TW201037041A - Pigment dispersion liquid, colored composition for color filter, color filter, and liquid crystal - Google Patents
Pigment dispersion liquid, colored composition for color filter, color filter, and liquid crystal Download PDFInfo
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- TW201037041A TW201037041A TW099117401A TW99117401A TW201037041A TW 201037041 A TW201037041 A TW 201037041A TW 099117401 A TW099117401 A TW 099117401A TW 99117401 A TW99117401 A TW 99117401A TW 201037041 A TW201037041 A TW 201037041A
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/003—Pigment pastes, e.g. for mixing in paints containing an organic pigment
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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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
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
- C09B69/108—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing a phthalocyanine dye
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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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
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/41—Organic pigments; Organic dyes
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/1303—Apparatus specially adapted to the manufacture of LCDs
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133514—Colour filters
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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Abstract
Description
201037041 六、發明說明: 【發明所屬之技術領域】 本發明係關於一種顏料分散液、彩色濾、光片用著色組成 物、彩色遽光片、液晶顯示裝置及有機el顯示器。更詳細 而言,侧於—種使經高度微粒化之難高效率且穩定地分 散之顏料分散液、顏色特性非常優異且適於製版製程之具有 顯影性之彩色㈣片用著色組絲、具有使肋著色組成物 而形成之像素之彩色濾、光片、以及具備該彩色遽光片 之液晶 、貝示裝置及有機EL顯示器。 【先前技術】 習知’作為製造液晶顯示裝置等中所使用之彩色濾光片之 法’,已知有顏料分散法、染色法、電鑛法、印刷法。其中, '刀光特f生耐久性、圖案形狀及精度等觀點而言,最廣泛 地知用具有均衡優異特性的顏料分散法。 j年來’技術革新潮流迅速發展,對於彩⑽光片提出更 =牙透、更高對比叙更高濃度之要求。就耐熱性、耐光性 等觀點而s ’作為決絲色濾光$的顏色之色材,通常使用 顏料。作為顏料,適合使料見錢長區域的时穿透吸收 光譜與背光(back light)的螢光體發光光譜—致者。例如, 作為綠色賴,自古以來是將鹵化銅崎(phthalocyanine) 、、’彔色顏料與各種黃色顏料組合使用。 另方面,為了提昇對比度,重要的是將彩色遽光片層中 TF988407 201037041 之光散射抑制到最小限度,通常是藉由溶劑鹽磨㈤觀七 ,salt^ling)法、乾磨(drymilHng)法等將上述顏料微粒 化至-次粒#為數1Qnm之尺寸後使用。然而,因粒徑愈小 • 則其表面積愈大,故例如由於分散劑的吸附量不足而易於引 ,起再凝集,易使分散系變得不穩定。因此,如何將用以提昇 對比度而微粒化之顏料穩定地製成分散液而存在,則成為近 年來極為重要的技術課題。 〇 然而’近年來關於綠色像素之高亮度化,提出有如專利文 獻1及2所記載之具有特定色相的新穎酞菁綠色顏料,從而 達成與習知_化銅酞菁綠色顏料之差異化。然而,該新穎綠 . 色顏料、亦即溴化鋅酞菁顏料有如下問題點:為了提昇對比 • 度而進行微細化時,分散穩定性極度下降,由於因二次凝集 體所造成之光散射的影響,因此作為電視機用時其對比度會 變得不充分。 〇 為了解決此種問題’例如於專利文獻2中,揭示有使用(曱201037041 VI. Description of the Invention: [Technical Field] The present invention relates to a pigment dispersion liquid, a color filter, a coloring composition for a light sheet, a color calender sheet, a liquid crystal display device, and an organic EL display. More specifically, it is a coloring composition for coloring a color (four) sheet which is highly pigmented and highly stable and stably dispersed, and which has excellent color characteristics and is suitable for a plate making process. A color filter, a light sheet, and a liquid crystal, a display device, and an organic EL display including the color ray sheet formed by coloring the rib. [Prior Art] Conventionally, as a method of manufacturing a color filter used in a liquid crystal display device or the like, a pigment dispersion method, a dyeing method, an electric ore method, and a printing method are known. Among them, from the viewpoints of 'knife-light durability, pattern shape, precision, and the like, the pigment dispersion method having excellent balance characteristics is most widely known. In the past seven years, the trend of technological innovation has developed rapidly. For the color (10) light film, it is required to have a higher concentration of teeth and higher contrast. From the viewpoints of heat resistance, light resistance, etc., as a color material of a color of the filament color filter, a pigment is usually used. As the pigment, it is suitable for the material to see the absorption spectrum of the long-light region and the phosphor luminescence spectrum of the backlight. For example, as a green ray, phthalocyanine, a ochre pigment, and various yellow pigments have been used in combination since ancient times. On the other hand, in order to improve the contrast, it is important to minimize the light scattering of TF988407 201037041 in the color enamel sheet, usually by solvent salt grinding, salting, drymilHng method. The above pigment is micronized to a size of 1Qnm and used. However, the smaller the particle size is, the larger the surface area is. Therefore, for example, since the amount of adsorption of the dispersant is insufficient, it is easy to induce and reaggregate, which tends to make the dispersion unstable. Therefore, it has become an extremely important technical issue in recent years how to stably form a dispersion liquid which is obtained by increasing the contrast and atomizing the pigment. However, in recent years, regarding the high luminance of green pixels, a novel phthalocyanine green pigment having a specific hue as described in Patent Documents 1 and 2 has been proposed, thereby achieving differentiation from a conventional copper phthalocyanine green pigment. However, the novel green color pigment, that is, the zinc bromide phthalocyanine pigment has the following problems: when the micronization is performed to improve the contrast degree, the dispersion stability is extremely lowered due to light scattering due to the secondary aggregate. The effect is therefore insufficient when used as a TV set. 〇 In order to solve such a problem, for example, in Patent Document 2, it is disclosed that it is used (曱
基)丙烯酸系(共)聚物 Poly flow No. 75、No. 90、No. 95(共 榮社化學公司製造)、Megaface F17卜F172、F173(大日本 油墨化學工業公司製造)、Fluorad FC430、FC431(住友3MAcrylic (co)polymer Poly flow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), Megaface F17, F172, F173 (manufactured by Dainippon Ink and Chemicals, Inc.), Fluorad FC430, FC431 (Sumitomo 3M
I 公司製造)、Solsperse 13240、20000、24000、26000、28000 等各種Solsperse分散劑(Avecia公司製造)、Disperbyk 、16卜 162、163、164、182、2000、2001 等各種 Disperbyk 分散劑(畢克化學(BYK Chem i e)公司製造)、A j i sper PB711、 TF988407 5 201037041 PB411、PBl 11、PB821、PB822 等各種 ajiSpei* 分散劑(味之 素精密技術(Ajinomoto Fine-Techno)公司製造)等高分子 分散劑,來作為用以製備顏料分散液之分散劑。又,於實施 例中,係使用其中之畢克化學公司製造之丙烯酸系分散劑 「BYK-2001」。然而’根據本發明者們的驗證,即便使用該 等而分子分散劑亦無法充分保持上述經微粒化之溴化鋅酞 菁顏料的分散穩定性,有由於再凝集而造成黏度增加或由於 經時凝集而造成對比度下降等問題。 專利文獻1 :日本專利特開2004-70342號公報 專利文獻日本專利特開2004-70343號公報 【發明内容】 (發明所欲解決之問題) 本發曰明係馨於上述課題而完成者,其目的如下所述。 Λ-(,)提仏可用上篁的添加量即可高效率地將近年來經高度 ㈣分散’其結果可製造高穿透率、高對比度、低 散液及著色組成物。 ⑵特別疋提供達成了在以綠色像素之高亮度化為目的之 使用化鋅賦菁綠色顏料時所存在之問題 3== 一編用著色組: 有乂下專優點之彩色遽光片用著色組成物:對 又,於美:奋解陵良好’於顯影步驟中可在特定時間内顯影, 土反上之非圖像部分不殘留著色樹脂組成物之未溶解 TF988407 6 201037041 物,與基板之密著性優異,不使硬化性等圖像形成能力下 降,可製造兩穿透率.高對比度.低膜厚之彩色濾光片。 (4) 使用上述彩色濾光片用著色組成物,而提供高品質彩 ' 色濾、光片。 (5) 提供使用了上述彩色濾光片之高品質液晶顯示裝置及 -有機EL顯示器。 (解決問題之手段) ❹ 本如明者們為了解決上述課題而進行了努力研究,結果發 現:藉由使用特徵為由具有親溶劑性之A嵌段與具有含氮原 子的官能基之B嵌段所構成之嵌段共聚物、且其胺價以有效 • 固形分換算計為80 mgKOH/g以上之分散劑,即便對於經微 . 粒化之顏料亦可達成充分的分散穩定性,並可提供作為液晶 電視用而顯示充分高對比度之彩色濾光片,從而最終完成本 發明。 Q 本發明係由複數個相關發明所構成,各發明之要點如下。 [1] 一種顏料分散液,其特徵為:含有顏料、溶劑及分散 劑’該分散劑含有由具有親溶劑性之A嵌段與具有含氮原子 的官能基之B欲段所構成之嵌段共聚物,該分散劑之胺價以 ' 有效固形分換算計為80 mgKOH/g以上且150 mgKOH/g以下。 [2] 如上述[1]之顏料分散液’其中’上述顏料含有填化辞 醜菁。 [3] 如上述[1]或[2]之顏料分散液,其中,進而含有芳香 TF988407 7 201037041 族羧酸系化合物。 [4]如上述[3]之顏料分散液,其中,上述芳香族叛酸系化 合物係以下述通式(VI)所表示之化合物。 [化1]Various Disperbyk dispersants (made by Company I), Solsperse 13240, 20000, 24000, 26000, 28000, etc., various Dispersby dispersants (made by Avecia), Disperbyk, 16 Bu 162, 163, 164, 182, 2000, 2001 (Bick Chemical (BYK Chemie) company, A ji sper PB711, TF988407 5 201037041 PB411, PBl 11, PB821, PB822 and other ajiSpei* dispersants (Ajinomoto Fine-Techno) The agent acts as a dispersant for preparing a pigment dispersion. Further, in the examples, an acrylic dispersant "BYK-2001" manufactured by BYK Chemical Co., Ltd. was used. However, according to the verification by the present inventors, even if such a molecular dispersant is used, the dispersion stability of the above-mentioned micronized zinc bromide phthalocyanine pigment cannot be sufficiently maintained, and the viscosity is increased due to reaggregation or due to the passage of time. Aggregation causes problems such as decreased contrast. [Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-70343 (Patent Document) Japanese Patent Application Laid-Open No. Hei No. 2004-70343. The purpose is as follows. Λ-(,) 仏 仏 仏 仏 仏 仏 仏 仏 仏 仏 仏 仏 仏 仏 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 (2) Special problems have been achieved in the use of zinc-based cyanine green pigments for the purpose of high-brightness of green pixels. 3== Coloring group for coloring: Coloring for coloring films with special advantages of underarms Composition: Yes, Yumei: Fenjieling good' can be developed in a certain time in the development step, and the non-image portion on the soil does not leave the undissolved TF988407 6 201037041, and the substrate Excellent in adhesion, and it is possible to produce a color filter having two transmittances, high contrast, and low film thickness without deteriorating image forming ability such as hardenability. (4) Using the coloring composition for color filters described above, a high-quality color filter and a light sheet are provided. (5) A high-quality liquid crystal display device using the above color filter and an organic EL display are provided. (Means for Solving the Problem) ❹ In order to solve the above problems, the present inventors have made diligent research and found that by using a B-block having a solvophilic A-block and a functional group having a nitrogen-containing atom a block copolymer composed of a segment and a dispersant having an amine valence of 80 mgKOH/g or more in terms of effective solid content, and sufficient dispersion stability can be achieved even for the micro-granulated pigment. The present invention has been completed by providing a color filter which is used as a liquid crystal television to display a sufficiently high contrast. Q The present invention is composed of a plurality of related inventions, and the gist of each invention is as follows. [1] A pigment dispersion liquid comprising a pigment, a solvent, and a dispersant, wherein the dispersant contains a block composed of a B-block having a solvophilic property and a B-functional segment having a functional group containing a nitrogen atom. The copolymer has an amine valence of 80 mgKOH/g or more and 150 mgKOH/g or less in terms of 'effective solids. [2] The pigment dispersion liquid of the above [1], wherein the above pigment contains a filling ugly. [3] The pigment dispersion according to the above [1] or [2], which further contains an aromatic TF988407 7 201037041 group carboxylic acid compound. [4] The pigment dispersion liquid according to the above [3], wherein the aromatic tickic acid compound is a compound represented by the following formula (VI). [Chemical 1]
COOH (於上述通式(VI)中,Z1表示亞曱基或-0-,m表示0〜3之 整數。其中,當m為2或3時,m個Z1可相同亦可不同。 X3表示氫原子、羥基、碳數1〜4之烷基、碳數2〜5之烯 基、碳數1〜4之烷氧基、苄基、苯乙基、苄氧基、或者 -O30X4(其中,X4表示碳數1〜7之烷基或苯基),該等基均 可具有取代基。) [5] 如上述[4]之顏料分散液,其中,以上述通式(VI)所表 示之化合物為鄰苯二甲酸單酯化合物。 [6] 如上述[1]至[5]中任一項之顏料分散液,其中,於上 述嵌段共聚物中,具有含氮原子的官能基之重複單元中的 20莫耳%以上為具有--三級胺基之重複單元。 [7] 如上述[1]至[6]中任一項之顏料分散液,其中,於上 TF988407 8 201037041 具有含氮原子的官能基之重複單元為具有 祕乙I。 該重複單元係來自(曱基)丙稀酸二甲 [8],上述⑴至⑺中任_項之顏料分散液,其中,於上 物+ ’上述A嵌段含有5〜仙莫耳%之以下述通 式(IV)所表示之部分結構。 [化2]COOH (In the above formula (VI), Z1 represents an anthracenylene group or a-0-, and m represents an integer of 0 to 3. wherein, when m is 2 or 3, m Z1 may be the same or different. a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyl group, a phenethyl group, a benzyloxy group, or -O30X4 (wherein X4 represents an alkyl group having a carbon number of 1 to 7 or a phenyl group, and the group may have a substituent. [5] The pigment dispersion liquid of the above [4], which is represented by the above formula (VI) The compound is a phthalic acid monoester compound. [6] The pigment dispersion liquid according to any one of the above [1] to [5] wherein, in the block copolymer, 20 mol% or more of the repeating unit having a functional group containing a nitrogen atom has - a repeating unit of a tertiary amine group. [7] The pigment dispersion liquid according to any one of the above [1] to [6] wherein the repeating unit having a functional group containing a nitrogen atom in the above TF988407 8 201037041 has a secret group I. The repeating unit is a pigment dispersion liquid of the above-mentioned (1) to (7), wherein the above-mentioned A block contains 5% by mass% of the pigment dispersion liquid of the above-mentioned (1) to (7). Part of the structure represented by the following general formula (IV). [Chemical 2]
(IV) 5中之任一整數。R5°表示氫 (於上述通式(IV)申,η表示i Q 原子或甲基。) [9]如上述[1]至⑻巾任—項之㈣分散液,其中,上述 顏料之平均一次粒徑為〇 〇4 以下。 [1〇]一種彩色濾光片用著色組成物,其含有上述[1]至[9] 中任一項之顏料分散液及黏合劑樹脂。 Π1]-種#色it光片用著色組成物,其特徵為:含有顏 料、溶劑、分散劑、及黏合劑樹脂,該分散劑含有由具有親 溶劑性之A嵌段與具有含氮原子的官能基之B嵌段所構成之 TF988407 201037041 嵌段共聚物,該分散劑之胺價以有效固形分換算气 mgK0H/g 以上且 150 mgKOH/g 以下。 為 8〇 化 [⑵如上述[11]之著色組成物,其中,上咖料含有淳 鋅献菁。 、' 進而含有芳 [13]如上述[11]或[12]之著色組成物,其中 香族羧酸系化合物。 [14]如上述[13]之著色組成物’其中,上述芳香族 化合物係以下述通式(VI)所表示之化合物。 文糸 [化3](IV) Any of the integers of 5. R5° represents hydrogen (in the above formula (IV), η represents an i Q atom or a methyl group.) [9] The above (1) dispersion of the above [1] to (8), wherein the pigment is averaged once. The particle size is below 〇〇4. [1] A coloring composition for a color filter, which comprises the pigment dispersion liquid and the binder resin according to any one of the above [1] to [9].着色1] - a coloring composition for a color light sheet, comprising: a pigment, a solvent, a dispersing agent, and a binder resin, the dispersing agent comprising an A block having a solvophilic property and having a nitrogen atom The TF988407 201037041 block copolymer composed of the B block of the functional group, the amine valence of the dispersant is in the range of mgK0H/g or more and 150 mgKOH/g or less in terms of the effective solid content. (2) The colored composition according to [11] above, wherein the top coffee contains bismuth zinc. Further, the coloring composition of the above [11] or [12], wherein the aromatic carboxylic acid compound is contained. [14] The coloring composition of the above [13], wherein the aromatic compound is a compound represented by the following formula (VI). Documentary [Chemical 3]
(VI) (於上述通式(VI)中’ z1表示亞甲基或者_〇_,m表示〇〜3 之整數。其中’當m為2或3時,π^ζ1可相同亦可不同。 X表不氫原子、羥基、碳數丨〜4之烷基、碳數2〜5之烯 基、石反數1〜4之烧氧基、苄基、苯乙基、苄氧基、或者 -C00X4(其中,X4表示碳數i〜7之烷基或苯基),該等基團 均可具有取代基。) [15]如上述[14]之著色組成物,其中,以上述通式(γι) 所表示之化合物為鄰笨二甲酸單酯化合物。 TF988407 201037041 [16] 如上述[11]至[15]中任一項之著色組成物,其中,於 上述嵌段共聚物中,具有含氮原子的官能基之重複單元中的 20莫耳%以上為具有一〜三級胺基之重複單元。 [17] 如上述[11]至[16]中任一項之著色組成物,其中,於 上述嵌段共聚物中,具有含氮原子的官能基之重複單元為具 有三級胺基之重複單元,該重複單元係來自(曱基)丙烯酸二 曱胺基乙酯。 [18] 如上述[11]至[17]中任一項之著色組成物,其中,於 上述嵌段共聚物中,上述A嵌段含有5〜40莫耳%之以下述 式(IV)所表示之部分結構。 [化4](VI) (In the above formula (VI), 'z1 represents a methylene group or _〇_, and m represents an integer of 〇~3. wherein 'when m is 2 or 3, π^ζ1 may be the same or different. X represents a hydrogen atom, a hydroxyl group, an alkyl group having a carbon number of 44, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having a radii of 1 to 4, a benzyl group, a phenethyl group, a benzyloxy group, or C00X4 (wherein X4 represents an alkyl group having a carbon number of i to 7 or a phenyl group), and the groups may each have a substituent. [15] The coloring composition of the above [14], wherein the above formula ( The compound represented by γι) is an o-dicarboxylic acid monoester compound. [16] The colored composition according to any one of [11] to [15] wherein, in the block copolymer, 20 mol% or more of the repeating unit having a functional group containing a nitrogen atom It is a repeating unit having one to three amine groups. [17] The coloring composition according to any one of [11] to [16] wherein, in the above block copolymer, the repeating unit having a functional group containing a nitrogen atom is a repeating unit having a tertiary amino group The repeating unit is derived from (indenyl) decylaminoethyl acrylate. [18] The colored composition according to any one of [11] to [17] wherein, in the block copolymer, the A block contains 5 to 40 mol% of the following formula (IV) Indicates part of the structure. [Chemical 4]
(於上述通式(IV)中,η表示1〜5中之任一整數。R5°表示氫 原子或曱基。) [19] 如上述[11]至[18]中任一項之著色組成物,其中,上 述顏料之平均一次粒徑為0.04 /zm以下。 [20] 如上述[10]至[19]中任一項之著色組成物,其中,上 TF988407 11 201037041 述黏合劑樹脂包含以下樹脂:對於含有環氧基之(甲基)丙烯 酸酯與其他自由基聚合性單體之共聚物,在該共聚物所具有 的環氧基之至少一部分上加成不飽和一元酸而成之樹脂,或 者在藉由該加成反應而產生的羥基之至少一部分上加成多 元酸酐而獲得之鹼可溶性樹脂。 [21] 如上述[10]至[20]中任一項之著色組成物,其中,進 而含有光聚合起始系及熱聚合起始劑中之至少一種。 [22] 如上述[21]之著色組成物,其中,上述光聚合起始系 含有肟酯系化合物。 [23 ]如上述[22 ]之著色組成物,其中,上述月亏醋系化合物 係以下述通式(I )所表示之化合物。 [化5] /OR2 O n II if , --(η Y—C—X—C—R1 [於上述通式(I )中,R1表示氫原子、碳數1〜20之烷基、 複數2〜25之稀基、複數3〜20之雜芳基或者碳數4〜25 之雜芳烷基,該等均可具有取代基。或者,R1可與X或Y鍵 結而形成環。 R2表示碳數2〜20之烷醯基、碳數3〜25之烯醯基、碳數 4〜8之環烷醯基、碳數7〜20之芳醯基(aryloyl)、碳數2 〜10之烷氧羰基、碳數7〜20之芳氧羰基、碳數2〜20之 TF988407 12 201037041 雜芳基、碳數3〜2G之雜芳酿基或者碳數2〜2q之烧基胺基 羰基’該等均可具有取代基。 X表示可具有取代基之、由2個以上環縮合而成之2價芳 香族烴基及芳香族雜環基中的至少一種。 Y表示可具有取代基之芳香族基。] [24]如上述間之著色組成物,其中,以上述通式⑴ 所表示之化合物係以下述結構式(j)所表示之化合物。 [化6](In the above formula (IV), η represents an integer of any one of 1 to 5. R5° represents a hydrogen atom or a fluorenyl group. [19] The color composition of any one of the above [11] to [18] The average primary particle diameter of the above pigment is 0.04 /zm or less. [20] The coloring composition according to any one of the above [10] to [19] wherein, the upper TF988407 11 201037041 binder resin comprises the following resin: (meth) acrylate containing an epoxy group and other freedoms a copolymer of a base polymerizable monomer, a resin obtained by adding an unsaturated monobasic acid to at least a part of an epoxy group of the copolymer, or at least a part of a hydroxyl group produced by the addition reaction An alkali-soluble resin obtained by adding a polybasic acid anhydride. [21] The colored composition according to any one of [10] to [20] above which further comprises at least one of a photopolymerization initiation system and a thermal polymerization initiator. [22] The coloring composition according to [21] above, wherein the photopolymerization initiation system contains an oxime ester compound. [23] The coloring composition according to the above [22], wherein the monthly vinegar-based compound is a compound represented by the following formula (I). /OR2 O n II if , --(η Y—C—X—C—R1 [In the above formula (I), R1 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a plural number 2 And a heteroaryl group of 3 to 20 or a heteroarylalkyl group having 4 to 25 carbon atoms, which may have a substituent. Alternatively, R1 may be bonded to X or Y to form a ring. An alkanoyl group having 2 to 20 carbon atoms, an olefin group having 3 to 25 carbon atoms, a cycloalkyl fluorenyl group having 4 to 8 carbon atoms, an arylloyl group having 7 to 20 carbon atoms, and a carbon number of 2 to 10 Alkoxycarbonyl, aryloxycarbonyl having 7 to 20 carbons, TF988407 having a carbon number of 2 to 20, 12, 2010, 370, s, s, s, aryl, aryl, aryl, aryl, aryl Each of these may have a substituent. X represents at least one of a divalent aromatic hydrocarbon group and an aromatic heterocyclic group which may have a substituent and is condensed by two or more rings. Y represents an aromatic group which may have a substituent. [24] The coloring composition of the above formula (1), wherein the compound represented by the above formula (1) is a compound represented by the following structural formula (j).
[於上述通式⑴中,R!、以Y與上述通式(1 )中之含義相 同:環^表示與苯環XI合之環,可為單環,亦可為由2 個以上%所構成之縮合環。又,χ2可縮合於笨環^之任意 位置。苯環χ1及與其縮合之環χ2,進而可具有取代基。f [25] 如上述[10]至[24]中任一項之著色組成物,其中,進 而含有聚合性單體。 [26] 如上述[25]之著色组成物,其中,上述聚合性單體為 具^至少1個⑽性雙鍵之可加絲合之化合物,該化合物 之分子量為650以下且雙鍵當量為15〇以下。 [27] 一種彩色濾光片,其具備基板及形成於該基板上之像 素一特彳攻為’該像素的一部分或全部係使用上述[10]至[26] TF988407 13 201037041 中任一項之著色組成物而形成。 [28] —種液晶顯示裝置,其具備上述[27]之彩色濾光片。 [29] —種有機EL顯示器’其具備上述[27]之彩色濾光片。 (發明效果) 本發明發揮以下所舉出之效果。 (1) 可提供可用少量的添加量即可高效率地使近年來經汽 度微粒化之顏料分散,其結果可製造高穿透率、高對比度7 低膜厚的彩色濾光片之顏料分散液及著色組成物。 (2) 特別是可提供達成了以綠色像素之高亮度化為目的而 使用溴化鋅酞菁綠色顏料時所存在之問題,亦即兼具高對比 度與分散穩定性的顏料分散液及彩色濾光片用著色級成物。 (3) 可提供具有以下等優點之彩色濾光片用著色組成物. 對顯影液之溶解性良好,於顯影步驟中可在特定時間内顯 影’於基板上之非圖像部分不殘留著色樹脂組成物之未溶解 物,與基板之密著性優異,不使硬化性等圖像形成能力 降,可製造高穿透率.高對比度.低膜厚之彩色濾光片。 (4) 可使用上述彩色濾光片用著色組成物,而提 。 彩色濾光片。 〜貝 (5) 可提供使用了上述彩色濾、光片之高品質液晶顯示 及有機EL顯示器。 、、置 【實施方式】 以下,就本發明之構成要件等加以詳細說明,但讀等構成 TF988407 201037041 要件係本發明實施態樣之一例,本發明並不限定於該等内 容。 • 再者,「(曱基)丙烯基」等意指「丙烯基及甲基丙烯基中 之至少一者」;「(甲基)丙烯酸酯」等意指「丙烯酸酯及曱基 丙烯酸酯中之至少一者」等,例如「(甲基)丙烯酸」意指「兩 烯酸及曱基丙烯酸中之至少一者」。 又,所謂「總固形分」,意指顏料分散液或者著色組成物 0 中所包含之除後述溶劑成分以外之總成分。 於本發明中,所謂重量平均分子量,係指利用GPC法(gel permeation chromatography,凝膠滲透層析法)所測定之聚 • 苯乙烯換算之重量平均分子量(Mw)。 . 又,於本發明中,所謂「胺價」,只要未加以特別說明, 則表示有效固形分換算之胺價,係以與每lg分散劑固形分 的鹼量等當量之Κ0Η的重量所表示之值。再者,測定方法於 後加以敍述。 [1 ]顏料分散液 . 町說明本㈣之顏料分散液之各構成成分。本發明之顏 料分散液係以顏料、溶劑及分散劑作為必f成分,視需要, 可進而含有除上述成分以外之添加物等。 而 以下,說明各構成成分。 [卜1]顏料 作為顏料’可使用:藍色顏料、綠色顏料、红色顏料、黃 TF988407 201037041 色顏料、紫色顏料、撥色顏料、棕色顏料、黑色顏料等各種 顏色之顏料。又,作為其結構,除偶氮系、s太菁系、啥吖咬 酮(quinacridone)系、苯并咪0坐酮(benzimidazolone)系、 異吲哚啉酮(isoindolinone)系、二0号啡(dioxazine)系、陰 丹士林(indanthrene)系、茈(perylene)系等有機顏料之 外,亦可使用各種無機顏料等。以下,以顏料編號來表示可 使用顏料之具體例。以下所舉出之「C. I·色素紅2」等術語, 意指色指數(C. I.)。 作為紅色顏料,例如可舉出:C. I.色素紅1、2、3、4、5、 6、7、8、9、12、14、15、16、17、21、22、23、31、32、 37、38、4卜 47、48、48:卜 48:2、48:3、48:4、49、49:1、 49:2、50:卜 52:卜 52:2、53、53:卜 53:2、53:3、57、57:1、 57:2、58:4、60、63、63:1、63:2、64、64:1、68、69、81、 81:1 ' 81:2 > 81:3 > 81:4'83'88 ' 90:1 Ί01 Ί01:1 >104 ' 108、108:;1、109、112、113、114、122、123、144、146、 147、149、15卜166、168、169、170、172、173、174、175、 176、177、178、179、18卜 184、185、187、188、190、193、 194、200、202、206、207、208、209、210、214、216、220、 221、224、230、23卜 232、233、235、236、237、238、239、 242、243、245、247、249、250、25卜 253、254、255、256、 257、258、259、260、262、263、264、265、266、267、268、 269、270、27卜 272、273、274、275、276 等。其中,較 TF988407 16 201037041 佳為可舉出:C. I.色素紅48:卜122、166、168、Π7、2〇2、 2〇6、207、209、224、242、254 等,更佳為可舉出:c 工 .色素紅⑽、177、209、224、242、254 等。 · · . 作為藍色顏料,例如可舉出:C. I.色素藍1、1:2、9、14、 15、15:卜 15:2、15:3、15:4、15:6、16、17、19、25、27、 28、29、33、35、36、56、56:卜 60、61、61:1、62、63、 66、67、68、71、72、73、74、75、76、78、79 等。其中, G 較佳為可舉出:C. L 色素藍 15、15: ;1、15:2、15:3、15:4、 15:6等,更佳為可舉出c.丨.色素藍15:6。 作為綠色顏料,例如可舉出:以c· L色素綠丨、2、4、7、 8、10、13、14、15、π、18、19、26、36、45、48、50、 51 54、55及58為代表之演化鋅駄菁等。其中,較佳為可 舉出以C.I.色素綠7、36及58為代表之溴化鋅酞菁等,特 佳為C. I.色素綠G58。再者,對以C. I色素綠G58為代表之 ❹溴化鋅酞菁的詳細内容,於後加以敍述。 作為黃色顏料,例如可舉出:C. I.色素黃卜ι:ι、2、3、 4、5、6、9、10、12、13、14、16、17、24、31、32、34、 35、35:卜 36、36:卜 37、37:卜 40、4卜 42、43、48、53、 ' 55、6卜 62、62:卜 63、65、73、74、75、8卜 83、87、93、 [ ’ 94、95、97、100、1(Π、1〇4、105、108、109、110、ill、 116、117、119、120、126、127、127:卜 128、129、133、 134、136、138、139、142、147、148、150、151、153、154、 TF988407 17 201037041 155、157、158、159、160、161、162、163、164、165、166、 167、168、169、170、172、173、174、175、176、180、18卜 182、183、184、185、188、189、190、191、191:1、192、 193、194、195、196、197、198、199、200、202、203、204、 205、206、207、208等。其中,較佳為可舉出:c I.色素 黃 83 、 117 、 129 、 138 、 139 、 150 、 154 、 155 、 180 、 185 等,更佳為可舉出:c_ I.色素黃83、138、139、150、180 等。 作為橙色顏料’例如可舉出:C·丨.色素橙1、2、5、13、 16、17、19、20、2卜 22、23、24、34、36、38、39、43、 46、48、49、6卜 62、64、65、67、68、69、70、7卜 72、 73 74、75、77、78、79等。其中’較佳為可舉出c·色 素橙38、71等。 作為紫色顏料,例如可舉出:C I.色素紫卜1:卜2、2:2、 3、3:卜3:3、5、5:;1、14、15、16、19、23、25、27、29、 31、32、37、39、42、44、47、49、50、色素藍 8〇 等。其 中’較佳為可舉出c. I·色素紫19、23等,更佳為可舉出c ( 色素紫23。 · · 作為黑色顏料,可使用單獨之黑色顏料,或者使用將紅 綠、藍色等顏料混合而成之黑色顏料。該等黑色顏料,可 無機或有機顏料、_中適#選擇,可單獨使 種混合使用。 TF988407 18 201037041 作為單獨之黑色顏料,可舉出:碳黑、乙炔黑、燈黑、骨 炭(bone black)、石墨、鐵黑、苯胺黑、花青黑(cyanine • black)、鈦黑等。該等之中,就遮光率、圖像特性之觀點而 , 言,特佳為碳黑、鈦黑。作為碳黑之市售品之例’例如可舉 出如下之品牌。 * 三菱化學公司製造:MA7、MA8、MA11、MA100、MA220、MA230、 #52、#50、#47、#45、# 2700、# 2650、# 2200、# 1000、 0 # 990、# 900 等。[In the above formula (1), R! has the same meaning as in the above formula (1): ring ^ represents a ring which is bonded to the benzene ring XI, and may be a single ring or may be composed of 2 or more%. The condensed ring formed. Further, χ2 can be condensed at any position of the stupid ring ^. The benzene ring oxime 1 and the oxime 2 condensed therewith may further have a substituent. [25] The coloring composition according to any one of [10] to [24] above which further contains a polymerizable monomer. [26] The coloring composition according to the above [25], wherein the polymerizable monomer is a wire-bondable compound having at least one (10) double bond, and the molecular weight of the compound is 650 or less and the double bond equivalent is 15〇 or less. [27] A color filter comprising a substrate and a pixel formed on the substrate, wherein a part or all of the pixel is used in any one of [10] to [26] TF988407 13 201037041 It is formed by coloring the composition. [28] A liquid crystal display device comprising the color filter of the above [27]. [29] An organic EL display comprising the color filter of the above [27]. (Effect of the Invention) The present invention exerts the effects described below. (1) It is possible to efficiently disperse the pigment which has been subjected to vapor micronization in recent years with a small amount of addition, and as a result, it is possible to produce a pigment dispersion of a color filter having a high transmittance and a high contrast ratio and a low film thickness. Liquid and coloring composition. (2) In particular, it is possible to provide a problem of using a zinc bromide phthalocyanine green pigment for the purpose of high luminance of green pixels, that is, a pigment dispersion having high contrast and dispersion stability and a color filter. The light sheet is colored with a coloring grade. (3) It is possible to provide a coloring composition for a color filter having the following advantages. The solubility in the developer is good, and it can be developed in a specific time in the developing step, and the non-image portion on the substrate does not remain colored resin. The undissolved matter of the composition is excellent in adhesion to the substrate, and the image forming ability such as hardenability is not lowered, and a color filter having high transmittance, high contrast, and low film thickness can be produced. (4) It is possible to use the coloring composition for the above color filter. Color filter. ~Bei (5) High-quality liquid crystal display and organic EL display using the above-mentioned color filter and light film are available. [Embodiment] Hereinafter, the constituent elements of the present invention and the like will be described in detail, but the reading and the like constitute a TF988407 201037041. An embodiment of the present invention is not limited to the contents. • In addition, “(indenyl)propenyl” and the like means “at least one of a propylene group and a methacryl group”; “(meth)acrylate” and the like means “in acrylate and methacrylate” For example, "(meth)acrylic acid" means "at least one of a dienoic acid and a methacrylic acid". In addition, the "total solid content" means a total component other than the solvent component described later contained in the pigment dispersion liquid or the coloring composition 0. In the present invention, the weight average molecular weight means a weight average molecular weight (Mw) in terms of polystyrene measured by GPC (gel permeation chromatography). Further, in the present invention, the "amine price" means an amine value converted into an effective solid content, unless otherwise specified, and is expressed by the weight equivalent to the amount of alkali per lg of the solid content of the dispersant. The value. Further, the measurement method will be described later. [1] Pigment Dispersion . The town describes the components of the pigment dispersion of (4). The pigment dispersion of the present invention contains a pigment, a solvent, and a dispersant as essential components, and may further contain additives other than the above components, if necessary. Hereinafter, each constituent component will be described. [Bu 1] Pigment As a pigment, a pigment of various colors such as a blue pigment, a green pigment, a red pigment, a yellow TF988407 201037041 color pigment, a purple pigment, a dial pigment, a brown pigment, and a black pigment can be used. Further, as its structure, in addition to the azo system, the sylvanine system, the quinacridone system, the benzimidazolone system, the isoindolinone system, the morphine In addition to organic pigments such as (dioxazine), indanthrene, and perylene, various inorganic pigments and the like can be used. Hereinafter, specific examples of the usable pigments are indicated by pigment numbers. The terms "C.I. Pigment Red 2" as used hereinafter refer to the color index (C.I.). Examples of the red pigment include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32. 37, 38, 4 Bu 47, 48, 48: Bu 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50: Bu 52: Bu 52:2, 53, 53: Bu 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1 ' 81:2 > 81:3 > 81:4'83'88 ' 90:1 Ί01 Ί01:1 >104 '108, 108:; 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 15 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 18 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 23, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 25, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 27, 272, 273, 274, 275, 276, etc. . Among them, more than TF988407 16 201037041 good can be cited: CI pigment red 48: Bu 122, 166, 168, Π 7, 2 〇 2, 2 〇 6, 207, 209, 224, 242, 254, etc., more preferably Out: c. Pigment red (10), 177, 209, 224, 242, 254, etc. · · · As a blue pigment, for example, CI Pigment Blue 1, 1: 2, 9, 14, 15, 15: Bu 15:2, 15:3, 15:4, 15:6, 16, 17 , 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: Bu 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, etc. In particular, G is preferably C. L. Pigment blue 15, 15:; 1, 15:2, 15:3, 15:4, 15:6, etc., more preferably c. Blue 15:6. Examples of the green pigment include c· L pigment green 丨, 2, 4, 7, 8, 10, 13, 14, 15, π, 18, 19, 26, 36, 45, 48, 50, 51. 54, 55 and 58 are representative of the evolution of zinc phthalocyanine and the like. Among them, zinc bromide phthalocyanine represented by C.I. Pigment Green 7, 7, and 58 is preferable, and C. I. Pigment Green G58 is particularly preferable. Further, the details of the bismuth bromide phthalocyanine represented by C. I pigment green G58 will be described later. As the yellow pigment, for example, CI pigment yellow ι: ι, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35 35: Bu 36, 36: Bu 37, 37: Bu 40, 4 Bu 42, 43, 48, 53, '55, 6 Bu 62, 62: Bu 63, 65, 73, 74, 75, 8 Bu 83, 87, 93, [ ' 94, 95, 97, 100, 1 (Π, 1〇4, 105, 108, 109, 110, ill, 116, 117, 119, 120, 126, 127, 127: Bu 128, 129 , 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, TF988407 17 201037041 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 18, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, etc. Among them, preferred are: c I. Pigment yellow 83, 117, 129, 138, 139, 150 , 154, 155, 180, 185, etc., more preferably: c_I. Pigment yellow 83, 138, 139, 150, 180, etc. as orange The material 'for example, C. 丨. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 2, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48 , 49, 6 Bu 62, 64, 65, 67, 68, 69, 70, 7 Bu 72, 73 74, 75, 77, 78, 79, etc., wherein 'c preferably is c·color orange 38, 71 As the purple pigment, for example, C I. Pigment Violet 1 : Bu 2, 2: 2, 3, 3: Bu 3:3, 5, 5:; 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50, pigment blue 8 〇, etc., wherein 'preferably, c. I · pigment purple 19, 23, etc. More preferably, it is c (pigment violet 23). · As a black pigment, a black pigment alone or a black pigment obtained by mixing pigments such as red green and blue may be used. Or organic pigments, _ Zhong Shi # choice, can be used alone to mix. TF988407 18 201037041 Examples of the black pigment alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, nigrosine, cyanine black, and titanium black. Among these, from the viewpoint of the light-shielding ratio and the image characteristics, carbon black and titanium black are particularly preferable. As an example of a commercial product of carbon black, for example, the following brands can be mentioned. * Made by Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA100, MA220, MA230, #52, #50, #47, #45, #2700, #2650, #2200, #1000, 0#990, #900, etc.
Degussa 公司製造:Printex95、Printex90、Printex85、 Printex75、Printex55、Printex45、Printex40、Printex30、 . Printex3'PrintexA'PrintexG'Special Black550'Special . Black350 、 Special Black250 、 Special BlacklOO 等。Made by Degussa: Printex95, Printex90, Printex85, Printex75, Printex55, Printex45, Printex40, Printex30, Printex3'PrintexA'PrintexG'Special Black550'Special. Black350, Special Black250, Special BlacklOO, etc.
Cabot 公司製造:Monarch460、Monarch430、Monarch280、 Monarchl20 、 Monarch800 、 Monarch4630 、 REGAL99 、 q REGAL99R、REGAL415、REGAL415R、REGAL250、REGAL250R、 REGAL330 、 BLACK PEARLS 480 、 PEARLS130 等。Cabot manufactures: Monarch460, Monarch430, Monarch280, Monarchl20, Monarch800, Monarch4630, REGAL99, q REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, BLACK PEARLS 480, PEARLS130, etc.
Columbian Carbon 公司製造:RAVEN11、RAVEN15、 ' RAVEN30 、 RAVEN35 、 RAVEN40 、 RAVEN410 、 RAVEN420 、 RAVEN450 、 RAVEN500 、 RAVEN780 、 RAVEN850 、 RAVEN890H 、 ' RAVEN1000 、 RAVEN1020 、 RAVEN1040 等。 繼而,對混合而成之黑色顏料加以說明。作為成為混合之 基材的色材之具體例,例如可舉出:維多利亞純藍(42595)、 TF988407 19 201037041 金胺 0(41000)、Cathilon Brilliant Flavin(Basic 13)、 玫瑰紅 6GCP(45160)、玫瑰紅B(45170)、番紅 0K7(h 100(50240)、羊毛罌紅 X(42080)、No. 120/雷奥諾爾 黃(21090)、雷奥諾爾黃 GRO(21090)、Symuler Fast Yellow 8GF(21105)、聯苯胺黃 4T-564D(21095)、Symuler Fast Red 4015(12355)、雷奥諾爾紅 7B4401 (15850)、Fastogen Blue TGR-L(74160)、雷奥諾爾藍SM(26150)、雷奥諾爾藍ES(色 素藍15:6)、Lionogen Red GD(色素紅168)、雷奥諾爾綠 2YS(色素綠36)等(再者,上述()内之數字意指色指數 (C. I.))。 又,進而以C. I.編號表示其他可混合使用之顏料,則例 如可舉出:C. I.黃色顏料 20、24、86、93、109、110、117、 125、137、138、147、148、153、154、166 等;C. I·橙色 顏料 36、43、51、55、59、61 等;C· I.紅色顏料 9、97、 122、123、149、168、177、180、192、215、216、217、220、 223、224、226、227、228、240 等;C. I.紫色顏料 19、23、 29、30、37、40、50 等;C. I.藍色顏料 15、15:1、15:4、 22、60、64等;C. I.綠色顏料7 ; C. I.棕色顏料23、25、 26等。 再者,上述碳黑亦可與其他黑色或有色之無機、有機顏料 併用。其他顏料與碳黑相比,遮光性或圖像特性低,因此混 合比率自然受到限制。 TF988407 20 201037041 作為鈦黑之製造方法,有以下等方法:將二氧化鈦與金屬 鈦之混合物於還原環境中進行加熱還原之方法(日本專利特 開昭49-5432號公報)、將四氯化鈦藉由高溫水解所獲得之 超微細二氧化鈦於含氫還原環境中進行還原之方法(日本專 利特開昭57-205322號公報)、將〕氧化鈇或氫氧化欽於氨 存在下進行高溫還原之方法(日本專利特開昭6〇_65〇69號Made by Columbian Carbon: RAVEN11, RAVEN15, 'RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, 'RAVEN1000, RAVEN1020, RAVEN1040, etc. Next, the mixed black pigment will be described. Specific examples of the color material to be a mixed base material include Victoria Pure Blue (42595), TF988407 19 201037041 Goldamine 0 (41000), Cathilon Brilliant Flavin (Basic 13), Rose Red 6GCP (45160), Rose Red B (45170), Safranin 0K7 (h 100 (50240), Wool Poppy Red X (42080), No. 120 / Leonor Yellow (21090), Leonor Yellow GRO (21090), Symerer Fast Yellow 8GF (21105), benzidine yellow 4T-564D (21095), Symerer Fast Red 4015 (12355), Leonor Red 7B4401 (15850), Fastogen Blue TGR-L (74160), Leonor Blue SM (26150), Ray Onol blue ES (pigment blue 15:6), Lionogen Red GD (pigment red 168), Leonor green 2YS (pigment green 36), etc. (again, the number in the above () means color index (CI) Further, in addition, other pigments which can be used in combination are indicated by CI numbers, and examples thereof include CI yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, and 153. 154, 166, etc.; C. I· orange pigments 36, 43, 51, 55, 59, 61, etc.; C·I. red pigments 9, 97, 122, 123, 149, 168, 177, 18 0, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, etc.; CI violet pigments 19, 23, 29, 30, 37, 40, 50, etc.; CI blue pigments 15, 15 : 1, 15: 4, 22, 60, 64, etc.; CI green pigment 7; CI brown pigment 23, 25, 26, etc. Further, the above carbon black can also be used together with other black or colored inorganic and organic pigments. Compared with carbon black, pigments have low light-shielding properties or image characteristics, so the mixing ratio is naturally limited. TF988407 20 201037041 As a method for producing titanium black, there are the following methods: heating a mixture of titanium dioxide and titanium metal in a reducing environment Method for reduction (Japanese Patent Laid-Open Publication No. SHO 49-5432), a method for reducing ultrafine titanium dioxide obtained by high temperature hydrolysis of titanium tetrachloride in a hydrogen reduction environment (Japanese Patent Laid-Open No. Sho 57-205322) No.), a method of high-temperature reduction in the presence of ammonia in the presence of ammonia (Japanese Patent Laid-Open No. 6-65〇69)
公報、特開昭61-201610號公報)、使釩化合物附著於二氧 化鈦或氫氧化鈦上,於氨存在下進行高溫還原之方法(曰本 專利特開昭61-201610號公報);但並不限定於該等方法 作為欽黑之市售品之例,例如可舉出:^ , 干山二曼材料公司 (MITSUBISHI MATERIALS CORPORATION)製造之鈦累 12S、13R、13M、13M-C 等。 該等顏料,可單獨使用丨種,亦可併用2種以上。又,= 等顏料之平均—次粒徑通常為G.2 μ以下,較佳又’該 Ο 以下,更佳為Q.Q4/zm以下,特佳為 ’、、、.1 又,通常為〇篇_以上。 · 25 _以下’ 方法 在進行顏料之·化時,適合制如後述之溶 劑鹽磨法之 作為上述綠色顏料 通常之鋅㈣係於1分子中具有16個氮; 原子以_子錢原子進餘代者,係 ^該等氫 之漠化辞駄菁顏料。其中,就顯示極:所,佳使用 芽逯率、適於形成 TF9S8407 21 201037041 彩色濾光片之綠色料的方面而言,較 有13個以上溴原子之溴化铉苴 *、、刀中平均含 卞之属化鋅欧青。更佳為卜 〜16㈣原子、且1分子中不含氣原子或者奸且右有13 以下氣原,祕為1分個 16個溴原子、且1分子中含 八有14〜 下氣原子之鋅料。_子或者平均具有2個以 此種溴化躲菁顏料,可藉由日本專利特_ 號公報等中所揭示之公知的製造方法而製造。例如可舉出乂 下方法:將以纽㈣㈣原子取絲麵上的-部分= 部氮原子而得之鄰笨二甲酸、或鄰 枓’來合成顏枓。此時,視需要亦可使用錮酸銨等觸媒。 作為其他方法,可舉出以下方法:在由氣化無、氣化I 漠化鈉等的混合物倾紅11G〜17n:左右线融物中, 將鋅醜菁以減進行漠化。於該方法中,可藉由調節溶融鹽 中氣化物錢化物之比率、或者氣導人量或反應時 間,而任意地控_含量不_各_化雜菁之比率。 反應結束後’若將所得混合物投Μ鹽酸等酸性水溶液 中,則所生成之>臭化鋅駄菁會發生沈殺。魏,進行過遽、 清洗、乾燥等後處理,而獲得溴化鋅酞菁。 視需要’將如此獲得H辞酞菁顏料於磨碎機、球磨 機、振磨冑振動球磨機等粉碎機内進行乾式磨碎,繼而以 溶劑鹽磨法或溶劑沸騰法等進行顏料化,藉此獲得穿透率或 TF988407 22 201037041 對比度較高之發綠色光之溴化鋅酿菁顏料。顏料化方法並無 特別限制,就可容易抑制結晶成長、且獲得比表面積較大之 ‘ 顏料粒子的方面而言,較佳為採用溶劑鹽磨法。 所謂溶劑鹽磨法,意指將剛合成後的粗顏料與無機鹽以及 '有機溶劑進行混練磨碎。具體而言,係將粗顏料、無機鹽、 ' 及不溶解其之有機溶劑加入混練機,於混練機中進行混練磨 碎。作為此時之混練機,例如適合使用捏合機或混捏機、或 q 者如日本專利特開2006-77062號公報中記載的具有環狀固 定圓盤與同心的旋轉圓盤之間隙部分所形成之粉碎空間的 連續混練機等。 . 作為上述無機鹽,可適合使用水溶性無機鹽,較佳為使用 . 例如氯化納、氯化卸、硫酸納等無機鹽。又,更佳為該等無 機鹽之粒徑為0. 5〜50 // m。此種無機鹽係可藉由將通常的 無機鹽加以微粉碎而容易獲得。 Q 如此獲得之溴化鋅酞菁,可單獨使用,亦可與溴化率或氯 化率不同的溴化鋅酞菁、或在不損及本發明效果之範圍内與 中心金屬被其他金屬取代之溴化酞菁等混合使用。藉由改變 氯化率及溴化率或改變中心金屬而使作為顏料之色調發生 ' 變化,從而可期待可再現之色相變化的增加。又,即便同樣 ' 的綠色顏料,亦可與C. I.色素綠(P. G. )36或7等鹵化銅酞 菁混合。 包含溴化鋅酞菁之綠色顏料之平均一次粒徑,通常為0. 1 TF988407 23 201037041 _以下,較佳為0.04 _以下,更佳為〇 〇3 _以下, 特佳為0. 025 μm以下,又,通常為〇. 〇〇5 以上。 若平均一次粒徑過大,則消偏特性惡化因而對比度變得不 充分’在嚴重的情釘有時會產生穿透率下降之使根本性的 顏色特性發生劣化之虞,或者會產生形成粗粒而產生突起異 物,從而使彩色滤光片的良率下降,或導致製程過濾器閉塞 等生產上之問題。反之,若平均一次粒徑過小,則會產生以 下等問題:由於顏料之比表φ積增A而造成分散穩定性下 降,或由於顏料接近分子狀態而造成耐熱性、耐光性惡化。 再者,顏料之平均一次粒徑可藉由以下方法而求出。即, 將顏料於氣仿中進行超音波分散’並滴加至貼附膠棉膜之網 格上進行乾燥’利用穿透型電子顯微鏡(transmission electron microscope,TEM)觀察而獲得顏料之一次粒子 像。根據該圖像測定一次粒徑,依照下式之計算式計算單個 平均值,並求出平均粒徑。 在有機顏料的情形’係將各顏料粒子之粒徑作為換算為成 為相同面積之圓的直徑之面積圓相當徑,分別求出複數個、 通常為200〜300個左右的顏料粒子之粒徑後,依照下式之 計算式計算單個平均值,而求出平均粒徑。 各顏料粒子之粒徑:Xl、X2、X3、X4、…、Xi....... 平均粒徑= ΣΧί/πΐ 再者,為了調色成所期望之顏色,亦可將上述各顏料中的 TF988407 24 201037041 2種以上顏料混合使用。例如,在㈣紅色或綠色之顏料分 •、或著色、,域㈣,為了調整Μ目,可分別在紅色顏料或 綠色顏料中組合至幻種以上的黃色顏料。作為此種黃色顏 -料^如可舉丨上述之各種黃色賴。又,為了製備藍色之 •顏料分散液或著色組成物,可將藍色顧與至少丨種以上的 紫色顏料加以組合,轉以外,根制触之色度,可適 當混合使用各色顏料。 〇 私月之顏料刀散液中之顏料含量,係相對於固形分總 量’財為90重量化下,較佳為85重量%以下,更佳為 80重里%以下’又,通常為2〇重量%以上,較佳為別重量% • 以上’更佳為40重量%以上。 本务月之彩色,慮光片用著色組成物中之顏料含量,係 相對於固形分總量,通常為75重量%以下,較佳為70重量% 以下’更佳為60重量%以下,又,通常為1〇重量%以上,較 〇佳為20重量%以上,更佳為25重量%以上。 若顏料之量過多,則難以維持顏料之分散狀態,從而發生 凝集或沈降,絲有可能產生減❹或亮度、對比灯降 之問題。另一方面,若顏料之量過少,則色濃度較淡,有可 能產生無法充分發揮作為彩色濾光片之功能的問題。 [1-2]溶劑 溶劑在本發明之顏料分散液或後述之著色組成物中,具有 如下功能:除顏料、分散劑之外,亦使視情況而調配之上述 TF988407 25 201037041 以外的成分等溶解或分散,並調整黏度。 作為該溶齊I,為可使各成分溶解或分散者即可。 作為此種_,例如可舉H醇單_、乙二醇單乙 醚、乙二醇單丙醚、乙二 。 00 矸早''丙一醇早甲醚、丙二醇 車乙驗、丙二醇單正頂、丙二醇第三頂、二乙二醇單甲 醚、二乙二醇單***、- 平匕蜒一乙一転早正丁醚、甲氧基尹基戊醇、 丙二醇單***、二丙二醇單***、二丙二醇單甲醚、3-甲基 醚、三丙 -3-甲氧基丁醇、三乙二醇單甲喊、三乙二醇單乙 " 二醇單甲醚之類的二醇單烷基醚類; 一乙二醇二甲醚、二乙二 乙一醇二丁趟、二丙二醇二 乙二醇二甲鍵、乙二醇二乙趟 醇二***、二乙二醇二丙醚、 甲醚之類的二醇二烷基醚類; 乙二醇單甲謎乙酸醋、乙二醇單乙崎乙酸醋、乙二醇單正 丁醚乙酸S旨、丙二醇單甲鍵乙酸g旨、丙二醇單***乙酸醋、 丙二醇單丙ϋ乙酸g旨、丙二醇單·^乙酸g旨、乙酸曱氧基丁 醋、乙酸-3-甲氧基丁酯、乙酸甲氧基戊醋、二乙二醇單甲 醚乙酸酯、一乙二醇單***乙酸酯、二乙二醇單正丁醚乙酸 酯、二丙二醇單曱醚乙酸酯、三乙二醇單曱醚乙酸酯、三乙 二醇單***乙酸酯、乙酸-3-曱基—3_甲氧基丁酯之類的二醇 烷基醚乙酸酯類; 乙二醇二乙酸酯、1,3-丁二醇二乙酸酯、丨,6_己二醇二乙 酸酯等二醇二乙酸酯類; TF988407 26 201037041 環己醇乙酸酯等烷基乙酸酯類; 戊鍵、丙鍵、二乙鍵、二丙鍵、二異丙謎、丁鍵、二戊鍵、 ' 乙基異丁醚、二己醚之類的醚類; • 丙酮、曱基乙基酮、甲基戊基酮、甲基異丙基酮、曱基異 戊基酮、二異丙基酮、二異丁基酮、甲基異丁基酮、環己酮、 1 乙基戊基酮、曱基丁基酮、曱基己基酮、甲基壬基酮、曱氧 基甲基戊酮之類的酮類; 0 乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、丙二醇、丁 二醇、二乙二醇、二丙二醇、三乙二醇、甲氧基曱基戊醇、 甘油、苄醇之類的一元或多元醇類; 正戊烷、正辛烷、二異丁烯、正己烷、己烯、異戊二烯、 . 雙戊稀(dipentene)、十二烧之類的脂肪族烴類; 環己烷、甲基環己烷、曱基環己烯、聯環己烷 (bicyclohexyl)之類的脂環式烴類; Q 苯、曱笨、二曱苯、異丙苯之類的芳香族烴類; 曱酸戊酯、甲酸乙酯、乙酸乙酯、乙酸丁酯、乙酸丙酯、 乙酸戊酯、異丁酸曱酯、乙二醇乙酸酯、丙酸乙酯、丙酸丙 ' 酯、丁酸丁酯、丁酸異丁酯、異丁酸曱酯、辛酸乙酯、硬脂 酸丁酯、苯曱酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙 _ 酯、3-曱氧基丙酸曱酯、3-曱氧基丙酸乙酯、3-曱氧基丙酸 丙酯、3-曱氧基丙酸丁酯、7-丁内酯之類的鏈狀或環狀酯 類;. TF988407 27 201037041 3-曱氧基丙酸、3-乙氧基丙酸之類的烷氧基羧酸類; 氣丁烷、氣戊烷之類的鹵化烴類; 曱氧基曱基戊酮之類的醚酮類; 乙腈、苄腈之類的腈類等。 作為符合上述之市售溶劑,可舉出:礦油精(mineral spirit)、Varsol# 2、Apco#18 Solvent、Apco thinner、 Socal Solvent No. 1 及 No. 2、Solvesso# 150、Shell TS28 Solvent、卡必醇、乙基卡必醇、丁基卡必醇、曱基赛璐蘇、 乙基赛璐蘇、乙基賽璐蘇乙酸酯、曱基賽璐蘇乙酸酯、二乙 二醇二甲鱗(diglyme)(均為商品名)等。該等溶劑可單獨使 用1種,亦可併用2種以上。 〈以光微影法形成彩色濾光片之像素之情形> 在以光微影法形成彩色遽光片之像素的情形,作為溶劑, 較佳為選擇沸點為1〇〇〜200°c(壓力1013.25 [hPa]條件 下。以下,涉及到沸點均完全相同。)之範圍者。更佳為具 有120〜17(TC之沸點者。 就塗佈性、表面張力等之平衡性良好’組成物中之構成成 分之溶解度相對較高而言’上述溶劑中較佳為乙二醇烷基醚 乙酸S旨類。 又,乙一醇烧基醚乙酸酯類可單獨使用,亦可與其他溶劑 併用。作為併用之溶劑,特佳為乙二醇單烷基醚類。其中, 特別是就組成物中之構成成分之溶解性而言,較佳為丙二醇 TF988407 28 201037041 單甲醚。再者’乙二醇單絲_之極性較高,若添加量過 多,則有顏料易於凝集、隨後所得著色組成物之黏度上升等 保存穩定性下降之傾向,因此溶财之乙二料絲嶋之 比例較佳為5重量%〜3〇重量%,更佳為5重量%〜2()重量%。 Ο ❹ 又,亦較佳為併用具有15代以上之彿點的溶劑。藉錢 用此種高沸點溶劑,而使得著色組成物不易乾燥,具^難以 引起f於迅速乾燥而造成顏料分散液之相互關係缺陷之效 果^沸點溶劑之含量,係相對於溶劑較佳為3重量%〜50 佳為5重量%〜仙重量%,特佳為5重量%〜3〇重 里於右4點溶劑之量過少,财可能在 端發生色材成分等析出·固化而引起異物缺陷,又,二多 =Γ燥速度會變慢,從而擔憂引起後述彩色遽光片 針跡之問題Γ减壓“製程的黏性(tack)不良或預洪烤的 類再上之溶劑,可為二醇__旨 有沸叫15(^ 嶋,在此㈣下,亦可不另外含 令币為150 c以上之溶劑。 〈以噴墨法形成彩色料片之像素之情形〉 較= Ϊ = = 之像素的情形下,作為溶劑, °C以上斷以下者°。以上3〇rc以下、較^ 變差之傾向。反之,:弗點過低’則有所得塗膜之均勾性 右'弗點過局,則如後述般,硬化性樹脂 TF988407 29 201037041 組成物之乾_舰果較高,較在減減塗财亦殘留 許多溶劑,⑽會產生品f上之_,或者由於真 之乾燥時_長而產生使輸時間增大等問題。… 又就所得塗膜之均勾性之 麗通常為1〇_以下、較隹灸點而吕’可使用溶劍之蒸汽 以下者。 為5咖Hg以下、更佳為 再者,於使用喷墨法之彩 油墨為非常細微之數〜數十’[光片製造中,自喷嘴吐出之 嘴口周邊或像素陣列(pixeUP ’因此有在將油墨噴射至喷 墨濃縮·乾燥之傾向。為了避崎)内之前’溶劑蒸發而使油 較高,具體而言,較佳為含免此現象,較佳為溶劑之沸點 佳為含有彿點為20{rCj^H^為⑽。c以上之溶劑。更 ◦C以上之溶劑。又,沸點為18=、’特佳,含有沸點為220 顏料分散液及/或彩色濾光片^以上之鬲沸點溶劑,係在 中,幸父佳為5 〇重量%以μ 著色組成物中所含之總溶劑 90重量%以上。在高沸點溶二為70重量%以上’最佳為 有時亦無法充分發揮防止3夏未滿50重量%的情形下’ 作為較佳之高濟點溶劑發之效果。 二乙二醇單正丁醚乙酸酯、二 牛出.上述各種溶劑中之 醇單甲醚乙酸酯、丨,3_ *乙一醇單***乙酸酯、二丙二 酯、甘油三乙酸酯等。 ·夂酯、丨,6-己二醇二乙酸 進而,為了調整顏料分散液 色組成物之黏度或固形分 TF988407 201037041 之溶解度,部分含有沸點低於180°C之溶劑亦較有效。作為 此種溶劑,較佳為黏度低且溶解性高、表面張力低之類的溶 ' 劑,較佳為醚類、酯類或酮類等。其中,特佳為環己酮、二 ' 丙二醇二甲醚、環己醇乙酸酯等。 ’另一方面,若溶劑中含有醇類,則有時喷墨法中之吐出穩 定性會發生劣化。因此,醇類在總溶劑中之含量,較佳為 20重量%以下,更佳為10重量%以下,特佳為5重量%以下。 0 〈溶劑之含量〉 溶劑在本發明之著色組成物整體中所占之含量,並無特別 限制,其上限通常為9 9重量%以下。在溶劑含量超過9 9重 - 量%的情形下,顏料、分散劑等則變得過少,而不適於形成 . 塗佈膜。另一方面,考慮到適於塗佈之黏性等,溶劑含量之 下限通常為75重量%以上,較佳為80重量%以上,更佳為 82重量%以上。 Q [卜3]分散劑: 本發明所使用之分散劑,含有由具有親溶劑性之A嵌段及 具有含氮原子的官能基之B嵌段所構成之嵌段共聚物,其胺 價以有效固形分換算計為80 mgKOH/g以上且150 mgKOH/g . 以下。 作為嵌段共聚物,較佳為(曱基)丙烯酸系嵌段共聚物,以 下,以上述嵌段共聚物為(曱基)丙烯酸系嵌段共聚物之情形 為中心,就本發明之分散劑加以說明。 TF988407 31 201037041 B嵌段係具有含氮原子之官能基,作為該官能基,較佳為 一〜三級胺基。一〜三級胺基之含有比率,較佳為含氮原子 官能基整體的20莫耳%以上,更佳為50莫耳%以上。一〜三 級胺基t,特佳為三級胺基。作為該三級胺基,特佳可舉出 以-NR41R42(其中,R41及R42分別獨立表示可具有取代基之環 狀或鏈狀烷基、可具有取代基之芳基、或者可具有取代基之 芳烷基。)所表示之基,較佳的含有該三級胺基之部分結構 (重複單元),例如以下述式表示。 [化7] R44Japanese Patent Publication No. 61-201610, a method in which a vanadium compound is adhered to titanium dioxide or titanium hydroxide, and is subjected to high-temperature reduction in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610); Examples of such a method are commercially available as Chinhe, and examples thereof include titanium, Titanium 12S, 13R, 13M, and 13M-C manufactured by MITSUBISHI MATERIALS CORPORATION. These pigments may be used singly or in combination of two or more. Further, the average-secondary particle diameter of the pigment such as = is usually G. 2 μ or less, preferably Ο or less, more preferably Q.Q4/zm or less, and particularly preferably ', ,, .1, and usually 〇篇_above. · 25 _ below' method is suitable for the preparation of a pigment, such as the solvent salt milling method described later as the above-mentioned green pigment, usually zinc (4) has 16 nitrogens in one molecule; Generation, the hydrogen desertification phthalocyanine pigment. Among them, the display pole: the best use of the bud rate, suitable for the formation of TF9S8407 21 201037041 color filter green material, more than 13 bromine atoms of bromine 铉苴 *, the average in the knife Containing the genus Zinc Oxide. More preferably, it is a ~16 (four) atom, and one molecule does not contain a gas atom or a traitor, and the right has 13 or less gas atoms, the secret is 1 minute 16 bromine atoms, and 1 molecule contains 8 to 14 ~ lower gas atom of zinc material. The _ sub- or an average of two such brominated phthalocyanine pigments can be produced by a known production method disclosed in Japanese Patent Laid-Open Publication No. Hei. For example, there is a method of synthesizing Yanqi by using an o-dicarboxylic acid or an o-ruthenium obtained by taking a part of the nitrogen atom of the (4) (4) atom on the silk surface. At this time, a catalyst such as ammonium citrate may be used as needed. As another method, there is a method in which zinc ugly phthalocyanine is reduced in desertification by mixing 11G to 17n in a mixture of vaporized, vaporized, or dissected sodium. In this method, the ratio of the content of the heteropolyphthalocyanine can be arbitrarily controlled by adjusting the ratio of the vapor compound in the molten salt, or the amount of the gas or the reaction time. After the completion of the reaction, when the obtained mixture is poured into an acidic aqueous solution such as hydrochloric acid, the resulting <small zinc phthalocyanine will be killed. Wei, after treatment with hydrazine, washing, drying, etc., obtained zinc bromide phthalocyanine. If necessary, the H phthalocyanine pigment is obtained by dry grinding in a pulverizer such as an attritor, a ball mill, a vibrating 胄 vibrating ball mill, and then pigmented by a solvent salt milling method or a solvent boiling method. Permeability or TF988407 22 201037041 High-contrast green-light zinc bromide pigment. The method of pigmentation is not particularly limited, and it is preferable to use a solvent salt milling method in order to easily suppress crystal growth and obtain a larger specific surface area. The solvent salt milling method means that the crude pigment immediately after the synthesis is kneaded with an inorganic salt and an organic solvent. Specifically, a crude pigment, an inorganic salt, and an organic solvent in which it is not dissolved are added to a kneading machine, and kneaded in a kneading machine. As the kneading machine at this time, for example, it is suitable to use a kneader or a kneader, or a gap portion having a ring-shaped fixed disk and a concentric rotating disk as described in Japanese Laid-Open Patent Publication No. 2006-77062. A continuous kneading machine that smashes the space. As the inorganic salt, a water-soluble inorganic salt can be suitably used, and it is preferably used, for example, an inorganic salt such as sodium chloride, chlorination or sodium sulfate. 5〜50 // m。 The particle size of the inorganic salt is 0. 5~50 // m. Such an inorganic salt can be easily obtained by finely pulverizing a usual inorganic salt. Q The zinc bromide phthalocyanine thus obtained may be used singly or as a zinc bromide phthalocyanine having a different bromination rate or chlorination rate, or may be replaced with another metal in the range which does not impair the effects of the present invention. The brominated phthalocyanine or the like is used in combination. By changing the chlorination rate and the bromination rate or changing the center metal, the color tone of the pigment is changed, and an increase in the reproducible hue change can be expected. Further, even the same 'green pigment' may be mixed with a copper halide phthalocyanine such as C. I. Pigment Green (P. G.) 36 or 7. 025微米以下以下。 The average primary particle size of the green pigment comprising zinc bromide phthalocyanine, usually 0. 1 TF988407 23 201037041 _ or less, preferably 0.04 _ or less, more preferably 〇〇 3 _ or less, particularly preferably 0. 025 μm or less , again, usually 〇. 〇〇5 or more. If the average primary particle diameter is too large, the depolarization characteristic is deteriorated and the contrast is insufficient. In severe cases, the penetration rate may be lowered to deteriorate the fundamental color characteristics, or coarse particles may be formed. However, a foreign matter is generated, which causes a decrease in the yield of the color filter, or causes a problem in production such as process filter clogging. On the other hand, if the average primary particle diameter is too small, there is a problem that the dispersion stability is lowered due to the increase in the ratio φ of the pigment, or the heat resistance and light resistance are deteriorated due to the close proximity of the pigment to the molecular state. Further, the average primary particle diameter of the pigment can be determined by the following method. That is, the pigment was ultrasonically dispersed in a gas pattern and added dropwise to a grid attached to a rubber film to be dried, and a primary particle image of the pigment was obtained by observation using a transmission electron microscope (TEM). . The primary particle diameter was measured from the image, and a single average value was calculated according to the calculation formula of the following formula, and the average particle diameter was determined. In the case of an organic pigment, the particle diameter of each pigment particle is defined as the area circle equivalent of the diameter of a circle having the same area, and the particle diameters of a plurality of pigment particles of about 200 to 300 are determined. The average average particle diameter is determined by calculating a single average value according to the calculation formula of the following formula. Particle size of each pigment particle: Xl, X2, X3, X4, ..., Xi.... Average particle diameter = ΣΧί/πΐ Furthermore, in order to color the desired color, each of the above pigments may be used. TF988407 24 201037041 Two or more kinds of pigments are used in combination. For example, in (4) red or green pigments, or coloring, and (4), in order to adjust the eye, the yellow pigments above the illusion can be combined in red pigment or green pigment, respectively. As such a yellow pigment, the above various yellow ray can be mentioned. Further, in order to prepare a blue pigment dispersion or a coloring composition, a blue pigment may be combined with at least two or more kinds of purple pigments, and in addition to the rotation, the color of the touch may be appropriately mixed and used. The pigment content in the pigment knives in the smuggling month is based on the total amount of solids, which is 90% by weight, preferably 85% by weight or less, more preferably 80% by weight or less, and usually 2 〇. The weight % or more is preferably more than the weight %. The above is more preferably 40% by weight or more. In the color of the current month, the pigment content in the coloring composition for the light-sensitive sheet is usually 75% by weight or less, preferably 70% by weight or less, more preferably 60% by weight or less, relative to the total amount of the solid content. It is usually 1% by weight or more, more preferably 20% by weight or more, and still more preferably 25% by weight or more. If the amount of the pigment is too large, it is difficult to maintain the dispersion state of the pigment, and aggregation or sedimentation may occur, and the yarn may have a problem of reduction in enthalpy or brightness and contrast lamp. On the other hand, if the amount of the pigment is too small, the color density is light, and there is a possibility that the function as a color filter cannot be sufficiently exhibited. [1-2] Solvent solvent The pigment dispersion liquid of the present invention or a coloring composition to be described later has a function of dissolving components other than the above-mentioned TF988407 25 201037041, which are optionally formulated, in addition to the pigment and the dispersing agent. Or disperse and adjust the viscosity. The solvent I may be dissolved or dispersed in each component. Examples of such a compound include H alcohol mono-, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene. 00 矸早'' propanol early methyl ether, propylene glycol car test, propylene glycol single positive top, propylene glycol third top, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, - Pingyi Yiyiyi N-butyl ether, methoxy-indoylol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl ether, tripropyl-3-methoxybutanol, triethylene glycol monomethyl a diol monoalkyl ether such as triethylene glycol monoethyl ether glycol monomethyl ether; ethylene glycol dimethyl ether, diethylene glycol dibutyl hydrazine, dipropylene glycol diethylene glycol Glycol dialkyl ethers such as methyl bond, ethylene glycol diethyl ether diethyl ether, diethylene glycol dipropyl ether, methyl ether; ethylene glycol monomethyl acetate acetate, ethylene glycol monoacetate acetic acid Ethylene glycol mono-n-butyl ether acetate S, propylene glycol monomethyl acetate acetic acid, propylene glycol monoethyl ether acetate, propylene glycol monopropylene acetic acid g, propylene glycol mono-acetic acid g, acetic acid methoxy butyl vinegar, acetic acid -3-methoxybutyl ester, methoxyacetic acid acetate, diethylene glycol monomethyl ether acetate, monoethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate a diol such as dipropylene glycol monoterpene ether acetate, triethylene glycol monoterpene ether acetate, triethylene glycol monoethyl ether acetate, or acetic acid-3-mercapto-3-methoxybutyl ester Alkyl ether acetates; glycol diacetates such as ethylene glycol diacetate, 1,3-butanediol diacetate, hydrazine, 6-hexanediol diacetate; TF988407 26 201037041 ring Alkyl acetates such as hexanol acetate; pentyl bond, propyl bond, diethyl bond, dipropyl bond, diisopropyl mystery, butyl bond, dipenta bond, 'ethyl isobutyl ether, dihexyl ether, etc. Ethers; • Acetone, mercaptoethyl ketone, methyl amyl ketone, methyl isopropyl ketone, decyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl Ketones such as ketone, cyclohexanone, 1 ethyl amyl ketone, decyl butyl ketone, decyl hexyl ketone, methyl decyl ketone, decyloxymethyl pentanone; 0 ethanol, propanol, butyl Mono- or poly-alcohols such as alcohol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxydecyl amyl alcohol, glycerol, benzyl alcohol Alcohols; n-pentane, n-octane, diiso Aliphatic hydrocarbons such as olefin, n-hexane, hexene, isoprene, dipentene, and dodecacin; cyclohexane, methylcyclohexane, nonylcyclohexene, and hydrazine An alicyclic hydrocarbon such as hexane (bicyclohexyl); an aromatic hydrocarbon such as benzene, hydrazine, diphenylbenzene or cumene; amyl phthalate, ethyl formate, ethyl acetate, butyl acetate Ester, propyl acetate, amyl acetate, decyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, decyl isobutyrate , ethyl octanoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, decyl 3-methoxypropionate, 3- a chain or cyclic ester such as ethyl methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate or 7-butyrolactone; TF988407 27 201037041 3- An alkoxycarboxylic acid such as a nonoxypropionic acid or a 3-ethoxypropionic acid; a halogenated hydrocarbon such as a gas butane or a pentane; an ether ketone such as a decyloxypentanone; A nitrile such as acetonitrile or benzonitrile. As the commercially available solvent in accordance with the above, there may be mentioned mineral spirit, Varsol # 2, Apco #18 Solvent, Apco thinner, Socal Solvent No. 1 and No. 2, Solvesso # 150, Shell TS28 Solvent, Carbitol, ethyl carbitol, butyl carbitol, thioglycol, ethyl cyanohydrazide, ethyl cyproterone acetate, thioglycolate acetate, diethylene glycol Dimlyme (both trade names) and the like. These solvents may be used alone or in combination of two or more. <Case where a pixel of a color filter is formed by photolithography> In the case of forming a pixel of a color calender by photolithography, as a solvent, it is preferred to select a boiling point of 1 〇〇 to 200 ° C ( Under the pressure of 1013.25 [hPa], the following relates to the range where the boiling points are all the same. More preferably, it has a boiling point of 120 to 17 (the boiling point of TC. The balance between coating property and surface tension is good.) The solubility of the constituents in the composition is relatively high. Further, the ethyl ether alkyl ether acetate may be used singly or in combination with other solvents. The solvent used in combination is particularly preferably an ethylene glycol monoalkyl ether. The solubility of the constituent components in the composition is preferably propylene glycol TF988407 28 201037041 monomethyl ether. Further, the polarity of the 'ethylene glycol monofilament _ is high, and if the amount added is too large, the pigment is easily aggregated, and subsequently obtained. The storage stability such as the increase in viscosity of the colored composition tends to decrease. Therefore, the ratio of the bismuth bismuth is preferably 5% by weight to 3% by weight, more preferably 5% by weight to 2% by weight. Ο ❹ Further, it is also preferred to use a solvent having a Buddha's point of 15 or more. By borrowing such a high-boiling solvent, the colored composition is not easily dried, and it is difficult to cause the pigment to be dried quickly. Effect of mutual relationship defects The content of the boiling point solvent is preferably 3% by weight to 50% by weight to 5% by weight to 5% by weight, particularly preferably 5% by weight to 3% by weight of the solvent, and the amount of the solvent is too small at the right 4 points. At the end, a color material component is precipitated and solidified to cause a foreign matter defect, and more than two times, the drying speed is slowed, and there is a concern that the color ray sheet stitching problem described later is caused by decompression and "defect" of the process. Or the pre-flooded type of solvent, which may be a diol __ has a boiling point of 15 (^ 嶋, under this (four), or may not contain a solvent of 150 c or more. <Formed by inkjet method In the case of a pixel of a color material > In the case of a pixel with a = Ϊ = =, as a solvent, °C is equal to or less than the above. The above 3 〇rc is less likely to be worse than the ^. Conversely, the point is too low. 'There is a uniform coating film on the right side of the right point, as described later, the hardening resin TF988407 29 201037041 composition of the dry _ ship fruit is higher, more than a lot of solvent remaining in the reduction of wealth, (10) It will produce _ on the product f, or it will cause problems such as increasing the transmission time due to the fact that it is dry. The uniformity of the obtained coating film is usually 1〇_ or less, which is lower than that of the moxibustion point and can be used for the steam of the solution sword. It is 5 coffee Hg or less, more preferably, the inkjet method is used. The color inks are very fine to tens of tens [in the manufacture of light sheets, the periphery of the nozzles that are ejected from the nozzles or the pixel array (the pixeUP 'has a tendency to eject the ink to the inkjet to concentrate and dry. To avoid the saki) The solvent is evaporated to make the oil higher. Specifically, it is preferable to contain the phenomenon. Preferably, the boiling point of the solvent is preferably a solvent containing a point of 20{rCj^H^ (10).c or more. Solvents above ◦C. Also, the boiling point is 18 =, 'excellent, containing a boiling point of 220 pigment dispersion and / or color filter ^ above the boiling point solvent, in the middle, the good father is 5 〇 wt% The total solvent contained in the composition is colored by 90% by weight or more. The high boiling point is preferably 70% by weight or more. Optimum may not be sufficient to prevent the use of 50% by weight of the summer. Diethylene glycol mono-n-butyl ether acetate, dioxan. Alcohol monomethyl ether acetate, hydrazine, 3_ * ethyl alcohol monoethyl ether acetate, dipropylene diester, triacetin Ester and the like. Ester ester, hydrazine, 6-hexanediol diacetic acid Further, in order to adjust the viscosity of the pigment dispersion liquid composition or the solubility of the solid fraction TF988407 201037041, it is also effective to partially contain a solvent having a boiling point lower than 180 °C. As such a solvent, a solvent having a low viscosity, a high solubility, and a low surface tension is preferred, and an ether, an ester or a ketone is preferable. Among them, cyclohexanone, bis-propylene glycol dimethyl ether, cyclohexanol acetate, and the like are particularly preferred. On the other hand, when an alcohol is contained in the solvent, the discharge stability in the inkjet method may be deteriorated. Therefore, the content of the alcohol in the total solvent is preferably 20% by weight or less, more preferably 10% by weight or less, and particularly preferably 5% by weight or less. 0 <Content of solvent> The content of the solvent in the entire coloring composition of the present invention is not particularly limited, and the upper limit thereof is usually 99% by weight or less. In the case where the solvent content exceeds 9 9 wt%, the pigment, the dispersant, etc. become too small to be formed. The film is coated. On the other hand, the lower limit of the solvent content is usually 75% by weight or more, preferably 80% by weight or more, and more preferably 82% by weight or more, in view of viscosity or the like suitable for coating. Q [Bu 3] Dispersant: The dispersant used in the present invention contains a block copolymer composed of a solvophilic A block and a B block having a functional group containing a nitrogen atom, and the amine valence is The effective solid content conversion is 80 mgKOH/g or more and 150 mgKOH/g. The block copolymer is preferably a (mercapto)acrylic block copolymer. Hereinafter, the dispersant of the present invention is centered on the case where the block copolymer is a (fluorenyl)acrylic block copolymer. Explain. TF988407 31 201037041 The B block has a functional group containing a nitrogen atom, and as the functional group, a mono- to tertiary amino group is preferable. The content ratio of the mono- to tertiary amino groups is preferably 20 mol% or more, more preferably 50 mol% or more based on the entire nitrogen atom-containing functional group. One to three amine groups t, particularly preferably a tertiary amine group. As the tertiary amine group, particularly, -NR41R42 (wherein R41 and R42 each independently represent a cyclic or chain alkyl group which may have a substituent, an aryl group which may have a substituent, or may have a substituent) The group represented by the aralkyl group) is preferably a partial structure (repeating unit) containing the tertiary amino group, and is represented, for example, by the following formula. [化7] R44
Μ r41/、r42 (其中,R41及R42,與上述R41及R42之含義相同,R43表示碳數 1以上之伸烷基,R44表示氫原子或曱基。) 其中,R41及R42較佳為曱基,R43較佳為亞曱基、伸乙基, R44較佳為氫原子或曱基。作為此種部分結構,特別適合使 用以下述式所表示之來自丙烯酸二曱胺基乙酯或曱基丙烯 酸二曱胺基乙酯之結構等。 TF988407 32 201037041 [化8]Μ r41/, r42 (wherein R41 and R42 have the same meanings as defined above for R41 and R42, R43 represents an alkylene group having a carbon number of 1 or more, and R44 represents a hydrogen atom or a fluorenyl group.) wherein R41 and R42 are preferably fluorene. Further, R43 is preferably an anthracenylene group or an ethyl group, and R44 is preferably a hydrogen atom or a fluorenyl group. As such a partial structure, a structure derived from diamylaminoethyl acrylate or decylaminoethyl decyl acrylate represented by the following formula is particularly suitable. TF988407 32 201037041 [Chem. 8]
0 1個B纽巾可含有2㈣上如上狀含有絲之部分結 構。此時,於該B嵌段中,可以無規共聚或嵌段共聚之任一 態樣,含有2種以上之含有胺基之部分結構。又,B嵌段中 亦可部分地含有不含胺基之部分結構,作為此種部分結構之 例,可舉出來自(曱基)丙烯酸酯系單體之部分結構等。該不 含胺基之部分結構在B嵌段中之含量,較佳為〇〜5〇重量0/〇, 更佳為0〜20重量%,但最佳係B嵌段中不含有該不含胺基 U之部分結構。 另一方面,構成分散劑之嵌段共聚物的親溶劑性之A嵌 段,若係不含有上述胺基等含氮原子之官能基,並可與構成 上述B嵌段之單體進行共聚合的單體所構成者,則無特別限 • 制。 作為親溶劑性之A嵌段,例如可舉出:苯乙烯、α _甲基 苯乙烯等笨乙烯系單體;(甲基)丙烯酸曱醋、(甲基)丙烯酸 TF9S8407 33 201037041 乙醋 ' (甲基)丙_丙酉旨、(甲基)丙烯酸異丙醋、(甲基) 丙烯酸丁醋、(甲基)丙婦酸辛醋、(甲基)丙烯酸_2_乙基己 醋、(甲基)丙稀酸環氧丙s旨、(甲基)丙婦酸节醋、(甲基) 丙稀酸經基乙醋、乙基丙烯酸環氧丙醋、聚乙二醇(甲基) 丙稀酸醋、聚丙二醇(甲基)丙稀酸酉旨等(甲基)丙稀酸醋系單 體;(f基)丙婦醯氯等(甲基)丙_氣系單體;乙酸乙稀醋 系單體;稀丙基環氧丙基趟、丁_環氧㈣等環氧丙_ 單體等共單體進行共聚合而得之聚合物結構。 -中作為A嵌段’較佳為含有聚乙二醇(甲基)丙婦酸 醋、聚丙二醇(甲基)丙婦酸醋等聚燒二醇(甲基)丙稀酸醋作 ^共聚合成分(即,含有來自聚燒二醇(甲基)丙婦酸醋之部 分結構)者,特佳為具有以下述式⑼所表示之部分結構之 A嵌段。 [化9] R 500 1 B towel may contain 2 (4) a part of the structure containing silk as above. In this case, the B block may have a partial structure containing two or more kinds of amine groups in any of random copolymerization or block copolymerization. Further, the B block may partially contain a partial structure containing no amine group, and examples of such a partial structure include a partial structure derived from a (fluorenyl) acrylate monomer. The content of the amino group-free partial structure in the B block is preferably 〇~5〇 by weight 0/〇, more preferably 0 to 20% by weight, but the optimum B block does not contain the content. Part of the structure of the amine group U. On the other hand, the solvophilic A block of the block copolymer constituting the dispersant may be copolymerized with a monomer constituting the above B block if it does not contain a functional group containing a nitrogen atom such as the above amine group. There is no special limit on the composition of the monomer. Examples of the solvophilic A block include a stupid vinyl monomer such as styrene or α-methylstyrene; a (meth)acrylic acid vinegar, (meth)acrylic acid TF9S8407 33 201037041 ethyl vinegar' ( Methyl) propyl propyl acrylate, (meth)acrylic acid isopropyl vinegar, (meth)acrylic acid butyl vinegar, (methyl) glyceryl vinegar vinegar, (meth) acrylate 2 - ethyl hexanoic acid, (a Base) acrylic acid propylene s, (methyl) propylene vinegar vinegar, (meth) acrylic acid via ethyl vinegar, ethyl acrylate propylene vinegar, polyethylene glycol (methyl) propyl (meth)acrylic acid vinegar monomer such as dilute vinegar, polypropylene glycol (methyl) acrylate, etc.; (meth) propyl sulfonate and other (methyl) propylene-gas monomer; A polymer structure obtained by copolymerizing a rare vinegar-based monomer; a propylene group such as a propylene group; a propylene group such as a propylene group; - as the A block' is preferably a polyglycol diol (methyl) acrylate vinegar such as polyethylene glycol (methyl) propylene vinegar, polypropylene glycol (methyl) propylene vinegar, etc. The polymerization component (that is, the partial structure containing the polyalkylene glycol (meth) acetoacetate) is particularly preferably an A block having a partial structure represented by the following formula (9). [Chemical 9] R 50
(IV) 特佳為am中含有5〜4G莫耳%之以上述式^)。戶核矛 TF988407 34 201037041 之部分結構。 雖然詳細的作用機制不明,但一般認為作用機制為:籍由 ' 具有來自聚烷二醇(甲基)丙烯酸酯之部分結構、特別是以上 • 述式所表示之部分結構,而可提高分散劑分子之氫鍵性,從 而提昇與分散溶劑之親和性,且分散系之穩定性增加。 本發明中所使用之分散劑,含有由此種A嵌段與B嵌段所 構成之共聚物,較佳為含有AB嵌段或者ΑΒΑ嵌段共聚物。 0 其中,較佳為ΑΒ嵌段共聚物。此種嵌段共聚物例如可藉由 以下所示之活性聚合法而製備。 活性聚合法有陰離子活性聚合法、陽離子活性聚合法、自 由基活性聚合法。陰離子活性聚合法之聚合活性種為陰離 子,例如下述流程所示。 [化 10] (陰離子活性聚合法〉 〇 在單體①:H2C=fH、單體②:H2C=fH 時 Ar1 Ar2 H2C=CH Ar1 +有機金屬(Μ)化合物 的CH2 —C㊆"…·ΜΦ(IV) It is particularly preferable that the am contains 5 to 4 G mol% of the above formula ^). Part of the structure of the nuclear spear TF988407 34 201037041. Although the detailed mechanism of action is unknown, it is generally believed that the mechanism of action is: by the partial structure of the polyalkylene glycol (meth) acrylate, especially the partial structure represented by the above formula, the dispersant can be improved. The hydrogen bonding property of the molecule enhances the affinity with the dispersion solvent, and the stability of the dispersion increases. The dispersing agent used in the present invention contains a copolymer composed of such an A block and a B block, and preferably contains an AB block or a fluorene block copolymer. Among them, a fluorene block copolymer is preferred. Such a block copolymer can be produced, for example, by the living polymerization method shown below. The living polymerization method includes an anionic living polymerization method, a cationic living polymerization method, and a free radical active polymerization method. The polymerization active species of the anionic living polymerization method are anions, as shown in the following scheme. [Anion 10] (Anionic Living Polymerization Method) 〇 In the monomer 1: H2C = fH, monomer 2: H2C = fH Ar1 Ar2 H2C = CH Ar1 + organometallic (Μ) compound CH2 - C7 "...·ΜΦ
Ar1 單體①Ar1 monomer 1
pCH^—CH^I 單體② ^CH2—CH-I1 Θ < —CH ""*“M CHo—CH^l n-*-1 :CH2—CH-pCH^—CH^I monomer 2 ^CH2—CH-I1 Θ < —CH ""*“M CHo—CH^l n-*-1 :CH2—CH-
Ar1. n+1 . Ar2 m+1 TF988407 35 201037041 自由基活性聚合法(石肖醯(ni troxy 1)法、ATRP法(Atom Transfer Radical Polymerization,原子轉移自由基聚合 法))之聚合活性種為自由基,例如下述流程所示。 [化 11] (自由基活性聚合法:硝醯法) 在單體①:Ar1. n+1 . Ar2 m+1 TF988407 35 201037041 The polymerization activity of the radical living polymerization method (ni troxy 1 method, ATRP method (Atom Transfer Radical Polymerization)) is Free radicals are shown, for example, in the scheme below. [Chemical 11] (radical active polymerization method: nitroxide method) in monomer 1:
H2C :CHIAr h2c: (1):體單H2C : CHIAr h2c: (1): body order
時 H 9r :c—M ηH 9r :c—M η
ch3 h3c' 〉c—ch2 CH2-CH""""〇-N 、CH2 I ,^c—ch2Ch3 h3c' 〉c—ch2 CH2-CH""""〇-N , CH2 I ,^c—ch2
At1 h3c ch3 單體① 單體② CH2—-CH- ch3 H3c、占一Ch2 / \z .CH2—CH"ium〇—N CH2At1 h3c ch3 monomer 1 monomer 2 CH2—CH-ch3 H3c, occupies a Ch2 / \z .CH2—CH"ium〇—N CH2
Ar1 -1Γ CH3 H3c、i—ch2 >CH2—CH: -CH2—CH-I ir1· n+1 L Ar2. CH 之•"-CH"""11。一CH2 ^ 1 \ / ,C—CH2Ar1 -1Γ CH3 H3c, i_ch2 >CH2—CH: -CH2—CH-I ir1· n+1 L Ar2. CH·"-CH"""11. One CH2 ^ 1 \ / , C-CH2
Ar2 H3C" 36 TF988407 201037041 [化 12] (自由基活性聚合法:ATRP法) 在單體①:H2C=|H 、單體②:H2C=fH 時 COORa COORb 'Η2〇=〇Η I a COORa +有機金屬(Me)化合物 (Me袅示過渡金屬。) COORa Ο 單體①. 單體氙Ar2 H3C" 36 TF988407 201037041 (Free radical living polymerization method: ATRP method) COORa COORb 'Η2〇=〇Η I a COORa + in monomer 1:H2C=|H, monomer 2:H2C=fH Organometallic (Me) compound (Me indicates transition metal.) COORa Ο Monomer 1. Monomer 氙
CH2—CH-ICH2—CH-I
COORaJ -CH2—CH""…“ Me COORa >CH2—CH- COOR8 n+1 CH2—CH-COORaJ -CH2—CH""..." Me COORa >CH2—CH- COOR8 n+1 CH2—CH-
CO〇R&J -CH2—CH“"""Me | . COORb 在合成此種(曱基)丙烯酸系嵌段共聚物時’可採用日本專 q 利特開昭60-89452號公報;特開平9-62002號公報;P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984) ; B. C. Anderson, G. D. Andrews etal, Macromolecules, 14, 1601 (1981) ; K. Hatada, K. Ute, et al, Polym. J. 17, 977 • (1985) ; K. Hatada, K. Ute, et al, Polym. J. 18, 1037 (1986);右手浩一、畑田耕一’高分子加工,36,366 (1987); 東村敏延、沢本光男,高分子論文集’ 46,189 (1989) ; M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737 (1987); TF988407 37 201037041 相田卓三、井上祥平,有機合成化學,43, 300 (1985) ; D. Y. Sogoh, W. R. Hertleretal, Macromolecules, 20, 1473 (1987) ; K. Matyaszewski et al, Chem. Rev. 2001, 101, 2921 - 2990等中所記載之公知方法。 本發明之含有上述嵌段共聚物之分散劑的1 g固形分中之 胺價,以有效固形分換算計為80 mgKOH/g以上且 150mgKOH/g以下,較佳為90〜150 mgKOH/g,更佳為100〜 140 mgKOH/g。 若胺價過低,則分散劑分子對顏料表面之吸附力變得不充 分,無法獲得充分的分散穩定性。另一方面,若胺價過高, 則相對地A嵌段之分子量變小,分散穩定性變得不充分。換 言之,為了表現最佳分散性,而將胺價設定在上述範圍。 再者,分散劑之胺價(有效固形分換算),係以與除去分散 劑試料中之溶劑的每1 g固形分之鹼量等當量之K0H的重量 來表示,係藉由以下方法測定。於100 mL燒杯中精確秤取 0.5〜1.5 g分散劑試料,用50 mL乙酸將其溶解。使用具 備pH電極之自動滴定裝置,將該溶液以0· 1 mol/L之HCl〇4 乙酸溶液進行中和滴定。將滴定pH曲線之拐點作為滴定終 點,根據下式求出胺價。 胺價[mgKOH/g] = (561xV)/(WxS) (其中,W表示分散劑試料秤取量[g],V表示滴定終點之滴 定量[mL],S表示分散劑試料之固形分濃度[Wt%]。) TF988407 38 201037041 又,該嵌段共聚物之酸價’亦取決於成為該酸價之基礎的 酸性基之有無及種類,一般較佳為低酸價,通常為5〇 mgKOH/g以下,較佳為40 mgKOH/g以下,更佳為30 mgKOH/g . 以下。 於本發明中,亦可應用具有與上述化合物同樣結構之市售 的(曱基)丙烯酸系嵌段共聚物。 本發明之顏料分散液’必須使用含有上述由A嵌段及B 0 嵌段所構成之共聚物的分散劑。藉由使用此種嵌段共聚物作 為分散劑,可同時滿足對顏料表面的牢固吸附及較高的溶劑 親和性,因此可實現較高分散穩定性。又,藉由提高分散劑 - 之胺價,則特別是對經酸性處理的顏料表面之吸附力增加, . 因此可使分散穩定性進一步提高。 特佳為,B嵌段中具有含氮原子的官能基之重複單元中的 20莫耳%以上為具有一〜三級胺基之重複單元。若胺基之量 〇 小於20莫耳% ’則即便胺價為80 mgKOH/g以上,亦無法獲 得充分的吸附力,有時亦無法獲得高分散穩定性。 再者,當顏料之平均一次粒徑較小時,比表面積增大,因 • 此顏料之平每單位表面積之分散劑吸附量變少。在此種情形 下,含有上述嵌段共聚物之分散劑,與其他結構之分散劑相 比’非常顯著地表現出效果的差異,因此特別適合使用。相 對於顏料分散液中或著色組成物中之顏料總量,本發明之分 散劑之使用量較佳為5〜2〇〇重量%左右,更佳為1〇〜剛 TF988407 39 201037041 重量%左右。 本發明之顏料分散液及著色組成物,在不損及本發明效果 之範圍内,可含有除上述嵌段共聚物以外之分散劑。作為此 種分散劑,例如可舉出:日本專利特開2006-343648號公報 中記載之各種分散劑等。 [1-4]分散助劑 本發明之顏料分散液及著色組成物,亦可含有用以提高顏 料之分散性、提高分散穩定性之分散助劑。作為分散助劑, 例如可舉出顏料衍生物等。 作為顏料衍生物,例如可舉出:偶氮系、酞菁系、喹吖啶 酮系、苯并咪唑酮系、喹酞酮(quin〇phthal〇ne)系、異吲哚 啉酮系、二今井系、蒽醌(anthraqui_e)系、陰丹士林系、 茈系、哌瑞酮(perin〇ne)系、二酮吡咯并吡咯 (d i ketopyrro 1 opyrro 1 e)系顏料等衍生物。 作為該等顏料衍生物之取代基,可舉出:磺酸基、磺醯胺 基及其四級鹽、鄰苯二甲醯亞胺甲基、二烷基胺基烷基、羥 基、羧基、醯胺基等。該等取代基,可直接鍵結於顏料骨架 上,或者可經由烷基、芳基、雜環基等而鍵結。上述取代基 中,較佳為磺醯胺基及其四級鹽、磺酸基,更佳為磺酸基。 該等取代基可在一個顏料骨架上進行複數次取代,亦可為 取代數不同之化合物的混合物。 作為顏料衍生物之具體例,可舉出:偶氮系顏料之磺酸衍 TF988407 40 201037041 生物、酞菁系顏料之磺酸衍生物、喹酞酮系顏料之磺酸衍生 物、蒽醌系顏料之磺酸衍生物、喹吖啶酮系顏料之磺酸衍生 物、二酮吡咯并吡咯系顏料之磺酸衍生物、二巧讲系顏料之 石黃酸衍生物等。其巾,較佳為可舉出:色素黃138之績酸街 生物、色素黃139之石黃酸衍生物、色素紅254之績酸街生物、 色素紅255之磺酸衍生物、色素紅2料之磺酸衍生物、色素CO〇R&J -CH2—CH“"""Me | . COORb When synthesizing such a (fluorenyl) acrylic block copolymer, it can be used in Japanese Patent No. 60-89452 Unexamined 9-62002; P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984); BC Anderson, GD Andrews etal, Macromolecules, 14, 1601 (1981); K. Hatada, K. Ute, et al, Polym. J. 17, 977 • (1985); K. Hatada, K. Ute, et al, Polym. J. 18, 1037 (1986); Right hand Hao Yi, Putian Gengyi' polymer processing , 36, 366 (1987); Dong Cun, Min Yan, Sakamoto K., Polymer Proceedings, '46, 189 (1989); M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737 (1987); TF988407 37 201037041 Xiangtian Zhuo San, Inoue Xiangping, Organic Synthetic Chemistry, 43, 300 (1985); DY Sogoh, WR Hertleretal, Macromolecules, 20, 1473 (1987); K. Matyaszewski et al, Chem. Rev. 2001, 101, 2921 - a known method described in 2990, etc. The amine value in 1 g of the solid content of the dispersant containing the above block copolymer of the present invention is 80 mgKOH in terms of effective solid content. /g or more and 150 mgKOH/g or less, preferably 90 to 150 mgKOH/g, more preferably 100 to 140 mgKOH/g. If the amine value is too low, the adsorption force of the dispersant molecule on the surface of the pigment becomes insufficient. On the other hand, if the amine valence is too high, the molecular weight of the A block is relatively small, and the dispersion stability is insufficient. In other words, the amine valence is exhibited in order to exhibit optimum dispersibility. In addition, the amine valence (effective solid fraction conversion) of the dispersing agent is expressed by the weight of K0H equivalent to the amount of alkali per 1 g of the solid in the solvent of the dispersant sample. It was determined by the following method: 0.5 to 1.5 g of the dispersant sample was accurately weighed in a 100 mL beaker, and dissolved in 50 mL of acetic acid. Using an automatic titrator equipped with a pH electrode, the solution was 0.1 mol/L of HCl. Neutralization titration of 〇4 acetic acid solution. The inflection point of the titration pH curve was taken as the end point of the titration, and the amine value was determined according to the following formula. Amine value [mgKOH/g] = (561xV) / (WxS) (where W represents the dispersant sample weigh [g], V represents the titration end point titer [mL], and S represents the solids concentration of the dispersant sample [Wt%].) TF988407 38 201037041 Further, the acid value of the block copolymer also depends on the presence or absence of an acidic group which is the basis of the acid value, and is generally preferably a low acid value, usually 5 〇 mg KOH. Below /g, it is preferably 40 mgKOH/g or less, more preferably 30 mgKOH/g. In the present invention, a commercially available (fluorenyl) acrylic block copolymer having the same structure as the above compound can also be used. The pigment dispersion liquid of the present invention must use a dispersant containing the above-mentioned copolymer composed of the A block and the B 0 block. By using such a block copolymer as a dispersing agent, strong adsorption to the surface of the pigment and high solvent affinity can be simultaneously satisfied, so that high dispersion stability can be achieved. Further, by increasing the amine valence of the dispersant, the adsorption force on the surface of the acid-treated pigment is particularly increased, so that the dispersion stability can be further improved. Particularly preferably, 20 mol% or more of the repeating unit having a functional group containing a nitrogen atom in the B block is a repeating unit having a mono- to tertiary amino group. If the amount of the amine group 〇 is less than 20 mol%, even if the amine value is 80 mgKOH/g or more, sufficient adsorption force cannot be obtained, and high dispersion stability may not be obtained in some cases. Further, when the average primary particle diameter of the pigment is small, the specific surface area is increased because the amount of the dispersant adsorbed per unit surface area of the pigment is small. In this case, the dispersant containing the above block copolymer exhibits a difference in effect very significantly in comparison with the dispersant of other structures, and thus is particularly suitable for use. The dispersing agent of the present invention is preferably used in an amount of about 5 to 2% by weight, more preferably about 1 to about TF988407 39 201037041% by weight, based on the total amount of the pigment in the pigment dispersion or in the colored composition. The pigment dispersion liquid and the coloring composition of the present invention may contain a dispersing agent other than the above block copolymer, within the range not impairing the effects of the present invention. Examples of such a dispersing agent include various dispersing agents and the like described in JP-A-2006-343648. [1-4] Dispersing aid The pigment dispersion liquid and coloring composition of the present invention may further contain a dispersing aid for improving the dispersibility of the pigment and improving the dispersion stability. Examples of the dispersing aid include a pigment derivative and the like. Examples of the pigment derivative include an azo type, a phthalocyanine type, a quinacridone type, a benzimidazolone type, a quinacridone type, an isoindolinone type, and two. Derivatives such as the current well, anthraqui_e, indanthrene, lanthanide, perin〇ne, diketopyrro 1 opyrro 1 e pigments. Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonylamino group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, and Amidoxime and the like. These substituents may be bonded directly to the pigment skeleton or may be bonded via an alkyl group, an aryl group, a heterocyclic group or the like. Among the above substituents, a sulfonamide group and a quaternary salt thereof, a sulfonic acid group, and more preferably a sulfonic acid group are preferable. These substituents may be substituted a plurality of times on one pigment skeleton, or may be a mixture of compounds having different numbers of substitutions. Specific examples of the pigment derivative include sulfonic acid derivatives of azo pigments TF988407 40 201037041 Sulfonic acid derivatives of phthalocyanine pigments, sulfonic acid derivatives of quinacridone pigments, fluorene pigments A sulfonic acid derivative, a sulfonic acid derivative of a quinacridone pigment, a sulfonic acid derivative of a diketopyrrolopyrrole pigment, a rhein derivative of a dimethophoric pigment, and the like. The towel is preferably a pigment yellow 138, a acid street creature, a pigment yellow 139 rhein derivative, a pigment red 254 acid street creature, a pigment red 255 sulfonic acid derivative, a pigment red 2 Sulfonic acid derivative, pigment
紅272之橫酸衍生物、色素紅咖之續酸衍生物、色素撥 71之磺酸衍生物、色素紫23之磺酸衍生轉。 ,、且 又’分散助劑即便非上述所舉出之顏料本身之衍生物,亦 可為化學結構與其類似之化合物。 分散助劑之添加量,係相對於顏料通常為〇 ι重量%以 上,又’通常為30重量%以下,較佳為2〇重量%以下,更佳 為10重量%以下’特佳為5重量%以下。其原因在於,若六 加量較少則有難以發揮其效果之傾向, — 久 < 右添加量過多 則分散性、分散穩定性反而會變差。 [1-5]分散樹脂 本發明之顏料分散液,可含有自後述黏合劑樹脂 樹脂之-部分或全部。具體而言,彳_料分散液製= t分散處理步射,由於與上述分散_時切黏合創二 脂,该黏合劑樹脂顯示出與分散劑之相乘玫果" 矿 顏料之分散穩定性。結果有可能減&而有助於 刀政劑之添加量’因A 較佳。又,亦發揮提昇顯影性、在基板 u而 部分不殘留 TF98S407 201037041 未溶解物、提昇像素對基板之密著性的效果,因而較佳。 將如此用於分散處理步驟之黏合劑樹脂稱為分散樹脂。 相對於顏料分散液中之㈣總量,分賴脂之使用量較佳 為5〜200重量%左右,更佳為10〜100重量%左右。 .作為分散樹脂,可使用後述之各種黏合劑樹脂,特佳為後 述之[2 1 2](甲基)丙稀酸系樹脂。 刀政树月曰之酸價’較佳為10 mgKOH/g以上,更佳為30 S § 乂上,最佳為50 mgK0H/g以上,又,較佳為500 mgKOH/g以下,更佳為謂以下最佳為 mgK〇H/g 、I右自文價過尚,則變成高黏度,而有難以合成或操作之 "^ + 右駄仏過低,則有時會難以應用於鹼性顯影。 、,又、刀政柯脂之藉由Gpc法所測定之聚苯乙稀換算之重量 平句刀子$較佳為1000以上,更佳為1500以上,最佳為 7以上’又’較佳為2_以下,更佳為5GGGG以下, 影=1_〇以I。若分子量過大’則有難以應用於鹼性顯 ’又’若分子量過小,則有時分散穩定性下降。 [卜6]芳香族羧酸系化合物 本發明之顏料分散液及著色組成物中之至少 含有芳香錢1¾化合物。 14 地t Γ所使用之含有上核段共聚物之分錢,可效率佳 及經雜化之顏料分散,因而較佳,但使用其之顏料分散 液及衫色渡光片用著色組成物,經時性黏度增加之傾向較 TF988407 42 201037041 门又使用該著色組成物而形成之像素,有產生缺陷之傾 向。 因此’藉由使本發明之顏料分散液及著色組成物中之至少 者a有芳香族羧酸系化合物,可抑制該等之經時黏度增 .· ~τ防止所得像素之缺陷,因而較佳。 • 再者藉由在製備顏料分散液時含有該芳香族羧酸系化合 物可抑制顏料分散液本身之經時黏度增加,又,亦可抑制 〃所製備之彩色濾光片用著色組成物之經時黏度增 加#又,在向顏料分散液中添加各種成分而製備彩色濾光片 用者色組成物時’由於係作為隨後所添加成分之—而含有, ,、可抑制彩色慮光片用著色組成物之經時黏度增加。進 在不衣備顏料分散液*是—次性地或者依序調配構成彩 ,-光片用著色組成物之成分,藉此製備該著色組成物的情 形下’作為構成成分之一,可依任意之時機進行調配。 以下,就芳香族羧酸系化合物加以說明。 料芳香频m合物,若為具有料録及缓基者, 貝1可為具有任意結構者。作為芳香族基,例如可舉出苯基、 萘基等。該等之中,特佳為苯基。 ' 料芳香族基可具有取絲,其取代基之種類紐量並無 . 特別限疋。具體而言,例如較佳為後述通式(VI)中以χ3所 表不之取代基。又’縣可為丨個’亦可為複數個、例如2 至3個’但就上述之該化合物之效果較顯著之方面而言,較 TF988407 43 201037041 佳為1分子中為1個。 芳香族羧酸系化合物之分子量,通常為500以下,較佳為 350以下,又,通常為15〇以上。藉由將分子量設為以 下,如後述般,使該化合物容易接近顏料,可確實發揮抑制 黏度增加之效果。 作為芳香族羧酸系化合物,特佳為以下述通式(γι)所表示 之化合物 [化 13]The cross-acid derivative of red 272, the acid derivative of the pigment red coffee, the sulfonic acid derivative of the pigment dial 71, and the sulfonic acid derivative of the pigment purple 23 are converted. Further, the dispersing aid may be a chemical structure or the like even if it is not a derivative of the above-mentioned pigment itself. The amount of the dispersing aid to be added is usually 3% by weight or more based on the pigment, and is usually '30% by weight or less, preferably 2% by weight or less, more preferably 10% by weight or less, and particularly preferably 5 parts by weight. %the following. The reason for this is that if the amount of addition is small, it is difficult to exert its effect. - If the amount of right addition is too large, the dispersibility and dispersion stability may worsen. [1-5] Dispersion resin The pigment dispersion liquid of the present invention may contain part or all of the binder resin resin described later. Specifically, the 分散_dispersion liquid is prepared as a dispersion treatment step, and the binder resin exhibits dispersion with the dispersant by the dispersion of the dispersant. Sex. As a result, it is possible to reduce & and contribute to the addition amount of Knife. Moreover, it is preferable to improve the developability and to prevent the TF98S407 201037041 undissolved material from remaining on the substrate u and to improve the adhesion of the pixel to the substrate. The binder resin thus used for the dispersion treatment step is referred to as a dispersion resin. The amount of the lysate used is preferably from about 5 to 200% by weight, more preferably from about 10 to 100% by weight, based on the total amount of the (IV) in the pigment dispersion. As the dispersion resin, various binder resins to be described later can be used, and particularly preferred are [2 1 2] (meth)acrylic resin. The acid value of the knife sap is preferably 10 mgKOH/g or more, more preferably 30 S § 乂, preferably 50 mg K0H/g or more, more preferably 500 mgKOH/g or less, more preferably It is said that the following is best for mgK〇H/g, I right is too high for the price, but it is difficult to synthesize or manipulate the "^ + right 駄仏 too low, sometimes it is difficult to apply to alkaline development. Further, the weight of the polystyrene converted by the Gpc method is preferably 1000 or more, more preferably 1500 or more, and most preferably 7 or more. 2_ or less, more preferably 5GGGG or less, shadow=1_〇I. If the molecular weight is too large, it is difficult to apply to basicity. If the molecular weight is too small, the dispersion stability may be lowered. [Bu 6] Aromatic carboxylic acid-based compound The pigment dispersion liquid and the colored composition of the present invention contain at least an aromatic money compound. 14 The amount of money used in the copolymer containing the upper core segment is better, and the pigment is dispersed by the hybrid, so it is preferable to use the pigment dispersion liquid and the coloring composition for the shirt color light-receiving sheet. The tendency of the viscosity to increase with time is higher than that of TF988407 42 201037041. The pixel formed by using the coloring composition has a tendency to cause defects. Therefore, by making the at least one of the pigment dispersion liquid and the coloring composition of the present invention a compound having an aromatic carboxylic acid compound, it is possible to suppress the increase in the viscosity of the film by the time-dependent viscosity increase. . Further, by containing the aromatic carboxylic acid-based compound in the preparation of the pigment dispersion liquid, the increase in the viscosity of the pigment dispersion liquid itself can be suppressed, and the coloring composition for the color filter prepared by the ruthenium can also be suppressed. In addition, when a color filter coloring composition is prepared by adding various components to a pigment dispersion liquid, it is contained as a component to be added later, and coloring of the coloring sheet can be suppressed. The composition has an increased viscosity over time. In the case of the non-coating pigment dispersion liquid*, it is a sub-component or a sequential composition of the coloring composition, and the component of the coloring composition is used as a light-weighting composition, thereby preparing the coloring composition as one of the constituent components. Configure at any time. Hereinafter, the aromatic carboxylic acid compound will be described. The aromatic frequency M compound, if it has a record and a slow base, the shell 1 can have any structure. Examples of the aromatic group include a phenyl group and a naphthyl group. Among these, a phenyl group is particularly preferred. The aromatic group can have a wire, and the type of the substituent is not limited. It is particularly limited. Specifically, for example, a substituent represented by oxime 3 in the above formula (VI) is preferred. Further, the county may be plural, for example, 2 to 3, but in terms of the effect of the above-mentioned compound, it is preferably one in one molecule compared with TF988407 43 201037041. The molecular weight of the aromatic carboxylic acid compound is usually 500 or less, preferably 350 or less, and is usually 15 or more. By setting the molecular weight to be as follows, the compound can be easily brought close to the pigment as described later, and the effect of suppressing an increase in viscosity can be surely exhibited. The aromatic carboxylic acid compound is particularly preferably a compound represented by the following formula (γι).
(上述通式(VI)中’ ζι表示亞曱基或者_〇_ ’ m表示〇〜3之 I數其中,當m為2或3時,m個Z1可相同亦可不同。 X3表示氫原子、羥基、碳數丨〜4之烷基、碳數2〜5之烯 基、碳數1〜4之烷氧基、苄基、苯乙基、苄氧基、或者 COOX (其中,X表示碳數1〜7之烧基或苯基),該等基團 均可具有取代基。)。 上述通式(VI)中之X3,表示氫原子、經基、碳數1〜4之 烷基、碳數2〜5之烯基、碳數丨〜4之烷氧基、苄基、苯乙 基、苄氧基、或者-C00X4(其中,X4表示碳數1〜7之烧基或 TF988407 44 201037041 苯基)。· 以下,對X3之定義中的碳數1〜4之烷基、碳數2〜5之 烯基、及碳數1〜4之烷氧基,說明其具體例。 碳數1〜4之烷基,例如:如曱基、乙基、正丙基、異丙 基等碳數4以下之烷基。 碳數2〜5之烯基,例如:如乙烯基、烯丙基、1-丙烯基、 丁稀基、1,3 -丁二稀基等碳數2〜5之稀基。 碳數1〜4之烷氧基,例如··如曱氧基、乙氧基、丙氧基、 異丙氧基等碳數約為4以下之烷氧基。 又,於X3之定義中,C00X4中之X4為碳數1〜7之烷基或 苯基。作為碳數1〜7之烧基之例,例如可舉出:曱基、乙 基、正丙基、異丙基、正丁基、第二丁基、第三丁基、正戊 基、異戊基、新戊基、第三戊基、正己基、異己基、5-曱基 己基等。 該等基均可具有取代基,作為其取代基之具體例,例如可 舉出下列之基。 羥基; 低級烷基;例如:如曱基、乙基、正丙基、異丙基、正丁 基、第二丁基、第三丁基、正戊基、異戊基、新戊基、第三 戊基、正己基、異己基、5-曱基己基等碳數為7以下之烷基。 低級炫氧基;例如:如曱氧基、乙氧基、正丙氧基、異丙 氧基、正丁氧基、第二丁氧基、第三丁氧基、正己氧基、異 TF988407 45 201037041 己氧基、5-甲基己氧基等碳數為7以下之烧氧基。 低級烯基幾氧基;例如:如丙烯酿氧基、丁_氧基等烯 基部分之碳數為3以下之烯基羰氧基。 苯基; 苄基; 苯氧基; 苄氧基。 '丄㈣iUVI)所表示之化合物巾,就該化合物之 上述效果較顯著之方面而言,作為取代基χ3,較佳為自可且 有取代基之魏1〜4之絲、可具絲代基之碳數2〜i 二中選擇之基。作為取代基χ3之更佳的具 =二舉出1氧織、甲氧縣、乙烯絲氧基伸乙基 厌基、異丙基、第三丁基、㈣基、乙婦基等。 進而,取代基X3之位詈,芒+ 制,相對於苯環上之無特別限 特佳為僅在鄰位進行取代。i紐為鄰位或對位, 於取代基X中’以上未具體記載之基,可對已舉出之某 加以任意組合,或者根據通常所知的常識加以選擇。土 以上述通式(V!)所表示之化合物,特佳 _ ^ 化合物。具體而言,例如可舉出* ‘、'、本-甲酸單酯 出乂下者,但並不限定於該等。 TF988407 46 201037041 [化 14](In the above formula (VI), 'ζι denotes an anthracene group or _〇_' m represents an I number of 〇~3, wherein when m is 2 or 3, m Z1 may be the same or different. X3 represents a hydrogen atom. a hydroxyl group, an alkyl group having a carbon number of 44, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyl group, a phenethyl group, a benzyloxy group, or COOX (wherein X represents carbon) A group of 1 to 7 or a phenyl group, each of which may have a substituent.). X3 in the above formula (VI) represents a hydrogen atom, a trans group, an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having a carbon number of 丨4, a benzyl group, and a phenyl group. A group, a benzyloxy group, or -C00X4 (wherein X4 represents a carbon number of 1 to 7 or a TF988407 44 201037041 phenyl group). In the following, specific examples of the alkyl group having 1 to 4 carbon atoms, the alkenyl group having 2 to 5 carbon atoms, and the alkoxy group having 1 to 4 carbon atoms in the definition of X3 will be described. The alkyl group having 1 to 4 carbon atoms is, for example, an alkyl group having 4 or less carbon atoms such as a mercapto group, an ethyl group, a n-propyl group or an isopropyl group. The alkenyl group having 2 to 5 carbon atoms is, for example, a carbon group having 2 to 5 carbon atoms such as a vinyl group, an allyl group, a 1-propenyl group, a butyl group or a 1,3-dibutyl group. The alkoxy group having 1 to 4 carbon atoms, for example, an alkoxy group having a carbon number of about 4 or less, such as a nonyloxy group, an ethoxy group, a propoxy group or an isopropoxy group. Further, in the definition of X3, X4 in C00X4 is an alkyl group having 1 to 7 carbon atoms or a phenyl group. Examples of the alkyl group having 1 to 7 carbon atoms include an anthracenyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, a second butyl group, a third butyl group, a n-pentyl group, and an isobutyl group. A pentyl group, a neopentyl group, a third amyl group, a n-hexyl group, an isohexyl group, a 5-decylhexyl group and the like. Each of these groups may have a substituent, and specific examples of the substituent thereof include, for example, the following groups. Hydroxy; lower alkyl; for example: fluorenyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, An alkyl group having 7 or less carbon atoms such as tripentyl, n-hexyl, isohexyl or 5-decylhexyl. Lower ethoxyl; for example: decyloxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, second butoxy, tert-butoxy, n-hexyloxy, iso-TF988407 45 201037041 Alkoxy group having a carbon number of 7 or less, such as a hexyloxy group or a 5-methylhexyloxy group. The lower alkenyloxy group; for example, an alkenylcarbonyloxy group having an alkyl group having 3 or less carbon atoms such as an acryloxy group or a butoxy group. Phenyl; benzyl; phenoxy; benzyloxy. The compound towel represented by '丄(四)iUVI), as a substituent χ3, is preferably a filament of 1,4-1, which may have a substituent, and may have a silk-based group, in terms of the above-mentioned effect of the compound. The carbon number is 2~i. More preferred as the substituent χ3 = 2 oxywoven, methoxy, vinyloxyethyl, isopropyl, t-butyl, (tetra), ethenyl and the like. Further, the position of the substituent X3 is not limited to the benzene ring, and it is preferably substituted only in the ortho position. i New is an ortho or para position, and the substituents which are not specifically described above in the substituent X may be arbitrarily combined with any of the above-mentioned ones, or may be selected according to common knowledge. The compound represented by the above formula (V!) is particularly preferably a compound. Specifically, for example, *', ', or the present-formic acid monoester may be mentioned, but it is not limited to these. TF988407 46 201037041 [Chem. 14]
上述芳香族羧酸系化合物、更具體而言係以上述通式(VI) 所表示之芳香族羧酸系化合物,可藉由購入市售品或者以已 知方法加以合成而容易獲得。 本發明之顏料分散液或著色組成物中的芳香族羧酸系化 合物之含量,若在不損及作為著色組成物之效果的範圍内, 則無特別限制,但相對於最終所製備之著色組成物之總固形 分,通常為20重量%以下,較佳為10重量%以下,更佳為5 TF988407 47 201037041 重量%以下,又,通常較佳為ο. 1重量%以上。 藉由在此範圍内含有芳香族羧酸系化合物,可防止顏料分 散液或著色組成物之黏度增加,又’可形成“缺陷,,較少且 直線性優異之像素。 雖不拘泥於任何理論且其詳細内容不明,但含有芳香族缓 酸系化合物而防止黏度增加之理由推測如下。即,本發明中 用作分散劑之嵌段共聚物,含有許多胺基等含氮原子之官能 基,於某種組成中,有可能該分散劑之胺基等與其他成分反 應而導致黏度上升。 此處,通常顏料係作為微粒子而存在,分散劑則吸附於顏 料粒子上而發揮分散能力。顏料通常係具有芳香族基之化合 物,並與其他芳香族基具有親和性。 -般認為,由於本案發明之芳香族羧酸系化合物所具有的 芳香族基親和性,若該化合物接近顏料粒子,則必然羧基亦 接近顏料,而可與吸附於顏料上的分散劑產生相互作用。一 般認為,由於該㈣表面之㈣族魏系化合物的羧基與分 散劑之胺基的相互仙’而抑制分散劑之胺基所參與的黏度 上升。進而,一般認為,接近顏料粒子係在高分子化合物中 較困難,因此為了使其變得容易,分子量為5〇〇以下較有效。 [2]著色組成物 本發明之著色組成物至少含有作為構成顏料分散液之成 分的上述顏料、溶劑、分散劑以及後述黏合劑樹脂。再者, TF988407 48 201037041 本發明之著色組成物,可藉由將其他成分混合於預先製備好 的顏料分散液中而加以製備,又,亦可同時將全部成分加以 • 混合或依序混合。 作為該等必需成分以外之成分,除本申請案說明書中所記 載之各種成分以外,若為亦可用作彩色濾光片形成材料者, '則可無特別限制地使用。 [2-1]黏合劑樹脂 ❹ 作為本發明所使用之黏合劑樹脂,若為可用於彩色濾光片 者,則可無特別限制地使用。 例如可舉出:日本專利特開昭60一1842〇2號公報等中記载 之所s胃脫膜(lift off)方式之彩色渡光片製造步驟中所使 用的熱硬化性樹脂組成物、日本專利特開2〇〇4_22〇〇36號公 報等中記載之噴墨方式之彩色濾光片製造步驟中所使用的 熱硬化性樹脂組成物、後述光聚合性樹脂組成物等。根據利 ❹用何種方法使著色組成物硬化而製作彩色濾光片,來選擇合 適類型之樹脂組成物即可。在著色組成物為光聚合性組成^ 的情形下,較佳為含有後述光聚合起始系。 α下,以本發明之著色組成物為光聚合性樹脂組成物之情 ' 形為例進行詳細說明,但本發明並不限定於此。 月 •纟本發明之著色組成物為光聚合性樹脂組成物的情形 下,作為黏合劑樹脂,例如可使用:日本專利特開平 7-207211 號、特開平 8-259876 號、特開平 10_3〇〇922 號、: TF988407 49 201037041 特開平11-140144號、特開平11-Π4224號、特開 2000-56118 號、特開 2003-233179 號、特開 2〇〇7_27〇147 號等各公報等中記載之公知的高分子化合物,較佳為例如可 舉出: [2-1-1]:對於含有環氧基之(曱基)丙烯酸酯與其他自由 基聚合性單體之共聚物’在該共聚物所具有的環氧基之至少 -部分上加成不飽和-元酸而成之_,或者在藉由該加成 反應而產生的經基之至少一部分上加成多元酸肝而獲得之 鹼可溶性樹脂、 [2-1-2](甲基)丙烯酸系樹脂等。 以下’就該等各樹脂加以說明。 [2-^1]對於含有環氧基之(甲基)丙埽酸酿與其他自由基聚 口 !·生單體之共聚物’在該共聚物所具有的環氧基之至少一部 上加成不飽和一元酸而成之樹脂,或者在藉由該加成反應而 產生的&基之至少一部分上加成多元酸肝而獲得之驗可溶 性樹脂 於本發明中’作為特佳的黏合劑樹脂之-,可舉出:「對 於3有環氧基之(甲基)丙烯酸酯與其他自由基聚合性單體 之共聚物’在該共聚物所具有的環氧基之至少一部分上加成 不飽和-元酸而成之樹脂,或者在藉由該加成反應而產生的 〜 I ’ °卩上加成多元酸酐而獲得之驗可溶性樹脂」 (以下,稱為「[2-1-1]樹脂」)。更具體而言,可舉出:「對 TF988407 50 201037041 40莫耳%與其他自由基 在談共聚物所具有的環 一元酸而成之樹脂,或 於含有環氧基之(f基)丙烯酸酯5〜g 聚合性單體10〜95莫耳%之共聚物,在 氧基之10〜100莫耳%上加成不飽和一 . 者在藉由該加成反應而產生的羥基之10〜100莫耳%上加成 多元酸酐而獲得之鹼可溶性樹脂」。 含有經微粒化之顏料、特別是經微粒化之溴化鋅酞菁顏料 的彩色濾、光片用著色組成物,具有對顯影液之溶解性差之傾 0 向’實際上,有時難以將該組成物進行塗佈、乾燥、曝光及 顯影而製造彩色濾、光片。 又,一般而言’即便例如顏料分散液之黏度穩定性較低, - 且經日守黏度增加’但若向其中加入黏合劑樹脂或溶劑等而製 備彩色濾光片用著色組成物,則多數情形是該組成物之黏度 下降,並改善黏度穩定性。但是,已知在含有溴化鋅酞菁顏 料之顏料分散液的情形下,將其製成彩色遽光片用著色組成 ❹ 物,藉此反而有黏度迅速增加之傾向,從而難以確保黏度穩 定性。進而,該彩色濾光片用著色組成物在保存中有以下傾 向:異物容易經時性地產生.增加,對比度亦經時性地下降。 為了解決此種問題,並使含有經微粒化之顏料、特別是經 . 微粒化之溴化鋅酞菁顏料的顏料分散液或彩色濾光片用著 色組成物達成: •提昇顏料分散液或彩色濾光片用著色組成物之黏度穩定 性, TF988407 51 201037041 提昇該著色組成物對顯影液之溶解性,並且抑制對比度 經時下降或異物產生,進而 •防止所得像素之缺陷、以及提昇直線性等, 特別有效的是使用以下所說明之[2_1 —丨]樹脂。 作為構成[2-1-1]樹敵「含有環祕之(?基)丙烯酸 酯」’例如可例示:(曱基)丙烯酸環氧丙酯、(曱基)丙烯酸 3, 4-環氧基丁酯、(甲基)丙烯酸(3, 4_環氧基環己基)甲酯、 (曱基)丙烯酸4-羥基丁酯環氧丙醚等。其中,較佳為(曱基) 丙烯酸環氧丙酯。 該等含有環氧基之(曱基)丙烯酸酯,可單獨使用丨種,亦 可併用2種以上。 作為與上述含有環氧基之(曱基)丙烯酸酯進行共聚合之 其他自由基聚合性單體,較佳為具有以下述通式〇)所表示 之結構的單(甲基)丙烯酸酯。 [化 15]The aromatic carboxylic acid-based compound, more specifically, the aromatic carboxylic acid-based compound represented by the above formula (VI) can be easily obtained by purchasing a commercially available product or by a known method. The content of the aromatic carboxylic acid-based compound in the pigment dispersion liquid or the coloring composition of the present invention is not particularly limited as long as it does not impair the effect as a coloring composition, but is different from the final colored composition. The total solid content of the material is usually 20% by weight or less, preferably 10% by weight or less, more preferably 5 TF988407 47 201037041% by weight or less, and still more preferably ο. 1% by weight or more. By containing an aromatic carboxylic acid-based compound in this range, it is possible to prevent an increase in the viscosity of the pigment dispersion liquid or the coloring composition, and to form a pixel having a small defect and excellent linearity, which is not limited to any theory. However, the reason for the fact that the aromatic acid-lowering compound is contained and the viscosity is increased is presumed to be as follows. That is, the block copolymer used as a dispersing agent in the present invention contains a plurality of functional groups such as a nitrogen atom containing an amine group. In a certain composition, the amino group of the dispersing agent may react with other components to cause an increase in viscosity. Here, the pigment is usually present as fine particles, and the dispersing agent is adsorbed on the pigment particles to exhibit dispersibility. It is a compound having an aromatic group and has affinity with other aromatic groups. It is considered that the aromatic group affinity of the aromatic carboxylic acid compound of the present invention is inevitable if the compound is close to the pigment particles. The carboxyl group is also close to the pigment, and can interact with the dispersant adsorbed on the pigment. It is generally believed that due to the surface of the (four) The carboxyl group of the Wei-based compound and the amine group of the dispersing agent are mutually inhibited to inhibit the increase in the viscosity of the amine group of the dispersing agent. Further, it is considered that it is difficult to make the pigment particles close to the polymer compound, so that it is changed. It is easy to obtain a molecular weight of 5 Å or less. [2] Coloring composition The coloring composition of the present invention contains at least the above-mentioned pigment, a solvent, a dispersing agent, and a binder resin which will be described later as components constituting the pigment dispersion liquid. TF988407 48 201037041 The coloring composition of the present invention can be prepared by mixing other components in a previously prepared pigment dispersion, or all of the components can be mixed or sequentially mixed as such. In addition to the various components described in the specification of the present application, the component other than the component can be used as a color filter forming material, and can be used without particular limitation. [2-1] Adhesive Resin ❹ The binder resin used in the present invention can be used without any particular limitation as long as it can be used for a color filter. The thermosetting resin composition used in the step of manufacturing the color light-emitting sheet of the s stomach lift off method described in Japanese Laid-Open Patent Publication No. SHO 601-1842, and the like, Japanese Patent Laid-Open No. 2 The thermosetting resin composition used in the color filter manufacturing step of the ink jet method described in the above-mentioned Japanese Patent Publication No. 4/22, No. 36, the photopolymerizable resin composition described later, etc. When the coloring composition is cured to form a color filter, a resin composition of a suitable type may be selected. When the coloring composition is a photopolymerizable composition, it is preferable to contain a photopolymerization initiation system to be described later. Although the coloring composition of the present invention is a photopolymerizable resin composition as an example, the present invention is not limited thereto. The coloring composition of the present invention is a photopolymerizable resin composition. In the case of the binder resin, for example, Japanese Patent Laid-Open No. Hei 7-207211, No. Hei 8-259876, and No. 10_3〇〇922, No.: TF988407 49 201037041, No. 11-140144, and No. 11 - For example, a known polymer compound described in each of the publications of the Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. 1-1]: a copolymer of an epoxy group-containing (fluorenyl) acrylate and another radical polymerizable monomer 'adds an unsaturated-member to at least a portion of an epoxy group of the copolymer An alkali-soluble resin or a [2-1-2] (meth)acrylic resin obtained by adding an acid to the at least a part of the radical formed by the addition reaction . Hereinafter, each of these resins will be described. [2-^1] For the (meth)propionic acid containing epoxy groups, it is brewed with other free radicals! a copolymer of a raw monomer, a resin obtained by adding an unsaturated monobasic acid to at least one of the epoxy groups of the copolymer, or at least a & base generated by the addition reaction A part of the soluble resin obtained by adding a polyacid liver is used as a particularly good binder resin in the present invention, and it can be exemplified as "(3) epoxy group-containing (meth) acrylate and other radicals. a copolymer of a polymerizable monomer 'a resin obtained by adding an unsaturated-acid acid to at least a part of an epoxy group of the copolymer, or ~ I '° produced by the addition reaction A soluble resin obtained by adding a polybasic acid anhydride (hereinafter referred to as "[2-1-1] resin"). More specifically, it can be mentioned that "the TF988407 50 201037041 40 mol% and other free radicals are copolymerized with a cyclic monobasic acid, or an epoxy group-containing (f-based) acrylate. 5~g copolymer of 10~95 mol% of polymerizable monomer, additive unsaturated at 10~100 mol% of oxy group. 10~100 of hydroxyl group produced by the addition reaction An alkali-soluble resin obtained by adding a polybasic acid anhydride to a molar %. A color filter containing a micronized pigment, particularly a micronized zinc bromide phthalocyanine pigment, and a coloring composition for a light sheet, having a poor solubility to a developer, may actually be difficult to The composition is coated, dried, exposed, and developed to produce a color filter or a light sheet. Further, in general, even if, for example, the viscosity stability of the pigment dispersion liquid is low, and the viscosity is increased by the day-keeping, the coloring composition for a color filter is prepared by adding a binder resin or a solvent thereto. The situation is that the viscosity of the composition is lowered and the viscosity stability is improved. However, in the case of a pigment dispersion liquid containing a zinc bromide phthalocyanine pigment, it is known that it is used as a coloring composition for a color calendering sheet, whereby a viscosity tends to increase rapidly, and it is difficult to ensure viscosity stability. . Further, the coloring composition for a color filter has the following tendency to be stored during storage: foreign matter is likely to be generated over time, and the contrast is also lowered with time. In order to solve such a problem, a pigment dispersion or a color filter containing a micronized pigment, in particular, a micronized zinc bromide phthalocyanine pigment, is used for the coloring composition: • Lifting the pigment dispersion or color Viscosity stability of the coloring composition for the filter, TF988407 51 201037041 Improves the solubility of the coloring composition to the developer, and suppresses the decrease in contrast over time or foreign matter generation, thereby preventing defects of the resulting pixel, and improving linearity, etc. It is particularly effective to use the [2_1 - 丨] resin described below. As a constituent [2-1-1], it is exemplified as a "ring-containing acrylate ("-based acrylate", for example, (meth)acrylic acid propyl acrylate, (mercapto)acrylic acid 3, 4-epoxy butyl Ester, (3,4-epoxycyclohexyl)methyl (meth)acrylate, 4-hydroxybutyl (meth) acrylate, and the like. Among them, preferred is (fluorenyl) propylene acrylate. These epoxy group-containing (fluorenyl) acrylates may be used singly or in combination of two or more. The other radical polymerizable monomer which is copolymerized with the above-mentioned epoxy group-containing (fluorenyl) acrylate is preferably a mono(meth)acrylate having a structure represented by the following formula (〇). [化15]
於上述通式(1)中,R31〜R38分別獨立表示氫原子、或者碳 數1〜3之烷基,但R37與R38可相互連接而形成環。 TF988407 52 201037041 於通式(1)中,R37與R38連接而形成之環,較佳為脂肪族 環,飽和或者不飽和均可,又,碳數較佳為5〜6。 * 其中,作為以通式(1)所表示之結構,較佳為以下述式 • (la)、(lb)、或(lc)所表示之結構。 ’在藉由將該等結構導入至黏合劑樹脂中,並將本發明之著 色組成物用於彩色濾光片或液晶顯示元件的情形下,可提昇 該著色組成物的财熱性,或者增加使用該著色組成物所形成 0 之像素的強度。 再者,具有以通式(1)所表示之結構的單(曱基)丙烯酸 酯,可單獨使用1種,亦可併用2種以上。In the above formula (1), R31 to R38 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, but R37 and R38 may be bonded to each other to form a ring. TF988407 52 201037041 In the formula (1), a ring formed by linking R37 and R38 is preferably an aliphatic ring, saturated or unsaturated, and preferably has a carbon number of 5 to 6. * The structure represented by the formula (1) is preferably a structure represented by the following formula: (la), (lb), or (lc). 'In the case where the structures are introduced into a binder resin and the colored composition of the present invention is used for a color filter or a liquid crystal display element, the heat of the coloring composition can be improved, or the use can be increased. The intensity of the pixel of 0 formed by the colored composition. In addition, the mono(indenyl) acrylate having a structure represented by the formula (1) may be used alone or in combination of two or more.
(1 b) (1 a) Π c) 作為具有以上述通式(1)所表示之結構的單(曱基)丙烯酸 TF988407 53 201037041 ’但特佳為以下述 醋’只要具有該結構财使用各種公知者 通式(2)所表示者。 [化 17] R39 H2C=C—c—0—R40 (2) ο 表示以上述通式(1) 式(2)中’ R39表示氫原子或甲基,R4〇 所表示之結構。 於上述含有環氧基之(甲基)丙烯酸醋與其他自由基聚入 性單體之共聚财,來自具有以上述通式⑴所表示之㈣ 的甲基)丙稀酸醋之重複單A,在來自「其他自由基聚合 性単體」之重複單元巾的含量,難為5〜9G莫耳%,更佳 為10〜70莫耳%,特佳為15〜50莫耳%。 再者,作為具有以上述通式(1)所表示之結構的單(曱基) 丙稀酸S旨以外之「其他.自由絲合性單體」,並無特別限定。 具體而言,例如可舉出:苯乙烯,苯乙烯之讀、鄰位、間 位或對位為錄基、硝基、氰基、酿胺基、§旨基等取代而成 之衍生物等乙烯基芳香族類;丁二烯、2, 3-二甲基丁二烯、 一戊一烯、氣丁一烯等二烯類;(甲基)丙浠酸甲酯、(甲基) 丙浠馱乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、 (甲基)丙烯酸正丁酯、(曱基)丙烯酸第二丁酯、(甲基)丙烯 酸第二丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸新戊酯、(甲 TF988407 54 201037041 基)丙烯酸異戊酯、(甲基)丙烯酸己酯、(曱基)丙烯酸_2_ 乙基己酯、(曱基)丙烯酸月桂酯、(曱基)丙烯酸十二烷基 ' 酯、(曱基)丙烯酸環戊酯、(甲基)丙烯酸環己酯、(甲基) • 丙烯酸―2—曱基環己酯、(曱基)丙烯酸二環己酯、(曱基)丙 烯酸異降福酯、(甲基)丙烯酸金剛烷酯、(曱基)丙烯酸炔丙 酯、(曱基)丙烯酸苯酯、(甲基)丙烯酸萘酯、(曱基)丙烯酸 蒽酯、(曱基)丙烯酸鄰胺苯甲酯、(曱基)丙烯酸胡椒酯、(曱 0 基)丙烯酸鄰羥基苄酯、(甲基)丙烯酸呋喃酯、(甲基)丙烯 酸呋喃甲酯、(甲基)丙烯酸四氫呋喃酯、(曱基)丙烯酸吡喃 醋、(曱基)丙烯酸苄酯、(曱基)丙烯酸苯乙酯、(曱基)丙烯 酸曱苯酯、(甲基)丙烯酸-1,1,1-三氟乙酯、(甲基)丙烯酸 全氟乙酯、(曱基)丙烯酸全氟正丙酯、(曱基)丙烯酸全氟異 丙酯、(甲基)丙烯酸三苯基曱酯、(甲基)丙烯酸異丙苯酯、 (曱基)丙烯酸-3-(N,N-二甲胺基)丙酯、(甲基)丙烯酸一2-Q 羥基乙酯、(甲基)丙烯酸-2-羥基丙酯等(曱基)丙烯酸酯 類;(曱基)丙稀醯胺、(曱基)丙烯酸-N,N-二甲基酿胺、(曱 基)丙烯酸-N,N-二乙基醯胺、(甲基)丙烯酸-N,N-二丙基醯 胺、(甲基)丙烯酸-N,N-二異丙基醯胺、(曱基)丙烯酸蒽基 • 醯胺等(甲基)丙烯醯胺;(甲基)丙烯酸醯苯胺、(甲基)丙烯 醯腈、丙婦酸、氯乙稀、偏二氣乙稀、氟乙烯、偏二氟乙烯、 N-乙烯吡咯啶酮、乙烯吡啶、乙酸乙烯酯等乙烯化合物類; 擰康酸二乙酯、馬來酸二乙酯、富馬酸二乙酯、衣康酸二乙 TF988407 55 201037041 酯等不飽和二羧酸二酯類;N-苯基馬來醯亞胺、N-環己基馬 來醯亞胺、N-月桂基馬來醯亞胺、N-(4-羥基苯基)馬來醯亞 胺等單馬來醯亞胺類;N-(甲基)丙烯醯基鄰苯二曱醯亞胺 為了對著色組成物賦予優異的耐熱性及強度,較有效的是 在該等「其他自由基聚合性單體」之中,使用自苯乙烯、(甲 基)丙烯酸苄酯、及單馬來醯亞胺中所選擇的至少一種。特 別是在來自「其他自由基聚合性單體」之重複單元中,來自 自該等笨乙烯、(甲基)丙烯酸苄酯、及單馬來醯亞胺中所選 擇的至少一種之重複單元的含有比例,較佳為1〜莫耳 %,更佳為3〜50莫耳%。 再者’上述含有環氧基之(曱基)丙烯酸酯與上述其他自由 基聚合性單體之共聚合反射,可應用公知的溶液聚合法。 所使用之溶劑,若係對自由基聚合為惰性者則無特別限定, 可使用通常所用之有機溶劑。(1 b) (1 a) Π c) As a mono(indenyl)acrylic acid having a structure represented by the above formula (1), TF988407 53 201037041 'But it is preferably vinegar as described below' It is known by the general formula (2). R39 H2C=C—c—0—R40 (2) ο represents a structure represented by R 4 以 in the above formula (1), wherein R 5 represents a hydrogen atom or a methyl group. The copolymerization of the above-mentioned epoxy group-containing (meth)acrylic acid vinegar and other radically-aggregating monomers is from a repeating single A having methyl (meth) acrylate vinegar represented by the above formula (1). The content of the repeating unit towel from the "other radical polymerizable steroid" is difficult to be 5 to 9 Gmol%, more preferably 10 to 70 mol%, and particularly preferably 15 to 50 mol%. In addition, the "other free silky monomer" other than the mono(indenyl)acrylic acid S having the structure represented by the above formula (1) is not particularly limited. Specific examples thereof include styrene, styrene reading, ortho, meta or para are substituted with a nitro group, a cyano group, a amide group, a ruthenium group, and the like. Vinyl aromatics; butadienes such as butadiene, 2, 3-dimethylbutadiene, monopentene, and butylene; methyl (meth)propionate, (meth) propyl Ethyl ethyl ester, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, dibutyl (meth) acrylate, second butyl (meth) acrylate Ester, amyl (meth)acrylate, neopentyl (meth)acrylate, (amyl TF988407 54 201037041) isoamyl acrylate, hexyl (meth) acrylate, (2-mercapto) acrylate 2-ethylhexyl acrylate , (fluorenyl) lauryl acrylate, lauryl (mercapto) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylate - 2- fluorenyl Cyclohexyl ester, dicyclohexyl (decyl) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, ( Propyl propionate, phenyl (meth) acrylate, naphthyl (meth) acrylate, decyl acrylate, o-aminobenzyl (meth) acrylate, piperonyl acrylate (曱0 base) o-hydroxybenzyl acrylate, furyl (meth) acrylate, furan methyl (meth) acrylate, tetrahydrofuran (meth) acrylate, pyridyl acrylate (mercapto), (mercapto) acrylate Benzyl ester, phenylethyl (mercapto) acrylate, decyl phenyl (meth) acrylate, 1,1,1-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, (曱) Perfluoropropyl n-propyl acrylate, perfluoroisopropyl (meth) acrylate, triphenyl decyl (meth) acrylate, cumyl (meth) acrylate, (mercapto) acrylate-3- ( N,N-dimethylamino)propyl ester, 2-methylhydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc. (mercapto) acrylate; Dilute amine, (mercapto)acrylic acid-N,N-dimethyl-branched amine, (mercapto)acrylic acid-N,N-diethylguanamine, (meth)acrylic acid-N,N-dipropyl decylamine, (meth)acrylic acid-N,N-diisopropyldecylamine, (mercapto)acrylic acid decylamine (meth)acrylic acid aniline, (meth) acrylonitrile, propylene glycol, vinyl chloride, ethylene dichloride, vinyl fluoride, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine, acetic acid Ethylene compounds such as vinyl ester; diethyl thioconate, diethyl maleate, diethyl fumarate, diethyl itaconate TF988407 55 201037041 unsaturated dicarboxylic acid diesters such as esters; N-benzene a monomaleimide such as carbamazepine, N-cyclohexylmaleimide, N-lauryl maleimide, N-(4-hydroxyphenyl)maleimide; N-(meth)acryloyl fluorenyl phthalimide is effective for imparting excellent heat resistance and strength to a colored composition, and is preferably used among such "other radical polymerizable monomers". At least one selected from the group consisting of styrene, benzyl (meth) acrylate, and monomaleimide. Particularly, in the repeating unit derived from "other radical polymerizable monomer", a repeating unit derived from at least one selected from the group consisting of stupid ethylene, benzyl (meth) acrylate, and monomaleimide The content ratio is preferably from 1 to mol%, more preferably from 3 to 50 mol%. Further, a known solution polymerization method can be applied to the copolymerization reflection of the above-mentioned epoxy group-containing (fluorenyl) acrylate and the above other radical polymerizable monomer. The solvent to be used is not particularly limited as long as it is inert to radical polymerization, and an organic solvent which is usually used can be used.
TF988407 醇、乙基卡必醇、丁基卡必醇等二乙二醇二烷 —醇二烧基醚類;丙二醇二燒基賴;二丙二 56 201037041 醇-院基_ ; 四氫吱喃等賴;丙酮、甲基 乙基酮甲基異丁基酮、環己酮等酮類;苯、曱笨、二曱苯、 辛烷、癸烷等烴類;石油醚、石油腦、氳化石油腦、溶劑石 =腦等石油系溶劑;乳酸曱酯、乳酸乙酯、乳酸丁酯等乳酸 ㈣’ —Ψ基曱醯胺、N_甲基^各咬酮等。該等溶劑可單獨 使用,亦可併用2種以上。TF988407 Alcohol, ethyl carbitol, butyl carbitol, diethylene glycol dialkyl-alcohol dialkyl ether; propylene glycol dialkyl lysine; dipropylene two 56 201037041 alcohol-hospital base _; tetrahydrofuran Equivalent; ketones such as acetone, methyl ethyl ketone methyl isobutyl ketone, cyclohexanone; hydrocarbons such as benzene, hydrazine, diphenyl, octane, and decane; petroleum ether, petroleum brain, and bismuth Petroleum brain, solvent stone = petroleum solvent such as brain; lactic acid such as decyl lactate, ethyl lactate or butyl lactate (IV) '-mercaptodecylamine, N-methyl group and each biting ketone. These solvents may be used singly or in combination of two or more.
相對於所獲得之共聚物100重量份,該等溶劑之使用量通 常為30〜1000重量份,較佳為5〇〜8〇()重量份。若溶劑之 使用1在此範圍之外,則難以控制共聚物之分子量。 又,共聚合反應中所使用之自由基聚合起始劑,若係可引 毛自由絲合者則無特靠定,可使用通常所帛之有機過氧 =物觸媒或偶氮化合物觸媒。作為該有機過氧化物觸媒,可 、於被刀類成公知的過氧化酮、過氧化縮酮、過氧化氫、 二氧化—歸丙基、過氧化二乙醯、過氧化S旨、過氧化二碳酸 ^具體例’可舉心過氧化笨化、過氧化二異丙笨、 二〜異丙基、過氧化二第三丁基、過氧化笨甲酸第三丁 二氣化苯甲酸第三己醋、過氧化2 乂基己酸第三丁輯、 =基己酸第三以旨、i,卜雙(第三丁基過氧 ,三甲基環己院、2, 5—二甲基—2, 5,(第三丁基過 化::己基,3—異丙基過氧化氫、第三丁基過氧化氫、過氧 4笨、二異丙苯基過氧化氫、過氧化乙酿、過氧化二 TF988407 57 201037041 碳酸雙(4-第三丁基環己基)酯、過氧化二碳酸二異丙酯、過 氧化異丁基、過氧化3, 3, 5-三曱基己醯、過氧化月桂美、 M-雙(第三丁基過氧基)3, 3, 5-三甲基環己烷、丨,卜雙(第 三己基過氧基)3, 3, 5-三甲基環己烷等。 又,作為偶氮化合物觸媒,可舉出:偶氮雙異丁腈、偶氮 二甲醯胺(azobiscarbonamide)等。 該等之中,根據聚合溫度,可使用丨種或2種以上具有適 當半农期之自由基聚合絲劑。相對於共聚合反應中所使用 之單體的合計1GG重量份,自由基聚合起始劑之使用量為 0. 5〜20重量份,較佳為重量份。 共聚合反應既可將共聚合反應中所使用的單體及自由基 聚合起始劑溶解於溶财,—面_—面升溫而進行;村 將添加有自由基聚合起始劑之單體滴加至經升溫、攪摔之容 劑中而進行。又,亦可於溶劑中添加自由基聚合㈣劑,= 在升溫過程巾滴加單體。反雜件可㈣目標分 地改變。 至u曰田 :本發明中,作為上述含有環氧基之(甲 ^其㈣由絲合性單體之絲物,較麵由來自= 基之(甲基)丙稀酸S旨之重複單元5〜9 ㈣ 自由基聚合性單體之會满一 1n 4耳’°、與來自其他 土^生早體之重稷早幻卜的莫物斤構 為由前者2G〜8G莫耳%與後者80〜2〇料%所構成者^ 為由前者30〜7G莫耳%與後者7G〜3Q莫耳%所構成者。、土 TF988407 58 201037041 若含有環氧基之(甲基)丙烯酸酯過少,則有時後述聚合性 成分及鹼可溶性成分之加成量變得不充分;另一方面,若人 有環氧基之(曱基)丙烯酸酯過多,而其他自由基聚合性單體 過少’則有可能耐熱性或強度變得不充分。 r 繼而,使不飽和一元酸(聚合性成分)、多元酸酐(鹼可溶 性成分)與含有環氧基之(曱基)丙烯酸酯與其他自由基聚人 性單體之共聚物的環氧基部分產生反應。 口 〇 作為加成於環氧基上之「不飽和一元酸」,可使用公知者, 例如可舉出具有乙烯性不飽和雙鍵之不飽和羧酸。 作為具體例,可舉出:(曱基)丙烯酸,丁烯酸,鄰、間、 . 或對乙烯基苯甲酸,α位經鹵化烷基、烷氧基、_素原子、 硝基、或氰基等取代之(曱基)丙烯酸等單羧酸等。其中,浐 佳為(曱基)丙烯酸。可單獨使用該等之丨種,亦可併用2 種以上。 〇 藉由加成此種成分,可對本發明所使用之黏合劑樹脂 聚合性。 θ 該等不飽和一元酸通常加成於上述共聚物所具有之枣氧 基的10〜100莫耳%上,較佳為30〜100莫耳%,更佳為卯 100莫耳%。若不飽和一元酸之加成比例過小,則擔心殘 存之環氧基會對著色組成物之經時穩定性等造成不g, 曰再者’作為將不飽和一元酸加成於共聚物之環氣義上之 方法’可採用公知方法。 TF988407 59 201037041 進而,作為在將不飽和一元酸加成於共聚物之環氧基時所 產生羥基上進行加成的「多元酸酐」,可使用公知者。 例如可舉出:馬來酸酐、琥珀酸酐、衣康酸酐、鄰苯二曱 酸酐、四虱鄰苯二曱酸肝、六氫鄰苯二曱酸針、氣菌酸軒等 二元酸酐;偏苯三酸酐、均苯四甲酸酐、二苯基酮四曱酸酐、 聯苯四曱酸酐等三元以上之酸酐。其中,較佳為四氫鄰苯二 甲酸針及號站酸酐。該等多元酸酐可單獨使用1種,亦可併 用2種以上。 藉由加成此種成分,可對本發明所使用之黏合劑樹脂賦予 驗可溶性。 «亥等夕7L酸軒通常加成於藉由使不飽和一元酸加成至上 述共聚物所具有的環氧基上所產生之經基的10〜1GG莫耳% 上’較佳為20〜90莫耳%,更佳為30〜80莫耳%。若該加成 比例過多,則右ni a 3予顯影時之殘膜率會下降,若過少則有可能 溶解性變得不充八 ^刀。再者,作為使多元酸酐加成於該羥基上 之Π,可採用公知之方法。 :了提昇對'光的敏感度,可於加成上述多元酸酐 後’使(甲基)丙烁 二m人 呵&^氧丙酯或具有聚合性不飽和基之環氧 丙醚化合物加成 吨於所生成羧基的一部分上。 又’為了提昇盘 石料外人此 4影性,可將不具有聚合性不飽和基之環氧 丙醚化合物加成 ^ 所生成羧基的一部分上。 又,可加成讀兩者。 TF988407 201037041 作為不具有聚合性不飽和基之環氧丙鍵化合物之且體 例’可舉出:具有苯基或烷基之環氧丙醚化合物等。作為市 售品’例如有:長瀨化成工業(NagasechemteX)公司製造之 商品名「Denacol EX-lll」、「Denacol EX-121」、「Denacol EX-141」、「Denacol EX-145」、「Denacol EX-146」、「Denacol EX-171」、「Denacol EX-192」等。 再者,關於此種樹脂之結構,例如記載於日本專利特開平 〇 8_297366號公報或特開2001-89533號公報中。 上述黏合劑樹脂以GPC法所測定之經聚苯乙烯換算之重 量平均分子量(Mw),較佳為3000〜100000,特佳為5〇〇〇〜 50000。若分子量未滿3〇〇〇則有可能耐熱性或膜強度較差, 若分子量超過100000則有對顯影液之溶解性不足之傾向。 又,作為分子量分布標準,重量平均分子量(Mw)/數量平均 分子量(Μη)之比,較佳為2. 〇〜5.0。 〇 [2一1_2](甲基)丙烯酸系樹脂 於本發明中’作為特佳之黏合劑樹脂之一’可舉出「(甲 基)丙烯酸系樹脂」(以下,稱為「[2-1—2]樹脂」)。本發明 之所謂「(甲基)丙烯酸系樹脂」,意指使含有以下述通式(ν) .所表不化合物作為必需成分之單體成分進行聚合而成之共 聚物。 TF988407 61 (V) 201037041 [化 18]The solvent is used in an amount of usually 30 to 1000 parts by weight, preferably 5 to 8 parts by weight, based on 100 parts by weight of the copolymer obtained. If the use of the solvent 1 is outside this range, it is difficult to control the molecular weight of the copolymer. Further, the radical polymerization initiator used in the copolymerization reaction is not particularly limited if it can be free-knitted, and the organic peroxide/catalyst or azo catalyst which is usually used can be used. . As the organic peroxide catalyst, a known ketone peroxide, a ketal, a hydrogen peroxide, a oxidized-propyl group, a ruthenium peroxide, a peroxidation, or a Oxidized dicarbonic acid ^Specific example 'is exemplified by stupidization of peroxidation, diisopropyl benzoate, di-isopropyl, dibutyl butyl peroxide, benzoic acid, third dimethyl dibenzoate benzoic acid, third Hex vinegar, peroxidic 2 decylhexanoic acid, third butyl, = hexanoic acid, third, i, bis (tertiary butyl peroxy, trimethylcyclohexyl, 2, 5-dimethyl —2, 5,(Third butyl per pass:: hexyl, 3-isopropyl hydroperoxide, tert-butyl hydroperoxide, peroxy 4 stupid, dicumyl hydroperoxide, peroxide B Brewing, peroxidation two TF988407 57 201037041 bis(4-t-butylcyclohexyl) carbonate, diisopropyl peroxydicarbonate, isobutyl peroxide, 3, 3, 5-trimethylhexyl peroxide , oxidized laurel, M-bis(t-butylperoxy) 3,3,5-trimethylcyclohexane, anthracene, bis (trihexylperoxy) 3, 3, 5-three Methylcyclohexane, etc. Examples of the compound catalyst include azobisisobutyronitrile, azobiscarbonamide, etc. Among these, depending on the polymerization temperature, one type or two or more types of free half-agricultural freedom can be used. 5〜20重量份优选优选重量份。 The copolymerization agent is used in an amount of from 0.5 to 20 parts by weight, preferably parts by weight, based on the total of 1 GG parts by weight of the monomers used in the copolymerization reaction. The monomer used in the copolymerization reaction and the radical polymerization initiator can be dissolved in the solvent, and the surface is heated to a temperature; the monomer added with the radical polymerization initiator is added dropwise to the temperature. In addition, the free radical polymerization (four) agent may be added to the solvent, and the monomer may be added dropwise during the heating process. The anti-missing component may (4) change the target to the ground. In the invention, as the above-mentioned methyl group-containing (four) filament-containing monomer filament, the surface is composed of a repeating unit derived from the (meth)acrylic acid S. The polymerizable monomer will be full of 1n 4 ears '°, and it will be different from other soils. The composition of the Moji is composed of 2% to 8G% of the former and 80% to 2% of the latter. The composition of the former is 30 to 7G% and the latter is 7G to 3Q%. 58 201037041 When the (meth) acrylate containing an epoxy group is too small, the amount of addition of the polymerizable component and the alkali-soluble component described later may be insufficient. On the other hand, if a person has an epoxy group (fluorenyl group) If the amount of the acrylate is too large and the amount of the other radical polymerizable monomer is too small, heat resistance or strength may be insufficient. r Next, an unsaturated monobasic acid (polymerizable component), a polybasic acid anhydride (alkali soluble component), and a ring-containing ring may be obtained. The oxy (indenyl) acrylate reacts with the epoxy moiety of the copolymer of other free radical polytropic monomers. Oral 〇 As the "unsaturated monobasic acid" to be added to the epoxy group, a known one can be used, and examples thereof include an unsaturated carboxylic acid having an ethylenically unsaturated double bond. Specific examples thereof include (fluorenyl)acrylic acid, crotonic acid, o-, m-, or p-vinylbenzoic acid, α-position halogenated alkyl group, alkoxy group, _ atom, nitro group, or cyanide. A monocarboxylic acid such as a (fluorenyl)acrylic acid substituted with a group. Among them, 浐 is a (fluorenyl) acrylic acid. These may be used alone or in combination of two or more.聚合 By adding such a component, the adhesive resin used in the present invention can be polymerized. θ The unsaturated monobasic acids are usually added to 10 to 100 mol% of the jujube oxygen group of the above copolymer, preferably 30 to 100 mol%, more preferably 100 mol%. If the addition ratio of the unsaturated monobasic acid is too small, there is a fear that the remaining epoxy group may cause a decrease in the stability of the colored composition, etc., and further, as a ring in which an unsaturated monobasic acid is added to the copolymer. The method of qi can use a well-known method. TF988407 59 201037041 Further, as a "polybasic acid anhydride" which is added to a hydroxyl group generated by adding an unsaturated monobasic acid to an epoxy group of a copolymer, a known one can be used. For example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetraterpene phthalate liver, hexahydrophthalic acid needle, gas acid acid and other dibasic acid anhydride; trimellitic anhydride; And an acid anhydride of three or more kinds such as pyromellitic anhydride, diphenyl ketone tetraphthalic anhydride, and biphenyl tetraphthalic anhydride. Among them, a tetrahydrophthalic acid needle and a station anhydride are preferred. These polybasic acid anhydrides may be used alone or in combination of two or more. By adding such a component, the binder resin used in the present invention can be imparted with solubility. «Hai et al. 7L acid Xuan is usually added to the base of 10~1GG mol% by adding an unsaturated monobasic acid to the epoxy group of the above copolymer, preferably 20~ 90% by mole, more preferably 30 to 80% by mole. If the addition ratio is too large, the residual film ratio at the time of development of the right ni a 3 will decrease, and if it is too small, the solubility may become insufficient. Further, as a ruthenium obtained by adding a polybasic acid anhydride to the hydroxyl group, a known method can be employed. : Enhance the sensitivity to 'light', after adding the above polybasic acid anhydride, 'make (meth) propylene bromide m om & oxypropyl ester or a glycidyl ether compound with a polymerizable unsaturated group Tons of a portion of the carboxyl groups formed. Further, in order to enhance the four-color property of the disc stone material, an epoxy propylene ether compound having no polymerizable unsaturated group may be added to a part of the carboxyl group formed. Also, you can add both to read. TF988407 201037041 The epoxy propylene bond compound having no polymerizable unsaturated group is exemplified by a glycidyl ether compound having a phenyl group or an alkyl group. As a commercial item, for example, the product names "Denacol EX-lll", "Denacol EX-121", "Denacol EX-141", "Denacol EX-145", "Denacol" manufactured by Nagase Chemte Industries, Inc. EX-146", "Denacol EX-171", "Denacol EX-192", etc. In addition, the structure of the resin is described in, for example, Japanese Laid-Open Patent Publication No. Hei 8-297366 or JP-A-2001-89533. The weight average molecular weight (Mw) of the above-mentioned binder resin measured by a GPC method in terms of polystyrene is preferably from 3,000 to 100,000, particularly preferably from 5 Å to 50,000. If the molecular weight is less than 3, the heat resistance or the film strength may be inferior, and if the molecular weight exceeds 100,000, the solubility in the developer tends to be insufficient. Further, as a molecular weight distribution standard, the ratio of the weight average molecular weight (Mw) / the number average molecular weight (??) is preferably 2. 〇 to 5.0. In the present invention, the "(meth)acrylic resin" (hereinafter referred to as "[2-1-" is exemplified as the "(2)-(2)] (meth)acrylic resin. 2] Resin"). The "(meth)acrylic resin" of the present invention means a copolymer obtained by polymerizing a monomer component containing a compound represented by the following formula (ν) as an essential component. TF988407 61 (V) 201037041 [Chem. 18]
具有取代基之碳數1〜25之烴基。 如前所述,含有經微粒化之顏料、特別是經微粒化之溴化 鋅酞菁顏料的顏料分散液或彩色濾光片用著色組成物,因經 時性地容易發生黏度增加,從而對顯影液的溶解性比較低, 因此有時實際上難以製造彩色濾光片。假設利用調整顯影液 或長時間顯影等方法,即便製成彩色濾光片圖案,但所獲得 之像素亦容易有缺陷,而破片再附著於像素表面上,或者像 素之直線部分缺陷成尖銳狀,因此可知易引起面板之漏光。 為了解決此種問題、並使含有經微粒化之顏料、特別是經 微粒化之溴化鋅酞菁顏料的顏料分散液或彩色濾光月用著 色組成物達成: •提昇顏料分散液或彩色濾光片用著色組成物之黏度穩定 性、 •提昇該著色組成物對顯影液之溶解性、 •進而防止所得像素之缺陷、提昇直線性等, 特別有效的是使用以下所說明之[2-1-2]樹脂。 以下,首先針對以通式(V)所表示之化合物加以說明。 TF988407 62 201037041 一於以通式(v)所表示之趟二聚物中,作為以Rib及^所表 示之可具有取代基的碳數1〜25之烴基,並無特別限制,例 2可舉出:甲基、乙基、正丙基、異丙基、正丁基、異丁基、 第三丁基、第三戊基、十人烧基、月桂基、2_乙基己基等直 鏈狀或支鏈狀縣;苯基#絲;環己基、第三丁基環己基、A hydrocarbon group having 1 to 25 carbon atoms having a substituent. As described above, a pigment dispersion liquid containing a finely divided pigment, particularly a micronized zinc bromide phthalocyanine pigment, or a coloring composition for a color filter is likely to have an increased viscosity over time, thereby Since the solubility of the developer is relatively low, it is sometimes difficult to manufacture a color filter. It is assumed that even if a color filter pattern is formed by using a developing solution or a long-time development method, the obtained pixel is likely to be defective, and the fragment is attached to the surface of the pixel, or the linear portion of the pixel is sharply pointed. Therefore, it is known that it is easy to cause light leakage of the panel. In order to solve this problem, a pigment dispersion containing a micronized pigment, in particular a micronized zinc bromide phthalocyanine pigment, or a color filter coloring composition is achieved: • Lifting the pigment dispersion or color filter The viscosity stability of the coloring composition for the light sheet, the solubility of the coloring composition to the developer, the prevention of defects in the obtained pixel, the improvement of linearity, etc., and the use of the following [2-1] -2] Resin. Hereinafter, the compound represented by the general formula (V) will be described first. TF988407 62 201037041 In the ruthenium dimer represented by the formula (v), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by Rib and ^ is not particularly limited, and Example 2 can be exemplified. Out: straight chain such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, third pentyl, ten-membered, lauryl, 2-ethylhexyl Or branched-chain county; phenyl# silk; cyclohexyl, tert-butylcyclohexyl,
二環戊二烯基、三環癸基、異葙基、金剛烷基、2_甲基—2一 金剛燒基等脂環式基;、經卜甲氧基乙基、卜乙氧基乙基等 烷氧基取代之烷基;經节基等芳基取代之烷基等。就耐熱性 方面而言,該等之中特佳為甲基、乙基、環己基、苄基等般 之難以利用酸或熱使其脫離之一級或二級碳之取代基。再 者,1^及R2b可為相同之取代基,亦可為不同之取代基。An alicyclic group such as a dicyclopentadienyl group, a tricyclodecanyl group, an isodecyl group, an adamantyl group, a 2-methyl-2-adamantyl group; a methoxyethyl group and an ethoxylated group An alkyl group substituted with an alkoxy group; an alkyl group substituted with an aryl group such as a benzyl group; and the like. In terms of heat resistance, among these, a substituent such as a methyl group, an ethyl group, a cyclohexyl group or a benzyl group which is difficult to remove from a primary or secondary carbon by an acid or heat is particularly preferable. Further, 1^ and R2b may be the same substituent or different substituents.
作為上述縫二聚物之具體例,例如可舉出:2, 2,-[氧基雙 (亞曱基)]雙-2-丙酸二曱酯、2, 2’ -[氧基雙(亞甲基)]雙一2_ 丙酸二乙酯、2, 2’-[氧基雙(亞曱基)]雙-2-丙酸二(正丙基) 酯、2, 2’-[氧基雙(亞曱基)]雙-2-丙酸二(異丙基)酯、 2, 2’ -[氧基雙(亞曱基)]雙-2-丙酸二(正丁基)酯、2, 2’ -[氧 基雙(亞曱基)]雙-2-丙酸二(異丁基)g旨、2, 2’-[氧基雙(亞 曱基)]雙-2-丙酸二(第三丁基)酯、2, 2’-[氧基雙(亞曱基)] 雙-2-丙酸二(第三戊基)酯、2,2’-[氧基雙(亞曱基)]雙-2-丙酸二(十八烷基)酯、2, 2’ -[氧基雙(亞曱基)]雙-2-丙酸二 (月桂基)酯、2, 2’-[氧基雙(亞甲基)]雙-2-丙酸二(2-乙基 己基)酯、2, 2’ -[氧基雙(亞曱基)]雙-2-丙酸二(1-曱氧基乙 TF988407 63 201037041 基)酯、2, 2,-[氧基雙(亞曱基)]雙-2-丙酸二(丨―乙氧基乙基) 酯、2, 2,-[氧基雙(亞曱基)]雙-2-丙酸二苄醋、2, 2’ -[氧基 雙(亞曱基)]雙-2-丙酸二苯酯、2, 2,-[氧基雙(亞曱基)]雙 -2-丙酸二環己酯、2, 2,-[氧基雙(亞曱基)]雙_2—丙酸二(第 三丁基環己基)酯、2, 2’ -[氧基雙(亞曱基)]雙―2—丙酸二(二 環戊二烯基)酯、2, 2,-[氧基雙(亞曱基)]雙—2-丙酸二(三環 癸基)酯、2, 2’-[氧基雙(亞曱基)]雙-2-丙酸二(異福基) 酯、2, 2’-[氧基雙(亞曱基)]雙-2-丙酸二金剛烷酯、 2, 2’ -[氧基雙(亞甲基)]雙-2-丙酸二(2-曱基-2-金剛烷基) S旨等。 該等之中,特佳為2, 2’-[氧基雙(亞甲基)]雙-2-丙酸二 曱酯、2, 2’ -[氧基雙(亞曱基)]雙_2_丙酸二乙酯、2, 2’ -[氧 基雙(亞甲基)]雙-2-丙酸二環己酯、2, 2’-[氧基雙(亞甲基)] 雙-2-丙酸二节g旨。 該等驗二聚物可單獨使用1種,亦可併用2種以上。 獲得上述[2-1-2]樹脂時,上述醚二聚物在單體成分中之 比例,並無特別限制,但醚二聚物在總單體成分中之比例, 通常為2〜60重量%,較佳為5〜55重量%,更佳為5〜5〇 重$%。若醚二聚物之量過多,則有時在聚合時難以獲得低 刀子罝者或者易於凝膠化;另一方面,若鍵二聚物之量過 少,則有時透明性或耐熱性等塗膜性能變得不充分。 [2 1 2]¼脂較佳為具有酸基。由於具有酸基,故所獲得 TF988407 64 201037041 之者色組成物係藉由酸基與環氧基反應形成賴的交聯反 應(以下,簡稱為酸-環氧基硬化),而形成可硬化之著色組 成物、或者可祕_f彡財使未硬化部分麟之組成物。 ,作為上述^基,亚無特職制,例如可舉出:絲、紛性經 基、羧酸酐基等。 ’ [2-卜2]樹脂i分子令所含之該等酸基,可僅為ι種,亦 可為2種以上。 〇 / 了將酸基導人至[2-1-2]樹脂中,係例如將具有酸基之 單體及/或「聚合後可提供酸基之單體」(以下亦稱為「用以 導入酸基之單體」。)用作單體成分即可。再者,將「聚合後 -可提供酸基之單體」用作單體成分的情形下,於聚合後必須 • 進行用以提供如後述的酸基之處理。 作為上述具有酸基之單H,例如可舉出:(甲基)丙稀酸或 衣康酸等具錢基之賴;N_經基苯基馬來酿亞胺等具有盼 〇 性羥基之單體;馬來酸酐、衣康酸酐等具有鲮酸酐基之單體 專;該等之中特佳為(曱基)丙浠酸。 作為於上述聚合後可提供酸基之單體,例如可舉出:(甲 基)丙烯酸-2-羥基乙醋等具有羥基之單體;(甲基)丙烯酸環 • 氧丙醋等具有環氧基之單體;2-異氰酸基(曱基)丙烯酸乙酿 等具有異氰酸基之單體等。 用以導入該等酸基之單體’可僅為1種,亦可為2種以上。 在獲得[2-1-2]樹脂時之單體成分亦含有上述用以導入酸 TF988407 65 201037041 基之單體的情形下,其含有比例並無特別限制,通常為總單 體成分中之5〜70重量%,較佳為10〜60重量%。若用以導 入酸基之單體之量過多,則變為高黏度而有可能難以形成塗 膜,或者鹼可溶性變得過剩而圖案形成或塗膜之耐化學藥品 性有可能下降;反之,若過少,則所得共聚物之酸價變低, 而有可能無法充分發揮由於導入酸價所帶來之優點。 又,[2-1-2]樹脂可為具有自由基聚合性雙鍵者。 為了將自由基聚合性雙鍵導入至上述[2-1-2]樹脂中,例 如,可將「聚合後可賦予自由基聚合性雙鍵之單體」(以下 亦稱為「用以導入自由基聚合性雙鍵之單體」。)作為單體成 分進行聚合後,進行用以賦予如後述之自由基聚合性雙鍵之 處理即可。 作為於聚合後可賦予自由基聚合性雙鍵之單體,例如可舉 出:(曱基)丙烯酸、衣康酸等具有羧基之單體;馬來酸酐、 衣康酸酐等具有羧酸酐基之單體;(曱基)丙烯酸環氧丙酯、 (曱基)丙烯酸-3, 4-環氧基環己基曱酯、鄰(或間、或對)乙 烯基苄基環氧丙醚等具有環氧基之單體等。該等用以導入自 由基聚合性雙鍵之單體,可僅為1種,亦可為2種以上。 在獲得[2-1-2]樹脂時之單體成分亦含有上述用以導入自 由基聚合性雙鍵之單體的情形下,其含有比例並無特別限 制,但通常為總單體成分中之5〜70重量%,較佳為10〜60 重量%。 TF988407 66 201037041 進而本發明之[2-1-2]樹脂,較佳為具有環氧基。 & 了導入環氧基,係例如將具有環氧基之單體(以下亦稱 為「用以導入環氧基之單體」。)作為單體成分進行聚合即 可。 為上述具有環氧基之單體,例如可舉出:(甲基)丙稀酸 環氧丙S旨、(甲基)丙烯酸_3,4_環氧基環己基甲醋、鄰(或 間、或對)乙烯基苄基環氧丙醚等。該等用以導入環氧基之 Ο 單體,可僅為1種’亦可為2種以上 在獲得[2+2]麵狀賴成分亦含有上述用以導入環 氧基之單體的情形下,其含有_並無特別限制,但通常為 總單體成分中之5〜70重量%,較佳為1〇〜6〇重量%。 . 獲得[mi樹脂時之單體成分,除上述單體成分外,視 需要亦可含有其他可共聚合之單體。 作為其他可共聚合之單體,例如可舉出:(曱基)丙烯酸曱 O 、(甲基)丙婦酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯 酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲 基)丙烯酸第三丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙 烯酸環己酯、(甲基)丙烯酸节酯、(〒基)丙烯酸_2_羥基乙 酯等(甲基)丙烯酸酯類;苯乙烯、乙烯基甲苯、α —甲基苯 乙烯等芳香族乙烯化合物;Ν-苯基馬來醯亞胺、n—環己基馬 來醯亞胺等Ν-取代馬來醯亞胺類;丁二烯、異戊二烯等丁 二烯或取代丁二烯化合物;乙烯、丙烯、氣乙烯、丙烯腈等 TF988407 67 201037041 乙烯或取代乙烯化合物;乙酸乙烯酯等乙烯酯類等。 就透明性良好且不易損害耐熱性方面而言,該等之中,較 佳為(曱基)丙烯酸甲酯、(曱基)丙烯酸環己酯、(曱基)丙烯 酸苄酯、苯乙烯。該等可共聚合之其他單體,可僅使用1 種,亦可併用2種以上。 又,特別是在將[2-1-2]樹脂之一部分或者全部用作上述 分散樹脂的情形下(即,在後述分散處理步驟中使用的情形 下),較佳為使用(甲基)丙烯酸苄酯,其含量通常為總單體 成分中之1〜70重量%,較佳為5〜60重量%。 在獲得上述[2-1-2]樹脂時之單體成分亦含有上述可共聚 合之其他單體的情形下,其含有比例並無特別限制,較佳為 95重量%以下,更佳為85重量%以下。 再者,作為本發明之[2-1-2]樹脂,特佳為實質上由下列 單體所構成之共聚物: •上述通式(V)所表示之單體、 •具有酸基之單體及/或於聚合後可賦予酸基之單體、以 及 •其他可聚合之單體。 以下,就[2-1-2]樹脂之製造方法(聚合方法)加以說明。 上述單體成分之聚合方法並無特別限制,可採用習知公知 的各種方法,但特佳為溶液聚合法。再者,聚合溫度或聚合 濃度(聚合濃度=[單體成分之總重量/(單體成分之總重量 TF988407 68 201037041 +溶劑重量)]χ100),因所使用之單體成分之種類或比率、 目標聚合物之分子量而不同。聚合溫度較佳為40〜150°C, ' 更佳為60〜130°C。又,聚合濃度較佳為5〜50%,更較佳為 • 10 〜40%。 ‘又,在聚合時使用溶劑的情形下,使用通常在自由基聚合 ’反應中所使用之溶劑即可。具體而言,例如可舉出:四氫呋 喃、二哼烷、乙二醇二曱醚、二乙二醇二曱醚等醚類;丙酮、 0 曱基乙基酮、曱基異丁基酮、環己酮等酮類;乙酸乙酯、乙 酸丁酯、丙二醇單曱醚乙酸酯、乙酸-3-曱氧基丁酯等酯類; 曱醇、乙醇、異丙醇、正丁醇、乙二醇單甲醚、丙二醇單曱 - 醚等醇類;曱苯、二曱苯、乙苯等芳香族烴類;氯仿;二曱 . 亞砜等。該等溶劑可僅使用1種,亦可併用2種以上。 在使上述單體成分進行聚合時,視需要可使用聚合起始 劑。聚合起始劑並無特別限制,例如可舉出:過氧化氫異丙 Q 苯、過氧化氫二異丙苯、過氧化二第三丁基、過氧化月桂醯、 過氧化苯曱醯、過氧化異丙基碳酸第三丁酯、過氧化2-乙 基己酸第三戊酯、過氧化2-乙基己酸第三丁酯等有機過氧 ' 化物;2, 2’ -偶氮雙(異丁腈)、1, Γ -偶氮雙(環己烷甲腈)、 ' 2, 2’ -偶氮雙(2, 4-二曱基戊腈)、2, 2’ -偶氮雙(2-曱基丙酸) _ 二曱酯等偶氮化合物。該等聚合起始劑可僅使用1種,亦可 併用2種以上。 再者,起始劑之使用量係根據所使用之單體的組合或反應 TF988407 69 201037041 條件、目標聚合物之分子4等進行料歧即可,並無特別 限定,但就錢膠化即可重量平均好量魏千〜數萬 之聚合物方面而言,通常相對於總單體成分而為〇1叫5 重量%,更佳為〇. 5〜1〇重量%。 又,為了調整分子量,可添加鏈轉移 作為鏈轉移劑, 例如可舉出:正十二烧基硫醇、《乙酸、Μ基乙酸曱醋等 硫醇系鏈轉移劑;基苯乙烯二聚物等;較佳為鍵^移 效果較高、可減少殘留單體、亦容易獲得的正十二烧基硫 醇、·乙酸。在使用鏈轉移劑的情形下,其使用量係= 所使用之單體的組合或反應條件、目縣合物之分子量等進 行適當設定即可’並錢別限定,但就减釈tg卩可獲得重 量平均分子量為數千〜數萬之聚合物方面而言,通常相對於 總早體成分而為(U〜15重量%,更佳為〇 5〜1〇重量%。 再者,-般認為,謂通式(v)U合物 分的情形下,於上述繁人及廄由 而早肢成 “口反應中’亦同時進行醚二聚物之環 化反應,此_二聚物之環化率未必為刪莫耳%。 在獲得上述[2-1-2]樹脂時,葬 错由使用上述可職予酸基之 早m作為皁體成分而導入酸 mI的情形下’於聚合後必須進粁 用以賦1予酸基之處理。該處 、 地 4慝理因所使用之單體 同,例如在使用(甲其)而咗略 股旳種類而不 〇〇 任使用(曱基)丙烯酸、2,基乙g旨般之 單體的情形下,可加成琥珀酸〃 土 町四風4本 甲酿?tF·、0L忠 酉夂酐專酸酐。在使用(甲美) ’、、、 之 (甲基)两歸酸環氧丙醋等具有環氧基 TF988407 70 201037041 單體的情形下,可加成N-甲基胺基笨甲酸、N一甲基胺基酚 等具有胺基及酸基之化合物,或者首先加成(曱基)丙烯酸般 之酸’再使琥珀酸酐、四氫鄰苯二曱酸酐、馬來酸針等酸酐 加成於結果所生成的羥基上。在使用2〜異氰酸基(曱基)丙 稀酸乙酷等具有異氰酸基之單體的情形下,例如可加成2-經基丁酸4具有經基及酸基之化合物即可。 處理。 在獲得上述[2-1-2]樹脂時,藉由使用上述可賦予自由基 ❹雙鍵之單體作為單體成分而♦人自由基聚合性雙鍵 的情形下’於聚合後必須進行用以賦予自由基聚合性雙鍵之 該處理因所使用之單體的種類而不同Specific examples of the slit dimer include 2,2,-[oxybis(indenyl)]bis-2-propionic acid dinonyl ester, 2,2'-[oxybis ( Methylene)]di- 2-propionic acid diethyl ester, 2, 2'-[oxybis(indenyl)]bis-2-propionic acid di(n-propyl) ester, 2, 2'-[oxygen Bis(n-decyl)]bis(isopropyl) bis-2-propionic acid, di(n-butyl) 2,2'-[oxybis(indenyl)]bis-2-propionic acid , 2, 2'-[oxybis(indenyl)]bis-2-propionic acid di(isobutyl)g, 2, 2'-[oxybis(indenyl)]di-2- Di(tert-butyl)propionate, 2,2'-[oxybis(indenyl)]bis-2-propionic acid di(tripentyl)ester, 2,2'-[oxy double (arylene)]bis(octadecyl) bis-2-propionate, 2,2'-[oxybis(indenyl)]bis-2-propionic acid bis(lauryl)ester, 2 , 2'-[oxybis(methylene)]bis-2-propionic acid di(2-ethylhexyl) ester, 2, 2'-[oxybis(indenyl)]bis-2-propane Acid di(1-decyloxyethyl TF988407 63 201037041 base) ester, 2, 2,-[oxybis(indenyl)]bis-2-propionic acid di(indenyl-ethoxyethyl) Ester, 2, 2,-[oxybis(indenyl)]bis-2-propionic acid dibenzyl vinegar, 2, 2'-[oxybis(indenyl)]bis-2-propionic acid diphenyl Ester, 2, 2,-[oxybis(indenyl)]bis-2-propionic acid dicyclohexyl ester, 2, 2,-[oxybis(indenyl)]di-2-propionic acid (T-butylcyclohexyl) ester, 2, 2'-[oxybis(indenyl)]bis-2-propionic acid bis(dicyclopentadienyl), 2, 2,-[oxy Bis(indenyl)] bis-(tricyclodecyl) bis(2-cyclopropionate), 2,2'-[oxybis(indenyl)]bis-2-propionic acid bis(isofos) ester , 2, 2'-[oxybis(indenyl)]bis-2-propanoic acid diadamantyl ester, 2, 2'-[oxybis(methylene)]bis-2-propionic acid di(II) 2-Mercapto-2-adamantyl) S is intended. Among these, it is particularly preferably 2,2'-[oxybis(methylene)]bis-2-propionic acid dinonyl ester, 2, 2'-[oxybis(indenyl)] double _ 2_Diethyl propionate, 2, 2'-[oxybis(methylene)]bis-2-propionic acid dicyclohexyl ester, 2, 2'-[oxybis(methylene)] double 2-propionic acid two-section g. These dimers may be used alone or in combination of two or more. When the above [2-1-2] resin is obtained, the ratio of the above ether dimer in the monomer component is not particularly limited, but the ratio of the ether dimer in the total monomer component is usually from 2 to 60% by weight. %, preferably 5 to 55% by weight, more preferably 5 to 5 % by weight. When the amount of the ether dimer is too large, it may be difficult to obtain a low-knife or easy gelation during polymerization; on the other hand, if the amount of the bond dimer is too small, the transparency or heat resistance may be applied. The film properties become insufficient. The [2 1 2] 1⁄4 grease preferably has an acid group. Since it has an acid group, the color composition of TF988407 64 201037041 obtained by reacting an acid group with an epoxy group forms a crosslinking reaction (hereinafter, simply referred to as acid-epoxy hardening) to form a hardenable group. The coloring composition, or the composition of the unhardened part of the lining. Further, as the above-mentioned group, there is no special-purpose system, and examples thereof include silk, a divalent group, and a carboxylic anhydride group. The acid groups contained in the [2-b 2] resin i molecule may be used alone or in combination of two or more. 〇 / The introduction of an acid group into the [2-1-2] resin, for example, a monomer having an acid group and/or a "monomer capable of providing an acid group after polymerization" (hereinafter also referred to as "using The monomer which introduces an acid group" can be used as a monomer component. In the case where "the monomer after the polymerization-providing acid group" is used as the monomer component, it is necessary to carry out a treatment for providing an acid group as described later after the polymerization. Examples of the mono-H having an acid group include a mercapto group such as (meth)acrylic acid or itaconic acid; and N-pyridyl phenyl maleimine having a promiscuous hydroxyl group. Monomer; a monomer having a phthalic anhydride group such as maleic anhydride or itaconic anhydride; particularly preferred among these are (mercapto)propionic acid. Examples of the monomer which can provide an acid group after the above polymerization include a monomer having a hydroxyl group such as (meth)acrylic acid-2-hydroxyethyl vinegar; and an epoxy group such as (meth)acrylic acid acetophenone a monomer having a base; a monomer having an isocyanate group such as 2-isocyanato(indenyl)acrylic acid. The monomer ' used to introduce the acid groups' may be one type or two or more types. In the case where the monomer component when the [2-1-2] resin is obtained also contains the above-mentioned monomer for introducing the acid TF988407 65 201037041, the content ratio thereof is not particularly limited, and is usually 5 of the total monomer components. ~70% by weight, preferably 10 to 60% by weight. If the amount of the monomer for introducing an acid group is too large, the viscosity may become high, and the coating film may be difficult to form, or the alkali solubility may become excessive, and the chemical resistance of the pattern formation or the coating film may be lowered; If the amount is too small, the acid value of the obtained copolymer becomes low, and the advantage due to the introduction of the acid value may not be sufficiently exhibited. Further, [2-1-2] the resin may be one having a radical polymerizable double bond. In order to introduce a radically polymerizable double bond into the above [2-1-2] resin, for example, "a monomer capable of imparting a radically polymerizable double bond after polymerization" (hereinafter also referred to as "introduction of freedom" The monomer which is a polymerizable double bond.) After the polymerization as a monomer component, a treatment for imparting a radical polymerizable double bond as described later may be carried out. Examples of the monomer which can impart a radically polymerizable double bond after the polymerization include a monomer having a carboxyl group such as (mercapto)acrylic acid or itaconic acid, and a carboxylic acid anhydride group such as maleic anhydride or itaconic anhydride. Monomer; (fluorenyl) propylene acrylate, (meth)acrylic acid-3, 4-epoxycyclohexyl decyl ester, ortho (or m, or p-) vinyl benzyl epoxidized propyl ether A monomer such as an oxy group. These monomers for introducing the radical-based polymerizable double bond may be used alone or in combination of two or more. In the case where the monomer component when the [2-1-2] resin is obtained also contains the above monomer for introducing a radical polymerizable double bond, the content ratio thereof is not particularly limited, but is usually in the total monomer component. 5 to 70% by weight, preferably 10 to 60% by weight. TF988407 66 201037041 Further, the [2-1-2] resin of the present invention preferably has an epoxy group. In the case of introducing an epoxy group, for example, a monomer having an epoxy group (hereinafter also referred to as "a monomer for introducing an epoxy group") may be polymerized as a monomer component. Examples of the monomer having an epoxy group include (meth)acrylic acid propylene acrylate, (meth)acrylic acid _3,4-epoxycyclohexyl ketone, and o (or Or or p-vinylbenzyl epoxidized propyl ether and the like. The monomer for introducing an epoxy group may be one type or two or more types. When the [2+2] surface-like component is also obtained, the monomer for introducing an epoxy group is also contained. The content thereof is not particularly limited, but is usually 5 to 70% by weight, preferably 1 to 6 % by weight, based on the total monomer component. The monomer component in the case of [mi resin] may contain other copolymerizable monomers in addition to the above monomer components. Examples of the other copolymerizable monomer include (fluorenyl) ruthenium acrylate O, (meth) propyl ethyl acrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate. N-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, ( (meth) acrylate such as methyl acrylate acrylate, (nonyl) acrylate 2-hydroxyethyl ester; aromatic vinyl compound such as styrene, vinyl toluene or α-methyl styrene; Ν-substituted maleidanilides such as maleic imine, n-cyclohexylmaleimide, butadiene or substituted butadiene compounds such as butadiene and isoprene; ethylene, propylene, and gas Ethylene, acrylonitrile, etc. TF988407 67 201037041 Ethylene or substituted ethylene compound; vinyl acetate such as vinyl acetate. Among these, in terms of good transparency and resistance to heat resistance, among these, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and styrene are preferable. These other monomers which can be copolymerized may be used alone or in combination of two or more. Further, particularly in the case where part or all of [2-1-2] resin is used as the above-mentioned dispersion resin (that is, in the case of use in a dispersion treatment step described later), it is preferred to use (meth)acrylic acid. The benzyl ester is usually contained in an amount of from 1 to 70% by weight, preferably from 5 to 60% by weight, based on the total of the monomers. In the case where the monomer component in the case where the above [2-1-2] resin is obtained also contains the other monomer copolymerizable, the content ratio thereof is not particularly limited, but is preferably 95% by weight or less, more preferably 85. Below weight%. Further, as the [2-1-2] resin of the present invention, a copolymer consisting essentially of the following monomers is preferable: • a monomer represented by the above formula (V), • a single having an acid group Monomers and/or monomers which can impart acid groups after polymerization, and other polymerizable monomers. Hereinafter, the method of producing [2-1-2] resin (polymerization method) will be described. The polymerization method of the above monomer component is not particularly limited, and various conventionally known methods can be employed, but a solution polymerization method is particularly preferred. Further, the polymerization temperature or the polymerization concentration (polymerization concentration = [total weight of the monomer component / (total weight of the monomer component TF988407 68 201037041 + solvent weight)] χ 100), depending on the type or ratio of the monomer component used, The molecular weight of the target polymer varies. The polymerization temperature is preferably from 40 to 150 ° C, and more preferably from 60 to 130 ° C. Further, the polymerization concentration is preferably from 5 to 50%, more preferably from 10 to 40%. Further, in the case where a solvent is used in the polymerization, a solvent which is usually used in the radical polymerization reaction may be used. Specific examples thereof include ethers such as tetrahydrofuran, dioxane, ethylene glycol dioxime ether, and diethylene glycol dioxime ether; acetone, 0-decylethyl ketone, decyl isobutyl ketone, and ring; Ketones such as ketone; esters such as ethyl acetate, butyl acetate, propylene glycol monoterpene ether acetate, and -3-butyloxybutyl acetate; sterol, ethanol, isopropanol, n-butanol, ethylene Alcohol monomethyl ether, propylene glycol monoterpene-ether and other alcohols; aromatic hydrocarbons such as toluene, diphenylbenzene, ethylbenzene; chloroform; diterpene. These solvents may be used alone or in combination of two or more. When the above monomer component is polymerized, a polymerization initiator can be used as needed. The polymerization initiator is not particularly limited, and examples thereof include isopropyl benzene hydrogen peroxide, dicumyl hydrogen peroxide, dibutyl butyl peroxide, laurel peroxide, benzoquinone peroxide, and Oxidation of tert-butyl isopropyl carbonate, triamyl peroxy 2-ethylhexanoate, tert-butyl peroxy 2-ethylhexanoate, etc.; 2, 2'-azo double (isobutyronitrile), 1, Γ-azobis(cyclohexanecarbonitrile), '2, 2'-azobis(2,4-dimercapto valeronitrile), 2, 2'-azo double An azo compound such as (2-mercaptopropionic acid) _ diterpene ester. These polymerization initiators may be used alone or in combination of two or more. Further, the amount of the initiator to be used may be determined according to the combination of the monomers to be used or the reaction conditions of TF988407 69 201037041, the molecule 4 of the target polymer, etc., and is not particularly limited, but may be gelled. The average weight of the polymer is from 10,000 to tens of thousands of polymers, and is usually 5% by weight, more preferably 〇. 5 to 1% by weight, based on the total monomer component. Further, in order to adjust the molecular weight, chain transfer may be added as a chain transfer agent, and examples thereof include n-dodecyl mercaptan, a mercaptan chain transfer agent such as acetic acid or mercaptoacetic acid vinegar; and a styrene dimer. And the like; preferably, the key transfer effect is high, the residual monomer can be reduced, and the n-dodecyl mercaptan and acetic acid are also easily obtained. In the case of using a chain transfer agent, the amount to be used = the combination of the monomers to be used, the reaction conditions, the molecular weight of the target compound, etc., can be appropriately set, and the amount can be limited, but the amount of tg can be reduced. In terms of obtaining a polymer having a weight average molecular weight of several thousands to several tens of thousands, it is usually (U 15 15% by weight, more preferably 〇 5 to 1 % by weight) relative to the total early body component. In the case of the general formula (v) U compound, the cyclization reaction of the ether dimer is carried out simultaneously in the "mouth reaction" in the above-mentioned pros and the above, and the ring of the dimer In the case where the above [2-1-2] resin is obtained, the accident is caused by the use of the above-mentioned m to the acid component of the acid group, and the acid mI is introduced. It must be used for the treatment of the acid group. The site and the site are treated by the same monomer, for example, in the use of (a), but not in use (曱基) In the case of acrylic acid, 2, and base-g-like monomers, it can be added to succinic acid, earth, and four winds, 4 pieces of brewing? tF·, 0L A phthalic anhydride-specific acid anhydride. In the case of using an epoxy group TF988407 70 201037041 monomer, such as (meth) ',,, (meth), two-acid epoxide propylene vinegar, N-methylamine can be added. a compound having an amine group and an acid group such as a benzoic acid or an N-methylaminophenol, or a first-added (mercapto)acrylic acid, and then succinic anhydride, tetrahydrophthalic anhydride, maleic acid An acid anhydride such as a needle is added to the hydroxyl group formed as a result. In the case of using a monomer having an isocyanate group such as 2-isocyanyl(indenyl)acrylic acid, for example, 2-addition can be added. The butyl group 4 has a compound having a trans group and an acid group. The treatment is carried out. When the above [2-1-2] resin is obtained, by using the above-mentioned monomer which can impart a radical ❹ double bond as a monomer component. In the case of a human radical polymerizable double bond, the treatment for imparting a radically polymerizable double bond after polymerization is different depending on the kind of the monomer to be used.
由基聚合性雙鍵之化合物 。在使用(甲基) 丙烯酸環氧肉酉旨 鄰(或間、或對); 情形下’可加成(甲基) ^、(曱基)兩埽酸_3,4_環氧基環己基甲醋、 )乙烯基#基環氧丙㈣具有環氧基之單體的 鍵之化合物。 兩烯酸等具有酸基及自由基聚合性雙 上述[2~1~ 2]樹脂之重量 平均分子量並無特別限制,但以 TF988407 201037041 GPC所測定之經聚笨乙烯換算之重量平均分子量,較佳為 2000〜200000,更佳為4〇〇〇〜looooo。當重量平均分子量 超過200000時’有時黏度會變得過高而難以形成塗膜,另 一方面’若重量平均分子量未滿2〇〇〇,則有難以表現充分 而f熱性之傾向。 在上述[2-1-2]樹脂具有酸基的情形下,樹脂之酸價較佳 為5〜500 mgKOH/g ’更佳為1〇〜4〇〇 mgK〇H/g。當酸價未滿 5 mgKOH/g時,有時變得難以應用於鹼性顯影。又’當酸價 超過500 mgKOH/g時,有黏度變得過高而難以形成塗膜之傾 向。 再者’當酸價相對較高時,含有其之著色組成物之黏度的 經時變化(黏度增加)不易發生,因而較佳;當酸價相對較低 時’含有其之著色組成物之對比度的經時變化(下降)不易產 生,因而較佳。 再者’ [2-1-2]樹脂、亦即將通式(v)所表示之化合物作 為必需單體成分之共聚物,例如可舉出:曰本專利特開 2004-300203號公報及特開2⑽4_3〇〇2()4號公報所記載之化 合物。 本發明之顏料分散液,較佳係將[2-1-2]樹脂作為上述分 散柄·脂(即’於後述分散處理步驟中,與分散劑或分散助劑 等一同使用)而獲得。 藉由使用[2-1-2]樹脂作為分散樹脂,顏料分散液之經時 TF988407 72 201037041 黏度不會上m可麟私之分肢,又 分散液而成之彩色濾光片用著色 §一 而較佳。 考色、錢物,《示高對比度,因 2放液中,或者祕不❹顏料分散液而製造之著色組成 、,中,精此所獲得之彩色濾光片㈣色組成物之黏度穩定, Ο ❹ 用㈣色組成物而形成之圖案不易 有’因而較佳。 再者,本發明之顏料分散液及彩色據光片用著色組成物, 右在不損及本發明效果之範圍内,則可含有除上述[2— 樹脂及[2-1_2]樹脂以外之黏合劑樹脂。 作為本發明之黏合劑樹脂,可單獨使用上述各種黏 脂中的1種,亦可併用2種以上。 於本發明之著色組成物中,黏合劑樹脂在總固形分中之人 有比例,通常為0. 1重量%以上,較佳為i重量%以上,又S, iff為80重WF ’圭為6〇重量%以下。若黏合劑樹脂 之含量少於此範圍,則膜變脆’對基板之密著性下降。反之: 若多於此範圍,則顯影液對料部之浸透性變高,有時像素 之表面平滑性或敏感度變差。 μ [2-2]其他成分 本發明之彩色遽光片用著色組成物,視需要可含有除上述 以外之成分。作為此種成分,可舉出:聚合性單體、光聚合 73 TF988407 201037041 起始系及/或熱聚合起始劑、界面活性劑、熱聚合抑制劑、 塑化劑、保存穩定劑、表面保護劑、密著改善劑、顯影改良 劑、染料等。 [2-2-1]聚合性單體 本發明之聚合性單體,若為可聚合之低分子化合物,則無 特別限制,但較佳為具有至少1個乙烯性雙鍵之可聚合之化 合物(以下,稱為「乙烯性化合物」)。所謂乙烯性化合物, 係指當本發明之著色組成物受到活性光線照射時,在後述光 聚合起始系統的作用下、或者利用加熱而在後述熱聚合起始 劑的作用下,進行加成聚合而硬化的具有乙烯性雙鍵之化合 物。再者,本發明之單體意指相對於高分子物質之概念,意 指除狹義之單體以外亦包括二聚體、三聚體、寡聚物之概念。 作為乙烯性化合物,例如可舉出:不飽和羧酸;其與單羥 基化合物之酯;脂肪族多羥基化合物與不飽和羧酸之酯;芳 香族多羥基化合物與不飽和羧酸之酯;藉由不飽和羧酸與多 元羧酸及上述脂肪族多羥基化合物、芳香族多羥基化合物等 之多經基化合物的醋化反應而獲得之醋;使聚異氰酸S旨化合 物與含有(曱基)丙烯醯基之羥基化合物反應而成之具有胺 基曱酸乙酯骨架之乙烯性化合物等。 作為脂肪族多羥基化合物與不飽和羧酸之酯,例如可舉 出:乙二醇二丙烯酸酯、三乙二醇二丙烯酸酯、三羥曱基丙 烷三丙烯酸酯、三羥曱基乙烷三丙烯酸酯、季戊四醇二丙烯 TF988407 74 201037041 酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊 四醇四丙烯酸g旨、二季戊四醇五丙烯酸g旨、二季戊四醇六丙 烯酸s旨、甘油丙烯酸醋等丙婦酸s旨。又,可舉出:將該等丙 ' 烯酸酯之丙烯酸部分,替換成曱基丙烯酸部分而得之曱基丙 烯酸酯、替換成衣康酸部分而得之衣康酸酯、替換成丁烯酸 部分而得之丁烯酸酯,又,替換成馬來酸部分而得之馬來酸 酉旨等。 0 作為芳香族多經基化合物與不飽和缓酸之醋,例如可舉 出:對苯二酚二丙烯酸酯、對苯二酚二曱基丙烯酸酯、間苯 二酚二丙烯酸酯、間苯二酚二甲基丙烯酸酯、鄰苯三酚三丙 烯酸i旨等。 藉由不飽和羧酸、多元羧酸與多羥基化合物之酯化反應而 獲得之酯,未必為單一物,亦可為混合物。作為代表例,例 如可舉出:丙烯酸、鄰苯二曱酸與乙二醇之縮合物;丙烯酸、 Q 馬來酸與二乙二醇之縮合物;甲基丙烯酸、對苯二曱酸與季 戊四醇之縮合物;丙烯酸、己二酸、與丁二醇、甘油之縮合 物等。 作為使聚異氰酸酯化合物與含有(曱基)丙烯醯基之羥基 ' 化合物反應而成之具有胺基曱酸乙酯骨架的乙烯性化合 物,例如可舉出:使六亞曱基二異氰酸酯、三曱基六亞曱基 二異氰酸酯等脂肪族二異氰酸酯,環己烷二異氰酸酯、異佛 爾酮二異氰酸酯等脂環式二異氰酸酯,曱苯二異氰酸酯、二 TF988407 75 201037041 苯基曱烷二異氰酸酯等芳香族二異氰酸酯等,與丙烯酸-2-羥基乙酯、曱基丙烯酸-2-羥基乙酯、3-羥基(1, 1,1-三丙烯 醯氧基曱基)丙烷、3-羥基(1,1,1-三甲基丙烯醯氧基曱基) 丙烷等含有(曱基)丙烯醯基之羥基化合物反應而成之反應 物。 另外,作為本發明所使用之乙烯性化合物,例如亦較有用 的是:伸乙基雙丙烯醯胺等丙烯醯胺類;鄰苯二曱酸二烯丙 酯等烯丙酯類;鄰苯二曱酸二乙烯酯等含有乙烯基之化合物 等。 又,乙烯性化合物亦可為具有酸基之單體。作為具有酸基 之單體,為脂肪族多羥基化合物與不飽和羧酸之酯,較佳為 使非芳香族羧酸酐與脂肪族多羥基化合物之未反應的羥基 反應而使其具有酸基之多官能單體,特佳為在該酯中,脂肪 族多羥基化合物係季戊四醇及二季戊四醇中之至少一者。 該等單體可單獨使用1種,但在製造上難以使用單一化合 物,故可將2種以上單體混合使用。又,視需要,亦可將作 為單體的不具有酸基之多官能單體與具有酸基之多官能單 體加以併用。 作為具有酸基之多官能單體的酸價,較佳為0.1〜40 mgKOH/g,特佳為5〜30 mgKOH/g。若多官能單體之酸價過 低,則顯影溶解特性下降,若過高則有製造或操作變困難且 光聚合性能下降,像素之表面平滑性等硬化性較差之傾向。 TF988407 76 201037041 因此,在併用2種以上具有不同酸基之多官能單體的情形 下,或者在併用不具有酸基之多官能單體的情形下,較佳係 ' 將作為總體之多官能單體的酸基調整為上述範圍内。 • 於本發明中,更佳的具有酸基之多官能單體,係以東亞合 成公司製造之T01382而市售之以二季戊四醇六丙烯酸酯、 二季戊四醇五丙稀酸酷、二季戊四醇五丙烯酸醋之琥%酸6旨 為主成分之混合物。亦可將該多官能單體以外之其他多官能 0 單體組合使用。 於本發明中,上述乙烯性化合物較佳為,分子量為650 以下、較佳為550以下、更佳為400以下,且雙鍵當量為 - 150以下、較佳為140以下、更佳為110以下者。又,其等 • 之下限並無特別限定,在可獲得可加成聚合之化學結構的範 圍内即可。 就可減少像素之“缺陷”、並形成直線性更優異之像素而 Q 言,該等之中,較佳為分子量相對較小且雙鍵當量較小之化 合物。例如較佳為可舉出:分子量為400以下且雙鍵當量為 110以下之、脂肪族多羥基化合物與不飽和羧酸之酯,更具 體而言,例如可舉出季戊四醇四丙烯酸S旨、季戊四醇三丙烯 酸酉旨等。 再者,就所獲得之彩色濾光片用著色組成物之敏感度而 言,較佳為使用分子量超過400之乙烯性化合物。作為此種 化合物,特佳為二季戊四醇四(曱基)丙烯酸酯、二季戊四醇 TF988407 77 201037041 酸’:二季戊四醇六(甲基)丙烯嶋。該等 、、9、與上述分子量為4〇〇以下且雙鍵當量為150 ' 為110以下)之乙烯性化合物組合使用,而可獲得 平衡性良好之組成物,因而較佳。 :單體在本發明著色組成物的總固形分中之調配 率旦吊為0重量。/°以上’較佳為5重量%以上,更佳為10 重^上’通常為80重量%以下,較佳為70重量。/。以下, 更佳為5(3重量%以下’特佳為40重量%以下。又,相對於色 =之tb率’通常為〇重量%以上’較佳為$重量%以上,更較 〇 '、、重里%以上,特佳為2〇重量%以上,通常為2〇〇重量 似下,較佳為1〇〇重量%以下,更佳為8〇重量%以下。 [2 3]光聚合起始系、熱聚合起始劑 為y使塗膜硬化’本發明之著色組成物較佳為含有光聚合 起始系及熱聚合起始劑中之至少—種。其中,硬化之方法可 為除使用料起始劑之方法以外的方法。 特別疋在本發明之著色組成物含有具有乙烯性雙鍵之樹 月曰作為黏合劑樹脂成分的情形下、或含有乙烯性化合物作為 上述聚合性單體的情形下,較佳為含有光聚合起始系以及熱 聚合起始劑中的至少一種,上述光聚合起始系係具有直接吸 收光或者經光敏化而引起分解反應或脫氫反應、並產生聚合 活性自由基的功能,上述熱聚合起始劑係藉由熱而產生聚合 活性自由基。 TF988407 78 201037041 [2-3-1 ]光聚合起始系 光聚合起始劑通常製成與加速劑等附加劑之混合物(光聚 • 合起始系)而使用。光聚合起始系係具有直接吸收光或者經 ' 光敏化而引起分解反應或脫氫反應、並產生聚合活性自由基 之功能的成分。 作為構成光聚合起始系成分之光聚合起始劑,例如可舉 出:日本專利特開昭59-152396號、特開昭61-151197號等 0 各公報記載之含有 二茂鈦(titanocene)化合物之二茂金屬 化合物;或日本專利特開平10-39503號公報中記載之六芳 基聯咪唑衍生物、鹵曱基均三讲衍生物、N-笨基甘胺酸等 - 芳基-α -胺基酸類、N-芳基-α -胺基酸鹽類、N-芳基-α - 胺基酸酯類等自由基活性劑,α-胺基烷基苯酮系化合物; 曰本專利特開2006-36750號公報、特開2002-323762號公 報、特開2000-80068號公報等中記載之肟酯系化合物等。 〇 以下’列舉出本發明中可使用之光聚合起始劑之具體例。 2-(4-曱氧基苯基)-4, 6-雙(三氯曱基)均三啡、2-(4-曱氧 基萘基)-4, 6-雙(三氯曱基)均三啡、2-(4-乙氧基萘 基)-4, 6-雙(三氯曱基)均三讲、2-(4-乙氧基羰基萘 " 基)-4, 6-雙(三氯曱基)均三讲等齒曱基均三畊衍生物; 二氣曱基-5-(2’-苯并σ夫喃基)-1,3,4-°号二嗤、2-三氣 曱基-5-[ yS -(2’ -苯并咬喃基)乙烯基]-1,3, 4-0号二〇坐、2_ 二氯曱基-5-[石-(2, -(6” -苯并D夫喃基)乙烯 TF988407 79 201037041 基)]-1,3, 4-噚二唑、2-三氯曱基-5-呋喃基-1,3,4-噚二唑 等鹵曱基化噚二唑衍生物; 2-(2’-氯苯基)-4,5-二苯基咪唑二聚體、2-(2’-氯苯 基)-4,5-雙(3’-曱氧基苯基)咪唑二聚體、2-(2’-氟苯 基)-4, 5-二苯基咪唑二聚體、2-(2’ -曱氧基苯基)-4, 5-二苯 基咪唑二聚體、(4’ -曱氧基苯基)-4, 5-二苯基咪唑二聚體等 11米°坐衍生物; 安息香曱醚、安息香苯醚、安息香異丁醚、安息香異丙醚 等安息香烷基醚類; 2-曱基蒽醌、2-乙基蒽醌、2-第三丁基蒽醌、1-氯蒽醌等 蒽酉昆衍生物; 二苯基酮、米其勒酮(Michler’ s Ketone)、二乙胺基二苯 基酮、2-曱基二苯基酮、3-曱基二苯基酮、4-曱基二苯基酮、 2-氯二苯基酮、4-溴二苯基酮、2-羧基二苯基酮等二苯基酮 衍生物; 2,2-二曱氧基_2-苯基苯乙嗣、2,2-二乙氧基苯乙嗣、1_ 羥基環己基苯基酮、羥基-2-曱基苯基丙酮、1-羥基-1-曱基乙基-(對異丙基苯基)酮、1-羥基-1-(對十二烷基苯基) 酮、2-曱基-1-[4-(曱硫基)苯基]-2-咮啉基丙烷-1-酮、 1,1,1-三氯曱基-(對丁基苯基)酮等苯乙酮衍生物; 〇塞σ頓酮(thioxanthone)、2-乙基°塞°頓酮、2-異丙基°塞〇頓 酮、2-氣噻噸酮、2, 4-二甲基噻噸酮、2,4-二乙基噻噸酮、 TF988407 80 201037041 2, 4-二異丙基售11镇酮等嗟"頓酮衍生物; 對二曱胺基苯曱酸乙酯、對二乙胺基苯曱酸乙酯等苯曱酸 酯衍生物; 9-苯基吖啶、9-(對曱氧基苯基)吖啶等吖啶衍生物; 9,10-二曱基苯并啡讲等啡〇井(卩]1611&21116)衍生物; 笨并蒽酮等蒽g同(anthrone)衍生物; 二環戊二烯基二氣化鈦、二環戊二烯基雙苯基鈦、二環戊 〇 二烯基雙-2,3,4,5,6_五氟苯-1-基鈦、二環戊二烯基雙 -2,3’5,6-四氟苯-1-基鈦、二環戊二烯基雙_2,4,6_三氟苯 _1-基鈦、二環戊二烯基-2, 6-二氟苯_丨_基鈦、二環戊二烯 . 基_2,4一二氟苯-1-基鈦、二甲基環戊二烯基雙-2, 3, 4, 5, 6- 五氟苯-1-基鈦、二曱基環戊二烯基雙_2,6_二氟苯_丨_基 鈦、一環戊二烯基-2, 6-二-氟-3-〇比略-1-基)—苯_ι_基鈦等 二茂鈦衍生物; Ο 2—曱基444-(曱硫基)苯基]-2-咮啉基丙烷-1 -酮、苄 基-2-二曱胺基-1-(4-咮啉基苯基丁酮一丨,2_苄基_2一二曱 胺基-1-(4-咮啉基苯基)丁烷一丨—酮、4_二曱胺基苯甲酸乙 酯、4-二曱胺基苯曱酸異戊酯、二乙胺基苯乙蜩、4一二甲 . 胺基苯丙酮、1,4-二曱胺基苯曱酸一2_乙基己酯、2, 5-雙(4- 二乙胺基亞苄基)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^_胺基烷基苯酮系化 合物; TF988407 81 201037041 I*乙基條甲基苯甲酸基⑷十終基]乙院 -卜肪-〇韻m祕峰冑㈣基)辛料2_二辆 -2-將-〇-苯甲酸酯等肟酯系化合物。 本發明所使用之光聚合起始系,較佳為含有㈣系化合物 作為光聚合起始劑,其中,料特佳者,可舉出以下述通式 (I )所表示之肟酯系化合物。 [化 19]a compound derived from a polymerizable double bond. In the case of (meth)acrylic epoxy ketones (or, or, or); in the case of 'additional (methyl) ^, (fluorenyl) bismuth _3,4_epoxycyclohexyl Methyl vinegar, a vinyl group - a methacrylic acid (iv) compound having a bond of a monomer of an epoxy group. The weight average molecular weight of the above-mentioned [2~1~2] resin having an acid group and a radical polymerizable property such as a dienoic acid is not particularly limited, but the weight average molecular weight in terms of polystyrene is measured by TF988407 201037041 GPC. Good for 2000~200000, better for 4〇〇〇~looooo. When the weight average molecular weight exceeds 200,000, the viscosity may become too high to form a coating film. On the other hand, if the weight average molecular weight is less than 2 Å, it tends to be insufficient to exhibit sufficient heat and f heat. In the case where the above [2-1-2] resin has an acid group, the acid value of the resin is preferably from 5 to 500 mgKOH/g', more preferably from 1 to 4 mgKKH/g. When the acid value is less than 5 mgKOH/g, it sometimes becomes difficult to apply to alkaline development. Further, when the acid value exceeds 500 mgKOH/g, the viscosity becomes too high and it is difficult to form a coating film. Furthermore, when the acid value is relatively high, the temporal change (viscosity increase) of the viscosity of the colored composition containing the same is not easy to occur, and therefore it is preferable; when the acid value is relatively low, the contrast of the colored composition containing the same It is preferable that the change (decrease) with time is not easy to occur. Further, '[2-1-2] resin, that is, a copolymer represented by the formula (v), as a copolymer of an essential monomer component, for example, JP-A-2004-300203 and JP-A-2004-300203 The compound described in 2(10)4_3〇〇2() No. 4 publication. The pigment dispersion liquid of the present invention is preferably obtained by using the [2-1-2] resin as the above-mentioned dispersion handle grease (i.e., in the dispersion treatment step described later, together with a dispersant or a dispersion aid). By using [2-1-2] resin as the dispersion resin, the viscosity of the pigment dispersion TF988407 72 201037041 will not be on the m-column of the limbs, and the color filter made of the dispersion will be colored. Better. Color test, money, "high contrast, color composition made by 2 liquid discharge, or secret pigment dispersion, medium, the color filter obtained by this fine (4) color composition is stable, Ο 图案 The pattern formed by the (4) color composition is not easy to have 'and thus is preferable. Further, the pigment dispersion liquid of the present invention and the coloring composition for a color light-emitting sheet may contain a binder other than the above [2-resin and [2-1_2] resin, within the range not impairing the effects of the present invention. Resin. The adhesive resin of the present invention may be used alone or in combination of two or more kinds. In the colored composition of the present invention, the binder resin is present in a proportion of the total solids, usually 0.1% by weight or more, preferably i% by weight or more, and S, iff is 80 WF. 6〇% by weight or less. If the content of the binder resin is less than this range, the film becomes brittle & the adhesion to the substrate is lowered. On the other hand, if it is more than this range, the permeability of the developer to the material portion becomes high, and the surface smoothness or sensitivity of the pixel may be deteriorated. μ [2-2] Other components The coloring composition for a color calender of the present invention may contain components other than the above as necessary. As such a component, a polymerizable monomer, photopolymerization 73 TF988407 201037041 starting system and/or thermal polymerization initiator, surfactant, thermal polymerization inhibitor, plasticizer, storage stabilizer, surface protection Agent, adhesion improver, development improver, dye, and the like. [2-2-1] Polymerizable monomer The polymerizable monomer of the present invention is not particularly limited as long as it is a polymerizable low molecular compound, but is preferably a polymerizable compound having at least one ethylenic double bond. (hereinafter, it is called "ethylene compound"). When the colored composition of the present invention is irradiated with active light, it is subjected to addition polymerization by the action of a photopolymerization initiation system described later or by heating under the action of a thermal polymerization initiator described later. And a hardened compound having an ethylenic double bond. Furthermore, the monomer of the present invention means the concept of a polymer substance, and means a concept including a dimer, a trimer, and an oligomer in addition to a narrowly defined monomer. Examples of the ethylenic compound include an unsaturated carboxylic acid; an ester thereof with a monohydroxy compound; an ester of an aliphatic polyhydroxy compound with an unsaturated carboxylic acid; an ester of an aromatic polyhydroxy compound with an unsaturated carboxylic acid; a vinegar obtained by a acetalization reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid, a polybasic compound such as the above aliphatic polyhydroxy compound or an aromatic polyhydroxy compound; and a polyisocyanate S compound and a thiol group An ethylenic compound having an amine decanoic acid ethyl ester skeleton obtained by reacting a hydroxy compound of an acrylonitrile group. Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trishydroxypropyl propane triacrylate, and trishydroxycarbonyl. Acrylate, pentaerythritol dipropylene TF988407 74 201037041 acid ester, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylic acid g, dipentaerythritol pentaacrylic acid g, dipentaerythritol hexaacrylic acid, glycerin acid vinegar s purpose. Further, the acrylic acid moiety obtained by replacing the acrylic acid moiety of the acrylic acid ester with the thioglycolic acid moiety, the itaconate ester obtained by replacing the itaconic acid moiety, and the substitution of the butenoic acid Part of the obtained butenoate, and the maleic acid moiety obtained by replacing it with a maleic acid moiety. Examples of the aromatic polybasic compound and the unsaturated sulphuric acid vinegar include hydroquinone diacrylate, hydroquinone dimercapto acrylate, resorcinol diacrylate, and isophthalic acid. Phenol dimethacrylate, pyrogallol triacrylate, etc. The ester obtained by the esterification reaction of an unsaturated carboxylic acid, a polyvalent carboxylic acid and a polyhydroxy compound is not necessarily a single substance or a mixture. As representative examples, condensates of acrylic acid, phthalic acid and ethylene glycol; condensates of acrylic acid, Q maleic acid and diethylene glycol; methacrylic acid, terephthalic acid and pentaerythritol; a condensate; a condensate of acrylic acid, adipic acid, butylene glycol, glycerin, and the like. The ethylenic compound having an amino decanoic acid ethyl ester skeleton obtained by reacting a polyisocyanate compound with a hydroxy group compound containing a (fluorenyl) acrylonitrile group may, for example, be hexamethylene diisocyanate or triterpene. Aliphatic diisocyanates such as hexamethylene diisocyanate, alicyclic diisocyanates such as cyclohexane diisocyanate and isophorone diisocyanate, terpene diisocyanate, and TF988407 75 201037041 phenyl decane diisocyanate Diisocyanate, etc., with 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy(1,1,1-tripropenyloxyindenyl)propane, 3-hydroxyl (1,1) a reaction product obtained by reacting a hydroxy compound containing a (fluorenyl) acrylonitrile group such as 1-trimethylacryloxycarbonyl group. Further, as the ethylenic compound used in the present invention, for example, an acrylamide such as ethyl bis propylene phthalamide or an allyl ester such as diallyl phthalate; phthalic acid; A vinyl group-containing compound or the like such as divinyl phthalate. Further, the ethylenic compound may be a monomer having an acid group. The monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and preferably a non-aromatic carboxylic anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound to have an acid group. The polyfunctional monomer is particularly preferably at least one of the aliphatic polyhydroxy compound pentaerythritol and dipentaerythritol in the ester. These monomers may be used singly, but it is difficult to use a single compound in the production, and thus two or more kinds of monomers may be used in combination. Further, if necessary, a polyfunctional monomer having no acid group as a monomer may be used in combination with a polyfunctional monomer having an acid group. The acid value of the polyfunctional monomer having an acid group is preferably from 0.1 to 40 mgKOH/g, particularly preferably from 5 to 30 mgKOH/g. When the acid value of the polyfunctional monomer is too low, the development and dissolution characteristics are lowered. When the acid value is too high, the production or handling becomes difficult, and the photopolymerization performance is lowered, and the surface smoothness of the pixel or the like tends to be poor. TF988407 76 201037041 Therefore, in the case where two or more kinds of polyfunctional monomers having different acid groups are used in combination, or in the case where a polyfunctional monomer having no acid group is used in combination, a preferred one will be a multi-functional single The acid group of the body is adjusted to the above range. • In the present invention, a more preferred polyfunctional monomer having an acid group is commercially available as T01382 manufactured by Toagosei Co., Ltd., dipentaerythritol hexaacrylate, dipentaerythritol pentapropan acid cool, dipentaerythritol pentaacrylate vinegar. The succinic acid 6 is a mixture of the main components. It is also possible to use a combination of other polyfunctional 0 monomers other than the polyfunctional monomer. In the present invention, the ethylene compound preferably has a molecular weight of 650 or less, preferably 550 or less, more preferably 400 or less, and a double bond equivalent of -150 or less, preferably 140 or less, more preferably 110 or less. By. Further, the lower limit of the ? is not particularly limited, and it may be within the range in which the chemical structure of the addition polymerization can be obtained. Further, it is possible to reduce the "defects" of the pixels and to form pixels having more excellent linearity, and among these, a compound having a relatively small molecular weight and a small double bond equivalent is preferable. For example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid having a molecular weight of 400 or less and a double bond equivalent of 110 or less is preferable, and more specifically, pentaerythritol tetraacrylic acid is used as the pentaerythritol. Triacrylate is intended. Further, in terms of the sensitivity of the color filter used for the color filter, it is preferred to use an ethylenic compound having a molecular weight of more than 400. As such a compound, particularly preferred is dipentaerythritol tetrakis(meth)acrylate, dipentaerythritol TF988407 77 201037041 acid ': dipentaerythritol hexa(methyl) propylene oxime. These, 9, and the above-mentioned ethylene compound having a molecular weight of 4 Å or less and a double bond equivalent of 150 '110 or less) are used in combination to obtain a composition having good balance, which is preferable. The ratio of the monomer in the total solid content of the colored composition of the present invention is 0 weight. /° or more is preferably 5% by weight or more, more preferably 10% by weight, and usually 80% by weight or less, preferably 70% by weight. /. More preferably, it is 5 (3 wt% or less), particularly preferably 40 wt% or less. Further, the tb ratio with respect to color = is usually 〇% by weight or more, preferably more than $% by weight, and more 〇', More than or equal to 2% by weight, particularly preferably 2% by weight or more, usually 2% by weight, preferably 1% by weight or less, more preferably 8% by weight or less. [2 3] Photopolymerization initiation And the thermal polymerization initiator is y to harden the coating film. The coloring composition of the present invention preferably contains at least one of a photopolymerization initiator and a thermal polymerization initiator. Among them, the hardening method may be used. A method other than the method of preparing a starting agent, particularly in the case where the colored composition of the present invention contains a resin having an ethylenic double bond as a binder resin component, or an ethylenic compound as the polymerizable monomer. In particular, it is preferred to contain at least one of a photopolymerization initiation system and a thermal polymerization initiator which directly absorbs light or is photoactivated to cause a decomposition reaction or a dehydrogenation reaction, and causes polymerization. The function of active free radicals, The polymerization initiator generates a polymerization active radical by heat. TF988407 78 201037041 [2-3-1 ] Photopolymerization Initiation The photopolymerization initiator is usually prepared as a mixture with an accelerator such as an accelerator (light polymerization). It is used in combination with the starting system. The photopolymerization initiating system has a function of directly absorbing light or a function of causing a decomposition reaction or a dehydrogenation reaction to cause a polymerization active radical. The photopolymerization initiator of the component, for example, a metallocene compound containing a titanocene compound described in each of the publications of JP-A-59-152396, JP-A-61-151197, and the like; Or a hexaarylbiimidazole derivative, a halogenated fluorenyl succinimide derivative, an N-phenyl glycine acid or the like, an aryl-α-amino acid, or a N-type described in Japanese Laid-Open Patent Publication No. Hei 10-39503. a radical active agent such as an aryl-α-amino acid salt or an N-aryl-α-amino acid ester, or an α-aminoalkylphenone compound; 曰本专利专利2006-36750号Japanese Patent Publication No. 2002-323762, JP-A-2000-80068, etc. A compound or the like. The following is a specific example of a photopolymerization initiator which can be used in the present invention. 2-(4-decyloxyphenyl)-4,6-bis(trichloroindenyl)-trientrine , 2-(4-decyloxynaphthyl)-4,6-bis(trichloroindenyl)-trientrine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloroindenyl) All three lectures, 2-(4-ethoxycarbonylnaphthalene "yl)-4,6-bis(trichloroindenyl) are all three sorghum bases; three gas sulfhydryl-5 -(2'-benzo-pyranoyl)-1,3,4-° diterpene, 2-trimethylsulfonyl-5-[ yS -(2'-benzopyranyl)vinyl]- 1,3, 4-0, two-spot, 2_dichloroindolyl-5-[spin-(2,-(6"-benzo-d-f-butyl)ethene TF988407 79 201037041 base)]-1,3, Halogenated oxadiazole derivatives such as 4-oxadiazole, 2-trichloroindolyl-5-furyl-1,3,4-oxadiazole; 2-(2'-chlorophenyl)-4 , 5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-nonyloxyphenyl)imidazole dimer, 2-(2'-fluorobenzene ,4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazole dimer, (4'-decyloxybenzene 4,5-diphenylimidazole dimer, etc. 11 m? sitting derivative; benzoin ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether and other benzoin alkyl ethers; 2-mercaptopurine Anthracene, 2-ethyl hydrazine, 2-tert-butyl fluorene, 1-chloroindole, etc.; diphenyl ketone, Michler's Ketone, diethylamine Diphenyl ketone, 2-mercaptodiphenyl ketone, 3-mercaptodiphenyl ketone, 4-mercaptodiphenyl ketone, 2-chlorodiphenyl ketone, 4-bromodiphenyl ketone, 2- a diphenyl ketone derivative such as carboxydiphenyl ketone; 2,2-dimethoxyoxy-2-phenylphenyridinium, 2,2-diethoxyphenyl hydrazine, 1 hydroxycyclohexyl phenyl ketone, Hydroxy-2-mercaptophenylacetone, 1-hydroxy-1-indolylethyl-(p-isopropylphenyl)one, 1-hydroxy-1-(p-dodecylphenyl) ketone, 2- Benzo-1-[4-(indolyl)phenyl]-2-indolylpropan-1-one, 1,1,1-trichloroindolyl-(p-butylphenyl)one, etc. Ketone derivatives; thioxanthone, 2-ethyl thiophene ketone, 2-isopropyl thioxanthone, 2-ox thioxanthone, 2,4-dimethyl thioxanthene Ketone, 2,4-diethyl thioxene Ketone, TF988407 80 201037041 2, 4-diisopropyl, 11 ketone, etc. "donone derivatives; p-benzoic acid benzoic acid ethyl ester, p-diethylaminobenzoic acid ethyl ester and other benzoquinone Acid ester derivatives; acridine derivatives such as 9-phenyl acridine, 9-(p-nonyloxyphenyl) acridine; 9,10-dimercaptobenzophenone; and other morphological wells (卩] 1611& 21116) Derivatives; anthrone derivatives such as benzoxanthone; dicyclopentadienyl di-titanized titanium, dicyclopentadienyl bisphenyltitanium, dicyclopentadienyl di- 2,3,4,5,6-pentafluorophenyl-1-yl titanium, dicyclopentadienyl bis-2,3'5,6-tetrafluorophenyl-1-yl titanium, dicyclopentadienyl Bis-2,4,6-trifluorobenzene-1-yl-titanium, dicyclopentadienyl-2,6-difluorobenzene-indole-based titanium, dicyclopentadiene. base_2,4-12 Fluorophenyl-1-yl titanium, dimethylcyclopentadienylbis-2,3,4,5,6-pentafluorophenyl-1-yl titanium, dimercaptocyclopentadienyl double_2,6 _Difluorobenzene-丨-based titanium, monocyclopentadienyl-2,6-di-fluoro-3-indolyl-1-yl)-benzene-based titanium and other titanocene derivatives; Ο 2 —mercapto 444-(indolyl)phenyl]-2-indolyl propane-1-one, benzyl-2-didecylamino-1-(4- Porphyrin phenylbutanone mono-, 2-benzyl-2-indenyl-1-(4-carbolinylphenyl)butane mono- ketone, ethyl 4-diguanidinobenzoate , 4-Bisylaminobenzoic acid isoamyl ester, diethylaminophenyl acetophenone, 4-dimethyl dimethyl acetonide, 1,4-diguanyl benzoic acid mono-2-ethylhexyl ester , 2, 5-bis(4-diethylaminobenzylidene)cyclohexanone, 7-diethylamino _3_(4-diethylaminobenzimidyl) coumarin, 4-(2-B Amino) chalcone and the like ^-aminoalkylphenone-based compound; TF988407 81 201037041 I*ethyl-methyl benzoic acid-based (4) ten-end group] 乙院-卜肥-〇韵m秘峰胄(四)基) 2 - 2 oxime ester compounds such as 2-p-indole-benzoate. The photopolymerization initiator used in the present invention preferably contains a (tetra) compound as a photopolymerization initiator. Among them, an oxime ester compound represented by the following formula (I) is preferred. [Chem. 19]
Ο II /OR2 (I) V—C—X—C—R1 [式⑴中’R1表示氫原子、碳數1〜20之烧基、碳數2〜 25之烯基、碳數3〜20之雜芳基或者碳數4〜25之雜芳燒 基,該㈣可财取錄。料,R1可與HY鍵結而 環。 R2表示碳數卜20之賊基、碳數3〜25之雜基、碳數 4〜8之環烧醯基、碳數7〜2q之芳酿基、碳數2〜ι〇 μ 氧幾基、碳數7〜2G之芳_基、碳數2〜2G之雜芳基、碳 數3〜20之雜芳醯基或者魏2〜2G找絲顧基,該等 均可具有取代基。 X表示可具有取代基之、由2個以上環縮合而成之2價芳 香族烴基及/或芳香族雜環基。 Y表示可具有取代基之芳香族基。] TF988407 82 201037041 S有經微粒化之顏料、特別是經微粒化之溴化酞菁顏料的 彩色濾'光片用著色組成物,易產生特微小的異物。異物係有 ’在著色組成物剛製造後所觀察到者,亦有在組成物保存中所 產生者。由研討絲可明瞭’異物之產生與光聚合起始劑有 著特別緊密的關係。 又,於衫色濾光片用著色組成物中,綠色係對照射光之高 敏感度化為最困難之顏色。作為其原因之一,可舉出:綠色 〇 顏料與其他顏色之㈣相比,㈣本身之著色力較低,因而 顏料之含量必然變高。 又,綠色組成物之最大穿透率波長約為530 nm,波長為 ' 450 nm以下之穿透率大致接近0。在使用光微影法之彩色濾 • 光片製造中,通常使用之曝光機為高壓水銀燈,與其相對應 之光聚合起始劑中,亦有可對自紫外部分至410 nm附近的 光引起硬化反應者,但對於綠色,可舉出無法利用長波長部 〇 分之光能量。 若著色組成物之敏感度不充分則無法獲得規定之線寬,在 極端情形下,塗膜之硬化性較差,亦會引起無法形成透明塗 .膜之現象。又,彩色濾光片在進行面板化時塗佈配向膜,但 .若塗膜硬化性較低,則對於通常用作配向膜溶劑之N_曱基 吼咯啶酮(NMP),會產生以顏料為主之析出物。 總之,要獲得含有經微粒化之顏料、其中含有綠色顏料、 特別是糾b鋅料減且對曝光之光具有充分的敏感度、並 TF988407 83 201037041 抑制異物產生之彩色滤光片用著色組成物,係非常困難。 針對此情形,在數種光聚合起始劑中,使用由職系化合 物、特別是以上述通式⑴所表示之㈣化合物所構成之光 聚合起始劑,藉此可解決上述問題,因而較佳。 於上述月亏i系化合物⑴中,Y_c(=〇)_x部分形成吸光 部’將結構部:-CXDLp分則形成自由基產生部位。 吸光部:y-c(.x高效率地吸收光並將所吸收之能量高效 率地轉移錢結構部,藉此達成高的敏感度。—般認為,以 y-c(=o)-x部分所表示之吸光部,特別是以高濃度地添加於 組成物中的情形下,分子彼此之間會相互結合,而在外觀上 複數個分子作成為單個分子而運動,因此有吸光度及吸收效 率下降之傾向。再者,本發明之肟酯系化合物(ι),由於γ 部分形成體積大之基,因此即便在以高濃度添加的情形下, 亦可具有高吸光度,因而較佳。 又’重要的是Y-C(=G)-X部分高效率地生成細結構部中 容易活用於自由基產生的三重態能量,為了達成分子内有效 率的能量轉移’重要的是ΙΥ-C(鲁X冑分與將結構部在空 間上儘可能地接近。 以上述通式(I )所表示之化合物,因Y_c(=〇)_x部分含有 自單重態向三重態之狀態變化效率較高的二苯基酮結構或 與其類似之結構,故可將所吸收之光高效率地變換成三重態 能量。 TF988407 84 201037041 進而,以上述通式(i)所表示之化合物,因係二苯基酮結 構或與其相類似之結構藉由分子内之空間性旋轉而易於與 月亏結構部重疊之化合物,因此可在分子内進行有效率的能量 • 轉移,並可達成更高的敏感度。 於通式(I )中,X表示可具有取代基之、由2個以上環縮 合而成之2價芳香族烴基及/或芳香族雜環基之基。 作為X,具體而言,例如可舉出:來自萘環、蒽環、 0 葸(chrysene)環、菲環、奠(azulene)環、苐(florene)環、 苊(acenaphthylene)環、茚(indene)環等由芳香族烴環所構 成之縮合環之基;來自吖咬環、菲咬(phenanthridine)環、 • 二苯并旅喃(xanthene)環、味β坐環、啡π井環、二苯并0塞 • D井(phenothiazine)環、啡今》井(phenoxazine)環、苯并嘆0坐 (benzothiazole)環等由芳香族烴環與芳香族雜環所構成之 縮合環之基等。 ❹ 該等均可具有任意之取代基。對於該「任意之取代基」, 於後加以敍述。 以通式(I )所表示之化合物中,特佳為以下述通式(i ) 所表示之化合物,即通式(I )中之X基係以通式(i )中之苯 壞X及與其縮合之破X2所表示的結構之化合物。 [化 20]Ο II /OR2 (I) V—C—X—C—R1 [In the formula (1), 'R1 represents a hydrogen atom, a carbon number of 1 to 20, an alkenyl group having 2 to 25 carbon atoms, and a carbon number of 3 to 20. A heteroaryl group or a heteroaryl group having a carbon number of 4 to 25, which can be taken. Material, R1 can be bonded to HY and ring. R2 represents a thief base of carbon number 20, a hetero group having a carbon number of 3 to 25, a cycloalkyl group having a carbon number of 4 to 8, a aryl group having a carbon number of 7 to 2, and a carbon number of 2 to ι 〇 oxy group. And an aromatic group having a carbon number of 7 to 2 G, a heteroaryl group having a carbon number of 2 to 2 G, a heteroaryl group having a carbon number of 3 to 20, or a fluorene 2 to 2 G group, which may have a substituent. X represents a divalent aromatic hydrocarbon group and/or an aromatic heterocyclic group which may have a substituent and is condensed by two or more rings. Y represents an aromatic group which may have a substituent. ] TF988407 82 201037041 S A coloring composition for a color filter of a micronized pigment, in particular, a micronized brominated phthalocyanine pigment, is liable to generate extremely small foreign matter. The foreign matter system has a 'observed after the coloring composition has just been produced, and is also produced in the storage of the composition. It is clear from the study that the generation of foreign matter has a particularly close relationship with the photopolymerization initiator. Further, in the coloring composition for the shirt color filter, the high sensitivity of the green light to the irradiation light is the most difficult color. One of the reasons for this is that the green 〇 pigment is inferior to the other colors (4), and the coloring power of the pigment is inevitably high. Further, the green composition has a maximum transmittance wavelength of about 530 nm, and a transmittance of wavelengths below 450 nm is approximately close to zero. In the production of color filter and light film using photolithography, the exposure machine usually used is a high-pressure mercury lamp, and the photopolymerization initiator corresponding thereto can also cause hardening of light from the ultraviolet portion to near 410 nm. The responder, but for green, it is possible to use light energy that cannot be separated by the long wavelength portion. If the sensitivity of the colored composition is insufficient, the prescribed line width cannot be obtained. In an extreme case, the hardenability of the coating film is poor, and the phenomenon of the transparent coating film cannot be formed. Further, when the color filter is applied to the alignment film at the time of panel formation, if the coating film has low curability, it is produced for N_mercaptoacridone (NMP) which is usually used as an alignment film solvent. Pigment-based precipitates. In short, a coloring composition for a color filter containing a micronized pigment, which contains a green pigment, particularly a buckling zinc material, and which is sufficiently sensitive to light to be exposed, and TF988407 83 201037041, which suppresses the generation of foreign matter, is obtained. It is very difficult. In view of the above, among the plurality of photopolymerization initiators, a photopolymerization initiator composed of a compound of a grade, particularly a compound represented by the above formula (1), is used, whereby the above problem can be solved, and thus good. In the above-mentioned monthly deficient compound (1), the Y_c(=〇)_x portion forms a light absorbing portion', and the structural portion: -CXDLp is divided into a radical generating portion. Light absorbing portion: yc (.x efficiently absorbs light and efficiently transfers the absorbed energy to the money structure portion, thereby achieving high sensitivity. It is generally considered to be represented by the yc(=o)-x portion. In the case where the light absorbing portion is added to the composition in a high concentration, the molecules are bonded to each other, and a plurality of molecules move as a single molecule in appearance, and thus the absorbance and the absorption efficiency tend to decrease. Further, since the oxime ester compound (I) of the present invention forms a bulky group in the γ moiety, it is preferable to have a high absorbance even when it is added at a high concentration. Further, it is important that YC (=G)-X part efficiently generates triplet energy in the fine structure part which is easy to be used for free radical generation. In order to achieve efficient intramolecular energy transfer, it is important that ΙΥ-C (Lu X胄分分和结构结构) The portion is as close as possible in space. The compound represented by the above formula (I) has a diphenyl ketone structure which is highly efficient in changing from the singlet state to the triplet state due to the Y_c(=〇)_x moiety or Similar structure, so The absorbed light is efficiently converted into triplet energy. TF988407 84 201037041 Further, the compound represented by the above formula (i) has a space in the molecule due to the structure of the diphenyl ketone or a structure similar thereto A compound that rotates easily and overlaps with the monthly structure, so that efficient energy transfer can be performed in the molecule, and higher sensitivity can be achieved. In the general formula (I), X represents a substituent. And a group of a divalent aromatic hydrocarbon group and/or an aromatic heterocyclic group which are condensed by two or more rings. Specific examples of X include a naphthalene ring, an anthracene ring, and a chrysene. a ring of a condensed ring composed of an aromatic hydrocarbon ring such as a ring, a phenanthene ring, an azulene ring, a florene ring, an acenaphthylene ring, an indene ring, or the like; Phenanthridine), xanthene ring, taste beta ring, morphine π well ring, dibenzoxe•D well (phenothiazine ring), phenoxazine ring, benzophenone ring The benzothiazole ring is composed of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. The base of the condensed ring, etc. ❹ These may have any substituent. The "optional substituent" will be described later. Among the compounds represented by the formula (I), it is particularly preferred to The compound represented by the formula (I), that is, the compound of the formula (I), is a compound having a structure represented by the benzene benzene X in the formula (i) and the condensed X2 condensed therewith.
TF988407 85 201037041 [式 + ’ R1、R2及 y,盥 μ 相主-式⑴令的Rl、R2及Υ之含義 相同。表示與裳擇y丨人 我 、衣X鈿5之裱,可為單環亦可為由9 個以上環所構成之縮合 ’、、、 ^ ^ t 又% X可縮合於苯環X1之任 位置。苯環X丨及與其 仕 ^ ’相可具有取代基。] …U 〇所表示之化合物,因苯環X1可與-C㈣-Υ — 二基崎構或與其類似之結構,故吸光度較高,並 早心至—重態的激發效率較高,因而較佳。 乍為k式⑴中之χ,較佳為含有芳香族雜環之基,特佳 為於通式⑴中與苯環^合之環X2為雜環之情形。 又’X通常為來自2〜4縮合環之2價基,就分子量變得 相對較小之方面而言,較佳為來自2或3縮合環之2價基, 絲易適合組成物光硬化中所使用照射光之波長之方面而 δ,更佳為來自3縮合環之2價基。 2作為通式⑴中之Χ、以及於通式⑴中由苯環χΐ及環 X所形成之結構,特佳為來自料環之基。在χ為來自味唾 基之基的情形下,不僅具有曝光時對照射光之適合性,亦係 牢固之骨架,因此較佳。 ” 於通式(I ) + ’ 表示氫原子、碳數丨〜別之絲、碳數 2〜25之縣 '碳數3〜2G之雜絲或者碳數4〜25之雜芳 烧基’該等燒基、烯基、雜芳基、雜芳烧基均可具有取代基。 藉由使R1成為此種基,與Ri為苯基等之化合物相比,對光 之敏感度變高。又,化合物之合成亦容易,因此就工業生產 TF988407 86 201037041 之親點而言亦較佳。 作為R1之碳數1〜20之烷基,可舉出曱基、乙基、丙某、 丁基等,較佳為碳數1〜12找基,更佳為碳數卜6二 • 基。 • 作為R1之碳數2〜25之烯基,可舉出乙稀基、丙婦基等, 較佳為⑽基等碳數3〜12之雜,更佳為碳數2〜5 基。 〇 作為R1之碳數3〜20之雜絲,可舉t亞硫縣、吱 。南基、咪嗤基、苯并癌唾基、笨并啊基等,較佳為魏3 〜15、更佳為碳數4〜10之雜芳基。 • 作為Rl之碳數4〜25之料絲,可舉出:亞硫醯基甲 基、吱喃曱基、味嗤基曱基、苯并嗟唾基甲基、苯并今坐基 曱基等’較佳為碳數4〜18、更佳為碳數4〜10之雜芳烷基。 再者,上述各基均可具有取代基。對該取代基於後加以敍 〇 述。 作為R1,特佳為可具有取代基之烷基。其中,就製造的容 易性方面而言,較佳為無取代之烷基。又,在如後述般將以 通式(I )所表示之化合物用於光聚合性組成物的情形下,就 該組成物對基板之密著性之觀點而言,較佳為以取代胺基所 取代之烷基,最佳為以N-乙醯基_N_乙醯氧基胺基所取代之 烷基。 於通式(I )中,R2表示碳數2〜2〇之烷醯基、碳數3〜25 TF988407 87 201037041 之烯醯基、碳數4〜8之環烷醯基、碳數7〜20之芳醯基、 碳數2〜10之烷氧羰基、碳數7〜20之芳氧羰基、碳數2〜 20之雜芳基、碳數3〜20之雜芳醯基、碳數2〜20之烷基 胺基羰基,該等烷醯基、烯醯基、環烷醯基、芳醯基、烷氧 羰基、芳氧羰基、雜芳基、雜芳醯基、烷基胺基羰基均可具 有取代基。藉由使R2成為此種基,而易於使肟部開裂,從 而易於獲得由於自由基之產生所導致之敏感度的提昇。 作為R2之碳數2〜20之烷醯基,可舉出:乙醯基、丙醯 基、丁醯基等,較佳為乙醯基等碳數2〜12、更佳為碳數2 〜7之烧醯基。 作為R2之碳數3〜25之烯醯基,可舉出丁烯醯基、丙烯 醯基等,較佳為丁烯醯基等碳數3〜12、更佳為碳數3〜7 之烯酿基。 作為R2之碳數4〜8之環烷醯基,可舉出環己基羰基、曱 基環己基羰基、環戊基羰基等,較佳為環己基羰基等碳數4 〜8、更佳為碳數4〜7之環烧醯基。 作為R2之碳數7〜20之芳醯基,可舉出苯曱醯基、曱基 苯曱醯基、萘甲醯基等,較佳為萘曱醯基等碳數7〜12、更 佳為碳數7〜10之芳醯基。 作為R2之碳數2〜10之烷氧羰基,可舉出曱氧羰基、乙 氧羰基、丙氧羰基等,較佳為曱氧羰基等碳數2〜10、更佳 為碳數2〜8之烷氧羰基。 TF988407 88 201037041 作為R2之碳數7〜刈夕艺与# * 甲A苯氧㈣* 可舉出苯氧縣、對 甲本歧基、秦氣幾基等 15、更佳為碳齡7 雜為奈氧域等碳數7〜 更仏為讀7〜1G之芳氧幾基。 作為R2之碳數2〜2〇夕埯-甘 赠等’較佳C’可舉出靖,基、 之雜芳基。為塞吩基等碳數2〜I更佳為破數2〜7 Ο ❹ 作為R2之碳數3〜2〇之雜装 、_基等=方基’可舉出_基、°比 遠私較佳為嗟賴基等碳數5〜15、更佳 為石反數7〜10之雜芳醯基。 作為R2之碳數9 u 縣,可舉㈣啉基羰 二二 胺基賴’較佳為二甲胺基羰基等 反、 佳為碳數2〜10之烧基胺基幾基。 上述各基中’就曝光敏感度方面而言,作為R2,較佳為院 醯基、%脑基、芳醯基,更佳狀醯基、芳酿基。 再者’對作為R2的上述各基可具有之取代基於後加以敍 述’作為上述各基,特佳為不具有取代基者。 於通式⑴中’ γ表示可具有取代基之芳香族基,更詳細 而言,Y係來自芳香族烴環或芳香族雜環之1價基,該等均 可具有取代基。再者,在γ為來自芳香族雜環之〗價基的情 形下,可為!個以上之環縮合於苯基上而成之基,亦可為! 個以上之環縮合於5或6員環的雜芳基上而成之基。 以通式(I )所表示之化合物,係如上述般,γ所具有之苯 TF988407 89 201037041 基或芳香族雜環之部分與X之一部分經由-(〇〇)-基,而形 成二苯基酮結構或與其類似之結構,因而較佳。 又,如上述般,以通式(I )所表示之化合物,係二苯基酮 結構或與其類似之結構藉由分子内之空間性旋轉而容易於 與肟結構部發生重疊之化合物,因此可在分子内進行有效率 的能量轉移,並可達成更高的敏感度,因此較好。 在Y係1個以上之環縮合於苯基而成之縮合環基的情形 下,較佳為來自1〜3個5或6員環縮合於自該苯基的2,3-位、3, 4-位及4, 5-位中所選擇的至少1處而成之2〜4縮合 環之基。又,縮合於Y中之苯基上之環,較佳為烴環,或者 芳香族烴環及/或芳香族雜環。就量子產率較高之方面而 言,縮合於Y中之苯基上之環較佳為烴環,又,就吸光波長 範圍變寬之方面而言,較佳為芳香族環。 作為Y之環,較佳為單環或2〜4縮合環基,就分子量不 變得過大之方面而言,更佳為單環或2〜3縮合環基,特佳 為單環及2縮合環基。再者,在Y為來自3〜4縮合環之基 的情形下,吸收波長區域發生較長波長化,亦適應廉價之光 源,因此在工業上較佳。 作為Y之環的具體例,可舉出:來自苯環之基;來自萘環、 蒽環、®環、菲環、奠環、苐環、苊環、茚環等2縮合環以 上之芳香族烴環之基;噻吩基、吡啶基、呋喃基、哼唑基、 d塞唾基等來自5或6員芳香族雜環之基;或者來自°丫n定環、 TF988407 90 201037041 非咬每、二苯并南環、味哇環、班 啡噚讲環、苯并噻唑環、 衣、一笨开噻讲環、 族雜環所__合^: ㈣麵朗與芳香 :二特佳為苯基、萘基、•基、蝴及 基。,敏感度之方面而言,最佳為笨基、萘基及嘆吩 Ο Ο 作=述γ中之環基可具有之取代基,例如可舉出:甲 暴乙基、丙基等碳數1〜2〇 數1〜20之~| 甲硫基、乙硫基等碳 〇之挽硫基;以-顯其中,R為甲基、乙基等碳數 石山數基)所表示之績酸烧基醋基;戊氧基、己氧基等 _G=氧基;環戊基、環己基等碳數5〜2G之環燒 土,衣Ά己氧基等碳數5〜20之環烧氧基;咪琳基、 底疋基:料。定基等原子數5〜20之環狀胺基;二異丙胺 土 第一丁基胺基等碳數4〜20之二烷基胺基;苯基、萘 基等芳基m定基等雜絲1基、苯乙基等綠nTF988407 85 201037041 [Formula + ′ R1, R2 and y, 盥 μ phase main-form (1) Let Rl, R2 and Υ have the same meaning. It means that it can be a single ring or a condensation consisting of more than 9 rings, ', , ^ ^ t and % X can be condensed in the benzene ring X1. position. The benzene ring X oxime and its phase may have a substituent. The compound represented by ... U ,, because the benzene ring X1 can be combined with the -C(tetra)-Υ-diyl group structure or the like, the absorbance is high, and the excitation efficiency of the early heart to the heavy state is high, so that it is preferable. . The oxime is in the formula (1), and is preferably a group containing an aromatic heterocyclic ring, and particularly preferably a ring in which the ring X2 which is bonded to the benzene ring in the formula (1) is a hetero ring. Further, 'X is usually a divalent group derived from a 2 to 4 condensed ring, and in terms of a relatively small molecular weight, it is preferably a divalent group derived from a 2 or 3 condensed ring, and the wire is liable to be suitable for photohardening of the composition. The δ of the wavelength of the irradiation light to be used is more preferably a divalent group derived from the 3 condensed ring. 2 is a structure derived from the oxime in the formula (1) and a benzene ring oxime and a ring X in the formula (1), and particularly preferably a group derived from a ring. In the case where the ruthenium is based on the base of the taste base, it is preferable not only to have suitability for irradiation light at the time of exposure but also to be a strong skeleton. " General formula (I) + ' represents a hydrogen atom, a carbon number 丨 ~ other filaments, a carbon number of 2 to 25, a carbon number of 3 to 2G or a heteroaryl group of carbon number 4 to 25 The alkyl group, the alkenyl group, the heteroaryl group or the heteroaryl group may have a substituent. By making R1 a such group, the sensitivity to light is higher than that of a compound in which Ri is a phenyl group or the like. Further, the synthesis of the compound is also easy, and it is also preferable in the industrial production of TF988407 86 201037041. Examples of the alkyl group having 1 to 20 carbon atoms of R1 include a mercapto group, an ethyl group, a propyl group, a butyl group, and the like. Preferably, it is a carbon number of 1 to 12, and more preferably a carbon number of 2 and 2. The alkenyl group having 2 to 25 carbon atoms of R1 may, for example, be a vinyl group or a propyl group. It is a (3) group having a carbon number of 3 to 12, more preferably a carbon number of 2 to 5. The hydrazine having a carbon number of 3 to 20 as R1 may be a sub-sulfur county, a ruthenium, a south base, or a mercapto group. Benzene cancer salino, stupid and basal, etc., preferably Wei 3 to 15, more preferably a heteroaryl group having a carbon number of 4 to 10. • As a filament of R1 having a carbon number of 4 to 25, it may be mentioned : sulfinylmethyl, bromomethyl, miso base The benzoxylmethyl group, the benzoxanthyl group, etc. are preferably a heteroarylalkyl group having a carbon number of 4 to 18, more preferably a carbon number of 4 to 10. Further, each of the above groups may have a substitution. The substitution is based on the following description. R1 is particularly preferably an alkyl group which may have a substituent. Among them, in terms of ease of production, an unsubstituted alkyl group is preferred. In the case where the compound represented by the formula (I) is used in the photopolymerizable composition as described later, the alkyl group is substituted with a substituted amine group from the viewpoint of the adhesion of the composition to the substrate. The alkyl group is preferably an alkyl group substituted with an N-ethylindenyl-N-acetoxyamino group. In the formula (I), R2 represents an alkylene group having a carbon number of 2 to 2, and a carbon number of 3 ~25 TF988407 87 201037041 olefinic group, cycloalkyl fluorenyl group having 4 to 8 carbon atoms, aryl fluorenyl group having 7 to 20 carbon atoms, alkoxycarbonyl group having 2 to 10 carbon atoms, and aryloxycarbonyl group having 7 to 20 carbon atoms a heteroaryl group having 2 to 20 carbon atoms, a heteroarylalkyl group having 3 to 20 carbon atoms, an alkylaminocarbonyl group having 2 to 20 carbon atoms, an alkane group, an olefin group, a cycloalkyl group, and an aromatic group. Mercapto, alkoxycarbonyl, aryloxy The carbonyl group, the heteroaryl group, the heteroaryl fluorenyl group, and the alkylaminocarbonyl group may each have a substituent. By making R2 a such group, it is easy to crack the crotch portion, thereby easily obtaining sensitivity due to generation of a radical. The alkylene group having 2 to 20 carbon atoms of R2 may, for example, be an ethyl group, a propyl group or a butyl group, and preferably has a carbon number of 2 to 12, more preferably a carbon number. 2 to 7 of the fluorenyl group. The olefin group having 3 to 25 carbon atoms of R2 may, for example, be a butenyl group or an acrylonitrile group, and preferably has a carbon number of 3 to 12, such as a butenyl group. The cycloalkane group having a carbon number of 3 to 7 may, for example, be a cyclohexylcarbonyl group, a nonylcyclohexylcarbonyl group or a cyclopentylcarbonyl group, and a cyclohexylcarbonyl group. The carbon number is 4 to 8, more preferably the carbon number is 4 to 7 ring-burning thiol. Examples of the aryl group having 7 to 20 carbon atoms of R2 include a benzoinyl group, a nonylphenyl fluorenyl group, a naphthylmethyl group, and the like, and a carbon number of 7 to 12 such as a naphthylquinone group is preferred. It is an aromatic fluorenyl group having a carbon number of 7 to 10. Examples of the alkoxycarbonyl group having 2 to 10 carbon atoms of R2 include a fluorenyloxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, and the like, and preferably have a carbon number of 2 to 10, more preferably a carbon number of 2 to 8 such as a fluorenyloxycarbonyl group. Alkoxycarbonyl. TF988407 88 201037041 As the carbon number of R2 7~刈夕艺和# * A A phenoxy (4)* can be exemplified by phenoxy prefecture, p-aziodo group, Qin gas base, etc. 15, more preferably carbon age 7 miscellaneous The carbon number of the naphthyl group is 7~~ It is the aryloxy group of 7~1G. The carbon number of R2 is 2 to 2, and the like, and the preferred C' is preferably a heteroaryl group. The carbon number of the thiophene group is preferably 2 to 7 Ο ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ ❹ Preferably, it is a heteroaryl group having a carbon number of 5 to 15, more preferably a stone inverse of 7 to 10. The carbon number of the R 2 is 9 u, and the (tetra) phenyl carbonyl diamine lysine y is preferably a dimethylaminocarbonyl group or the like, and preferably an alkylamino group having 2 to 10 carbon atoms. In the above-mentioned respective groups, in terms of exposure sensitivity, R2 is preferably a sulfhydryl group, a % brain group, an aryl fluorenyl group, a more preferred fluorenyl group or an aromatic aryl group. Further, the substitution of the above-mentioned respective groups as R2 will be described hereinafter as the above-mentioned respective groups, and it is particularly preferred that the substituents are not substituted. In the general formula (1), γ represents an aromatic group which may have a substituent, and more specifically, Y is derived from an aromatic hydrocarbon ring or a monovalent group of an aromatic heterocyclic ring, and these may have a substituent. Furthermore, in the case where γ is a valence group derived from an aromatic heterocyclic ring, it can be! More than one ring is condensed on the phenyl group, it can also be! More than one ring is condensed on the heteroaryl group of a 5 or 6 membered ring. The compound represented by the formula (I) is as described above, and the benzene TF 988 407 89 201037041 group or the aromatic heterocyclic ring portion and one of the X portions are substituted with a -(〇〇)- group to form a diphenyl group. A ketone structure or a structure similar thereto is preferred. Further, as described above, the compound represented by the formula (I) is a compound in which a diphenyl ketone structure or a structure similar thereto is easily separated from the fluorene structure by spatial rotation in the molecule, and thus It is better to carry out efficient energy transfer in the molecule and achieve higher sensitivity. In the case where a ring of one or more Y groups is condensed to a phenyl group to form a condensed ring group, it is preferred to condense from 1 to 3 groups of 5 or 6 members to the 2,3-position and 3 from the phenyl group. The base of the 2~4 condensed ring formed by at least one of the 4-position and the 4-, 5-position. Further, the ring condensed on the phenyl group in Y is preferably a hydrocarbon ring or an aromatic hydrocarbon ring and/or an aromatic hetero ring. The ring condensed on the phenyl group in Y is preferably a hydrocarbon ring in terms of a higher quantum yield, and is preferably an aromatic ring in terms of widening the absorption wavelength range. The ring of Y is preferably a monocyclic ring or a condensed ring group of 2 to 4, and more preferably a monocyclic or 2 to 3 condensed ring group, particularly preferably a monocyclic ring and a 2 condensed ring, in terms of a molecular weight not becoming too large. Ring base. Further, in the case where Y is a group derived from a 3 to 4 condensed ring, the absorption wavelength region is longer-wavelength and is also suitable for an inexpensive light source, and therefore it is industrially preferable. Specific examples of the ring of Y include a group derived from a benzene ring; and an aromatic group derived from a condensed ring such as a naphthalene ring, an anthracene ring, a ring, a phenanthrene ring, a ring-opening ring, an anthracene ring, an anthracene ring or an anthracene ring; a group of a hydrocarbon ring; a thienyl group, a pyridyl group, a furyl group, a carbazolyl group, a d-sialyl group, or the like, a group derived from a 5- or 6-membered aromatic heterocyclic ring; or a ring derived from °丫n, TF988407 90 201037041 Dibenzoin ring, taste wah ring, bannag ring, benzothiazole ring, clothing, a stupid ring, a heterocyclic ring __he: (4) face and aroma: two special is phenyl , naphthyl, base, butterfly and base. In terms of sensitivity, it is preferably a strepyl group, a naphthyl group, and an anisotropic ring. The substituent group in the γ group may have a substituent, and examples thereof include a carbon number such as a methyl group and a propyl group. 1~2〇1~20~~|||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||| Pyridyl acetate; pentyloxy, hexyloxy, etc. _G=oxy; cyclopentyl, cyclohexyl and other ring-burning soils having a carbon number of 5 to 2 G, hexyloxy and the like having a carbon number of 5 to 20 Oxyl; imiline, base thiol: material. a cyclic amine group having an atomic number of 5 to 20; a dialkylamine group having a carbon number of 4 to 20 such as a first butylamine group; a aryl group such as a phenyl group or a naphthyl group; Green, phenethyl, etc.
Br 1、F等齒素原子;氧化四氫嗟吩基等。 °亥等之中,較佳為烷基、烷氧基、~S〇3R、環狀胺基或者 一烷基胺基,就進—步提昇敏感度方面而言,特佳為環狀胺 基或一燒基胺基。 以通式(I )所表示之化合物中的特佳形態、即义係來自可 〃有取代基之π卡嗤環之基的化合物,係例如以下述通式(瓜) 來表示。 TF988407 201037041A dentate atom such as Br 1 or F; a tetrahydroindenyl group or the like. Among the above, etc., an alkyl group, an alkoxy group, a ~S〇3R group, a cyclic amine group or a monoalkylamine group is preferred, and a cyclic amine group is particularly preferred in terms of further improving the sensitivity. Or a nonylamino group. A particularly preferred form of the compound represented by the formula (I), that is, a compound derived from a group of a π-cyclium ring which may have a substituent, is represented, for example, by the following formula (guar). TF988407 201037041
[式中mY與上述通式⑴中之之含義 p 立表戟肝、或者自後述取代 中所選擇之基。] 作為上述通式⑴中之π具有的取代基(通式⑴中之 笨環X1及與其縮合之環h具有的取代基)、通式⑴、⑴ 及(m)中之具有的取代基、以及通式(幻中之R3 〜R9,分別獨立可舉出自以下取代基群z中所選擇之基。 [取代基群z] 、_可舉出:氟原子、氣原子4原子、峨原子㈣素原子; L基,硝基,氰基;或者任意之有機基等。 作為該任意之有機基,可舉出:甲基、乙基、正丙基、異 土正丁基討基、第三丁基、戊基、第三戊基、正己 正辛基、第二辛基等碳數1〜18之直鏈或支鏈 q土 &丙基¥丁基、&戊基、環己基、金剛烧基等碳數 亩〜二之觀基;乙稀基、丙稀基、己稀基等碳數2〜18之 或者支鏈烯基·,環戊烯基、環己等碳數3〜18之環 烯基,曱氧基、乙氧基、正兩与* 乳土錄JE丙乳基、異丙氧基、正丁氧基、 TF988407 92 201037041 第二丁氧基、第三丁氧基、正戊氧基、第三戊氧基、正己氧 基、正庚氧基、正辛氧基、第三辛氧基等碳數1〜18之直鏈 或支鏈烷氧基;曱硫基.、乙硫基、正丙硫基、異丙硫基、正 丁硫基、第二丁硫基、第三丁硫基、正戊硫基、第三戊硫基、 正己硫基、正庚硫基、正辛硫基、第三辛硫基等碳數丨〜18 之直鏈或支鏈烧硫基;苯基、曱苯基、二曱苯基、均三曱笨 基等可經碳數6〜18之烧基取代之芳基;节基、苯乙基等碳 ❹數7〜18之芳烷基;乙烯氧基、丙烯氧基、己烯氧基等碳數 2〜18之直鏈或支鏈烯氧基;乙烯硫基、丙烯硫基、己烯硫 基等碳數2〜18之直鏈或支鏈烯硫基;a_c〇Rn所表示之醯 . 基,幾基;以-0C0R18所表示之醯氧基;以_服19|^2。所表示之 • 胺基;以—NHC0R21所表示之醯胺基;以-NHCOOR22所表示之胺 甲酸酯基;以-CONR23R24所表示之胺曱醯基;所表 示之羧酸酯基;以-S(MR26R27所表示之胺磺醯基;以—別^ 〇 所表示之續酸酯基;2-°塞吩基、2-吡啶基、呋喃基、吟唑基、 苯并嘮唑基、噻唑基、苯并噻唑基、咪啉基、吼咯啶基、二 氧化四氫噻吩基等飽和或不飽和之芳香族雜環基;三甲基矽 燒基等三炫基矽烷基等。 再者,上述R〜R分別獨立表示氫原子、可經取代之烷 基、可經取代之烷醯基、可經取代之烷基羰氧基、可經取代 之烯基、可經取代之芳基、或者可經取代之芳烷基。該等之 位置關係並無特別限定,在具有複數個取代基的情形下,取 TF988407 93 201037041 代基可相同亦可不同。 於上述中,複數個取代基可彼此鍵結形成環,所形成之 可為飽和或不飽和之芳香族烴環或者芳香族雜環,環上可長 一步具有各取代基,取代基進而可形成環。 於通式(瓜)中,R3〜以別獨立為氫原子或者自上述 基群Z中所選擇者,取代基群Z中,較佳可舉出:可具有取 代基之甲基、乙基等碳數1〜20之烷基,可具有取代基之笨 基等碳數6〜20之芳基,可具有取代基之吡啶基等碳數 20之雜芳基,可具有取代基之碳數7〜18之芳烷基,可= 有取代基之三烷基矽烷基;特佳為烷基。 〃 再者,作為上述通式(I )中的X可具有之取代基(通式(i ) 中的苯環X1及與其縮合的環X2可具有之取代基)之較佳者, 係與作為上述R3〜R9之較佳者相同。 作為R1可具有之取代基,較佳為以所表示之胺基 及方基’作為R19及R2。,較佳為可經取代之烧醯基、可經取 代之烧基幾氧基。如前所述,因對組成物之密著性提昇亦較 有效’故特佳為Ν-乙醯基-Ν-乙醯氧基胺基等以_nri9r2Q所表 示之胺基。 本發明之以通式⑴所表示之化合物中,最佳為以下述通 式(Π)所表示之化合物。 TF988407 94 201037041 化22[wherein mY and the meaning of the above formula (1): p represents the liver, or a group selected from the substitutions described later. a substituent which the π of the above formula (1) has (a ring of the ring X1 in the formula (1) and a ring which is condensed with the ring h), a substituent of the formula (1), (1) and (m), And the formula (R3 to R9 in the phantom) are each independently selected from the group of the following substituent group z. [Substituent group z], _ can be exemplified by a fluorine atom, a gas atom of 4 atoms, and a ruthenium atom. (4) a aryl group; an L group, a nitro group, a cyano group; or an arbitrary organic group, etc. Examples of the optional organic group include a methyl group, an ethyl group, a n-propyl group, an iso-n-butyl-butyl group, and a a linear or branched q-spin & propyl butyl group, & pentyl group, cyclohexyl group having a carbon number of 1 to 18 such as tributyl, pentyl, pentyl, n-hexyl-octyl or second octyl , aramid base and other carbon number of ~ 2 of the base; ethylene, acryl, hexyl and other carbon number 2 ~ 18 or branched alkenyl ·, cyclopentenyl, cyclohexene and other carbon number 3 Cycloalkenyl group of ~18, decyloxy, ethoxy, positive two and * latex recorded JE propionyl, isopropoxy, n-butoxy, TF988407 92 201037041 second butoxy, third butoxy N-pentyloxy a linear or branched alkoxy group having a carbon number of 1 to 18, such as a third pentyloxy group, a n-hexyloxy group, a n-heptyloxy group, a n-octyloxy group or a third octyloxy group; a thiol group; an ethylthio group; , n-propylthio, isopropylthio, n-butylthio, second butylthio, tert-butylthio, n-pentylthio, tert-pentylthio, n-hexylthio, n-heptylthio, n-octyl a straight-chain or branched-chain sulfur-burning group having a carbon number of 丨18 or the like such as a thio group or a third octylthio group; a phenyl group, a fluorenylphenyl group, a diphenylene group, a stilbene group, etc., which may have a carbon number of 6 to 18 An alkyl group substituted with an alkyl group; an aralkyl group having a carbon number of 7 to 18 such as a benzyl group; a linear or branched olefin having a carbon number of 2 to 18 such as a vinyloxy group, a propyleneoxy group or a hexenyloxy group; a linear or branched olefinyl group having 2 to 18 carbon atoms such as an ethylenethio group, an acrylthio group or a hexenylthio group; a fluorenyl group represented by a_c〇Rn; a group; a group represented by -0C0R18 Alkoxy; amino group represented by _19|^2; an amidino group represented by -NHC0R21; a carbamate group represented by -NHCOOR22; an amine oxime represented by -CONR23R24 Carboxyl group; represented by -S (amine represented by MR26R27) Sulfhydryl; a phthalate group represented by - ^^ ;; 2-°-septyl, 2-pyridyl, furyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, a saturated or unsaturated aromatic heterocyclic group such as a phenyl group, an oxazolidinyl group or a tetrahydrothiophene group; a trisyl decyl group such as a trimethyl fluorenyl group; and the like, wherein R to R are each independently represented. a hydrogen atom, a substituted alkyl group, a substituted alkano group, a substituted alkylcarbonyloxy group, a substituted alkenyl group, a substituted aryl group, or a substituted aralkyl group The positional relationship is not particularly limited. In the case of having a plurality of substituents, the TF988407 93 201037041 may be the same or different. In the above, a plurality of substituents may be bonded to each other to form a ring, which may be a saturated or unsaturated aromatic hydrocarbon ring or an aromatic heterocyclic ring, and the substituent may have a substituent in the ring, and the substituent may be further formed. ring. In the formula (melon), R3~ is independently selected as a hydrogen atom or selected from the above group Z, and in the substituent group Z, a methyl group or an ethyl group which may have a substituent is preferable. An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms such as a substituent group, a heteroaryl group having a carbon number of 20 such as a pyridyl group having a substituent, and a carbon number 7 having a substituent An aralkyl group of -18, which may be a substituted trialkylsulfanyl group; particularly preferably an alkyl group. Further, as a substituent which the X in the above formula (I) may have (the benzene ring X1 in the formula (i) and the ring X2 condensed therewith may be preferred), The above preferred R3 to R9 are the same. The substituent which R1 may have is preferably R19 and R2 represented by the amine group and the radical '. Preferably, it may be a substituted decyl group which may be substituted with a methoxy group. As described above, it is also effective in improving the adhesion of the composition. Therefore, it is preferably an amine group represented by _nri9r2Q such as Ν-acetyl group-oxime-acetoxyamine group. Among the compounds represented by the formula (1) of the present invention, the compound represented by the following formula (Π) is most preferred. TF988407 94 201037041化22
式中,1^表示碳數1〜3之烷基、或者以下述式(Ha)所表 示之基。 [化 23] Ο XH2 c'h (Ha) ‘102 .101-In the formula, 1^ represents an alkyl group having 1 to 3 carbon atoms or a group represented by the following formula (Ha). [Chem. 23] Ο XH2 c'h (Ha) ‘102 .101-
R,… R (式中,R1{)1及R1()2分別獨立表示氫原子、苯基或者N-乙醯 基-N-乙醯氧基胺基。) ❹ 尺23表示碳數2〜4之烷醯基,Xa表示氮原子可經碳數1〜4 之烷基取代的2價咔唑基。Ya表示可經烷基取代之苯基、或 者可經咮啉基取代之萘基。] 以下例示作為本發明之光聚合起始劑之最佳肟酯系化合 物的具體例,但本發明所使用之光聚合起始劑,並不限定於 以下任何具體例。再者,以下Me表示曱基。 TF988407 95 201037041 [化 24]R, ... R (wherein R1{)1 and R1()2 each independently represent a hydrogen atom, a phenyl group or an N-ethinyl-N-acetoxyamino group. ❹ 23 represents a fluorenyl group having 2 to 4 carbon atoms, and Xa represents a divalent carbazolyl group in which a nitrogen atom may be substituted with an alkyl group having 1 to 4 carbon atoms. Ya represents a phenyl group which may be substituted by an alkyl group or a naphthyl group which may be substituted with a porphyrin group. Specific examples of the preferred oxime ester-based compound which is the photopolymerization initiator of the present invention are exemplified below, but the photopolymerization initiator used in the present invention is not limited to any of the following specific examples. Furthermore, the following Me represents a thiol group. TF988407 95 201037041 [Chem. 24]
TF988407 96 201037041 [化 25]TF988407 96 201037041 [Chem. 25]
ΟΟ
TF988407 97 201037041 [化 26]TF988407 97 201037041 [Chem. 26]
TF988407 98 201037041 [化 27]TF988407 98 201037041 [Chem. 27]
TF988407 99 201037041 [化 28]TF988407 99 201037041 [化 28]
TF988407 100 201037041 [化 29]TF988407 100 201037041 [Chem. 29]
Ο 以上述通式(I )所表示之肟酯系化合物,例如可依照 W02002/100903號公報、W02005/080337號公報、日本專利 特開2006-36750號公報等中記載之方法而合成。 〇 以上述通式(I )所表示之將醋系化合物,可單獨使用1 種,亦可併用2種以上。又,亦可將該等肟酯系化合物(J ^ 與其他光聚合起始劑併用,視情況可藉由併用而期待高敏感 度化。 作為構成光聚合起始系成分之加速劑,例如可使用:N,N_ 二曱胺基苯曱酸乙酯等N,N-二烷基胺基苯曱酸烷基酯,2- 魏基苯m、2-絲苯并辦等具有雜環之M基化合物或 者脂肪族多官能巯基化合物等。 TF988407 101 201037041 該等其他光聚合起始劑或加速劑,可分別單獨使用丨種, 亦可將2種以上混合使用。 若考慮到化合物所產生之自由基的種類,則較佳為併用複 數種光聚合起始劑,例如可舉出:以上述通式(I )所表示之 蔣酉曰系化δ物與I乙目時生物、α _胺基烧基苯_系化合 物、或者制_衍生物之組合。在此情形下,作為苯乙酮街 生物’例如較佳為2_f H、[4_(曱硫基)苯基卜卩―味琳基 丙烷-1-酮,作為〇_胺基烷基苯酮系化合物,較佳為2一二 甲胺基-2-(4-曱基—节基)+(4—味琳_4_基_苯基)丁燒+ 酮2苄基2-二甲胺基_丨_(4_咮啉基苯基)丁酮_丨;作為噻 °頓晒衍生物’較佳為噻噸酮、2, 4-二乙基噻噸酮等。 上述光聚合起始系成分之調配比例(即,光聚合起始劑與 加速劑之合計量),係在本發明彩色濾光片用著色組成物的 總固形分中,通常為〇. 1〜40重量%,較佳為0. 5〜30重量%。 右该调配比例顯著地低,則會導致對曝光光線之敏感度下 降’反之若該調配比例顯著地高,則未曝光部分對顯影液之 &解性下降’並引起顯影不良。 為了提高感應敏感度,視需要可於光聚合起始系成分中調 配對應於圖像曝光光源之波長的增感色素。作為該等增感色 素’可舉出:日本專利特開平4-221958號公報、特開平 4-219756號公報中記載之二笨并哌喃色素,日本專利特開 平3-239703號公報、特開平5-289335號公報中記載之具有 TF988407 102 201037041 雜環之香豆素色素,日本專利特開平3-239703號公報、特 開平5-289335號公報中記載之3-酮基香豆素 (3-ketocoumarin)化合物,日本專利特開平6-19240號公報 中記載之σ比咯亞甲基(pyrromethene)色素;其他可舉出:曰 ·, 本專利特開昭47-2528號公報、特開昭54-155292號公報、 特公昭45-373Ή號公報、特開昭48-84183號公報、特開昭 52-112681號公報、特開昭58-15503號公報、特開昭 Ο 60—88005號公報、特開昭59-56403號公報、特開平2一69 號公報、特開昭57-168088號公報、特開平5-107761號公 報、特開平5-210240號公報、特開平4-288818號公報中記 載之具有二烧基胺基笨骨架之色素等。 . 該等增敏色素中之較佳者,係含有胺基之增敏色素,更佳 者係同一分子内具有胺基及苯基之化合物。特佳者係例如 4,4 -二曱胺基二苯基酮、4,4,_二乙胺基二苯基酮、2_胺基 ❹一笨基_、4-細基一苯基_、4, 4’ _二胺基二笨基酮、3, 3, -二胺基二苯基酮、3,4-二胺基二苯基酮等二苯基酮系化合 物,2-(對一甲胺基苯基)苯并噚唑、2_(對二乙胺基苯基) 苯并噚唑、2-(對二甲胺基苯基)苯并[4,5]苯并噚唑、2_(對 一曱胺基苯基)苯并[6, 7]苯并气嗤、2, 5-雙(對二乙胺基苯 •基)1,3,4-噚唑、2-(對二曱胺基苯基)苯并噻唑、2_(對二乙 胺基苯基)苯并噻唑、對二曱胺基苯基)苯并咪唑、2_(對 二乙胺基苯基)笨并料、2,5_雙(對二乙胺基笨基)L3,4_ TF988407 201037041 嘆二唾、(對二甲胺基苯基)β比咬、(對二乙胺基苯基)π比咬、 (對二甲胺基苯基)喹啉、(對二乙胺基苯基)喹啉、(對二曱 胺基苯基)嘧啶、(對二乙胺基苯基)嘧啶等含有對二烷基胺 基苯基之化合物等。該等中之最佳者係4, 4,-二烷基胺基二 苯基酮。 又’增敏色素亦是可單獨使用1種,亦可將2種以上混合 使用。 本發明著色組成物中所占之增敏色素之調配率,係在著色 組成物總固形分中通常為0重量%以上,較佳為0.2重量% 以上’更佳為〇. 5重量%以上,又,通常為20重量%以下’ 較佳為15重量%以下’更佳為1〇重量%以下之範圍。 [2-3-2]熱聚合起始劑 作為本發明著色組成物中可含有之熱聚合起始劑之具體 例,可舉出.偶氮系化合物、有機過氧化物及過氧化氫等。 該等之中,適合使用偶氮系化合物。 作為偶氮系化合物,可舉出:2, 2, _偶氮雙異丁腈、2, 2’ -偶氮雙(2-甲基丁腈)、1,;[,_偶氮雙(環己烯一卜甲腈)、2, 2’ -偶氮雙(2,4-一曱基戊猜)、ι_[(ι_氰基-1 —甲基乙基)偶氮] 曱醯胺(2-(胺曱醯基偶氮)異丁腈)、2,2_偶氮雙丨2-曱基 邛-[1,1-雙(羥曱基)-2-羥乙基]丙醯胺}、2,2,-偶氮雙 [Ν-(2-丙烯基)-2-曱基丙醯胺]、2,2’_偶氮雙[Ν-(2-丙烯 基)-2-乙基丙醯胺]、2, 2,_偶氮雙[Ν-丁基-2-曱基丙醯 TF988407 104 201037041肟 The oxime ester compound represented by the above formula (I) can be synthesized, for example, according to the method described in WO2002/100903, WO2005/080337, and JP-A-2006-36750.醋 The vinegar-based compound represented by the above formula (I) may be used alone or in combination of two or more. Further, the above-mentioned oxime ester-based compound (J^ may be used in combination with other photopolymerization initiators, and may be used in combination as needed, and high sensitivity is expected. As an accelerator which constitutes a photopolymerization initiator component, for example, Use: N,N-diaminoaminobenzoic acid ethyl ester and other N,N-dialkylaminophenyl benzoic acid alkyl ester, 2- Weilkyl benzene m, 2-filament benzoic acid, etc. a compound or an aliphatic polyfunctional sulfhydryl compound, etc. TF988407 101 201037041 These other photopolymerization initiators or accelerators may be used singly or in combination of two or more. The type of the base is preferably a combination of a plurality of photopolymerization initiators, and examples thereof include the oxime-derived δ compound represented by the above formula (I), and the I-mesh organism, α-amino group. a combination of a benzoyl-based compound or a derivative thereof. In this case, as the acetophenone street organism, for example, preferably 2_f H, [4_(indolylthio)phenylpyrazine-------- 1-one, as a hydrazine-aminoalkylphenone compound, preferably 2-dimethylamino-2-(4-indolyl) Base) + (4 - Wei Lin _4_ _ phenyl) butadiene + ketone 2 benzyl 2-dimethylamino _ 丨 _ (4 咮 phenyl phenyl) butanone 丨 丨; as a thiophene The sun-derivative derivative is preferably thioxanthone, 2,4-diethylthioxanthone, etc. The proportion of the above-mentioned photopolymerization initiator component (that is, the total amount of the photopolymerization initiator and the accelerator) is In the total solid content of the coloring composition for a color filter of the present invention, it is usually from 1 to 40% by weight, preferably from 0.5 to 30% by weight. The ratio of the right distribution is remarkably low, which may result in The sensitivity of the exposure light is decreased. On the contrary, if the ratio is significantly high, the unexposed portion is degraded to the developing solution and causes poor development. In order to improve the sensitivity, the photopolymerization initiation system may be used as needed. A sensitizing dye corresponding to the wavelength of the image-exposure light source is blended in the composition. The sensitizing dyes are described in the Japanese Patent Application Laid-Open No. Hei-4-221958, No. Hei-4-219756. In the case of the TF988407 102, it is described in Japanese Laid-Open Patent Publication No. Hei 3-239703 In the case of the 3-ketocoumarin compound described in Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. The σ-pyrromethene dye described in the Japanese Patent Publication No. pp. 47-2528, JP-A-54-155292, and JP-A-45-373 Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. In the case of the dialkyl group-containing stupid skeleton described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. Pigments, etc. The preferred one of the sensitizing dyes is an amine group-containing sensitizing dye, and more preferably a compound having an amine group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4-diaminodiphenyl ketone, 4,4,diethylaminodiphenyl ketone, 2-amino fluorene-phenylene, 4-furyl-phenyl _ a diphenyl ketone compound such as 4, 4'-diaminodiphenyl ketone, 3,3,-diaminodiphenyl ketone or 3,4-diaminodiphenyl ketone, 2-(pair Monomethylphenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2_(p-monoaminophenyl)benzo[6,7]benzoindole, 2,5-bis(p-diethylaminophenyl) 1,3,4-carbazole, 2-(pair Diammonium phenyl)benzothiazole, 2-(p-diethylaminophenyl)benzothiazole, p-diamidinophenyl)benzimidazole, 2-(p-diethylaminophenyl) cumene , 2,5_bis (p-diethylamino), L3,4_ TF988407 201037041 sigh, (p-dimethylaminophenyl) β specific bite, (p-diethylaminophenyl) π ratio bite, (p-Dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-diaminophenyl)pyrimidine, (p-diethylaminophenyl)pyrimidine, etc. containing p-dioxane Aminophenyl compound . The best of these is 4,4,-dialkylaminodiphenyl ketone. Further, the sensitizing dye may be used singly or in combination of two or more. The blending ratio of the sensitizing dye in the colored composition of the present invention is usually 0% by weight or more, preferably 0.2% by weight or more, more preferably 5% by weight or more, based on the total solid content of the colored composition. Further, it is usually 20% by weight or less, preferably 15% by weight or less, more preferably 1% by weight or less. [2-3-2] Thermal polymerization initiator The specific examples of the thermal polymerization initiator which may be contained in the colored composition of the present invention include an azo compound, an organic peroxide, and hydrogen peroxide. Among these, an azo compound is suitably used. Examples of the azo-based compound include 2, 2, azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1, and [,_azo double (ring). Hexene-p-carbonitrile), 2, 2'-azobis(2,4-mercaptopurine), ι_[(ι-cyano-1-methylethyl)azo]guanamine 2-(Aminoguanidinoazo)isobutyronitrile), 2,2-azobisindole-2-indenyl-[1,1-bis(hydroxyindenyl)-2-hydroxyethyl]propanamide }, 2,2,-azobis[Ν-(2-propenyl)-2-mercaptopropionamide], 2,2'-azobis[Ν-(2-propenyl)-2-ethyl Propionamide], 2, 2, azobis[Ν-butyl-2-mercaptopropyl TF988407 104 201037041
胺]、2, 2’-偶氮雙(N_環已 (二甲基I甲基丙_)、2^Λ基㈣胺)、2,2,'偶氮雙 醋)、2, 2,-偶氮雙(2, 4, 4 :氮:(f甲基Ι甲基丙酸 2,2,-偶氮雙異丁腈、2,2,:;^#’該#之中較佳為 作為有機過氧化物,可舉出乳雙(2,4;^基戍腈)等。 三丁基、過氧化氫^^過祕本甲醯、過乳化二第 異丁…氧:::r:n舉出:過氧化二 辦癸酸異丙本酯(cumyl per〇Xyneodecanoate)、過氧化二碳酸二正丙酷、過氧化二 碳酸二異丙醋、過氧化二碳酸二第二丁醋、過氧化新癸酸 -1,1’ 3, 3-四曱基丁酯、過氧化二碳酸二(4-第三丁基環己基) 酯、過氧化新癸酸-1-環己基〜卜曱基乙酯、過氧化二碳酸二 (2-乙氧基乙基)醋、過氧化二碳酸二(2_乙基己基)酿、過氧 化新癸酸第三己醋、過氧化二碳酸二甲氧基丁隨、過氧化新 癸酸第三丁酯、過氧化特戊酸第三己酯、過氧化特戊酸第三Amine], 2, 2'-azobis (N-cyclohexyl (dimethyl Imethylpropan), 2^ fluorenyl (tetra)amine), 2,2, 'azobisacetic acid), 2, 2, - azobis (2, 4, 4: nitrogen: (f methyl Ι methyl propionic acid 2, 2, - azobisisobutyronitrile, 2, 2, :; ^ #' Examples of the organic peroxide include bis(2,4; carbonitrile), etc. Tributyl, hydrogen peroxide, ^^, and emulsified diterpene, oxygen:::r :n cite: cumyl per〇Xyneodecanoate, cumyl peroxydicarbonate, diisopropyl acrylate, diacetate, second vinegar, Peroxy neodecanoic acid-1,1' 3,3-tetradecylbutyl ester, di(4-tert-butylcyclohexyl)peroxydicarbonate, peroxy neodecanoate-1-cyclohexyl~diphenyl Ester, bis(2-ethoxyethyl)peroxydicarbonate, di(2-ethylhexyl)peroxydicarbonate, peroxy neodecanoic acid, third vinegar, dimethoxydicarbonate Butane, peroxidic neodecanoic acid tert-butyl ester, peroxidic pivalic acid third hexyl ester, peroxidic pivalic acid third
丁酉曰、過氧化二(3, 5, 5~三甲基己醯)、過氧化二正辛醯、過 氧化二月桂醯、過氧化二硬脂醯、過氧化2〜乙基己酸 -U’3’3—四甲基丁自旨、2,5_二甲基一2,5-二(2、己基己醯‘ 氧基)己烷、過氧化2-乙基己酸第三己酯、過氧化二(4— 基苯甲醯)、過氧化2-乙基己酸第三丁酯、過氧化二笨曱 酿、過氧化異丁酸第三丁酿、1,1-二(第三丁基過氣二=二 曱基環己烧、1,1-二(第三己基過氧基)-3, 3, 5、三曱義严己 烷、1,1-二(第三己基過氧基)環己烷、1,卜二(第— 〜〗基過 TF988407 105 201037041 氧基)環己烧、2,2~二(4, 4-二(第三丁基過氧基)環己基)丙 烧、過氧化異丙基單碳酸第三己醋、過氧化馬來酸第三丁 酉曰、過氧化3, 5, 5~三曱基己酸第三丁g旨、過氧化月桂酸第 二丁酯、2, 5—二甲基—2,5-二(過氧化3-f基苯甲醯基)己 院、過氧化異丙基單碳酸第三丁醋、過氧化2_乙基己基單 碳酸第三丁®1、過氧化苯曱酸第三己酉旨、2, 5-二曱基-2, 5-一(笨曱酿過氧基)己烷、過氧化乙酸第三丁酯、2, 2_二(第 三丁基過氧基)丁烷、過氧化苯甲酸第三丁酯、4, 4-二(第三 丁基過氧基)戊酸正丁 g旨、二(2_第三丁基過氧基異丙基) 本、過氧化二異丙苯、過氧化二第三己基、2, 5-二甲基_2, 5- 二(第三丁基過氧基)己烧、過氧化二第三丁基、過氧化复對 薄荷烧、2’5-二甲基—2,5_二(第三丁基過氧基)己块一3、過 ^化氣二異丙苯、過氧化氯l U,3-四甲基丁基、過氧化 =丙苯、過氧化氫第三丁基、過氧化第三丁基三甲基石夕炫 基、2’3-二甲基_2, 3_二苯基 盘I 垸、過巩化二(3~f基苯甲醯) 入物等。 显)从及過氧化二苯甲醯之混 …再者’[2-3]]項中所述之光聚合起始射 胺基烷絲料化合轉料 ' 此,作為…、聚合起始劑之作用者。因 此作為熱聚合起始劑,亦可 而舉出例中所選擇的化合物。乍為光聚合起始劑之例 該等熱聚合起始劑類可單獨 之用1種’亦可併用2種以上。 TF988407 106 201037041 若著色樹脂組成物中之熱聚合起始劑類之比例過少,則膜 硬化不充分,從而作為彩色遽光片之耐久性有時不足。若迅 多則熱收縮之程度變大,從而有於熱硬化後產生龜裂、裂縫 之虞。又,可見到保存穩定性下降之傾向。因此,熱聚合起 始劑類在本發明著色樹脂組成物之總固形分中的含有比 例,較佳為0〜30重量%,特佳為〇〜2〇重量%之範圍。 [2-2-4]界面活性劑 〇 作為界面活性劑,可使用陰離子系、陽離子系、非離子系 兩性界面活性劑等各種界面活性劑,但就對各特性造成不戾 影響的可祕較低而言,難為使用_子系界面活性劑< 作為界面活性狀濃度·,仙對於總組成物量,通常為 0. 001重以上,較佳為0 005重量%以上,更佳為〇 〇 重量%以上,最佳為0.03重量%以上,又,通常為1〇重量5 以下,較佳為1重量%以下,更較佳為Q 5重量%以下,最卷 為0. 3重量%以下之範圍。 [2-2-5]熱聚合抑制劑 作為熱聚合抑制劑,例如可使用:對苯二紛 :、鄰笨三齡、鄰笨二盼、2’6-第三丁基_對曱紛、二: „制劑之調配量係相對於組成物之總固形分,較 土…、重量%以上、3重量%以下之範圍。 [2-2-6]塑化劑 作為塑化劑,例如可使用:鄰苯二曱酸二辛醋、鄰苯二甲 TF988407 107 201037041 酸二(十二炫*基)s旨、二乙二醇一辛酸醋、鄰苯二曱酸二曱基 乙二酯(dimethylglycol phthalate)、磷酸三曱苯酯、己二 酸二辛酯、癸二酸二丁酯、三乙酸甘油酯等。該等塑化劑之 調配量係相對於組成物之總固形分,較佳為通常1 〇重量% 以下之範圍。 [3]著色組成物之製備 繼而,對製備本發明著色組成物之方法加以說明。 如前所述’本發明之彩色渡光片用著色組成物,可藉由向 預先製備之顏料分散液中混合入其他成分而製備,又,可將 全部成分同喊依纽合。町,以㈣前者方法進行製備 之情形為例進行說明,但並不限定於此。 又’本發明之彩色濾、光片用著色組成物,根據所應用之製 程,可為光硬化性(光聚合性)亦可為熱聚合性。以下,以係 光聚合性組成物(以下將其稱為「光阻劑」)之情形為例進行 說明,但本發明並不限定於此。 首先,分別秤取各特定量之顏料、分散劑及溶劑 ,於分散 處理步驟中使㈣分散而製備顏料分散液。於此分散處理步 驟中,可使用:漆料調節機(Paint Conditi贿)、砂磨機 (sandgnnder) '球磨機、幸昆磨機、石磨機、喷射磨機⑽ mill)、均質機等。藉由進行該分散處理而將色材微粒化, 因此可使者色組成物之塗佈特性提昇,並使製品之彩色遽光 片中之像素的穿透率提昇。 TF988407 108 201037041 在對顏料進行分散處理時,如上所述,較 散樹脂或分散助劑等。 Α適虽併用分 在使用妙磨機進行分散處理的情形下 至數咖直㈣朗珠或者氧德珠。進行分2使用0] 度,通常奴為π以上,較佳為室溫以上,又It之溫 為歌以下,較佳為8。。。以下之範圍。再者…通吊設定 Ο Ο 適當時間係因顏料分散液的细成以及砂磨機二:間之 而不同’因此必須進行適當調整。的大小等 向藉由上述分散處理而獲得之顏料分散液中混八 劑、聚合性單體,視情況進—步混合人黏合劑㈣1入溶 溶液,藉此獲得一。: :各步驟中’會有微細的雜物現入,因此較佳為:合 等對所得顏料分散液進行過濾處理。 °濾盗 [4 ]彩色遽光片之製造 繼而,對本發明之彩色滤光片加以說明。 本發明之彩色渡光片之特徵為:於 色組成物而形成之像素。 、土 八 用上述著 [4-1]透明基板(支持體) 作為彩色絲《之透明基板,若為透明且具 度,則對其材該無特職定。料㈣ 對笨二甲酸乙二醋等聚―聚—等= TF988407 109 201037041 =月曰聚石厌酸醋、聚甲基丙烯酸甲醋、聚礙等熱塑性樹脂 製薄月’ %氧樹月旨、不飽和聚酯樹脂、聚(甲基)丙稀酸系樹 月曰等熱硬化性樹脂薄# ;或者各種玻料。該等之_,就耐 熱性之觀點而言,較佳為玻璃或者耐熱性樹脂。 為了改良接者性等表面物性,視t要可對透明基板及黑色 料形成基板實施電暈放電處理、臭氧處理、魏偶合劑或 胺基甲樹料各種樹脂之薄卿成處理等。透明基板 =厚度通常為〇,05 mm以上,較佳為〇 ι _以上,又通 吊為10 mm以下’較佳為7咖以下之範圍。又,在進行各 種樹脂之薄卿成處理的情形下,其膜厚通常為〇 01 _ 以上,較佳為0.05㈣上,又,通常為·爪以下較 佳為5 //m以下之範圍。 [4-2 ]黑色矩陣 ;述透明基板上設置黑色矩陣,進而形成通常為紅色、 、,“以藍色之像素圖像,藉此可製造本發明之彩色遽光片。 =矩陣係利用遮光金屬薄膜或黑色矩陣用感光性著色 “、且成物而形成於透明基板上。作為遮光金屬材料 用金屬鉻’氧化鉻、氮化鉻等鉻化合物,鎳料之合 可為將該等積層為複數層狀者。 ’ =金屬遮光膜通常藉由濺鍍法而形成,在利 "以此合而成之餘刻液對鉻進行侧,對其他材料則 TF988407 110 201037041 使用對應於材料的触㈣進行钮刻,最 型光阻劑_,藉此可形成黑色矩陣。 後用專用剝離劑將 正 先猎由蒸鑛絲鍍法等於透明基板上形成 “專、:屬或者金屬·金屬氧化物之薄膜。繼而,在該薄膜上 形成著色組絲之塗相後,制具有條形、触形、三 形等重複圖案之光罩,對㈣膜進行曝光及顯影,而形成光Ding, diperoxide (3, 5, 5~trimethylhexanide), di-n-octyl peroxide, dilaurin peroxide, distearyl peroxide, 2-ethylhexanoic acid-U '3'3—Tetramethylbutyrate, 2,5-dimethyl- 2,5-di(2, hexylhexanyloxy)hexane, 3-hexyl peroxy 2-ethylhexanoate , bis(4-benzyl benzamidine) peroxide, tert-butyl peroxy 2-ethylhexanoate, second-boiled peroxidation, third butyl peroxybutyrate, 1,1-di (first Tributylperoxy bis = dimercaptocyclohexene, 1,1-di(t-hexylperoxy)-3, 3, 5, triterpene hexane, 1,1-di (third hexyl) Peroxy)cyclohexane, 1,di(n-) group over TF988407 105 201037041 oxy) cyclohexane, 2,2~bis(4,4-di(t-butylperoxy) ring Hexyl), propylene, peroxy isopropyl monocarbonate, third vinegar, peroxidized maleic acid, tributyl sulfonium, peroxy 3, 5, 5~ tridecyl hexanoic acid, third butyl ketone, oxidized lauric acid Second butyl ester, 2,5-dimethyl-2,5-di(3-f-propylbenzhydryl) hexanyl, isopropyl monocarbonate Tributyl vinegar, 2-ethylhexyl monocarbonate, third butyl ketone 1, benzoic acid, hexamethyl phthalate, 2, 5-dimercapto-2, 5- ace Hexane, tert-butyl peroxyacetate, 2,2-di(t-butylperoxy)butane, tert-butyl peroxybenzoate, 4,4-di(t-butylperoxy) Butyl valerate, di(2-tert-butylperoxyisopropyl), dicumyl peroxide, ditributyl peroxide, 2,5-dimethyl-2, 5- bis (tert-butylperoxy) hexanol, dibutyl butyl peroxide, peroxidized complex menthol, 2'5-dimethyl-2,5-di (t-butylperoxy) Base) 3, 3 gas, diisopropylbenzene, chlorine peroxide, U, 3-tetramethylbutyl, peroxybenzene, propylbenzene, hydrogen peroxide, tert-butyl peroxide, tert-butyl peroxide Trimethyl sulfonate, 2'3-dimethyl-2, 3_diphenyl disk I 垸, over-clearized di(3~f-based benzamidine), etc. Mixture of formazan... In addition to the photopolymerization starting from the [[2-3]] item, the amine alkylate compound is converted as a polymerization initiator. With those. Therefore, as the thermal polymerization initiator, the compound selected in the examples may also be mentioned.乍 is a photopolymerization initiator. These thermal polymerization initiators may be used alone or in combination of two or more. TF988407 106 201037041 If the ratio of the thermal polymerization initiator in the colored resin composition is too small, the film hardening is insufficient, and the durability as a color calender sheet may be insufficient. If it is rapid, the degree of heat shrinkage becomes large, which causes cracks and cracks after thermal hardening. Moreover, it is seen that the storage stability tends to decrease. Therefore, the content ratio of the thermal polymerization initiator to the total solid content of the colored resin composition of the present invention is preferably from 0 to 30% by weight, particularly preferably from 〇 to 2% by weight. [2-2-4] Surfactant 〇 As the surfactant, various surfactants such as an anionic, cationic or nonionic amphoteric surfactant can be used, but it is a secret that affects each characteristic. In the case of low level, it is difficult to use the _---------------------------------------------------------- %重量的范围的范围内的范围内的范围内的范围内的范围内的范围内的范围内的范围内的范围内。 . [2-2-5] Thermal polymerization inhibitors, as thermal polymerization inhibitors, for example, can be used: benzodiazepine: o, stupid, three-year-old, 2'6-t-butyl-p- 2: „ The dosage of the preparation is relative to the total solid content of the composition, which is in the range of ..., more than 3% by weight, and 3% by weight or less. [2-2-6] Plasticizer as a plasticizer, for example, can be used : phthalic acid dioctyl vinegar, phthalic acid TF988407 107 201037041 acid di(12 x yl) s, diethylene glycol monocapry vinegar, diamyl ethylene phthalate (dimethylglycol Phthalate), tridecyl phenyl phosphate, dioctyl adipate, dibutyl sebacate, triacetin, etc. The amount of the plasticizer is relative to the total solids of the composition, preferably Usually, the range is 1% by weight or less. [3] Preparation of Colored Composition Next, a method for preparing the colored composition of the present invention will be described. As described above, the coloring composition for a color light-emitting sheet of the present invention can be borrowed. It is prepared by mixing other components into the previously prepared pigment dispersion, and all the components can be combined with the same. The case where the preparation is carried out by the method of the former (4) is described as an example, but the invention is not limited thereto. Further, the coloring composition for a color filter or a light sheet of the present invention may be photocurable (light) depending on the applied process. The polymerizable property may be a thermal polymerization property. Hereinafter, a case where a photopolymerizable composition (hereinafter referred to as a "photoresist") will be described as an example, but the present invention is not limited thereto. First, each specific amount of the pigment, the dispersant, and the solvent are weighed separately, and (4) is dispersed in the dispersion treatment step to prepare a pigment dispersion liquid. In this dispersion treatment step, a paint conditioner (Paint Conditi), a sander (sandgnnder) 'ball mill, a lucky mill, a stone mill, a jet mill (10) mill), a homogenizer, and the like can be used. By performing the dispersion treatment to atomize the color material, the coating property of the color composition can be improved, and the transmittance of the pixel in the color light-emitting sheet of the product can be improved. TF988407 108 201037041 When the pigment is subjected to dispersion treatment, as described above, a resin or a dispersion aid or the like is dispersed. Α 虽 虽 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在The score is 2, and the slave is usually π or higher, preferably at room temperature or higher, and the temperature of It is below the song, preferably 8. . . The following range. Furthermore, the setting is 通 Ο 适当 The appropriate time is due to the fineness of the pigment dispersion and the difference between the sander and the second. Therefore, it is necessary to make appropriate adjustments. The size of the pigment dispersion obtained by the above dispersion treatment is mixed with eight or more polymerizable monomers, and the human binder (4) 1 is mixed as it is into the solution to obtain one. : : In each step, fine impurities are present, so it is preferred to filter the obtained pigment dispersion. ° Filter thief [4] Manufacture of color enamel sheet Next, the color filter of the present invention will be described. The color light-passing sheet of the present invention is characterized by a pixel formed by a color composition. [8] The above-mentioned [4-1] transparent substrate (support) is used as the transparent substrate of the colored yarn. If it is transparent and has a degree, it has no special purpose for its material. (4) For polystyrene diacetate, etc., poly-polymerization, etc. = TF988407 109 201037041 = month 曰 曰 厌 厌 厌 厌 聚 聚 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性 热塑性Unsaturated polyester resin, poly(methyl)acrylic acid tree, such as thermosetting resin thinner; or various glass materials. These are preferably glass or heat resistant resin from the viewpoint of heat resistance. In order to improve the surface properties such as the contact properties, the transparent substrate and the black material-forming substrate may be subjected to a corona discharge treatment, an ozone treatment, a Wei coupling agent, or a thinning treatment of various resins of an amine base tree material. Transparent substrate = thickness is usually 〇, 05 mm or more, preferably 〇 ι _ or more, and hoisted to 10 mm or less ‘preferably 7 Å or less. Further, in the case of performing the thinning treatment of various resins, the film thickness is usually 〇 01 _ or more, preferably 0.05 (four), and is usually preferably in the range of 5 // m or less. [4-2] Black matrix; a black matrix is disposed on the transparent substrate to form a red, and, respectively, "pixel image in blue, whereby the color light-emitting sheet of the present invention can be manufactured. The metal thin film or the black matrix is photosensitively colored and formed on the transparent substrate. As the light-shielding metal material, a chromium compound such as metal chromium chrome oxide or chromium nitride may be used, and the nickel material may be a plurality of layers. ' = metal light-shielding film is usually formed by sputtering method, in the balance of the mixture of the chrome side of the chrome, for other materials TF988407 110 201037041 using the corresponding material touch (four) for the button, The most type photoresist _, whereby a black matrix can be formed. After the special stripping agent is used, the first method of steaming is to form a film of “special, genus or metal·metal oxide on the transparent substrate. Then, after forming the coating phase of the colored silk on the film, a photomask having a repeating pattern of strips, contacts, and three shapes, exposing and developing the (four) film to form light
阻圖像。其後,對該塗佈膜實施㈣處理,從而可形成 矩陣。 "、、 在利用黑色矩陣用感光性著色樹脂組成物的情形下,係使 用含有黑色色材的著色樹脂組成物,而形成黑色矩陣。例 如,使用含有礙黑、石墨、鐵黑、苯胺黑、花青黑、欽黑等 黑色色材之單獨-種或複數種,或者自無機或有機顏料、染 料中所適當選擇的紅色、綠色、藍色等混合而成之黑色色材 的著色組成物,以與後述形成紅色、綠色、藍色像素之方法 同樣之方式,可形成黑色矩陣。 [4_3]像素之形成 像素之形成方法仙所使用著色組成物之種類而不同,如 前所述’此處以使用光聚合性組成物作為著色組成物之情形 為例進行說明。 / 於設置有黑色矩陣之透明基板上塗佈紅色、耗、藍色中 之一顏色的著色組成物,乾燥後於塗佈膜上重疊光罩,介隔 該光罩進行®像曝光、顯影,減要進行熱硬化或光硬化: TF988407 111 201037041 藉此形成像素。對紅色、綠色、g色三種顏色之著色級成物, 分別進行該操作,從而可形成彩色濾光片圖像。 , 本發明之衫色濾光片用著色組成物,可用來製成紅色、綠 色、藍色像素中之至少一種顏色之像素(光阻圖案)形成用= 佈液,如前所述,其中在用作綠色像素形成用材料、特別^ 含邊化鋅㈣顏料之綠色像素形成用材料時,其效果里 表現得最為顯著。 w 衫色濾光片用著色組成物之塗佈,可利用旋塗如叶 法、線棒(wire-bar)塗法、流塗(fl〇w⑽七)法、镇塗=) coat)法、輥塗(r0llC0at)法、嘴、塗(sprayc〇at)法等^行= 其中,右利用模塗法則可大幅減少塗佈液的使用i,並且八 無在利用旋塗法時所附著之霧滴等的影響,進而可抑制異全 產生等’就以上綜合觀點而言屬較佳。 、物 更佳Block the image. Thereafter, the coating film is subjected to (iv) treatment so that a matrix can be formed. ", In the case of using a photosensitive colored resin composition for a black matrix, a colored resin composition containing a black color material is used to form a black matrix. For example, a single type or a plurality of kinds of black color materials containing black, graphite, iron black, aniline black, cyanine black, and black, or red or green, which are appropriately selected from inorganic or organic pigments and dyes, are used. A coloring composition of a black color material obtained by mixing blue or the like can form a black matrix in the same manner as the method of forming red, green, and blue pixels described later. [4_3] Formation of Pixels The method of forming the pixels differs depending on the type of the coloring composition. As described above, the case where the photopolymerizable composition is used as the coloring composition will be described as an example. / Applying a colored composition of one of red, black, and blue to a transparent substrate provided with a black matrix, drying the film, superimposing a mask on the coating film, and interposing the mask to expose the image. Subtractive thermal hardening or photohardening: TF988407 111 201037041 This forms a pixel. This operation is performed on the color-grading products of the three colors of red, green, and g, so that a color filter image can be formed. The coloring composition for the shirt color filter of the present invention can be used to form a pixel (resist pattern) for forming at least one of red, green, and blue pixels, as described above, wherein When it is used as a material for forming a green pixel, and particularly a material for forming a green pixel containing a zinc hydride (tetra) pigment, the effect is most remarkable. w shirt color filter coating with coloring composition, can be used by spin coating such as leaf method, wire-bar coating method, flow coating (fl〇w (10) seven method), smear =) coat) method, Roll coating (r0llC0at) method, nozzle, coating (sprayc〇at) method, etc. = where the right coating method can greatly reduce the use of the coating liquid i, and the fog that is attached when using the spin coating method The influence of the droplets and the like can further suppress the occurrence of heterogeneity, etc., which is preferable from the above comprehensive viewpoint. Better
Mm以下,較佳為1〇 若塗佈膜過厚_轉影,或者難⑽液晶單元化 進行間隙調整。另-方面1塗佈膜過薄則難以提高顏料中 度,而無法顯現所需之顏色。塗佈狀厚度,係以乾操:濃 膜厚計,通常為0.2 /zm以上,較佳為〇5 以上',、彳之 為0.8 yin以上,又,通常為20 u m 以下,更佳為5 /im以下之範圍 [4-4]塗佈膜之乾燥 使用著色組成物於基板上所形成之塗佈膜之乾燥,較佳為 使用加熱板、紅外線(IR)洪相、對流极雜r m · ,、相(convection oven) TF988407 112 201037041 等進行乾燥。通常,在預備乾燥後,進行再加熱而使其乾燥。 預備乾燥之條件,可根據上述溶劑成分之種類、所使用乾 ' 燥機之性能等作適當選擇。乾燥溫度及乾燥時間,可根據溶 ' 劑成分之種類、所使用乾燥機之性能等加以選擇,具體而 言,乾燥溫度通常為40°C以上,較佳為50°C以上,又,通 常為80°C以下,較佳為70°C以下之範圍;乾燥時間通常為 15秒以上,較佳為3 0秒以上,又,通常為5分鐘以下,較 0 佳為3分鐘以下之範圍。 再加熱乾燥之溫度條件,較佳為高於預備乾燥溫度之溫 度,具體而言,通常為50°C以上,較佳為70°C以上,又, 通常為200°C以下,較佳為160°C以下,特佳為130°C以下 • 之範圍。又,乾燥時間雖亦取決於加熱溫度,但通常為10 秒以上,其中較佳為15秒以上,又,通常為10分鐘以下, 其中較佳為5分鐘之範圍。乾燥溫度愈高則對透明基板之接 〇 著性愈提高,但若乾燥溫度過高則黏合劑樹脂發生分解,有 時會誘發熱聚合而產生顯影不良。再者,作為該塗佈膜之乾 燥步驟,可採用不提高溫度而於減壓室内進行乾燥之減壓乾 燥法。 [4-5 ]曝光步驟 曝光步驟係於著色組成物之塗佈膜上重疊負型矩陣圖 案,介隔該光罩圖案照射紫外線或可見光。此時為了防止由 於氧氣所造成之聚合障礙,視需要可於塗佈膜上形成聚乙烯 TF988407 113 201037041 醇層等氧氣阻隔層後再進行曝光。 上述圖像曝光中所使用之光源,並無特別限定。作為光 源,例如可舉出:⑨氣燈、㈣燈、鎢絲燈、高壓水銀燈、 超高壓水銀燈、金屬鹵素燈、切水報燈、低壓水銀燈、碳 弧燈、發光燈等㈣源;或4離子f射、顺YttriumBelow Mm, it is preferably 1 〇 if the coating film is too thick _transfer, or difficult (10) liquid crystal unitization to perform gap adjustment. On the other hand, if the coating film is too thin, it is difficult to increase the degree of the pigment, and the desired color cannot be expressed. The thickness of the coating is usually 0.2 / zm or more, preferably 〇 5 or more, and 彳 is 0.8 yin or more, and usually 20 um or less, more preferably 5 /im below the range [4-4] Drying of the coating film Using the coating film formed on the substrate by the coloring composition, it is preferred to use a hot plate, an infrared (IR) flood phase, and a convection pole rm. , convection oven TF988407 112 201037041, etc. to dry. Usually, after preliminary drying, it is reheated and dried. The conditions for preliminary drying can be appropriately selected depending on the type of the solvent component and the performance of the dry dryer used. The drying temperature and the drying time can be selected according to the type of the component to be dissolved, the performance of the dryer to be used, and the like. Specifically, the drying temperature is usually 40 ° C or higher, preferably 50 ° C or higher, and usually, The temperature is 80 ° C or lower, preferably 70 ° C or lower; the drying time is usually 15 seconds or longer, preferably 30 seconds or longer, and usually 5 minutes or shorter, more preferably 0 minutes or less. The temperature condition for reheating and drying is preferably a temperature higher than the preliminary drying temperature. Specifically, it is usually 50 ° C or higher, preferably 70 ° C or higher, and usually 200 ° C or lower, preferably 160. Below °C, it is particularly preferably in the range of 130 ° C or less. Further, although the drying time depends on the heating temperature, it is usually 10 seconds or longer, preferably 15 seconds or longer, and usually 10 minutes or shorter, and preferably 5 minutes or less. The higher the drying temperature, the higher the adhesion to the transparent substrate. However, if the drying temperature is too high, the binder resin is decomposed, and sometimes thermal polymerization is induced to cause development failure. Further, as the drying step of the coating film, a vacuum drying method in which drying is performed in a reduced pressure chamber without increasing the temperature can be employed. [4-5] Exposure step The exposure step is performed by superposing a negative matrix pattern on the coating film of the colored composition, and irradiating the reticle pattern with ultraviolet rays or visible light. At this time, in order to prevent the polymerization barrier due to oxygen, an oxygen barrier layer such as a polyethylene layer TF988407 113 201037041 may be formed on the coating film as needed, and then exposed. The light source used in the above image exposure is not particularly limited. Examples of the light source include a 9-lamp, a (four) lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a water-cut lamp, a low-pressure mercury lamp, a carbon arc lamp, a illuminating lamp, and the like (4) source; or 4 Ion f shot, cis Yttrium
Alumi_Garnet ’脑石權石)雷射、準分子雷射(_ Laser)、£雷射、氦-鎘雷#、半導體雷射等雷射光源等。 在照射使用特定波長光的情形下’亦可利用光學濾光片。 [4-6]顯影步驟 至於本發明之彩色遽光月’係利用上述光源對使用本發明 著色組成物之塗佈膜進行圖像曝光後,使用有機溶劑或者含 界面活㈣丨錄性化合物之水溶Μ彳彡, 上形成圖像而製造。該水溶液中進而可含有㈣溶劑、緩衝 劑、錯合劑、染料或者顏料。 氧化納、氫氧化鉀、氫 、碳酸氫鉀、砍酸鈉、 作為鹼性化合物,例如玎舉出:氫 氧化鐘、碳酸納、碳酸钟、碳酸氫鈉 石夕酸鉀、偏石夕酸納、鱗酸納、磷酸鉀、蛾酸氣納、魏氮卸、 麟,二氫納、魏二氫鉀、氫氧化錢等無機驗性化合物;或 者單.二或三乙醇胺、單.二或三甲胺、單·二或三乙胺、單 或異丙胺、正丁胺、單.二或三異丙醇胺、伸乙亞胺、乙 亞胺、四曱基氫氧化錢(TMAH)、膽驗等有機驗性化合物。 該等驗性化合物可為2種以上之混合物。 TF988407 114 201037041 作為界面活性劑,例如可舉出:聚氧乙烯烷基醚類、聚氧 乙烯烷基芳基醚類、聚氧乙烯烷基酯類、山梨醇酐烷基酯 _ 類、單甘油酯烷基酯類等非離子系界面活性劑;烷基苯磺酸 ' 鹽類、烷基萘磺酸鹽類、烷基硫酸鹽類、烷基磺酸鹽類、磺 基琥珀酸酯鹽類等陰離子性界面活性劑;烷基甜菜鹼類;胺 基酸類等兩性界面活性劑。 作為有機溶劑,例如可舉出:異丙醇、苄醇、乙基賽璐蘇、 ❹ 丁基賽路蘇、苯基賽路蘇、丙二醇、二丙酮醇(diacetone alcohol)等。有機溶劑可單獨使用,亦可與水溶液併用而使 用。 顯影處理之條件並無特別限制,顯影溫度通常為10°C以 - 上,其中較佳為15°C以上,更佳為20°C以上,又,通常為 50°C以下,其中較佳為45°C以下,更佳為40°C以下之範圍。 顯影方法可採用浸潰顯影法、喷霧顯影法、刷子顯影法、超 〇 音波顯影法等任一方法。 [4-7]熱硬化處理 對顯影後之彩色濾光片實施熱硬化處理。此時之熱硬化處 理條件,溫度通常在100°C以上、較佳為150°C以上,又, 通常為280°C以下、較佳為250°C以下之範圍内選擇,時間 '在5分鐘以上、60分鐘以下之範圍内選擇。經過該等一系 列步驟,而完成單色之圖案化圖像形成。依序反覆進行該步 驟,將黑色、紅色、綠色、藍色圖案化,而形成彩色濾光片。 TF988407 115 201037041 再者,該等四色之圖案化之順序,並不限定於上述順序。 再者,本發明之彩色濾光片係除上述製造方法外,亦可藉 由(1)將含有聚醯亞胺系樹脂作為黏合劑樹脂之著色組成物 塗佈於基板上,再利用蝕刻法形成像素之方法來製造。又, 可舉出:(2)使用本發明之著色組成物作為著色墨水,利用 印刷機於透明基板上直接形成像素圖像之方法,或(幻使用 本發明之著色組成物作為電鍍液,使基板浸潰於該電鍍液 中,在形成特定圖案的IT0電極上析出著色膜之方法等。進 I”’可舉出:(4)將塗佈有夬發明惹色組成物之薄膜貼附於 蘧明基板上再將其剝離,進行圖像⑭光、顯影,形成像素^ 像之方法;或(5)使用本發明之著色組成物作為著色油墨, 利用噴墨列印機形成像素圖像之方法等。彩色濾光片之製造 奢法係根據彩色滤光片用著色組成物之組成,採用適合其之 方法。 1 [4-8]透明電極之形成 本發明之彩色濾光片,係在原有狀態下於像素上形成ΙΤ0 等透明電極,而用作有機EL顯示器、液晶顯示裝置等零件 的部分,但為了提高表面平滑性或耐久性,視需要亦可於 像素上設置聚醯胺、聚醯亞胺等表塗層。又,在平面配向型 驅動方式(IPS模式)等用途中,亦有其中一部分不形成透明 電極的情形。 [5]液晶顯示裝置(面板) TF988407 116 201037041 繼而,就本發明液晶顯示裝置(面板)之製造法加以說明。 至於本發明之液晶顯示裝置,通常於上述本發明之彩色遽光 片上形成配向膜,再將間隔件散布於該配⑽上,然後與對 肖基板相貼合而形麵晶單元,再將液晶 .晶單元中,並與對向電極接線而完成。配向膜較佳斤為= 胺等樹脂膜。配向膜之形成通常採用凹版印刷法及/或柔版 印刷法,將配向膜之厚度設為數1〇nm。利用熱燒成進行配 〇向叙硬彳b處理後’U由紫外線騎或使用研磨布之處理進 仃表面處理,加工成可調整液晶之斜度的表面狀態。 間件可使用與對向基板的間隙(gap)相對應之尺寸者, 通常較佳為2〜8 _者。亦可湘光微影法於彩色滤光片 基板上形成透明樹脂膜的感光性間隔件(ps, spacer) ’將其代替間隔件而活用。作為對向基板,通常可Alumi_Garnet 'brain stone') laser, excimer laser (_ Laser), £ laser, 氦-cadmium mine #, semiconductor laser and other laser sources. An optical filter can also be utilized in the case where illumination is performed using light of a specific wavelength. [4-6] Development step to the color light-emitting moon of the present invention, after imagewise exposure of a coating film using the coloring composition of the present invention by using the above-mentioned light source, using an organic solvent or an interface-containing living compound (IV) It is made by water-soluble enamel and formed on the image. The aqueous solution may further contain (iv) a solvent, a buffer, a binder, a dye or a pigment. Oxide, potassium hydroxide, hydrogen, potassium hydrogencarbonate, sodium chopped acid, as a basic compound, for example, hydrazine, sodium carbonate, carbonic acid clock, potassium hydrogencarbonate, potassium sulphate Inorganic compounds such as sodium sulphate, potassium phosphate, molybdenum gas, Weinitrogen, Lin, dihydronaphthalene, dihydrogen potassium, and hydrogen peroxide; or mono- or triethanolamine, mono- or tri-methylamine, Mono-di- or tri-ethylamine, mono- or isopropylamine, n-butylamine, mono- or di-isopropanolamine, ethyleneimine, ethylimine, tetradecyl hydroxide (TMAH), biliary test, etc. Test compound. These test compounds may be a mixture of two or more kinds. TF988407 114 201037041 Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglycerin. Nonionic surfactants such as ester alkyl esters; alkylbenzenesulfonic acid' salts, alkylnaphthalenesulfonates, alkyl sulfates, alkylsulfonates, sulfosuccinates Anionic surfactants such as anionic surfactants; alkyl betaines; amino acids and the like. Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cyproterone, butyl butyl sulfoxide, phenyl siroli, propylene glycol, diacetone alcohol, and the like. The organic solvent may be used singly or in combination with an aqueous solution. The conditions of the development treatment are not particularly limited, and the development temperature is usually 10 ° C or higher, preferably 15 ° C or higher, more preferably 20 ° C or higher, and usually 50 ° C or lower, of which Below 45 ° C, more preferably below 40 ° C. The developing method may be any one of a dipping development method, a spray development method, a brush development method, and an ultrasonic wave development method. [4-7] Thermal hardening treatment The developed color filter is subjected to a heat hardening treatment. In this case, the temperature is usually 100 ° C or higher, preferably 150 ° C or higher, and usually 280 ° C or lower, preferably 250 ° C or lower, and the time is '5 minutes. Select from the above range of 60 minutes or less. Through these series of steps, a monochromatic patterned image formation is completed. This step is repeated in sequence, and black, red, green, and blue are patterned to form a color filter. TF988407 115 201037041 Furthermore, the order of patterning of the four colors is not limited to the above order. Further, in addition to the above-described production method, the color filter of the present invention may be applied to a substrate by using (1) a colored composition containing a polyimide resin as a binder resin, and then using an etching method. A method of forming a pixel to manufacture. Further, (2) a method of directly forming a pixel image on a transparent substrate by using a coloring composition of the present invention as a colored ink, or using a coloring composition of the present invention as a plating solution A method in which a substrate is immersed in the plating solution, and a colored film is deposited on the IT0 electrode forming a specific pattern. The film I ′′ is: (4) the film coated with the enamel-inhibiting composition is attached to the film. The method of peeling off the substrate, and performing image 14 light and development to form a pixel image; or (5) using the color composition of the present invention as a coloring ink, and forming a pixel image by using an ink jet printer Method, etc. The manufacturing method of the color filter is based on the composition of the coloring composition for the color filter, and the method suitable for the method is used. 1 [4-8] Formation of the transparent electrode The color filter of the present invention is in the original In a state where a transparent electrode such as ΙΤ0 is formed on a pixel and used as a part of an organic EL display or a liquid crystal display device, in order to improve surface smoothness or durability, polyamine may be provided on a pixel as needed. Surface coatings such as polyimides. In addition, in the case of planar alignment type driving (IPS mode), some of them do not form transparent electrodes. [5] Liquid crystal display device (panel) TF988407 116 201037041 Then, The manufacturing method of the liquid crystal display device (panel) of the present invention will be described. As for the liquid crystal display device of the present invention, an alignment film is usually formed on the color light-emitting sheet of the present invention, and the spacer is spread on the package (10), and then The surface of the crystal substrate is bonded to the surface of the crystal substrate, and then the liquid crystal unit is connected to the counter electrode. The alignment film is preferably a resin film such as an amine. The alignment film is usually formed by gravure printing. And/or flexographic printing method, the thickness of the alignment film is set to several 〇nm. After the heat is fired, the 〇 〇 叙 叙 叙 ' ' ' U U U U U U U U U U U U U U U U U U U U U U U U U U The surface state of the slope of the liquid crystal can be adjusted. The size of the spacer can be used corresponding to the gap of the opposite substrate, and is usually preferably 2 to 8 _. It can also be used for color filter by Xiangguang lithography. Photo spacer member (ps, spacer) a transparent resin film formed on the substrates' spacer member and to utilize it in place. As a counter substrate, usually
特佳為 TFT(thin film transistor,薄祺 隙’因液晶顯示裝置之用途而不同, /zm以下之範圍内選擇。與對向基板 與對向基板貼合之間隙 通常在2 /zm以上、8 μ 加以密封。藉由UV照 液晶單元周邊密封。 貼合後,利用壞氧樹脂等密封材料將液晶注人口以外的部分It is particularly preferable that TFT (thin film transistor) differs depending on the application of the liquid crystal display device, and is selected within a range of /zm or less. The gap between the counter substrate and the counter substrate is usually 2 /zm or more, 8 μ is sealed. The liquid crystal unit is sealed by UV. After bonding, the liquid crystal is injected into the part other than the population by using a sealing material such as a bad oxygen resin.
周邊經密狀液晶單元,在域成©板單㈣,於真空室Peripheral dense liquid crystal cell, in the domain into a single sheet (four), in the vacuum chamber
TF98S407 117 201037041 室内漏氣’從而將液晶注入至液晶單元内。液晶單元内之減 壓度,通常為lxl〇-2pa以上、較佳為1χ1〇_3 %以上又, 通常為lxl〇-7 pa以下、較佳為lxl〇-6 Pa以下之範圍。又, 車又^土為在減壓時對液晶單元進行加溫,加溫溫度通常為 C以上、較佳為5〇 c以上,又,通常為1〇〇。匚以下較佳為 90°C以下之範圍。 減壓時之加溫保持時間通常設為1〇分鐘以上、⑼分鐘以 下之圍’其後浸潰於液晶中。注人有液晶之液晶單元係藉 由使UV硬化樹脂硬化而將液晶注人口密封,完成液晶顯示 裝置(面板)。 液曰曰之種類並無特別限制,為芳香族系、脂肪族系、多環 狀化合物等習知之液晶,且可為溶致型液晶(lyotropicTF98S407 117 201037041 Indoor air leakage' thus injects liquid crystal into the liquid crystal cell. The degree of depressurization in the liquid crystal cell is usually lxl 〇 -2 Pa or more, preferably 1 χ 1 〇 _ 3% or more, and is usually in the range of lxl 〇 -7 Pa or less, preferably lxl 〇 -6 Pa or less. Further, the vehicle is heated to warm the liquid crystal cell during decompression, and the heating temperature is usually C or more, preferably 5 〇 c or more, and is usually 1 Torr. The following is preferably in the range of 90 ° C or less. The heating holding time at the time of pressure reduction is usually set to 1 minute or more and (9 minutes or less) and then immersed in the liquid crystal. In the liquid crystal cell in which the liquid crystal is applied, the liquid crystal cell is sealed by curing the UV hardening resin, and the liquid crystal display device (panel) is completed. The type of the liquid helium is not particularly limited, and is a conventional liquid crystal such as an aromatic system, an aliphatic system or a polycyclic compound, and may be a lyotropic liquid crystal (lyotropic).
UqUld Crystal)、熱致型液晶(thermotropic liquid crystal)等之任一種。於熱致型液晶中,已知有向列型液晶 (nematic liquid crystal)、層列型液晶(smectic liquid crystal)及膽固醇狀液晶(ch〇lesteric iiquicj crystal) 等,可為任一者。 [6]有機EL顯示器 在使用本發明之彩色滅光片製作有機EL顯示器的情形 下,例如,如圖1所示,首先製作於透明支持基板10上形 成有樹脂黑色矩陣(未圖 示)而成之本發明之彩色遽光片’上 述祕脂黑色矩陣設置於像素2〇(其中’像素2〇中之至少一 TF988407 118 201037041 部分係使用本發明之著色組成物而形成者)以及相鄰的像素 20之間,介隔有機保護層3〇及無機氧化膜4〇,將有機發光 體500積層於該彩色濾光片上,藉此可製作有機乩元件。 作為有機發光體500之積層方法,可舉出:於彩色濾光片 上面逐次形成透明陽極5〇、電洞注入層51、電洞傳輪層52、 發光層53、電子注入層54、及陰極55之方法;或將形成於 其他基板上之有機發光體50()貼合於無機氧化骐4〇上之方 〇 法等。使用如此製作之有機EL元件100,藉由例如「有機 EL顯示器」(0hm公司,2〇〇4年8月2〇日發行,時任靜士、 安達千波矢、村田英幸著)所記載之方法等,可製作有機乩 • 顯示器。 再者,本發明之彩色濾光片既可應用於被動驅動方式之有 機EL顯示器,亦可應用於主動驅動方式之有機EL顯示器。 [實施例] ° Ο 繼而,舉出製造例、實施例及比較例更具體地說明本發 明,但只要不超過其要點則本發明並不限定於以下實施例。 再者,實施例1〜4及比較例1〜2係使用C. I.色素綠36 . 作為顏料之例,實施例5〜36及比較例3〜7係使用溴化鋅 酞菁顏料作為顏料之例’實施例37〜43係使用c.丨·色素紅 254等紅色顏料作為顏料之例。 該等例中,實施例7〜15及比較例5〜6,係進而使用「針 對含有環氧基之(曱基)丙烯酸酯與其他自由基聚合性單體 TF988407 119 201037041 之共聚物’在該共聚物所具有的環氧基之至少—部分上加成 不飽和-元酸而成之樹脂,或者在藉由該加成反應而產生口的 經基之至少-部分上加成多元酸酐而獲得之驗可溶性樹脂」 (相當於本申請案說明書中之[2+i]樹脂。以下,稱為」 [2-1-1]樹脂)作為黏合劑樹脂之例。 實施例16〜20及比較例7,係進而使用將以上述通式⑺ 所表示化合物料必需料的單體成分騎聚“成之共 聚物、即「(甲基)丙烯酸系樹脂」(相當於本申請案說明書 中之[2+2]樹脂。以下,稱為[2+2]樹脂)作為黏合齊^ 脂之例。 實施例21〜29係進而使用则旨系化合物作為光聚合起始 劑(光聚合起始糸成分)之例。 實施例3 0〜3 6係進而使用芳香族羧酸系化合物之例。 [合成例1 :溴化鋅酜菁之合成] 以鄰苯二曱腈(phthalodinitrile)及氯化辞為原料,製造 鋅駄菁。所獲得鋅酜菁之卜氯萘溶液,在_〜·⑽處 有光吸收。 至於鹵化’係將石黃醯氯3· i重量份、無水氯化铭3· 7重量 份、氯化鈉G. 46重量份、辞酞菁工重量份於机下混合, 再滴加漠4. 4重量份。於如。「τ c rt 1 ^ 別C下反應15小時,其後將反應 混合物投人水中,㈣化辞酞菁粗顏料析出。將該水性渡料 過滤’帛啊之熱水進行清洗,於阶下使其乾燥,而獲 TF988407 120 201037041 得3. 0重量份之經精製之溴化鋅酞菁粗顏料。 向雙腕型捏合機中加人上顧化鋅酞菁粗顏料i重量 份、經粉碎的氣化鈉12重量份、二乙二醇h 8重量份、及 二曱苯0. 09重量份,於70t下混練1〇小時。其後,取出 置於80°C之水1〇〇重量份令,_ i小時後,進行過滤、 熱水清洗、乾燥、粉碎,而獲得溴化鋅酞菁顏料。 根據質量分析之齒素含量分析可知,所獲得之漠化辞駄菁 ΟUqUld Crystal), any of thermotropic liquid crystals, and the like. Among the thermotropic liquid crystals, nematic liquid crystals, smectic liquid crystals, and cholesteric liquid crystals are known, and any of them may be used. [6] In the case of producing an organic EL display using the color extinction film of the present invention, for example, as shown in FIG. 1, first, a resin black matrix (not shown) is formed on the transparent support substrate 10; The colored calender sheet of the present invention is provided in the pixel 2 〇 (wherein at least one of the TF 988 407 118 201037041 portion of the pixel 2 形成 is formed using the color composition of the present invention) and adjacent Between the pixels 20, the organic protective layer 3 and the inorganic oxide film 4 are interposed, and the organic light-emitting body 500 is laminated on the color filter, whereby an organic germanium element can be produced. As a method of laminating the organic light-emitting body 500, a transparent anode 5, a hole injection layer 51, a hole transport layer 52, a light-emitting layer 53, an electron injection layer 54, and a cathode are sequentially formed on the color filter. The method of 55; or the method of bonding the organic light-emitting body 50 () formed on another substrate to the inorganic cerium oxide layer 4 or the like. By using the organic EL device 100 thus produced, for example, "organic EL display" (0hm company, issued on August 2nd, 2nd, 4th, 4th, 4th, 4th, 4th, 4th, 4th, 4th, and 5th) , can make organic 乩 • display. Furthermore, the color filter of the present invention can be applied to both an organic EL display of a passive driving mode and an organic EL display of an active driving mode. [Examples] The present invention will be more specifically described by way of Production Examples, Examples and Comparative Examples. However, the present invention is not limited to the following examples as long as the details are not exceeded. Further, in Examples 1 to 4 and Comparative Examples 1 and 2, CI Pigment Green 36 was used. As examples of the pigments, Examples 5 to 36 and Comparative Examples 3 to 7 were examples in which zinc bromide phthalocyanine pigment was used as a pigment. In Examples 37 to 43, a red pigment such as c. 丨·Pigment Red 254 was used as an example of the pigment. In these examples, Examples 7 to 15 and Comparative Examples 5 to 6 further used "a copolymer of an epoxy group-containing (fluorenyl) acrylate and another radical polymerizable monomer TF988407 119 201037041". a resin obtained by adding at least a part of an epoxy group to an unsaturated-acid acid, or a polybasic acid anhydride obtained by adding a polybasic acid anhydride to at least a portion of a radical formed by the addition reaction. The test "soluble resin" (corresponding to [2+i] resin in the specification of the present application. Hereinafter, it is referred to as "[2-1-1] resin) as an example of a binder resin. In each of Examples 16 to 20 and Comparative Example 7, a monomer obtained by the above-mentioned compound (7) is used as a copolymer, that is, a "(meth)acrylic resin" (equivalent to The [2+2] resin in the specification of the present application, hereinafter, referred to as [2+2] resin) is exemplified as a binder. In the examples 21 to 29, the compound is used as a photopolymerization initiator (photopolymerization initiator component). Example 3 0 to 3 6 Examples of an aromatic carboxylic acid compound were further used. [Synthesis Example 1: Synthesis of zinc bromide phthalocyanine] Zinc phthalocyanine was produced by using phthalodinitrile and chlorination as raw materials. The obtained phthalocyanine solution of zinc phthalocyanine has light absorption at _~·(10). As for the halogenated 'system, the scutellaria sulphate 3 · i parts by weight, anhydrous chlorinated 3.7 parts by weight, sodium chloride G. 46 parts by weight, the phthalocyanine weights are mixed under the machine, and then add the desert 4 . 4 parts by weight. Yu Ru. "τ c rt 1 ^ reacted for 15 hours under C, then the reaction mixture was poured into water, and (4) the crude pigment of phthalocyanine was precipitated. The aqueous mixture was filtered and washed with hot water. It is dried, and TF988407 120 201037041 is obtained, and 3.0 parts by weight of the purified zinc bromide phthalocyanine crude pigment is added. To the double-wrist type kneader, a zinc-based phthalocyanine crude pigment i by weight is added and pulverized. 12 parts by weight of sodium vapor, 8 parts by weight of diethylene glycol, and 0. 09 parts by weight of diphenylbenzene, and kneaded at 70 tons for 1 hour. Thereafter, 1 part by weight of water placed at 80 ° C was taken out. After _ i hours, filtration, hot water washing, drying, and pulverization were carried out to obtain zinc bromide phthalocyanine pigment. According to the analysis of dentin content of mass analysis, the obtained desertified phthalocyanine Ο
顏料係平均組成為ZnPcBruCKPc:酞菁),丨分子中平均含 有14個演原子者。又,用穿透型電子顯微鏡(曰立製作所: 司製造之「H-_麵」)所測定之—絲徑之平均 0. 023 // m。 再者,顏料之平均-次粒徑,係將顏料於氯仿中進行超音 波分散,再將分散液滴加至貼附膠棉膜之網格上,使其乾 燥,藉由穿透型電子顯微鏡(TEM)觀察獲得顏料之—次粒^ 像,根據該像測定一次粒徑,求出單個平均值(平均粒徑)。 [合成例2 :分散劑A’之合成] 二 除不將共聚物中之胺基(二曱胺基)進行四級化以外,依照 曰本專利特開平1-229014號公報之實施例1,合成具有一 級胺基之曱基丙烯酸系A-B嵌段共聚物。 、~ 胺價為121 所獲得共聚物之重量平均分子量Mw為90〇〇, mgKOH/g ’酸價為G mgK〇H/g。又’ B—嵌段中之「側鍵上具 有胺基之重複單元」係以下述式(a)所表示之結構,又,二 TF988407 121 201037041 下述式(b)所表示之重複單元在A-嵌段中之比例為11莫耳 % ° [化 31]The average composition of the pigment system is ZnPcBruCKPc: phthalocyanine, and the average molecular weight of the ruthenium molecule is 14 atoms. Further, the average diameter of the wire diameter was measured by a transmission electron microscope ("H-_face" manufactured by the company), which was 0. 023 // m. Furthermore, the average-sub-particle size of the pigment is obtained by ultrasonically dispersing the pigment in chloroform, and then adding the dispersed droplets to the grid of the attached rubber film, and drying it by a transmission electron microscope. (TEM) observation was carried out to obtain a pigment-subgranular image, and the primary particle diameter was measured from the image to obtain a single average value (average particle diameter). [Synthesis Example 2: Synthesis of Dispersant A'] In addition to the quaternization of the amine group (diammonium group) in the copolymer, in accordance with Example 1 of JP-A-1-229014, A mercaptoacrylic AB block copolymer having a primary amine group is synthesized. The weight average molecular weight Mw of the copolymer obtained at an amine price of 121 was 90 〇〇, and the acid value of mgKOH/g ' was an acid value of G mgK 〇H/g. Further, the "repeating unit having an amine group on the side bond" in the 'B-block" is a structure represented by the following formula (a), and further, TF 988407 121 201037041 The repeating unit represented by the following formula (b) is in A - the ratio in the block is 11 mol% ° [Chem. 31]
(b) 再者,藉由以下方法測定胺價及酸價。 [胺價之測定] 於100 mL燒杯中精確科取入0. 5〜1. 5 g分散劑,用50 mL 乙酸溶解。使用具備pH電極之自動滴定裝置,以0. 1 mol/L 之HCL〇4乙酸溶液對該溶液進行中和滴定。將滴定pH曲線 的拐點作為滴定終點,根據下式求出胺價。 TF988407 122 201037041 胺價[mgKOH/g] = (561xV)/(WxS) (其中’ W為分散劑試料秤取量[g],v為滴定終點之滴定量 [mL],S為分散劑試料之固形分濃度[wt%]。) [合成例3 :分散劑C之合成] t 將重量平均分子量約為5000之聚乙烯亞胺50重量份、n=5 之聚己内酯40重量份、及硬脂酸6重量份、與丙二醇單曱 醚乙酸酯300重量份混合,於氮氣環境中於15〇。〇下攪拌3 ❹小時。如此合成之分散劑C之胺價為54 mgKOH/g,酸價為 10 mgKOH/g。 [合成例4 :黏合劑樹脂d之合成] 準備附有冷卻管之分離式燒瓶作為反應槽 ’加入丙二醇單 ㈣乙酸自旨4GG重量份,進行氮氣置換後,一面㈣一面用 油浴加熱,將反應槽之溫度升溫至9(rc。 另-方面,向單體槽中加入2,2,_[氧基雙(亞甲基)]雙 ° _2_丙酸二曱酯30重量份、甲基丙烯酸60重量份、甲基丙 烯酸環己醋110重量份、過氧化2、乙基己酸第三丁醋5 2 重量份、丙二醇單甲㈣酸S旨4G重量份,向鏈轉移劑槽中 :加入正十二烧基硫醇5.2重量份、丙二醇單甲喊乙酸醋打 重量份’將反應槽之溫度穩定於9〇ΐ,然後自單體槽及鍵 轉移劑槽開始滴加反應物,使之開始聚合…面將溫度保持 於90 C -面分別卩135分鐘進行滴加,滴加結| 6〇分後, 開始升溫使反應槽達到11 〇°C。 TF988407 123 201037041 維持110°C達3小時後,將氣體導入管安裝在可分離式燒 瓶上,開始進行氧氣/氮氣=5/95(v/v)混合氣體之吹泡。繼 而’向反應槽中加入曱基丙烯酸環氧丙酯39. 6重量份、 2, 2’-亞甲基雙(4-曱基-6-第三丁基苯酚)0.4重量份、三乙 胺0. 8重量份,並直接於11 〇°c反應9小時。 冷卻至室溫’獲得藉由GPC法所測定的經聚苯乙婦換算之 重量平均分子量為8000、酸價為1〇1 mgK0H/g之聚合物溶 液。 [合成例5 :黏合劑樹脂E之合成] 準備附有冷卻管之分離式燒瓶作為反應槽,加入丙二醇單 曱醚乙酸酯4〇〇重量份,進行氮氣置換後,一面攪拌一面用 油浴加熱’將反應槽之溫度升溫至9(TC。 另一方面,向單體槽中加入2, 2’-[氧基雙(亞曱基)]雙 -2-丙酸二甲酯3〇重量份、曱基丙烯酸6〇重量份、曱基丙 稀酸节酿110重量份、過氧化2-乙基己酸第三丁酯5.2重 量伤、丙二醇單甲醚乙酸酯40重量份,向鏈轉移劑槽中加 入正十—燒基硫醇5. 2重量份、丙二醇單曱醚乙酸酯27重 ’將反應槽之溫度穩定於9(rc,然後自單體槽及鍵轉 移劑槽開始滴加反應物,使之開始聚合。-面將溫度保持於 9〇 C面分別以135分鐘進行滴加,滴加結束60分後,開 始升溫使反騎相11〇。〇。(b) Further, the amine value and the acid value were determined by the following methods. [Measurement of the amine value] In a 100 mL beaker, accurately take 0. 5~1. 5 g of a dispersant, dissolved in 50 mL of acetic acid. The solution was neutralized and titrated with a 0.1 mol/L HCL® 4 acetic acid solution using an automatic titration apparatus equipped with a pH electrode. The inflection point of the titration pH curve was taken as the end point of the titration, and the amine price was determined according to the following formula. TF988407 122 201037041 Amine value [mgKOH/g] = (561xV) / (WxS) (where 'W is the dispersant sample weigh [g], v is the titration end point [mL], S is the dispersant sample Solid content concentration [wt%].) [Synthesis Example 3: Synthesis of Dispersant C] t 50 parts by weight of polyethyleneimine having a weight average molecular weight of about 5,000, 40 parts by weight of polycaprolactone having n = 5, and 6 parts by weight of stearic acid and 300 parts by weight of propylene glycol monoterpene ether acetate were mixed at 15 Torr in a nitrogen atmosphere. Stir under the armpit for 3 hrs. The dispersant C thus synthesized had an amine value of 54 mgKOH/g and an acid value of 10 mgKOH/g. [Synthesis Example 4: Synthesis of binder resin d] A separation flask equipped with a cooling tube was prepared as a reaction vessel, and propylene glycol mono(tetra)acetic acid was added in an amount of 4 GG by weight, and after nitrogen substitution, one side (4) was heated in an oil bath. The temperature of the reaction vessel was raised to 9 (rc. On the other hand, 30 parts by weight of 2,2,-[oxybis(methylene)]bis- 2 -propionate dicarboxylate was added to the monomer tank, and methyl group was added. 60 parts by weight of acrylic acid, 110 parts by weight of cyclohexyl methacrylate, peroxide 2, 5 2 parts by weight of ethyl hexanoic acid, and 4 parts by weight of propylene glycol monomethyl (tetra) acid, in a chain transfer agent tank: Adding 5.2 parts by weight of n-dodecyl mercaptan, and propylene glycol monomethyl acetate vinegar tow parts by weight, the temperature of the reaction tank is stabilized at 9 Torr, and then the reactants are added dropwise from the monomer tank and the key transfer agent tank. At the beginning of the polymerization, the temperature was maintained at 90 C - the surface was 卩 135 minutes, and the addition was carried out. After 6 minutes, the temperature was raised to bring the reaction tank to 11 ° C. TF988407 123 201037041 Maintaining 110 ° C up to 3 After an hour, install the gas inlet tube on a separable flask and start oxygen/nitrogen = 5/95 (v/v) bubble blowing of the mixed gas. Then adding 'glycidyl methacrylate to the reaction vessel 39. 6 parts by weight, 2, 2'-methylenebis(4-mercapto-6 - butyl phenol) 0.4 parts by weight, triethylamine 0.8 parts by weight, and reacted directly at 11 ° C for 9 hours. Cooled to room temperature 'to obtain polystyrene conversion by GPC method A polymer solution having a weight average molecular weight of 8,000 and an acid value of 1〇1 mgK0H/g. [Synthesis Example 5: Synthesis of binder resin E] A separation flask equipped with a cooling tube was prepared as a reaction tank, and propylene glycol monoterpene was added. 4 parts by weight of ether acetate, after nitrogen substitution, heating with an oil bath while stirring 'The temperature of the reaction vessel was raised to 9 (TC. On the other hand, 2, 2'-[ 3 parts by weight of oxybis(indenyl)]bis-2-propionic acid dimethyl ester, 6 parts by weight of methacrylic acid, 110 parts by weight of mercaptopropionic acid, 2-ethylhexanoic acid peroxide 2重量份,丙丙苯单曱乙乙酯。 3% by weight of the butyl ester, propylene glycol monomethyl ether acetate 40 parts by weight, adding a n-decyl mercaptan to the chain transfer agent tank 5. 2 parts by weight, propylene glycol monoterpene ether acetate 27 weight 'stabilizes the temperature of the reaction tank at 9 (rc, then starts to add the reactants from the monomer tank and the bond transfer agent tank to start the polymerization. The surface is kept at 9 〇C surface for 135 minutes respectively. Adding dropwise, after the end of the addition of 60 minutes, the temperature is raised to make the anti-riding phase 11〇.
維持 1 1 Q L運3小時後,將氣體導入管安裝在分離式燒瓶 TF988407 124 201037041 上,開始進行氧氣/氮氣=5/95(v/v)混合氣體之吹泡。繼 而,向反應槽中加入曱基丙烯酸環氧丙酯39.6重量份、 ' 2, 2’-亞曱基雙(4-曱基-6-第三丁基苯酚)0.4重量份、三乙 ' 胺0.8重量份,並直接於110°C下反應9小時。 冷卻至室溫,獲得藉由GPC法所測定的經聚苯乙烯換算之 重量平均分子量為8000、酸價為103 mgKOH/g之聚合物溶 液。 0 [合成例6 :黏合劑樹脂F之合成] 一面進行氮氣置換一面將丙二醇單曱醚乙酸S旨145重量 份加以攪拌,升溫至120°C。向其中滴加苯乙烯20重量份、 • 甲基丙烯酸環氧丙酯57重量份以及具有三環癸烷骨架之單 - 丙烯酸酯(日立化成公司製造之「FA-513M」)82重量份,進 而於120°C下繼續攪拌2小時。繼而,將反應容器内變更置 換為空氣,向丙烯酸27重量份中投入參(二曱胺基甲基)苯 ❹ 酚0. 7重量份及對苯二酚0. 12重量份,於120°C下連續反 應6小時。其後,加入四氫鄰苯二曱酸酐(THPA)52重量份、 三乙胺0. 7重量份,於120°C下反應3. 5小時。 如此獲得之黏合劑樹脂F之藉由G P C法所測定的經聚苯乙 " 烯換算之重量平均分子量Mw約為15000。 [合成例7 :黏合劑樹脂G之合成] 向反應容器中加入丙二醇單甲醚乙酸酯35重量份、1-曱 氧基-2-丙醇8. 8重量份、偶氮系聚合起始劑(和光純藥公司 TF988407 125 201037041 製造之「V-59」)1. 5重量份,於氮氣環境中升溫至8〇〇c。 以2小時向其中滴加曱基丙烯酸苄酯9· 5重量份、曱基丙 烯酸曱酯6.5重量份、曱基丙烯酸2—羥基乙酯3. 5重量份、 以及曱基丙烯酸10. 7重量份,進而攪拌4小時,而獲得聚 合反應液。 向该t合反應液中添加丙二醇單曱趟乙酸酉旨25 5重量 份、對曱氧基苯酚0. 05重量份、三苯基膦〇. 3重量份,使 其浴解。繼而,滴加丙烯酸(3, 4-環氧基環己基)曱酯17. 5 重量份,於85°C下反應24小時,而獲得側鏈上具有乙烯性 不飽和基之樹脂溶液。 如此獲得之黏合劑樹脂G之藉由G P C法所測定之聚合平均 刀子里,經I本乙稀換算為18 〇 〇 〇。又,藉由中和滴定法所 測定之酸價為50。 又,根據反應前後之酸價可知,丙烯酸(3, 4-環氧基環己 基)曱酯向羧基之導入率為66%。 [合成例8 :黏合劑樹脂η之合成] 將具有三環癸烷骨架之單丙烯酸酯(日立化成公司製造之 「FA-513M」)10重量份、甲基丙烯酸環己酯43. 5重量份、 甲基丙烯酸曱酯3. 0重量份、以及曱基丙烯酸43. 5重量份 溶解於丙二醇單甲醚乙酸酯15〇重量份中’於氮氣環境中加 入偶氮雙異丁腈1. 25重量份,於80°C下反應7小時。 如此獲得之黏合劑樹脂Η之藉由GPC法所測定的經聚苯乙 TF988407 126 201037041 烯換算之重量平均分子量Mw約為7200,酸價為84。 [合成例9 :黏合劑樹脂I之合成] 一面進行氮氣置換一面將丙二醇單甲醚乙酸酯145重量 ' 份加以攪拌,升溫至120°C。向其中滴加苯乙烯10重量份、 曱基丙烯酸環氧丙酯85.2重量份以及具有三環癸烷骨架之 單丙烯酸酯(日立化成公司製造之「FA-513M」)66重量份, 以及以3小時滴加2, 2’ -偶氮雙-2-曱基丁腈9. 00重量份, ❹ 進而於90°C下繼續攪拌2小時。 繼而,將反應容器内變更置換為空氣,向丙烯酸43. 2重 量份中投入參(二曱胺基曱基)苯酚0.7重量份以及對苯二 酚0. 12重量份,於100°C下連續反應12小時。 其後,加入四氫鄰苯二甲酸酐(THPA)56. 2重量份、以及 三乙胺0. 7重量份,於100°C下反應3. 5小時。 如此獲得之黏合劑樹脂I之藉由GPC法所測定的經聚苯乙 ❹ 烯換算之重量平均分子量Mw約為6000,酸價為90mgKOH/g。 [合成例10 :黏合劑樹脂J之合成] 一面進行氮氣置換一面將丙二醇單曱醚乙酸酯145重量 份加以攪拌,升溫至120°C。 向其中滴加曱基丙烯酸苄酯30重量份、曱基丙烯酸環氧 '丙酯85.2重量份以及具有三環癸烷骨架之單丙烯酸酯(日 立化成公司製造之「FA-513M」)46重量份。進而,以3小 時滴加2, 2’ -偶氮雙-2-曱基丁腈7. 47重量份,於90°C下繼 TF988407 127 201037041 續攪拌2小時。 繼而,將反應容器内變更置換為空氣,向丙烯酸43. 2重 量份中投入參(二曱胺基曱基)苯酚0.7重量份以及對苯二 酚0. 12重量份,於100°C下連續反應12小時。其後,加入 四氫鄰苯二曱酸酐(THPA)50. 2重量份、三乙胺0. 7重量份, 於100°C下反應3. 5小時。 如此獲得之黏合劑樹脂之藉由GPC法所測定的經聚苯乙 烯換算之重量平均分子量Mw約為14000,酸價為80 mgKOH/g。 [合成例11 :黏合劑樹脂K之合成] 以與合成例9中所獲得樹脂I相同之方式,將苯乙烯、曱 基丙烯酸環氧丙酯、以及具有三環癸烷骨架之單丙烯酸酯 (曰立化成公司製造之「FA-513M」)進行聚合。 繼而,將反應容器内變更置換為空氣,向丙烯酸43.2重 量份中投入參(二曱胺基曱基)苯酚0.7重量份以及對苯二 酚0. 12重量份,於100°C下連續反應12小時。其後,加入 四氫鄰苯二曱酸酐(THPA)50. 2重量份、三乙胺0.7重量份, 於100°C下反應3. 5小時。 如此獲得之黏合劑樹脂K之藉由G P C法所測定的經聚苯乙 烯換算之重量平均分子量Mw約為8000,酸價為78 mgKOH/g。 [合成例12 :黏合劑樹脂L之合成] 一面進行氮氣置換一面將丙二醇單曱醚乙酸酯145重量 TF988407 128 201037041 伤加以撥拌,升溫至12Qt。向其中滴加苯乙烯Μ重量份、 • f ^烯酸環氧丙@旨115·2重量份、以及具有三環癸烧骨架 之單丙稀酸g旨(日立化成公司製造之「fa_513M」)46重量 伤。繼而’以3小時滴加2, 2’ ~偶氮雙_2_曱基丁腈7. 47重 量份,進而於90¾下繼續攪拌2小時。 繼而’將反應容器内變更置換為空氣,於丙烯酸58. 3重 里伤中投入參(二甲胺基曱基)苯酚〇 7重量份以及對苯二 〇盼〇. 12重里伤,於10〇°C下連續反應12小時。其後’加入 四氣鄰笨二甲酸酐(聰)57. 2重量份、三乙胺0.7重量份, 於100°c下反應3. 5小時》 如此獲得之黏合劑樹脂L之藉由GPC法所測定的經聚苯乙 烯換算之重量平均分子量Mw約為8〇〇〇 ,酸價為1〇〇 mgKOH/g 。 [合成例13 :黏合劑樹脂μ之合成] 〇 以與合成例9中所獲得樹脂I相同之方式,將苯乙稀、曱 基丙烯酸環氧丙酯、以及具有三環癸烷骨架之單丙烯酸酯 (日立化成公司製造之「FA-513M」)進行聚合。 繼而,將反應容器内變更置換為空氣,於丙烯酸2重 量份中投入參(一曱胺基甲基)苯紛〇· 7重量份以及對苯二 酚0. 12重量份,於l〇(Tc下連續反應12小時。其後,加入 號珀酸酐30. 1重量份、三乙胺〇. 7重量份,於1〇〇它下反 應3. 5小時。 TF988407 129 201037041 如此獲得之黏合劑樹㈣之藉由Gpc法所測定的經聚 烯換算之重量平均分子量Mw約為9〇〇〇,酸價為81爪侧厂 [合成例14 :黏合劑樹脂N之合成] g 以與合成例9所獲得樹脂!相同之方式,將笨乙婦、甲笑 丙烯酸環氧丙醋、以及具有三環魏骨架之單丙烯酸西旨(= 立化成公司製L之「FA-513M」)進行聚合。 繼而’將反應容器内變更置換為空氣,於丙烯酸43· 2重 量份中投入參(二甲胺基曱基)笨紛〇 7重量份以及對苯二 酚0· 12重重份’於l〇〇〇c下連續反應12小時。其後,加入 苯偏三甲酸針69.2重量份、三乙胺〇·7重量份,'於⑽。c 下反應3. 5小時。 如此獲得之黏合劑樹脂N之藉由Gpc法所測定的經聚苯乙 稀換算之重量平均分子量黯約為7〇〇〇,酸價為79邮斷。 [合成例15 :黏合劑樹脂p之合成] 將丙二醇單甲ϋ乙酸1旨114.q重量份加人至4口燒瓶中,〇 -面進行氮氣吹泡-面升溫至阶。以4小時向其中滴加 將曱基丙烯酸节醋96.8重量份、甲基丙稀酸33 3重量份、 以及2,2 -偶氮雙異丁腈4.93重量份溶解於丙二醇單曱謎 乙酸S旨96.5重量份中而成者。 滴加結束後,在將反應液保持於85t:下進而攪拌2小時, 其後停止氮氣吹泡,升溫至1〇〇它並攪拌1小時。 如此獲得之點合劑難p之藉由Gpc法所測定的經聚苯乙 TF988407 130 201037041 烯換算之重量平均分子量為15000 ’酸價為180 mgK0H/g。 [合成例16 :黏合劑樹脂Q之合成] 將丙二醇單曱醚乙酸酯114. 0重量份加入至4 口燒瓶中, . 一面進行氮氣吹泡一面升溫至85。(:。以4小時向其中滴加 將曱基丙烯酸苄酯96. 8重量份、曱基丙烯酸33. 3重量份、 以及2, 2’-偶氮雙異丁腈9.85重量份溶解於丙二醇單甲醚 乙酸酯96. 5重量份中而成者。 〇 滴加結束後’在將反應液保持於85°C下進而攪拌2小時, 其後停止氮氣吹泡,升溫至l〇(TC並攪拌1小時。 如此獲得之黏合劑樹脂Q之藉由GPC法所測定的經聚苯乙 • 稀換算之重量平均分子量為8000,酸價為175 mgK〇H/g。 • [合成例17:黏合劑樹脂R之合成] 將具有三環癸烷骨架之單丙烯酸酯(日立化成公司製造之 「FA-513M」)1〇重量份、曱基丙稀酸节g| 62.〇重量份、以 〇及甲基丙烯酸28.0重量份溶解於丙二醇單曱謎乙酸醋15〇 重罝份中’於鼠氣環境中加人偶氮雙異丁腈G. 65重量份, 於80°C下反應7小時。 如此獲得之黏合劑斯 :· 削树知R之藉由GPC法所測定的經聚苯乙 烯換算之重量平均分+县 刀于篁Mw約為17000,藉由中和滴定法 所測定之酸價為1〇2。 [合成例18 :黏合劑樹脂S之合成] 將丙二醇單甲醚乙酴 -夂知114重量份加入至4 口燒瓶中,一 TF988407 131 201037041 面進行氮氣吹泡一面升溫至85°C。以4小時向其中滴加將 曱基丙烯酸苄自旨114重量份、曱基丙烯酸26重量份、2, 2’ -偶氮雙異丁腈9.9重量份溶解於丙二醇單甲醚乙酸酯96重 量份中而成者。 滴加後,在將反應液保持於85°C下進而攪拌2小時,其 後停止氮氣吹泡,升溫至l〇〇°C並攪拌1小時。向其中加入 四乙基氣化銨0. 7重量份,於80°C下攪拌使其溶解,進而 以1小時滴加將丙烯酸-3, 4-環氧基環己基-1-曱酯16重量 份、丙二醇單甲醚乙酸酯24重量份混合而成之溶液。 在將反應溶液保持於80°C下攪拌30小時,獲得藉由GPC 法所測定的經聚苯乙稀換算之重量平均分子量為8000、酸 價為90 mgKOH/g之聚合物溶液。 [合成例19 :黏合劑樹脂D1之合成] 除了將上述合成例3(黏合劑樹脂D之合成)中之曱基丙烯 酸變更為丙烯酸以外,在與合成例3完全相同之條件下進行 合成,獲得重量平均分子量為8200、酸價為101 mgKOH/g 之聚合物溶液。 [合成例20 :黏合劑樹脂E1之合成] 除了將上述合成例3(黏合劑樹脂D之合成)中之曱基丙烯 酸環己酯變更為曱基丙烯酸曱酯以外,在與合成例3完全相 同之條件下進行合成,獲得重量平均分子量為8000、酸價 為102 mgKOH/g之聚合物溶液。 TF988407 132 201037041 [1]實施例1〜4及比較例1〜2 : c. I.色素綠36使用例 [著色組成物之製備] 將作為顏料的6.85重量份之平均一次粒徑為〇 ηις . 10 Urn 的C. I.色素綠36、及2. 93重量份之平均一次粒徑為〇 的C.I.色素黃150、作為溶劑之丙二醇單甲峻乙酸酉t 60. 00重量份、作為分散劑之表-1中記載之各種分散劑經固 形分換算1. 96重量份、以及作為分散樹脂之表~1中記载之 〇 各種黏合劑樹脂經固形分換算3.26重量份,與直徑為〇 5 mm之氧化锆珠225重量份一同填充至不鏽鋼容器中,藉由 塗料振動機(paint shaker)分散6小時,而製備綠色顏料分 散液。 繼而,將表-2中記載之各成分混合於所得綠色顏料分散 液中,而製備著色組成物。再者,表_2中之所謂「溶劑」, 係與「綠色顏料分散液」中所含之溶劑不同,為另外調配者。 Ο [表 1] 表~1 分散劑之種類/胺價 黏合劑樹脂 著 ^组成物之詞 1價 黏度變化 溶解時間 _對比度 實施例1 AV121 R 實施例2 AV121 w 〇 〇 ~〇 6096 gnoq 實施例3 AV121 ___ΙΤ Δ 〇 OvTCu 實加例4 AV121 IP 〇 Ο 1 ou 5820 比較例1 B,/40 —ϊ— R X h無法評僧 無法評僧 比較例2 C/10 __ Ε X 無法評僧 無法評僧 表中,为政劑A及分散劑c分別係上述合成例2及3中 TF988407 133 201037041 獲得之化合物,分散劑B’係以下化合物。 分散劑 B’ : Lubrizol 公司製造之「Solsperse 24000GR」 係吸附基為下述結構,胺價為39 mgKOH/g、酸價為33 mgKOH/g之由聚酯酸醯胺胺鹽所構成之高分子分散劑。 [化 32]After maintaining 1 1 Q L for 3 hours, the gas introduction tube was mounted on a separate flask TF988407 124 201037041, and bubble blowing of an oxygen/nitrogen = 5/95 (v/v) mixed gas was started. Then, 39.6 parts by weight of glycidyl methacrylate was added to the reaction vessel, and 0.4 parts by weight of '2,2'-fluorenylene bis(4-mercapto-6-t-butylphenol), triethyl'amine 0.8 parts by weight and reacted directly at 110 ° C for 9 hours. The mixture was cooled to room temperature to obtain a polymer solution having a weight average molecular weight of 8,000 and an acid value of 103 mgKOH/g as measured by a GPC method. [Synthesis Example 6: Synthesis of the binder resin F] While substituting nitrogen gas, 145 parts by weight of propylene glycol monoterpene ether acetic acid S was stirred and heated to 120 °C. 20 parts by weight of styrene, 57 parts by weight of glycidyl methacrylate, and 82 parts by weight of a mono-acrylate ("FA-513M" manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton were added dropwise thereto. Stirring was continued for 2 hours at 120 °C. Then, the reaction vessel is replaced with air, and the amount of bis(diamidomethyl) benzoquinone is 0. 7 parts by weight and hydroquinone is 0.12 parts by weight at 120 ° C. The reaction was continued for 6 hours. 5小时。 After the reaction was carried out at a temperature of 120 ° C for 3.5 hours. The weight average molecular weight Mw of the polystyrene-based olefin converted by the G P C method of the binder resin F thus obtained was about 15,000. [Synthesis Example 7: Synthesis of the binder resin G] To the reaction vessel, 35 parts by weight of propylene glycol monomethyl ether acetate, 8.1 parts by weight of 1-nonyloxy-2-propanol, and an initial polymerization of azo-based polymerization were added. 1.5 parts by weight of a "V-59" manufactured by Wako Pure Chemical Industries, Ltd. TF988407 125 201037041, and heated to 8 〇〇c in a nitrogen atmosphere. 5重量份, and methacrylic acid 10.7 parts by weight, 5% by weight of benzyl methacrylate, 6.5 parts by weight of decyl methacrylate, 5% by weight of 2-hydroxyethyl methacrylate Further, the mixture was stirred for 4 hours to obtain a polymerization reaction liquid. To the t-reaction liquid, 25 parts by weight of propylene glycol monoterpene acetic acid, 0.05 parts by weight of p-nonoxylphenol, and 3 parts by weight of triphenylphosphine. Then, 17.5 parts by weight of (3, 4-epoxycyclohexyl) decyl acrylate was added dropwise, and the mixture was reacted at 85 ° C for 24 hours to obtain a resin solution having an ethylenically unsaturated group in the side chain. The polymerization average resin obtained by the G P C method of the binder resin G thus obtained was converted into 18 〇 〇 by I of ethylene. Further, the acid value measured by the neutralization titration method was 50. Further, from the acid value before and after the reaction, the introduction rate of (3, 4-epoxycyclohexyl) decyl acrylate to the carboxyl group was 66%. [Comparative Example 8: Synthesis of the binder resin η] 10 parts by weight of a monoacrylate having a tricyclodecane skeleton ("FA-513M" manufactured by Hitachi Chemical Co., Ltd.), and a cyclohexyl methacrylate 43. 5 parts by weight , azobisisobutyronitrile is added to a nitrogen atmosphere, 1. 5 parts by weight, and 4 parts by weight of methacrylic acid is dissolved in 15 parts by weight of propylene glycol monomethyl ether acetate. The reaction was carried out at 80 ° C for 7 hours by weight. The weight average molecular weight Mw of the polystyrene TF988407 126 201037041 olefin converted by the GPC method thus obtained was about 7200, and the acid value was 84. [Synthesis Example 9: Synthesis of the binder resin I] While substituting nitrogen gas, 145 parts by weight of propylene glycol monomethyl ether acetate was stirred and heated to 120 °C. 10 parts by weight of styrene, 85.2 parts by weight of glycidyl methacrylate, and 66 parts by weight of a monoacrylate ("FA-513M" manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton, and 3 parts by weight were added thereto. 00 parts by weight of 2,2'-azobis-2-mercaptobutyronitrile was added dropwise over an hour, and further stirring was continued at 90 ° C for 2 hours. Then, the reaction vessel was changed to air, and 0.7 parts by weight of propylene (diguanamine fluorenyl) phenol and 0.72 parts by weight of hydroquinone were continuously added to the acrylic acid. Reaction for 12 hours. 5小时。 After the reaction was carried out at a temperature of 100 ° C for 3.5 hours. The binder resin I thus obtained had a weight average molecular weight Mw of about 6,000 in terms of polystyrene measured by a GPC method, and an acid value of 90 mgKOH/g. [Synthesis Example 10: Synthesis of binder resin J] 145 parts by weight of propylene glycol monoterpene ether acetate was stirred while being purged with nitrogen, and the temperature was raised to 120 °C. 30 parts by weight of benzyl methacrylate, 85.2 parts by weight of methacrylic acid epoxy propyl ester, and 46 parts by weight of monoacrylate having a tricyclodecane skeleton ("FA-513M" manufactured by Hitachi Chemical Co., Ltd.) were added thereto. . Further, 7.47 parts by weight of 2,2'-azobis-2-mercaptobutyronitrile was added dropwise over 3 hours, and stirring was continued at 90 °C for 2 hours under TF988407 127 201037041. Then, the reaction vessel was changed to air, and 0.7 parts by weight of propylene (diguanamine fluorenyl) phenol and 0.72 parts by weight of hydroquinone were continuously added to the acrylic acid. Reaction for 12 hours. 5小时。 After the reaction was carried out at a temperature of 100 ° C. 3. 5 hours. The polystyrene-equivalent weight average molecular weight Mw measured by the GPC method thus obtained was about 14,000, and the acid value was 80 mgKOH/g. [Synthesis Example 11: Synthesis of Binder Resin K] In the same manner as the resin I obtained in Synthesis Example 9, styrene, glycidyl methacrylate, and a monoacrylate having a tricyclodecane skeleton ( The "FA-513M" manufactured by the company was polymerized. Then, the reaction vessel was changed to air, and 0.7 parts by weight of bis(nonylaminodecyl)phenol and 0.12 parts by weight of hydroquinone were added to 43.2 parts by weight of acrylic acid, and the reaction was continuously carried out at 100 ° C. hour. 5小时。 Then, the reaction was carried out at a temperature of 100 ° C for 3.5 hours. The polystyrene-converted weight average molecular weight Mw measured by the G P C method thus obtained was as follows, and the acid value was 78 mgKOH/g. [Synthesis Example 12: Synthesis of binder resin L] propylene glycol monoterpene ether acetate 145 weight TF988407 128 201037041 was mixed while being subjected to nitrogen substitution, and the temperature was raised to 12 Qt. To the mixture, a styrene hydrazine weight fraction, a f olefinic acid propylene acrylate, a pH of 115·2 parts by weight, and a mono-acrylic acid g having a tricyclic sinter skeleton ("fa_513M" manufactured by Hitachi Chemical Co., Ltd.) were added dropwise. 46 weight injuries. Then, 7.47 parts by weight of 2,2'-azobis_2-mercaptobutyronitrile was added dropwise over 3 hours, and stirring was continued for 2 hours at 902⁄4. Then, the reaction vessel was changed to air, and 7 parts by weight of ginseng (dimethylamino fluorenyl) phenolphthalein was added to the 5.8 mil of the acrylic acid, and the benzoquinone was expected to be 〇. 12 rickies, at 10 〇 ° The reaction was continued for 12 hours at C. 5重量》 By the GPC method, the binder resin L thus obtained is reacted by adding 5 parts by weight of bismuth diacetic anhydride (Cong), 57.2 parts by weight, and 0.7 parts by weight of triethylamine. The polystyrene-equivalent weight average molecular weight Mw measured was about 8 Å, and the acid value was 1 〇〇 mgKOH/g. [Synthesis Example 13: Synthesis of binder resin μ] styrene, glycidyl methacrylate, and monoacrylic acid having a tricyclodecane skeleton, in the same manner as the resin I obtained in Synthesis Example 9. The ester ("FA-513M" manufactured by Hitachi Chemical Co., Ltd.) was polymerized. Then, the reaction vessel was replaced with air, and 2 parts by weight of acrylic acid was added to 7 parts by weight of acrylic acid and 1 part by weight of hydroquinone and 0. 12 parts by weight. The reaction was carried out for 12 hours. Thereafter, 30 parts by weight of acetoic anhydride and 7 parts by weight of triethylamine were added, and the reaction was carried out at 1 Torr for 3.5 hours. TF988407 129 201037041 The binder tree thus obtained (4) The polyether-equivalent weight average molecular weight Mw measured by the Gpc method is about 9 Å, and the acid value is 81 claw side plant [Synthesis Example 14: Synthesis of binder resin N] g and Synthesis Example 9 In the same manner, a stupid woman, a smiling acrylic propylene vinegar, and a mono acrylate having a tricyclic Wei skeleton (= "FA-513M" manufactured by Lihua Chemical Co., Ltd.) were polymerized. The inside of the reaction vessel was changed to air, and 7 parts by weight of ginseng (dimethylamino fluorenyl) was added to 43 parts by weight of acrylic acid, and 0. 12 parts by weight of hydroquinone was added to l〇〇〇c. The reaction was continued for 12 hours. Thereafter, 69.2 parts by weight of a benzene tricarboxylic acid needle was added, and triethylamine 〇·7 was added. The amount of the reaction, the reaction of the adhesive resin N thus obtained by the Gpc method, the weight average molecular weight of the polystyrene conversion is about 7 〇〇〇, the acid value [Synthesis Example 15: Synthesis of binder resin p] 144 parts by weight of propylene glycol monomethyl hydrazide acetic acid was added to a 4-neck flask, and the nitrogen-bubble-surface temperature was raised to the surface. 96.8 parts by weight of thioglycolic acid vinegar, 33 parts by weight of methacrylic acid, and 4.93 parts by weight of 2,2-azobisisobutyronitrile were dissolved in propylene glycol monoterpene acetic acid S dropwise thereto over 4 hours. After the completion of the dropwise addition, the reaction liquid was further stirred at 85 t: for 2 hours, and then nitrogen bubbling was stopped, and the temperature was raised to 1 Torr and stirred for 1 hour. The weight average molecular weight of the polyphenylene TF988407 130 201037041 measured by the Gpc method is 15000', and the acid value is 180 mgK0H/g. [Synthesis Example 16: Synthesis of Adhesive Resin Q] Propylene Glycol Single 11 parts by weight of hydrazine ether acetate was added to a 4-necked flask, and one side was purged with nitrogen gas. The temperature was 85. (:: 96.8 parts by weight of benzyl methacrylate, 33.3 parts by weight of methacrylic acid, and 9.85 parts by weight of 2,2'-azobisisobutyronitrile were added dropwise thereto over 4 hours. The mixture was dissolved in propylene glycol monomethyl ether acetate (16.5 parts by weight). After the completion of the dropwise addition, the reaction solution was further stirred at 85 ° C for 2 hours, after which nitrogen blowing was stopped, and the temperature was raised to l. 〇(TC was stirred for 1 hour. The thus obtained binder resin Q had a weight average molecular weight of 8,000 and an acid value of 175 mgK〇H/g as determined by the GPC method. [Synthesis Example 17: Synthesis of Binder Resin R] Monoacrylate having a tricyclodecane skeleton ("FA-513M" manufactured by Hitachi Chemical Co., Ltd.) 1 part by weight, mercaptopropionic acid group g| 62 〇 by weight, dissolved in 2,500 parts by weight of hydrazine and methacrylic acid in propylene glycol monoterpene acetate vinegar 15 〇 罝 ' 'Additional azobisisobutyronitrile G. 65 parts by weight in a rat atmosphere, at 80 The reaction was carried out at ° C for 7 hours. The adhesive thus obtained: · The average weight of the polystyrene converted by the GPC method is determined by the GPC method. The acid value measured by the neutralization titration method is about 17000. It is 1〇2. [Synthesis Example 18: Synthesis of Binder Resin S] 114 parts by weight of propylene glycol monomethyl ether ethyl hydrazine was added to a 4-necked flask, and the temperature was raised to 85 ° C while nitrogen blowing was performed on a surface of TF988407 131 201037041. 14 parts by weight of benzyl methacrylate, 26 parts by weight of methacrylic acid, and 9.9 parts by weight of 2,2'-azobisisobutyronitrile were dissolved in propylene glycol monomethyl ether acetate 96 weight by dropwise addition over 4 hours. The winner. After the dropwise addition, the reaction liquid was further stirred at 85 ° C for 2 hours, and then nitrogen bubbling was stopped, and the temperature was raised to 10 ° C and stirred for 1 hour. To this was added 0.7 parts by weight of tetraethylammonium hydride, and the mixture was stirred at 80 ° C to dissolve, and the weight of 3, 4-epoxycyclohexyl-1-decyl acrylate was added dropwise over 1 hour. A solution obtained by mixing 24 parts by weight of propylene glycol monomethyl ether acetate. The reaction solution was stirred at 80 ° C for 30 hours to obtain a polymer solution having a weight average molecular weight of 8000 and an acid value of 90 mg KOH/g as measured by a GPC method. [Synthesis Example 19: Synthesis of the binder resin D1] The synthesis was carried out under the same conditions as in Synthesis Example 3 except that the mercaptoacrylic acid in the above Synthesis Example 3 (synthesis of the binder resin D) was changed to acrylic acid. A polymer solution having a weight average molecular weight of 8,200 and an acid value of 101 mgKOH/g. [Synthesis Example 20: Synthesis of the binder resin E1] The same procedure as in Synthesis Example 3 except that the cyclohexyl methacrylate in the synthesis example 3 (synthesis of the binder resin D) was changed to decyl methacrylate. The synthesis was carried out under the conditions to obtain a polymer solution having a weight average molecular weight of 8,000 and an acid value of 102 mgKOH/g. TF988407 132 201037041 [1] Examples 1 to 4 and Comparative Examples 1 to 2: c. I. Pigment Green 36 Use Example [Preparation of Colored Composition] The average primary particle diameter of 6.85 parts by weight of the pigment was 〇ηις. 10 Urn CI Pigment Green 36, and 2.93 parts by weight of CI Pigment Yellow 150 having an average primary particle diameter of 〇, propylene glycol monomethylglycolate 酉t as a solvent, 60. 00 parts by weight, Table-1 as a dispersing agent The various dispersants described in the above are converted into a solid content of 1.96 parts by weight, and as described in Table 1 of the dispersion resin, various binder resins are converted into solid parts by 3.26 parts by weight, and zirconia having a diameter of 〇5 mm. 225 parts by weight of the beads were filled together in a stainless steel container, and dispersed by a paint shaker for 6 hours to prepare a green pigment dispersion. Then, each component described in Table-2 was mixed in the obtained green pigment dispersion to prepare a colored composition. In addition, the "solvent" in Table 2 is different from the solvent contained in the "green pigment dispersion" and is an additional blender. Ο [Table 1] Table ~1 Type of Dispersant / Amine Price Binder Resin Composition Word 1 Valence Change Dissolution Time _ Contrast Example 1 AV121 R Example 2 AV121 w 〇〇~〇6096 gnoq Example 3 AV121 ___ΙΤ Δ 〇OvTCu Actual addition example 4 AV121 IP 〇Ο 1 ou 5820 Comparative example 1 B,/40 —ϊ— RX h cannot be evaluated. Cannot be evaluated Comparative Example 2 C/10 __ Ε X Cannot be evaluated In the table, the chemical agent A and the dispersing agent c are the compounds obtained in the above-mentioned Synthesis Examples 2 and 3, respectively, TF988407 133 201037041, and the dispersing agent B' is the following compound. Dispersant B': "Solsperse 24000GR" manufactured by Lubrizol is a polymer composed of a polyester acid amide amine salt having an amine structure of 39 mgKOH/g and an acid value of 33 mgKOH/g. Dispersant. [化32]
[表2] 表-2 成分之種類 成分之詳細内容 調配量(重量份) 顏料分散液 53. 67 溶劑 丙二醇單曱醚乙酸酯 37. 09 黏合劑樹脂 追加與表-1中所記載者相同者 2. 20 聚合性單體 二季戊四醇六丙烯酸酯 5. 66 光聚合起始系成分1 2-巯基苯并噻唑 0. 46 光聚合起始系成分2 對二曱胺基苯甲酸 0. 46 光聚合起始系成分3 米其勒酮 0. 46 對所獲得之著色組成物,測定黏度變化、著色樹脂膜之溶 解時間、以及對比度。測定方法分別記載如下,測定結果示 於表~1。 [著色組成物之黏度變化] 使用東機產業公司製造之E型黏度計「RE-80L」,對上述 實施例及比較例中所獲得之著色組成物,分別測定 •剛製造(製備)後、以及 •於23°C之恆溫槽中靜置2週後之黏度(20 rpm)。 TF988407 134 201037041 、比較14日間之黏度變化率’將未滿4%者記為〇,將抄 以上未滿10%者記為△,將1〇%以上者記為X。 ° 其結果不於表—1 〇 [溶解時間之測定] 分別將上述實_及比較财轉著色㈣物旋塗於装 鍍有路之玻璃基板上,以8代之加熱板進行3分鐘預供烤,、,、 而製成乾燥塗佈膜。 再者,調整旋塗時之轉速,以使所獲得乾燥塗佈臈達到色 座標為y= 〇· 600之膜厚。 ==燈通過光罩圖案以6。—2對所得乾燥塗 ==。:用0.。4重量%氣氧一^^ /皿度23 C),以〇.25 MPa之壓力進行喷霧顯影。測定直至 乾燦塗佈膜溶解而露出基板面為止之時間、即「 之溶解時間」。 且战物 〇 對於各實施例及比較例中所得著色組成物之溶解時 未滿100秒者記為〇,將1〇〇秒以 上未滿120者記為△,將 120以上者記為X。其結果示於表。 [對比度之測定] 使用各實施例及比較例中所獲搵 Γ 又侍之者色組成物,以與上述 D谷解時間之測定]項中相同之方^ 式’於透明玻璃基板上進行 方疋塗及預烤。除了不介隔光罩圖幸 sa 糸以外,以與上述[溶解時 間之測定]項中相同之方式,對所 &传之乾燥塗佈膜進行曝 TF988407 135 201037041 光’並在與上述[溶解時間之測定]項中相同之條件下進行顯 影。繼而’践分量的水進行清洗後,㈣淨空氣騎乾燥。 於230 C烘箱中對所得乾燥塗佈膜進行30分鐘後烘烤, 而製成著色樹脂膜。所得著色樹脂膜之膜厚為2 4 _左 右。如此,製成於透明玻璃基板上具有著色樹脂膜之著色板。 圖2⑷及⑸均係用以說明測定著色板之平行穿透光及 正交穿透光之色度的方法之模式圖。 首先,如圖2⑷所示,在所得著色板(以下稱為「著色板 34」)之兩側重疊偏光板33及35,在使偏光板33與35之 偏光軸相互平行之狀態下’自—側偏光板35侧照射背光源 37之光36,使用色彩亮度計T〇pc〇N TECHN〇H〇USE製造之 「BM-5A」32,在2視野之條件下測定透過另一偏光板33 之光的亮度Lp(平行穿透光的亮度)。 繼而,如圖2(b)所示,在使偏光板33與35之偏光軸相 互正交之狀態下,自一側偏光板35側照射背光源37之光 36 ’使用色彩兜度計32 ’以與上述Lp相同之方式’測定透 過另一偏光板33之光的亮度Lc(正交穿透光的亮度)。 再者,背光源37係使用具有如圖3所示之發光光譜者。 該光譜之測定’係使用Konica Minolta製造之分光放射亮 度計CS-1000A,以及為了控制光量並使測定變得容易而使 用Kenko公司製造之濾光片「ND Filter ND4」進行測定, 並進行計算。 TF988407 136 201037041 又,偏光板33、35係使用具有圖4之光譜特性者。 各實施例及比較例之著色板的對比度,係利用式Lp/Lc 由平行穿透光之亮度Lp及正交穿透光之亮度Lc而算出。再 者’使用基本玻璃來代替各實施例及比較例之著色板進行測 定時之空白試驗值為12800。結果示於表-1。 [2]實施例5〜36及比較例3〜7:溴化鋅酞菁顏料使用例。 [2-1]實施例5〜6及比較例3〜4 :溴化鋅酞菁顏料使用 〇 例。 [顏料分散液之製備] 使用合成例i中獲得之漠化躲菁7. 24重量份、以及 2. 54重量份之!.色素黃⑽,將作為溶劑之丙二醇單甲 醚乙酸酯60. 00重量份、作為分散劑之表—3中^ 成分經固形分換算1.96重量份、以及作為分散; 〇 中記載之黏合劑樹脂經以固形分換算3. 26重量份,與直徑 為〇.5賴之氧化錯珠225重量份-同填充至不鑛鋼容琴 中’精由塗料振動機分散6小時,而製備顏料分散液t、u、 V及W。 [表3] 表-3 .顏料 合成例1中所獲得之 溴化鋅酞菁[Table 2] Table-2 Contents of the components of the components Details of the content (parts by weight) Pigment dispersion 53. 67 Solvent propylene glycol monoterpene ether acetate 37. 09 Adhesive resin is added as in Table-1 2. Photopolymerizable monomer dipentaerythritol hexaacrylate 5. 66 photopolymerization starting component 1 2-mercaptobenzothiazole 0. 46 photopolymerization starting component 2 p-diamine benzoic acid 0. 46 light Polymerization starting component 3 Miclotone 0. 46 For the coloring composition obtained, the viscosity change, the dissolution time of the colored resin film, and the contrast were measured. The measurement methods are described below, and the measurement results are shown in Table ~1. [Viscosity change of the coloring composition] The coloring composition obtained in the above examples and comparative examples was measured using the E-type viscometer "RE-80L" manufactured by Toki Sangyo Co., Ltd., and immediately after the manufacturing (preparation), And • Viscosity (20 rpm) after standing for 2 weeks in a 23 ° C thermostat. TF988407 134 201037041 , Comparing the viscosity change rate between the 14th days, the person who has less than 4% is marked as 〇, and the person who has less than 10% of the above is recorded as △, and the person who has 1% or more is recorded as X. ° The result is not in Table-1 〇 [Measurement of Dissolution Time] The above-mentioned actual _ and comparative financial conversion coloring (four) were spin-coated on a glass substrate plated with a road, and pre-supplied for 3 minutes with a heating plate of 8 generations. Bake, and, and make a dry coating film. Further, the rotation speed at the time of spin coating was adjusted so that the obtained dried coating enthalpy reached a film thickness of y = 〇 600. == The light passes through the reticle pattern at 6. - 2 pairs of dry coatings obtained ==. : Use 0. 4% by weight of gas oxygen - ^^ / dish degree 23 C), spray development at a pressure of 〇.25 MPa. The time until the dry coating film was dissolved to expose the substrate surface, that is, the "dissolution time" was measured. Further, the warfare element 〇 is less than 100 seconds when the coloring composition obtained in each of the examples and the comparative examples is dissolved, and is marked as Δ when 1 second or less is less than 120, and X is referred to as 120 or more. The results are shown in the table. [Measurement of Contrast] Using the color composition obtained in each of the examples and the comparative examples, the same method as in the above-mentioned measurement of the D solution time] was carried out on a transparent glass substrate. Spray and pre-bake. Except that in the same manner as in the above [Determination of Dissolution Time], the dried coating film of the & was exposed to TF988407 135 201037041 light 'and dissolved in the above Development was carried out under the same conditions as in the measurement of time. Then, after the water of the component is cleaned, (4) the net air rides dry. The obtained dried coating film was baked in a 230 C oven for 30 minutes to prepare a colored resin film. The film thickness of the obtained colored resin film was 2 4 _ left and right. Thus, a coloring plate having a colored resin film on a transparent glass substrate was produced. 2(4) and (5) are schematic diagrams for explaining a method of measuring the chromaticity of the parallel penetrating light and the orthogonal penetrating light of the colored plate. First, as shown in Fig. 2 (4), the polarizing plates 33 and 35 are superposed on both sides of the obtained colored plate (hereinafter referred to as "colored plate 34"), and the polarizing axes of the polarizing plates 33 and 35 are parallel to each other. The side of the side polarizing plate 35 illuminates the light 36 of the backlight 37, and the "BM-5A" 32 manufactured by the color luminance meter T〇pc〇N TECHN〇H〇USE is used to measure the transmission through the other polarizing plate 33 under the condition of two fields of view. The brightness of the light Lp (the brightness of the parallel penetrating light). Then, as shown in FIG. 2(b), in a state where the polarization axes of the polarizing plates 33 and 35 are orthogonal to each other, the light 36' of the backlight 37 is irradiated from the side of one side of the polarizing plate 35' using the color pocket meter 32'. The luminance Lc (the luminance of the orthogonal transmitted light) of the light transmitted through the other polarizing plate 33 is measured in the same manner as the above Lp. Further, the backlight 37 is a person having an emission spectrum as shown in FIG. The measurement of the spectrum was carried out by using a spectroradiometer manufactured by Konica Minolta, CS-1000A, and measuring the amount of light to facilitate measurement, using a filter "ND Filter ND4" manufactured by Kenko Corporation. TF988407 136 201037041 Further, the polarizing plates 33 and 35 are those having the spectral characteristics of FIG. The contrast of the color plates of the respective examples and comparative examples was calculated from the luminance Lp of the parallel penetrating light and the luminance Lc of the orthogonal penetrating light by the equation Lp/Lc. Further, the blank test value for the measurement using the base glass instead of the color plates of the respective examples and comparative examples was 12,800. The results are shown in Table-1. [2] Examples 5 to 36 and Comparative Examples 3 to 7: Examples of use of zinc bromide phthalocyanine pigments. [2-1] Examples 5 to 6 and Comparative Examples 3 to 4: Examples of zinc bromide phthalocyanine pigments were used. [Preparation of the pigment dispersion liquid] Using the desertified phthalocyanine obtained in Synthesis Example i 7.24 parts by weight, and 2.54 parts by weight of the pigment yellow (10), propylene glycol monomethyl ether acetate as a solvent.重量重量为为为为5。 5 parts by weight, as a dispersing agent, the composition of the ingredients in the form of a solid component of 1.96 parts by weight, and as a dispersion; 225 parts by weight of Laizhi Oxidation Beads - the same as the non-mineral steel Rongqin 'finely dispersed by a paint shaker for 6 hours to prepare pigment dispersions t, u, V and W. [Table 3] Table-3. Pigment Synthesis of zinc bromide phthalocyanine obtained in Example 1
實施例 實施例 比較例3 比較例 TF988407 137 201037041 其中,表-3中之分散劑A及B係以下化合物。 [分散劑A:畢克化學公司製造之分散劑「BYK-LPN6919」] 其係曱基丙烯酸系AB嵌段共聚物。胺價為121 mgKOH/g, 酸價為1 mgKOH/g以下。 B嵌段中所含之具有含氮原子的官能基之重複單元中約 100莫耳%為以下述式(a)所表示之結構,又,以下述式(b) 所表示之重複單元在A嵌段中之比例為11莫耳%。 [化 33]EXAMPLES EXAMPLES Comparative Example 3 Comparative Example TF988407 137 201037041 wherein Dispersants A and B in Table-3 are the following compounds. [Dispersant A: Dispersant "BYK-LPN6919" manufactured by BYK Chemical Co., Ltd.] This is a mercaptoacrylic AB block copolymer. The amine value is 121 mgKOH/g, and the acid value is 1 mgKOH/g or less. About 100% by mole of the repeating unit having a functional group containing a nitrogen atom contained in the B block is a structure represented by the following formula (a), and a repeating unit represented by the following formula (b) is in A The ratio in the block was 11 mol%. [化33]
(b) [分散劑B :畢克化學公司製造之「Disperbyk 2000」] 其係由具有親溶劑性之A嵌段及具有含氮原子的官能基 TF988407 138 201037041 之B嵌段所構成之曱基丙烯酸系AB嵌段共聚物。其係含氮 原子的官能基(吸附基)主要為下述結構, [化 34](b) [Dispersant B: "Disperbyk 2000" manufactured by BYK Chemical Co., Ltd.] which is a sulfhydryl group composed of a solvophilic A block and a B block having a nitrogen atom-containing functional group TF988407 138 201037041 Acrylic AB block copolymer. The functional group (adsorbing group) which is a nitrogen atom is mainly the following structure, [Chem. 34]
〇 胺價約為10 mgKOH/g,且主鏈為曱基丙烯酸之嵌段共聚 物。 [顏料分散液之黏度變化] ' 對實施例5〜6及比較例3〜4中所獲得之顏料分散液T、 • U、V及W,使用東機產業公司製造之E型黏度計「RE-80L」, 測定剛製備後之黏度、以及於23°C之恆溫槽中靜置7曰後 之黏度(均為20 rpm)。結果示於表-4。 Ο [表 4] 表_4 顏料 分散液 黏度(mPa· s) 剛製備後 7日後 實施例5 T 13. 2 13. 3 實施例6 U 12.8 13.0 比較例3 V 35. 4 255.4 比較例4 W 22. 1 45. 2 根據表-4可知,7日後之黏度變化率,於實施例5及6 之顏料分散液中為2%以下,相對於此,於不使用本發明分 TF988407 139 201037041 散劑之比較例3及4之顏料分散液中為100%以上。 [著色組成物之製備] 將其他成分混合於上述各顏料分散液中,而製備表-5中 所表示之著色組成物。再者,表-5之「溶劑1」及「溶劑2」 均與顏料分散液中所含之溶劑不同,而為另外調配者。 [表5] 表-5 成分之種類 成分之詳細内容 調配量 (重量 份) 顏夕 4分散液 57. 78 溶劑1 丙二醇單甲醚乙酸酯 25. 93 溶劑2 3-乙氧基丙酸乙酯 8. 00 黏合劑樹脂 黏合劑樹脂F 2. 94 聚合性單體 二季戊四醇六丙烯酸酯 3. 63 光聚合起始系成分1 2, 2’ -雙(鄰氣苯基)-4, 4’,5, 5’ -四苯基 -1,2 ’ _聯味°坐 0. 38 光聚合起始系成分2 4, 4’ -雙-二乙胺基二苯基酮 0. 19 光聚合起始系成分3 2-M基苯并噻唑 0. 38 [對比度之測定] 使用旋轉塗佈機,將上述實施例5〜6及比較例3〜4中所 獲得之著色組成物,塗佈於50 mm見方、厚度0. 7 mm之玻 璃基板(旭硝子公司製造之「AN100」)上,然後於80°C下乾 燥3分鐘。 再者,調整旋塗時之轉速,係以使所得乾燥塗佈膜達到色 座標為y^O. 600之膜厚。 繼而,利用2 kW高壓水銀燈,以300 mJ/cm2之曝光量進 TF988407 140 201037041 行整面曝光處理。其後,使用〇. 1重量%碳酸鈉水溶液,於 顯影液溫度23 C下進行顯影。繼而’以3 kg/cm2之水壓進 行30秒喷射水洗處理,於23(TC下進行30分鐘熱硬化處 理’而形成著色樹脂膜。如此’製成於透明玻璃基板上具有 著色樹脂膜之著色板。 繼而’測定所獲得著色板之對比度。測定方法與上述[1] 之[對比度之測定]項中所記載者相同。測定結果示於表_6。 〇 [表 6] 表-6 對比度 實施例5 8630 貫施例 8600 比較例?! 6830 1 比較t a — [7510 綜合表-4及表-6之結果开 不J知’使用本發明分散劑之實施 〇 例5〜6之著色組成物’與比 、比較例3〜4之著色組成物相比, 分散穩定性較好,且滿足汽料 阿對比度,其有用性極高。 [2-2]實施例7〜15及比較你丨ς ρ ^ Γ 例5〜6:使用[2-1-1]樹脂之例。 [顏料分散液之製備] 除了使用黏合劑樹脂Ε作Α八私糾n t , 刀散樹脂以外,以與上述顏料 分散液V相同之方式,製倕 備、、彔色顏料分散液X。(其用於後 述之比較例5。) [著色組成物之製備] TF988407 141 201037041 以表-7所示之比例,將上述顏料分散液T(其中,於比較 例5中為顏料分散液X,於比較例6中為顏料分散液W)、溶 劑、黏合劑樹脂、聚合性單體、光聚合起始系成分、以及界 面活性劑加以混合,而製備實施例7〜15及比較例5〜6之 著色組成物。再者,表-7中之數值為含量(重量份)。又, 表-7中,* 1(比較例5)為顏料分散液X之使用量(含量), * 2(比較例6)為顏料分散液Υ之使用量。 TF988407 142 〔卜4〕 卜丨< 比車交例6 I | 57.78*2 25.93 8.00 2.94 CO CO CO 〇 0.38 0.19 〇〇 CO Ci 0.76 c=) 比車交例5 [57.78*' I 25.93 I 8.00 I 2.94 3.63 I 0. 38 CD 1 Η <〇 0.38 0.76 s c> 實施例15 57.78 I 25. 93 CZ) 〇〇 〇* C73 oi 3.63 〇 00 CO <=> 0.19 0.38 0.76 g c=> 實施例14 1 57.78 I 25. 93 1 8.00 ,2.94 CD L 3‘63 0.38 σΰ ι Η Ο 00 CO 0.76 g o 實施例13 I 1 57.78 J 25.93 〇 〇 〇〇 od CO CD CO 0. 38 0.19 oo CO G5 CO g 實施例12 I 1 57.78 | 25.93 g od οα 3.63 | C=5 〇0 CO 0.19 0.38 0.76 s CD 實施例111 I 57.78 | 25.93 1 8.00 1 05 03 3.63 C5 0.38 σϊ ι1 Η 00 CO CD 0.76 g o 實施例ίο 1 I 57.78 | 25.93 Γ 8.00 1 ! 2.94 CO CO cd Ο 0.38 05 ^-Η Ο oo CO o' CO g o I實施例9 | I 57.78 | 25.93 1 8.00 1 ^£ί I 2.94Π [3.63 | CD 0.38 σ5 Τ"Η Ο 00 CO C3 CD g C3 1實施例8 | Γ 57.78 1 25.93 Γ 8.00 1 1 Γ 2.94 | CO CO CO 〇) 0.38 05 oo CO o 0.76 g c> 實施例7| I 57.78 25.93 8.00 ! 2.94 3.63 Ο 0.38 i_ CD r 1 i o 00 CO <〇 CD g o Γ成分 「顏料対欠液T 丙二醇單甲醚乙酸酯 3-乙氧基丙酸乙酯 調配量 二季戊四醇六丙烯酸醋 季戊四醇四丙稀S变醋 2,2’-(鄰氣苯基)-4,4’,5,5’-四 苯基聯咪唑 4,4’ -雙-二乙胺基二苯基_ 2-雜苯并杂坐 cja ^ I w 1 Φ5 T ® ¢- ^ 4 m 4< Vg <4 蛉麵 喊Η >si ^ w Jj LO f溶劑1 1溶劑2 黏合劑樹脂 聚合1·生單體 1φ 45 fz 光聚合起始 系成分3 光聚合起始 系成分4 界面活性劑 ε寸一 ZOSSSl 201037041 [著色組成物之黏度變化] 使用東機產業公司製造之E型黏度計「RE-80L」,測定將 實施例7〜15及比較例5〜6中所獲得之著色組成物 •於23°C下保存1日後,以及 •於35°C之恆溫槽中靜置7日後 之各自黏度(20 rpm)。結果示於表—8。 再者,表-8中之「黏度變化率」,簡略地以「7日後」之 黏度與「製備1日後」之黏度的差相對於「製備丨曰後」之 黏度的比例來表示。 [表8] 表-8The ruthenium amine has a valence of about 10 mg KOH/g and the main chain is a block copolymer of methacrylic acid. [Viscosity Change of Pigment Dispersion] The E-type viscometer "RE" manufactured by Toki Sangyo Co., Ltd. was used for the pigment dispersions T, U, V, and W obtained in Examples 5 to 6 and Comparative Examples 3 to 4. -80L", the viscosity immediately after preparation, and the viscosity after standing at 7 ° C in a thermostat at 23 ° C (both 20 rpm). The results are shown in Table-4. Ο [Table 4] Table_4 Pigment Dispersion Viscosity (mPa·s) Immediately after 7 days of preparation Example 5 T 13. 2 13. 3 Example 6 U 12.8 13.0 Comparative Example 3 V 35. 4 255.4 Comparative Example 4 W 22. 1 45. 2 According to Table-4, the viscosity change rate after 7 days is 2% or less in the pigment dispersion liquids of Examples 5 and 6, whereas the TF988407 139 201037041 powder is not used in the present invention. The pigment dispersion liquids of Comparative Examples 3 and 4 were 100% or more. [Preparation of colored composition] The coloring composition shown in Table-5 was prepared by mixing other components in each of the above pigment dispersions. In addition, "solvent 1" and "solvent 2" of Table-5 are different from the solvent contained in the pigment dispersion liquid, and it is another preparation. [Table 5] Table-5 Contents of the components of the components Details of the content (parts by weight) Yan Xi 4 dispersion 57. 78 Solvent 1 Propylene glycol monomethyl ether acetate 25. 93 Solvent 2 3-ethoxypropionic acid B Ester 8. 00 Adhesive Resin Adhesive Resin F 2. 94 Polymeric monomer dipentaerythritol hexaacrylate 3. 63 Photopolymerization initiation component 1 2, 2' - bis (o-phenyl)-4, 4' 5, 5' -Tetraphenyl-1,2 ' _ _ _ _ _ 0. 38 photopolymerization starting component 2 4, 4 '- bis-diethylaminodiphenyl ketone 0. 19 photopolymerization Starting component 3 2-M-based benzothiazole 0. 38 [Measurement of contrast] The coloring compositions obtained in the above Examples 5 to 6 and Comparative Examples 3 to 4 were applied to 50 using a spin coater. A glass substrate having a thickness of 0.7 mm and a thickness of 0.7 mm ("AN100" manufactured by Asahi Glass Co., Ltd.) was dried at 80 ° C for 3 minutes. Further, the rotation speed at the time of spin coating was adjusted so that the obtained dried coating film reached a film thickness of y^0.600. Then, using a 2 kW high-pressure mercury lamp, the exposure amount of 300 mJ/cm 2 was applied to the TF988407 140 201037041 for full-surface exposure treatment. Thereafter, development was carried out at a developing solution temperature of 23 C using a 1% by weight aqueous sodium carbonate solution. Then, a water-washing treatment was performed for 30 seconds at a water pressure of 3 kg/cm2, and a heat-hardening treatment was performed at 23 (TC for 30 minutes) to form a colored resin film. Thus, the coloring of the colored resin film was performed on a transparent glass substrate. Then, 'the contrast of the obtained colored plate is measured. The measurement method is the same as that described in the [Measurement of Contrast] of [1] above. The measurement results are shown in Table -6. 〇 [Table 6] Table-6 Contrast Implementation Example 5 8630 Example 8600 Comparative Example?! 6830 1 Comparison ta - [7510 Results of Tables 4 and 6 are not known. 'Using the dispersant of the present invention, the coloring composition of Examples 5 to 6' Compared with the color compositions of Comparative Examples 3 to 4, the dispersion stability is good, and the contrast of the vapor material is satisfied, and the usefulness thereof is extremely high. [2-2] Examples 7 to 15 and comparing you 丨ς ρ ^ Γ Examples 5 to 6: Examples using [2-1-1] resin. [Preparation of pigment dispersion] In addition to the use of a binder resin, it is used in combination with the above pigment dispersion. In the same manner as V, the preparation of the enamel pigment dispersion X (which is used for the later description) Example 5) [Preparation of coloring composition] TF988407 141 201037041 The above pigment dispersion liquid T (wherein the pigment dispersion liquid X in Comparative Example 5 and the pigment in Comparative Example 6) was used in the ratio shown in Table-7. The coloring compositions of Examples 7 to 15 and Comparative Examples 5 to 6 were prepared by mixing the dispersion W), the solvent, the binder resin, the polymerizable monomer, the photopolymerization initiator component, and the surfactant. The values in Table-7 are the contents (parts by weight). Further, in Table-7, *1 (Comparative Example 5) is the amount (content) of the pigment dispersion liquid X, and *2 (Comparative Example 6) is pigment dispersion. The amount of liquid helium used. TF988407 142 [Bu 4] Buddy <Comparative Example 6 I | 57.78*2 25.93 8.00 2.94 CO CO CO 〇0.38 0.19 〇〇CO Ci 0.76 c=) *' I 25.93 I 8.00 I 2.94 3.63 I 0. 38 CD 1 Η <〇0.38 0.76 s c> Example 15 57.78 I 25. 93 CZ) 〇〇〇* C73 oi 3.63 〇00 CO <=> 0.19 0.38 0.76 gc=> Example 14 1 57.78 I 25. 93 1 8.00 , 2.94 CD L 3'63 0.38 σΰ ι Η 00 00 CO 0.76 go Example 13 I 1 57.78 J 25.93 〇〇〇od CO CD CO 0. 38 0.19 oo CO G5 CO g Example 12 I 1 57.78 | 25.93 g od οα 3.63 | C=5 〇0 CO 0.19 0.38 0.76 s CD Example 111 I 57.78 | 25.93 1 8.00 1 05 03 3.63 C5 0.38 σϊ ι1 Η 00 CO CD 0.76 go Example ίο 1 I 57.78 | 25.93 Γ 8.00 1 ! 2.94 CO CO cd Ο 0.38 05 ^-Η Ο oo CO o' CO go I Example 9 | I 57.78 | 25.93 1 8.00 1 ^£ί I 2.94Π [3.63 | CD 0.38 σ5 Τ"Η Ο 00 CO C3 CD g C3 1 Example 8 | Γ 57.78 1 25.93 Γ 8.00 1 1 Γ 2.94 | CO CO CO 〇) 0.38 05 oo CO o 0.76 g c> Example 7| I 57.78 25.93 8.00 ! 2.94 3.63 Ο 0.38 i_ CD r 1 io 00 CO <〇CD go ΓIngredients "Pigment 対 液 液 T propylene glycol monomethyl ether acetate 3- ethoxy Ethyl propyl propionate blending amount dipentaerythritol hexaacrylate vinegar pentaerythritol tetrapropylene S vinegar 2,2'-(o-phenyl)-4,4',5,5'-tetraphenylbiimidazole 4,4' - bis-diethylaminodiphenyl-2-phenylbendazole cja ^ I w 1 Φ5 T ® ¢- ^ 4 m 4< Vg <4 蛉 Η Η >si ^ w Jj LO f Solvent 1 1 solvent 2 adhesive resin polymerization 1 1φ 45 fz Photopolymerization Initiating Component 3 Photopolymerization Initiating Component 4 Surfactant ε inch-ZOSSSl 201037041 [Viscosity change of coloring composition] Using the E-type viscometer "RE-80L" manufactured by Toki Sangyo Co., Ltd. The coloring compositions obtained in Examples 7 to 15 and Comparative Examples 5 to 6 were measured and stored at 23 ° C for 1 day, and the respective viscosity after standing for 7 days in a thermostat at 35 ° C (20 rpm) ). The results are shown in Table-8. In addition, the "viscosity change rate" in Table-8 is simply expressed as the ratio of the difference between the viscosity after "7 days" and the viscosity after "1 day after preparation" to the viscosity after "preparation". [Table 8] Table-8
根據表-8’對在35°C下靜置7日後之黏度變化率(黏度增 加率)比較可知’使用[2-1-1]樹脂之實施例7〜13之著色組 成物’黏度下降m 1%以下之黏度增加,與使用其 TF988407 144 201037041 他黏合劑樹脂之實施例14及15之著色組成物相比,黏度穩 定性更高。 另一方面可判明,未使用本發明分散劑之比較例4及5, 因快速地固化,故不適於製造彩色濾光片。 [對比度之測定] 將實施例7、14及15中所獲得之著色組成物於23°C下保 存1日後,使用該著色組成物,以與上述[2-1]之[對比度之 〇 測定]中相同之方式,製作成著色板。 又,準備將實施例7、14及15中所獲得之著色組成物分 別 •於23°C下保存7日者、以及 •於23t下保存12日者, 並使用該等,以相同之方式製成著色板。 對所製成之該等著色板,以與上述[2-1]之[對比度之測定] ❹相同之方式,測定對比度。結果示於表-9。 [表9] ^比度 7曰後 12日後 8448 8363 7091 6449 7041 6774According to Table-8', the viscosity change rate (viscosity increase rate) after 7 days of standing at 35 ° C is compared. 'The color composition of Examples 7 to 13 using [2-1-1] resin' viscosity is lowered. The viscosity of 1% or less is increased, and the viscosity stability is higher than that of the color compositions of Examples 14 and 15 using the TF988407 144 201037041 adhesive resin. On the other hand, it has been found that Comparative Examples 4 and 5 in which the dispersant of the present invention is not used are not suitable for producing a color filter because they are rapidly cured. [Measurement of Contrast] The colored compositions obtained in Examples 7, 14, and 15 were stored at 23 ° C for one day, and then the colored composition was used to determine [contrast of contrast] of [2-1] above. In the same way, it is made into a swatch. Further, the coloring compositions obtained in Examples 7, 14, and 15 were prepared to be stored at 23 ° C for 7 days, and • stored at 23 ° for 12 days, and used in the same manner. Into a swatch. The contrast was measured in the same manner as in [Measurement of Contrast] of [2-1] for the colored boards thus produced. The results are shown in Table-9. [Table 9] ^ Ratio 7 after 12 days 8448 8363 7091 6449 7041 6774
根據表〜9可知,使用[2-1 一丨]樹脂之實施例7之著色組成 TF988407 145 201037041 物,與使用其他黏合劑樹脂之實施例14及15之著色組成物 相比,可更長期地維持高對比度,故更佳。 [溶解時間之測定] 將實施例8〜15中所獲得之著色組成物分別旋塗於蒸鍍 有鉻之玻璃基板上,以80°C之加熱板進行3分鐘預烘烤, 而製成乾燥塗佈膜。再者,調整旋塗時之轉速,以使所得乾 燥塗佈膜達到色座標為y=〇. 600之膜厚。 繼而,利用高壓水銀燈通過寬度50 //m、長度3 mm之直 線狀光罩圖案,以60 mJ/cm2對所得乾燥塗佈膜進行曝光, 然後使用0.04重量%氫氧化鉀水溶液(顯影液溫度23°C), 以壓力0. 2 5 MPa進行喷霧顯影。 將未曝光部分之著色組成物完全溶解於顯影液中而露出 基板之時間,作為該著色組成物之溶解時間。結果示於表 -10。 [直線狀圖案之缺陷之測定] 使用實施例8〜15中所獲得之著色組成物,以與上述[溶 解時間之測定]相同之方式,於蒸鍍有鉻之玻璃基板上形成 乾燥塗佈膜,介隔光罩圖案進行曝光及顯影。再者,將顯影 時間設為上述[溶解時間之測定]中所測定之溶解時間的2 倍。 顯影後,用充分量的水清洗,然後用潔淨空氣乾燥。其後, 於230°C之烘箱中進行30分鐘後烘烤,而形成由著色樹脂 TF988407 146 201037041 膜所構成之直線狀圖案。著色樹脂膜之膜厚為1.8 /im左 右。 使用光學顯微鏡以10倍放大率觀察10條直線狀圖案,對 線邊緣的凹處加以計數,作為缺陷數。為了確認再現性而重 複2次,求出平均值。結果示於表-10。 再者,將直線狀圖案之代表例之顯微鏡觀察圖表示於圖 5 ° Ο [表 10] 表-10 溶解時間(秒) 缺陷數 實施例8 45 9. 5 實施例9 36 31 實施例10 21 21. 5 實施例11 30 13. 5 實施例12 57 38. 5 實施例13 20 2 實施例14 71 12. 5 實施例15 65 23 〇 根據表-10可知,使用含有[2-1-1]樹脂之著色組成物之 實施例8〜13,與使用其他黏合劑樹脂之實施例14及15相 比,溶解時間短至60秒以下,顯影性更佳。 又,可知,含有「分子量為400以下、且雙鍵當量為110 以下」之化合物(季戊四醇四丙烯酸酯。分子量為352,雙 鍵當量為88)作為聚合性單體之實施例13的著色組成物, 直線狀圖案之缺陷數特別少,從而獲得具有良好直線性之圖 案。 TF988407 147 201037041 [2-3 ]貫施例16〜20及比較例7 :使用[2_ 1 _2 ]樹脂作為黏 合劑樹脂之例 [顏料分散液之製備] 除了使用黏合劑樹脂R作為分散樹脂以外,以與上述顏料According to Tables -9, the coloring composition TF988407 145 201037041 of Example 7 using [2-1 丨] resin can be used for a longer period of time than the coloring compositions of Examples 14 and 15 using other binder resins. It is better to maintain high contrast. [Measurement of Dissolution Time] The colored compositions obtained in Examples 8 to 15 were spin-coated on a glass substrate on which chromium was deposited, and prebaked in a hot plate at 80 ° C for 3 minutes to prepare a dry film. Coating film. Further, the number of revolutions at the time of spin coating was adjusted so that the resulting dry coating film reached a film thickness of y = 〇 600. Then, the obtained dry coating film was exposed at 60 mJ/cm 2 through a linear reticle pattern having a width of 50 // m and a length of 3 mm using a high pressure mercury lamp, and then a 0.04% by weight aqueous potassium hydroxide solution (developing solution temperature 23) was used. °C), spray development at a pressure of 0.25 MPa. The time during which the coloring composition of the unexposed portion was completely dissolved in the developing solution to expose the substrate was used as the dissolution time of the colored composition. The results are shown in Table -10. [Measurement of Defects in Linear Patterns] Using the coloring compositions obtained in Examples 8 to 15, a dry coating film was formed on a glass substrate on which chromium was vapor-deposited in the same manner as in the above [Measurement of dissolution time]. Exposure and development are performed through a mask pattern. Further, the development time was set to be twice the dissolution time measured in the above [Measurement of Dissolution Time]. After development, it is washed with a sufficient amount of water and then dried with clean air. Thereafter, it was baked in an oven at 230 ° C for 30 minutes to form a linear pattern of a film of colored resin TF988407 146 201037041. The film thickness of the colored resin film was about 1.8 / im. Ten linear patterns were observed at 10 times magnification using an optical microscope, and the recesses at the edge of the line were counted as the number of defects. The average value was obtained by repeating twice in order to confirm the reproducibility. The results are shown in Table-10. Further, a microscopic observation view of a representative example of the linear pattern is shown in Fig. 5 ° Ο [Table 10] Table-10 Dissolution time (seconds) Number of defects Example 8 45 9. 5 Example 9 36 31 Example 10 21 21. 5 Example 11 30 13. 5 Example 12 57 38. 5 Example 13 20 2 Example 14 71 12. 5 Example 15 65 23 〇 According to Table-10, the use contains [2-1-1] In Examples 8 to 13 of the colored composition of the resin, the dissolution time was as short as 60 seconds or less as compared with Examples 14 and 15 using other binder resins, and the developability was further improved. Further, it is understood that the coloring composition of Example 13 containing a compound having a molecular weight of 400 or less and a double bond equivalent of 110 or less (pentaerythritol tetraacrylate, molecular weight: 352, double bond equivalent: 88) as a polymerizable monomer The number of defects in the linear pattern is particularly small, so that a pattern having good linearity is obtained. TF988407 147 201037041 [2-3] Examples 16 to 20 and Comparative Example 7: Example of using [2_ 1 _2 ] resin as a binder resin [Preparation of pigment dispersion liquid] In addition to using binder resin R as a dispersion resin, With the above pigments
I 分散液Τ相同之方式,製備顏料分散液γ。(其使用於後述 比較例7。) [著色組成物之製備] 如表-11所示,將各成分加以混合,而製備著色組成物。f) 於(其中,於實施例16〜20中使用顏料分散液τ,於比較例 7中使用顏料分散液Υ。)表—u中,「分散樹脂D」等之表述, 意指「使用黏合劑樹脂D作為分散樹脂」。 再者,表-11中之「溶劑丨」及「溶劑2」,表示「顏料分 政液」中所含之溶劑以外,重新調配之溶劑。 TF988407 148 201037041I Dispersion Τ In the same manner as in the preparation of the pigment dispersion γ. (This was used in Comparative Example 7 described later.) [Preparation of Colored Composition] As shown in Table-11, each component was mixed to prepare a colored composition. f) (wherein the pigment dispersion liquid τ is used in the examples 16 to 20, and the pigment dispersion liquid Υ is used in the comparative example 7). In the table -u, the expression "dispersion resin D" or the like means "use of adhesion" The resin D is used as a dispersion resin. In addition, the "solvent 丨" and "solvent 2" in Table-11 indicate the solvent to be re-formulated in addition to the solvent contained in the "pigmentation liquid". TF988407 148 201037041
〔11<〕ο Q 11丨< 成分之詳細内容 比較例7 分散劑A 分散樹脂R 丙二醇單甲醚乙酸酯 3-乙氧基丙酸乙酯 Cei 二季戊四醇六丙烯酸酯 2, 2’ -雙(鄰氣苯基)-4, 4’,5, 5’ -四苯基-1,2’ -聯咪唑 4, 4’ -雙-二乙胺基二苯基酮 2-Μ基苯并噻唑 2-曱基-1_[4 -(甲硫基)苯基]-2_味琳基丙院- 大曰本油墨化學工業公司製造之氟系界面活性劑「F-475」 實施例20 分散劑A 分散樹脂D CU 實施例19 分散劑A 分散樹脂D Ο* Ξ 實施例18 分散劑A 分散樹脂D 實施例17 分散劑A 分散樹脂D r-H 實施例16 分散劑A 分散樹脂D ω (重量 份) 57.78 25.93 <〇 〇〇 CO CO CO 〇〇 CO 〇 <〇 〇〇 CO <=> CO <3> C3 成分之種類 顏料分散液 溶劑1 溶劑2 黏合劑樹脂 聚合性單體 光聚合起始系成分1 光聚合起始系成分2 光聚合起始系成分3 光聚合起始系成分4 界面活性劑 6寸1 卜0-8£1 201037041 [溶解時間之測定] 使用實施例16〜20及比較例7中所獲得之著色組成物, 以與上述[2-2]之[溶解時間之測定]項中相同之方式,測定 著色組成物之溶解時間。其中,使用寬度25 //m之直線狀 光罩圖案,使該光罩圖案與基板之間距離為150 /zm並加以 固定,進行曝光。溶解時間之測定結果示於表-12。 [直線狀圖案之缺陷之測定] 使用實施例16〜20及比較例7中所獲得之著色組成物, 以與上述[2-2 ]之[直線狀圖案之缺陷之測定]相同之方式, 測定缺陷數。為了確認再現性而重複2次,求出平均值。結 果示於表-12。 [表 12] 表_12 溶解時間 缺陷數 實施例16 31 3 實施例17 31 4 實施例18 29 8 實施例19 71 12. 5 實施例20 65 23 比較例7 120 >100 根據表-12之結果可明瞭,使用[2-1-2]樹脂之實施例16 〜20之著色組成物,其溶解時間較短,顯影性更佳。又, 可知,因圖案之缺陷較少,故可獲得直線性更佳之圖案。 [2-4]實施例21〜29 :使用肟酯系化合物作為光聚合起始劑 之例。 TF988407 150 201037041 [著色組成物之製備] 將57. 78重量份之上述顏料分散液T、丙二醇單曱醚乙酸 酯25. 93重量份、3-乙氧基丙酸乙S旨8. 00重量份、進而其 他成分加以混合,而製備表-13所示之著色組成物。 再者,表-13中之光聚合起始系成分5〜8(肟酯系起始劑 _ a、b、c及d),分別為以下化合物。 [化 35][11<]ο Q 11丨< Details of the composition Comparative Example 7 Dispersant A Dispersion resin R Propylene glycol monomethyl ether acetate 3-ethoxypropionate ethyl ester Cei Dipentaerythritol hexaacrylate 2, 2' - Bis(o-phenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole 4,4'-bis-diethylaminodiphenyl ketone 2-mercaptobenzoene Thiazole 2-mercapto-1_[4-(methylthio)phenyl]-2_味琳基丙院 - Fluoride surfactant "F-475" manufactured by Otsuka Ink Chemical Industry Co., Ltd. Example 20 Dispersion Agent A Dispersing Resin D CU Example 19 Dispersant A Dispersing Resin D Ο* 实施 Example 18 Dispersant A Dispersing Resin D Example 17 Dispersant A Dispersing Resin D rH Example 16 Dispersant A Dispersing Resin D ω (parts by weight 57.78 25.93 <〇〇〇CO CO CO 〇〇CO 〇<〇〇〇CO <=> CO <3> C3 component type pigment dispersion solvent 1 solvent 2 binder resin polymerizable monomer light Polymerization Initiating Component 1 Photopolymerization Initiating Component 2 Photopolymerization Initiating Component 3 Photopolymerization Initiating Component 4 Surfactant 6 Inch 1 Bu 0-8 £1 201037041 [Dissolution time] Examples 16~20 and a coloring composition obtained in Comparative Example 7 Measurement] using the embodiment, the measurement of the same item] in [2-2] of the above-described [the dissolution time of the embodiment, the measurement time of dissolution of the coloring composition. Here, a linear mask pattern having a width of 25 / m was used, and the distance between the mask pattern and the substrate was 150 / zm, and the exposure was performed. The measurement results of the dissolution time are shown in Table-12. [Measurement of Defects in Straight Line Patterns] The coloring compositions obtained in Examples 16 to 20 and Comparative Example 7 were measured in the same manner as in [Measurement of defects in linear patterns] of [2-2] above. The number of defects. The average value was obtained by repeating twice in order to confirm reproducibility. The results are shown in Table-12. [Table 12] Table_12 Dissolution time defect number Example 16 31 3 Example 17 31 4 Example 18 29 8 Example 19 71 12. 5 Example 20 65 23 Comparative Example 7 120 > 100 According to Table-12 As a result, it was revealed that the coloring compositions of Examples 16 to 20 of [2-1-2] resin had a shorter dissolution time and better developability. Further, it can be seen that since the pattern has few defects, a more linear pattern can be obtained. [2-4] Examples 21 to 29: An example in which an oxime ester compound is used as a photopolymerization initiator. 00重量。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Parts and further components were mixed to prepare a coloring composition shown in Table-13. Further, the photopolymerization starting components 5 to 8 (an oxime ester-based initiators _ a, b, c and d) in Table-13 are the following compounds, respectively. [化35]
(肟酯系起始劑a) Ο [化 36](肟 ester-based initiator a) Ο [Chem. 36]
TF988407 151 201037041 [化 37]TF988407 151 201037041 [Chem. 37]
(肟酯系起始劑c) [化 38](肟 ester based initiator c) [Chem. 38]
(月亏酯系起始劑d :汽巴精化(Ciba Specialty Chemicals) 公司製造之「Irgacure OXE02」) TF988407 152 201037041 ο οοτ< 〔005 實施例29 1 Μ cn> csi 3.63 I 卜 〇· i 1 _ Η Τ—Η 1 1 〇 實施例28 Ε— 2. 94 _3.63 1 1 CD ο (Μ 1 1 1 I CZ5 實施例27 e- 寸 05 05 | 3.63 I 〇 CO 1 ο 1 1 I 1 S cz> 實施例26 | 1 2.94 1 CO CD CQ 卜 寸· CD 〇 寸 14.1 1 S ο 實施例25 2.94 1 [3.63 | 1 1 1 CO <Μ· 1 1 οα 1 < 1 g 實施例24 | 寸 05 OJ CO co CO 1 1 1 1 1 1 1 〇 卜‘ <=> 實施例23 寸 3.63 1 1 1 1 1 1 in CO 1 S ¢=5 實施例22 | E- 2.94 1 CO CO CQ 1 1 1 i I C3 卜· 1 1 C^l <=> o 實施例21 | e- 2. 94 CO CO CO 1 1 I 1 〇 卜· 1 1 1 s G3 顏料分散液 黏合劑樹脂F 二季戊四醇六丙烯酸酯 2, 2’-(鄰氣苯基)-4, 4’,5, 5’-四苯 基聯咪"坐 4, 4’ -雙-二乙胺基二笨基酮 2-疏基苯并噻唑 2-曱基-1_[4-(甲硫基)苯基]-2-ϊΙ未 淋基丙烧-1-_ 肟酯系起始劑a 肟酯系起始劑b 肟酯系起始劑c 肟酯系起始劑d U /-—N g ” ί Η M 齋\ί〇 ^ i 蜊岭 LO PL·* 成分之種類 黏合劑樹脂 聚合性單體 光聚合起始 系成分1 光聚合起始 系成分2 光聚合起始 系成分3 光聚合起始 系成分4 光聚合起始 系成分5 光聚合起始 系成分6 光聚合起始 系成分7 光聚合起始 系成分8 界面活性劑 e- ΖΌ 寸°°86,ϋ 201037041 [溶解時間之測定] 使用實施例21〜29中所獲得之著色組成物,以與上述 [2-3]之[溶解時間之測定]項相同之方式,測定著色組成物 之溶解時間。其中,所製成之乾燥塗佈膜之膜厚為2. 5 //m 左右。溶解時間之測定結果示於表-14。 [線寬之測定] 用光學顯微鏡觀測以與上述[溶解時間之測定]中相同之 方式而獲得之直線狀圖案,並測定其線寬。其結果示於表 -14。 [異物評價] 對於實施例21〜29中所獲得之著色組成物,分別將 (iii) 製備後於23°C下靜置1日者、以及 (iv) 於23°C下靜置1日後,於35°C之恆溫槽中保存6曰 者, 旋塗於5 cm見方之玻璃基板(旭硝子公司製造之「AN100」) 上,於80°C下加熱3分鐘,以60 mJ/cm2進行曝光,而形成 乾燥塗佈膜。 再者,調整旋塗之轉速,以使乾燥塗佈膜之膜厚在2〜3 // m之間。 使用光學顯微鏡以5倍放大率觀察所得乾燥塗佈膜之整 個表面,測定異物之個數。其結果示於表-14。 再者,於表-14中,〇意指無異物,〇△意指異物為5個 TF988407 154 201037041 以下,△意指異物為6個以上。 [丽P耐性] 將以與上述[異物評價]中之(iii)相同之方式形成有乾燥 塗佈膜的玻璃基板,設置於加入有N-曱基吡咯啶酮(NMP)之 試樣瓶中,以使其長度的一半浸潰於N-曱基0比咯咬酮(NMP) 中,並加蓋,於23°C下靜置30分鐘。 將基板取出後,進行水洗,並吹壓縮空氣進行乾燥。 〇 使用光學顯微鏡,以5倍放大率觀察基板上之乾燥塗佈膜 中的NMP非浸潰部分與浸潰部分之邊界附近。其結果示於表 -14。 ' 再者,對於觀察部分之表面狀態,於表-14中以如下方式 • 進行評價。 〇:與浸潰於NMP之浸潰部分無差異,表面光滑 〇△:於表面上可見少量析出物。丽P非浸潰部分之表面 Ο 變粗糙,或者雖然不明顯但仍可判明NMP浸潰部分/非浸潰 部分之邊界。 △:於表面上可見明顯的析出物,可明確地判明NMP浸潰 部分/非浸潰部分之邊界線。 TF988407 155 201037041 寸1—(—< 實施例29 CO od CO 〇〇 〇 <1 〇 < 實施例28 e- 28.0 寸 〇 〇 < 實施例27 28.2 LO 〇 〇 <] 實施例26 31.3 寸 CO < < <1 〇 實施例25 34.5 寸 οα 〇 〇 〇 實施例24 e- 〇> ai C<l LO (>α 〇 〇 〇 實施例23 | e- c=> CO CO LO 03 〇 〇 〇 實施例22 CO 寸’ CO LO oa 〇 〇 〇 實施例21 E- CO CT> (NI LO <N1 〇 〇 〇 實施例 顏料分散液’ 線寬(//m) 溶解時間(秒) 1曰後 7曰後 NMP耐性 異物評價 9- 201037041 根據表~14之姓s(monthly ester ester initiator d: "Irgacure OXE02" manufactured by Ciba Specialty Chemicals Co., Ltd.) TF988407 152 201037041 ο οοτ < 005 Example 29 1 Μ cn> csi 3.63 I 〇 〇 i 1 _ Η Τ—Η 1 1 〇 Example 28 Ε— 2. 94 _3.63 1 1 CD ο (Μ 1 1 1 I CZ5 Example 27 e-inch 05 05 | 3.63 I 〇CO 1 ο 1 1 I 1 S Cz> Example 26 | 1 2.94 1 CO CD CQ cd · CD 1 14.1 1 S ο Example 25 2.94 1 [3.63 | 1 1 1 CO < Μ · 1 1 οα 1 < 1 g Example 24 | Inch 05 OJ CO co CO 1 1 1 1 1 1 1 '卜 ' <=> Example 23 Inch 3.63 1 1 1 1 1 1 in CO 1 S ¢=5 Example 22 | E- 2.94 1 CO CO CQ 1 1 1 i I C3 卜 · 1 1 C^l <=> o Example 21 | e- 2. 94 CO CO CO 1 1 I 1 · · 1 1 1 s G3 Pigment Dispersion Binder Resin F Dipentaerythritol hexaacrylate 2, 2'-(o-phenyl)-4,4',5,5'-tetraphenyl-linked microphone"Sit 4,4'-bis-diethylaminodiphenyl ketone 2-carbylbenzothiazole 2-mercapto-1_[4-(methylthio)phenyl]-2-indolylpyranyl-1-yrylate Starting agent a oxime ester-based initiator b oxime ester-based initiator c oxime ester-based initiator d U /--N g ” Η Η M 斋 \ί〇^ i 蜊岭 LO PL·* Adhesive resin polymerizable monomer Photopolymerization initiator component 1 Photopolymerization initiator component 2 Photopolymerization initiator component 3 Photopolymerization initiator component 4 Photopolymerization initiator component 5 Photopolymerization initiator component 6 Light Polymerization Initiating Component 7 Photopolymerization Initiating Component 8 Surfactant e- ΖΌ ° ° 86, ϋ 201037041 [Measurement of Dissolution Time] The coloring compositions obtained in Examples 21 to 29 were used, as described above. 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。. The measurement results of the dissolution time are shown in Table-14. [Measurement of line width] A linear pattern obtained in the same manner as in the above [Measurement of dissolution time] was observed with an optical microscope, and the line width was measured. The results are shown in Table -14. [Foreign matter evaluation] The coloring compositions obtained in Examples 21 to 29 were respectively allowed to stand at 23 ° C for one day after the preparation of (iii), and (iv) after standing at 23 ° C for one day. 6 保存 in a 35 ° C thermostat, spin-coated on a 5 cm square glass substrate ("AN100" manufactured by Asahi Glass Co., Ltd.), heated at 80 ° C for 3 minutes, exposed at 60 mJ / cm 2 A dry coating film is formed. Further, the rotational speed of the spin coating is adjusted so that the film thickness of the dried coating film is between 2 and 3 // m. The entire surface of the obtained dried coating film was observed at 5 times magnification using an optical microscope, and the number of foreign matters was measured. The results are shown in Table-14. Further, in Table-14, 〇 means no foreign matter, 〇 △ means that foreign matter is 5 TF988407 154 201037041 or less, and Δ means 6 or more foreign matters. [L P resistance] A glass substrate having a dried coating film formed in the same manner as (iii) in the above [foreign matter evaluation] was placed in a sample bottle to which N-decylpyrrolidone (NMP) was added. Half of its length was immersed in N-mercapto 0-butanone (NMP), capped, and allowed to stand at 23 ° C for 30 minutes. After the substrate was taken out, it was washed with water, and compressed air was blown and dried.附近 The vicinity of the boundary between the NMP non-impregnated portion and the impregnated portion in the dried coating film on the substrate was observed at 5 times magnification using an optical microscope. The results are shown in Table -14. ' Again, for the surface state of the observed portion, the evaluation is performed in Table-14 as follows. 〇: No difference from the impregnation part of NMP, the surface is smooth 〇 △: A small amount of precipitates are visible on the surface. The surface of the non-impregnated portion of Li P is roughened or, although not obvious, the boundary of the NMP impregnated/non-impregnated portion is still known. △: Obvious precipitates were observed on the surface, and the boundary line of the NMP-impregnated portion/non-impregnated portion was clearly identified. TF988407 155 201037041 Inch 1 - (- < Example 29 CO od CO 〇〇〇 < 1 〇 < Example 28 e - 28.0 inch 〇〇 < Example 27 28.2 LO 〇〇 <] Example 26 31.3 Inch CO <<1 〇Example 25 34.5 inch οα 〇〇〇Example 24 e- 〇> ai C<l LO (>α 〇〇〇Example 23 | e- c=> CO CO LO 03 〇〇〇Example 22 CO Inch 'CO LO oa 〇〇〇Example 21 E-CO CT> (NI LO <N1 〇〇〇Example Pigment Dispersion' Line Width (//m) Dissolution Time (Second) Evaluation of NMP resistance foreign matter after 7曰 after 7曰 9- 201037041 According to the surname of Table~14
、、,α果可知,使用肟酯系化合物作為光聚合起 〇’、刀(光聚合起始劑)之實施例21〜25,與使用其他光 • 耳靶例26〜29相比較’並未產生異物,NMP • 亦優/、又’併用肟酯系化合物與苯乙酮衍生物作為光 聚合起始系成公夕举# <貫知例25,與其他實施例相比,雖然光 * σ &分之總含量相同或者較少’卻顯示更高敏感度 (可獲得線寬較粗之圖案)。 Ο [2-5]實_ 3〇〜36 :使料香賴酸系化合物之例。 於10· 55重里份之顏料分散液τ中’加入丙二醇單曱醚乙 酉文酉曰5. 96重量伤、〇. 42重量份之黏合劑樹脂e、汽巴精化 公司製造之光聚合起始劑「Irgaeure QXE()2」(化學結構參 照上述[2-5]中之「抑旨系起始劑d」)以及汽巴精化公司製 造之「Irgacure 907」(2~曱基曱硫基)苯基]一2_咮啉 基丙烧-1-綱)各0. 1〇重量份、作為聚合性單體之季戊四醇 Ο四丙烯酸酯〇.77重量份(其中,僅於實施例36中為0.86 重量份)’進而表-16中所記載之芳香族羧酸系化合物(或者 與其進行比較之化合物)0.085重量份,而製備著色組成物。 • 再者,實施例中所使用之芳香族羧酸系化合物(及與其進 行比較之化合物),分別如以下表-15所示。 TF988407 157 201037041 [表 15] 表-15 化合物No. 結構式 商品名或化合物名 1 α0^φ〇 〇 共榮社化學公司製造之 [H0A-MPL] 2 ΐ 鄰苯二甲酸單甲酯 (Aldrich公司製造) 3 °νΡ HO I ο入 α" 鄰苯二甲酸單苄酯 (Aldrich公司製造) 4 〇 0 共榮社化學公司製造之 「LIGHT ACRYLATE Η0Α-ΗΗ」 5 v9 ~〇 L I 鄰苯二曱酸二甲酯 (Aldrich公司製造) 6 「H0A-MS」 共榮社化學公司製造 [著色組成物之評價] 對將實施例30〜36中所獲得之著色組成物 (v )製備後於23°C下靜置1日者、以及 (vi)將(v )進而於35°C之恆溫槽中靜置6曰者, TF988407 158 201037041 分別進行以下之評價。結果示於表-16。 [組成物之黏度變化] 使用東機產業公司製造之E型黏度計「RE-80L」,分別對 ' 實施例30〜36中所得、並以上述(v)或(vi)之方法靜置後 的著色組成物之黏度(20 rpm)進行測定。再者,表-16中之 「黏度變化率」,係以「進而35°C、6日後」之黏度與「23 °C、1日後」之黏度的差相對於「於23°C下靜置1日後」之 〇 黏度的比例來表示。測定結果示於表-16。 [直線狀圖案之缺陷之測定] 對實施例30〜36中所獲得、並以上述(v)或(vi)之方法 ' 加以靜置後的著色組成物,分別以與上述[2-2]之[直線狀圖 案之缺陷之測定]項相同之方式進行測定。再者,對於各實 施例之(v )及(vi )之各著色組成物,各測定2次,求出平均 值。測定結果不於表-16。 〇 [線寬之測定] 對實施例30〜36中所獲得、並以上述(V)或(vi)之方法 加以靜置後的著色組成物,分別以與上述[2-4]之[線寬之測 定]相同之方式進行測定。結果不於表-16。 [6-4]溶解時間之測定 對實施例30〜36中所獲得、並以上述(v)或(vi)之方法 加以靜置後的著色組成物,分別以與上述[2-3]之[溶解時間 之測定]相同之方式進行測定。結果示於表-16。 TF988407 159 201037041 9T—|丨< 實施例36 1 4. 40 1—Η CJ5 LO CO CO CO § CO <=) o i—H LO CD CO 實施例35 1 化合物6 4. 32 卜 CD LO CO r-H CO § oo LO 卜 1—H CO CO s 导 實施例34 I 化合物5 I 4.59 LO 1—Η cd cr> CO CO CO OO CO 1—H CO LO cd OO 寸 實施例33 | 化合物4 | 4.11 5.43 32.1 CO CO s oo CO 1 32.1 1 LO csi 實施例32 化合物3 4.20 4. 05 -3.6 oo 1—H CO 03 τ-Η CO oa LO LO i—H 實施例31 化合物2 | 4.17 4.05 -2.9 g CO CM· CO 03 r-H CO LO oa LO CO C<1 實施例30 |化合物1^ 4.05 4. 05 CD CO LO CO LO | 32.1 I CO 1—H CO 14.5 CO 芳香族羧酸系化合物 23°C、1 曰後(mPa· s) 進而 35°C、6 日後(mPa· s) 黏度變化率 23°C、1日後 進而35°C、6日後 23°C、1日後 進而35°C、6日後 23。(:、1 日後 進而35°C、6日後 黏度變化 溶解時間(秒) 線寬(//m) 缺陷(個) 091 201037041 16 了知’含有芳香族叛酸系化合物之實施例3〇 一 /、不3該化合物之實施例33〜36相比,黏度穩定性 5谷解時間更短(顯影性優異)^·溶解性不經時性下降。 ,線覓之經時性減少(敏感度之經時性下降)更少,缺 陷之經時性增加亦較少。 [3]實施例37〜43 : C. I.色素紅254等使用例。 [顏料分散液之製備] G (1)P. R. 254顏料分散液之製備 添加作為紅色顏料之8. 50重量份之C.I·色素紅254、上 述分散劑A經固形分換算6.23重量份、合成例8中所獲得 之树知Η經固形分換算2.83重量份、作為溶劑之丙二醇單 甲謎乙酉夂酉曰50. 16重量份,與直徑0.5 mm之氧化錯珠225 重畺伤同填充至不鏽鋼容器中,藉由塗料振動機進行6 小時分散,而製備P.R· 254顏料分散液。 ❹⑵Pi m/P· Y. 顏料分散液之製備 將作為紅色顏料之22.40重量份之C. L色素紅177、作為 黃色顏料之5. 60重量份之αΐ,色素黃γΐ5〇、畢克化學公司 ;.製造之分散劑「Disperbyk 2001」經固形分換算8.48重量 伤、合成例18中獲得之樹脂s經固形分換算9. 〇3重量份、 以及作為溶劑之丙二醇單曱醚乙酸酯157. 66重量份,與直 徑0.5 mm之氧化鍅珠675重量份一同填充至不鏽鋼容器 中’藉由塗料振動機進行6小時分散,而製備 TF988407 161 201037041 P. R. 177/P. Y. 150 顏料分散液。 [著色組成物之製備] 於上述P.R. 254顏料分散液3.87重量份、以及上述 P. R. 177/P. Υ. 150顏料分散液4. 15重量份中,加入丙二醇 單甲醚乙酸酯5. 63重量份、合成例6中獲得之樹脂F經固 形分換算0. 44重量份、汽巴精化公司製造之光聚合起始劑 「Irgacure ΟΧΕ02」(化學結構參照上述[2-5 ]中之「月亏酯系 起始劑d」)0. 05重量份、汽巴精化公司製造之光聚合起始 劑「Irgacure 907」(2-曱基-1-[4-(曱硫基)苯基]-2-咮琳 基丙烷-1-酮)0.07重量份、大日本油墨公司製造之界面活 性劑「F475」0. 003重量份、作為聚合性單體之東亞合成公 司製造之「T01382」0. 70重量份(其中,僅於實施例43中 為0. 78重量份),進而表-17中記載之芳香族羧酸系化合物 (或者與其進行比較之化合物)0.08重量份,而製備紅色著 色組成物。 再者,各實施例中所使用之芳香族羧酸系化合物(以及與 其進行比較之化合物),分別如上述表-15所示。 [著色組成物之評價] 對將實施例37〜43中所獲得之著色組成物 (v) 製備後於23°C下靜置1曰者、以及 (vi) 將(v )進而於35°C之恆溫槽中靜置6日者, 分別進行以下之評價。結果示於表-17。 TF988407 162 201037041 [組成物之黏度變化] 使用東機產業公司製造之E型黏度計「RE-80L」,分別對 實施例37〜43中所獲得、並以上述(v)或(vi)之方法加以 靜置後的著色組成物之黏度(20 rpm)進行測定。再者,表-17 中之「黏度變化率」,係以「進而35°C、6日後」之黏度與 「23°C、1日後」之黏度的差相對於「23°C、1日後」之黏 度的比例來表示。測定結果示於表-17。 〇It is understood that the use of the oxime ester compound as the photopolymerization enthalpy', the knives (photopolymerization initiator) of Examples 21 to 25, compared with the use of other light and ear target examples 26 to 29 When a foreign matter is generated, NMP • is also excellent, and 'and an oxime ester compound and an acetophenone derivative are used as a photopolymerization initiation system to form a singular hoist # < 知知例25, compared with other examples, although light* σ &; the total content is the same or less 'but shows a higher sensitivity (a pattern with a thicker line width). Ο [2-5] Real _ 3 〇 ~ 36 : An example of a scented acid compound. In the pigment dispersion τ of 10·55 parts, 'add propylene glycol monoterpene ether 酉 酉 酉曰 5. 96 weight damage, 〇. 42 parts by weight of binder resin e, photopolymerization start by Ciba Specialty Chemicals Co., Ltd. "Irgaeure QXE()2" (for the chemical structure, refer to "Initiative d" in the above [2-5]) and "Irgacure 907" (2~曱-based thiol) manufactured by Ciba Specialty Chemicals Co., Ltd.苯基]]] 2 2 2 -1- -1- -1- -1- 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 77 A coloring composition was prepared by preparing 0.88 parts by weight of 0.86 parts by weight of the aromatic carboxylic acid-based compound (or a compound thereof) described in Table-16. Further, the aromatic carboxylic acid-based compounds (and the compounds to be compared therewith) used in the examples are shown in Table -15 below. TF988407 157 201037041 [Table 15] Table-15 Compound No. Structural formula or compound name 1 α0^φ〇〇[H0A-MPL] 2 ΐ Monomethyl phthalate (Aldrich) Manufactured by ° & I I I & & & & & LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT LIGHT Dimethyl ester (manufactured by Aldrich Co., Ltd.) 6 "H0A-MS" Manufactured by Kyoeisha Chemical Co., Ltd. [Evaluation of coloring composition] The coloring composition (v) obtained in Examples 30 to 36 was prepared at 23 ° C. The following evaluation was carried out for each of TF988407 158 201037041, which was left to stand still for 1 day, and (vi) was further placed in a thermostat at 35 ° C for 6 。. The results are shown in Table-16. [Viscosity change of the composition] After using the E-type viscometer "RE-80L" manufactured by Toki Sangyo Co., Ltd., the results obtained in Examples 30 to 36 were allowed to stand after the above method (v) or (vi). The viscosity of the colored composition (20 rpm) was measured. In addition, the "viscosity change rate" in Table-16 is the difference between the viscosity of "further after 35 °C, after 6 days" and the viscosity of "23 °C, after 1 day" with respect to "resting at 23 °C" The ratio of the viscosity after 1 day is indicated. The measurement results are shown in Table-16. [Measurement of Defects in Straight Line Patterns] The coloring compositions obtained in Examples 30 to 36 and held in the above method (v) or (vi) were respectively subjected to the above [2-2]. The measurement is performed in the same manner as in the measurement of the defect of the linear pattern. Further, each of the colored compositions of (v) and (vi) of each of the examples was measured twice to obtain an average value. The measurement results are not shown in Table-16. 〇 [Measurement of line width] The coloring compositions obtained in Examples 30 to 36 and allowed to stand by the above method (V) or (vi) are respectively subjected to the [lines of [2-4] above. Measurement of width] The measurement was carried out in the same manner. The results are not shown in Table-16. [6-4] Measurement of Dissolution Time The colored compositions obtained in Examples 30 to 36 and allowed to stand by the above method (v) or (vi) were respectively subjected to the above [2-3]. [Measurement of Dissolution Time] The measurement was carried out in the same manner. The results are shown in Table-16. TF988407 159 201037041 9T—|丨< Example 36 1 4. 40 1—Η CJ5 LO CO CO CO § CO <=) oi—H LO CD CO Example 35 1 Compound 6 4. 32 CD CD LO CO rH CO § oo LO 卜 1 - H CO CO s Example 34 I Compound 5 I 4.59 LO 1 - Η cd cr > CO CO CO OO CO 1 - H CO LO cd OO Example 33 | Compound 4 | 4.11 5.43 32.1 CO CO s oo CO 1 32.1 1 LO csi Example 32 Compound 3 4.20 4. 05 -3.6 oo 1—H CO 03 τ-Η CO oa LO LO i—H Example 31 Compound 2 | 4.17 4.05 -2.9 g CO CM · CO 03 rH CO LO oa LO CO C<1 Example 30 | Compound 1^ 4.05 4. 05 CD CO LO CO LO | 32.1 I CO 1—H CO 14.5 CO Aromatic carboxylic acid compound 23°C, 1 曰After (mPa·s), 35° C., after 6 days (mPa·s), the viscosity change rate was 23° C., 1 day later, 35° C., 6 days later, 23° C., 1 day later, 35° C., and 6 days later. (:, after 1 day and then 35 ° C, after 6 days, viscosity change dissolution time (seconds) line width (//m) defect (unit) 091 201037041 16 Knowing the example 3 containing an aromatic tickic acid compound In comparison with Examples 33 to 36 of the compound, the viscosity stability 5 is shorter (the development property is excellent), the solubility is not deteriorated, and the lapse of time is reduced (sensitivity) There is less time-dependent decrease, and the time-dependent increase of defects is also less. [3] Examples 37 to 43: Examples of use of CI Pigment Red 254, etc. [Preparation of Pigment Dispersion] G (1) PR 254 Pigment Dispersion The preparation of the liquid was added as a red pigment of 8.5 parts by weight of CI·dye red 254, the dispersant A was converted to 6.23 parts by weight in terms of solid content, and the obtained obtained in Synthesis Example 8 was converted into a solid content of 2.83 parts by weight. 50. 16 parts by weight of a propylene glycol monomethyl acetazone as a solvent, filled with a 0.5 mm diameter oxidized wrong bead 225, and filled into a stainless steel container, and dispersed by a paint shaker for 6 hours to prepare a PR· 254 pigment dispersion. ❹(2)Pi m/P· Y. Preparation of pigment dispersion As a red pigment, 22.40 parts by weight of C. L pigment red 177, as a yellow pigment 5.60 parts by weight of αΐ, pigment yellow γΐ5〇, BYK Chemical Co., Ltd.; manufactured dispersant "Disperbyk 2001" by solid content Conversion: 8.48 weight loss, the resin s obtained in Synthesis Example 18 was converted into solids by 9. 〇 3 parts by weight, and propylene glycol monoterpene ether acetate as a solvent, 157.66 parts by weight, and cerium oxide beads 675 having a diameter of 0.5 mm. The parts by weight were filled together in a stainless steel container to prepare a TF988407 161 201037041 PR 177/PY 150 pigment dispersion by a paint shaker for 6 hours. [Preparation of the coloring composition] 3.87 parts by weight of the above PR 254 pigment dispersion And the resin F obtained in the synthesis example 6 is converted into a solid fraction by 0.44 parts by weight, and the propylene glycol monomethyl ether acetate is added in an amount of 5.63 parts by weight.重量重量,汽巴, by weight, the photopolymerization initiator "Irgacure ΟΧΕ02" manufactured by Ciba Specialty Chemicals Co., Ltd. (the chemical structure is referred to the "monthly ester ester starter d" in the above [2-5]). Refined company made light Starting agent "Irgacure 907" (2-mercapto-1-[4-(indolylthio)phenyl]-2-indolyl propan-1-one) 0.07 parts by weight, interface activity by Dainippon Ink Co., Ltd. The "F475" was 0.001 parts by weight, and the "T01382" manufactured by the East Asia Synthetic Co., Ltd., which is a polymerizable monomer, was 0.70 parts by weight (including only 0.78 parts by weight in Example 43), and further Table -17 0.08 parts by weight of the aromatic carboxylic acid-based compound (or a compound thereof) described above was prepared to prepare a red colored composition. Further, the aromatic carboxylic acid-based compounds (and the compounds to be compared with them) used in the respective examples are shown in Table -15 above. [Evaluation of coloring composition] The coloring composition (v) obtained in Examples 37 to 43 was prepared and allowed to stand at 23 ° C for 1 、, and (vi) (v) further at 35 ° C In the thermostatic bath, which was left to stand for 6 days, the following evaluations were performed. The results are shown in Table-17. TF988407 162 201037041 [Viscosity change of composition] Using the E-type viscometer "RE-80L" manufactured by Toki Sangyo Co., Ltd., respectively, the methods obtained in Examples 37 to 43 and using the above (v) or (vi) The viscosity (20 rpm) of the colored composition after standing was measured. In addition, the "viscosity change rate" in Table-17 is based on the difference between the viscosity of "further after 35 °C, after 6 days" and the viscosity of "23 °C, 1 day later" versus "23 °C, 1 day later". The ratio of the viscosity is expressed. The measurement results are shown in Table-17. 〇
TF988407 163 201037041 卜I—< 〔卜 ϊ<〕 實施例43 | 1 〇〇 寸· 5.13 ◦ cd 實施例42 化合物6 4. 95 5.04 00 1-Η 實施例41 化合物5 4. 77 C75 LO οο od 實施例40 化合物4 | 4.83 CO LO cn> ai 實施例39 化合物3 | 4. 53 CO r-H 實施例38 化合物2 | 4. 55 4. 50 r-M 1 實施例37 化合物1 4. 68 4. 62 1-1.3 | 芳香族羧酸系化合物 23°C、1 日後(mPa· s) 進而 35°C、6 日後(mPa. s) 黏度變化率(%) 黏度變化 sl- ΖΌ 寸886^1 201037041 根據表-17可知,含有芳香族叛酸系化合物之實施例37 〜39 ’與不含該化合物之實施例40〜43相比,經時性黏度 增加較少,黏度穩定性更高。 以上詳細且參照特定之實施態樣說明了本發明,但業者應 明瞭,在不脫離本發明之精神及範圍下當可作各種變更或修 正。本申請案係根據2007年6月21日申請之日本專利申請 案(特願2007-163914)、2007年7月27日申請之日本專利 〇 申請案(特願2007-196441)、2008年2月6日申請之日本專 利申請案(特願2008-026120)、2008年2月13日申請之日 本專利申請案(特願2008-031884)、2008年4月7日申請之 日本專利申請案(特願2008-099747)、以及2008年5月30 曰申請之日本專利申請案(特願2〇〇8-143372),引用其内容 於此作為參照。 (產業上之可利用性) 〇 本發明發揮如下之有用效果,其產業上之利用價值極大。 (1)可提供可用少量的添加量即可高效率地將近年來經高 度微粒化之顏料分散,結果可製造高穿透率、高對比度、低 : 膜厚的彩色濾光片之顏料分散液及著色組成物。 ..()特別疋可提供達成了在以綠色像素之高亮度化為目的 而使m鋅酞菁綠色㈣時所存在之問題、即兼具高對比 度與分散穩定性的顏料分散液及彩色遽光片用著色組成物。 (3)可提供具有以下等優點之彩色遽光#著色組成物:對 TF988407 165 201037041 顯影液之溶解性良好、於顯影步驟中可在特定時間内顯影; 於基板上之非圖像部分不殘留著色樹脂組成物之未溶解 物;與基板之密著性優異;不使硬化性等圖像形成能力下降 即可製造高穿透率·高對比度·低膜厚之彩色濾光片。 (4) 使用上述彩色濾光片用著色組成物,而可提供高品質 彩色滤光片。 (5) 可提供使用了上述彩色濾光片之高品質液晶顯示裝置 及有機EL顯示器。 【圖式簡單說明】 圖1係表示具備本發明之彩色濾光片的有機EL元件之一 例的剖面概略圖。 圖2(a)及(b)均用以說明於實施例中測定著色板之平行 穿透光及正交穿透光之色度的方法之模式圖。 圖3係表示於實施例中,在測定所製成之像素的XYZ表色 系色度圖之色度座標(X、y)時、以及測定對比度時所使用之 背光光源的發光光譜之圖。 圖4係表示顯示實施例中測定對比度時所使用偏光板之 特性的光譜之圖。 圖5係用顯微鏡觀察實施例中測定缺陷所使用之直線狀 圖案(像素)之代表例之圖。(a)為無缺陷之圖案,(b)為缺陷 數為57之圖案,(c)為缺陷數為100以上之圖案。 【主要元件符號說明】 TF988407 166 201037041 ίο 20 30 ’ 32 33、35 34 36 Ο 37 40 50 51 52 53 54 Ο 55 100 500 透明支持基板 像素 有機保護層 色彩亮度計 偏光板 著色板 光 背光源 無機氧化膜 透明陽極 電洞注入層 電洞傳輸層 發光層 電子注入層 陰極 有機EL元件 有機發光體 TF988407 167TF988407 163 201037041 卜 I-< </ br> <br /> Example 43 | 1 · · 5.13 ◦ cd Example 42 Compound 6 4. 95 5.04 00 1-Η Example 41 Compound 5 4. 77 C75 LO οο od Example 40 Compound 4 | 4.83 CO LO cn> ai Example 39 Compound 3 | 4. 53 CO rH Example 38 Compound 2 | 4. 55 4. 50 rM 1 Example 37 Compound 1 4. 68 4. 62 1- 1.3 | Aromatic carboxylic acid compound 23°C, 1 day later (mPa·s) Further 35°C, 6 days later (mPa. s) Viscosity change rate (%) Viscosity change sl- ΖΌ inch 886^1 201037041 According to the table - 17 It is understood that Examples 37 to 39' containing an aromatic tickic acid compound have less temporal viscosity increase and higher viscosity stability than Examples 40 to 43 which do not contain the compound. The present invention has been described in detail above with reference to the specific embodiments thereof. It is understood that various changes and modifications may be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application filed on Jun. 21, 2007 (Japanese Patent Application No. 2007-163914), Japanese Patent Application No. 2007-196441 filed on July 27, 2007, and February 2008. Japanese patent application filed on the 6th (Japanese Patent Application No. 2008-026120), Japanese Patent Application No. 2008-031884 filed on Feb. 13, 2008, and Japanese Patent Application filed on Apr. 7, 2008 Japanese Patent Application No. 2-8-143372, the entire disclosure of which is hereby incorporated by reference. (Industrial Applicability) 〇 The present invention exerts the following useful effects, and its industrial use value is extremely large. (1) It is possible to efficiently disperse highly-micronized pigments in recent years with a small amount of addition, and as a result, a pigment dispersion having a high transmittance, a high contrast ratio, a low-density color filter and a color filter can be produced. Coloring composition. In particular, it is possible to provide a pigment dispersion liquid and a color enamel which have both high-contrast and dispersion stability in the case of m-zinc phthalocyanine green (four) for the purpose of increasing the luminance of green pixels. The light sheet is colored composition. (3) It is possible to provide a coloring composition having the following advantages: a coloring composition: good solubility to a developing solution of TF988407 165 201037041, development in a specific time in a developing step; no non-image portion remaining on a substrate The undissolved matter of the colored resin composition is excellent in adhesion to the substrate, and a color filter having high transmittance, high contrast, and low film thickness can be produced without lowering image forming ability such as hardenability. (4) A high-quality color filter can be provided by using the coloring composition for the above color filter. (5) A high-quality liquid crystal display device and an organic EL display using the above color filter can be provided. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an example of an organic EL device including a color filter of the present invention. 2(a) and 2(b) are views for explaining a method of measuring the chromaticity of the parallel penetrating light and the orthogonal penetrating light of the colored plate in the embodiment. Fig. 3 is a view showing the luminescence spectrum of a backlight source used when measuring the chromaticity coordinates (X, y) of the XYZ color chromaticity diagram of the pixel produced and the contrast ratio in the embodiment. Fig. 4 is a view showing a spectrum showing the characteristics of a polarizing plate used for measuring contrast in the examples. Fig. 5 is a view showing a representative example of a linear pattern (pixel) used for measuring defects in the examples by a microscope. (a) is a pattern having no defects, (b) is a pattern having a defect number of 57, and (c) is a pattern having a number of defects of 100 or more. [Main component symbol description] TF988407 166 201037041 ίο 20 30 ' 32 33, 35 34 36 Ο 37 40 50 51 52 53 54 Ο 55 100 500 Transparent support substrate Pixel organic protective layer Color luminance meter Polarizer coloring plate Light backlight Inorganic oxide film Transparent anode hole injection layer hole transport layer light-emitting layer electron injection layer cathode organic EL element organic light-emitting body TF988407 167
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JP4094260B2 (en) * | 2001-08-24 | 2008-06-04 | 株式会社日本触媒 | Polycarboxylic acid production method, polycarboxylic acid and cement additive |
JP2003064139A (en) * | 2001-08-24 | 2003-03-05 | Dainippon Toryo Co Ltd | Pigment-dispersing resin and coloring paint composition containing the same resin |
JP2004054213A (en) * | 2002-05-30 | 2004-02-19 | Sakata Corp | Pigment dispersed body for color filter and pigment dispersed resist composition for color filter containing the same |
US7781129B2 (en) * | 2002-07-24 | 2010-08-24 | Dai Nippon Printing Co., Ltd. | Green pigment for color filter, green pigment dispersion, photosensitive color composition, color filter, and liquid crystal panel |
JP4133267B2 (en) * | 2002-11-29 | 2008-08-13 | 三菱化学株式会社 | Pigment dispersion composition and color filter using the same |
JP4182887B2 (en) * | 2003-02-07 | 2008-11-19 | 三菱化学株式会社 | Colored resin composition, color filter, and liquid crystal display device |
JP2006293226A (en) * | 2005-04-14 | 2006-10-26 | Mitsubishi Chemicals Corp | Hardening resin composition for color filter, color filter, and liquid crystal display device |
JP5092326B2 (en) * | 2005-09-26 | 2012-12-05 | 三菱化学株式会社 | Color material dispersion, colored resin composition, color filter, and liquid crystal display device |
-
2008
- 2008-06-19 TW TW097122823A patent/TWI620800B/en active
- 2008-06-19 TW TW104114250A patent/TWI620801B/en active
- 2008-06-19 TW TW107100360A patent/TWI643909B/en active
- 2008-06-19 KR KR1020107011051A patent/KR100984994B1/en active IP Right Grant
- 2008-06-19 TW TW099117401A patent/TWI347966B/en active
- 2008-06-19 KR KR1020147006961A patent/KR20140042931A/en not_active Application Discontinuation
- 2008-06-19 KR KR1020097003437A patent/KR101443928B1/en active IP Right Grant
- 2008-06-19 TW TW100107767A patent/TW201124479A/en unknown
- 2008-06-19 CN CN201210201440.4A patent/CN102719148B/en active Active
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI588142B (en) * | 2012-07-31 | 2017-06-21 | 住友化學股份有限公司 | Colored curable resin composition |
TWI831950B (en) * | 2019-03-22 | 2024-02-11 | 日商大日精化工業股份有限公司 | water-based pigment dispersion |
Also Published As
Publication number | Publication date |
---|---|
TWI620801B (en) | 2018-04-11 |
TWI620800B (en) | 2018-04-11 |
KR20140042931A (en) | 2014-04-07 |
KR100984994B1 (en) | 2010-10-04 |
KR20100021993A (en) | 2010-02-26 |
KR101443928B1 (en) | 2014-09-29 |
TWI347966B (en) | 2011-09-01 |
TW200911930A (en) | 2009-03-16 |
TW201529753A (en) | 2015-08-01 |
TW201811928A (en) | 2018-04-01 |
TWI643909B (en) | 2018-12-11 |
KR20100061864A (en) | 2010-06-09 |
TW201124479A (en) | 2011-07-16 |
CN102719148A (en) | 2012-10-10 |
CN102719148B (en) | 2015-04-08 |
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