcohol Alcohols; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol Monomethyl ether B Esters, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxy butyl acetate -3- (poly)olefin diol monoalkyl ether acetates such as methyl-3-methoxybutyl ester; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol II Other ethers such as ethyl ether and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; propylene glycol diacetate, 1,3-butylene glycol diacetate, Diacetate such as 1,6-hexanediol diacetate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Alkoxycarboxylates such as ethyl ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutyl propionate; ethyl acetate, n-propyl acetate, acetic acid Isopropyl ester, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, butyric acid Other esters such as butyl ester, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxobutanoate, etc.; toluene, xylene Aromatic hydrocarbons; N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyridinium A guanamine or an indoleamine such as a bromo ketone.
該等溶媒之中,從溶解性、顏料分散性、塗布性等之觀點來看,以(聚)烯烴基二醇單烷基醚類、乳酸烷酯類、(聚)烯烴基二醇單烷基醚乙酸酯類、其他的醚類、酮類、二乙酸酯類、烷氧基羧酸酯類、其他的酯類較為理想,特別是以丙二醇單甲基醚、丙二醇單乙基醚、乙二醇單甲基醚乙酸酯、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、乙酸-3-甲氧基丁酯、二乙二醇 二甲基醚、二乙二醇甲基乙基醚、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、丙酸-3-甲基-3-甲氧基丁酯、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、丙酮酸乙酯等較為理想。 Among these solvents, (poly)alkylene glycol monoalkyl ethers, lactated alkyl esters, (poly)alkylene glycol monoalkanes from the viewpoints of solubility, pigment dispersibility, coating properties and the like Ethyl ether acetates, other ethers, ketones, diacetates, alkoxycarboxylates, and other esters are preferred, especially propylene glycol monomethyl ether, propylene glycol monoethyl ether, and B. Glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, acetic acid-3-methoxybutyl ester, diethylene glycol Dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butanediol diacetate, 1,6-hexanediol diethyl Acid ester, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxypropionate Butyl ester, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate I am more ideal.
在本發明中,溶媒可單獨使用或混合2種以上而使用。混合而使用時,較佳為至少將(聚)烯烴基二醇單烷基醚類與(聚)烯烴基二醇單烷基醚乙酸酯類、(聚)烯烴基二醇單烷基醚乙酸酯類與烷氧基羧酸酯類混合而使用。 In the present invention, the solvent may be used singly or in combination of two or more. When used in combination, it is preferred to use at least (poly) alkene diol monoalkyl ethers and (poly) olefin diol monoalkyl ether acetates, (poly) olefin diol monoalkyl ether acetates The ester is used in combination with an alkoxycarboxylic acid ester.
溶媒的含量並沒有特別限定,但以排除著色組成物之溶媒的各成分之合計濃度成為5~50質量%的量較為理想,成為10~40質量%的量更為理想。藉由成為如前述的態樣,可得到分散性、安定性良好的著色劑分散液、以及塗布性、安定性良好的著色組成物。 The content of the solvent is not particularly limited. However, the total concentration of each component of the solvent excluding the coloring composition is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass. By the aspect as described above, a colorant dispersion having good dispersibility and stability, and a coloring composition excellent in coatability and stability can be obtained.
本發明的著色組成物,視需要也可包含種種的添加劑。 The colored composition of the present invention may contain various additives as needed.
作為添加劑,例如,可舉出玻璃、氧化鋁等之填充劑;聚乙烯醇、聚(氟烷基丙烯酸酯)類等之高分子化合物;氟系界面活性劑、矽系界面活性劑等之界面活性劑;乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基參(2-甲氧基乙氧基)矽烷、N-(2-胺乙基)-3-胺丙基甲基二甲 氧基矽烷、N-(2-胺乙基)-3-胺丙基三甲氧基矽烷、3-胺丙基三乙氧基矽烷、3-環氧丙氧丙基三甲氧基矽烷、3-環氧丙氧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-甲基丙烯醯氧丙基三甲氧基矽烷、3-硫醇基丙基三甲氧基矽烷等之密合促進劑;2,2-硫基雙(4-甲基-6-第三丁酚)、2,6-二-第三丁酚、季戊四醇肆[3-(3,5-二-第三丁基-4-羥苯基)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、硫基二乙烯基雙[3-(3,5-二-第三丁基-4-羥苯基)丙酸酯]等之抗氧化劑;聚丙烯酸鈉等之抗凝聚劑;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-丁二醇等之殘渣改善劑;琥珀酸單[2-(甲基)丙烯醯氧基乙酯]、鄰苯二甲酸單[2-(甲基)丙烯醯氧基乙酯]、ω-羧基聚己內酯單(甲基)丙烯酸酯等之顯影性改善劑等。再者,在本發明中,不一定需要包含苯并***、二苯甲酮、苯甲酸酯、氰基丙烯酸酯等之紫外線吸收劑。 Examples of the additive include a filler such as glass or alumina; a polymer compound such as polyvinyl alcohol or poly(fluoroalkyl acrylate); an interface of a fluorine-based surfactant or a lanthanoid surfactant; Active agent; vinyl trimethoxy decane, vinyl triethoxy decane, vinyl ginseng (2-methoxyethoxy) decane, N-(2-aminoethyl)-3-aminopropylmethyl Dimethyl Oxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3- Glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropane An adhesion promoter such as trimethoxy decane, 3-methyl propylene oxypropyl trimethoxy decane, 3-thiol propyl trimethoxy decane; 2,2-thiobis(4-methyl -6-t-butylphenol), 2,6-di-t-butylphenol, pentaerythritol 肆[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3, 9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)-propenyloxy]-1,1-dimethylethyl]-2,4, Resistance to 8,10-tetraoxa-spiro[5.5]undecane, thiodivinylbis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] An oxidizing agent; an anti-agglomerating agent such as sodium polyacrylate; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol , 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, etc. Slag improver; succinic acid mono [2-(methyl) propylene methoxyethyl ester], phthalic acid mono [2-(methyl) propylene methoxyethyl ester], ω-carboxy polycaprolactone A developability improving agent such as (meth) acrylate or the like. Further, in the present invention, an ultraviolet absorber containing benzotriazole, benzophenone, benzoate or cyanoacrylate is not necessarily required.
本發明的著色組成物,可利用適當的方法進行製備,作為其製備方法,例如,可舉出揭露於日本特開2008-58642號公報、日本特開2010-132874號公報等的方法。作為著色劑,使用染料與顏料之雙方時,可採用如日本特開2010-132874號公報所揭露,藉由使染料溶液通過第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過濾器而進行製備的方法。又,亦可採用藉由將染料與前述(B)~(C)成分以及視需要使用的其他成分溶解於溶媒,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等混合,使得到的著色組成物通過第2過濾器而進行製備的方法。又,也可採用使染料溶液通過第1過濾器後,將通過第1過濾器的染料溶液與前述(B)~(C)成分以及視需要使用的其他成分混合與溶解,使得到的溶液通過第2過濾器,並且將通過第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過濾器而進行製備的方法。 The coloring composition of the present invention can be produced by an appropriate method. For example, a method of the method of the present invention, which is disclosed in JP-A-2008-58642, JP-A-2010-132874, and the like. When both the dye and the pigment are used as the coloring agent, as disclosed in Japanese Laid-Open Patent Publication No. 2010-132874, the dye solution passing through the first filter can be passed after passing the dye solution through the first filter. A method of preparing a colored composition by mixing with a separately prepared pigment dispersion or the like through a second filter. Further, it is also possible to dissolve the solution passing through the first filter by passing the dye and the components (B) to (C) and other components as needed in the solvent, so that the obtained solution passes through the first filter. Further, a prepared pigment dispersion liquid or the like is mixed, and the obtained coloring composition is prepared by passing through a second filter. Further, after the dye solution is passed through the first filter, the dye solution passing through the first filter may be mixed and dissolved with the components (B) to (C) and other components as needed, so that the obtained solution passes. The second filter, and a method in which the solution of the second filter is mixed with the separately prepared pigment dispersion, and the resulting colored composition is passed through a third filter.
本發明的著色硬化膜為使用本發明的著色組成物形成者,具體而言,意指用於彩色濾光片的各色畫素、黑色矩陣、黑色間隔件等。 The colored cured film of the present invention is formed by using the colored composition of the present invention, and specifically means each color pixel, black matrix, black spacer, or the like used for the color filter.
以下對於用於彩色濾光片的著色硬化膜及其形成方法進行說明。 Hereinafter, a colored cured film for a color filter and a method of forming the same will be described.
作為製造彩色濾光片的方法,第一可舉出以下的方法。首先,在基板的表面上視需要分隔形成畫素的部分而形成遮光層(黑色矩陣)。其次,在該基板上,例如,塗布紅色的本發明之感放射線性著色組成物的液狀組成物之後,進行預烤並使溶媒蒸發,形成塗膜。接著,對該塗膜隔著光罩進行曝光後,使用鹼顯影液進行顯影,溶解除去塗膜的未曝光部。之後,藉由進行後烘烤,形 成紅色之畫素圖案(著色硬化膜)以一定的排列配置的畫素陣列。 As a method of manufacturing a color filter, the following method is mentioned first. First, a light shielding layer (black matrix) is formed on the surface of the substrate as needed to separate the portions where the pixels are formed. Next, on the substrate, for example, a red liquid composition of the radiation sensitive coloring composition of the present invention is applied, and then pre-baked and the solvent is evaporated to form a coating film. Next, the coating film was exposed through a mask, and then developed using an alkali developing solution to dissolve and remove the unexposed portion of the coating film. After that, by post-baking, the shape A pixel array in which a red pixel pattern (colored cured film) is arranged in a certain arrangement.
接著,使用綠色或藍色的各感放射線性著色組成物,與前述同樣地進行,並進行各感放射線性著色組成物之塗布、預烤、曝光、顯影及後烘烤,使綠色的畫素陣列及藍色的畫素陣列依序形成於同一基板上。根據前述,可得到藍色、綠色及紅色之三原色的畫素陣列配置於基板上的彩色濾光片。但是,在本發明中,形成各色畫素的順序並沒有限定於前述者。 Next, each of the green or blue radiation-sensitive coloring compositions is used in the same manner as described above, and each of the radiation-sensitive coloring compositions is coated, pre-baked, exposed, developed, and post-baked to make green pixels. The array and the blue pixel array are sequentially formed on the same substrate. According to the above, a color filter in which the pixel arrays of the three primary colors of blue, green, and red are arranged on the substrate can be obtained. However, in the present invention, the order in which the respective color pixels are formed is not limited to the above.
又,黑色矩陣可藉由使利用濺鍍或蒸鍍成膜的鉻等之金屬薄膜,利用光微影法成為所需的圖案而形成,但也可使用分散有黑色顏料的感放射線性著色組成物,與前述畫素之形成的情況同樣地進行而形成。 Further, the black matrix can be formed by using a metal thin film such as chromium which is formed by sputtering or vapor deposition to form a desired pattern by photolithography, but it is also possible to use a radiation-sensitive coloring composition in which a black pigment is dispersed. The object is formed in the same manner as in the case of forming the aforementioned pixels.
作為在形成彩色濾光片之際使用的基板,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 polyimine.
又,在該等之基板中,也可根據所需預先實施利用矽烷偶合劑等的藥品處理、電漿處理、離子鍍覆、濺鍍、氣相反應法、真空蒸鍍等之適當的前處理。 Further, in these substrates, appropriate pretreatment such as drug treatment, plasma treatment, ion plating, sputtering, gas phase reaction, vacuum vapor deposition, or the like using a decane coupling agent or the like may be performed in advance. .
在將感放射線性著色組成物塗布於基板之際,可採用噴灑法、輥塗法、旋轉塗布法(旋塗法)、縫模塗布法(狹縫塗布法)、棒塗布法等之適當的塗布法,特別是以採用旋塗法、縫模塗布法較為理想。 When the radiation sensitive coloring composition is applied to the substrate, a suitable method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method (slit coating method), or a bar coating method may be employed. The coating method is particularly preferably a spin coating method or a slit die coating method.
預烤通常係組合減壓乾燥與加熱乾燥而進行。減壓乾燥,通常進行到達50~200Pa為止。又,加熱乾燥的條件,通常為在70~110℃下1~10分鐘左右。 Pre-baking is usually carried out by combining dry-pressure drying and heat drying. Dry under reduced pressure, usually until 50 to 200 Pa. Further, the conditions of heat drying are usually about 1 to 10 minutes at 70 to 110 °C.
塗布厚度,作為乾燥後的膜厚,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, as the film thickness after drying.
作為在形成選自於畫素及黑色矩陣之至少1種時使用的放射線之光源,例如,可舉出氙氣燈、鹵素燈、鎢絲燈、高壓水銀燈、超高壓水銀燈、金屬鹵素燈、中壓水銀燈、低壓水銀燈等之燈具光源或氬離子雷射、YAG雷射、XeCl準分子雷射、氮雷射等之雷射光源等。作為曝光光源,也可使用紫外線LED。波長係以在190~450nm之範圍內的放射線較為理想。 Examples of the light source for radiation used to form 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 voltage. Luminous light sources such as mercury lamps, low-pressure mercury lamps, or laser sources such as argon ion lasers, YAG lasers, XeCl excimer lasers, and nitrogen lasers. As the exposure light source, an ultraviolet LED can also be used. The wavelength is preferably in the range of 190 to 450 nm.
放射線的曝光量,一般而言,以10~10,000J/m2較為理想。 The exposure amount of the radiation is generally preferably from 10 to 10,000 J/m 2 .
又,作為前述鹼顯影液,例如,以碳酸鈉、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]-7-十一烷、1,5-二氮雜雙環-[4.3.0]-5-壬烯等之水溶液較為理想。 Further, as the alkali developing solution, for example, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0] An aqueous solution of -7-undecane or 1,5-diazabicyclo-[4.3.0]-5-decene is preferred.
在鹼顯影液中,例如,亦可適量添加甲醇、乙醇等之水溶性有機溶劑或界面活性劑等。再者,鹼顯影後,通常進行水洗。 In the alkali developing solution, for example, a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added in an appropriate amount. Further, after alkali development, water washing is usually carried out.
作為顯影處理法,可應用噴淋顯影法、噴灑顯影法、浸漬(dip)顯影法、浸置(盛裝)顯影法等。顯影條件係以在常溫下5~300秒鐘較為理想。 As the development treatment method, a shower development method, a spray development method, a dip development method, a dipping (filling) development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at normal temperature.
後烘烤的條件通常為在180~280℃下10~60分鐘左右。 The post-baking conditions are usually about 10 to 60 minutes at 180 to 280 °C.
如前述進行而形成的畫素之膜厚通常為0.5~5μm,較佳為1.0~3μm。 The film thickness of the pixel formed as described above is usually 0.5 to 5 μm, preferably 1.0 to 3 μm.
又,作為製造彩色濾光片的第二方法,係揭露於日本特開平7-318723號公報、日本特開2000-310706號公報等,且可採用利用噴墨方式得到各色畫素的方法。在該方法中,首先,在基板的表面上形成也兼具遮光機能的間隔壁。其次,在形成的間隔壁內,例如,利用噴墨裝置吐出藍色之本發明的熱硬化性著色組成物之液狀組成物後,進行預烤使溶媒蒸發。接著,視需要將該塗膜曝光後,藉由進行後烘烤使其硬化,形成藍色的畫素圖案。 In addition, as a second method of producing a color filter, a method of obtaining each color pixel by an inkjet method can be employed as disclosed in JP-A-H07-318723, JP-A-2000-310706, and the like. In this method, first, a partition wall which also has a shading function is formed on the surface of the substrate. Next, in the formed partition, for example, a liquid composition of the thermosetting coloring composition of the present invention in which blue is emitted by an inkjet device is ejected, 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.
其次,使用綠色或紅色的各熱硬化性著色組成物,與前述同樣地進行,使綠色的畫素圖案及紅色的畫素圖案依序形成於同一基板上。根據前述,可得到藍色、綠色及紅色之三原色的畫素圖案配置於基板上的彩色濾光片。但是,在本發明中,形成各色畫素的順序並沒有限定於前述者。 Next, each of the green or red thermosetting coloring compositions was used in the same manner as described above, and the green pixel pattern and the red pixel pattern were sequentially formed on the same substrate. According to the above, a color filter in which the pixel patterns of the three primary colors of blue, green, and red are arranged on the substrate can be obtained. However, in the present invention, the order in which the respective color pixels are formed is not limited to the above.
再者,間隔壁不僅有遮光機能,且也發揮用以在分隔內吐出的各色之熱硬化性著色組成物不會混色的機能,因此相較於前述第一方法所使用的黑色矩陣,膜厚較厚。因此,間隔壁通常使用黑色感放射線性組成物形成。 Further, the partition wall not only has a light-shielding function, but also exhibits a function of not mixing colors of the thermosetting coloring composition for discharging the color in the partition, and therefore the film thickness is thinner than that of the black matrix used in the first method. Thicker. Therefore, the partition walls are usually formed using a black sensitizing radioactive composition.
在形成彩色濾光片之際使用的基板或放射線之光源、或是預烤或後烘烤的方法或條件,係與前述第一方法為相同。如前述進行,利用噴墨方式形成的畫素之膜厚,與間隔壁的高度為同程度。 The substrate or the source of radiation used in forming the color filter, or the method or condition of pre-baking or post-baking is the same as the first method described above. As described above, the film thickness of the pixel formed by the ink jet method is the same as the height of the partition wall.
在如前述進行而得到的畫素圖案上,視需要形成保護膜後,利用濺鍍形成透明導電膜。形成透明導電膜後,也可進一步形成間隔件而製成彩色濾光片。間隔件,通常使用感放射線性組成物形成,且也可製成具有遮光性的間隔件(黑色間隔件)。該情況中使用分散有黑色著色劑的著色感放射線性組成物,但本發明的著色組成物也可適當使用於該黑色間隔件之形成。 On the pixel pattern obtained as described above, a protective film is formed as needed, and then 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, and can also be made into a light-shielding spacer (black spacer). In this case, a colored radiation linear composition in which a black colorant is dispersed is used, but the colored composition of the present invention can also be suitably used for the formation of the black spacer.
本發明的著色組成物,在前述彩色濾光片所使用的各色畫素、黑色矩陣、黑色間隔件等之任一著色硬化膜之形成中也可適當使用。 The coloring composition of the present invention can be suitably used in the formation of any of the coloring cured films, the black matrix, and the black spacer used in the color filter.
包含如前述進行而形成的本發明之著色硬化膜的彩色濾光片,因為輝度及著色力極高,所以對彩色液晶顯示元件、彩色攝像管元件、彩色檢測器、有機EL顯示元件、電子紙等極為有用。再者,後述的顯示元件,只要具備使用本發明之著色組成物形成的著色硬化膜至少1個以上即可。 The color filter including the colored cured film of the present invention formed as described above has a high luminance and coloring power, and thus has a color liquid crystal display element, a color image pickup element, a color detector, an organic EL display element, and an electronic paper. It is extremely useful. Further, the display element to be described later may have at least one coloring cured film formed using the colored composition of the present invention.
本發明的顯示元件為具備本發明之著色硬化膜者。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 is provided with 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.
具備本發明之著色硬化膜的彩色液晶顯示元件,可為透射型亦可為反射型,且可採用適當的結構。例如,可採用:在與配置有薄膜電晶體(TFT)的驅動用基板為不同的基板上形成彩色濾光片,且驅動用基板與形成有彩色濾光片的基板隔著液晶層為相對向的結構;甚至也可 採用:在配置有薄膜電晶體(TFT)的驅動用基板之表面上形成有彩色濾光片的基板與形成有ITO(摻雜錫的氧化銦)電極或IZO(酸化銦與氧化鋅之混合物)電極的基板隔著液晶層為相對向的結構。後者的結構具有可顯著的提高開口率、且具有可得到明亮且高精細的液晶顯示元件之優點。再者,採用後者的結構時,黑色矩陣或黑色間隔件,亦可形成於形成有彩色濾光片的基板側、以及形成有ITO電極或IZO電極的基板側之任一側。 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 may have an appropriate structure. For example, a color filter may be formed on a substrate different from a driving substrate on which a 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 a liquid crystal layer. Structure; even A substrate having a color filter formed on a surface of a driving substrate on which a thin film transistor (TFT) is disposed, and an ITO (tin-doped indium oxide) electrode or IZO (a mixture of indium acid and zinc oxide) is formed. The substrate of the electrode has a structure in which the liquid crystal layer is opposed to each other. The latter structure has an advantage that the aperture ratio can be remarkably improved, and a liquid crystal display element which can obtain a bright and high definition can be obtained. Further, in the latter configuration, the black matrix or the black spacer may be formed on either the substrate side on which the color filter is formed and the substrate side on which the ITO electrode or the IZO electrode is formed.
具備本發明之著色硬化膜的彩色液晶顯示元件,除冷陰極螢光管(CCFL:Cold Cathode Fluorescent Lamp)以外,可具備將白色LED作為光源的背光單元。作為白色LED,例如,可舉出藉由組合紅色LED、綠色LED與藍色LED並混色而得到白色光的白色LED、藉由組合藍色LED、紅色LED與綠色螢光體並混色而得到白色光的白色LED、藉由組合藍色LED、紅色發光螢光體與綠色發光螢光體並混色而得到白色光的白色LED、藉由藍色LED與YAG系螢光體之混色而得到白色光的白色LED、藉由組合藍色LED、橘色發光螢光體與綠色發光螢光體並混色而得到白色光的白色LED、藉由組合紫外線LED、紅色發光螢光體、綠色發光螢光體與藍色發光螢光體並混色得到白色光的白色LED等。 A color liquid crystal display device including the colored cured film of the present invention may include a backlight unit having a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL). As the white LED, for example, a white LED in which white light is obtained by combining a red LED, a green LED, and a blue LED, and white light is obtained by combining blue LEDs, red LEDs, and green phosphors, and white color is obtained. A white LED that is light, a white LED that combines a blue LED, a red luminescent phosphor, and a green luminescent phosphor to obtain white light, and a white light obtained by mixing a blue LED and a YAG-based phosphor White LED, white LED with white light by combining blue LED, orange luminescent phosphor and green luminescent phosphor, by combining ultraviolet LED, red luminescent phosphor, green luminescent phosphor A white LED or the like that is mixed with a blue luminescent phosphor to obtain white light.
在具備本發明之著色硬化膜的彩色液晶顯示元件中,可應用TN(Twisted Nematic)型、STN(Super Twisted Nematic)型、IPS(In-Planes Switching)型、VA(Vertical Alignment)型、OCB(Optically Compensated Birefringence)型等之適當的液晶模式。 In a color liquid crystal display device having the colored cured film of the present invention, a TN (Twisted Nematic) type, an STN (Super Twisted Nematic) type, an IPS (In-Planes Switching) type, a VA (Vertical Alignment) type, or an OCB ( Appropriate liquid crystal mode such as Optically Compensated Birefringence).
又,具備本發明之著色硬化膜的有機EL顯示元件可取適當的結構,例如,可舉出揭露於日本特開平11-307242號公報的結構。 In addition, the organic EL display device 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.
又,具備本發明之著色硬化膜的電子紙可取適當的結構,例如,可舉出揭露於日本特開2007-41169號公報的結構。 In addition, the electronic paper which has the coloring-hardening film of this invention is a suitable structure, and, for example, the structure disclosed by Unexamined-Japanese-Patent No. 2007-41169 is mentioned.
以下舉出實施例進一步具體地說明本發明的實施形態。但是,本發明並沒有限定於下述實施例。 Hereinafter, embodiments of the present invention will be specifically described by way of examples. However, the present invention is not limited to the following examples.
將下述式(1)所示的化合物20質量份與N-十二基苯胺(東京化成工業股份有限公司製)200質量份於遮光條件下混合,將得到的溶液在110℃下攪拌6小時。將得到的反應液冷卻直到室溫後,添加至水800質量份及35%鹽酸50質量份的混合液中,在室溫下攪拌1小時。將析出的結晶吸引過濾,並將得到的殘渣乾燥,得到式(A-1)所示的化合物24質量份。根據MS光譜,確認得到的紅色固體為下述式(A-1)所示的化合物。將得到的化合物作為著色劑(A-1)。 20 parts by mass of the compound represented by the following formula (1) and 200 parts by mass of N-dodecylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed under a light-shielding condition, and the obtained solution was stirred at 110 ° C for 6 hours. . The obtained reaction liquid was cooled to room temperature, and then added to a mixed liquid of 800 parts by mass of water and 50 parts by mass of 35% hydrochloric acid, and stirred at room temperature for 1 hour. The precipitated crystals were suction-filtered, and the obtained residue was dried to obtain 24 parts by mass of the compound represented by the formula (A-1). From the MS spectrum, it was confirmed that the obtained red solid was a compound represented by the following formula (A-1). The obtained compound was used as a coloring agent (A-1).
依據日本特開2010-254964號公報之合成例1的記載,進行下述式(a-1-1)~(a-1-5)所示的化合物之混合物的合成。將得到的化合物之混合物作為著色劑(a-1)。 According to the description of Synthesis Example 1 of JP-A-2010-254964, a mixture of compounds represented by the following formulas (a-1-1) to (a-1-5) is synthesized. A mixture of the obtained compounds was used as a coloring agent (a-1).
依據日本特開2012-181505號公報之合成例2的記載,進行下述式(a-2)所示的化合物之合成。將得到的化合物作為著色劑(a-2)。 The synthesis of the compound represented by the following formula (a-2) is carried out according to the description of Synthesis Example 2 of JP-A-2012-181505. The obtained compound was used as a coloring agent (a-2).
混合著色劑(A-1)5質量份與作為溶媒之環己酮95質量份,製備染料溶液(A-1)。 A dye solution (A-1) was prepared by mixing 5 parts by mass of the coloring agent (A-1) with 95 parts by mass of cyclohexanone as a solvent.
在製備例1中,使用下述式(A-2)~(A-14)所示的著色劑代替著色劑(A-1),除此以外係與製備例1同樣地進行,製備染料溶液(A-2)~(A-14)。 In the preparation example 1, a dye solution represented by the following formulas (A-2) to (A-14) was used instead of the colorant (A-1), and a dye solution was prepared in the same manner as in Production Example 1. (A-2)~(A-14).
在製備例1中,使用著色劑(a-1)~著色劑(a-2)代替著色劑(A-1),除此以外係與製備例1同樣地進行,製備染料溶液(a-1)~染料溶液(a-2)。 In the preparation example 1, a dye solution (a-1) was prepared in the same manner as in Preparation Example 1 except that the colorant (a-1) to the colorant (a-2) were used instead of the colorant (A-1). ) ~ dye solution (a-2).
使用15質量份的作為著色劑之C.I.顏料藍15:6、作為分散劑之BYK-LPN21116(BYK公司製)12.5質量份(固體成分濃度40質量%)、作為溶媒之丙二醇單甲基醚乙酸酯72.5質量份,利用珠磨進行處理,製備顏料分散液(a-3)。 15 parts by mass of CI Pigment Blue 15:6 as a coloring agent, 12.5 parts by mass of BYK-LPN21116 (manufactured by BYK Co., Ltd.) as a dispersing agent (solid content concentration: 40% by mass), propylene glycol monomethyl ether acetate as a solvent 72.5 parts by mass of the ester was treated by a bead mill to prepare a pigment dispersion liquid (a-3).
在具備冷卻管與攪拌機的燒瓶,加入丙二醇單甲基醚乙酸酯100質量份並進行氮取代。在80℃下加熱,且在同溫度下花費1小時滴加丙二醇單甲基醚乙酸酯100質量份、甲基丙烯酸20質量份、苯乙烯10質量份、甲基丙烯酸苯甲酯5質量份、甲基丙烯酸-2-羥乙酯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-丙烯醯氧基乙酯)15質量份及2,2'-偶氮雙(2,4-二甲基戊腈)6質量份的混合溶液,保持該溫度聚合2小時。之後,使反應溶液的溫度升溫至100℃,並且藉由聚合1小時,得到黏結劑樹脂溶液(固體成分濃度33質量%)。得到的黏結劑樹脂,Mw為12,200,Mn為6,500。將該黏結劑樹脂作為「黏結劑樹脂(B1)」。 In a flask equipped with a cooling tube and a stirrer, 100 parts by mass of propylene glycol monomethyl ether acetate was added and nitrogen substitution was carried out. The mixture was heated at 80 ° C, and 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, and 5 parts by mass of benzyl methacrylate were added dropwise at the same temperature for 1 hour. 15 parts by mass of 2-hydroxyethyl methacrylate, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, and succinic acid mono(2-propene oxide) A mixed solution of 15 parts by mass of ethyl ester) and 6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) was polymerized at this temperature for 2 hours. Thereafter, the temperature of the reaction solution was raised to 100 ° C, and by polymerization for 1 hour, a binder resin solution (solid content concentration: 33% by mass) was obtained. The resulting binder resin had a Mw of 12,200 and an Mn of 6,500. This binder resin is referred to as "adhesive resin (B1)".
混合顏料分散液(a-3)46.0質量份、染料溶液(A-1)24.3質量份、作為黏結劑樹脂之黏結劑樹脂(B1)溶液24.6質量份、作為交聯劑之東亞合成股份有限公司製M-402(二季戊四醇六丙烯酸酯與二季戊四醇五丙烯酸酯的混合物)7.1質量份、作為光聚合起始劑之2-苯甲基-2-二甲胺基-1-(4-N-啉基苯基)丁-1-酮(Ciba Specialty Chemicals公司製、商品名IRGACURE369)2.1質量份、作為界面活性劑之MEGAFACE F-554(DIC股份有限公司製)0.05質量份、及作為溶媒之乳酸乙酯,製備固體成分濃度20質量%的著色組成物。 46.0 parts by mass of the mixed pigment dispersion (a-3), 24.3 parts by mass of the dye solution (A-1), 24.6 parts by mass of the binder resin (B1) solution as a binder resin, and East Asia Synthetic Co., Ltd. as a crosslinking agent M-402 (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) 7.1 parts by mass of 2-benzyl-2-dimethylamino-1-(4-N- as a photopolymerization initiator 2.1 parts by mass of morphylphenyl)butan-1-one (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name IRGACURE 369), 0.05 parts by mass of MEGAFACE F-554 (manufactured by DIC Corporation) as a surfactant, and lactic acid as a solvent Ethyl ester, a coloring composition having a solid concentration of 20% by mass was prepared.
使用旋塗機將得到的著色組成物塗布於玻璃基板上後,以80℃的熱板進行10分鐘預烤,形成膜厚不同之3片的塗膜。 The obtained coloring composition was applied onto a glass substrate by a spin coater, and then prebaked on a hot plate at 80 ° C for 10 minutes to form three coating films having different film thicknesses.
其次,將該基板冷卻至室溫後,使用高壓水銀燈,未隔著光罩,對塗膜使用包含365nm、405nm及436nm之各波長的放射線以2,000J/m2的曝光量進行曝光。如前述進行,在基板上形成藍色的評價用硬化膜。 Next, after the substrate was cooled to room temperature, the coating film was exposed to an exposure amount of 2,000 J/m 2 using radiation of respective wavelengths of 365 nm, 405 nm, and 436 nm without using a photomask. As described above, a blue evaluation cured film was formed on the substrate.
將形成有硬化膜的基板以2片偏向板夾持,自背面側以螢光燈(波長範圍380~780nm)照射,同時使前面側之偏向板旋轉,利用輝度計LS-100(Minolta(股)製)測定穿透的光強度之最大值與最小值。然後,對於各個的硬化膜,將最大值除以最小值的值作為對比比。根 據測定結果,求得在色度座標值y=0.080的對比比。將評價結果示於表1。再者,對比比的數值越大,意指越為良好。 The substrate on which the cured film is formed is sandwiched between two deflecting plates, and is irradiated with a fluorescent lamp (wavelength range of 380 to 780 nm) from the back side while rotating the deflecting plate on the front side, using a luminance meter LS-100 (Minolta) )) Determine the maximum and minimum values of the transmitted light intensity. Then, for each of the cured films, the value obtained by dividing the maximum value by the minimum value was used as a comparison ratio. root Based on the measurement results, the contrast ratio at the chromaticity coordinate value y = 0.080 was obtained. The evaluation results are shown in Table 1. Furthermore, the larger the value of the contrast ratio, the better the meaning.
將形成有硬化膜的基板,使用彩色分析儀(大塚電子(股)製MCPD2000),以C光源、2度視野測定CIE表色系的色度座標值(x,y)及刺激值(Y)。 A substrate having a cured film was formed, and a color coordinate analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.) was used to measure the chromaticity coordinate value (x, y) and the stimulus value (Y) of the CIE color system using a C light source and a 2 degree field of view. .
其次,在230℃的潔淨烘箱內後烘烤1小時後,測定色度座標值(x,y)及刺激值(Y),評價在追加烘烤前後之顏色變化,亦即△E* ab。其結果將△E* ab小於3.0的情況評價為「◎」,將3.0以上小於5.0的情況評價為「○」,將5.0以上的情況評價為「×」。將評價結果示於表1。 Next, after post-baking in a clean oven at 230 ° C for 1 hour, the chromaticity coordinate value (x, y) and the stimulating value (Y) were measured, and the color change before and after the additional baking, that is, ΔE * ab was evaluated. As a result, the case where ΔE * ab was less than 3.0 was evaluated as “◎”, the case where 3.0 or more was less than 5.0 was evaluated as “○”, and the case of 5.0 or more was evaluated as “×”. The evaluation results are shown in Table 1.
在表面形成有防止鈉離子溶出的SiO2膜,並且在將ITO(銦-氧化錫合金)電極蒸鍍為所定形狀的鈉玻璃基板上,旋塗得到的著色組成物後,以100℃的熱板進行1分鐘預烤,形成膜厚2.0μm的塗膜。其次,未隔著光罩,對塗膜以700J/m2的曝光量進行曝光。之後,將該基板浸漬於23℃之包含0.04質量%的氫氧化鉀水溶液之顯影液1分鐘,進行顯影後,以超純水清洗且風乾,並且在230℃下進行後烘烤30分鐘,使塗膜硬化,形成永久硬化膜。接著,將形成有永久硬化膜的基板與僅將ITO電極蒸鍍為所定形狀的基板,以混合1.8mm之玻璃珠的密封劑貼合後,注入Merck製液晶(MLC6608),製作液晶胞。其次,將液晶胞放入60℃的恆溫層,利用液 晶電壓保持率測定系統(VHR-1A型、TOYO Corporation)測定液晶胞的電壓保持率。此時的施加電壓為5.5V的方形波,測定頻率為60Hz。在此之電壓保持率為利用(16.7毫秒後之液晶胞電位差/緊接於施加後的電壓)求得的數值。液晶胞的電壓保持率為90%以下的話,液晶胞無法將16.7毫秒的時間、施加電壓保持為所定等級,意指無法充分地配向液晶,且有引起殘像等之「烙印」的可能。 An SiO 2 film for preventing elution of sodium ions is formed on the surface, and an ITO (indium-tin oxide alloy) electrode is vapor-deposited on a soda glass substrate having a predetermined shape, and the obtained colored composition is spin-coated, and then heatd at 100 ° C. The plate was prebaked for 1 minute to form a coating film having a film thickness of 2.0 μm. Next, the coating film was exposed at an exposure amount of 700 J/m 2 without passing through a photomask. Thereafter, the substrate was immersed in a developing solution containing a 0.04% by mass aqueous potassium hydroxide solution at 23 ° C for 1 minute, and after development, it was washed with ultrapure water and air-dried, and post-baked at 230 ° C for 30 minutes. The coating film is hardened to form a permanent cured film. Next, the substrate on which the permanent cured film was formed and the substrate on which only the ITO electrode was formed into a predetermined shape were bonded, and the sealing agent was mixed with a glass bead of 1.8 mm, and then a liquid crystal (MLC6608) manufactured by Merck was injected to prepare a liquid crystal cell. Next, the liquid crystal cell was placed in a constant temperature layer at 60 ° C, and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage retention ratio measurement system (VHR-1A type, TOYO Corporation). The applied voltage at this time was a square wave of 5.5 V, and the measurement frequency was 60 Hz. The voltage holding ratio here is a value obtained by using (the liquid crystal cell potential difference after 16.7 msec/the voltage immediately after application). When the voltage holding ratio of the liquid crystal cell is 90% or less, the liquid crystal cell cannot maintain the time and the applied voltage of 16.7 milliseconds at a predetermined level, which means that the liquid crystal cannot be sufficiently aligned, and there is a possibility of causing "burn in" of the afterimage or the like.
在實施例1中,將顏料分散液及染料溶液的種類及量如表1所示進行變更,除此以外係與實施例1同樣地製備著色組成物。然後,對於得到的著色組成物,與實施例1同樣地進行,並進行評價。將評價結果示於表1。 In the same manner as in Example 1, except that the type and amount of the pigment dispersion liquid and the dye solution were changed as shown in Table 1, a colored composition was prepared. Then, the obtained colored composition was evaluated in the same manner as in Example 1, and evaluated. The evaluation results are shown in Table 1.
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KR102170466B1 (en) | 2020-10-28 |
KR20140122183A (en) | 2014-10-17 |
JP2014219663A (en) | 2014-11-20 |
TWI627233B (en) | 2018-06-21 |
JP6299329B2 (en) | 2018-03-28 |
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