TW202035578A - Yellow-colored curable composition - Google Patents
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- TW202035578A TW202035578A TW109104105A TW109104105A TW202035578A TW 202035578 A TW202035578 A TW 202035578A TW 109104105 A TW109104105 A TW 109104105A TW 109104105 A TW109104105 A TW 109104105A TW 202035578 A TW202035578 A TW 202035578A
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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
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
- C09B67/0034—Mixtures of two or more pigments or dyes of the same type
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B25/00—Quinophthalones
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09B57/00—Other synthetic dyes of known constitution
- C09B57/04—Isoindoline dyes
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Abstract
Description
本發明是有關於一種黃色的著色硬化性組成物,特別是有關於一種包含染料索引(Color Index,C.I.)顏料黃(pigment yellow)138及C.I.顏料黃185作為著色劑(A)的黃色著色硬化性組成物。The present invention relates to a yellow coloring and hardening composition, in particular to a yellow coloring hardening composition containing dye index (Color Index, CI) pigment yellow (pigment yellow) 138 and CI pigment yellow 185 as colorants (A) Sexual composition.
近年來,正在推進開發的電荷耦合器件(Charge Coupled Device,CCD)或互補金屬氧化物半導體(Complementary Metal Oxide Semiconductor,CMOS)感測器等的固體攝像元件中所使用的彩色濾光片由複雜的顏色構成的著色組成物形成,且具有高的顏色特性。作為達成複雜的顏色構成的手段,謀求黃色顏色特性優異的黃色著色組成物。 專利文獻1中,揭示了一種形成液晶顯示裝置以及有機發光顯示裝置中所使用的彩色濾光片的黃色樹脂組成物。為了設計高亮度、高對比度且抑制顏料凝聚體析出的彩色濾光片,該黃色樹脂組成物中所含的黃色顏料分散液含有:作為喹酞酮顏料的C.I.顏料黃138、作為異吲哚啉顏料的C.I.顏料黃139、以及喹酞酮顏料的醯亞胺烷基化衍生物。 [現有技術文獻] [專利文獻]In recent years, the color filters used in solid-state imaging devices such as charge coupled devices (CCD) or complementary metal oxide semiconductor (CMOS) sensors, which are under development, are composed of complex The coloring composition of color composition is formed and has high color characteristics. As a means to achieve a complicated color composition, a yellow coloring composition with excellent yellow color characteristics is sought. Patent Document 1 discloses a yellow resin composition forming a color filter used in a liquid crystal display device and an organic light emitting display device. In order to design a high-brightness, high-contrast color filter that suppresses the precipitation of pigment aggregates, the yellow pigment dispersion contained in the yellow resin composition contains: CI Pigment Yellow 138 as a quinophthalone pigment and isoindoline Pigment CI Pigment Yellow 139, and quinophthalone pigments are alkylated derivatives of imines. [Prior Art Literature] [Patent Literature]
[專利文獻1]日本專利特開2012-211266號公報[Patent Document 1] Japanese Patent Laid-Open No. 2012-211266
[發明所欲解決之課題] 但是,本發明者等人進行了研究,結果確認到以下課題:於如專利文獻1般含有C.I.顏料黃138與C.I.顏料黃139的黃色樹脂組成物中,C.I.顏料黃139於波長400 nm~460 nm附近的短波長側具有弱吸收,且遍及自波長400 nm~460 nm附近的短波長側至波長500 nm附近的長波長側為止的廣範圍具有吸收,因此,含有該黃色顏料的黃色樹脂組成物亦遍及至500 nm附近為止的廣範圍具有吸光,自短波長側向長波長側的透過率的曲線變得平緩,黃色顏色特性不佳。[The problem to be solved by the invention] However, the inventors of the present invention have conducted studies, and as a result, the following problems have been confirmed: In a yellow resin composition containing CI Pigment Yellow 138 and CI Pigment Yellow 139 as in Patent Document 1, CI Pigment Yellow 139 has a wavelength of 400 nm to 460 The short-wavelength side near nm has weak absorption, and it has absorption over a wide range from the short-wavelength side near the wavelength of 400 nm to 460 nm to the long-wavelength side near the wavelength of 500 nm. Therefore, the yellow resin composition containing the yellow pigment The substance also has light absorption in a wide range up to around 500 nm, the curve of transmittance from the short-wavelength side to the long-wavelength side becomes gentle, and the yellow color characteristic is poor.
因此,本發明的課題在於提供一種對製造具有良好的黃色顏色特性的彩色濾光片而言有用的黃色著色硬化性組成物。 [解決課題之手段]Therefore, the subject of the present invention is to provide a yellow colored curable composition useful for manufacturing a color filter having good yellow color characteristics. [Means to solve the problem]
本發明者等人為了解決所述課題反覆進行了努力研究,結果發現於黃色著色硬化性組成物中,若於著色劑中分別以某一特定的含有率以上來組合使用C.I.顏料黃138及C.I.顏料黃185,則黃色顏色特性變得良好,因此可獲得能夠解決所述課題的著色硬化性組成物,從而完成了本發明。The inventors of the present invention have repeatedly studied hard to solve the above-mentioned problems. As a result, they have found that in a yellow coloring curable composition, if the colorant is used in combination at a specific content rate or more, CI Pigment Yellow 138 and CI Pigment Yellow 185 has improved yellow color characteristics, so a coloring curable composition that can solve the above-mentioned problem can be obtained, and the present invention has been completed.
即,本發明的黃色著色硬化性組成物的要旨在於以下方面。 [1] 一種黃色著色硬化性組成物,包含著色劑(A)、樹脂(B)、聚合性化合物(C)及聚合起始劑(D), 作為所述著色劑(A),包含C.I.顏料黃138及C.I.顏料黃185, 所述著色劑(A)100質量%中的所述C.I.顏料黃138的含有率為70質量%以上,且所述C.I.顏料黃185的含有率為1質量%以上。 [2] 如[1]所述的黃色著色硬化性組成物,其中,所述著色劑(A)100質量%中的所述C.I.顏料黃185的含有率為2質量%以上。 [3] 如[1]或[2]所述的黃色著色硬化性組成物,其中,作為所述著色劑(A),更包含所述C.I.顏料黃138及所述C.I.顏料黃185以外的黃色色材。 [4] 一種彩色濾光片,由如[1]至[3]中任一項所述的黃色著色硬化性組成物形成。 [5] 一種固體攝像元件,包含如[4]所述的彩色濾光片。 [發明的效果]That is, the main points of the yellow colored curable composition of the present invention are as follows. [1] A yellow colored curable composition comprising a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), As the colorant (A), C.I. Pigment Yellow 138 and C.I. Pigment Yellow 185 are included, The content rate of the C.I. Pigment Yellow 138 in 100% by mass of the colorant (A) is 70% by mass or more, and the content rate of the C.I. Pigment Yellow 185 is 1% by mass or more. [2] The yellow colored curable composition according to [1], wherein the content of the C.I. Pigment Yellow 185 in 100% by mass of the colorant (A) is 2% by mass or more. [3] The yellow colored curable composition according to [1] or [2], wherein the colorant (A) further contains yellow other than the CI Pigment Yellow 138 and the CI Pigment Yellow 185 Color material. [4] A color filter formed of the yellow colored curable composition according to any one of [1] to [3]. [5] A solid-state imaging device including the color filter described in [4]. [Effects of the invention]
根據本發明,能夠提供一種黃色顏色特性優異的彩色濾光片。According to the present invention, it is possible to provide a color filter having excellent yellow color characteristics.
本發明的黃色著色硬化性組成物包含著色劑(A)、樹脂(B)、聚合性化合物(C)及聚合起始劑(D),作為所述著色劑(A),於所述著色劑(A)中包含特定比例以上的C.I.顏料黃138及C.I.顏料黃185。若使用包含特定比例以上的C.I.顏料黃138及C.I.顏料黃185的黃色著色硬化性組成物,則可獲得黃色顏色特性優異的彩色濾光片。 再者,本說明書中,作為各成分例示的化合物只要無特別說明,則可單獨使用或將多種組合使用。The yellow colored curable composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D) as the colorant (A), and the colorant (A) contains CI Pigment Yellow 138 and CI Pigment Yellow 185 in a specific ratio or more. If a yellow coloring curable composition containing C.I. Pigment Yellow 138 and C.I. Pigment Yellow 185 in a specific ratio or more is used, a color filter with excellent yellow color characteristics can be obtained. In addition, in this specification, the compound illustrated as each component can be used individually or in combination of multiple types unless otherwise stated.
<著色劑(A)> 本發明的黃色著色硬化性組成物包含C.I.顏料黃138及C.I.顏料黃185作為著色劑(A)。<Colorant (A)> The yellow colored curable composition of the present invention contains C.I. Pigment Yellow 138 and C.I. Pigment Yellow 185 as colorants (A).
本說明書中,所謂「固體成分的總量」是指自本發明的黃色著色硬化性組成物中除去溶劑(E)後的成分的合計量。固體成分的總量及相對於此的各成分的含量例如可藉由液相層析法(Liquid Chromatography)或氣相層析法(Gas Chromatography)等公知的分析手段來測定。In this specification, the "total amount of solid content" refers to the total amount of the components after removing the solvent (E) from the yellow-colored curable composition of the present invention. The total amount of solid components and the content of each component relative to this can be measured by known analysis means such as liquid chromatography (Liquid Chromatography) or gas chromatography (Gas Chromatography), for example.
再者,作為著色劑(A),亦可含有作為C.I.顏料黃138及C.I.顏料黃185以外的著色劑的顏料(以下,有時稱為顏料(A1))及/或染料(以下,有時稱為染料(A2))。Furthermore, as the colorant (A), pigments (hereinafter, sometimes referred to as pigments (A1)) and/or dyes (hereinafter, sometimes referred to as pigments (A1)) and/or dyes as coloring agents other than CI Pigment Yellow 138 and CI Pigment Yellow 185 may be contained Called dye (A2)).
作為顏料(A1),並無特別限定,亦可使用公知的顏料,例如可列舉染料索引(Color Index)(染料及色彩師協會(The Society of Dyers and Colourists)出版)中分類為顏料(pigment)的顏料。 作為分類為顏料(pigment)的顏料,例如可列舉:C.I.顏料黃1、3、12、13、14、15、16、17、20、24、31、53、83、86、93、94、109、110、117、125、128、137、139、147、148、150、153、154、166、173、194、214等黃色顏料; C.I.顏料橙(pigment orange)13、31、36、38、40、42、43、51、55、59、61、64、65、71、73等橙色顏料; C.I.顏料紅(pigment red)9、97、105、122、123、144、149、166、168、176、177、180、192、202、209、215、216、224、242、254、255、264、265、269、291等紅色顏料; C.I.顏料藍(pigment blue)15、15:3、15:4、15:6、60等藍色顏料; C.I.顏料紫(pigment violet)1、19、23、29、32、36、38等紫色顏料; C.I.顏料綠(pigment green)7、36、58等綠色顏料; C.I.顏料棕(pigment brown)23、25等棕色顏料; C.I.顏料黑(pigment black)1、7等黑色顏料等。The pigment (A1) is not particularly limited, and well-known pigments can also be used. For example, the Color Index (published by The Society of Dyers and Colourists) can be classified as a pigment. Of paint. Examples of pigments classified as pigments include: CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109 , 110, 117, 125, 128, 137, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and other yellow pigments; C.I. Pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; CI pigment red (pigment red) 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 202, 209, 215, 216, 224, 242, 254, 255, 264 , 265, 269, 291 and other red pigments; C.I. Pigment blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments; C.I. purple pigments such as pigment violet 1, 19, 23, 29, 32, 36, 38; C.I. Pigment green (pigment green) 7, 36, 58 and other green pigments; C.I. pigment brown (pigment brown) 23, 25 and other brown pigments; C.I. pigment black (pigment black) 1, 7 black pigments, etc.
另外,作為顏料(A1),亦可為並非分類為所述顏料的異吲哚啉黃色顏料,例如可列舉式(Y)所表示的化合物。In addition, as the pigment (A1), an isoindoline yellow pigment that is not classified as the above-mentioned pigment may also be used. For example, a compound represented by the formula (Y) may be mentioned.
[化1] [化1]
[式(Y)中,R1 ~R5 相互獨立地表示氫原子、鹵素原子、氰基、硝基、-SO3 M、-CO2 M、可具有取代基的碳數1~20的烴基或可具有取代基的雜環基。 M表示氫原子或鹼金屬原子。 R6 及R7 表示可具有取代基的碳數1~20的烴基或可具有取代基的雜環基。 L1 及L2 表示-CO-或-SO2 -。][In formula (Y), R 1 to R 5 independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, -SO 3 M, -CO 2 M, an optionally substituted hydrocarbon group having 1 to 20 carbons Or a heterocyclic group which may have a substituent. M represents a hydrogen atom or an alkali metal atom. R 6 and R 7 represent an optionally substituted hydrocarbon group having 1 to 20 carbon atoms or an optionally substituted heterocyclic group. L 1 and L 2 represent -CO- or -SO 2 -. ]
作為R1 ~R7 所表示的碳數1~20的烴基,可為脂肪族烴基及芳香族烴基,該脂肪族烴基可為飽和或不飽和,且可為鏈狀或脂環。The hydrocarbon group having 1 to 20 carbon atoms represented by R 1 to R 7 may be an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and the aliphatic hydrocarbon group may be saturated or unsaturated, and may be chain or alicyclic.
作為R1 ~R7 所表示的雜環基,可為單環,亦可為多環。The heterocyclic group represented by R 1 to R 7 may be monocyclic or polycyclic.
作為R1 ~R5 ,較佳為氫原子。As R 1 to R 5 , a hydrogen atom is preferred.
作為R6 及R7 ,較佳為具有取代基的碳數6~20的芳香族烴基,更佳為具有取代基的碳數6~10的芳香族烴基,進而佳為具有羧基作為取代基的碳數6~10的芳香族烴基。R 6 and R 7 are preferably substituted aromatic hydrocarbon groups having 6 to 20 carbons, more preferably substituted aromatic hydrocarbon groups having 6 to 10 carbons, and still more preferably having a carboxyl group as a substituent Aromatic hydrocarbon group having 6 to 10 carbon atoms.
作為L1 及L2 ,較佳為-CO-。As L 1 and L 2 , -CO- is preferable.
作為顏料(A1),較佳為C.I.顏料黃1、3、12、13、14、15、16、17、20、24、31、53、83、86、93、94、109、110、117、125、128、137、139、147、148、150、153、154、166、173、194、214、及式(Y)所表示的異吲哚啉黃色顏料等黃色顏料。 該些顏料(A1)可單獨使用,亦可使用兩種以上。The pigment (A1) is preferably CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214, and yellow pigments such as the isoindoline yellow pigment represented by formula (Y). These pigments (A1) may be used alone, or two or more kinds may be used.
C.I.顏料黃138、C.I.顏料黃185及顏料(A1)視需要亦可實施有松香處理、使用導入有酸性基或鹼性基的顏料衍生物或顏料分散劑等的表面處理、利用高分子化合物等對顏料表面的接枝處理、利用硫酸微粒化法等的微粒化處理、或用以將雜質去除的利用有機溶劑或水等的清洗處理、離子性雜質的利用離子交換法等的去除處理等。另外,顏料較佳為粒徑均勻。藉由含有顏料分散劑並進行分散處理,可獲得顏料於溶液中均勻地分散的狀態的顏料分散液。CI Pigment Yellow 138, CI Pigment Yellow 185 and Pigment (A1) may be treated with rosin, surface treatment using pigment derivatives or pigment dispersants introduced with acidic or basic groups, and polymer compounds as needed. Grafting treatment on the surface of the pigment, atomization treatment by sulfuric acid atomization method, etc., cleaning treatment with organic solvent or water to remove impurities, removal treatment for ionic impurities by ion exchange method, etc. In addition, the pigment preferably has a uniform particle size. By containing the pigment dispersant and performing the dispersion treatment, a pigment dispersion liquid in a state where the pigment is uniformly dispersed in the solution can be obtained.
作為所述顏料分散劑,例如可使用界面活性劑,可列舉:矽酮系、氟系、酯系、陽離子系、陰離子系、非離子系、兩性、聚酯系、多胺系、丙烯酸系等的界面活性劑等。作為所述界面活性劑,不僅可列舉聚氧乙烯烷基醚類、聚氧乙烯烷基苯基醚類、聚乙二醇二酯類、脫水山梨糖醇脂肪酸酯類、脂肪酸改質聚酯類、三級胺改質聚胺基甲酸酯類、聚乙亞胺類等,亦可以商品名列舉KP(信越化學工業(股)製造)、弗洛倫(Flowlen)(共榮社化學(股)製造)、索努帕斯(Solsperse)(註冊商標)(捷利康(Zeneca)(股)製造)、艾夫卡(EFKA)(註冊商標)(日本巴斯夫(BASF Japan)(股)製造)、阿吉斯帕(Ajisper)(註冊商標)(味之素精密科技(Ajinomoto Fine-Techno)(股)製造)、迪斯帕畢克(Disperbyk)(註冊商標)(畢克化學(BYK-Chemie)公司製造)等。作為分散劑,亦可使用後述的樹脂(B)。 該些分別可單獨使用,亦可將兩種以上組合使用。As the pigment dispersant, for example, surfactants can be used, including: silicone, fluorine, ester, cationic, anionic, nonionic, amphoteric, polyester, polyamine, acrylic, etc. The surface active agent and so on. Examples of the surfactant include not only polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, and fatty acid modified polyesters. , Tertiary amine modified polyurethanes, polyethyleneimines, etc., trade names can also be listed KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (Kyoeisha Chemical Co., Ltd.) Manufacturing), Solsperse (registered trademark) (manufactured by Zeneca (stock)), EFKA (registered trademark) (manufactured by BASF Japan (stock)), Ajisper (registered trademark) (manufactured by Ajinomoto Fine-Techno (stock)), Disperbyk (registered trademark) (BYK-Chemie) Manufacturing) etc. As a dispersant, the resin (B) mentioned later can also be used. These can be used alone or in combination of two or more kinds.
於使用顏料分散劑的情況下,其使用量相對於顏料而較佳為100質量%以下,更佳為5質量%以上且50質量%以下。若顏料分散劑的使用量處於所述範圍內,則存在可獲得均勻的分散狀態的顏料分散液的傾向。In the case of using a pigment dispersant, the amount used is preferably 100% by mass or less with respect to the pigment, more preferably 5% by mass or more and 50% by mass or less. If the amount of the pigment dispersant used is within the above range, there is a tendency that a pigment dispersion in a uniformly dispersed state can be obtained.
C.I.顏料黃138、C.I.顏料黃185及顏料(A1)可於分別作為顏料分散液使用時混合。另外,於使用兩種以上的顏料(A1)的情況下,亦可於分別作為顏料分散液使用時混合。C.I. Pigment Yellow 138, C.I. Pigment Yellow 185, and pigment (A1) can be mixed when used as a pigment dispersion. In addition, when two or more types of pigments (A1) are used, they may be mixed when used as pigment dispersions.
作為所述顏料分散液中所使用的溶劑,並無特別限定,可列舉與後述的溶劑(E)相同的溶劑。其中,較佳為丙二醇單甲醚乙酸酯、乳酸乙酯、丙二醇單甲醚、3-乙氧基丙酸乙酯、乙二醇單甲醚、二乙二醇單甲醚、二乙二醇單***、3-甲氧基丁基乙酸酯、3-甲氧基-1-丁醇、4-羥基-4-甲基-2-戊酮(亦稱為二丙酮醇)、N,N-二甲基甲醯胺等,更佳為丙二醇單甲醚乙酸酯、丙二醇單甲醚、二丙二醇甲醚乙酸酯、乳酸乙酯、3-甲氧基丁基乙酸酯、3-甲氧基-1-丁醇、3-乙氧基丙酸乙酯、4-羥基-4-甲基-2-戊酮等。The solvent used in the pigment dispersion liquid is not particularly limited, and examples thereof include the same solvents as the solvent (E) described later. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxy ethyl propionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monomethyl ether are preferred. Alcohol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone (also known as diacetone alcohol), N, N-dimethylformamide, etc., more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3 -Methoxy-1-butanol, ethyl 3-ethoxypropionate, 4-hydroxy-4-methyl-2-pentanone, etc.
所述顏料分散液中的溶劑的使用量並無特別限定,溶劑宜為以顏料分散液中的固體成分濃度可調整為5質量%~35質量%、更佳為10質量%~30質量%的方式使用。The amount of the solvent used in the pigment dispersion is not particularly limited, and the solvent is preferably one whose solid content concentration in the pigment dispersion can be adjusted to 5% to 35% by mass, more preferably 10% to 30% by mass Way to use.
作為染料(A2),並無特別限定,可使用公知的染料,例如可列舉溶劑染料、酸性染料、直接染料、媒染染料等。作為染料,例如可列舉染料索引(染料及色彩師協會(The Society of Dyers and Colourists)出版)中分類為顏料(pigment)以外的具有色相者的化合物、或染色筆記(色染公司)中記載的公知的染料。另外,根據化學結構,可列舉:偶氮染料、花青染料、三苯基甲烷染料、呫噸染料、酞菁染料、蒽醌染料、萘醌染料、醌亞胺染料、次甲基染料、偶氮次甲基染料、方酸內鎓染料、吖啶染料、苯乙烯基染料、香豆素染料、喹啉染料及硝基染料等。該些中,較佳為有機溶劑可溶性染料。該些染料(A2)可單獨使用亦可使用兩種以上。The dye (A2) is not particularly limited, and well-known dyes can be used. For example, solvent dyes, acid dyes, direct dyes, and mordant dyes can be mentioned. Examples of dyes include compounds that have hues other than pigments classified by the Dyes Index (published by The Society of Dyers and Colourists), or those described in the dyeing notes (color dyeing company) Well-known dyes. In addition, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinonimine dyes, methine dyes, azo Azidine dyes, squaraine dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes and nitro dyes. Among these, organic solvent-soluble dyes are preferred. These dyes (A2) may be used alone or in two or more kinds.
再者,將黃色顏料及/或黃色染料合稱為黃色色材。In addition, the yellow pigment and/or yellow dye are collectively referred to as a yellow color material.
為了形成黃色組成物,黃色著色硬化性組成物較佳為於著色劑(A)100質量%中含有90質量%以上的黃色色材成分。In order to form a yellow composition, the yellow colored curable composition preferably contains 90% by mass or more of the yellow color material component in 100% by mass of the coloring agent (A).
於著色劑(A)100質量%中,C.I.顏料黃138的含有率為70質量%以上,更佳為80質量%以上。另外,於著色劑(A)100質量%中,C.I.顏料黃138的含有率較佳為99質量%以下。The content rate of C.I. Pigment Yellow 138 in 100% by mass of the colorant (A) is 70% by mass or more, more preferably 80% by mass or more. In addition, in 100% by mass of the colorant (A), the content of C.I. Pigment Yellow 138 is preferably 99% by mass or less.
於著色劑(A)100質量%中,C.I.顏料黃185的含有率為1質量%以上,更佳為1.5質量%以上,進而佳為2質量%以上,尤佳為5質量%以上。另外,於著色劑(A)100質量%中,C.I.顏料黃185的含有率較佳為30質量%以下,更佳為20質量%以下,進而佳為10質量%以下。In 100% by mass of the colorant (A), the content of C.I. Pigment Yellow 185 is 1% by mass or more, more preferably 1.5% by mass or more, still more preferably 2% by mass or more, and particularly preferably 5% by mass or more. In addition, in 100% by mass of the colorant (A), the content of C.I. Pigment Yellow 185 is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less.
於使用C.I.顏料黃138及C.I.顏料黃185以外的黃色色材的情況下,相對於C.I.顏料黃138及C.I.顏料黃185的合計量100質量份,C.I.顏料黃138及C.I.顏料黃185以外的黃色色材的含量較佳為30質量份以下,更佳為20質量份以下,進而佳為15質量份以下。作為所述黃色色材,較佳於波長400 nm~500 nm之間具有極大吸收,更佳於波長400 nm~480 nm之間具有極大吸收。於藉由市售的吸光光度計測定吸光度時,所述極大吸收較佳為吸光度為0.5以上。黃色色材只要於所述波長範圍內具有極大吸收即可,亦可於除此之外的波長範圍內具有吸收。 另外,作為黃色色材,較佳為黃色顏料,更佳為式(Y)所表示的化合物。In the case of using yellow color materials other than CI Pigment Yellow 138 and CI Pigment Yellow 185, with respect to 100 parts by mass of the total amount of CI Pigment Yellow 138 and CI Pigment Yellow 185, yellows other than CI Pigment Yellow 138 and CI Pigment Yellow 185 The content of the color material is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 15 parts by mass or less. As the yellow color material, it preferably has a maximum absorption between 400 nm and 500 nm, and more preferably has a maximum absorption between 400 nm and 480 nm. When the absorbance is measured by a commercially available absorbance photometer, the maximum absorption is preferably 0.5 or more. The yellow color material only needs to have maximum absorption in the above-mentioned wavelength range, and may have absorption in other wavelength ranges. In addition, as the yellow color material, a yellow pigment is preferred, and a compound represented by formula (Y) is more preferred.
另外,於著色劑(A)100質量%中,C.I.顏料黃138及C.I.顏料黃185的合計量較佳為75質量%以上,更佳為80質量%以上。In addition, in 100% by mass of the colorant (A), the total amount of C.I. Pigment Yellow 138 and C.I. Pigment Yellow 185 is preferably 75% by mass or more, more preferably 80% by mass or more.
於黃色著色硬化性組成物的固體成分100質量%中,著色劑(A)的含有率較佳為20質量%~60質量%,更佳為25質量%~55質量%,進而佳為30質量%~50質量%。In 100% by mass of the solid content of the yellow colored curable composition, the content of the colorant (A) is preferably 20% by mass to 60% by mass, more preferably 25% by mass to 55% by mass, and still more preferably 30% by mass %~50% by mass.
若黃色著色硬化性組成物中的著色劑(A)的含有率高,則可獲得濃色且顏色特性優異的彩色濾光片。另外,藉由使含有率為60質量%以下,可保持圖案形成的良好性。If the content of the coloring agent (A) in the yellow coloring curable composition is high, a color filter having deep colors and excellent color characteristics can be obtained. In addition, by making the content rate 60% by mass or less, the goodness of pattern formation can be maintained.
<樹脂(B)> 作為樹脂(B),並無特別限定,較佳為鹼可溶性樹脂,更佳為具有源自選自由不飽和羧酸及不飽和羧酸酐所組成的群組中的至少一種(a)(以下有時稱為「(a)」)的結構單元的樹脂。樹脂(B)進而佳為具有選自由如下結構單元所組成的群組中的至少一種結構單元,即源自具有碳數2~4的環狀醚結構與乙烯性不飽和鍵的單體(b)(以下有時稱為「(b)」)的結構單元、源自能夠與(a)共聚的單體(c)(其中,與(a)及(b)不同)(以下有時稱為「(c)」)的結構單元、以及於側鏈具有乙烯性不飽和鍵的結構單元。<Resin (B)> The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and more preferably has at least one (a) derived from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride (hereinafter When called "(a)") the resin of the structural unit. The resin (B) further preferably has at least one structural unit selected from the group consisting of the following structural units, that is, a monomer (b) derived from a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond ) (Hereinafter sometimes referred to as "(b)") structural unit derived from monomer (c) (which is different from (a) and (b)) which can be copolymerized with (a) (hereinafter sometimes referred to as The structural unit of "(c)") and the structural unit having an ethylenically unsaturated bond in the side chain.
作為(a),具體而言,例如可列舉:丙烯酸、甲基丙烯酸、馬來酸酐、衣康酸酐、3,4,5,6-四氫鄰苯二甲酸酐、琥珀酸單[2-(甲基)丙烯醯氧基乙基]酯等,較佳為丙烯酸、甲基丙烯酸、馬來酸酐。Specific examples of (a) include acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, and succinic acid mono[2-( The meth)acryloxyethyl]ester and the like are preferably acrylic acid, methacrylic acid, and maleic anhydride.
(b)較佳為具有碳數2~4的環狀醚結構(例如,選自由氧雜環丙烷環、氧雜環丁烷環及四氫呋喃環所組成的群組中的至少一種)與(甲基)丙烯醯氧基的單體。 再者,本說明書中,所謂「(甲基)丙烯酸」表示選自由丙烯酸及甲基丙烯酸所組成的群組中的至少一種。「(甲基)丙烯醯基」及「(甲基)丙烯酸酯」等表述亦具有相同的含義。 作為(b),例如可列舉:(甲基)丙烯酸縮水甘油酯、乙烯基苄基縮水甘油醚、(甲基)丙烯酸3,4-環氧基三環[5.2.1.02 ,6 ]癸酯、3-乙基-3-(甲基)丙烯醯氧基甲基氧雜環丁烷、(甲基)丙烯酸四氫糠酯等,較佳為(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸3,4-環氧基三環[5.2.1.02 ,6 ]癸酯、3-乙基-3-(甲基)丙烯醯氧基甲基氧雜環丁烷。(B) It preferably has a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxetane ring, an oxetane ring, and a tetrahydrofuran ring) and (former Group) propylene oxy monomer. In addition, in this specification, the "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. Expressions such as "(meth)acryloyl" and "(meth)acrylate" also have the same meaning. As (b), for example, glycidyl (meth)acrylate, vinyl benzyl glycidyl ether, 3,4-epoxytricyclo[5.2.1.0 2 ,6 ]decyl (meth)acrylate , 3-ethyl-3-(meth)acryloxymethyloxetane, tetrahydrofurfuryl (meth)acrylate, etc., preferably glycidyl (meth)acrylate, (methyl) ) 3,4-epoxytricyclo[5.2.1.0 2 ,6 ]decyl acrylate, 3-ethyl-3-(meth)acryloyloxymethyloxetane.
作為(c),例如可列舉:(甲基)丙烯酸甲酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸2-甲基環己酯、三環[5.2.1.02,6 ]癸烷-8-基(甲基)丙烯酸酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸2-羥基乙酯、N-苯基馬來醯亞胺、N-環己基馬來醯亞胺、N-苄基馬來醯亞胺、苯乙烯、乙烯基甲苯等,較佳為苯乙烯、(甲基)丙烯酸苄酯、乙烯基甲苯、N-苯基馬來醯亞胺、N-環己基馬來醯亞胺、N-苄基馬來醯亞胺等。As (c), for example, methyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclic [ 5.2.1.0 2,6 ]decane-8-yl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N-phenylmaleimide, N -Cyclohexyl maleimide, N-benzyl maleimide, styrene, vinyl toluene, etc., preferably styrene, benzyl (meth)acrylate, vinyl toluene, N-phenyl horse Leximine, N-cyclohexylmaleimide, N-benzylmaleimide, etc.
具有於側鏈具有乙烯性不飽和鍵的結構單元的樹脂可藉由於(a)與(c)的共聚物上加成(b)、或於(b)與(c)的共聚物上加成(a)來製造。該樹脂亦可為於(b)與(c)的共聚物上加成(a)並進一步使羧酸酐反應而得的樹脂。Resins having structural units with ethylenically unsaturated bonds in the side chain can be added to the copolymer of (a) and (c) (b), or added to the copolymer of (b) and (c) (A) Come to manufacture. The resin may be a resin obtained by adding (a) to the copolymer of (b) and (c) and further reacting carboxylic anhydride.
樹脂(B)的聚苯乙烯換算的重量平均分子量(Mw)較佳為3,000~100,000,更佳為5,000~50,000,進而佳為5,000~30,000。若分子量處於所述範圍內,則存在未曝光部對顯影液的溶解性高、所獲得的圖案的殘膜率或硬度亦高的傾向。 樹脂(B)的分散度[重量平均分子量(Mw)/數量平均分子量(Mn)]較佳為1.1~6,更佳為1.2~4。The weight average molecular weight (Mw) in terms of polystyrene of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. If the molecular weight is within the above range, the solubility of the unexposed portion to the developer is high, and the residual film rate or hardness of the obtained pattern tends to be high. The degree of dispersion [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1-6, more preferably 1.2-4.
樹脂(B)的酸價(固體成分換算值)較佳為10 mg-KOH/g~200 mg-KOH/g,更佳為20 mg-KOH/g~180 mg-KOH/g,進而佳為25 mg-KOH/g~150 mg-KOH/g。此處,酸價是作為中和樹脂1 g所需的氫氧化鉀的量(mg)而測定的值,例如可藉由使用氫氧化鉀水溶液進行滴定而求出。The acid value (solid content conversion value) of the resin (B) is preferably 10 mg-KOH/g to 200 mg-KOH/g, more preferably 20 mg-KOH/g to 180 mg-KOH/g, and still more preferably 25 mg-KOH/g~150 mg-KOH/g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and it can be determined, for example, by titration using an aqueous potassium hydroxide solution.
於黃色著色硬化性組成物的固體成分100質量%中,樹脂(B)的含量較佳為2質量%~50質量%,更佳為3質量%~40質量%,進而佳為10質量%~30質量%。若樹脂(B)的含量處於所述範圍內,則存在未曝光部對顯影液的溶解性高的傾向。In 100% by mass of the solid content of the yellow colored curable composition, the content of resin (B) is preferably 2% by mass to 50% by mass, more preferably 3% by mass to 40% by mass, and still more preferably 10% by mass to 30% by mass. If the content of the resin (B) is within the above range, the unexposed part tends to have high solubility in the developer.
<聚合性化合物(C)> 聚合性化合物(C)若為可藉由自聚合起始劑(D)產生的活性自由基及/或酸進行聚合的化合物則並無特別限定,可列舉聚合性的具有乙烯性不飽和鍵的化合物等。<Polymerizable compound (C)> The polymerizable compound (C) is not particularly limited as long as it is a compound that can be polymerized by living radicals and/or acids generated from the polymerization initiator (D), and examples thereof include polymerizable ethylenically unsaturated bonds Compound etc.
其中,作為聚合性化合物(C),較佳為具有三個以上的乙烯性不飽和鍵的聚合性化合物,例如可列舉:三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、三季戊四醇八(甲基)丙烯酸酯、三季戊四醇七(甲基)丙烯酸酯、四季戊四醇十(甲基)丙烯酸酯、四季戊四醇九(甲基)丙烯酸酯、三(2-(甲基)丙烯醯氧基乙基)異氰脲酸酯、乙二醇改質季戊四醇四(甲基)丙烯酸酯、乙二醇改質二季戊四醇六(甲基)丙烯酸酯、丙二醇改質季戊四醇四(甲基)丙烯酸酯、丙二醇改質二季戊四醇六(甲基)丙烯酸酯、己內酯改質季戊四醇四(甲基)丙烯酸酯、己內酯改質二季戊四醇六(甲基)丙烯酸酯等。其中,較佳為二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯等。Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(methyl) )Acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate Acrylate, pentaerythritol deca(meth)acrylate, pentaerythritol non(meth)acrylate, tris(2-(meth)acryloxyethyl) isocyanurate, ethylene glycol modified pentaerythritol Tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate, propylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth)acrylate, caprolone Ester modified pentaerythritol tetra(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, etc. Among them, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like are preferred.
聚合性化合物(C)的重量平均分子量較佳為150以上且3,000以下,更佳為250以上且1,500以下。The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 3,000 or less, more preferably 250 or more and 1,500 or less.
相對於黃色著色硬化性組成物中的樹脂(B)100質量份,聚合性化合物(C)的含量較佳為20質量份~200質量份,更佳為80質量份~180質量份。The content of the polymerizable compound (C) is preferably 20 parts by mass to 200 parts by mass, and more preferably 80 parts by mass to 180 parts by mass, relative to 100 parts by mass of the resin (B) in the yellow colored curable composition.
<聚合起始劑(D)> 聚合起始劑(D)若為可藉由光或熱的作用而產生活性自由基、酸等並使聚合開始的化合物則並無特別限定,可使用公知的聚合起始劑。作為產生活性自由基的聚合起始劑,例如可列舉:N-苯甲醯基氧基-1-(4-苯基巰基苯基)丁烷-1-酮-2-亞胺、N-苯甲醯基氧基-1-(4-苯基巰基苯基)辛烷-1-酮-2-亞胺、N-苯甲醯基氧基-1-(4-苯基巰基苯基)-3-環戊基丙烷-1-酮-2-亞胺、N-乙醯基氧基-1-(4-苯基巰基苯基)-3-環己基丙烷-1-酮-2-亞胺(以下,亦稱為1-[4-(苯硫基)苯基]-3-環己基-丙烷-1,2-二酮-2-(鄰乙醯基肟))、2-甲基-2-嗎啉基-1-(4-甲基巰基苯基)丙烷-1-酮、2-二甲基胺基-1-(4-嗎啉基苯基)-2-苄基丁烷-1-酮、1-羥基環己基苯基酮、2,4-雙(三氯甲基)-6-胡椒基-1,3,5-三嗪、2,4,6-三甲基苯甲醯基二苯基氧化膦、2,2'-雙(2-氯苯基)-4,4',5,5'-四苯基聯咪唑等。<Polymerization initiator (D)> The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate active radicals, acids, etc. by the action of light or heat and initiate polymerization, and a known polymerization initiator can be used. As a polymerization initiator that generates living radicals, for example, N-benzyloxy-1-(4-phenylmercaptophenyl)butan-1-one-2-imine, N-benzene Formyloxy-1-(4-phenylmercaptophenyl)octane-1-one-2-imine, N-benzyloxy-1-(4-phenylmercaptophenyl)- 3-cyclopentylpropane-1-one-2-imine, N-acetyloxy-1-(4-phenylmercaptophenyl)-3-cyclohexylpropane-1-one-2-imine (Hereinafter, also referred to as 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(o-acetyloxime)), 2-methyl- 2-morpholin-1-(4-methylmercaptophenyl)propane-1-one, 2-dimethylamino-1-(4-morpholinylphenyl)-2-benzylbutane- 1-ketone, 1-hydroxycyclohexyl phenyl ketone, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4,6-trimethylbenzyl Diphenylphosphine oxide, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, etc.
相對於樹脂(B)及聚合性化合物(C)的合計量100質量份,聚合起始劑(D)的含量較佳為0.1質量份~30質量份,更佳為1質量份~25質量份,進而佳為2質量份~20質量份。若聚合起始劑(D)的含量處於所述範圍內,則存在高感度化而曝光時間縮短的傾向,因此彩色濾光片的生產性提高。The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, and more preferably 1 to 25 parts by mass relative to 100 parts by mass of the total amount of the resin (B) and polymerizable compound (C) , More preferably 2 parts by mass to 20 parts by mass. If the content of the polymerization initiator (D) is within the above-mentioned range, the sensitivity tends to increase and the exposure time is shortened, so the productivity of the color filter improves.
<聚合起始助劑(D1)> 本發明的黃色著色硬化性組成物亦可包含聚合起始助劑(D1)。聚合起始助劑(D1)為用以促進藉由聚合起始劑而開始聚合的聚合性化合物的聚合的化合物、或增感劑。於包含聚合起始助劑(D1)的情況下,可與聚合起始劑(D)組合使用。 作為聚合起始助劑(D1),可列舉胺化合物、烷氧基蒽化合物、硫雜蒽酮化合物及羧酸化合物等。其中,較佳為硫雜蒽酮化合物。亦可含有兩種以上的聚合起始助劑(D1)。<Polymerization initiator (D1)> The yellow colored curable composition of the present invention may also contain a polymerization initiation assistant (D1). The polymerization start auxiliary agent (D1) is a compound or a sensitizer for accelerating the polymerization of a polymerizable compound that starts polymerization by a polymerization initiator. When the polymerization initiator (D1) is included, it can be used in combination with the polymerization initiator (D). Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds. Among them, a thioxanthone compound is preferred. It may also contain two or more polymerization start aids (D1).
作為胺化合物,可列舉:三乙醇胺、甲基二乙醇胺、三異丙醇胺、4-二甲基胺基苯甲酸甲酯、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸異戊酯、苯甲酸2-二甲基胺基乙酯、4-二甲基胺基苯甲酸2-乙基己酯、N,N-二甲基對甲苯胺、4,4'-雙(二甲基胺基)二苯甲酮(通稱米其勒酮(Michler's ketone))、4,4'-雙(二乙基胺基)二苯甲酮及4,4'-雙(乙基甲基胺基)二苯甲酮等,其中,較佳為4,4'-雙(二乙基胺基)二苯甲酮。另外,作為胺化合物,亦可使用EAB-F(保土谷化學工業(股)製造)等市售品。Examples of amine compounds include: triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethyl Isoamyl aminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4 '-Bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone and 4,4'-bis (Ethylmethylamino)benzophenone, etc., among them, 4,4'-bis(diethylamino)benzophenone is preferred. In addition, as the amine compound, commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) can also be used.
作為烷氧基蒽化合物,可列舉:9,10-二甲氧基蒽、2-乙基-9,10-二甲氧基蒽、9,10-二乙氧基蒽、2-乙基-9,10-二乙氧基蒽、9,10-二丁氧基蒽及2-乙基-9,10-二丁氧基蒽等。Examples of alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl- 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene and 2-ethyl-9,10-dibutoxyanthracene, etc.
作為硫雜蒽酮化合物,可列舉:2-異丙基硫雜蒽酮、4-異丙基硫雜蒽酮、2,4-二乙基硫雜蒽酮、2,4-二氯硫雜蒽酮及1-氯-4-丙氧基硫雜蒽酮等。Examples of the thioxanthone compound include: 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone Anthrone and 1-chloro-4-propoxythioxanthone, etc.
作為羧酸化合物,可列舉:苯基巰基乙酸、甲基苯基巰基乙酸、乙基苯基巰基乙酸、甲基乙基苯基巰基乙酸、二甲基苯基巰基乙酸、甲氧基苯基巰基乙酸、二甲氧基苯基巰基乙酸、氯苯基巰基乙酸、二氯苯基巰基乙酸、N-苯基甘胺酸、苯氧基乙酸、萘基硫代乙酸、N-萘基甘胺酸及萘氧基乙酸等。Examples of carboxylic acid compounds include: phenylthioglycolic acid, methylphenylthioglycolic acid, ethylphenylthioglycolic acid, methylethylphenylthioglycolic acid, dimethylphenylthioglycolic acid, and methoxyphenylthioglycolic acid. Acetic acid, dimethoxyphenylthioglycolic acid, chlorophenylthioglycolic acid, dichlorophenylthioglycolic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine And naphthoxyacetic acid and so on.
於使用該些聚合起始助劑(D1)的情況下,相對於樹脂(B)及聚合性化合物(C)的合計量100質量份,其含量較佳為0.1質量份~30質量份,更佳為1質量份~20質量份。若聚合起始助劑(D1)的量處於所述範圍內,則可進而以高感度形成著色圖案,且存在彩色濾光片的生產性提高的傾向。In the case of using these polymerization initiation aids (D1), relative to 100 parts by mass of the total amount of resin (B) and polymerizable compound (C), the content is preferably 0.1 to 30 parts by mass, and more It is preferably 1 part by mass to 20 parts by mass. If the amount of the polymerization initiation assistant (D1) is within the above-mentioned range, a colored pattern can be further formed with high sensitivity, and the productivity of the color filter tends to improve.
<溶劑(E)> 本發明的黃色著色硬化性組成物較佳為包含溶劑(E)。作為溶劑(E),例如可列舉:酯溶劑(分子內包含-COO-而不含-O-的溶劑)、醚溶劑(分子內包含-O-而不含-COO-的溶劑)、醚酯溶劑(分子內包含-COO-與-O-的溶劑)、酮溶劑(分子內包含-CO-而不含-COO-的溶劑)、醇溶劑(分子內包含OH而不含-O-、-CO-及-COO-的溶劑)、芳香族烴溶劑、醯胺溶劑及二甲亞碸等。<Solvent (E)> The yellow colored curable composition of the present invention preferably contains a solvent (E). As the solvent (E), for example, ester solvents (solvents containing -COO- but not -O- in the molecule), ether solvents (solvents containing -O- but not -COO- in the molecule), ether esters Solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- but not -COO- in the molecule), alcohol solvents (containing OH but not -O-,-in the molecule) CO- and -COO- solvents), aromatic hydrocarbon solvents, amide solvents and dimethyl sulfide, etc.
作為酯溶劑,可列舉:乳酸甲酯、乳酸乙酯、乳酸丁酯、2-羥基異丁酸甲酯、乙酸乙酯、乙酸正丁酯、乙酸異丁酯、甲酸戊酯、乙酸異戊酯、丙酸丁酯、丁酸異丙酯、丁酸乙酯、丁酸丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、環己醇乙酸酯及γ-丁內酯等。Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, and isoamyl acetate , Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, cyclic Hexanol acetate and γ-butyrolactone, etc.
作為醚溶劑,可列舉:乙二醇單甲醚、乙二醇單***、乙二醇單丙醚、乙二醇單丁醚、二乙二醇單甲醚、二乙二醇單***、二乙二醇單丁醚、丙二醇單甲醚、丙二醇單***、丙二醇單丙醚、丙二醇單丁醚、3-甲氧基-1-丁醇、3-甲氧基-3-甲基丁醇、四氫呋喃、四氫吡喃、1,4-二噁烷、二乙二醇二甲醚、二乙二醇二***、二乙二醇甲基***、二乙二醇二丙醚、二乙二醇二丁醚、苯甲醚、苯***及甲基苯甲醚等。Examples of ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and Ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, Tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol Dibutyl ether, anisole, phenethyl ether and methyl anisole, etc.
作為醚酯溶劑,可列舉:甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、丙二醇單丙醚乙酸酯、乙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、二乙二醇單***乙酸酯、二乙二醇單丁醚乙酸酯及二丙二醇甲醚乙酸酯等。Examples of ether ester solvents include: methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, 3-methoxypropionic acid Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionic acid Ethyl ester, 2-methoxypropyl propionate, 2-ethoxy methyl propionate, 2-ethoxy ethyl propionate, 2-methoxy-2-methyl propionate, 2- Ethoxy-2-methyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol mono Ethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether ethyl Ester and dipropylene glycol methyl ether acetate, etc.
作為酮溶劑,可列舉:4-羥基-4-甲基-2-戊酮、丙酮、2-丁酮、2-庚酮、3-庚酮、4-庚酮、4-甲基-2-戊酮、環戊酮、環己酮及異佛爾酮等。Examples of the ketone solvent include: 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2- Pentanone, cyclopentanone, cyclohexanone and isophorone, etc.
作為醇溶劑,可列舉:甲醇、乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、丙二醇及甘油等。 作為芳香族烴溶劑,可列舉:苯、甲苯、二甲苯及均三甲苯等。 作為醯胺溶劑,可列舉:N,N-二甲基甲醯胺、N,N-二甲基乙醯胺及N-甲基吡咯啶酮等。Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin. As an aromatic hydrocarbon solvent, benzene, toluene, xylene, mesitylene, etc. are mentioned. Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like.
該些溶劑(E)亦可併用兩種以上。 就塗佈性、乾燥性的方面而言,溶劑(E)較佳為1 atm下的沸點為120℃以上且180℃以下的有機溶劑。其中,溶劑(E)較佳為丙二醇單甲醚乙酸酯、乳酸乙酯、丙二醇單甲醚、3-乙氧基丙酸乙酯、乙二醇單甲醚、二乙二醇單甲醚、二乙二醇單***、3-甲氧基丁基乙酸酯、3-甲氧基-1-丁醇、4-羥基-4-甲基-2-戊酮及N,N-二甲基甲醯胺,更佳為丙二醇單甲醚乙酸酯、丙二醇單甲醚、二丙二醇甲醚乙酸酯、乳酸乙酯、3-甲氧基丁基乙酸酯、3-甲氧基-1-丁醇、3-乙氧基丙酸乙酯及4-羥基-4-甲基-2-戊酮。These solvents (E) may be used in combination of two or more kinds. In terms of coating properties and drying properties, the solvent (E) is preferably an organic solvent having a boiling point of 120°C or more and 180°C or less at 1 atm. Among them, the solvent (E) is preferably propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxy ethyl propionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone and N,N-dimethyl Methamide, more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy- 1-butanol, ethyl 3-ethoxypropionate and 4-hydroxy-4-methyl-2-pentanone.
於黃色著色硬化性組成物的總量中,溶劑(E)的含有率較佳為70質量%~95質量%,更佳為75質量%~92質量%。換言之,於黃色著色硬化性組成物的總量中,黃色著色硬化性組成物的固體成分的含有率較佳為5質量%~30質量%,更佳為8質量%~25質量%。若溶劑(E)的含有率處於所述範圍內,則塗佈時的平坦性變良好,另外,於形成彩色濾光片時色濃度不會不足,因此存在特性變良好的傾向。In the total amount of the yellow colored curable composition, the content of the solvent (E) is preferably 70% by mass to 95% by mass, more preferably 75% by mass to 92% by mass. In other words, in the total amount of the yellow colored curable composition, the solid content of the yellow colored curable composition is preferably 5 mass% to 30 mass %, more preferably 8 mass% to 25 mass %. If the content of the solvent (E) is within the above range, the flatness during coating becomes good, and the color density is not insufficient when forming a color filter, so there is a tendency that the characteristics become good.
<調平劑(F)> 本發明的黃色著色硬化性組成物亦可包含調平劑(F)。作為調平劑(F),可列舉:矽酮系界面活性劑、氟系界面活性劑及具有氟原子的矽酮系界面活性劑等。該些亦可於側鏈上具有聚合性基。<Leveling agent (F)> The yellow colored curable composition of this invention may contain a leveling agent (F). As the leveling agent (F), silicone-based surfactants, fluorine-based surfactants, silicone-based surfactants having fluorine atoms, and the like can be cited. These may have a polymerizable group on the side chain.
作為矽酮系界面活性劑,可列舉分子內具有矽氧烷鍵的界面活性劑等。具體而言,可列舉:東麗矽酮(Toray silicone)DC3PA、東麗矽酮(Toray silicone)SH7PA、東麗矽酮(Toray silicone)DC11PA、東麗矽酮(Toray silicone)SH21PA、東麗矽酮(Toray silicone)SH28PA、東麗矽酮(Toray silicone)SH29PA、東麗矽酮(Toray silicone)SH30PA、東麗矽酮(Toray silicone)SH8400(東麗道康寧(Toray Dow Corning)(股)製造)、KP321、KP322、KP323、KP324、KP326、KP340、KP341(信越化學工業(股)製造)、TSF400、TSF401、TSF410、TSF4300、TSF4440、TSF4445、TSF4446、TSF4452及TSF4460(日本邁圖高新材料(Momentive Performance Materials Japan)有限責任公司製造)等。Examples of the silicone-based surfactant include a surfactant having a siloxane bond in the molecule, and the like. Specifically, it can include: Toray silicone (Toray silicone) DC3PA, Toray silicone (Toray silicone) SH7PA, Toray silicone (Toray silicone) DC11PA, Toray silicone (Toray silicone) SH21PA, Toray silicone Toray silicone (Toray silicone) SH28PA, Toray silicone (Toray silicone) SH29PA, Toray silicone (Toray silicone) SH30PA, Toray silicone (Toray silicone) SH8400 (manufactured by Toray Dow Corning (stock)) , KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (Momentive Performance Materials Japan) Co., Ltd.), etc.
作為氟系界面活性劑,可列舉分子內具有氟碳鏈的界面活性劑等。具體而言,可列舉:弗拉德(Fluorad)(註冊商標)FC430、弗拉德(Fluorad)FC431(住友3M(股)製造)、美佳法(Megafac)(註冊商標)F142D、美佳法(Megafac)F171、美佳法(Megafac)F172、美佳法(Megafac)F173、美佳法(Megafac)F177、美佳法(Megafac)F183、美佳法(Megafac)F554、美佳法(Megafac)R30、美佳法(Megafac)RS-718-K(迪愛生(DIC)(股)製造)、艾福拓(Eftop)(註冊商標)EF301、艾福拓(Eftop)EF303、艾福拓(Eftop)EF351、艾福拓(Eftop)EF352(三菱材料電子化成(股)製造)、沙福隆(Surflon)(註冊商標)S381、沙福隆(Surflon)S382、沙福隆(Surflon)SC101、沙福隆(Surflon)SC105(旭硝子(股)製造)及E5844(大金精細化學品(Daikin Fine Chemicals)研究所(股)製造)等。Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule, and the like. Specifically, it can include: Fluorad (registered trademark) FC430, Fluorad (Fluorad) FC431 (manufactured by Sumitomo 3M (stock)), Megafac (registered trademark) F142D, Megafac ) F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, Megafac RS-718-K (manufactured by DIC (shares)), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop ) EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (Asahi Glass (Stock) Manufacturing) and E5844 (Daikin Fine Chemicals (Daikin Fine Chemicals) Research Institute (Stock) Manufacturing) etc.
作為具有氟原子的矽酮系界面活性劑,可列舉分子內具有矽氧烷鍵及氟碳鏈的界面活性劑等。具體而言,可列舉美佳法(Megafac)(註冊商標)R08、美佳法(Megafac)BL20、美佳法(Megafac)F475、美佳法(Megafac)F477、美佳法(Megafac)F473及美佳法(Megafac)554(迪愛生(DIC)(股)製造)等。Examples of the silicone-based surfactant having a fluorine atom include surfactants having a silicone bond and a fluorocarbon chain in the molecule. Specifically, it can include Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, Megafac F473 and Megafac 554 (manufactured by DIC (Stock)) etc.
相對於黃色著色硬化性組成物的總量,調平劑(F)的含有率較佳為0.001質量%以上且0.2質量%以下,更佳為0.002質量%以上且0.1質量%以下,進而佳為0.0035質量%以上且0.05質量%以下。另外,該含有率不包含所述顏料分散劑的含有率。若調平劑(F)的含有率處於所述範圍內,則可使彩色濾光片的平坦性良好。The content of the leveling agent (F) is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass or less, and still more preferably, with respect to the total amount of the yellow coloring curable composition 0.0035 mass% or more and 0.05 mass% or less. In addition, this content rate does not include the content rate of the said pigment dispersing agent. If the content rate of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.
<其他成分> 本發明的著色硬化性組成物中,視需要亦可併用填充劑、其他高分子化合物、密接促進劑、抗氧化劑、硫醇化合物、紫外線吸收劑、防凝聚劑、有機酸、有機胺化合物、硬化劑等該技術領域中公知的添加劑。<Other ingredients> In the colored curable composition of the present invention, fillers, other polymer compounds, adhesion promoters, antioxidants, thiol compounds, ultraviolet absorbers, anti-agglomeration agents, organic acids, organic amine compounds, curing agents, Agents and other additives known in the technical field.
<黃色著色硬化性組成物的製造方法> 本發明的黃色著色硬化性組成物可藉由含有著色劑(A)、樹脂(B)、聚合性化合物(C)及聚合起始劑(D)、以及視需要混合溶劑(E)、調平劑(F)、聚合起始助劑(D1)及其他成分來製備。 C.I.顏料黃138、C.I.顏料黃185及視需要所使用的作為顏料(A1)的顏料較佳為預先與溶劑(E)的一部分或全部混合,並使用珠磨機等分散至顏料的平均粒徑為0.2 μm以下左右。此時,視需要亦可調配所述顏料分散劑、樹脂(B)的一部分或全部。藉由於以所述方式獲得的顏料分散液中以成為規定濃度的方式混合剩餘的成分,可製備著色硬化性組成物。<Method for manufacturing yellow colored curable composition> The yellow colored curable composition of the present invention can be prepared by containing a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), as well as mixing a solvent (E) and leveling if necessary. Agent (F), polymerization initiator (D1) and other ingredients. CI Pigment Yellow 138, CI Pigment Yellow 185 and the pigment used as the pigment (A1) as needed are preferably mixed with a part or all of the solvent (E) in advance and dispersed to the average particle size of the pigment using a bead mill or the like It is about 0.2 μm or less. At this time, if necessary, a part or all of the pigment dispersant and resin (B) may be blended. By mixing the remaining components in the pigment dispersion liquid obtained in the above manner so as to have a predetermined concentration, a colored curable composition can be prepared.
<彩色濾光片的製造方法> 作為由本發明的黃色著色硬化性組成物製造著色圖案的方法,可列舉光微影法、噴墨法、印刷法等。其中,較佳為光微影法。光微影法是於基板上塗佈所述黃色著色硬化性組成物,使其乾燥而形成著色組成物層,並介隔光罩來對該著色組成物層進行曝光、顯影的方法。於光微影法中,藉由於曝光時不使用光罩、及/或不進行顯影而可形成作為所述著色組成物層的硬化物的著色塗膜。以所述方式形成的著色圖案或著色塗膜為本發明的彩色濾光片。<Method of manufacturing color filter> As a method of producing a colored pattern from the yellow colored curable composition of the present invention, a photolithography method, an inkjet method, a printing method, etc. may be mentioned. Among them, the photolithography method is preferred. The photolithography method is a method of applying the yellow colored curable composition on a substrate, drying it to form a colored composition layer, and exposing and developing the colored composition layer through a photomask. In the photolithography method, a colored coating film that is a hardened product of the colored composition layer can be formed by not using a photomask during exposure and/or not performing development. The colored pattern or colored coating film formed in the manner described above is the color filter of the present invention.
作為基板,可使用石英玻璃、硼矽酸玻璃、氧化鋁矽酸鹽玻璃、對表面進行了二氧化矽塗佈的鈉鈣玻璃等玻璃板;或聚碳酸酯、聚甲基丙烯酸甲酯、聚對苯二甲酸乙二酯等樹脂板;矽;於所述基板上形成有鋁、銀、銀/銅/鈀合金薄膜等者。亦可於該些基板上形成其他的彩色濾光片層、樹脂層、電晶體、電路等。As the substrate, glass plates such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass coated with silica; or polycarbonate, polymethylmethacrylate, polycarbonate, etc. can be used. Resin plates such as ethylene terephthalate; silicon; aluminum, silver, silver/copper/palladium alloy thin films, etc. formed on the substrate. Other color filter layers, resin layers, transistors, circuits, etc. can also be formed on these substrates.
利用光微影法來形成各顏色畫素可於公知或慣用的裝置或條件下進行。例如可以如下方式來製作。 首先,將著色硬化性組成物塗佈於基板上,藉由進行加熱乾燥(預烘烤)及/或減壓乾燥而將溶劑等揮發成分去除來加以乾燥,獲得平滑的著色組成物層。 作為塗佈方法,可列舉旋塗法、狹縫塗佈法、狹縫及旋塗法等。 進行加熱乾燥時的溫度較佳為30℃~120℃,更佳為50℃~110℃。另外,作為加熱時間,較佳為10秒~5分鐘,更佳為30秒~3分鐘。 於進行減壓乾燥的情況下,較佳為於50 Pa~150 Pa的壓力下、以20℃~25℃的溫度範圍來進行。The use of photolithography to form each color pixel can be performed under known or customary devices or conditions. For example, it can be produced as follows. First, the colored curable composition is coated on the substrate, and volatile components such as the solvent are removed by heat drying (pre-baking) and/or reduced pressure drying to dry, thereby obtaining a smooth colored composition layer. As the coating method, a spin coating method, a slit coating method, a slit and spin coating method, etc. can be cited. The temperature during heat drying is preferably 30°C to 120°C, more preferably 50°C to 110°C. In addition, the heating time is preferably 10 seconds to 5 minutes, and more preferably 30 seconds to 3 minutes. In the case of drying under reduced pressure, it is preferably performed under a pressure of 50 Pa to 150 Pa in a temperature range of 20°C to 25°C.
繼而,對著色組成物層介隔用以形成目標著色圖案的光罩來進行曝光。該光罩上的圖案並無特別限定,可使用與目標用途相應的圖案。 作為曝光中所使用的光源,較佳為產生250 nm~450 nm的波長的光的光源。例如,可對於小於350 nm的光,使用截止該波長範圍的濾光片進行截止,或者對於436 nm附近、408 nm附近、365 nm附近的光,使用提取該些波長範圍的帶通濾光片進行選擇性提取。具體而言,作為光源,可列舉水銀燈、發光二極體、金屬鹵化物燈、鹵素燈等。 為了對曝光面整體均勻地照射平行光線、或者可進行光罩與形成有著色組成物層的基板的準確的對位,較佳為使用遮罩對準器及步進機等曝光裝置。Then, the colored composition layer is exposed via a photomask for forming a target colored pattern. The pattern on the mask is not particularly limited, and a pattern corresponding to the intended use can be used. As the light source used for exposure, a light source that generates light with a wavelength of 250 nm to 450 nm is preferred. For example, for light less than 350 nm, use a filter that cuts off the wavelength range, or for light near 436 nm, near 408 nm, and near 365 nm, use band-pass filters that extract these wavelength ranges Perform selective extraction. Specifically, as the light source, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. can be cited. In order to uniformly irradiate the entire exposure surface with parallel light or to accurately align the mask and the substrate on which the colored composition layer is formed, it is preferable to use an exposure device such as a mask aligner and a stepper.
藉由使曝光後的著色組成物層接觸顯影液來進行顯影,而於基板上形成著色圖案。藉由顯影,著色組成物層的未曝光部溶解於顯影液中而被去除。作為顯影液,例如較佳為氫氧化鉀、碳酸氫鈉、碳酸鈉、氫氧化四甲基銨等鹼性化合物的水溶液。該些鹼性化合物於水溶液中的濃度較佳為0.01質量%~10質量%,更佳為0.03質量%~5質量%。進而,顯影液亦可包含界面活性劑。 顯影方法可為覆液法、浸漬法及噴霧法等的任一種。進而亦可於顯影時將基板傾斜為任意的角度。 顯影後,較佳為進行水洗。By contacting the exposed coloring composition layer with a developing solution for development, a coloring pattern is formed on the substrate. By developing, the unexposed part of the colored composition layer is dissolved in the developing solution and removed. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, and tetramethylammonium hydroxide is preferred. The concentration of these basic compounds in the aqueous solution is preferably 0.01% by mass to 10% by mass, more preferably 0.03% by mass to 5% by mass. Furthermore, the developer may contain a surfactant. The development method may be any of a liquid coating method, a dipping method, and a spray method. Furthermore, the substrate may be inclined to an arbitrary angle during development. After development, it is preferable to wash with water.
進而,較佳為對所獲得的著色圖案進行後烘烤。後烘烤溫度較佳為150℃~250℃,更佳為160℃~235℃。後烘烤時間較佳為1分鐘~120分鐘,更佳為3分鐘~60分鐘。Furthermore, it is preferable to post-bak the obtained colored pattern. The post-baking temperature is preferably 150°C to 250°C, more preferably 160°C to 235°C. The post-baking time is preferably 1 minute to 120 minutes, more preferably 3 minutes to 60 minutes.
因所獲得的彩色濾光片的膜厚對鄰接畫素造成影響,因此較佳為儘可能薄。若膜厚較厚,則有可能發生與鄰接畫素的光的混色。後烘烤後的彩色濾光片的膜厚例如較佳為3 μm以下,更佳為2.8 μm以下,進而佳為2.5 μm以下,進而更佳為2.0 μm以下。彩色濾光片的膜厚的下限並無特別限定,通常為0.3 μm以上,亦可為0.5 μm以上。Since the film thickness of the obtained color filter affects adjacent pixels, it is preferably as thin as possible. If the film thickness is thick, color mixing with the light of adjacent pixels may occur. The film thickness of the post-baked color filter is, for example, preferably 3 μm or less, more preferably 2.8 μm or less, still more preferably 2.5 μm or less, and even more preferably 2.0 μm or less. The lower limit of the film thickness of the color filter is not particularly limited, but it is usually 0.3 μm or more, and may be 0.5 μm or more.
關於本發明的黃色著色硬化性組成物,於使用該黃色著色硬化性組成物來形成膜厚0.6 μm的著色圖案或著色塗膜時的透過率較佳為於波長430 nm下為7%以下,並且於波長500 nm下為85%以上。另外,較佳為自短波長側向長波長側的透過率曲線不平緩、且不過陡,具體而言,較佳為460 nm下的透過率與485 nm下的透過率的差異(透過率(485 nm)-透過率(460 nm))為55以上且75以下。若透過率以及透過率曲線處於所述範圍內,則可使作為黃色的顏色特性良好。再者,作為波長430 nm的透過率,更佳為6%以下,進而佳為5%以下。作為波長500 nm中的透過率,更佳為86%以上,進而佳為87%以上。460 nm下的透過率與485 nm下的透過率之間的差異更佳為60以上。Regarding the yellow colored curable composition of the present invention, when the yellow colored curable composition is used to form a colored pattern or colored coating film with a film thickness of 0.6 μm, the transmittance is preferably 7% or less at a wavelength of 430 nm, And it is over 85% at a wavelength of 500 nm. In addition, it is preferable that the transmittance curve from the short-wavelength side to the long-wavelength side is not smooth and not too steep. Specifically, the difference between the transmittance at 460 nm and the transmittance at 485 nm (transmittance ( 485 nm)-Transmittance (460 nm)) is 55 or more and 75 or less. If the transmittance and the transmittance curve are within the above range, the color characteristic as yellow can be made good. Furthermore, the transmittance at a wavelength of 430 nm is more preferably 6% or less, and still more preferably 5% or less. As the transmittance at a wavelength of 500 nm, it is more preferably 86% or more, and still more preferably 87% or more. The difference between the transmittance at 460 nm and the transmittance at 485 nm is more preferably 60 or more.
藉由使用本發明的黃色著色硬化性組成物,可製造特別是作為固體攝像元件用途而具有良好的黃色顏色特性的彩色濾光片。該彩色濾光片可用於固體攝像元件,但亦可有效用作其他顯示裝置(例如液晶顯示裝置、有機電致發光(electroluminescence,EL)裝置、電子紙等)中使用的彩色濾光片。By using the yellow colored curable composition of the present invention, it is possible to manufacture a color filter having good yellow color characteristics especially as a solid-state imaging device. The color filter can be used for solid-state imaging devices, but can also be effectively used as a color filter used in other display devices (for example, liquid crystal display devices, organic electroluminescence (EL) devices, electronic paper, etc.).
本申請案主張基於2019年2月28日提出申請的日本專利申請第2019-036599號的優先權的利益。於本申請案中引用2019年2月28日提出申請的日本專利申請第2019-036599號的說明書的全部內容以供參考。 [實施例]This application claims the benefit of priority based on Japanese Patent Application No. 2019-036599 filed on February 28, 2019. The entire contents of the specification of Japanese Patent Application No. 2019-036599 filed on February 28, 2019 are cited in this application for reference. [Example]
以下列舉實施例來更具體地說明本發明,但本發明原本便不因下述實施例而受到限制,當然亦能夠於可適合於前述/後述的主旨的範圍內適當施加變更而實施,該些均包含於本發明的技術範圍內。再者,以下,只要無特別說明,則「份」是指「質量份」,「%」是指「質量%」。The following examples are given to illustrate the present invention more specifically, but the present invention is not originally limited by the following examples. Of course, it can also be implemented with appropriate changes within the scope that can be adapted to the above/after gist. All are included in the technical scope of the present invention. In addition, in the following, unless otherwise specified, "parts" means "parts by mass", and "%" means "% by mass".
合成例1 於具備回流冷卻器、滴液漏斗及攪拌機的燒瓶內適量流通氮氣來置換成氮氣環境,加入丙二醇單甲醚乙酸酯340份,一面攪拌一面加熱至80℃。接著,歷時5小時滴加丙烯酸57份、3,4-環氧基三環[5.2.1.02,6 ]癸烷-8-基丙烯酸酯及3,4-環氧基三環[5.2.1.02,6 ]癸烷-9-基丙烯酸酯的混合物(含有比以莫耳比計為1:1)54份、甲基丙烯酸苄酯239份、丙二醇單甲醚乙酸酯73份的混合溶液。另一方面,歷時6小時滴加將聚合起始劑2,2-偶氮雙(2,4-二甲基戊腈)40份溶解於丙二醇單甲醚乙酸酯197份中而得的溶液。起始劑溶液的滴加結束後,於80℃下保持3小時後,冷卻至室溫,獲得藉由B型黏度計(23℃)測定的黏度127 mPa·s、固體成分37.0%的共聚物(樹脂B1)溶液。所生成的共聚物的重量平均分子量Mw為9.4×103 、分散度為1.89,固體成分換算的酸價為114 mg-KOH/g。樹脂B1具有以下的結構單元。Synthesis Example 1 An appropriate amount of nitrogen was circulated in a flask equipped with a reflux cooler, a dropping funnel, and a stirrer to replace it with a nitrogen atmosphere, 340 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80°C while stirring. Next, 57 parts of acrylic acid, 3,4-epoxy tricyclo[5.2.1.0 2,6 ]decane-8-yl acrylate and 3,4-epoxy tricyclo[5.2.1.0 were added dropwise over 5 hours. 2,6 ] A mixture of 54 parts of decane-9-yl acrylate (containing 1:1 in molar ratio), 239 parts of benzyl methacrylate, and 73 parts of propylene glycol monomethyl ether acetate. . On the other hand, a solution obtained by dissolving 40 parts of a polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) in 197 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours . After the dropwise addition of the starter solution was completed, it was kept at 80°C for 3 hours and then cooled to room temperature to obtain a copolymer with a viscosity of 127 mPa·s and a solid content of 37.0% measured by a B-type viscometer (23°C) (Resin B1) Solution. The weight average molecular weight Mw of the produced copolymer was 9.4×10 3 , the degree of dispersion was 1.89, and the acid value in terms of solid content was 114 mg-KOH/g. Resin B1 has the following structural units.
[化2] [化2]
〔顏料分散液(A-1)的製備〕 將C.I.顏料黃138 15.1份 丙烯酸系顏料分散劑 4.5份 樹脂B1(固體成分換算) 4.5份 丙二醇單甲醚乙酸酯 75.9份 混合,並使用珠粒磨機使C.I.顏料黃138充分分散,藉此獲得顏料分散液(A-1)。[Preparation of pigment dispersion (A-1)] Add C.I. Pigment Yellow 138 15.1 copies Acrylic pigment dispersant 4.5 copies Resin B1 (solid content conversion) 4.5 copies Propylene glycol monomethyl ether acetate 75.9 copies Mix and use a bead mill to fully disperse C.I. Pigment Yellow 138, thereby obtaining a pigment dispersion (A-1).
[顏料分散液(A-2)的製備] 將C.I.顏料黃185 10.1份 丙烯酸系顏料分散劑 4.0份 樹脂B1(固體成分換算) 4.5份 丙二醇單甲醚乙酸酯 77.3份 丙二醇單甲醚 4.1份 混合,並使用珠磨機使C.I.顏料黃185充分分散,藉此獲得顏料分散液(A-2)。[Preparation of pigment dispersion (A-2)] C.I. Pigment Yellow 185 10.1 copies Acrylic paint dispersant 4.0 copies Resin B1 (Solid content conversion) 4.5 copies Propylene glycol monomethyl ether acetate 77.3 copies Propylene glycol monomethyl ether 4.1 copies Mix and use a bead mill to fully disperse C.I. Pigment Yellow 185, thereby obtaining a pigment dispersion (A-2).
[顏料分散液(A-3)的製備] 將C.I.顏料黃138 12.0份 丙烯酸系顏料分散劑 4.8份 樹脂B1(固體成分換算) 3.2份 丙二醇單甲醚乙酸酯 80.0份 混合,並使用珠磨機使C.I.顏料黃138充分分散,藉此獲得顏料分散液(A-3)。[Preparation of pigment dispersion (A-3)] C.I. Pigment Yellow 138 12.0 copies Acrylic pigment dispersant 4.8 copies Resin B1 (solid content conversion) 3.2 copies Propylene glycol monomethyl ether acetate 80.0 copies Mix and use a bead mill to fully disperse C.I. Pigment Yellow 138, thereby obtaining a pigment dispersion (A-3).
[顏料分散液(A-4)的製備] 將黃色色材Y4 8.0份 丙烯酸系顏料分散劑 4.0份 樹脂B1(固體成分換算) 8.0份 丙二醇單甲醚乙酸酯 75.0份 二丙酮醇 5.0份 混合,並使用珠磨機使黃色色材Y4充分分散,藉此獲得顏料分散液(A-4)。 此處,所謂黃色色材Y4,表示4,4'-(2,2'-((1Z,3Z)-異吲哚啉-1,3-二亞基)雙(2-氰基乙醯基))二苯甲酸。[Preparation of pigment dispersion (A-4)] Put 8.0 copies of the yellow color material Y4 Acrylic paint dispersant 4.0 copies Resin B1 (solid content conversion) 8.0 copies Propylene glycol monomethyl ether acetate 75.0 copies Diacetone alcohol 5.0 copies Mix and use a bead mill to fully disperse the yellow color material Y4, thereby obtaining a pigment dispersion (A-4). Here, the so-called yellow color material Y4 means 4,4'-(2,2'-((1Z,3Z)-isoindoline-1,3-diylidene) bis(2-cyanoacetoxy) )) Dibenzoic acid.
[顏料分散液(A-5)的製備] 將C.I.顏料黃139 10.1份 丙烯酸系顏料分散劑 4.0份 樹脂B1(固體成分換算) 4.5份 丙二醇單甲醚乙酸酯 77.3份 丙二醇單甲醚 4.1份 混合,並使用珠磨機使C.I.顏料黃139充分分散,藉此獲得顏料分散液(A-5)。[Preparation of pigment dispersion (A-5)] C.I. Pigment Yellow 139 10.1 copies Acrylic paint dispersant 4.0 copies Resin B1 (Solid content conversion) 4.5 copies Propylene glycol monomethyl ether acetate 77.3 copies Propylene glycol monomethyl ether 4.1 copies Mix and use a bead mill to fully disperse C.I. Pigment Yellow 139, thereby obtaining a pigment dispersion (A-5).
實施例1~實施例6及比較例1~比較例5 [黃色著色硬化性組成物的製備] 將表1所記載的成分混合,獲得黃色著色硬化性組成物。另外,以黃色著色硬化性組成物的固體成分成為15%的方式混合丙二醇單甲醚乙酸酯。Example 1 to Example 6 and Comparative Example 1 to Comparative Example 5 [Preparation of yellow colored curable composition] The components described in Table 1 were mixed to obtain a yellow colored curable composition. In addition, propylene glycol monomethyl ether acetate was mixed so that the solid content of the yellow colored curable composition became 15%.
[表1]
於表1中,各成分如下。 著色分散液(A1):上述中所獲得的顏料分散液(A-1) 著色分散液(A2):上述中所獲得的顏料分散液(A-2) 著色分散液(A3):上述中所獲得的顏料分散液(A-3) 著色分散液(A4):上述中所獲得的顏料分散液(A-4) 著色分散液(A5):上述中所獲得的顏料分散液(A-5) 樹脂溶液(B1):上述中所獲得的樹脂B1 聚合性化合物(C):二季戊四醇聚丙烯酸酯 聚合起始劑(D):1-[4-(苯硫基)苯基]-3-環己基-丙烷-1,2-二酮-2-(O-乙醯基肟)(PBG-327;強力(Tronly)公司製造) 調平劑(F):含氟寡聚物(美佳法(Megafac)(註冊商標)F554;迪愛生(DIC)(股)製造)In Table 1, the components are as follows. Colored dispersion (A1): The pigment dispersion (A-1) obtained in the above Colored dispersion (A2): The pigment dispersion (A-2) obtained in the above Colored dispersion (A3): The pigment dispersion (A-3) obtained in the above Colored dispersion (A4): The pigment dispersion (A-4) obtained in the above Colored dispersion (A5): The pigment dispersion (A-5) obtained in the above Resin solution (B1): Resin B1 obtained in the above Polymerizable compound (C): Dipentaerythritol polyacrylate Polymerization initiator (D): 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime) (PBG-327 ; Manufactured by Tronly) Leveling agent (F): Fluorinated oligomer (Megafac (registered trademark) F554; manufactured by DIC (Stock))
[著色圖案的製作] 於4英吋的矽酮基板上,利用旋塗法塗佈黃色著色硬化性組成物後,於80℃下預烘烤2分鐘,獲得著色組成物層。冷卻後,使用曝光機(NSR-1755i7A;尼康(Nikon)(股)製造),以300 mJ/cm2 的曝光量對形成於該基板的著色組成物層進行光照射。將光照射後的著色組成物層,於包含氫氧化四甲基銨的水系顯影液中於23℃下浸漬顯影50秒,於水洗後,於烘箱中於230℃下進行後烘烤10分鐘,從而獲得著色圖案。[Preparation of Colored Pattern] A yellow colored curable composition was applied on a 4-inch silicone substrate by spin coating, and then pre-baked at 80°C for 2 minutes to obtain a colored composition layer. After cooling, an exposure machine (NSR-1755i7A; manufactured by Nikon (stock)) was used to irradiate the coloring composition layer formed on the substrate with light at an exposure amount of 300 mJ/cm 2 . The colored composition layer irradiated with light is immersed and developed in an aqueous developer containing tetramethylammonium hydroxide at 23°C for 50 seconds, washed with water, and post-baked in an oven at 230°C for 10 minutes. Thus, a colored pattern is obtained.
[膜厚測定] 對於所獲得的著色圖案,使用膜厚測定裝置(DEKTAK3;日本真空技術(股)製造)測定膜厚(μm)。將結果示於表2中。[Film thickness measurement] For the obtained colored pattern, the film thickness (μm) was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 2.
[透過率評價] 對於所獲得的著色圖案,使用分光測光裝置(LvmicroV;拉姆達視野(LambdaVision)(股)製造)進行分光測定,評價透過率。將結果示於表2中。將波長430 nm中的透過率為7%以下的情況設為黃色顏色特性(430 nm)良好(○),將波長500 nm中的透過率為85%以上的情況設為黃色顏色特性(500 nm)良好(○)。將所述範圍外的情況設為黃色顏色特性不良(×)。另外,對於自短波長側向長波長側的透過率曲線,以如下方式進行評價。若460 nm下的透過率與485 nm下的透過率的差異(透過率(485 nm)-透過率(460 nm))大於75,則透過率曲線過陡,若小於55,則透過率曲線平緩,因此設為黃色顏色特性不良(×),若460 nm下的透過率與485nm下的透過率的差異(透過率(485 nm)-透過率(460 nm))為55以上且75以下,則可獲得良好的黃色顏色特性,因此設為黃色顏色特性良好(○)。[Transmittance Evaluation] The obtained colored pattern was subjected to spectrophotometric measurement using a spectrophotometer (LvmicroV; manufactured by LambdaVision (Stock)) to evaluate the transmittance. The results are shown in Table 2. If the transmittance at a wavelength of 430 nm is 7% or less, the yellow color characteristic (430 nm) is good (○), and if the transmittance at a wavelength of 500 nm is 85% or more, the yellow color characteristic (500 nm) ) Good (○). The case outside the above-mentioned range is regarded as yellow color characteristic poor (×). In addition, the transmittance curve from the short-wavelength side to the long-wavelength side was evaluated in the following manner. If the difference between the transmittance at 460 nm and the transmittance at 485 nm (transmittance (485 nm)-transmittance (460 nm)) is greater than 75, the transmittance curve is too steep, if it is less than 55, the transmittance curve is flat Therefore, it is assumed that the yellow color characteristic is poor (×). If the difference between the transmittance at 460 nm and the transmittance at 485 nm (transmittance (485 nm)-transmittance (460 nm)) is 55 or more and 75 or less, then Since good yellow color characteristics can be obtained, the yellow color characteristics are good (○).
[表2]
根據本發明的黃色著色硬化性組成物,可製造黃色顏色特性良好的彩色濾光片。According to the yellow colored curable composition of the present invention, a color filter with good yellow color characteristics can be manufactured.
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