TW200911930A - Pigment dispersion liquid, colored composition for color filter, color filter, liquid crystal display and organic electroluminescence display - Google Patents
Pigment dispersion liquid, colored composition for color filter, color filter, liquid crystal display and organic electroluminescence display Download PDFInfo
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- TW200911930A TW200911930A TW097122823A TW97122823A TW200911930A TW 200911930 A TW200911930 A TW 200911930A TW 097122823 A TW097122823 A TW 097122823A TW 97122823 A TW97122823 A TW 97122823A TW 200911930 A TW200911930 A TW 200911930A
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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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- 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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- 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
200911930 九、發明說明: 【發明所屬之技術領域】 本發明係關於-種顏料分散液、彩色濾 物、彩色濾光片、液曰銪+驻罢士 用者色、、且成 =之顏料分散液、顏色特性非常優== 之具有顯影性之彩色渡光片用著色組成物、具有使用= ❿之像素之☆色Μ片、以及具備該彩色遽 先片之液阳顯示裝置及有機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 ^法’已知有顏料分散法、染色法、電鍵法、㈣i。 其中、,就分光特性、耐久性、圖案形狀及精度等觀點而言, 最廣泛地採用具有均衡優異特性的顏料分散法。 =年來,技術革新潮流迅速發展,對於彩色濾光片提出 〇更高穿透、更高對比度且更高濃度之要求。就耐熱性、耐 光性等觀點而言,作為決定彩色濾光片的顏色之色材,通 常使用顏料。作為顏料,適合使用可見光波長區域的固有 穿透吸收光譜與背光(back 1 ight )的螢光體發光光譜一 致者。例如’作為綠色顏料’自古以來是將齒化銅酞菁 Cphthalocyanine)綠色顏料與各種黃色顏料組合使用。 另一方面’為了提昇對比度,重要的是將彩色濾光片層 中之光散射抑制到最小限度,通常是藉由溶劑鹽磨 (solvent salt milling)法、乾磨(dry milling)法等將 97122823 6 200911930 上述顏料微粒化至-次粒徑為數IGnm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 附里不足而易於引起再凝集’易使分散系變得不穩定。因 如何將用以提昇對比度而微粒化之顏料穩定地製成分 放液而存在,則成為近年來極為重要的技術課題。 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所記载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。 為了解決此種問題,例如於專利文獻2中,揭示有使用 (甲基)丙烯酸系(共)聚物p〇lyflow No. 75、No. 90、200911930 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a pigment dispersion liquid, a color filter, a color filter, a liquid helium + a slinger color, and a pigment dispersion Liquid color and color characteristics are excellent == a coloring composition for a color developing sheet having a developability, a ☆ color film having a pixel using ❿, and a liquid positive display device and an organic EL display having the color enamel film . [Prior Art] Conventionally, a pigment dispersion method, a dyeing method, a key method, and (4) i have been known as methods used in the production of liquid crystal display devices and the like. Among them, a pigment dispersion method having excellent balance characteristics is most widely used from the viewpoints of spectral characteristics, durability, pattern shape, and precision. In the past few years, the trend of technological innovation has developed rapidly, requiring higher penetration, higher contrast and higher concentration requirements for color filters. From the viewpoints of heat resistance, light resistance, and the like, a pigment is usually used as a color material for determining the color of the color filter. As the pigment, it is suitable to use the intrinsic penetration absorption spectrum of the visible light wavelength region in accordance with the backlight luminescence spectrum of the backlight. For example, 'as a green pigment' has been used since the ancient times to combine a green pigment of Cphthalocyanine with various yellow pigments. On the other hand, in order to improve the contrast, it is important to minimize the light scattering in the color filter layer, usually by solvent salt milling, dry milling, etc. 97102823 6 200911930 The above pigment is micronized to a size of - IGnm and used. However, the smaller the particle size is, the larger the surface area is. Therefore, for example, re-aggregation is liable to occur due to insufficient adsorption of the dispersant, which tends to make the dispersion unstable. It has become an extremely important technical issue in recent years because of how the pigment which is micronized to enhance the contrast is stably produced as a dispersion liquid. 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 pigment, that is, the zinc bromide phthalocyanine pigment has the following problems: when the micronization is performed to improve the contrast, the dispersion stability is extremely lowered, and the light scattering due to the secondary aggregate is affected by the light scattering. When used as a television set, the contrast becomes insufficient. In order to solve such a problem, for example, Patent Document 2 discloses the use of (meth)acrylic (co)polymer p〇lyflow No. 75, No. 90,
No.95(共榮社化學公司製造)、Mega face F171、F172、 FI 73(大日本油墨化學工業公司製造)、Fiuorad FC430、 FC431(住友 3M 公司製造)、Sol sperse 13240、20000、 24000、26000、28000 等各種 Solsperse 分散劑(Avecia 公 司製造)、Disperbyk 111、161、162、163、164、182、 2000、2001等各種Disperbyk分散劑(畢克化學(βγκNo. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), Mega face F171, F172, FI 73 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.), Fiuorad FC430, FC431 (manufactured by Sumitomo 3M), Sol sperse 13240, 20000, 24000, 26000 , 28000 and other Solsperse dispersants (made by Avecia), Disperbyk 111, 161, 162, 163, 164, 182, 2000, 2001 and other Disperbyk dispersants (BY κ κ
Chemie)公司製造)、A j isper ΡΒ711、ΡΒ411、ΡΒ111、 PB821、PB822等各種Ajisper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 97122823 7 200911930 使用其中之畢克化風八1 兄彳匕干公司製造之丙烯酸系分散劑 「BYK-2001」。然而,柄4务丄 ' 很據本發明者們的驗證,即便使用 -亥等间刀ί1 ”月欠劑亦#法充分保持上述經微粒化之溴化 鋅酜菁顏料的分散穩定性,有由於再凝集而造絲度增加 或由於經時凝集而造朗比度下降等問題。 專利文獻1 :日本專利特開2004-70342號公報 專利文獻2 :曰本專利特開2004-70343號公報 【發明内容】A polymer dispersant such as Aji isper ΡΒ711, ΡΒ411, ΡΒ111, PB821, PB822 and other Ajisper dispersants (manufactured by Ajinomoto Fine-Techno Co., Ltd.) is used as a pigment to prepare pigments. Dispersing agent for the dispersion. Further, in the examples, the system 97720823 7 200911930 uses the acrylic dispersant "BYK-2001" manufactured by the Beacon Wind VIII Brothers Dry Company. However, the handle 4 is very difficult to maintain the dispersion stability of the above-mentioned micronized zinc bromide phthalocyanine pigment even if it is verified by the inventors of the present invention. The problem of the increase in the degree of the gradation due to the re-aggregation or the decrease in the gradation due to the agglutination over time. Patent Document 1: Japanese Patent Laid-Open No. 2004-70342, Patent Document 2: Japanese Patent Laid-Open No. 2004-70343 SUMMARY OF INVENTION
(發明所欲解決之問題) 本發,係馨於上述課題而完成者,其目的如下所述。 ⑴提供可用少量的添加卩可高效率地將近年來經高 度微粒化之顏料分Im 散其結果可製造高穿透率、高對比 又低膜厚的杉色遽光片之顏料分散液及著色組成物。 =)特別是提供達成了細綠色像素之高亮度化為目的 :化:駄菁綠色顏料時所存在之問題,亦即兼 ==比度與分散敎性的_分散液及濾、以 ^ 1 ^V 'Λ"^ ^ : 旦^ Π二 好’於顯影步驟中可在特定時間内顯 :、二非圖像部分不殘留著色樹脂組成物之 ==基板^著性優異,不使硬化性㈣像形成 下,可製造尚穿透率.高對比度.低膜厚之彩色滤光 而提供高品質 (4)使用上述彩色濾光片用著色組成物 97122823 200911930 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) 本發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8〇 mgK〇H/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@顯示充分高對比度之彩色濾光片,從 而最終完成本發明。 本發明係由複數個相關發明所構成’各發明之要點如 下。 ’ []種顏料刀放液,其特徵為:含有顏料、溶劑及分 政知政劑含有由具有親溶劑性之A散段與具有含氮 3 基之B嵌段所構成之欲段共聚物,該分散劑之 L 分換算計為8〇 以上且脱 mgKOH/g 以下。 辞H上述⑴之顏料分散液,其中,上述顏料含有漠化 [3] 如上述⑴或⑵之顏料分散液 香族羧酸系化合物。 r進而3有方 [4] 如上述[3]之顏料分散液, 化合物係以下述通式㈤所表示之化合物U香—糸 97122823 200911930 [化1](Problems to be Solved by the Invention) The present invention has been completed in accordance with the above problems, and its purpose is as follows. (1) Providing a small amount of added bismuth to efficiently disperse the highly micronized pigment in recent years, and as a result, a pigment dispersion and a coloring composition of a high-transparency, high contrast and low film thickness can be produced. Things. =) In particular, it provides the goal of achieving high brightness of fine green pixels: the problem of phthalocyanine green pigments, that is, the _dispersion and filtration of both == ratio and dispersion enthalpy, ^ 1 ^V 'Λ"^ ^ : 丹^ Π二好' can be displayed in a specific time in the development step: the second non-image portion does not leave a colored resin composition == the substrate is excellent, and the hardenability is not (4) Under the formation of the image, the color transmittance of the high transmittance, high contrast, and low film thickness can be manufactured to provide high quality. (4) The coloring composition for the above color filter is used, 97122823 200911930 color filter. (5) A high-quality liquid crystal display device and an organic EL display using the above color filter are provided. (Means for Solving the Problems) The inventors of the present invention have diligently studied to solve the above problems, and as a result, have found that a B block characterized by having a solvophilic A block and a functional group having a nitrogen atom is used. The block copolymer which is composed of the dispersant having an amine valence of 8 〇 mg K 〇 H/g or more in terms of an effective solid content, can achieve sufficient dispersion stability even for the microparticulated pigment, and can be provided as The liquid crystal television uses @ to display a sufficiently high contrast color filter, thereby finally completing the present invention. The present invention is composed of a plurality of related inventions. The gist of each invention is as follows. '[] A pigmented knife discharge liquid characterized by containing a pigment, a solvent, and a sub-regulator comprising a copolymer having a solvophilic A-part and a B-block having a nitrogen-containing 3-group. The dispersing agent has an L content of 8 Å or more and a MPa KOH/g or less. The pigment dispersion liquid of the above (1), wherein the pigment contains desertification [3] a pigment dispersion liquid of the above (1) or (2). r and 3 are square [4] The pigment dispersion liquid of the above [3], the compound is a compound represented by the following general formula (5), fragrant 糸 97122823 200911930 [Chemical 1]
X3 (VI)X3 (VI)
COOH (於上述通式(VI)中,Z1表示亞曱基或_〇-,m表示〇〜3 之整數。其中’當m為2或3時,m個Z1可相同亦可不同。 X表不氫原子、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、 者—C〇〇X4(其中,χ4表示碳數1〜7之烷基或苯基),該箄L 均可具有取代基。) 丞 [5] 如上述[4]之顏料分散液,其中,以上述通式(讥) 所表不之化合物為鄰苯二曱酸單酯化合物。 [6] 如上述[!]至[5]中任—項之顏料分散液,其中 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。 ⑺如上述⑴至[6]中任—項之顏料分散液,其中,於 上述:段㈣勿中’具有含氮原子的官能基之重複單元為 具有二級胺基之重複單元,該重複單元係來自 = 酸二曱胺基乙酯。 、 甲土)丙烯 [8]如上述[1]至[7]中任一項之顏料 上述截段共聚物中,上述Α极段含 政,夜、、中’於 4 Λ肷杈3有5〜4〇莫耳%之以下 97122823 200911930 述通式(ιν)所表示之部分結構。 [化2]COOH (In the above formula (VI), Z1 represents an anthracene group or _〇-, and m represents an integer of 〇~3. wherein 'w when m is 2 or 3, m Z1's 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 a C group X4 (wherein χ4 represents an alkyl group having a carbon number of 1 to 7 or a phenyl group), and the oxime L may have a substituent. 丞 [5] The pigment dispersion liquid of the above [4], wherein the above formula (讥) The compound represented by the formula is an phthalic acid monoester compound. [6] The pigment dispersion according to any one of the above [!] to [5], wherein the above block copolymer has more than 20 mol% of the repeating unit having a functional group containing a nitrogen atom. A repeating unit of a tertiary amine group. (7) The pigment dispersion according to any one of the above items (1) to (6) wherein, in the above paragraph (4), the repeating unit having a functional group having a nitrogen atom is a repeating unit having a secondary amine group, and the repeating unit From the acid diamylaminoethyl ester. [A] propylene [8] The above-mentioned segmented copolymer of the pigment according to any one of the above [1] to [7], wherein the above-mentioned bungee segment contains politics, night, and middle '5 to 4 at 4 Λ肷杈 3 〇莫耳% below 97122923 200911930 The partial structure represented by the general formula (ιν). [Chemical 2]
(於上述通式(IV)中,n表示 氫原子或甲基。) 1〜5中之任一整數 R5°表示 如上述Π]至[8]中任一項之顏料分散液,其中,上 述顏料之平均一次粒徑為〇.〇4 以下。 [叫一種彩色遽光片用著色組成物,其含有上述⑴至 [9]中任一項之顏料分散液及黏合劑樹脂。 Π1 ] —種衫色濾光片用著色組成物,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3嵌段所構 成之嵌段共聚物,該分散劑之胺價以有效固形分換算計為 mgKOH/g 以上且 150 mgKOH/g 以下。 [12 ]如上述[11 ]之著色組成物,其中’上述顏料含有漠 化鋅酞菁。 ' [13]如上述[11]或[12]之著色組成物’其中,進而含有 芳香族羧酸系化合物。 97122823 11 200911930 [14] 如上述[13]之著色組成物,其中,上述芳香族羧酸 系化合物係以下述通式(γι)所表示之化合物。 [化3] (VI) 21(In the above formula (IV), n represents a hydrogen atom or a methyl group.) Any one of the above-mentioned integers of 5 to 5, wherein the pigment dispersion liquid according to any one of the above-mentioned items [1] to [8], wherein The average primary particle size of the pigment is 〇.〇4 or less. [A coloring composition for a color light-receiving sheet, which comprises the pigment dispersion liquid and the binder resin according to any one of the above (1) to [9]. Π1] - a coloring composition for a shirt color filter, 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 block copolymer composed of the block of the functional group has an amine valence of not more than mgKOH/g and not more than 150 mgKOH/g in terms of an effective solid content. [12] The colored composition according to [11] above, wherein the above pigment contains desert zinc phthalocyanine. [13] The coloring composition of the above [11] or [12], which further contains an aromatic carboxylic acid compound. [14] The colored composition of the above [13], wherein the aromatic carboxylic acid compound is a compound represented by the following formula (γι). [Chemical 3] (VI) 21
COOH (於上述通式(VI)中’ Z1表示亞曱基或者_〇_,^表示〇〜3 之正數。其中’當m為2或3時,m個Z1可相同亦可不同。 χ3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C00X (其中,χ表示碳數1〜7之烧基或苯基),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(贝) I、所表示之化合物為鄰苯二甲酸單酯化合物。 [16] 如上述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(甲基 丙烯酸二甲胺基乙酯。 土 Π8]如上述[11]至[17]尹任一項之著色組成物,其中, 97122823 12 200911930 5〜40莫耳%之以 於上述嵌段共聚物中,上述A嵌段含有 下述式(IV)所表示之部分結構。 [化4]COOH (in the above formula (VI), 'Z1 represents an anthracene group or _〇_, and ^ represents a positive number of 〇~3. wherein 'w when m is 2 or 3, m Z1's may be the same or different. χ3 indicates 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 C00X (wherein The group which has a carbon number of 1 to 7 or a phenyl group, and the group may have a substituent. [15] The coloring composition of the above [14], wherein the above formula (Bei) I, The compound represented is a phthalic acid monoester compound. [16] The coloring composition according to any one of the preceding claims, wherein, in the block copolymer, 20 mol% or more of the repeating unit having a functional group containing a nitrogen atom is a group having a mono- to tertiary group Repeat unit. [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 (dimethylaminoethyl methacrylate. Earthworm 8). The colored composition of any one of the above [11] to [17] Yin, wherein 97122823 12 200911930 5~40% by mole In the above block copolymer, the A block contains a partial structure represented by the following formula (IV).
(IV)(IV)
表示 (於上述通式(IV)中,n表Representation (in the above formula (IV), n table
氫原子或5中之任—整數。FA hydrogen atom or any of 5 - an integer. F
[19] 如上述[⑴至[18]中任一項之著色組成物,盆中, 述顏料之平均一次粒徑為〇.〇4㈣以下。 [20] 如上述[1()]至[19]中任—項之著色組成物,立中, 述黏合劑樹脂包含以下樹脂:對於含有環氧其之( :烯酸S旨與其他自由基聚合性單體之共^ 土 基之至少一部分上加成不飽和-元酸二 = 或者細由該加成反應而產生_基之至少-部 刀上加成多70酸酐而獲得之鹼可溶性樹脂。 叫如上述[叫至[2附任—項之著色組成物,其令, 進而含有光聚合起始系及熱聚合起始劑t之至少-種。 述[川之著Μ成物,其中,上述光聚合起始 糸含有脖酉曰糸化合物。 97122823 13 200911930 [2 3 ]如上述[2 2 ]之著色組成物’其中,上述厢g旨系化合 物係以下述通式(I )所表示之化合物。 [化5] /OR2 f切…⑴ Y—C 一 X—c—R1 [於上述通式(I )中’R1表示氫原子、碳數1〜2〇之烷基、 ,碳數2〜25之烯基、碳數3〜20之雜芳基或者碳數4〜25 之雜芳炫基,该等均可具有取代基。或者,Ri可與X或γ 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(aryl〇yl)、碳 數2〜10之烷氧魏基、碳數7〜2〇之芳氧隸基、碳數2〜 2〇之雜芳基、碳數3〜20之雜芳酿基或者碳數2〜2〇之 烷基胺基羰基,該等均可具有取代基。 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—種。 Y表示可具有取代基之芳香族基。] [24]如上述[23]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⑴所表示之化合物。 [化6][19] The colored composition of any one of the above [1] to [18], wherein the average primary particle diameter of the pigment in the pot is 〇.〇4 (four) or less. [20] The coloring composition of any of the above [1()] to [19], wherein the binder resin comprises the following resin: for the epoxy group (: the olefinic acid S and other radicals) Addition of at least a part of the common base of the polymerizable monomer to the unsaturated-acid acid II = or the alkali-soluble resin obtained by the addition reaction to produce at least a portion of the acylate-added acid anhydride It is called the above [[2], which is the coloring composition of the attached item, and further contains at least one of the photopolymerization initiation system and the thermal polymerization initiator t. The photopolymerization initiator contains a neck compound. 97122823 13 200911930 [2 3] The coloring composition of the above [2 2 ], wherein the above-mentioned compound is represented by the following formula (I) (Chemical Formula 5) /OR2 f-cut (1) Y-C-X-c-R1 [In the above formula (I), 'R1 represents a hydrogen atom, an alkyl group having a carbon number of 1 to 2 Å, and a carbon number An alkenyl group of 2 to 25, a heteroaryl group having 3 to 20 carbon atoms or a heteroaryl group having 4 to 25 carbon atoms, which may have a substituent. Alternatively, Ri may be bonded to X or γ to form R2 represents an alkylene group having 2 to 20 carbon atoms, an olefin group having 3 to 25 carbon atoms, a cycloalkylindenyl group having 4 to 8 carbon atoms, a aryl〇yl group having 7 to 20 carbon atoms, and carbon. Alkoxy thiol group of 2 to 10, an aryloxy group of 7 to 2 carbon atoms, a heteroaryl group having 2 to 2 carbon atoms, a heteroaryl group having a carbon number of 3 to 20 or a carbon number of 2 to 2 The alkylaminocarbonyl group may have a substituent, and may represent at least one of a divalent aromatic hydrocarbon group and an aromatic heterocyclic group which may have a substituent and are condensed by two or more rings. [24] The coloring composition of the above [23], wherein the compound represented by the above formula (1) is a compound represented by the following structural formula (1).
200911930 [於上述通式⑴中,Ri、Y與上述通式⑴中之 相同。環X2表示與笨環χ1縮合之環,可為單環,亦可為 由2個以上環所構成之縮合環。又,χ2可縮合於苯環χΐ 之任意位置。苯環X1及與其縮合之環Χ2,進而可具有取代 基。] ' [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]之著色組成物,其中,上述聚合性單體 為具有至少1個乙烯性雙鍵之可加成聚合之化合物,該化 合物之分子量為650以下且雙鍵當量為15〇以下。 [27] —種彩色濾光片,其具備基板及形成於該基板上之 像素,其特徵為,該像素的一部分或全部係使用上述[1〇] 至[26 ]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。 μ [29] —種有機EL顯示器,其具備上述[27]之彩色濾 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 尚度微粒化之顏料分散,其結果可製造高穿透率、高對比 度、低臈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 97122823 15 200911930 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β ’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,不使硬純#圖像形成 ,力下降,可製造高穿透率.高對比度.低膜厚之彩色遽光 片。 ()可使用上述彩色遽光片用著色組成物,而提供高品 質彩色遽光片。 ⑸可提供使用了上述彩色濾光片之高品質液晶顯示褒 置及有機EL顯示器。 【實施方式】 以下,就本發明之構成要件等加以詳細說明,但該等構 成要件係本發明實施態樣之一例,本發明並不限定於該 内容。 、'^ 再者,「(甲基)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 :基丙烯酸醋中之至少一者」等,例如「(甲基)丙烯酸」 意指「丙烯酸及曱基丙浠酸中之至少一者」。 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 97122823 16 200911930 測定之聚苯乙烯換算之重量平均分子量(Mw)。 只要未加以特別說明, 以與每1g分散劑固形 示之值。再者,測定方 又’於本發明中,所謂「胺價」, 則表示有效固形分換算之胺價,係 分的驗量等當量之Κ0Η的重量所表 法於後加以敍述。 [1 ]顏料分散液 以下說明本發明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需成分,視需 要,可進而含有除上述成分以外之添加物等。 - 以下’說明各構成成分。 [1-1]顏料 廿作為顏料’可使用:藍色顏料、綠色顏料、紅色顏料、 K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I系、酞菁系、 喹吖啶酮(quinacrid〇ne)系、苯并咪唑酮 (benzimidazolone)系、異吲哚啉酮(is〇ind〇lin〇ne)系、 二嘮讲(di〇Xazine)系、蔭丹士林(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.丨.)。 作為紅色顏料’例如可舉出:c.丨.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 ^ 50:1 > 52:1 > 52:2 ' 53 ' 53:1 > 53:2 ' 53:3 ^ 97122823 17 200911930 57、57:1、57:2、58:4、60、63、63:1、63:2、 68、69、81、81:1、81:2、81:3、81:4、83、 101 123 、 144 101:1、104、108、108:1、109、112、 122、123、144、146、147、149、151、166 170 、 172 、 173 、 174 、 175 、 176 184 、 185 、 187 、 188 、 190 、 193 207 、 208 、 209 、 210 、 214 、 216 231 、 232 、 233 、 235 、 236 、 237 245 、 247 、 249 、 250 、 251 、 253 258 、 259 、 260 、 262 、 263 、 264 269 、 270 、 271 、 272 、 273 、 274 64 ' 64:1 88 > 90:1 113 、 114 177 194 220 238 254 265 275 122 168 、 169 , 179 、 181 202 、 206 224 、 230 242 > 243 256 、 257 ' 267 、 268 , 276等。其中, 166、168、177 178 200 221 239 255 266 較佳為可舉出:C· I.色素紅48:ι 202、206、207、209、224、242、254 等,更佳為可舉出: C· L 色素紅 166、177、209、224、242、254 等。 作為藍色顏料,例如可舉出:C I•色素藍i、Η、9、 25、27、Η 2、15:3、15:4、15:6、16、17、19、 62、63、66 : 697、、3638、^ 等。其中,較佳為可舉出72、:辛74 ; 75、76、78、79 15:3、1^、色素藍 15、15:1、仏2、 作為绰名更4土為可舉出C.I.色辛ΐ5·6ο 作為,、彔色顏料,例如 巴I瓜ib.b 7、8、、13、14、J 了 + 出.以 C. L 色素綠 1、2、4、 50、51、54、55及、58=17、18、19、26、36、45、48、 佳為可舉出以C I洛主,、、代表之溴化鋅酞菁等。其中,較 ’ ’素綠7、36及58為代表之 酞 97122823 18 200911930 菁等,特佳為c. I.色素綠G58。再者,對以c.丨色素綠 G58為代表之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· L色素黃ii ·· 1、2、 3、4、5、6、9' 10、12、13、14、16、17、24、31、32、 34、35、35:卜 36、36Π、37、37:1、40、41、42、43、 48 、 53 、 55 、 6卜 62 、 62:卜 63 、 65 、 73 、 74 、 75 、 81 、 83 、 87 、 93 、 94 、 95 、 97 、 1〇〇 、 1〇1 、 1〇4 、 105 、 108 、 109、110、111、116、117、119、12〇、126、127、127:1、 128 、 129 、 133 、 134 、 136 、 138 、 139 、 142 、 147 、 148 、 150 、 151 、 153 、 154 、 155 、 157 、 158 、 159 、 160 、 161 、 162 、 163 、 164 、 165 、 166 、 167 、 168 、 169 、 170 、 172 、 173 、 174 、 175 、 176 、 180 、 181 、 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. j•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、丨3、 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. j 色素橙38、71等。 · · 作為紫色顏料’例如可舉出:c. j.色素紫1、1·^、2、 2:2 、 3 、 3:1 、 3:3 、 5 、 5:1 、 14 、 15 、 16 、 19 、 23 、 25 、 97122823 19 200911930 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. I.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, 可自無機或有機顏料、染料中適當選擇,可單獨使用或者 將複數種混合使用。 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 、# 990 、# 900 等。200911930 [In the above formula (1), Ri and Y are the same as those in the above formula (1). Ring X2 represents a ring condensed with a stupid ring, and may be a single ring or a condensed ring composed of two or more rings. Further, χ2 can be condensed at any position of the benzene ring oxime. The benzene ring X1 and the cyclic oxime 2 condensed therewith may further have a substituent. [25] The colored 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 an addition polymerizable compound having at least one ethylenic double bond, and the compound has a molecular weight of 650 or less and a double bond equivalent of 15 〇The following. [27] A color filter comprising: a substrate; and a pixel formed on the substrate, wherein a part or all of the pixel is colored using any one of the above [1〇] to [26] Formed by matter. [28] A liquid crystal display device comprising the color filter of the above [27]. μ [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 micronized 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 high transmittance, high contrast, and low thickness. Liquid and coloring composition. (2) In particular, it is possible to provide a pigment dispersion liquid having a contrast and dispersion stability of 97102228 15 200911930 for the purpose of using a zinc bromide phthalocyanine green pigment for the purpose of increasing the luminance of green pixels. And coloring compositions for coloring sheets. (3) A coloring composition for a color calender sheet having the following advantages can be provided. The solubility in the developer is good, and in the developing step, the non-image portion on the substrate can be left in the specific time without coloring. The undissolved matter of the resin composition is excellent in adhesion to the substrate, and the hard-purity # image is formed without a force, and a high-contrast, high-contrast, low-thickness color calender sheet can be produced. () A high-quality color calender can be provided by using the coloring composition for a color calender described above. (5) A high-quality liquid crystal display device and an organic EL display using the above color filter can be provided. [Embodiment] Hereinafter, the constituent elements of the present invention and the like will be described in detail. However, the constituent elements are examples of the embodiment of the present invention, and the present invention is not limited thereto. '^ Further, "(meth)acrylyl" and the like means "at least one of a propylene group and a methacryl group"; "(meth) acrylate" or the like means "acrylate": acryl "At least one of vinegar", etc., for example, "(meth)acrylic acid" means "at least one of acrylic acid and mercaptopropionate". In addition, the term "total solid content" means a total component other than the solvent component described later contained in the pigment dispersion or the coloring composition. In the present invention, the weight average molecular weight means a weight average molecular weight (Mw) in terms of polystyrene measured by Gpc method (gel permeation chromatography) 97122823 16 200911930. Unless otherwise specified, the value is solidified with 1 g of dispersant. Further, in the present invention, the "amine price" means an amine value in which the effective solid content is converted, and the weight of the equivalent amount of the test is expressed as follows. [1] Pigment Dispersion Liquid The respective constituent components of the pigment dispersion liquid of the present invention will be described below. The pigment dispersion liquid 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, as needed. - The following 'describes each component. [1-1] Pigment 廿 As a pigment, a pigment of various colors such as a blue pigment, a green pigment, a red pigment, a K color pigment, a purple pigment, a dial pigment, a brown pigment, and a black pigment can be used. Further, as the structure thereof, in addition to the I system, the phthalocyanine system, the quinacridone system, the benzimidazolone system, and the isoindolinone (is〇ind〇lin〇ne) system In addition to organic pigments such as di〇Xazine, indanthrene, and perylene, various inorganic pigments may be used. The following is a specific example of a pigment that can be used by a pigment number. The terms "C. I. Pigment Red 2" as exemplified below mean the color index (c.丨.). As the red pigment, for example, c. 丨. 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 ^ 50:1 > 52:1 > 52: 2 ' 53 ' 53:1 > 53:2 ' 53:3 ^ 97122823 17 200911930 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 101 123, 144 101:1, 104, 108, 108: 1, 109, 112, 122, 123, 144, 146, 147, 149, 151, 166 170, 172, 173, 174, 175, 176 184, 185, 187, 188, 190, 193 207, 208, 209, 210, 214, 216 231, 232, 233, 235, 236, 237 245 , 247 , 249 , 250 , 251 , 253 258 , 259 , 260 , 262 , 263 , 264 269 , 270 , 271 , 272 , 273 , 274 64 ' 64:1 88 > 90:1 113 , 114 177 194 220 238 254 265 275 122 168 , 169 , 179 , 181 202 , 206 224 , 230 242 > 243 256 , 257 ' 267 , 268 , 276 , etc. Among them, 166, 168, 177 178 200 221 239 255 266 preferably include C·I. Pigment Red 48: ι 202, 206, 207, 209, 224, 242, 254, etc., more preferably : C· L Pigment Red 166, 177, 209, 224, 242, 254, etc. Examples of the blue pigment include CI•pigment blue i, Η, 9, 25, 27, Η 2, 15:3, 15:4, 15:6, 16, 17, 19, 62, 63, 66. : 697, 3638, ^, etc. Among them, it is preferable to mention 72,: sin 74; 75, 76, 78, 79 15:3, 1^, pigment blue 15, 15:1, 仏2, as the name of the 4th soil, the CI can be cited辛辛ΐ5·6ο As,, 彔色 pigment, for example, I I ib.b 7, 8, 13, 14, J + out. Take C. L pigment green 1, 2, 4, 50, 51, 54 55, and 58=17, 18, 19, 26, 36, 45, and 48, and the like, and the zinc bromide phthalocyanine represented by CI, and the like are exemplified. Among them, it is represented by ’ 97122823 18 200911930 菁, etc., particularly preferably c. I. Pigment green G58. Further, the details of the zinc bromide phthalocyanine represented by c. anthraquinone green G58 will be described later. Examples of the yellow pigment include c·L pigment yellow ii··1, 2, 3, 4, 5, 6, 9' 10, 12, 13, 14, 16, 17, 24, 31, 32, 34 35, 35: Bu 36, 36Π, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 6 Bu 62, 62: Bu 63, 65, 73, 74, 75, 81, 83 , 87, 93, 94, 95, 97, 1〇〇, 1〇1, 1〇4, 105, 108, 109, 110, 111, 116, 117, 119, 12〇, 126, 127, 127:1 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 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. Preferably, c. j. pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, etc., more preferably: CI pigment yellow 83, 138, 139, 150, 180, etc. Examples of the orange pigment include c. 丨. Pigment orange 1, 2, 5, 丨 3, 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, and the like. Among them, c. j color orange 38, 71 and the like are preferable. · · As a purple pigment, for example, cj pigment purple 1, 1 · ^, 2, 2: 2, 3, 3:1, 3:3, 5, 5:1, 14 , 15 , 16 , 19 23, 25, 97122823 19 200911930 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50, pigment blue 8 〇, etc. Among them, C. I. Pigment Violet 19, 23 and the like are preferable, and C. I. Pigment Violet 23 is more preferable. As the black pigment, a single black pigment may be used, or a black pigment obtained by mixing pigments such as red, green, and blue may be used. These black pigments may be appropriately selected from inorganic or organic pigments and dyes, and may be used singly or in combination of plural kinds. 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, carbon black and titanium black are particularly preferable from the viewpoint of light blocking ratio and image characteristics. As an example of a commercial item of carbon black, the following brands are mentioned, for example. Mitsubishi Chemical Corporation manufactures: MA7, MA8, MA11, MA100, MA220, MA230, #52, #50, #47, #45, #2700, #2650, #2200, #1000, #990, #900, etc.
Degussa 公司製造:Pr intex95、Printex90、Pr intex85、 Printex75 、 Printex55 、 Printex45 、 Printex40 、 Printex30 、 Printex3 、 PrintexA 、 PrintexG 、 Special Black550 ' Special Black350 'Special Black250'Special BlacklOO 等。Made by Degussa: Pr intex95, Printex90, Pr intex85, 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、REGAL99R、REGAL415、REGAL415R、REGAL250、 REGAL250R 、 REGAL330 、 BLACK PEARLS 480 、 PEARLS130 97122823 20 200911930 等。Cabot manufactures: Monarch460, Monarch430, Monarch280, Monarchl20, Monarch800, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, BLACK PEARLS 480, PEARLS130 97122823 20 200911930, etc.
Columbian Carbon 公司製造:RAVENll、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)、金胺 0(41000) 、 Cathilon Brilliant Flavin (Basic 13)、玫瑰紅 6GCP(4 5160)、玫瑰紅 B(45170)、番紅 OK70:100(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(211〇5)、聯苯胺黃 4T-564D(21 095)、Symuler Fast Red 4015(12355)、雷奥 諾爾紅 7B440K15850)、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 97122823 21 200911930Made by Columbian Carbon: RAVENll, 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 substrate include Victoria Pure Blue (42595), Auramine 0 (41000), Cathilon Brilliant Flavin (Basic 13), Rose Red 6GCP (4 5160), and Rose Red. B (45170), Safranin OK70: 100 (50240), Wool Poppy Red X (42080), No. 120/Leonor Yellow (21090), Leonor Yellow GRO (21090), Symuler Fast Yellow 8GF (211〇) 5), benzidine yellow 4T-564D (21 095), Symerer Fast Red 4015 (12355), Leonor Red 7B440K15850), Fastogen Blue TGR-L (74160), Leonor Blue SM (26150), Leonor Blue ES (pigment blue 15:6), Lionogen Red GD (pigment red 168), Leonor Green 2YS (pigment green 36), etc. (Further, the number in the above () means color index (CI). Further, in addition, the other pigments which can be used in combination are denoted by C.I., and examples thereof include CI yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, and 148. 153, 154, 166, etc.; C. I· Orange pigments 36, 43, 51, 55, 59, 61, etc.; CI red pigments 9, 97, 122, 123, 149, 168, 177, 180, 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 pigment 97122823 21 200911930
64等;C· L綠色顏料7 ; C. I 15 、 15:1 、 15:4 、 22 、 6〇 標色顏料23、25、26等。 再者’上述碳黑亦可與其他黑色或 料併用。其他顏料與碳黑相比,遮:::有機顏 此混合比率自然受到_。 圖像特性低,因 作為鈦黑之製造方法,有 屬…合物於還原環境中進行加上將之-二化, 獲得之超微广 氯化鈦藉由高溫水解所 氧化鈦於含氫還原環境 法(日本專利特開昭5 還原之方 氧化鈦於角" 湯322旎公報)、將二氧化鈦或氫 乳化鈦於乳存在下進行高溫還原飞 60-65069號公報、特開昭6卜2〇 (八日本專利特開昭 物附著於_氧彳卜# < # $ 唬A報)、使釩化合 原之方法(曰本專利特開昭61 進仃❸皿還 定於該等方法。 ⑼161〇號公報);但並不限 作為鈦黑之市售品之例,例如可:64, etc.; C·L green pigment 7; C. I 15 , 15:1 , 15:4 , 22 , 6 〇 color pigments 23, 25, 26, etc. Furthermore, the above carbon black can also be used in combination with other black materials. Other pigments are compared to carbon black.::: Organic pigment This mixing ratio is naturally subject to _. The image characteristics are low, and as a method for producing titanium black, a compound is added in a reducing environment, and the obtained ultra-aluminum chloride is obtained by high-temperature hydrolysis of titanium oxide by hydrogen reduction. Environmental Law (Japanese Patent Laid-Open No. 5, reduced titanium oxide in the corner " Soup 322旎 bulletin), titanium dioxide or hydrogen emulsified titanium in the presence of milk for high-temperature reduction fly 60-65069, special open Kai 6 2 〇 (eight Japanese patent special open 昭 附着 attached to _ 彳 彳 # # <# $ 唬 A report), the method of making vanadium compound (曰 专利 专利 专利 61 61 61 仃❸ 仃❸ 仃❸ 仃❸ 还 还 还 还 还 还 还 还 还 还 还 还 还 还 还(9) 161 公报 ) ); but it is not limited to the case of a commercial product of titanium black, for example:
C〇RP〇RATI〇N>»^^/l〇V 13R、13M、13M-C 等。 c亥專顏料》可單猶择用1播 兮…丄 早蜀使用1種,亦可併用2種以上。又,C〇RP〇RATI〇N>»^^/l〇V 13R, 13M, 13M-C, etc. c Hai special pigments can be used alone to broadcast 1 兮...丄 1 type can be used as early as possible, or 2 or more types can be used together. also,
忒荨顏枓之平均一次粒徑通常為Q 〇 1 // m -ΤΓ * . Z “ m 以下’較佳為 以下,又,、二佳為〇· 〇4 “以下,特佳為0.025 ’通帛為0.005 /zm以上。 之=行顏料之微粒化時,適合採用如後述之溶劑鹽磨法 97122823 22 200911930 作為上述綠色顏料,特佳為溪化辞狄菁顏料。 之Γ菁係於1分子中具有“個氯原+,將該等 =子Μ原子或氣原子進行取代者,係本發明中= 使用之漠化鋅酜菁顏料。其中,就顯示極高之穿透率、, :形成彩色遽光片之綠色像素的方面而言,較佳=4 :均3 # 13個以上漠原子之溴化鋅酿菁。更佳為工分 :中具有13〜16個溴原子、且丨分子中不含氣原子或者 平均具有3個以下氯原子之漠化鋅駄菁,特佳為 ^句具有14〜16個漠原子、幻分子中不含氣原子或I 平均具有2個以下氣原子之漠化鋅酞菁。 ”化鋅酞菁顏料’可藉由曰本專利特開昭 13081 6號公報等中所揭示之公知的製造方法而製造。 例如可舉出以下方法:將以漠及氣等鹵素原子取代芳香環 上的邛分或全部氫原子而得之鄰苯二甲酸、或鄰苯二腈 \ 適當用作起始原料,來合成顏料。此時,視需要亦可使用 鉬酸銨等觸媒。 、乍為其他方法,可舉出以下方法:在由氯化鋁、氯化鈉、 漠化納等的混合物所組成之i 1G〜17(rc左右之炫融物 中,將辞酞菁以漠氣進行漠化。於該方法中,可藉由調節 熔融鹽中氯化物與溴化物之比率、或者改變氯氣導入量或 μ夺間而任思地控制溴含量不同的各種溴化鋅酞菁之 比率。 反應結束後,若將所得混合物投入至鹽酸等酸性水溶液 中則所生成之溴化鋅酞菁會發生沈澱。其後,進行過濾、 97122823 23 200911930 ’月洗、乾燥等後處理,而獲得漠化鋅酞菁。 視需,’將如此獲得之演化辞駄菁顏料 機、振磨機、振動球磨機等粉碎機内進行乾' = 以溶劑鹽磨法或 丁祀八馆砰’繼而 率或對比'錢寻進行歸化,#此獲得穿透The average primary particle size of 忒荨颜枓 is usually Q 〇1 // m -ΤΓ * . Z "below m is preferably the following, and the second is 〇· 〇 4" below, especially preferably 0.025 'pass帛 is 0.005 / zm or more. In the case of atomization of the pigment, it is suitable to use a solvent salt milling method as described later, 97122823 22 200911930, as the above-mentioned green pigment, and particularly preferably a sulphuric acid crystal. The phthalocyanine has a "chlorinogen +" in one molecule, and is substituted with the sulfonium atom or a gas atom in the present invention, and is a desertified zinc phthalocyanine pigment used in the present invention. Transmittance, , : In terms of forming a green pixel of a color calender, it is preferable to = 4: 3 # 13 or more of the zinc bromide of the desert atom. More preferably, the work has 13 to 16 a bromine atom and a desertified zinc phthalocyanine having no gas atom or an average of 3 or less chlorine atoms, particularly preferably having 14 to 16 desert atoms, no crystal atoms in the magic molecule, or I having an average A zinc-zinc phthalocyanine having two or less gas atoms. The "zinc-zinc phthalocyanine pigment" can be produced by a known production method disclosed in Japanese Laid-Open Patent Publication No. 13081 6 or the like. For example, a method of synthesizing a pigment by substituting a halogen atom such as an indifferent gas for a halogen atom or an entire hydrogen atom to obtain a phthalic acid or phthalonitrile is suitably used as a starting material. . At this time, a catalyst such as ammonium molybdate may be used as needed. For other methods, the following method can be used: in the i 1G~17 (circle of rc) composed of a mixture of aluminum chloride, sodium chloride, desertification, etc. The gas is subjected to desertification. In this method, various zinc bromide phthalocyanines having different bromine contents can be controlled by adjusting the ratio of chloride to bromide in the molten salt or changing the amount of chlorine introduced or intercalating. After the completion of the reaction, the resulting mixture is precipitated in an acidic aqueous solution such as hydrochloric acid, and the resulting zinc bromide phthalocyanine is precipitated. Thereafter, it is subjected to filtration, 97122823 23 200911930 'month washing, drying, etc., to obtain Desertification of zinc phthalocyanine. Depending on the need, 'the evolution of the phthalocyanine pigment machine, vibrating mill, vibrating ball mill and other pulverizers to be dried in this way' = Solvent salt grinding method or Ding Biao eight museums' then rate or contrast 'The money seeks to be naturalized, # this gets penetrated
St s綠色光之漠化辞駄菁顏料。顏料化方 積車限制’就可容易抑制結晶成長、且獲得比表面 粒子的方面而言’較佳為採用溶劑鹽磨法。 及將剛合成後的粗顏料與無編 鹽、及不ΛΐΓ 具體而言’㈣粗顏料、無機 ,合解八之有機溶劑加入混練機,於混練機中進行 作匕練磨碎。作為卜士 τ進仃 捏機、或去石”、、b、、東機,例如適合使用捏合機或混 ^ 〇日本專利特開2〇〇6_77062號公報中記載的 =城固定圓盤與同心的旋轉圓盤之間隙部分所开1 之粉碎空間的連續混練機等。 刀斤开夕成 作為上述無機鹽,可適合 用例如氯化鈉、氣化鈿h …、、H父佳為使 等無機鹽之粒徑鈉等無機鹽。又,更佳 通常的無機鹽力口以微粉碎而容㈣得。 精由將 =獲得之演化鋅㈣,可單獨使用,亦 乳化率不同的減紐¥ 1化羊或 内與中心金Vi#並Ml 明效果之範圍 由改㈣m 屬取代之溴化酞菁等混合使用。藉 交氣化率及溴化率或改變中心金屬而使作曰 又,生變化,從而可期待可再現之色相變化的择加 又,即便同樣的綠色顏料,亦可…色素綠二 97122823 24 200911930 或7等鹵化銅酞菁混合。 之平均一次粒徑,通常為 m以下’更佳為〇. 03 # m 又,通常為〇. 〇〇5 //m以 包含漠化鋅酞菁之綠色顏料 0.1 以下,較佳為0.04 # 以下’特佳為0. 〇 2 5 # m以下, 上。 若平均-次粒徑過大,則消偏特性惡化因而對比度變得 ==在嚴重的情形下有時會產生穿透率下降之使根本 f 顏色雜發生劣化之虞,或者會產生形成粗粒而產生 二::二從而使彩色濾光片的良率下降,或導致製程過 W 產上之問4反之,若平均—次粒徑過小, 以下等問題:由於顏料之比表面積增大而造成分 :=下降,或由於顏料接近分子狀態而造 性、 耐光性惡化。 再者’顏料之平均—次粒徑可藉由以下方法而求出。 t將顏料於氯仿中進行超音波分散,並滴加至貼附_ (;ra、’罔格i,進行乾燥,利用穿透型電子顯微鏡 顏料 rilsslGn eleGtrQn mierGseQpe,tem)觀察而獲得 ^ "、之一次粒子像。根據該圖像測定一次 之計算式計算單個平均值,並求出平均粒徑。依”,、下式 成將各顏料粒子之粒徑作為換算為 個、積圓相當#’分別求出複數 =200〜300個左右的顏料粒子之粒徑後,依照 :叶异式計算單個平均值’而求出平均粒徑。 各顏料粒子之粒徑:、χ2、χ3、χ4........ γ 97122823 25 200911930 干巧粒徑=IXi/m 的Γΐ、,了調色成所期望之顏色,亦可將上述各顏料中 、以顏料混合使用。例如,在製備紅色或綠色之顏 料分散液或著色組成物時,為了調整色相,可頁 顏料或綠色顏料中組合至少 、色 锸立a知u 王夕1種以上的頁色顏料。作為此 製:ίΓ翁例如可舉出上述之各種黃色顏料。又,為了 ”:以:的散液或著色組成物’可將藍色顏料與至 夕1種以上的糸色顏料加以組合。 望之色度’可適當混合使用各色顏料。 ’ < 斤期 量 H ί H& t # &111 形分總 8〇重田卜 里乂以下,較佳為85重量%以下,更佳為 列重1%以下,又,i甬赍盔%去 旦0/、,L 、㊉為20重量%以上,較佳為30重 里/以上,更佳為40重量%以上。 又’本發明之彩色濾光片用著色組成物中之顏料含量, 對於固形分總量,通常為75重量%以下,較佳為7〇 以I。以rV/佳為6〇重量%以下,又’通常為1〇重量% ,較L為20重量%以上,更佳為25重量%以上。 之量過多’則難以維持顏料之分散狀態,從而發 =或沈降,結果有可能產生黏度增加或亮度、對比度 :降之問題。另-方面’若顏料之量過少,則色濃度較淡, ^可成產生無法充分發揮作為彩色濾、光片之功能 L卜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,旦 有如下功能:除顏料、分散劑之外,亦使視情況而調配; 97122823 26 200911930 上述以外的成分等溶解或分散,並調整黏度。 該溶劑,為可使各成分溶解或分散者即可 作為此種溶劑,例如可舉出:乙二醇單甲 乙_、乙二醇單丙鍵、乙二醇單丁 =二醇單 二醇單乙"、-二醇單正丁喊、丙二醇第丙 醇單甲醚、二乙二醇單⑽、二乙二醇單正-"乙二 曱基戊醇、丙二醇單&^ …甲氧基 f κ \ 甲…甲基:甲Γ:丙一二酵皁乙鍵、二兩二醇單 甲乳基丁醇、二乙一醇單甲趟、三乙一 醇單***、三丙二醇單甲酸之類的二醇單燒基_^一 乙二醇二甲崎、乙二醇二乙⑽、二乙二醇二甲醚、 ,醇二***、二乙二醇二丙醚、二乙二醇二丁醚、二丙二 醇一甲醚之類的二醇二烧基醚類; 乙二醇單甲_乙酸g旨、乙二醇單***乙酸醋、乙二醇單 ,丁醚乙酸酯、丙二醇單曱醚乙酸酯、丙二醇單***乙酸 醋、丙二醇單丙驗乙酸酯、丙二醇單丁驗乙酸3旨、乙酸甲 氧基丁酯、乙酸-3-甲氧基丁酯、乙酸甲氧基戊酯、二乙 二醇單甲醚乙酸酯、二乙二醇單***乙酸酯、二乙二醇單 正丁醚乙酸酯、二丙二醇單甲醚乙酸酯、三乙二醇單甲醚 乙酸酯、三乙二醇單***乙酸酯、乙酸_3_曱基_3_曱氧基 丁酯之類的二醇烷基醚乙酸酯類; 乙二醇二乙酸酯、丨,3-丁二醇二乙酸酯、1,6-己二醇二 乙酸酯等二醇二乙酸酯類; 環己醇乙酸酯等烧基乙酸酯類; 戊醚、丙醚、二***、二丙醚、二異丙醚、丁醚、二戊 97122823 27 200911930 醚、乙基異丁醚、二己醚之類的醚類;St s green light desertification phthalocyanine pigment. It is preferable to use a solvent salt milling method because it is easy to suppress crystal growth and to obtain a surface-particle-reducing method. And the crude pigment immediately after the synthesis and the unsalted salt, and not specifically, the (4) crude pigment, the inorganic, and the organic solvent of the combined solution are added to the kneading machine, and the mixture is honed and ground in a kneading machine. For example, it is suitable to use a kneading machine or a kneading machine, for example, a kneading machine or a kneading machine, which is described in Japanese Patent Laid-Open Publication No. Hei 2-6-77062. A continuous kneading machine for pulverizing the space in which the gap portion of the rotating disk is opened, etc. The above-mentioned inorganic salt can be suitably used, for example, sodium chloride, gasification 钿h ..., H parent, etc. The inorganic salt has a particle size such as sodium and other inorganic salts. Moreover, it is better to use the usual inorganic salt to make it slightly pulverized (4). The refined zinc obtained by the = will be used alone, and the emulsification rate is different. 1 The range of the sheep or the inner and the center gold Vi# and Ml is determined by the combination of the brominated phthalocyanine substituted by the (4) m genus. By using the gasification rate and the bromination rate or changing the central metal, Change, so that you can expect the reproducible change of hue change, even if the same green pigment, can also be mixed with pigment green 297122823 24 200911930 or 7 such as copper phthalocyanine. The average primary particle size, usually below m' More preferably 〇. 03 # m again, usually 〇. 〇〇5 //m The green pigment containing the desertified zinc phthalocyanine is 0.1 or less, preferably 0.04 # or less, and particularly preferably 0. 〇 2 5 # m or less, above. If the average-secondary particle diameter is too large, the depolarization characteristic is deteriorated and the contrast becomes == In severe cases, there is a case where the penetration rate is lowered to cause the fundamental f color to deteriorate, or a coarse grain is formed to produce a second:: 2, so that the yield of the color filter is lowered, or Causes the process to pass the production of the product. 4 Conversely, if the average-secondary particle size is too small, the following problems: due to the increase in the specific surface area of the pigment, the score is: = decreased, or the pigment is close to the molecular state, and the light resistance deteriorates. Furthermore, the average particle size of the pigment can be determined by the following method: t The pigment is ultrasonically dispersed in chloroform and added to the attached _ (;ra, '罔格i, dried, A single particle image of ^ " is obtained by observation using a penetrating electron microscope pigment rilsslGn eleGtrQn mierGseQpe, tem). A single average value is calculated according to the calculation formula of the image, and the average particle diameter is determined. The following formula will be As the material of the particle diameter in terms of a, circle-equivalent product # '= the diameter of a plurality of pigment particles of about 200 to 300 months, were determined in accordance with: the average of single leaf iso Calculate' and determine the average particle diameter. Particle size of each pigment particle: χ, χ3, χ4........ γ 97122823 25 200911930 干 粒径 = IX IX IX IX IX IX IX IX IX , , , , , IX IX IX IX IX IX IX IX IX Each pigment is mixed and used as a pigment. For example, when preparing a red or green pigment dispersion or a coloring composition, in order to adjust the hue, at least one of the pigments of the page pigment or the green pigment may be combined with one or more pigments of the color. As such a system, for example, various yellow pigments mentioned above can be mentioned. Further, in order to ": a dispersion or a coloring composition of:", a blue pigment may be combined with one or more kinds of ochre pigments. The chromaticity of the color may be appropriately mixed and used for each color pigment. ' < The amount of H ί H & t # & 111 is generally 8 〇 重田卜里乂, preferably 85% by weight or less, more preferably 1% or less, and i. , L and 10 are 20% by weight or more, preferably 30% by weight or more, more preferably 40% by weight or more. Further, the pigment content in the coloring composition for a color filter of the present invention, for the total amount of solid content, Usually, it is 75% by weight or less, preferably 7 Å to I. It is rV/preferably 6 〇% by weight or less, and is usually '1% by weight, more than 20% by weight, more preferably 25% by weight or more. If the amount is too large, it is difficult to maintain the dispersion state of the pigment, and then the hair = or sedimentation. As a result, there is a possibility that the viscosity is increased or the brightness and contrast are lowered. On the other hand, if the amount of the pigment is too small, the color density is light. ^ can be produced into a function that can not be fully utilized as a color filter, light film L 2 2 solvent solvent The pigment dispersion liquid of the present invention or the colored composition described later has the following functions: in addition to the pigment and the dispersant, it is also formulated as appropriate; 97122823 26 200911930 The components other than the above are dissolved or dispersed, and the viscosity is adjusted. The solvent can be used as such a solvent in order to dissolve or disperse each component, and examples thereof include ethylene glycol monomethyl bromide, ethylene glycol monopropyl bond, and ethylene glycol monobutane = glycol monoglycol. B",-diol mono-n-butyl, propylene glycol propylene glycol monomethyl ether, diethylene glycol mono (10), diethylene glycol mono----------------- Oxygen f κ \ A... methyl: formazan: propanol diacetate soap, diammonium glycol monomethylbutanol, diethyl alcohol monomethyl hydrazine, triethylene glycol monoethyl ether, tripropylene glycol monocarboxylic acid a diol-based monoalkyl group _^-ethylene glycol dimethyl sulphate, ethylene glycol di(10), diethylene glycol dimethyl ether, alcohol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl a diol dialkyl ether such as ether or dipropylene glycol monomethyl ether; ethylene glycol monomethyl-acetic acid g, ethylene glycol monoethyl ether acetate, and Alcohol mono, butyl ether acetate, propylene glycol monoterpene ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl acetate, propylene glycol monobutyl acetate, methoxybutyl acetate, acetic acid-3- Methoxybutyl ester, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl Glycol alkyl ether acetate such as ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, acetic acid _3_mercapto_3_decyloxybutyl ester a glycol diacetate such as ethylene glycol diacetate, hydrazine, 3-butanediol diacetate or 1,6-hexanediol diacetate; or a cyclohexane alcohol acetate or the like Acetate; pentyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl 97102823 27 200911930 ethers such as ether, ethyl isobutyl ether, dihexyl ether;
丙酮、甲基乙基酮、甲基戊基酮 異戊基酿1、二異丙基@同、二異丁基 己酉同、 己酮、乙基戊基酮、甲基丁基酮、甲基已 酮、甲氧基甲基戊g同之類的酮類; 乙一酵、丙二醇、 淳、甲氧基甲基戊 乙醇、丙醇、丁醇、己醇、環己醇、乙 一乙二醇、二丙二醇、三乙二醇、 醇、甘油、苄醇之類的一元或多元醇類; 二異丁烯、正己烷、己烯、異戊二烯、 正戊烧、正辛烧、二 雙戊烯(dipentene)、十二烷之類的脂肪族烴類; 裱己烷、曱基環己烷、甲基環己烯、聯環己烷 (bicyclohexyl)之類的脂環式烴類; 笨、甲苯、二曱笨、異丙苯之類的芳香族烴類; 甲酸戊酯、曱酸乙酯、乙酸乙酯、乙酸丁酯、乙酸丙酯、 乙酸戊酷、異丁酸甲酯、乙二醇乙酸酯、丙酸乙酯、丙酸 丙醋、丁酸丁酯、丁酸異丁酯、異丁酸甲酯、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-甲氧基丙酸曱酯、3_甲氧基丙酸乙酯、3-曱氧基丙酸丙酯、3-曱氧基丙酸丁酯、r-丁内酯之類的 鏈狀或環狀酯類; 3-曱氧基丙酸、3-乙氧基丙酸之類的烷氧基羧酸類; 氯丁烷、氯戊烷之類的齒化烴類; 甲氧基甲基戊酮之類的醚酮類; 乙腈、苄腈之類的腈類等。 97122823 28 200911930 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 'Acetone, methyl ethyl ketone, methyl amyl ketone isoamyl ketone 1, diisopropyl@同, diisobutylhexyl hexanone, ketone, ethyl amyl ketone, methyl butyl ketone, A Ketones such as ketone and methoxymethylpentan; B-fermented, propylene glycol, hydrazine, methoxymethylpentanethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol , mono- or polyhydric alcohols such as dipropylene glycol, triethylene glycol, alcohol, glycerol, benzyl alcohol; diisobutylene, n-hexane, hexene, isoprene, n-pentane, n-octyl, di-p-pentene (dipentene), an aliphatic hydrocarbon such as dodecane; an alicyclic hydrocarbon such as hexane, decylcyclohexane, methylcyclohexene or bicyclohexyl; Aromatic hydrocarbons such as dioxane and cumene; amyl formate, ethyl citrate, ethyl acetate, butyl acetate, propyl acetate, pentaethyl acetate, methyl isobutyrate, ethylene glycol Acetate, ethyl propionate, propionic acid propyl vinegar, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octanoate, butyl stearate, ethyl benzoate, 3_B Oxypropionic acid Ester, ethyl 3-ethoxypropionate, decyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-pylopropoxypropanoate Chain or cyclic esters such as esters and r-butyrolactone; alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; chlorobutane and chloropentane Toxic hydrocarbons of the type; ether ketones such as methoxymethylpentanone; nitriles such as acetonitrile and benzonitrile. 97122823 28 200911930 As a commercially available solvent in accordance with the above, it can be mentioned: mineral spirit ^ Varsol # 2 > Apco # 18 Solvent > Apco thinner '
Socal Solvent No. 1 及 No. 2、Solvesso# 150、Shel 1 TS28Socal Solvent No. 1 and No. 2, Solvesso # 150, Shel 1 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、曱基赛璐蘇乙酸酯、 二乙二醇二甲醚(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濾光片之像素的情形,作為溶 劑,較佳為選擇沸點為100〜200〇c(壓力1〇13·25 [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 成刀之各解度相對較高而言,上述溶劑中較佳為乙二醇燒 基鱗乙酸酯類。Solvent, carbitol, ethyl carbitol, butyl carbitol, thiopyrrolidine, ethyl cyproterone, ethyl cyanohydrin, thiopyranyl acetate, diethyl Diethylene glycol (diglyme) (all trade names) and the like. These solvents may be used alone or in combination of two or more. <In the case of forming a pixel of a color filter by photolithography> In the case of forming a pixel of a color filter by photolithography, as a solvent, it is preferred to select a boiling point of 100 to 200 〇c (pressure 1 〇) 13·25 [hPa] Under the conditions, 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.), and the balance between coatability and surface tension is good, and the degree of solution of the constituents in the composition is relatively high. Ethylene glycol ketone acetate.
,乙二醇烷基醚乙酸酯類可單獨使用,亦可與其他产 劑併用。作為併用之溶劑,特佳為乙二醇單燒基趟類二 中:特別是就組成物中之構成成分之溶解性而言,較佳: 酉子單甲驗。再者’乙二醇單燒基輕類之極性較高,若 ^量過ί ’則有顏料易於凝集、隨後所得著色組成物之 :又上升等保存穩定性Τ降之傾向,因此溶劑中之乙二於 單燒基_類之比例較佳為5 #旦〇/ Q η去 芋 重量卜20㈣ 重“〜3〇重量更佳為5 又 亦較佳為併用具有 150°C以上之沸點的溶劑。藉由 97122823 29 200911930 併用此種高彿點溶劑,而使得著色組成物不易 難以引起由於迅速乾燥而造成顏料分散液之相、、: 陷之效果。高洮、—句. 之相互關係缺 双禾…弗點洛劑之含量,係相對於 量%〜50重量%,更佳為 4為3重 量%〜30重量%。若n二 重特佳為5重 如狹縫喷嘴前端發生色 、有可此在例 陷,又,若仍夕曰, 析出·固化而51起異物缺 夕,則組成物之乾燥速度會變尸,…二谈i 引起後述彩色濾光片製造步驟 上,而擔憂 不良或賴烤的㈣之_。W錢程的黏性 再者,沸點為l5(rc以上之 醋類,又,亦可為二醇烧基嶋’在2;„乙酸 外含有彿點為15代以上之溶劑。在此_下’亦可不另 〈以喷墨法形成彩色濾光片之像素之情形〉 在= 墨法形成彩色遽光片之像素 為啊以上28〇。^下者=以上_以下'較佳 之均句性變差之傾向。反之二貝有所传塗膜 硬化性樹月匕έ日#私·ν ± ”、、咼,則如後述般’ ”月曰組成物之乾燥抑制效 塗膜中亦殘留許多溶劑,有 ”更在.、,丄成後 由於真空乾燥等之乾丄時有門時//生品f上之問 等問題。 ” Τ間變長而產生使黏性時間增大 ,、二塗膜之均勾性之觀點而言,可使用溶劑之I /飞^通书為1 〇 mmHg以下、 … 1 minHg以丁者。 較佳為5 minHg以下、更佳為 97122823 30 200911930 f 再者’於使心墨法之彩色遽光片製造中,自 :油墨為非常細微之數〜數十pL,因此有在將油墨喷: =嘴口周曲邊或像素陣列(pixelbank)内之前,溶劑蒸發 為j之:墨'辰縮.乾燥之傾向。為了避免此現象’較佳為溶 ':沸點較南,具體而言,較佳為含有沸點為18〇。。以上 劑。更佳為含有沸點為·。c以上之溶劑,特佳為含 ’ 為220 C以上之溶劑。又,沸點為180。。以上之高 物’係在顏料分散液及/或彩色濾、光片用著色誕成 :!斤含之總溶劑中’較佳為5〇重量%以上,更佳為7〇 重以上,最佳兔⑽壬曰 、土 cn 取彳為90重置%以上。在高沸點溶劑含量未 滴蒸形下,有時亦無法充分發揮防止溶劑自液 作為較佳之高彿點溶劑,例如可舉出:上述各種溶劑中 丙二==乙:Τ;二:二醇單乙"乙_、二 二_旨、甘油;:酸:旨::二醇二乙酸,、U-己二醇 八為了調整顏料分散液或著色組成物之黏度或固形 :為部分含有沸點低於18rc之溶劑亦較有效。 類的、二:佳為黏度低且溶解性高、表面張力低之 、岭悧,較佳為醚類、酯類或酮類等。其中, 己顯I、二丙二醇二曱醚、環己醇乙酸酯等。、’’、、衣 ^方面,若溶劑中含有醇類,則有時嘴墨法中之吐出 ::。生會發生劣化。因此’醇類在總溶劑中之含量,較佳 為20重^以下,更佳為10重量%以下,特佳為5重量% 97122823 31 200911930 以下。 〈溶劑之含量> 溶劑在本發明之著色組成物 別限制,其上限通常為99重旦^斤占之含置,亚無特 99重量%的情形下,顏 里在溶劑含量超過 ^ ^ ^ ^ " 刀政蜊等則變得過少,而不適 劑人旦* 丁 考慮到適於塗佈之黏性等,溶 上,更佳為82重量%以上。…較佳為8。重量%以 [1 - 3 ]分散劑: :::所使用之分散劑’含有由具有親溶劑性之Α喪段 物原子的官能基之B嵌段所構成之嵌段共聚 _ 有效固形分換算計為80 mgK,以上且15〇 mgKOH/g 以下。 、作為叙段共聚物’較佳為(甲基)丙稀酸系嵌段共聚物, =下:以上述嵌段共聚物為(甲基)丙烯酸系嵌段共聚物之 十月形為中心,就本發明之分散劑加以說明。 B喪段係具有含氮原子之官能基,作為該官能基,較佳 為-〜三級胺基。—〜三級胺基之含有比率,較 原子官能基整體的2〇莫耳%以上,更佳為5G莫耳%以上。 -〜三級胺基中’特佳為三級胺基。作為該三級胺基 佳可舉出以,Y(其中H『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。 97122823 32 200911930 [化7] R44The ethylene glycol alkyl ether acetates may be used singly or in combination with other preparations. As a solvent to be used in combination, it is particularly preferred to use ethylene glycol monoalkyl phthalocyanine: particularly, in terms of solubility of the constituent components in the composition, it is preferred to use a scorpion single test. Furthermore, the 'ethylene glycol monolithic light type has a higher polarity, and if the amount is too high, the pigment tends to aggregate, and the coloring composition obtained subsequently has a tendency to lower the storage stability, and thus the solvent The ratio of the ethylene to the monolithic group is preferably 5 #旦〇 / Q η 芋 芋 weight 20 (4) ""3 〇 more preferably 5 is also preferably used in combination with a boiling point of 150 ° C or more By using 97122923 29 200911930 in combination with such a high-foam solvent, it is difficult to cause the coloring composition to be difficult to cause the phase of the pigment dispersion due to rapid drying, and the effect of the depression is high. The content of the sulphate agent is relative to the amount of % to 50% by weight, more preferably 4 to 3% by weight to 30% by weight. If n is particularly good, the weight is 5, such as the color of the front end of the slit nozzle, However, if it is still smashed, if it is still smashed, precipitated and solidified, and 51 foreign bodies are missing, the drying speed of the composition will change to corpse, and secondly, i causes the color filter manufacturing step described later, and the worry is bad. Or simmered (four) _. W money course viscosity, the boiling point is l5 (rc The vinegar, in addition, may also be a diol-based hydrazine 'in 2; „acetic acid contains a solvent having a Buddha's point of 15 or more. In this case, it may be replaced by an inkjet method to form a color filter. In the case of pixels> In the case of = ink method, the pixels of the color grading film are more than 28 〇. ^ The lower one = the above _ below the preferred tendency of the uniformity of the sentence. Conversely, the two shells have a film-hardening tree. On the day of the month, #私·ν± ”, 咼, as described later, there is also a lot of solvent remaining in the drying suppression coating film of the composition of the sputum, which is “more in, and after vacuuming, vacuum drying, etc.” When there is a door when dry, there is a problem such as the question of raw material f. ” I can use solvent I from the viewpoint that the time is longer and the viscosity time is increased, and the two coating films are uniform. / 飞^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ The ink is very fine ~ tens of pL, so there is solvent evaporation before the ink is sprayed: = the mouth is curved or the pixel array (pixelbank) For the sake of j: ink 'Chen shrink. Dry tendency. To avoid this phenomenon 'preferably dissolve': the boiling point is relatively south, specifically, it preferably contains a boiling point of 18 〇. The above agent. More preferably contains The solvent having a boiling point of c·c or more is particularly preferably a solvent containing '220 C or more. Further, the boiling point is 180. The above high substance is produced by pigment dispersion and/or color filter and coloring. :! In the total solvent contained in the kg, it is preferably 5% by weight or more, more preferably 7 〇 or more, and the best rabbit (10) 壬曰, soil cn is 90 90 90% or more. The high boiling point solvent content is not In the case of dripping steaming, it is sometimes impossible to sufficiently prevent the solvent from being liquid as a preferred high-foam solvent. For example, in the above various solvents, C 2 == B: Τ; 2: diol B&B; , two or two, glycerin;: acid: the purpose:: diol diacetic acid, U-hexanediol eight in order to adjust the viscosity or solidity of the pigment dispersion or coloring composition: for some of the solvent containing a boiling point below 18rc More effective. Class II, preferably: low viscosity, high solubility, low surface tension, ridge, preferably ether, ester or ketone. Among them, I, dipropylene glycol dioxime ether, cyclohexanol acetate, and the like. In the case of ', ', and clothing, if the solvent contains alcohol, the discharge in the mouth ink method may be ::. Degeneration will occur. 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 of 97122823 31 200911930 or less. <Content of Solvent> The solvent is limited in the coloring composition of the present invention, and the upper limit is usually 99% by weight, and the content of the solvent is more than ^^^. ^ " Knife 蜊 蜊 变得 变得 , , , , , , 不适 不适 不适 不适 不适 不适 不适 不适 不适 不适 不适 不适 不适 不适 不适 不适 不适 不适 不适 不适 不适 不适 不适 不适 不适 不适 不适... preferably 8. % by weight of [1 - 3 ] dispersant: ::: Dispersant used - Block copolymerization consisting of B blocks of functional groups having solvophilic groups of atoms - Effective solids conversion It is calculated to be 80 mgK or more and 15 〇 mgKOH/g or less. The copolymer of the segment is preferably a (meth)acrylic block copolymer, and the lower portion is centered on the shape of the block of the (meth)acrylic block copolymer. The dispersant of the present invention will be described. The B segment is a functional group having a nitrogen atom, and as the functional group, a -3 tertiary amine group is preferred. The content ratio of the -3 tertiary amine group is 2 〇 mol% or more, more preferably 5 G mole % or more, based on the entire atomic functional group. - The tertiary amine group is particularly preferably a tertiary amine group. As the tertiary amine group, Y (wherein H " each independently represents a cyclic or chain alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent The group represented by the above is preferably a partial structure (repeating unit) containing the tertiary amino group, and is represented, for example, by the following formula. 97122823 32 200911930 [Chemical 7] R44
:41/、R42 ,Ν (其中,R41及Ρ,與上述R“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較佳為甲基,r43較佳為亞甲基、伸乙基, R“較佳為氫原子或甲基。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甲胺基乙酯或甲基丙 烯酸二甲胺基乙酯之結構等。 [化8] R44:41/, R42, Ν (wherein R41 and Ρ have the same meanings as R and r42 above, 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 more Preferably, it is a methyl group, and r43 is preferably a methylene group or an ethyl group, and R is preferably a hydrogen atom or a methyl group. As such a partial structure, a structure derived from dimethylaminoethyl acrylate or dimethylaminoethyl methacrylate represented by the following formula is particularly suitable. [化8] R44
(式中,R44與上述含義相同。) 1個B嵌段中可含有2種以上如上述之含有胺基之部分 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 97122823 33 200911930 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社 構等。該=含胺基之部分結構在B鼓段中之含量,較佳^ 〇〜50重里%,更佳為〇〜2〇重量%,但最佳係B嵌段中 含有該不含胺基之部分結構。 凡另: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欣段之單體進行共聚合的單體所構成者,則無特 別限制。 :為親溶劑性之A嵌段,例如可舉出:苯乙烯…甲 基苯乙烯等苯乙烯系單體;(曱基)丙烯酸甲_、(甲基) 丙烯I乙S日、(甲基)丙烯酸丙_、(甲基)丙烯酸異丙醋、(wherein R44 has the same meaning as defined above.) The one B block may contain two or more kinds of the above-mentioned partial structure containing an amine group. 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, b 97122823 33 200911930 may partially contain a partial structure containing no amine group, and examples of such a partial structure include a part of a structure derived from a (fluorenyl) acrylate monomer. The content of the partial structure containing the amine group in the B drum section is preferably from 〇50 to 50% by weight, more preferably 〇~2〇% by weight, but the optimum B group contains the amine-free group. Part of the structure. Wherein, the solvophilic A block of the block copolymer constituting the dispersing agent is a functional group which does not contain a nitrogen atom such as the above amine group, and may be a monomer which is formed into the above-mentioned B xin segment The composition of the monomer to be copolymerized is not particularly limited. Examples of the solvophilic A block include styrene monomers such as styrene methyl styrene; methyl ketone, (meth) propylene I ethyl s day, (methyl) ) Acrylic acid propyl, (meth)acrylic acid isopropyl vinegar,
(甲基)丙婦酸丁酉旨、(甲基)丙烯酸辛醋、(曱基)丙稀酸I 乙基己g曰(甲基)丙烯酸環氧丙酯、(甲基)丙烯酸苄酯、 (甲基)丙烯酸羥基乙,、乙基丙烯酸環氧丙酯、聚乙二醇 〇 (f基)丙烯酸酯、聚丙二醇(甲基)丙烯酸醋等(甲基)丙烯 酸醋系單體;(甲基)丙烯醯氯等(甲基)丙烯醯氯系單體; 乙酸乙烯醋系單體;婦丙基環氧丙基轉、丁婦酸環氧丙喊 4環氧丙㈣單體等共單體進行共聚合而得之聚合物結 構。 其令’作為A嵌段,較佳為含有聚乙二醇”基)丙婦酸 醋、聚丙二醇(甲基)丙婦酸醋等聚垸二醇(甲基)丙婦酸醋 作為共聚合成分(即,含有來自聚規二醇(甲基)丙稀酸醋 之部分結構)者,特佳為具有以下述式(ιν)所表示之部分 97122823 34 200911930 結構之A嵌段 [化9] R so f(methyl) propyl acetophenate, (meth) acrylate vinegar, (mercapto) acrylic acid I ethylhexyl hydrazide (meth) acrylate, benzyl (meth) acrylate, ( (meth)acrylic acid vinegar monomer such as methyl methacrylate, butyl propyl acrylate, polyethylene glycol fluorene (f) acrylate, polypropylene glycol (meth) acrylate vinegar; ) (meth) propylene fluorene-based monomer such as acrylonitrile chloride; vinyl acetate vine monomer; propyl propyl epoxide, butylated acid propylene propylene, 4 epoxy propylene (tetra) monomer, etc. The polymer structure obtained by copolymerization. It is used as a copolymerization of polydecanediol (methyl) acetoacetate such as A block, preferably containing polyethylene glycol propylene glycol vinegar or polypropylene glycol (meth) acetoacetate. The component (that is, a partial structure containing a polyglycol diol (meth) acrylate vinegar) is particularly preferably an A block having a structure represented by the following formula (ιν) 9712823 34 200911930 structure [Chemical 9] R so f
示之部分結構。 〜4(3莫耳%之以上述式αν)所表 雖然详細的作用機制不一切 由具有來自聚烷_妒w 為作用機制為:藉 聚凡一% (甲基)丙婦酸酯之部 以上述式所表示之部分 =構特別疋 性,您而坦曰Λ \ 而了挺同刀散劑分子之氫鍵 加。*外與分散溶劑之親和性,且分散系之穩定性增 ::明中所使用之分散劑,含有由此 :構2共聚物,較佳為含有ΑΒ嵌段 嵌= 物。其中,較佳為ΑΒ嵌段丑聚物…… U 可夢、 種嵌段共聚物例如 Γ糟由以下所不之活性聚合法而製備。 ==合法有陰離子活性聚合法、陽離子活性聚合法、 二:基二性聚合法。陰離子活性聚合法之聚合 離子’例如下述流程所示。 ^ [化 10] 97122823 35 200911930 (陰離子活性聚合法) 在單體①:H2C=fH、單體②:H2C==^H 時 Ar1 Ar2 HZC=CH' Ar1 +有機金屬(M)化合物 -► -wv\ch2-丫 H2"丨""Μ f 單體φ ΘPart of the structure shown. ~4 (3 mol% is expressed by the above formula αν) Although the detailed mechanism of action is not all due to the mechanism of action from polyalkylene_妒w: by the poly(%) (methyl) propionate The part represented by the above formula = special structure, you are arrogant \ and the hydrogen bond of the same powder. *Affinity to the dispersion solvent and the stability of the dispersion system. The dispersant used in the present invention contains the copolymer of the structure 2, preferably containing a ruthenium block. Among them, a hafnium block oligopolymer is preferred. U Umbrella, a block copolymer such as barium is prepared by the following living polymerization method. == Legally, there are anionic living polymerization method, cationic living polymerization method, and two: basic two-dimensional polymerization method. The polymerization ion of the anionic living polymerization method is shown, for example, in the following scheme. ^ [Chemical 10] 97122823 35 200911930 (anionic living polymerization method) In the monomer 1: H2C = fH, monomer 2: H2C = = ^ H Ar1 Ar2 HZC = CH' Ar1 + organometallic (M) compound - ► - Wv\ch2-丫H2"丨""Μ f monomer φ Θ
-CH2—CH '"""M CH2—CHi Ar1 广 ch2- :ch2- 一 CH, I Ar1. n+1 L Ar2』 >όη2- r CH2'- —CH, I Ar1· n+1 Ar2. -CH2一CH "丨…丨M ir2 i /\r m+1 單體② Η 自由基活性聚合法(墙酸(nitroxyl)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。 36 97122823 200911930 [化 11] 在單體①: (自由基活性聚合法:硝醯法: H2C=CH、单體②:H2C=CH 時丁 I Ar1 Ar2 h2c=ch Ar1 ch3 h3c、占 _CH / \ O-^N CH2 i-CH2 h3c' ch3 ch3 H3C^C—ch2 / \ ^wiACHo-CH'»ih»i〇·--N CH2 單體①. CH2—CH- ch3 h3c〜占_CH / \z •GH2_CH ……"O-N CH2-CH2—CH '"""M CH2—CHi Ar1 broad ch2- :ch2- a CH, I Ar1. n+1 L Ar2』 >όη2- r CH2'- —CH, I Ar1· n+ 1 Ar2. -CH2-CH "丨...丨M ir2 i /\r m+1 Monomer 2 Η Free radical living polymerization method (nitroxyl method, ATRP method (Atom Transfer Radical Polymerization) The polymerization active species of the polymerization method)) is a radical, for example, as shown in the following scheme. 36 97122823 200911930 [Chemical 11] In monomer 1: (radical active polymerization method: nitroxide method: H2C=CH, monomer 2: H2C=CH) I Ar1 Ar2 h2c=ch Ar1 ch3 h3c, _CH / \ O-^N CH2 i-CH2 h3c' ch3 ch3 H3C^C—ch2 / \ ^wiACHo-CH'»ih»i〇·--N CH2 monomer 1. CH2—CH- ch3 h3c~zhan_CH / \z •GH2_CH ......"ON CH2
Ar1 單體②. ,CH2 ?H_ •CH2 CH-I Ar1. n+1 L Ar2 . CH3 H3C^C-CH2 CHg—^Η”""11。—~N CH2 1 ch2Ar1 monomer 2., CH2 ?H_ •CH2 CH-I Ar1. n+1 L Ar2 . CH3 H3C^C-CH2 CHg—^Η”""11.—~N CH2 1 ch2
Ar2 H3C^ ch3 97122823 37 200911930 [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 COORbAr2 H3C^ ch3 97122823 37 200911930 (Free radical living polymerization method: ATRP method) In the monomer 1: H2C = | H, monomer 2: H2c = fH COORa COORb
H2C==CH C00R3 +有機金屬(Me)化合物 (Me表示過渡金屬。) /w\ach2— COORaH2C==CH C00R3 +organometallic (Me) compound (Me means transition metal.) /w\ach2—COORa
單體①t 單體②Monomer 1t monomer 2
CH2一 —CH-l·- COORaJ π I a COORa 广CH2 CH- CHZ——CH-: 1 ft L COORaJ n+1 COORb. m CH2——CH"……Me COORb 在合成此種(甲基)丙烯酸系嵌段共聚物時,可採用曰本 專利特開昭60-89452號公報;特開平9-62002號公報; P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1 984); B. C. Anderson, G. D. Andrews et al, Macromolecules, 14, 1 601 (1 981 ) i K. Hatada, K. Ute, et al, Polym. J. 1 7, 977 (1 985) ; K. Hatada, K. Ute, et al, Polym. J. 18,1 037 (1 986);右手浩一、畑田耕一,高分子加工, 36,366 (1 987);東村敏延、沢本光男,高分子論文集, 46, 189 (1 989) ; M. Kuroki, T. Aida, J. Am. Chem. Sic, 109,4737 (1 987);相田卓三、井上祥平,有機合成化學, 43, 300 (1985) ; D. Y. Sogoh, W. R. Hertler et al, 97122823 38 200911930CH2-CH-l·- COORaJ π I a COORa 广 CH2 CH- CHZ——CH-: 1 ft L COORaJ n+1 COORb. m CH2——CH"......Me COORb in the synthesis of this (methyl) In the case of the acrylic block copolymer, JP-A-60-89452; JP-A-9-62002; P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1 984) BC Anderson, GD Andrews et al, Macromolecules, 14, 1 601 (1 981 ) i K. Hatada, K. Ute, et al, Polym. J. 1, 7, 977 (1 985) ; K. Hatada, K Ute, et al, Polym. J. 18,1 037 (1 986); Right Hand Hao Yi, Putian Gengyi, Polymer Processing, 36, 366 (1 987); Dong Cun Min Yan, Sakamoto Kou, Polymer Proceedings, 46 , 189 (1 989) ; M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737 (1 987); Xiang Tian Zhuo San, Jing Shang Xiangping, Organic Synthetic Chemistry, 43, 300 (1985) ; DY Sogoh , WR Hertler et al, 97122823 38 200911930
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§固形分中 之胺價,以有效固形分換算計為8〇 mgK〇H/g以上且 150mgKOH/g以下,較佳為90〜15〇 mgK〇H/g,更佳為ι〇〇 〜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 南,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’ ^ 了表現最佳分散性,而將胺價設定在 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lgg]形分之驗量等當量之κ〇Η的 重量來表不,係藉由以下方法測定。於1〇〇此燒杯中精 確秤取0. 5 1 · 5 g分散劑試料,用5Q此乙酸將其溶解。 使用具備pH電極之自勤Macromolecules, 20, 1473 (1987); K. Matyaszewski et al, Chem. Rev. 2001, 101, 2921 - 2990, etc., are well known methods. The amine valence in the 1 § solid content of the dispersant containing the above block copolymer of the present invention is 8 〇 mg K 〇 H / g or more and 150 mg KOH / g or less, preferably 90 〜 15 以 in terms of effective solid content. mgK〇H/g, more preferably ι〇〇~140 mgKOH/g. If the amine value is too low, the adsorption force of the dispersant molecule on the surface of the pigment becomes insufficient, and sufficient dispersion stability cannot be obtained. On the other hand, if the amine value is too large, the molecular weight of the relatively A block becomes small, and the dispersion stability becomes insufficient. In other words, '^ is the best dispersion, and the amine price is set in the range. Further, the amine value of the dispersant (effective solid fraction conversion) is expressed by the weight of the equivalent amount of κ 每 per ng of the solvent in the dispersant sample, and is expressed by the following Method determination. In a beaker of this size, accurately weigh 0.51 · 5 g of dispersant sample and dissolve it with 5Q of this acetic acid. Use a self-service with a pH electrode
目動滴疋裝置,將該溶液以0. 1 m〇l/L 之HC1 〇4乙酸溶液進行中$ $ + 退仃干和“ °將滴定pH曲線之拐點作 為滴疋終點,根據下式求出胺價。 胺價[mgK0H/g]= (561xV)/(WxS) (其中,W表示分散劑試料 _ 滴定量叫,s表示分散㈣H] 疋終點之 又,抖之固形分濃度[wt%]。) 的於性iiir 酸價’亦取決於成為該酸價之基礎 的^生基之有無及種類,—般較佳為低酸價,通常為50 97122823 39 200911930 mgKOH/g以下’較佳為4〇 mgj(〇H/g以下,更佳為3〇 mgK〇H/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。 山f發明之顏料分散液,必須使用含有上述由a嵌段及B 甘欠&所構成之共聚物的分散劑。藉由使用此種後段共聚物 作為分散劑,可同時滿足對顏料表面的牢固吸附及較高的 洛劑親和性,因此可實現較高分散穩定性。又,藉由提高 刀政劑之胺價’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。 佳為B肷!又中具有含氮原子的官能 的20莫耳%以上為具有一〜二 里腹早疋〒 +旦, ^ —級胺基之重複單元。若胺基 ^小於20莫耳%,則即便胺價為8〇 __以上,亦 U得充分的吸附力,有時亦無法獲得高分散穩定性。 因= ί平均一次粒徑較小時,比表面積增大, 产形;:母早:表面積之分散劑吸附量變少。在此種 月/ ,3有上述嵌段共聚物之分散劑,盘盆他社構之八 散劑相比,非常顯著地表現出效果的差/、二;;構之刀 使用。相對於顏料分散液中或著此特別適合 為一重=為5〜2〇°重量%左右,更佳 果料分散液及著色峰,在不損及本發明效 ttr可含有除上述嵌段共聚物以外之分散劑。作 ”、*散劑’例如可舉出:日本專利特開鳩_343648 97122823 200911930 號公報中記载之各種分散劑等 [1-4]分散助劑 声頁顏料分散液及著色組成物,亦可含有用以提高 二、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㈣:偶㈣、料系、七丫 疋,糸、苯㈣㈣系、伽_UinQPhthal_)系、異 引木琳嗣系、二〇fD井系、惠醌(anthraquinone)系、陰丹士 林系、花系、娘瑞酮(perinQne)系' 二酮料并吼口各 (diketopyrrolopyrr〇le)系顏料等衍生物。 作為該等顏料衍生物之取代基,可舉出:賴基、確醯 胺基、及其四級鹽、鄰苯二甲醯亞胺甲基、二烷基胺基烷 基、經基、羧基、酿胺基等。該等取代基,可直接鍵結於 顏料骨架上,或者可經由烧基、彡基、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 佳為續酸基。 、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 竹生物、酜著糸顏料之績酸衍生物、喧酜酮系顏料之石黃酸 衍生物、蒽靦系顏料之磺酸衍生物、啥吖咬酮系顏料之石黃 酸衍生物、二酮吡咯并吡咯系顏料之磺酸衍生物、二β号讲系 顏料之續酸衍生物等。其中’較佳為可舉出:色素黃^ 3 8 之確酸衍生物、色素黃139之續酸衍生物、色素紅254之 97122823 41 200911930 酉文竹生物色素紅2 5 5之績酸衍生物、色素紅2 6 4之續 酉文衍生物、色素紅272之磺酸衍生物、色素紅209之磺酸 何生物、色素橙71之磺酸衍生物、色素紫23之磺酸衍生 物等。 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. 1重量%以 上’又,通常為30重量%以下,較佳為2〇重量%以下 佳為10重量%以下,特佳為5重量%以下。其原因在於, f添加量較少則有難以發揮其效果之傾向,反之,若添加 置過多則分散性、分散穩定性反而會變差。 Π-5]分散樹脂 ,之顏料分散液’可含有自後述黏合劑樹脂中選擇 曰之—部分或全部。具體而言’於後述顏料分散液製 分散處理步驟中,由於與上述分散劑同時含有黏合 :二曰’該黏合劑樹脂顯示出與分散劑之相乘效果,從而 量,分散敎性。結果有可能減少分散劑之添加 邻八不°又’亦發揮提昇顯影性、在基板之非像素 解物、提昇像素縣板之密著性的效果, 處步驟之黏合劑樹脂稱為分散樹脂。 佳為Ϊ 9 液中之顏料總量,分散樹脂之使用量較 佳為5〜_重量%左右,更佳讀 作為分散樹脂,可徒用播泞々々 更里%左右。 述之各種黏合劑樹脂,特佳為 97122823 42 200911930 後述之[2-1 -2 ](曱基)丙烯酸系樹脂。 分散樹脂之酸價,較佳為1〇 mgK〇H/g以上,更佳為3〇 mgKOH/g以上,最佳為5〇mgK〇H/g以上,又,較佳 〇 mgKOH/g以下,更佳為3〇〇 mgK〇H/g以下最佳為2〇〇 mgKOH/g以下。若酸價過高,則變成高黏度,而有難以合 成或操作之傾向,又,若酸價過低,則有時㈣以應用於 驗性顯影。 r 又,分散樹脂之藉由GPC法所測定之聚苯乙婦換算之重 量平均分子量,較佳為以上,更佳為15⑽以上,最 Y土為2 0 0 〇以上’又,齡伟么9 η η η η λ 、 1仏為200000以下,更佳為50000 二為30000以下。若分子量過大,則有難以應用 性下降㉙影之傾向’又’若分子量過小’則有時分散穩定 Π -6 ]芳香族羧酸系化合物 顏料分散液及著色組成物中之至少—者 為含有芳香族羧酸系化合物。 本發明所使用之含有上述與, # ^ ^ , 啕上11又共聚物之分散劑,可效率 將,ϋ粒化之顏料分散,因而較佳 分散液及彩色濾、光片用著色 —使用…之顏科 陷=向使用該著色組成物而形成之像素,有產生缺 少Sit由 =發明之顏料分散液及著色組成物中之至 增加’又,可防止所得像素之缺陷了 經時黏度 97122823 43 200911930 合物,可^ ΐ在氣備顏料分散液時含有該芳香族魏酸系化 抑制使用其所製借政液本身之經時黏度增加’又,亦可 度增加。又 之彩色濾光片用著色組成物之經時黏 溏朵Η田-令在向顏料分散液中添加各種成分而製備彩色 成物時,由於係作為隨後所添加成分之-辦力、鱼故亦可抑制彩色遽光片用著色組成物之經時黏度 二美成:二?W顏料分散液而是-次性地或者依序 色組成物的情形下,作Mm/77错此H亥者 進行調配。 料構成成分之―,可依任意之時機 以下,就芳香族羧酸系化合物加以說明。 者作=香族叛酸系化合物,若為具有芳香族基及羧基 、I為具有任意結構者。作為芳錢基,例如可舉出 土二萘基等。該等之中,特佳為苯基。 ㈣基可具有取代基,其取代基之種類或數量並 \ 限疋。具體而言,例如較佳為後述通式㈤中以 代基:又:羧基可為⑽,亦可為複數個、 至3個,但就上述之該化合物之效果較顯著之方面 而言’較佳為1分子中為1個。 、芳香族羧酸系化合物之分子量,通常為5〇〇以 為350以下’又,通常為150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,可確每 發揮抑制黏度增加之效果。 Λ 作為芳香族羧酸系化合物,特佳為以下述通式(贝)所表 97122823 44 200911930 示之化合物 [化 13]In the manual drip device, the solution is subjected to 0.1% 〇l/L of HC1 〇4 acetic acid solution for the middle of the $$ + 仃 仃 dry and " ° the inflection point of the titration pH curve as the end point of the drip, according to the following formula The amine price [mgK0H/g] = (561xV) / (WxS) (where W is the dispersant sample _ the titration is called, s is the dispersion (4) H] 疋 the end point, the solid concentration of the shake [wt% The acidity of the iiir is also dependent on the presence or absence of the base of the acid, and is generally preferably a low acid value, usually 50 97122823 39 200911930 mgKOH/g or less. It is 4 〇mgj (〇H/g or less, more preferably 3 〇mgK 〇H/g or less. In the present invention, commercially available (mercapto) acrylic block copolymer having the same structure as the above compound can also be used. In the pigment dispersion of the invention, it is necessary to use a dispersant containing the above-mentioned copolymer composed of the a block and the B tributary & and by using such a post-copolymer as a dispersing agent, the pigment can be simultaneously satisfied. Strong adsorption of the surface and high affinity of the agent, thus achieving higher dispersion stability. The amine price' is particularly an increase in the adsorption force on the surface of the acid-treated pigment, so that the dispersion stability can be further improved. Preferably, more than 20 mol% of the functional group having a nitrogen atom has a ~二里里腹早疋〒+旦, ^—A repeating unit of the amine group. If the amine group is less than 20 mol%, even if the amine price is 8〇__ or more, U has sufficient adsorption force, sometimes It is also impossible to obtain high dispersion stability. Because ί average primary particle size is small, the specific surface area is increased, and the shape is formed;: mother early: the surface area of the dispersant adsorbed less. In this month /, 3 has the above block The dispersing agent of the copolymer, compared with the eight powders of the disc basin, shows the difference of the effect very significantly, and the second; the knife is used. It is especially suitable for the weight of the pigment dispersion or the weight = 5 ~2〇°% by weight, a better fruit dispersion and a coloring peak, and a dispersing agent other than the above-mentioned block copolymer may be contained without impairing the effect ttr of the present invention. For example, “* powder” may be exemplified by: Patent Publication No. _343648 97122823 200911930 Dispersing agent, etc. [1-4] dispersing aid, acoustic sheet pigment dispersion and coloring composition, may also contain a dispersing aid for improving the dispersion stability. As a dispersing aid, for example, a pigment derivative may be mentioned. Etc. As a pigment derivative, for example, (4): even (four), material system, heptazone, anthracene, benzene (four) (four) system, gamma _UinQPhthal_) system, heterogeneous wood linden, two 〇fD well, anthraquinone ), indanthrene, flower, and perinQne are derivatives of diketone and diketopyrrolopyrr〇le pigments. Examples of the substituent of the pigment derivative include a lysine group, a decylamino group, a quaternary salt thereof, a phthalimidomethyl group, a dialkylaminoalkyl group, a trans group, and a carboxyl group. , brewing amine and so on. These substituents may be bonded directly to the pigment skeleton or may be bonded via a mercapto group, a mercapto 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 an 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 a sulfonic acid bamboo organism of an azo pigment, a acid derivative of an anthraquinone pigment, a rhein derivative of an anthrone pigment, and a sulfonate of an anthraquinone pigment. An acid derivative, a pyruvic acid derivative of a ketone-based pigment, a sulfonic acid derivative of a diketopyrrolopyrrole pigment, a derivative of a second β-based pigment, and the like. Among them, 'preferably, it is: acid yellow 3 8 acid derivative, pigment yellow 139 acid derivative, pigment red 254 97122823 41 200911930 酉文竹生物色红2 5 5 acid derivative And the red pigment of the pigment red 264, the sulfonic acid derivative of the pigment red 272, the sulfonic acid derivative of the pigment red 209, the sulfonic acid derivative of the pigment orange 71, the sulfonic acid derivative of the pigment purple 23, and the like. Further, the dispersing aid may be a compound having 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 added is usually 〇. 1% by weight or more, and usually 30% by weight or less, preferably 2% by weight or less, preferably 10% by weight or less, particularly preferably 5% by weight. the following. The reason for this is that when the amount of addition of f is small, it is difficult to exhibit the effect, and if it is added too much, the dispersibility and dispersion stability are rather deteriorated. Π-5] The dispersion resin, the pigment dispersion liquid ' may be selected from a part or all of the binder resin described later. Specifically, in the step of dispersing the pigment dispersion liquid to be described later, the binder is contained together with the dispersant: the binder resin exhibits a synergistic effect with the dispersant, and the amount is dispersed. As a result, it is possible to reduce the addition of the dispersant, and to improve the developability, the non-pixel-resolving property on the substrate, and the adhesion of the pixel plate. The adhesive resin in the step is called a dispersion resin. The amount of the pigment in the liquid is preferably about 5 to _% by weight of the dispersion resin, and it is better to read it as a dispersion resin. The various binder resins described above are particularly preferably 97122823 42 200911930 [2-1 - 2 ] (fluorenyl) acrylic resin to be described later. The acid value of the dispersion resin is preferably 1 〇 mg K 〇 H / g or more, more preferably 3 〇 mg KOH / g or more, most preferably 5 〇 mg K 〇 H / g or more, and more preferably 〇 mgKOH / g or less. More preferably, it is preferably 2 〇〇 mgKOH/g or less below 3 〇〇 mg K 〇 H / g. If the acid value is too high, it becomes a high viscosity, and there is a tendency to be difficult to synthesize or operate. Further, if the acid value is too low, it is sometimes applied to the development. r Further, the weight average molecular weight of the polystyrene converted by the GPC method of the dispersion resin is preferably at least 15 (10) or more, and the most Y soil is more than 20,000 Å. η η η η λ , 1 仏 is 200,000 or less, more preferably 50,000 2 is 30,000 or less. When the molecular weight is too large, there is a tendency that it is difficult to reduce the applicability by 29, and if the molecular weight is too small, the dispersion may be stabilized. -6 -6 The at least one of the aromatic carboxylic acid compound pigment dispersion liquid and the coloring composition is contained. An aromatic carboxylic acid compound. The dispersing agent containing the above-mentioned copolymer of #^^, 啕上11 and the copolymer used in the present invention can efficiently disperse the granulated pigment, so that the dispersion liquid and the color filter and the light sheet are colored for use. The face formed by the use of the coloring composition has a lack of Sit from the pigment dispersion of the invention and the coloring composition to increase ', and can prevent the defect of the resulting pixel from having a viscosity of time 97122923 43 The compound of 200911930 can be used in the case of the gas-containing pigment dispersion, and the increase in the viscosity of the aromatic acidification system by the use of the chemical liquid itself can be increased. In addition, when the color filter is used as a coloring composition, it is added to the pigment dispersion to prepare a color product, and the color filter is used as a component to be added later. It is also possible to suppress the time-dependent viscosity of the coloring composition for a color glazing sheet. In the case where the W pigment dispersion is in a sub- or sub-color composition, the Mm/77 is mismatched. The constituents of the material can be described in terms of an arbitrary carboxylic acid compound. For the compound of the stagnation of the sulphate, if it has an aromatic group and a carboxyl group, and I has an arbitrary structure. Examples of the aryl group include a soil naphthyl group and the like. Among these, a phenyl group is particularly preferred. (4) The group may have a substituent, the type or amount of the substituent, and the limitation. Specifically, for example, it is preferably a substituting group in the following formula (5): the carboxyl group may be (10), or may be plural or up to three, but in terms of the effect of the above-mentioned compound being more remarkable, It is one in one molecule. The molecular weight of the aromatic carboxylic acid compound is usually 5 Å or less and 350 or less, and is usually 150 or more. By setting the molecular weight to the following, the compound can be easily brought close to the pigment as described later, and the effect of suppressing the increase in viscosity can be confirmed. Λ As the aromatic carboxylic acid compound, a compound represented by the following formula (Bei) 97122823 44 200911930 [Chemical 13]
T ㈤ cooh (述k式(V!)中,21表示亞甲 之整數。丨丨丨衣不ϋ〜3 二’“為2或3時’“固ζ丨可相同亦可不同。 Τ氧原子、經基、碳數卜4之烧基、碳數Μ之 稀基、石反數1〜4之炫氢美 惑沉虱基卞基、苯乙基、苄氧基、4 者-C00X4(其中,Υ4志、山机,η ^ 、甲X表不石反數1〜7之烷基或苯基),該等美 團均可具有取代基。)。 /寺基 上述通式(VI)中之X3,表示氫原子、羥基、碳數丨〜4 之烧基兔數2〜5之烯基、碳數1〜4之烧氧基、节基、 苯乙基、苄氧基、或者—C00X4(其中,X4表示碳數丄〜7之 烧基或苯基)。 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之稀基’例如:如乙烯基、烯丙基、1 —丙稀 基、2 -丁稀基、1,3 -丁二婦基等碳數2〜5之稀基。 碳數1〜4之烷氧基,例如:如曱氧基、乙氧基、丙氧 97122823 45 200911930 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之烷基之例,例如可舉出:甲基、 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-甲基己基等。 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。 經基; 低級烷基;例如:如曱基、乙基、正丙基、異丙基、正 y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—甲基己基等碳數為7以下 之烷基。 ,級烷氧基;例如:如曱氧基、乙氧基、正丙氧基、異 丙乳,、正丁氧基、第二丁氧基、第三丁氧基、正己氧基、 ,、己氧基、5-甲基己氧基等石炭數為7以下之烧氧基。 低級烯基碳氧基;例如:如丙烯醯氧基、丁烯醯氧基等 稀基部分之碳數為3以下之烯基羰氧基。 苯基; 苄基; 笨氧基; 苄氧基。 ^於以上述通式(YJ)所表示之化合物中,就該化合物 上逑效果較顯著之方面而言,作為取代基χ3,較佳為自 97122823 46 200911930 可具有取代基之碳數1〜4之烷基、可具有取代基之碳數 2〜5之烯基、及_c〇〇x4中選擇之基。作為取代基f之更 佳的具體例,可舉出:苄氧羰基、甲氧羰基、乙烯基羰氧 基伸乙基氧基羰基、異丙基、第三丁基、羥甲基、乙烯基 等。 進而,取代基X3之位置,若在可能的範圍内則熟将別限 制’相對於苯環上lcooh基,較佳為鄰位或對位, 特佳為僅在鄰位進行取代。 於取代基X3中’以上未具體記载之基 加以任意組合,或者粝嬙、s ^ 彳◦羋®之基 :者根據通常所知的常識加以選擇。 以上述通式(VI)所表示之化合物, 醋化合物。具體而言,例如 -甲酸單 該等。 F者’但並不限定於 [化 14] 97122823 47 200911930T (5) cooh (in the k formula (V!), 21 represents the integer of the armor. The coat is not ϋ~3 2'" is 2 or 3" "solid ζ丨 can be the same or different. Τ oxygen atom , base group, carbon number b 4, the carbon number 稀 thin base, stone inverse number 1 ~ 4 of the hydrazone beauty 虱 虱 base, phenethyl, benzyloxy, 4 -C00X4 (which , Υ 4 志, 山机, η ^, A, X, or phenyl, or phenyl), which may have a substituent. / X3 in the above formula (VI), which represents a hydrogen atom, a hydroxyl group, a carbon number of 丨~4, an alkyl group of 2 to 5, a carbon number of 1 to 4, an alkoxy group, a benzyl group, and a benzene group. Ethyl, benzyloxy, or -C00X4 (wherein X4 represents a carbon group of 丄~7 or a phenyl group). Hereinafter, 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 an anthracenyl group, an ethyl group or a n-propyl 'isopropyl group. The rare group having a carbon number of 2 to 5 is, for example, a rare carbon group having 2 to 5 carbon atoms such as a vinyl group, an allyl group, a 1-propyl group, a 2-butanyl group or a 1,3-butanyl 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 decyloxy group, an ethoxy group, a propoxy group 97122823 45 200911930 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 methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, second butyl group, tert-butyl group, n-pentyl group and isobutyl group. A pentyl group, a neopentyl group, a third amyl group, a n-hexyl group, an isohexyl group, a 5-methylhexyl group and the like. Each of these groups may have a substituent ' as a specific example of the substituent, and examples thereof include the following groups. Lower alkyl; for example: fluorenyl, ethyl, n-propyl, isopropyl, n-yl, t-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl An alkyl group having a carbon number of 7 or less such as a third amyl group, an n-hexyl group, an isohexyl group or a 5-methylhexyl group. Alkoxy; for example: decyloxy, ethoxy, n-propoxy, isopropyl, n-butoxy, second butoxy, tert-butoxy, n-hexyloxy, An alkoxy group having a charcoal number of 7 or less such as a hexyloxy group or a 5-methylhexyloxy group. Lower alkenylcarbonyloxy; for example, an alkenylcarbonyloxy group having a carbon number of 3 or less in a dilute moiety such as a propylene decyloxy group or a butenyloxy group. Phenyl; benzyl; phenyloxy; benzyloxy. In the compound represented by the above formula (YJ), as the substituent χ3, it is preferred that the number of carbon atoms which may have a substituent from 97122823 46 200911930 is 1 to 4 in terms of the compounding effect of the compound. The alkyl group, the alkenyl group having 2 to 5 carbon atoms which may have a substituent, and the group selected from _c〇〇x4. More preferable specific examples of the substituent f include a benzyloxycarbonyl group, a methoxycarbonyl group, a vinylcarbonyloxyethylideneoxycarbonyl group, an isopropyl group, a tert-butyl group, a hydroxymethyl group, a vinyl group, and the like. . Further, the position of the substituent X3, if it is within the range possible, is limited to the lcooh group on the benzene ring, preferably the ortho or para position, and it is particularly preferred to carry out the substitution only in the ortho position. Any combination of the substituents not specifically described above in the substituent X3 or the base of 粝嫱, s ^ 彳◦芈® is selected according to common knowledge. A compound represented by the above formula (VI), a vinegar compound. Specifically, for example, - formic acid alone. F person's but not limited to [Chem. 14] 97122823 47 200911930
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重量%以下,又,通常較佳為0. 1重量%以上。 藉由在此範圍内含有芳香族缓酸系化合物,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 97122823 48 200911930 少且直線性優異之像素。 雖不拘泥於任何理論且其 羧酸系化合物而防止黏产^、,,田谷不明’但含有芳香族 明㈣分散劑之嵌1;二之人理:推測如下。即,本發 之官能基,於*種組成;有二有許多胺基等含氮原子 他成分反應而導致黏度上升有可月匕該分散劑之胺基等與其 f 化合物,並與其係具有芳香族基之 白d又:由於本案發明之芳香族幾酸系化合物所且有 ::::基親和性’若該化合物接近顏料粒子,則必;續 用。-般-為上枓上的分散劑產生相互作 祕與分散劑之胺基二5用2 m酸系化合物的 夂伽,w f作用而抑制分散劑之胺基所 參/、的黏度上升。進而,一般認為 分子化合物中較困難,因此Ατ你甘近顏科粒子係在兩 _以下較有效。難因此為了使其變得容易,分子量為 [2 ]著色組成物 本發明之著色組成物至少含有作 Α八μ 、+、i u 有作為構成顏料分散液之 成刀的上述顏料、溶劑、分散劑以及後述黏合劑樹脂。再 ΐ備it!t者色組成物’可藉由將其他成分混合於預先 :備子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,除本巾請㈣明書中所 97122823 49 200911930 :己載=各種成分以外,若為亦可用作彩色遽光片形 者’則可無特別限制地使用。 [2-1 ]黏合劑樹脂 作為本發明所使用之黏合劑 片者,則可無特別限制地❹ 為可用於彩色遽光 =可舉出:日本專利特開昭60 — 18侧號公報等中記 脫r(llft0⑴方式之彩色遽光片製造步驟中 所使用的熱硬化性樹脂組 2004-220036號公報等中記载喷 開 硬化性樹脂組成物、後述光聚合性樹 利用何種方法使著色組獅 电成合適類型之樹脂組成物即可。在著色 合成物的情形下,較佳為含有後述光聚 “I例色=物為光聚合性樹脂組成物之 …丁》平細說明,但本發明並不限定於此。 下著色組成物為光聚合性樹脂組成物的情形 二t;、?樹脂’例如可使用:曰本專利特開平 特開平ΐΓΐ4ί!開平8 — 259876號、特開平10_300922號、 -40144號、特開平η_17 2000-561 18 f#u > 9ππ〇 〇〇〇 唬特開 號等各公報等中之2 —233179號、特開 可舉出: 载之A知的高分子化合物,較佳為例如 ]對於3有環氧基之(甲基)丙烯酸酯與其他自 97122823 50 200911930 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、 [2-1 -2](甲基)丙烯酸系樹脂等。 以下,就該等各樹脂加以說明。 [2-1-1 ]對於含有環氧基之(甲基)丙烯酸酯與其他自由基 聚口性單體之共聚物,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 反應而產生的經基之至少—部分上加成多㈣酐而獲得 之鹼可溶性樹脂 於本發明中,作為特佳的黏合劑樹脂之一,可舉出:「對 於含有環氧基之(甲基)丙烯酸醋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^而 產生的&基之至少-部上加成多元酸酐而獲得之驗可溶 性樹脂」(以下’稱為「[2 + n樹脂」)。更具體而言, 可舉出:「對於含有環氧基之(T基)㈣酸醋卜⑽莫耳% 與其他自由基聚合性單體1G〜95莫耳%之共聚物,在該共 聚物所具有的環氧基之1〇〜1〇〇莫耳%上加成不飽和一元 酉夂而成之树月s ’或者在藉由該加成反應而產生的經基之 10〜m莫耳%上加成多元酸酐而獲得之鹼可溶性樹脂」。 3有,,工微/粒化之顏料、特別是經微粒化之漠化鋅駄菁顏 料的彩色濾光片用著色組成物,具有對顯影液之溶解性差 97122823 51 200911930 之傾向’ a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。 ’、 f \ 1而σ,即便例如顏料分散液之黏度穩定性 :’:經日!黏度增加’但若向其中加入黏合劑樹脂或溶劑 而:備衫色遽光片用著色組成物,則多數情形是該组 物之黏度下降’並改善黏度穩定性。但是,已知在含 化鋅,菁顏料之顏料分散液的情形下,將其製成彩色 片用者色組成物,藉此反而有黏度迅速增加之傾向 度穩定性。進而,該彩色滤光片用著色組成: 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 、讀粒化之填化转菁顏料的顏料分散 用著色組成物達成: € ^ 用著色組成物之黏度穩 •提昇顏料分散液或彩色濾光片 定性, •提昇該著色組成物對顯影 度經時下降或異物產生,進而 液之溶解性,並且抑制對 比 士•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」_u樹脂。 作為構成[2刊樹脂之「含有環氧基之(甲基)丙埽酸 ;」3 1例示:(甲基)丙烯酸環氧丙醋、(甲基)丙烯 甲r’、Γ 丁醋、基)丙稀酸(3,4-環氧基環己基) 曰(曱基)丙烯酸4_羥基丁酯環氧丙轉等。其中,較 97122823 52 200911930 佳為(甲基)丙烯酸環氧丙酯。 »亥等含有環氧基之(曱基)丙烯酸酯,可單獨使用 亦可併用2種以上。 種’ 作為與上述含有環氧基之(甲基)丙烯酸酯進行共严 之其他自由基聚合性單體,較佳為具有以下述通式、(二合 表示之結構的單(甲基)丙烯酸酯。 所 [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 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. 1重量百分比以上。 The total solids, usually more than 20% by weight, preferably 10% by weight or less, more preferably 5% by weight or less, and more preferably, preferably 0.1% by weight or more. By including an aromatic acid-lowering compound in this range, the viscosity of the pigment dispersion or the coloring composition can be prevented from increasing, and a pixel having less "defect" than 97122823 48 200911930 and having excellent linearity can be formed. Although it is not limited to any theory and its carboxylic acid-based compound prevents sticking, it is unknown, but contains an aromatic (4) dispersing agent. The second one is presumed as follows. That is, the functional group of the present invention has a composition of *; a compound having a nitrogen atom such as a plurality of amine groups reacts to cause an increase in viscosity, and an amine group such as a dispersant such as a dispersant and a compound thereof are aromatic. The white base d of the group is further: due to the aromatic acid compound of the invention of the present invention and having: ::: base affinity 'if the compound is close to the pigment particles, it is necessary; In general, the amino group 5 which is a mutual dispersing agent for the dispersing agent on the upper side and the dispersing agent are used to suppress the increase in the viscosity of the amine group of the dispersing agent by the action of the gamma of the 2 m acid compound. Furthermore, it is generally considered to be more difficult in molecular compounds, so the Ατ You Gan Nian Yankee particle system is more effective than two _. It is difficult to make it easy, and the molecular weight is [2] colored composition. The colored composition of the present invention contains at least the above-mentioned pigment, solvent, and dispersant which are used as a pigment dispersion liquid. And a binder resin to be described later. Further, it can be prepared by mixing the other components into the pigment dispersion of the preparation beforehand. Alternatively, all the components may be mixed or sequentially mixed. In addition to the above-mentioned essential components, it is not particularly limited as long as it can be used as a color calender sheet in addition to the various components, in the case of the above-mentioned article (4). [2-1] Adhesive resin as the adhesive sheet used in the present invention can be used for color glare without any particular limitation = exemplified in Japanese Patent Laid-Open No. 60-18 No. In the thermosetting resin group No. 2004-220036, which is used in the production process of the color ray-receiving sheet of the llft0 (1) type, the spray-curable resin composition and the photopolymerizable tree described later are used for coloring. In the case of a colored composition, it is preferable to contain a light-polymerized composition, which is described below, but the light-polymerized "I case color = material is a photopolymerizable resin composition". The present invention is not limited thereto. The case where the lower coloring composition is a photopolymerizable resin composition is the same as that of the photopolymerizable resin composition; for example, the resin can be used as follows: 曰 专利 专利 专利 专利 专利 ΐΓΐ ί ί ί ί ί ί ί ί ί ί ί — — — — — — — — — — — — — — — — — No. -40144, special Kaikai η_17 2000-561 18 f#u > 9ππ〇〇〇〇唬 special opening and other publications, etc. 2 - 233179, special opening can be cited: A molecular compound, preferably for example, has an epoxy for 3 a copolymer of a (meth) acrylate and another copolymer of a base polymerizable monomer from 97122823 50 200911930, a resin obtained by adding an unsaturated monobasic acid to at least a part of an epoxy group of the copolymer, or An alkali-soluble resin, a [2-1-2] (meth)acrylic resin obtained by adding a polybasic acid anhydride to at least a part of a hydroxyl group generated by the addition reaction, etc. Hereinafter, these resins are used. [2-1-1] A copolymer of an epoxy group-containing (meth) acrylate and another radical unc about monomer is added to at least one of the epoxy groups of the copolymer. A resin obtained by forming an unsaturated monobasic acid, or an alkali-soluble resin obtained by adding at least a part of a radical formed by the addition reaction to a poly(tetra) anhydride, is a particularly excellent binder in the present invention. One of the resins is: "A copolymer of an epoxy group-containing (meth)acrylic acid vinegar and another radical polymerizable monomer is added to at least a part of the epoxy group of the copolymer. Saturated-acid acid resin, or A soluble resin obtained by adding a polybasic acid anhydride to at least a portion of the & base generated by the addition ^ (hereinafter referred to as "[2 + n resin"). More specifically, For the following: "A copolymer of an epoxy group-containing (T-based) (tetra) acid vinegar (10) mol% and other radical polymerizable monomers 1 G to 95 mol%, the epoxy group of the copolymer 1〇~1〇〇mol% is added to the unsaturated monobasic tree s ' or the addition of polybasic anhydride on the 10~m mole % of the radical generated by the addition reaction And the obtained alkali-soluble resin". 3,, the micro/granulated pigment, especially the micronized desert zinc phthalocyanine pigment color filter for coloring composition, has poor solubility to the developer 97122923 51 200911930 The tendency to 'on the other' is sometimes difficult to apply the composition, dry exposure and development to produce a color filter. ', f \ 1 and σ, even if, for example, the viscosity stability of the pigment dispersion: ': by day! viscosity increase', but if a binder resin or solvent is added thereto: for the coloring composition of the shirt color In most cases, the viscosity of the group decreases, and the viscosity stability is improved. However, it is known that in the case of a pigment dispersion containing zinc or a cyanine pigment, it is used as a color composition for a color sheet, whereby the viscosity is rapidly increased. Further, the color filter has a coloring composition: The following tendency is observed during storage. The foreign matter is likely to be generated and increased over time, and the contrast is also lowered with time. In order to solve this problem, a pigmented composition for pigment dispersion containing a micronized pigment, a special, and a granulated filler is obtained: € ^ The viscosity of the colored composition is stabilized • The pigment dispersion is lifted Or the color filter is qualitative, and it is particularly effective to increase the degree of development of the coloring composition over time or the generation of foreign matter, and the solubility of the liquid, and to suppress contrast, prevent defects of the obtained pixel, and improve linearity. Use the [2"_u resin described below. As a composition, the "epoxy group-containing (meth)propionic acid;" 31 is exemplified by (meth)acrylic acid propylene vinegar, (meth) propylene methyl ru', butyl vinegar, and the base. Acetic acid (3,4-epoxycyclohexyl) fluorene (mercapto)acrylic acid 4-hydroxybutyl ester epoxidation. Among them, 97122823 52 200911930 is preferably (meth)acrylic acid propyl acrylate. The epoxy group-containing (fluorenyl) acrylate may be used singly or in combination of two or more. The other radical polymerizable monomer which is coherent with the above-mentioned epoxy group-containing (meth) acrylate is preferably a mono(meth)acrylic acid having a structure represented by the following formula: Ester.
K〜K分別獨立表示氫原子 ^38 於上述通式(1)中 碳數1〜3之燒基,但R”與"相互連接^成丁環風者 产於(1)中’『與R38連接而形成之環,較佳為脂肪族 衣,飽和或者不飽和均可,又,碳數較佳為卜6。、 (1二為以通式⑴所表示之結構,較佳為以下述式 db)、或〇c)所表示之結構。 著亥等結構導入至黏合劑樹财,並將本發明之 用於彩色遽光片或液晶顯示元件的情形下,可 成物的封熱性’或者增加使用該著色組成物 所办成之像素的強度。 醋再有以通式⑴所表示之結構的單(甲基)丙烯酸 -了早獨使用1種’亦可併用2種以上。 97122823 53 200911930 [化 16]K to K independently represent a hydrogen atom ^38 in the above formula (1) in the carbon number of 1 to 3, but R" and "connected to each other" into a ring of wind produced in (1) '" with The ring formed by the connection of R38 is preferably an aliphatic coating, either saturated or unsaturated, and the carbon number is preferably a carbon number. (1) is a structure represented by the formula (1), preferably the following The structure represented by the formula db), or 〇c). When the structure such as the sea is introduced into the adhesive, and the present invention is applied to a color light-receiving sheet or a liquid crystal display element, the heat-sealing property of the object can be obtained. Alternatively, the strength of the pixel formed by using the colored composition may be increased. The vinegar may have a single (meth)acrylic acid having a structure represented by the formula (1) - one type may be used alone or two or more types may be used in combination. 97122823 53 200911930 [化16]
(1 a)(1 a)
(1 b) O c) ㈣具有从工…'⑴所表……皁c 酸酯,只要具有該結構則可使用各種公知者,但、 下述通式(2)所表示者。 *''' 1 [化 17] R39 (2) H2C=c—C一〇一r4〇 Ο 式(2)中,R39表示氫原子或甲基,表示以上述通式 所表示之結構。 於上述含有環氧基之(甲基)丙烯酸酯與其他自由基聚 合性單體之共聚物申,來自具有以上述通式(1)所表示之 結構的單(甲基)丙烯酸酯之重複單元,在來自「其他自由 97122823 54 200911930 基來口 ! 生早體」之重複單元中的含量, 〇/ , * /+ ^ n 1土為 5〜90 莫耳 /〇 ,更佳為1〇〜70莫耳%,特佳為15〜5〇莫耳、今 再者’作為具有以上述通式⑴所表示之結構的 丙烯酸酯以外《「其他自由基聚合性單體」,並: 定。具體而言,例如可舉出:苯乙烯,笨 “'、、义 尽G埤之α位、鄰 位、間位或對位為經烧基、確基、氰基、醯胺基、㊉基等 =代而成之衍生物等乙烯基芳香族類;丁二婦、2,=甲 基丁一細、異戊二烯、氯丁二烯等二稀類;(甲基)丙稀酸 甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基) 丙烯酸異丙酯、(曱基)丙烯酸正丁酯、(甲基)丙烯酸第"二 丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲 基)丙烯酸新戊酯、(甲基)丙烯酸異戊酯、(甲基 己酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸月桂酯、 (甲基)丙浠酸十二烧基酯、(甲基)丙稀酸環戊酯、(甲基) 丙烯酸環己酯、(曱基)丙烯酸-2-甲基環己酯、(曱基)丙 烯酸一環己酯、(曱基)丙烯酸異降稻酯、(甲基)丙稀酸金 剛烷酯、(甲基)丙烯酸炔丙酯、(甲基)丙烯酸苯酯、(甲 基)丙烯酸萘酯、(甲基)丙烯酸蒽酯、(甲基)丙烯酸鄰胺 苯甲酯、(甲基)丙稀酸胡椒酯、(甲基)丙烯酸鄰經基节 酉旨、(甲基)丙坤酸D夫喃酯、(甲基)丙稀酸D夫U南甲醋、(甲 基)丙烯酸四氫呋喃酯、(甲基)丙烯酸Π比喃酯、(甲基)丙 烯酸苄酯、(甲基)丙稀酸苯乙酯、(甲基)丙烯酸甲苯酯、 (甲基)丙烯酸三氟乙酯、(甲基)丙烯酸全氟乙 酯、(甲基)丙烯酸全氟正丙酯、(曱基)丙烯酸全氟異丙 97122823 55 200911930 酯、(曱基)丙烯酸三苯基甲酯、(曱基)丙烯酸異丙苯酯、 (甲基)丙烯酸-3-(N,N-二甲胺基)丙酯、(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸-2-羥基丙酯等(甲基)丙烯酸酯 類;(甲基)丙烯醯胺、(曱基)丙烯酸-N,N-二甲基醯胺、(甲 基)丙烯酸-N,N-二乙基醯胺、(曱基)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、(曱 基)丙烯醯腈、丙烯醛、氯乙烯、偏二氯乙烯、氟乙烯、 'f、 1 偏二氟乙浠、N-乙烯吼β各唆酮、乙稀η比α定、乙酸乙烯酯等 乙浠化合物類;擰康酸二乙酯、馬來酸二乙酯、富馬酸二 乙酯、衣康酸二乙酯等不飽和二羧酸二酯類;Ν_苯基馬來 醯亞胺、Ν-環己基馬來ϋ亞胺、Ν-月桂基馬來醯亞胺、 Ν-(4-羥基苯基)馬來醯亞胺等單馬來醯亞胺類;Ν_(甲基) 丙烯醯基鄰苯二曱醯亞胺等。 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、 (曱基)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之重複單元的含有比例,較佳為 1〜70莫耳%,更佳為3〜50莫耳%。 再者’上述含有環氧基之(甲基)丙烯酸酯與上述其他自 由基聚合性單體之共聚合反應中,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 97122823 56 200911930 限定’可使用通常所用之有機溶劑。 ,為該溶劑,例如可舉出:乙酸乙酯、乙酸異丙酯 路蘇乙酸醋、丁基賽路蘇乙酸醋等乙二醇單烧基喊乙酸酉旨 類,二^二醇單曱趟乙酸醋、卡必醇乙酸醋、丁基卡必^ =酉曰等一乙一醇單烷基醚乙酸酯類;丙二醇單烷基醚乙 &酉曰類,—丙—醇單燒基喊乙酸s旨類等乙酸s旨類;乙二, 二烧基f基卡必醇、乙基卡必醇、丁基卡必料二子 乙一醇二絲三乙二醇二烧細類丨丙 醚類;二丙二醇二烷基:烷基 類;丙,、甲基乙基酮二 _ τI吳丁基酮、%己酮等酮類; -i 广甲苯、辛烷、癸烷等烴類;石油醚、石油腦、 乙醋、乳酸丁』乳==劑;乳酸甲"酸 日斧孔s夂g曰類,二甲基甲醯 ㈣等。該等溶劑可單獨使用,亦可併用2種以上各 :對於所獲得之共聚物100重量份 通常為30〜loon舍县/八τ合Mi便用里 南j之使用曰 刀,較佳為50〜800重量份。若溶 1使^在此範圍之外,則難以控制共聚物之分子量。 …:聚合反應中所使用之自由基聚合起始劑,若係可 媒,可舉出:被分類成公二= 氧化氫、過氧化二烯丙基、過氧:化=過:化縮酮、過 氧化二碳酸S旨者。 减—乙醯、過錢醋、過 作為其具體例’可舉出:過氧化苯甲醯、過氧化二異丙 97122823 57 200911930 本、過氧化二異雨其、长 第三丁酯、過氧化;甲:二匕—第三丁基、過氧化苯甲酸 第-丁醋、過三己醋、過氧化2-乙基己酸 基過氧基)-3二2;\基二酸第三己醋、雙(第三丁 一 ,〜ΰ二甲基核己烷、2 二丁基過氧基)己基_3,3_異 氧:广-雙(第 化氫、過氧化二異丙苯、二異丙笨=風弟三丁基過氧 醯、過氧化二碳酸雙("三 Υ氧:氧、過氧化乙 r ,酸二異丙醋、過氧化異丁基、過氧化3土 )曰、過氧化二石炭 過氧化月桂基、u-雙(第三丁基過λα3)35-3三甲基己醯、 己烷、第三己基過氧基)3, 3,卜三…:甲T 又,作為偶氤化合物觸媒,可舉出 ::己烷專。 氮二^胺 UZ〇biscarbo_ide)等。.又 ” 丁腈、偶 “等之t,根據聚合溫度’可使用 適當半衰期之自由基聚合起始劑 上具有 T單體的合請重量份,1自: !為〇.5〜20重量份,較佳為1叫。重量份^之使用 =合:應既可將共聚合反應中所使用的單體及自由 ^ S起始劑溶解於溶劑中,—面授拌—面升溫而進行; ^可將添加有自由基聚合起始劑之單體滴加至經升溫 拌之溶劑中而進行。又’亦可於溶劑中添加自由基聚心 並在升溫過程中滴加單體。反應條件可根據 子置而自由地改變。 於本發明令,作為上述含有環氧基之(甲基)丙稀酸酿與 上述其他自由基聚合性單體之共聚物’較佳為由來自含有 97122823 58 200911930 %氧基之(甲基)丙烯酸酯之重複單元5〜9〇莫耳%、與來 自其他自由基聚合性單體之重複單元1〇〜95莫耳%^構 成者;更佳為由前者20〜80莫耳%與後者8〇〜2〇莫耳% 所構成者,特佳為由前者3〇〜7〇莫耳%與後者〜如 耳%所構成者。 、 右含有環氧基之(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^有環氧基之(甲基)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。口 〜繼而,使不飽和一元酸(聚合性成分)、多元酸酐(驗可 溶性成分)與含有環氧基之(曱基)丙烯酸酯與其他自由其 聚合性單體之共聚物的環氧基部分產生反應。 ^ 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’ “位㈣化烧基,氧基、論素原子、 硝基、或氰基等取代之(曱基)丙烯酸等單羧酸等。其中, 較佳為(甲基)丙烯酸。可單獨使用該等之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 予聚合性。 。亥等不飽和一元酸通常加成於上述共聚物所具有之環 氧基的10〜100莫耳η/◦上,較佳為3〇〜1〇〇莫耳%,更佳^ 50〜100莫耳%。若不飽和一元酸之加成比例過小,則擔 97122823 59 200911930 “殘存之環氧基會對著色組成物之經時穩定性等造成不 良y s再者,作為將不飽和一元酸加成於共聚物之& 其夕士、+ < ί衣氣 基上之方法,可採用公知方法。 進而,作為在將不飽和—元酸加成於共聚物之環 所產生.基上進行加成的「多元酸酐」,可使用公知^ / 例如可舉出:馬來酸酐、琥珀酸酐、衣康酸酐 曱酉夂酐㈤氫鄰苯二曱酸酐、六氫鄰苯二曱酸酐 酐等二元酸酐.傯婪-缺 氧囷酸 夂酐,偏本二酸酐、均苯四曱酸酐、二 甲酸酐、聯苯四曱酸^:笪_ _ L , 本基輞四 四氫鄰苯二甲酸酐::二 。其中’較佳為 1種’亦可併用2種以上。 」早獨使用 藉由加成此種成分’可對本發明所使用之黏 予驗可溶性。 ^树如職 邊等多元酸酐通常加成於 上述共聚物张目士 ^ 70酸加成至 ^w〇/± ”有的環氧基上所產生之羥基的1〇〜1()() =上,較佳為20〜90莫耳%,更佳為30〜 〇。 比例過多,則有時顯影時之 、耳: 少則有可能溶解性變^右過 成於該絲上之方Γ 刀 作為使多元酸酐加 上之方法,可採用公知之方法。 氧丙鍵化合物加H 或具㈣合性不飽和基之環 Γ成所生成鲮基的一部分上。 :、了提昇顯影性,可將 _化合物加成於所生成幾基的有一餘和基之環 97122823 200911930 又,可加成該兩者。 作為不具有聚合性不飽和基之環氧丙醚化合物之具體 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)&司製 造之商品名「Denacol EX-lll」、「Denacol Εχ_121」二 「 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8-297366號公報或特開2〇〇1一89533號公報中。 ^述黏合劑樹脂以GPC法所測定之經聚苯乙烯換算之 重1平均刀子車父佳為3000〜100000,特佳為5〇〇〇 50000。右分子量未滿3000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=。X,作為分子量分布標準,重量平均分子量 數量平均分子量(Μη)之比,較佳為2. 〇〜5. 〇。 [2-1-2](甲基)丙烯酸系樹脂 於本毛明中,作為特佳之黏合劑樹脂之一,可舉出「(曱 基)丙烯酸系樹脂」(以下’稱為「[2_卜2]樹脂」)。本發 月之所明(甲基)丙烯酸系樹脂」,意指使含有以下述通 式(V)所表示化合物作為必需成分之單體成分進行聚合 而成之共聚物。 [化 18] 97122823 61 200911930(1 b) O c) (4) The saponin c ester represented by the work of '(1), as long as it has such a structure, various publicly known persons can be used, but it is represented by the following general formula (2). *''' 1 [Chemical Formula 17] R39 (2) H2C = c - C - r - r4 〇 In the formula (2), R39 represents a hydrogen atom or a methyl group, and represents a structure represented by the above formula. The copolymer of the above epoxy group-containing (meth) acrylate and another radical polymerizable monomer is derived from a repeating unit of a mono(meth) acrylate having a structure represented by the above formula (1) , in the content of the repeating unit from "Other Freedom 97122823 54 200911930 基来口! 生早体", 〇 / , * / + ^ n 1 soil is 5~90 m / 〇, more preferably 1 〇 ~ 70 Mol %, particularly preferably 15 to 5 〇 耳 、 今 今 今 今 作为 作为 作为 「 「 「 「 「 「 「 「 「 「 「 「 「 「 「 「 「 「 「 「 「 「 「 「 「 「 「 「 「 「 「 「 「 Specifically, for example, styrene, stupid, ortho, ortho, meta or para is a burnt group, an exact group, a cyano group, a guanamine group, or a decyl group. Vinyl aromatics such as derivatives such as derivatives; disaccharides such as dibutyl, 2, = methyl butyl, isoprene, chloroprene; (methyl) acrylate Ester, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, (meth)acrylic acid "dibutyl ester, ( Tert-butyl methacrylate, amyl (meth)acrylate, neopentyl (meth)acrylate, isoamyl (meth)acrylate, (methylhexyl), (meth)acrylic acid-2-B Hexyl hexyl ester, lauryl (meth) acrylate, dodecyl (meth)propionate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, (mercapto) acrylate -2-methylcyclohexyl ester, monocyclohexyl (decyl) acrylate, isodecyl (meth) acrylate, adamantyl (meth) acrylate, propargyl (meth) acrylate Ester, phenyl (meth) acrylate, naphthyl (meth) acrylate, decyl (meth) acrylate, o-benzyl benzyl (meth) acrylate, piperonyl (meth) acrylate, (methyl) Acrylic ortho-based ketone, (methyl)-propionic acid D-fusyl ester, (methyl) acrylic acid D-fu Nannan vinegar, (meth)acrylic acid tetrahydrofuran ester, (meth)acrylic acid bismuth ratio Butyl ester, benzyl (meth) acrylate, phenethyl (meth) acrylate, toluene (meth) acrylate, trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, (Meth)acrylic acid perfluoro-n-propyl ester, (fluorenyl)acrylic acid perfluoroisopropyl 97102223 55 200911930 ester, triphenylmethyl (mercapto) acrylate, cumyl (mercapto) acrylate, (methyl) a (meth) acrylate such as 3-(N,N-dimethylamino)propyl acrylate, 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate; Methyl) acrylamide, (mercapto)acrylic acid-N,N-dimethyldecylamine, (meth)acrylic acid-N,N-diethylguanamine, (fluorenyl) (methyl) acrylamide such as N-N-N-dipropyl decylamine, (meth)acrylic acid-N,N-diisopropyldecylamine, (mercapto)acrylic acid decylamine; ) anthranilamide, (fluorenyl) acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, 'f, 1 difluoroacetamidine, N-vinyl fluorene beta fluorenone, ethylene η ratio Ethylene oxime compounds such as α-ding and vinyl acetate; unsaturated dicarboxylic acid diesters such as diethyl thioconate, diethyl maleate, diethyl fumarate and diethyl itaconate; _Phenylmaleimide, fluorene-cyclohexylmaleimide, guanidine-lauryl maleimide, Ν-(4-hydroxyphenyl)maleimide, etc. Ν_(methyl) propylene fluorenyl phthalimide, etc. In order to impart excellent heat resistance and strength to the colored composition, it is more effective in the "other radical polymerizable monomers" Among them, at least one selected from the group consisting of styrene, benzyl (meth) acrylate, and monomaleimide is used. 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 styrene, benzyl (meth) acrylate, and monomaleimide The content ratio is preferably from 1 to 70 mol%, more preferably from 3 to 50 mol%. Further, in the copolymerization reaction of the above epoxy group-containing (meth) acrylate with the above other radical polymerizable monomer, a known solution polymerization method can be applied. The solvent to be used is not particularly useful if it is inert to radical polymerization. 97122823 56 200911930 Qualified The organic solvent which is usually used can be used. Examples of the solvent include ethylene glycol, isopropyl acetate, sulphate acetate, and butyl sulphate acetate, and the like. Acetate vinegar, carbitol acetate vinegar, butyl carbene = hydrazine, etc. monoethyl ether monoalkyl ether acetate; propylene glycol monoalkyl ether B & hydrazine, - propylene - alcohol monoalkyl ketone s intended to be the class of acetic acid s; Ethylene, dicalcyl f carbitol, ethyl carbitol, butyl carbene diethylene glycol diethylene glycol diethylene glycol di-succinimide oxime ether; Dipropylene glycol dialkyl: alkyls; propyl, methyl ethyl ketone dioxin, ketones such as methyl ketone; -i hydrocarbons such as polytoluene, octane, decane; petroleum ether, petroleum brain , Ethyl vinegar, lactic acid butyl milk = = agent; lactate A " acid day axe hole s夂g曰 class, dimethylformamidine (four) and so on. These solvents may be used singly or in combination of two or more kinds: for the obtained copolymer, 100 parts by weight is usually 30 to Loon She County/eight τ and Mi, and the use of the lining knife is preferably 50. ~800 parts by weight. If the solubility is outside the range, it is difficult to control the molecular weight of the copolymer. ...: the radical polymerization initiator used in the polymerization reaction, if it is a mediator, it can be categorized as: dioxin = hydrogen peroxide, diallyl peroxide, peroxygenation: oxidization = over ketal , the peroxydicarbonate S is intended. —- 醯, 钱 vinegar, as a specific example of it can be mentioned: benzammonium peroxide, diisopropyl peroxide 97102923 57 200911930, hydrogen peroxide, long third ester, peroxidation A: diterpene - tert-butyl, benzoic acid benzoic acid - butyl vinegar, trihexyl vinegar, 2-ethylhexanoic acid peroxy) - 3 bis; Vinegar, bis (third butyl, ΰ dimethyl dimethyl hexane, 2 dibutylperoxy) hexyl _3, 3 _ isox: broad-double (hydrogenated hydrogen, dicumyl peroxide, Diisopropyl stupid = Fengdi tributylperoxy bismuth, peroxydicarbonate double (" trioxane: oxygen, peroxide b, acid diisopropyl vinegar, isobutyl peroxide, 3 soils peroxidation) Bismuth, peroxydicarbonate, peroxidic lauryl, u-bis (t-butylper λα3) 35-3 trimethylhexyl hexane, hexane, third hexylperoxy) 3, 3, 卜... T Further, as a catalyst for the oxime compound, a: hexane is used. Nitrodiazepine UZ〇biscarbo_ide). Further, "butyronitrile, even", etc., according to the polymerization temperature, may be used with a suitable half-life of the radical polymerization initiator having a weight fraction of the T monomer, 1 from: ! to 5 to 20 parts by weight Preferably, it is 1 call. Use of parts by weight = combination: It should be possible to dissolve the monomer used in the copolymerization reaction and the free starting agent in the solvent, and to carry out the surface heating; The monomer of the initiator is added dropwise to the solvent heated to the temperature. Further, it is also possible to add a radical concentrate to the solvent and to add a monomer during the temperature increase. The reaction conditions can be freely changed depending on the sub-set. In the present invention, the copolymer of the above-mentioned epoxy group-containing (meth)acrylic acid and the above other radical polymerizable monomer is preferably obtained from (meth) containing 9712823 The repeating unit of the acrylate is 5 to 9 mol%, and the repeating unit 1 to 95 mol% from other radical polymerizable monomers; more preferably 20 to 80 mol% of the former and the latter 8 〇~2〇莫耳% The composition is particularly good for the former 3〇~7〇莫耳% and the latter~如耳%. 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 the epoxy group is (meth)acrylic acid When the amount of the ester is too large and the amount of other radical polymerizable monomer is too small, heat resistance or strength may be insufficient. Mouth-thin, an epoxy group of an unsaturated monobasic acid (polymerizable component), a polybasic acid anhydride (test soluble component), and a copolymer of an epoxy group-containing (mercapto) acrylate and other freely polymerizable monomers Produce a reaction. ^ 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 'position (tetra) decyl group, oxy group, arsenic atom, nitro group, or cyano group, etc. The monocarboxylic acid, such as a (mercapto) acrylic acid, etc., is preferable, and (meth)acrylic acid is preferable. These 1 type may be used individually, and 2 or more types may be used together. The binder resin used in the invention is prepolymerizable. The unsaturated monobasic acid is usually added to 10 to 100 mol η/◦ of the epoxy group of the above copolymer, preferably 3 〇 1 to 1 〇. 〇mol%, better ^ 50~100 mol%. If the addition ratio of unsaturated monobasic acid is too small, then 97122823 59 200911930 "The residual epoxy group will cause adverse effects on the stability of the colored composition, etc. Further, as a method of adding an unsaturated monobasic acid to a copolymer, and a method of adding a gas to a gas, a known method can be employed. Further, as the "polybasic acid anhydride" which is added to the group produced by adding the unsaturated-acid acid to the ring of the copolymer, a known compound can be used. For example, maleic anhydride, succinic anhydride, and itacon are mentioned. Anhydride anhydride (5) Hydrogen phthalic anhydride, hexahydrophthalic anhydride, and other dibasic anhydrides. 偬婪-oxophthalic acid phthalic anhydride, partial dianhydride, pyromellitic anhydride, dicarboxylic anhydride , biphenyl tetradecanoic acid ^: 笪 _ _ L, the base 辋 tetrahydrogen phthalic anhydride:: two. Among them, 'preferably one type' may be used in combination of two or more kinds. The use of the addition of such a component by the early use of the present invention can be used to determine the solubility of the adhesive used in the present invention. ^The polybasic anhydride such as the working edge of the tree is usually added to the above-mentioned copolymer, Zhang Shishi, 70 acid addition to ^w〇/±", the hydroxyl group produced on the epoxy group is 1〇~1()() = Preferably, it is 20 to 90% by mole, more preferably 30 to 〇. If the ratio is too large, sometimes the ear is developed, and when it is small, the solubility may be changed to the right. As a method of adding a polybasic acid anhydride, a known method can be employed. The oxo-bonding compound is added with H or a ring having a (tetra)-unsaturated unsaturated group is formed on a part of the formed fluorenyl group. The compound is added to the ring of the group formed and the ring of the group is 97122823 200911930. Both of them can be added. Specific examples of the glycidyl ether compound having no polymerizable unsaturated group include: A phenyl group or an alkyl group of a glycidyl ether compound, etc. As a commercial item, for example, the product name "Denacol EX-lll" manufactured by Nagase Chemical Co., Ltd., and "Denacol Εχ_121" 2 "Denacol EX" -141 ", Denacol EX-145", "Denacol EX-146", "Denacol EX-171", "D Enacol EX-192" and so on. In addition, the structure of such a resin is described in, for example, Japanese Laid-Open Patent Publication No. Hei 8-297366 or JP-A No. Hei. No. Hei. The viscosity of the adhesive resin measured by the GPC method is 1 to 3,000 to 100,000, and particularly preferably 5 to 50,000. If the right molecular weight is less than 3,000, heat resistance or film strength may be inferior. If the molecular weight exceeds 100,000, the solubility in the developer may be insufficient. 〇〜5. 〇。 X, as a molecular weight distribution standard, the ratio of the weight average molecular weight of the number average molecular weight (? [2-1-2] (Meth) Acrylic Resin In the present invention, one of the most excellent binder resins is "(fluorenyl) acrylic resin" (hereinafter referred to as "[2_b 2 ] resin"). The (meth)acrylic resin as used in the present invention means a copolymer obtained by polymerizing a monomer component containing a compound represented by the following formula (V) as an essential component. [化 18] 97122823 61 200911930
(V) 取代基之碳數1〜25之炉Λ。 斗外丁我有 如前所述,含有經微粒化之㈣ 化鋅酞菁顏料的顏料分散液;=經:,化之漠 :比較低,因此有時實際上難以製4 =液f溶解 ,,但所獲得之像素亦容易有缺陷,而更:=遽光片 J表面上,或者像素之直線部分缺陷成尖銳:再:者於像 易引起面板之漏光。 因此可知 '經微粒:之:::並使含有經微粒化之顏料、特別是 用著色組成物二耿青顏料的顏料分散液或彩色遽先片 定性提昇顏料分散液或彩色㈣用著色組成物之黏度穩 提昇該著色組成物對顯影液之溶解性、 特別所得像素之㈣、提昇直線性等, 以^的是使用以下所說明之[2 + 2]樹脂。 於;通式⑺所表示之化合物加以說明 所表示之聚物中,作為及心 97122823 有取代基的碳數1〜25之煙基’並無特別限 62 200911930 制,例如可舉出:曱基、乙基、正丙基、異丙基、正丁基、 異丁基、第三丁基、第三戊基、十八烷基、月桂基、2_ 乙基己基等直鏈狀或支鏈狀烷基;苯基等芳基;環己基、 第三丁基環己基、二環戊二烯基、三環癸基、異稻基、金 剛烷基、2-甲基-2-金剛烷基等脂環式基;經丨_曱氧基乙 基、1-乙氧基乙基等烷氧基取代之烷基;經苄基等芳基取 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 1級或二級碳之取代基。再者,Rlb& R2b可為相同之取代基, 亦可為不同之取代基。 作為上述_二聚物之具體例,例如可舉出:2,2 ’ _ [氧基 又(亞甲基)]雙-2 -丙酸二曱酉旨、2, 2’-[氧基雙(亞甲基)] 雙-2-丙酸二乙酯、2, 2’-[氧基雙(亞甲基)]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(亞甲基)]雙-2-丙酸二(正丁基) 〇 6旨、2, 2’-[氧基雙(亞曱基)]雙-2-丙酸二(異丁基)g旨、 2’2’-[氧基雙(亞甲基)]雙-2-丙酸二(第三丁基)醋、 2, 2’ -[氧基雙(亞甲基)]雙—2—丙酸二(第三戊基)g旨、 2’ 2’ -[氧基雙(亞曱基)]雙—2-丙酸二(十八烷基)醋、 2’2’-[氧基雙(亞曱基)]雙—2—丙酸二(月桂基)醋、 2’ 2’ -[氧基雙(亞曱基)]雙—2-丙酸二(2-乙基己基)醋、 2’2’-[氧基雙(亞曱基)]雙-2-丙酸二(1-甲氧基乙基) 醋、2, 2’-[氧基雙(亞曱基)]雙-2-丙酸二(1-乙氧基乙基) 酉曰、2, 2 -[氧基雙(亞曱基)]雙—2-丙酸二苄醋、2, 2,-[氧 97122823 63 200911930 基雙(亞甲基)]雙_2一丙酸二苯醋、2,2,_[氧基雙(亞T基)] 雙丙酸二環己酯、2, 2, _[氧基雙(亞甲基)]雙_2_丙酸 一(第一丁基環己基)酯、2, 2,_[氧基雙(亞甲基)]雙一2 一 丙酉文一(一ί衣戊二烯基)酯、2, 2’ _[氧基雙(亞甲基)]雙一2一 丙酉文一(一環癸基)酯、2, 2’-[氧基雙(亞甲基)]雙_2_丙酸 二(異稍基)醋、2, 2’-[氧基雙(亞甲基)]雙_2_丙酸二金剛 烷酯、2,2,-[氧基雙(亞曱基)]雙_2—丙酸二(2_甲基_2一 金剛烷基)酯等。 »亥#之中特佳為2,2 -[氧基雙(亞甲基)]雙_2_丙酸 二甲醋二2,2’-[氧基雙(亞甲基)]雙_2_丙酸二乙醋、 2’2 [氧基雙(亞甲基)]雙-2-丙酸二環己|旨、2, 2,-[氧基 雙(亞甲基)]雙-2-丙酸二节酉旨。 该等醚二聚物可單獨使用丨種,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 二50重量%。若醚二聚物之量過多,則有時在聚合時難以 獲得低分子量者,或者易於凝膠化;另一方面,若醚二聚 物之量過少,則有時透明性或耐熱性等塗膜性能變得=充 分。 [2-1-2]樹脂較佳為具有酸基。由於具有酸基,故所獲 得之著色組成物係藉由酸基與環氧基反應形成酯鍵的^ 聯反應(以下,簡稱為酸-環氧基硬化),而形成可硬化= 著色組成物、或者可在鹼性顯影液中使未硬化部分顯像之 97122823 64 200911930 組成物。作為上述酸基,並無特別限制,例如可舉出··羧 基、酚性羥基、羧酸酐基等。 [2一卜2]樹脂1分子令所含之該等酸基,可僅為i種, 亦可為2種以上。 為了將I基‘人至[2-卜2]樹腊中’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」肖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體’例如可舉出:(甲基)丙烯酸 或衣康酸等具有羧基之單體;N_經基苯基馬來酸亞胺等具 有,性經基之單體;馬來酸針、衣康酸酐等具有緩酸肝基 之單體等;該等之中特佳為(甲基)丙烯酸。 作為於上述聚合後可提供酸基之單體,例如可舉出.(甲 基)丙浠酸-2-經基乙料具有經基之單體;(甲基)丙稀酸 壞氧丙醋等具有環氧基之單體;2_異氰酸基(甲基)丙稀酸 乙S旨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i種,亦可為2種以 上。 在獲得[2 + 2]樹脂時之單體成分亦含有上述用以導入 酸,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1〇〜6〇重量%。若 用以導入酸基之單體之量過多,貝,j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 97122823 65 200911930 耐化學藥品性有可能降. Λ J此卜降,反之右過少,則所得共聚物 之駄彳貝變低,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^ —丨—”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 =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。 作為於聚合後可料自由基聚合性雙鍵之單體,例如可 舉出:(甲基)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㈣基之單體;(甲基)丙_環氧 丙酯、(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j種,亦^為 2種以上。 在獲得[2 + 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5〜7〇重量%,較佳 〜6 0重量%。 .、'、 進而,本發明之[2-1-2]樹脂,較佳為具有環氧基。 為了導入環氧基,係例如將具有環氧基之單體(以下亦 稱為「用以導人環氧基之單體」。)作為單體成分進行聚^ 97122823 66 200911930 作為上述具有環氧基之單體 酸環氧丙K曱基)丙稀酸-3,4_環^^^甲基)丙婦 pe々w、 衣乳基^己基甲酯、鄰 一 S、或對)乙烯基苄基環氧丙醚等。 基之單體,可僅為丨種,亦可為2種以上寺用乂導入㈣ 产?f导[,2]樹脂時之單體成分亦含有上述用以導入 ::土之早體的情形下,其含有比例並無特別限制,但通 书為總單體成分中之5〜70重量%,較佳為1〇〜6〇重量%。 、獲得[2-1-2]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 甲酯、(曱基)丙烯酸乙酯、(曱基)丙烯酸正丙酯、(曱基) =烯酸異丙醋、(甲基)丙烯酸正丁醋、(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、 (曱基)丙烯酸環己酯、(曱基)丙烯酸苄酯、(曱基)丙烯酸 -2-經基乙酯等(曱基)丙烯酸酯類;苯乙烯、乙烯基曱苯、 α曱基笨乙烯等芳香族乙烯化合物;N-苯基馬來醯亞 月女Ν 5衣己基馬來酿亞胺等Ν_取代馬來酿亞胺類;丁二 烯、異戊一烯等丁二稀或取代丁二烯化合物;乙烯、丙烯、 氯乙烯、丙烯腈等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财熱性方面而言,該等之中, 較佳為(曱基)丙稀酸曱酯、(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。 97122823 67 200911930 ^特別是在將[2 —卜2]樹脂之一部分或者全部用作上 ^刀/樹脂的情形下(即’在後述分散處理步驟中使用的 •月形下)’較佳為使用(曱基)丙烯酸苄酯為 總單體成分中之卜70重量%,較佳為5〜6〇重量里%通吊為 在獲侍上述[2-1 —2 ]樹脂時之單體成分亦含 聚合之其他單體的情形下,其含有 制可:、 佳為95重量UX下,更佳為85重量%以下期限制,較 再者,作為本發明之[24 — 2]樹脂, 列單體所構成之共聚物: ;佳為實g上由下 •上述通式(V)所表示之單體、 乂及具有酸基之單體及/或於聚合後可賦予酸基之單體、 •其他可聚合之單體。 就S"]樹脂之製造方法(聚合方法)加以說明。 知的各:方:分之聚合方法並無特別限制’可採用習知公 勺各種方法’但特佳為溶液聚合法。再者,聚合 聚合f度(聚合濃度=[單體成分之總重量/(單::二: 總重量+溶劑重量)]xl()Q),因所使用之單體 ς 或㈣、。目標聚合物之分子量而不同。聚合 0 150 C,更佳為6Q〜。又,聚人 〜⑽,更較佳為10〜4M C 1*度較佳為5 又,在聚合時使用溶劑的情形下,使目通常在 合反應中所使用之溶劑即可。具體而言:四 氫吱喃、二料、乙二醇二甲醚、二乙二:二::四 , 叶一 等峻類; 97122823 68 200911930 『二甲基乙基酮、甲基異丁基_、環己 乙1:乙酸丁醋、丙二醇單甲-乙_、乙酸二= r 了旨類1醇、乙醇、異丙醇、正丁醇、乙二醇單; 越、丙二醇單甲料醇類;f苯、 知早甲 烴類;氯仿;二甲亞磾等。# 乙本4芳香族 併用2種以上。風4 3亥專洛劑可僅使用1種,亦可 在使上述單體成分進行聚合時,視 劑。聚合起始劑並無特別限制,例如可舉 氧二= =、過氧化氮二異丙苯、過氧化二第三丁基:二異 ::、過氧化苯甲酿、過氧化異丙基碳酸第三丁醋、過氧 乙基己酸第三戊酯、過氧化2_乙基己酸第三 有機過氧化物;2,2,-偶氮·4 己烷甲轳、”,… 腈)~偶氮雙(環 雙(2甲二”:氮雙 =甲基丙酸)二甲醋等偶氮化合物。該等聚合起始劑可 僅使用1種,亦可併用2種以上。 一1 了 起始劑之使用量係根據所使用之單體的組合或反 :::牛二目標聚合物之分子量等進行適當設定即可,並無 〜數I定取但就不凝膠化即可獲得重量平均分子量為數千 之聚合物方面而言’通常相對於總單體成分而為 .1〜15重量%,更佳為0.5〜1〇重量%。 又’為了調整分子量,可添加鏈轉移劑。作為鏈轉移劑, ^ :可舉出:正十二垸基硫醇、魏基乙酸、疏基乙酸甲酯 鏈轉㈣’· ^甲基苯乙婦二聚物等;較佳為鏈 移效果較高、可減少殘留單體、亦容易獲得的正十二炫 97122823 69 200911930 基硫醇、巯基乙酸。在使用鏈轉移劑的情形下,其使用量 係根據所使用之單體的組合或反應條件、目標聚合物之= f量等進行適當衫即可,並純駭定,但就不凝膠化 二可獲得重量平均分子量為數千〜數萬之聚合物方面而 吕,通常相對於總單體成分而為0.丨〜15重量%,更佳 〇 · 5〜10重量%。 料’-般認為,在將通式(V)之化合物用作必需單體 =的情形下’於上述聚合反應中,亦同時進㈣二聚物 之%化反應,此時醚二聚物之環化率未必為100莫耳%。 之述[2~卜2]樹脂時’藉由使用上述可賦予酸基 =體作為單體成分而導人酸基的情形下,於聚合後必須 仃用以賦予酸基之處理。該處理因所使用之單體的種類 經如在使用(甲基)丙稀酸|經基乙s旨般之具有 基之早體的情形下,可加成琥、四氫鄰苯二甲酸 有广馬^酐等酸酐。在使用(甲基)丙烯酸環氧丙醋等具 2基之早體的情形下,可加成N_甲基胺基苯甲酸、 土胺基盼等具有胺基及酸基之化合物,或者首先加成 土丙烯酸般之酸,再使琥珀酸酐、四氫鄰苯二甲酸 -2來酉夂酐等酸酐加成於結果所生成的羥基上。在使用 ^鼠酉夂基(P基)丙稀酸乙醋等具有異氰酸基之單體的 ^物:可例如可加A 2—經基丁酸等具有經基及酸基之化 灵取^仵上述[2~1-2]樹脂時,藉由使用上述可賦予自由 性雙鍵之單體作為單體成分而導人自由基聚合性 97122823 200911930 雙鍵的情形下’於聚合後必須進行用以賦予自由基聚合性 雙鍵之處理。 。亥處理因所使用之單體的種類而不同’例如在使用(甲 基)丙烯酸或衣康酸等具有羧基之單體的情形下,可加成 (甲基)丙稀酸環氧丙酯、(甲基)丙烯酸_3, 4_環氧基環己 基甲知、鄰(或間、或對)乙烯基苄基環氧丙醚等具有環氧 基及基聚合性雙鍵之化合物。在使用馬來酸酐或衣康 I酐等具有羧酸酐基之單體的情形下,可加成(甲基)丙烯 酉文2-羥基乙酯等具有羥基及自由基聚合性雙鍵之化合 ,三在使用(甲基)丙烯酸環氧丙酯、(曱基)丙烯酸~3, 4-環氧基基甲自旨、鄰(或間、㈣)乙烯基¥基環氧丙喊 等具有壞氧基之單體的情形下,可加成(曱基)丙烯酸等具 有酉欠基及自由基聚合性雙鍵之化合物。 上述[2-1-2]樹脂之重量平均分子量並無特別限制,但 以GPC所測定之經聚苯乙烯換算之重量平均分子量,較佳 為2000〜200000,更佳為4〇〇〇〜1〇〇〇〇〇。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= 膜,另一方面,若重量平均分子量未滿2〇〇〇,則有難以 表現充分财熱性之傾向。 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 〜400 mgK〇H/g。當二 ^ 未滿5 mgKOH/g時,有時變得難以應用於鹼性顯影。夂只 當酸價超過500 mgKOH/g時,有黏度變得過高而難又 塗膜之傾向。 、形成 97122823 71 200911930 再者,當酸價相對較高時,含#其^ _ 的經時變化(黏度增加)不易發生,著色、、且成物之黏度 較低時,含有其之著色組成物之對=佳:酸價相對 不易產生,因而較佳。 對比度的經時變化(下降) 再者,[2-1-2]樹脂、亦即將通式 作為必需單體成分之共聚物,例如可兴 不之化合物 2004-300203號公報及特開2〇〇4牛日,專利特開 化合物。 _2〇4戒公報所記载之 Γ 本發明之顏料分散液,較佳係將 分散樹脂(即,於後述分散處理步 ^ 9為上述 助劑等-同使用)而獲得。^中’與分散劑或分散 藉^=[2 + 2]樹脂作為分散樹脂,顏料 時黏度不會上升,從而可獲得敎之分散性,又,使用; 顏枓分散液而成之彩色渡光片用著色組成物,顯^ 度,因而較佳。 门司·比 又豸[2 1 2]樹脂作為圖案形成用樹脂,隨後加入 顏料分散液中,或者用於不使用顏料分散液而製造之 組f勿中,藉此所獲得之彩色濾光片用著色Μ成物之黏度 穩疋,亚且使用該彩色遽光片用著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遽光片用著色 物,若在不損及本發明效果之範圍内,則可含有除上 [2 一卜1]樹脂及— 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合劑 97122823 72 200911930 樹脂中的1種,亦可併用2種以上。 二月之者色組成物中’黏合劑樹脂在總固形分中之 :有常為〇」重量%以上’較佳為刚%以上, 财η量%以下,較佳為6°重量%以下。若黏合 劑树月曰之含量少;^ 士卜!^ pq 0 . 咏+ 此乾圍,則膜變脆,對基板之密著性下 降。反之’若多於此範圍 > 士士 固則顯衫液對曝光部之浸透性變 局,有%像素之表面平滑性或敏感度變差。 [2-2]其他成分 述色濾光片用著色組成物,視需要可含有除上 為此種成分,可舉出:聚合性單體、光 制劑、塑化劑、保存稃定VI面活性劑、熱聚合抑 ”存稔Μ、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 k 無特別限制,但較佳為具有之低刀子化合物,則 ,、/、有至夕1個乙稀性雙鍵可 之化合物(以下,稱Α7祕U , Λ 又埏乙j永口 ^, ,^ 烯性化5物」)。所謂乙烯性化 口物係才曰¥本發明之菩洛έη 4、*1/·, 者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 $本^ m 舳取人, 用下、或者利用加熱而在後述 熱水合起始劑的作用下,進许 ^ 進仃加成聚合而硬化的具有乙烯 性雙鍵之化合物。再者,太欢 肺 &所 冉者,本發明之單體意指相對於高分子 物貝之概念’意指除狹義之單㈣丨”从+ —』 我 < 早體以外亦包括二聚體、二奄 體、寡聚物之概念。 一承 作為乙稀性化合物,例如可舉出:不飽和羧酸;其與單 97122823 73 200911930 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 基化合物等之多羥基化合物的酯化反應而獲得之酯;使聚 異氰酸醋化合物與含有(甲基)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 〆 出.乙一醇一丙細酸醋、三乙二醇二丙烯酸醋、三經甲基 丙烷三丙烯酸酯、三羥甲基乙烷三丙烯酸酯、季戊四醇二 丙烯酸酯、季戊四醇三丙稀酸酯、季戊四醇四丙烯酸酯、 一季戊四醇四丙烯酸酯、二季戊四醇五丙浠酸酯、二季戊 四醇六丙烯酸酯、甘油丙烯酸酯等丙烯酸酯。又,可舉出: 將該等丙烯酸酯之丙烯酸部分,替換成甲基丙烯酸部分而 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 t 分而得之馬來酸酯等。 作為芳香族多羥基化合物與不飽和羧酸之酯,例如可舉 f ·對苯二酚二丙烯酸酯、對苯二酚二甲基丙烯酸酯、間 ,二酚二丙烯酸酯、間苯二酚二甲基丙烯酸酯、鄰苯三酚 三丙烯酸酯等。 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:丙稀酸、鄰苯二甲酸與乙二醇之縮合物;丙 婦酸、馬來酸與二乙二醇之縮合物;甲基丙稀酸、對苯二 97122823 74 200911930 甲酸與季戊四醇之縮合物;丙烯 甘油之縮合物等。 ,、丁一私 作^吏聚異亂酸g旨化合物與含有(甲基)丙稀酿基之經 二⑯反應而成之具有胺基甲酸乙_骨架的乙稀性化 5物,例如可舉出:使六亞甲基二異氰酸酯、三甲基六亞 甲基-異氰酸醋等脂肪族二異氰酸酯,環己烷二異氰酸 醋、異佛_二異氰酸s旨等脂環式二異氰酸_,甲苯二異 IU夂s曰—苯基甲燒二異說酸醋等芳香族二異氯酸醋等, 與丙稀酸I經基乙酉旨、甲基丙烯酸-2-經基乙酯、3一經基 (1^1,1-三丙烯醯氧基甲基)丙烷、3 —羥基αι,卜三曱基 丙烯醯氧基甲基)丙烷等含有(甲基)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;鄰苯二甲酸二 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 的經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 97122823 75 200911930 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,較佳為〇.丨〜4〇 mgKOH/g,特佳為5〜30 mgK0H/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。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稀酸 酯、二季戊四醇五丙烯酸酯、二季戊四醇五丙烯酸酯之琥 珀酸酯為主成分之混合物。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65〇 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14〇以下、更佳為11〇以下者。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4〇〇以下且雙鍵 當量為110以下之、脂肪族多羥基化合物與不飽和羧酸之 97122823 76 200911930 更/、體而5,例如可舉出季戊四醇四丙酸酯、 四醇三丙烯酸酯等。 于乂 古再ίν沈所獲仔之彩色遽光片用著色組成物之敏感度而 二卜1:為使用分子量超過400之乙烯性化合物。作為此 0 ,特佳為二季戊四醇四(曱基)丙烯酸酯、二季戊 等二基)丙烯酸醋、二季戊四醇六(甲基)丙稀酸醋 旦A 化'σ物係藉由與上述分子量為_以下且雙鍵當 ^,以下(更佳為11G以下)之乙烯性化合物組合使 :而可!得平衡性良好之組成物,因而較佳。 聚早體在本發明著色組成物的總固形分中之調配 \ i。重曰;為0重量%以上,較佳為5重量%以上’更佳為 ^以上’通常為80重量%以下,較佳為7〇重量%以 二佳為5。重量%以下,特佳為4〇重量%以下。又,相 以:材之比率,通常為0重量%以上,較佳為5重量% 常為佳為10重量%以上’特佳為20重量%以上,通 =2、〇0重量%以下,較佳為1〇〇重量%以下,更佳為8〇 里里/6以下。 [2^3]光聚合起始系、熱聚合起始劑 入使塗膜硬化,本發明之著色組成物較佳為含有光聚 聚合起始劑中之至少—種。其中,硬化之方 法可為:使用該等起始劑之方法以外的方法。 在本發明之著色組成物含有具有乙烯性雙鍵之 劑樹脂成分的情形下、或含有乙烯性化合物 作為上迹聚合性單體的情形下,較佳為含有光聚合起始系 97122823 77 200911930 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氣反 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。 [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59452396號、特開昭61一151197號 等各么報s己載之含有二茂鈦(titan〇cene)化合物之二茂 金屬化合物;或曰本專利特開平10_39503 之六芳基物衍生物、,甲基均三讀生物、N= 胺,等N-芳基胺基酸類、N—芳基胺基酸鹽類、 Ν-芳基-α-胺基酸酯類等自由基活性劑,胺基烷基笨 酮系化合物;日本專利特開2〇〇6_3675〇號公報、特開 2002-323762 f虎公報、特㈤2〇〇〇_8〇〇68號公報等中記 之將酯系化合物等。 以下’列舉出本發明中可使用之光聚合起始劑之具體 例。 一 斤2-(4-甲氧基苯基)_4,6 —雙(三氯曱基)均三啡、一曱 乳基奈基)-4,6-雙(三氯甲基)均三讲、2_(4_乙氧基笼 基)-4,6-雙(三氣甲基)均三畊、2_(4_乙氧基羰基^ 97122823 78 200911930 基)-ϋ雙(三氯甲基)均三讲等齒甲基均三讲衍生物; 々2-三氯甲基-5 —(2,_苯并十南基hjm二峻、^三 乳甲基:5-[万-(2’ -苯并呋喃基)乙烯基]_j,3, 4_σ等二 唾、2-三氯甲基_5_[万_(2、(6” _苯和夫喃基)乙婦 基)]-1,3, 4-噚二唑、2 —三氯甲基—5_呋喃基q,3, 4—哼二唑 專鹵甲基化σ号二唾衍生物; 2-« _氯苯基)—4,5_二苯基咪唑二聚體、2_(2,_氯笨 基)-4,5-雙(3,_f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,-甲氧基苯基)一4, 5一 二笨基咪唑二聚體、(4’_甲氧基苯基)_4, 5_二苯基咪唑二 聚體等咪唑衍生物; 安息香曱醚、安息香苯醚、安息香異丁醚、 醚等安息香烧基賴; ^ 2-甲基恩醌、2-乙基蒽醌、2-第三丁基蒽醌、卜氣蒽醌 等蒽醌衍生物; " 二苯基酮、米其勒酮(Michler,s Ket〇ne)、二乙胺基二 苯基酮、2-甲基二苯基酮、3一甲基二苯基酮、4_甲基二笨 基酮、2-氣二苯基酮、4_溴二苯基酮、2_羧基二苯基酮等 二苯基綱衍生物; 2’ 2-二曱氧基_2 —苯基苯乙酮、2, 2-二乙氧基苯乙酮、 卜羥基環己基苯基酮、α_羥基-2-甲基苯基丙酮、卜羥基 -1-曱基乙基-(對異丙基苯基)酮、經基_丨_(對十二烧基 苯基)酮、2-曱基-1-[4-(曱硫基)苯基]-2-咮啉基丙烷一二 酮、M’l-三氯甲基-(對丁基苯基)酮等苯乙g同衍生物; 97122823 79 200911930 0塞0頓酮(thioxanthone)、2_乙基嘆°頓酮、異丙基β塞嘴 酮、2-氯噻噸酮、2, 4-二曱基噻噸酮、2, 4-二乙基噻噸網、 2, 4-二異丙基噻噸酮等噻噸酮衍生物; 對二甲胺基苯曱酸乙酯、對二乙胺基苯曱酸乙酯等苯平 酸醋衍生物; 9-苯基吖啶、9-(對甲氧基苯基)吖啶等吖啶衍生物; 9, 10-二甲基苯并η非讲等π非讲(phenazine)衍生物; 苯并蒽S同等蒽酮(anthrone)衍生物; " 二環戊二烯基二氯化鈦、二環戊二烯基雙苯基鈦、二環 戊二烯基雙-2, 3, 4, 5, 6-五氟苯-卜基鈦、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-1-基鈦、二環戊 二烯基-2, 4-二氟苯-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-1-基鈦、二環戊二烯基_2, 6-二-氟-3-(吡咯-卜 f 基)~苯-1-基鈦等二茂鈦衍生物; 2-曱基-1-[4-(曱硫基)苯基]_2_咮琳基丙烷-酮、2-苄基-2-二曱胺基-1-(4-咮啉基苯基)_ 丁酮2一苄基一2-二甲胺基-1-(4-咪啉基苯基)丁烷_丨_酮、4一二甲胺基苯甲 酸乙酯、4-二曱胺基苯曱酸異戊酯、4_二乙胺基苯乙酮、 4-二曱胺基苯丙酮、1,4-二甲胺基苯曱酸_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; 97122823 80 200911930 1 [9—乙基~6~(2—甲基苯甲醯基)-9.Η·-咔唑基] 烷1肟〇~乙酸酯、1-(4-苯基胺苯磺基-苯基)辛烷―丨 一酮2肟苯甲酸酯等肟酯系化合物。 物用之光聚合起始系,較佳為含有肟酯系化合 乍為先::起始劑’其中,作為特佳者,可舉出以下述 式(1 )所表示之肟酯系化合物。 [化 19] ? /Vp/n (I) Y C —XQ一p1 [式⑴中’R表示氫原子、碳數卜2()之絲、碳數^ :25之烯基、碳數3〜2〇之雜芳基或者碳數4〜25之雜 一 土該等均可具有取代基。或者,Rl可與X或 而形成環。 表示炭數2〜20之烷醯基、碳數3〜25之烯醯基、碳 數、=8之環㈣基、碳數7〜2()之芳㈣、碳數2〜1〇 =乳幾基、碳數7〜2〇之芳氧羰基、碳數2〜2()之雜芳 ^、碳數3〜20之雜芳醯基或者碳數2〜2〇之烷基胺基羰 基’該等均可具有取代基。 # X表不可具有取代基之、& 2個以上環縮合而成之2價 方香族烴基及/或芳香族雜環基。 γ表示可具有取代基之芳香族基。] 二有經微粒化之顏料、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 97122823 81 200911930 係有在著色组成物剛製造後所觀察到者,亦有在組成物保 存中所產生者。由研討結果可明瞭,異物之產生 起始劑有著特別緊密的關係。 /、九汆口 〜又,、於彩色濾、光片用著色組成物中,綠色係對照射光之 局敏感度化為最困難之顏色。作為其原因之一,可舉出: 綠色顏料與其他顏色之顏料相比’顏料本身之著色牛力較 低’因而顏料之含量必然變高。 乂 綠色組成物之最大穿透率波長約為53g⑽,波長 為450⑽以下之穿透率大致接近〇。在使用光微影法之 :色:光片製造中’通常使用之曝光機為高壓水銀燈,* 八相對應之光聚合起始财,亦有可對自紫外部分至副 ⑽附近的光引起硬化反應者,但對於綠色,可舉出 利用長波長部分之光能量。 …、 /著色組成物之敏感度不充分則無法獲得規 ^ ’在極端情形下,塗膜之硬化性較差,亦會 # =塗膜之現象。又’彩色遽光片在進行面板化時塗: :向臈’但若塗膜硬化性較低,則對於通常用: 剑之N-甲基吡咯啶酮(NMp),會產生以顏料 ° 、办 總之’要獲得含有經微粒化之顏料、1中人斤出物。 ㈣菁顏料且對曝光之光;有== =難。'抑制異物產生之彩色遽光片用著色組成物,係非常 合:對劑中,由— 特別疋以上述通式⑴所表示之μ化合物所構成 97122823 82 200911930 之光聚合起始劑,藉此可解決上述問題,因而較佳。 於上述月亏酉旨系化合物⑴中,Y_c(=〇)_x部分形成吸光 部’肪結構部:-c(—R1)=N—〇R2部分則形成自由基產生部 ,>吸光. Y C(-Q)—X高效率地吸收光並將所吸收之能 里冋效率地轉移至&結構部,藉此達成高的敏感度。一般 〜為以Y C(-0)-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 口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,本發明之將醋系 化CT物(I )’由於Y部分形成體積大之基,因此即便在以 咼濃度添加的情形下,亦可具有高吸光度,因而較佳。 又,重要的是Y-C(=〇)-X部分高效率地生成在肟結構部 中谷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,重要的是使Y_c(=〇)_x部分與肟結構 部在空間上儘可能地接近。(V) A furnace with a carbon number of 1 to 25. I have the pigment dispersion containing micronized (4) zinc phthalocyanine pigment as mentioned above; = by:, desertification: relatively low, so sometimes it is difficult to make 4 = liquid f dissolution, However, the obtained pixel is also prone to defects, and more: = on the surface of the calender J, or the linear portion of the pixel is sharpened: again: the image is likely to cause light leakage of the panel. Therefore, it is known that the fine particles::: and the pigment dispersion containing the micronized pigment, in particular, the pigmented composition of the diterpenoid pigment, or the colored enamel first qualitatively enhances the pigment dispersion or the colored (four) coloring composition The viscosity is such that the solubility of the coloring composition to the developer, the (four) of the obtained pixel, the linearity of the lift, and the like are improved, and the [2 + 2] resin described below is used. In the polymer represented by the formula (7), the nicotinyl group having a carbon number of 1 to 25 which has a substituent of 9712823 is not particularly limited to 62,119,119, and examples thereof include a mercapto group. , linear, branched, etc., ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-pentyl, octadecyl, lauryl, 2-ethylhexyl An alkyl group; an aryl group such as a phenyl group; a cyclohexyl group, a tert-butylcyclohexyl group, a dicyclopentadienyl group, a tricyclodecanyl group, an isoric rice group, an adamantyl group, a 2-methyl-2-adamantyl group, or the like An alicyclic group; an alkyl group substituted with an alkoxy group such as a hydrazine-methoxyethyl group or a 1-ethoxyethyl group; an alkyl group substituted with an aryl group such as a benzyl group; and the like. In terms of heat resistance, it is particularly preferable that such a methyl group, an ethyl group, a cyclohexyl group, a benzyl group or the like is difficult to be separated from a substituent of a primary or secondary carbon by an acid or heat. Further, Rlb&R2b may be the same substituent or a different substituent. Specific examples of the above-mentioned dimer include, for example, 2,2'-[oxy(methylene)]bis-2-propionic acid, 2, 2'-[oxy double (methylene)] diethyl bis-2-propionate, 2, 2'-[oxybis(methylene)]bis-2-propionic acid di(n-propyl) ester, 2, 2,- [oxybis(indenyl)]bis-2-propionic acid di(isopropyl) ester, 2, 2,-[oxybis(methylene)]bis-2-propionic acid di(n-butyl) 〇6, 2, 2'-[oxybis(indenyl)]bis-2-propionic acid di(isobutyl)g, 2'2'-[oxybis(methylene)] Bis-2-butyric acid di(t-butyl) vinegar, 2, 2'-[oxybis(methylene)] bis-2-propionic acid di(tripentyl)g, 2' 2' -[oxybis(indenyl)]bis-2-propionic acid di(octadecyl)acetate, 2'2'-[oxybis(indenyl)]bis-2-propionic acid (lauric) Base) vinegar, 2' 2'-[oxybis(indenyl)]bis-2-propionic acid di(2-ethylhexyl) vinegar, 2'2'-[oxybis(indenyl)] Bis-2-propionic acid bis(1-methoxyethyl) vinegar, 2, 2'-[oxybis(indenyl)]bis-2-propionic acid di(1-ethoxy) Base ethyl) 酉曰, 2, 2 -[oxybis(indenyl)] bis- 2-propionic acid dibenzyl vinegar, 2, 2,-[oxygen 97228923 63 200911930 bis (methylene)] double _2-propionic acid diphenyl vinegar, 2,2,_[oxybis(sub-T-)]dipropionic acid dicyclohexyl ester, 2, 2, _[oxybis(methylene)] double_2 _propionic acid mono(first butylcyclohexyl) ester, 2, 2, _[oxybis(methylene)] bis- 2 propyl hydrazine (a pentyl pentadienyl) ester, 2, 2' _[oxybis(methylene)] bis- 2 propyl benzoate (monocyclic fluorenyl) ester, 2, 2'-[oxybis(methylene)] bis-2-propionic acid (isosyl) vinegar, 2, 2'-[oxybis(methylene)]bis-2-propionic acid diadamantyl ester, 2,2,-[oxybis(indenyl)] double _ 2-propionic acid di(2-methyl-2-monoadamantyl) ester. »海# Among the best 2,2-[oxybis(methylene)]bis_2-propionic acid dimethyl acetonate 2,2'-[oxybis(methylene)] double_2 _propionic acid diethyl acetoacetate, 2'2 [oxybis(methylene)] bis-2-propionic acid dicyclohexan, 2, 2,-[oxybis(methylene)] bis-2 - Propionate two knots. These ether dimers may be used singly 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 (for example, usually 2) ~60% by weight, preferably 5 to 55% by weight, more preferably 5 to 50% by weight. If the amount of the ether dimer is too large, it is sometimes difficult to obtain a low molecular weight at the time of polymerization, or it is easy to gel; On the other hand, when the amount of the ether dimer is too small, the coating film properties such as transparency and heat resistance may become sufficient. [2-1-2] The resin preferably has an acid group. Therefore, the colored composition obtained by the reaction of an acid group with an epoxy group to form an ester bond (hereinafter, simply referred to as acid-epoxy hardening) forms a hardenable = colored composition, or can be used in a base. The composition of the 97122823 64 200911930 which is an unhardened part in the developing solution is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, a carboxylic acid anhydride group, and the like. [2 Ib 2] The number of the acid groups contained in one molecule of the resin may be only one type or two or more types. In order to set the I group to the person [2-b 2] In the tree wax, 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 "a monomer for introducing an acid group") is used as a monomer component. In the case where the monomer which can provide an acid group after polymerization is used as a monomer component, it is necessary to carry out a treatment for providing an acid group as described later after the polymerization. Examples of the body ' include a monomer having a carboxyl group such as (meth)acrylic acid or itaconic acid; and a monomer having a transradical group such as N-phenylphenylmaleic acid imide; maleic acid needle and clothing. A monomer having a hyaluronic acid-containing group such as a cannic anhydride; etc.; among these, (meth)acrylic acid is particularly preferable. As the monomer which can provide an acid group after the above polymerization, for example, (meth)propene can be mentioned. The acid-2-carbyl group has a monomer having a trans-group; an epoxy group-containing monomer such as (meth)acrylic acid or acetoacetic acid; 2-isocyanato (meth)acrylic acid B The monomer having an isocyanate group or the like may be used alone or in combination of two or more kinds. The monomer for obtaining [2 + 2] resin may be used. In the case where the component also contains the above-mentioned monomer for introducing an acid, the content thereof is not particularly limited, and is usually 5 to 70% by weight, preferably 1 to 6 % by weight, based on the total monomer component. The amount of the monomer used to introduce the acid group is too large, the shell, j becomes a high viscosity, and it may be difficult to form a coating film, or the alkali solubility becomes excessive and the pattern is formed or coated. 97102923 65 200911930 Chemical resistance may be lowered ΛJ This is a drop, and if the right is too small, the mussels of the obtained copolymer become low, and the advantages due to the introduction of the acid value may not be fully exerted. Further, the [2~1-2] resin may be In order to introduce a radically polymerizable double bond into the above-mentioned resin, for example, a monomer capable of imparting a radical polymerizable double bond after polymerization can be used (hereinafter also It is called "a monomer for introducing a radically polymerizable double bond". After the polymerization is carried out as a single component, a treatment for imparting a radical polymerizable double bond as described later may be carried out. Examples of the monomer which can be subjected to a radically polymerizable double bond after polymerization include a monomer having a carboxyl group such as (meth)acrylic acid or itaconic acid, and a carboxylic acid (tetra) group such as maleic anhydride or itaconic anhydride. Monomer; (methyl) propyl-glycidyl propyl ester, (meth)acrylic acid-3,4-epoxycyclohexyl methyl vinegar, o- (or m-, or p-) vinyl benzyl epoxidized propyl ether A monomer such as an epoxy group. These monomers for introducing a radically polymerizable double bond may be used alone or in combination of two or more. In the case where the monomer component when the [2 + 2] resin is obtained also contains the monomer for introducing a radical polymerizable double bond, the content ratio thereof is not particularly limited, but is usually 5 of the total monomer component. 〜7〇% by weight, preferably ~60% by weight. Further, the [2-1-2] resin of the present invention preferably has an epoxy group. In order to introduce an epoxy group, for example, a monomer having an epoxy group (hereinafter also referred to as "a monomer for introducing a human epoxy group") is used as a monomer component. 97122823 66 200911930 Monobasic acid epoxidized methyl ketone) acrylic acid-3,4_cyclo^^^methyl) propyl pe々w, lacyl methyl hexyl methyl ester, ortho-S, or p-vinyl Benzyl epoxidized ether and the like. The base monomer can be used only for the species, or can it be imported into two or more temples (4)? When the monomer component of the resin [f2] is also contained in the case of introducing the above-mentioned:: the early body of the soil, the content ratio thereof is not particularly limited, but the book is 5 to 70 weights in the total monomer component. %, preferably from 1 〇 to 6 〇 by weight. The monomer component in the case of obtaining [2-1-2] resin may contain other copolymerizable monomers in addition to the above monomer components. Examples of the other copolymerizable monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (decyl) acrylate, and decyl acrylate. N-butyl acrylate (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, Benzyl) benzyl acrylate, (mercapto)acrylic acid-2-ylaminoethyl ester (mercapto) acrylate; aromatic vinyl compound such as styrene, vinyl benzene, α fluorenyl ethylene; N-benzene基马基醯亚月女Ν 5 衣己基马来亚亚胺等Ν_substituted maleimine; butadiene, isoprene and other butadiene or substituted butadiene compounds; ethylene, propylene, Ethylene or substituted ethylene compounds such as vinyl chloride and acrylonitrile; vinyl esters such as vinyl acetate; and the like. Among the above, in terms of good transparency and not easily impairing the heat, among these, decyl acrylate, cyclohexyl acrylate, benzyl (meth) acrylate, styrene are preferred. . These other monomers which can be copolymerized may be used alone or in combination of two or more. 97122823 67 200911930 ^ Especially in the case where part or all of [2 - 2] resin is used as the upper knife / resin (that is, 'in the shape of the moon used in the dispersion processing step described later)' is preferably used (mercapto) benzyl acrylate is 70% by weight of the total monomer component, preferably 5 to 6 〇% by weight, and the monomer component when the above [2-1-2] resin is obtained In the case of other monomers containing a polymerization, the content of the monomer may be: preferably 95 weight UX, more preferably 85% by weight or less, and moreover, as the [24-2] resin of the present invention, a copolymer composed of a body: a monomer represented by the above formula (V), a monomer having an acid group, and/or a monomer capable of imparting an acid group after polymerization, • Other polymerizable monomers. The S"] resin manufacturing method (polymerization method) will be described. Each of the known methods: the polymerization method is not particularly limited, and various methods can be employed, but a solution polymerization method is particularly preferred. Further, the polymerization polymerization f degree (polymerization concentration = [total weight of monomer components / (single: : two: total weight + solvent weight)] xl () Q), because of the monomer ς or (4) used. The molecular weight of the target polymer varies. Aggregation 0 150 C, more preferably 6Q~. Further, the poly-(10), more preferably 10 to 4 M C 1* is preferably 5, and when a solvent is used for the polymerization, the solvent used in the usual reaction may be used. Specifically: tetrahydrofuran, di-, ethylene glycol dimethyl ether, diethylene two: two:: four, leaf one class; 97122823 68 200911930 "dimethyl ethyl ketone, methyl isobutyl _, cyclohexyl 1: acetic acid butyl vinegar, propylene glycol monomethyl-ethyl _, acetic acid two = r steroids, ethanol, isopropanol, n-butanol, ethylene glycol mono; propylene glycol monomethyl alcohol Class; f benzene, chlorinated hydrocarbons; chloroform; dimethyl hydrazine. #乙本4Aromatic Use two or more types. It is also possible to use only one type of the wind 4 3 hailuo agent, and it is also possible to use a visual agent when the above monomer components are polymerized. The polymerization initiator is not particularly limited, and examples thereof include oxygen ===, dicumyl peroxide, dibutyl peroxide: diiso::, benzoyl peroxide, and isopropyl peroxycarbonate. Third butan vinegar, third amyl peroxyethylhexanoate, third organic peroxide of 2-ethylhexanoic acid peroxide; 2,2,-azo·4 hexane formazan, “,... nitrile) An azo compound such as azobis(cyclobis(2methyldi):nitrogen bis-methylpropionic acid) dimethyl vinegar. These polymerization initiators may be used alone or in combination of two or more. The amount of the initiator to be used may be appropriately set according to the combination of the monomers to be used or the molecular weight of the reverse:::Non-target polymer, and may be determined without the number I, but may not be gelled. In terms of obtaining a polymer having a weight average molecular weight of several thousands, it is usually from 1 to 15% by weight, more preferably from 0.5 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, ^: may be exemplified by n-dodecyl mercaptan, weiji acetic acid, methyl mercaptoacetate chain (tetra) 'methyl benzene dimer, etc.; It is a high-strength chain shifting effect, which can reduce residual monomers, and is also easily obtained. It is also easy to obtain. It is easy to obtain, and it is easily obtained. In the case of using a chain transfer agent, the amount used is based on the single used. The combination of the body or the reaction conditions, the amount of the target polymer = f amount, etc. can be properly smocked, and purely determined, but without gelling, a polymer having a weight average molecular weight of several thousand to several tens of thousands can be obtained. , generally, relative to the total monomer component, is 0. 丨 15% by weight, more preferably 〜 5 to 10% by weight. It is generally considered that the compound of the formula (V) is used as an essential monomer = In the case of the above polymerization, the (4) dimerization reaction of the dimer is also carried out at the same time, and the cyclization rate of the ether dimer is not necessarily 100 mol% at this time. In the case where the above-mentioned acid group can be imparted as a monomer component to conduct a human acid group, it must be used for the treatment of the acid group after the polymerization. The treatment is used as the type of the monomer used ( Methyl)acrylic acid|In the case of the base of the base, it can be added Anhydrous anhydride such as sulphate and tetrahydrophthalic acid can be added to N-methylaminobenzoic acid in the case of using a precursor of 2 bases such as (meth)acrylic acid propylene glycol vinegar. A compound having an amine group and an acid group, or a first addition of a acrylic acid, and an anhydride such as succinic anhydride or tetrahydrophthalic acid-2 phthalic anhydride is added to the result. On the hydroxyl group, a monomer having an isocyanate group such as acetaminophen (P-based) acetoacetate or the like can be used: for example, A 2 - peroxybutyric acid or the like having a trans group and an acid group can be added. When the above-mentioned [2~1-2] resin is used, the monomer capable of imparting a free double bond is used as a monomer component to introduce a radical polymerizable property 97102223 200911930 double bond. It is necessary to carry out a treatment for imparting a radical polymerizable double bond after the polymerization. . The treatment is different depending on the type of the monomer to be used. For example, in the case of using a monomer having a carboxyl group such as (meth)acrylic acid or itaconic acid, (meth)acrylic acid glycidyl ester can be added. A compound having an epoxy group and a radically polymerizable double bond such as (meth)acrylic acid _3,4-epoxycyclohexyl, or o- (or m- or p-)vinylbenzyl epoxidized propyl ether. When a monomer having a carboxylic acid anhydride group such as maleic anhydride or itaconic anhydride is used, a compound having a hydroxyl group and a radical polymerizable double bond such as 2-methylethyl acrylate can be added. 3. In the use of (meth)acrylic acid propyl acrylate, (mercapto) acrylic acid ~ 3, 4-epoxy group, the ortho (or m, (4)) vinyl ketone propylene propylene shunt, etc. have bad oxygen In the case of a monomer, a compound having a fluorenyl group and a radical polymerizable double bond such as (fluorenyl)acrylic acid can be added. The weight average molecular weight of the above [2-1-2] resin is not particularly limited, but the weight average molecular weight in terms of polystyrene measured by GPC is preferably from 2,000 to 200,000, more preferably from 4 to 10,000. Hey. When the weight average molecular weight exceeds 200,000, the viscosity may become too high to form a film. On the other hand, if the weight average molecular weight is less than 2 Å, it tends to be difficult to express sufficient 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 400 mgK〇H/g. When 2 ^ is less than 5 mgKOH/g, it sometimes becomes difficult to apply to alkaline development.夂 Only when the acid value exceeds 500 mgKOH/g, the viscosity becomes too high and it is difficult to coat the film. Forming 97122923 71 200911930 Furthermore, when the acid value is relatively high, the change with time (the viscosity increase) of #^^_ is not easy to occur, and when the coloring is low, the color composition of the product is low. The right pair = good: acid price is relatively difficult to produce, so it is better. Change in contrast (change) over time. Further, [2-1-2] a resin, that is, a copolymer having a general formula as an essential monomer component, for example, Compound No. 2004-300203 and JP-A-2002 4 cattle day, patent special compound. The pigment dispersion liquid of the present invention is preferably obtained by dispersing a resin (that is, using the dispersion treatment step described later as the above-mentioned auxiliary agent or the like). ^中' with dispersing agent or dispersing borrowing ^=[2 + 2] resin as the dispersing resin, the viscosity of the pigment will not rise, so that the dispersibility of the crucible can be obtained, and, in addition, the colored light of the pigment dispersion is used; The sheet is colored with a composition, and is preferred, and thus is preferred. Moss ratio 豸 [2 1 2] resin is used as a resin for pattern formation, and then added to a pigment dispersion liquid, or used in a group produced without using a pigment dispersion liquid, thereby obtaining a color filter It is preferable that the color of the colored enamel is stable, and the pattern formed by using the colored luminescent sheet with the colored composition is not preferable. Further, the pigment dispersion liquid of the present invention and the coloring matter for a color calender sheet may contain a binder resin other than the resin of the [2]1 resin and the resin, without impairing the effects of the present invention. . </ RTI> As the binder resin of the present invention, one type of the above-mentioned various binders 97122823 72 200911930 may be used alone, or two or more types may be used in combination. In the color composition of February, the binder resin is usually 〇% by weight or more in the total solid content, preferably 8% or more, and 7% by weight or less, preferably 6% by weight or less. If the amount of adhesive tree is less than that of the moon; ^ Shi Bu! ^ pq 0 . 咏 + This dry circumference, the film becomes brittle and the adhesion to the substrate is lowered. On the other hand, if it is more than this range >, the permeability of the exposed body is changed, and the surface smoothness or sensitivity of % pixels is deteriorated. [2-2] The coloring composition for the other component color filter may be contained as a component, and may be a polymerizable monomer, a photoreceptor, a plasticizer, or a preservative. Agent, thermal polymerization, storage, surface protection agent, adhesion improver, development improver, dye, etc. [2-2-1] Polymerizable monomer The polymerizable monomer of the present invention, if k is not special Restricted, but preferably has a low knife compound, then, /, there is a compound which can be one ethylene double bond in the evening (hereinafter, it is called Α7 Secret U, Λ 埏 埏 j j 永口 ^, , ^ ene Sexualized 5"). When the color composition is irradiated with active light, the effect of the photopolymerization initiation system described later is obtained by the use of the photopolymerization initiation system. The compound having an ethylenic double bond which is hardened by addition polymerization by a hydrazine addition polymerization is carried out by heating or under the action of a hot water start initiator described later by heating. Furthermore, the singularity of the lungs & the singularity of the present invention means the concept relative to the polymer ’ ” means “except for the narrow sense of the single (four) 丨” from + — 』 I < The concept of dimers, dioxins, and oligomers is also included in addition to the early body. As an ethylene compound, for example, an unsaturated carboxylic acid; an ester of a hydroxy compound with a single 97122823 73 200911930; an ester of an aliphatic polyhydroxy compound with an unsaturated carboxylic acid; an aromatic polyhydroxy compound and an unsaturated group; An ester of a carboxylic acid; an ester obtained by esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid, a polyhydroxy compound such as the above aliphatic polyhydroxy compound or an aromatic polyhydroxy compound; and a polyisocyanate compound and An ethylenic compound having an amine decanoic acid ethyl ester skeleton obtained by reacting a hydroxy compound having a (meth) acrylonitrile group. Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethyl acetate monopropionic acid vinegar, triethylene glycol diacrylate vinegar, trimethyl propylene triacrylate, and trishydroxymethyl B. An acrylate such as an alkyl triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentapropionate, dipentaerythritol hexaacrylate or glycerin acrylate. Further, the acrylic acid moiety of the acrylate may be replaced by a methacrylic acid moiety, a itaconate ester obtained by replacing the itaconic acid moiety, and a butyric acid moiety may be substituted. The butenoate is replaced by maleic acid ester such as maleic acid. Examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include f. hydroquinone diacrylate, hydroquinone dimethacrylate, m-diphenol diacrylate, and resorcinol. Methacrylate, pyrogallol triacrylate, and the like. 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 propyl benzoic acid, maleic acid and diethylene glycol; methyl acrylate, p-phenylene 97122823 74 200911930 A condensate of formic acid and pentaerythritol; a condensate of propylene glycerol, and the like. , Ding Yi privately 吏 异 异 异 异 g 旨 旨 与 与 与 与 与 与 与 与 与 与 旨 旨 旨 旨 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙For example, an aliphatic diisocyanate such as hexamethylene diisocyanate or trimethylhexamethylene-isocyanate, an alicyclic ring such as cyclohexane diisocyanate or isophora diisocyanate Diisocyanate _, toluene diiso IU 夂 曰 苯基 phenyl carbaryl bismuth vinegar and other aromatic diisochloric acid vinegar, etc., with acrylic acid I, methacrylic acid -2- (Methyl) propylene oxime, such as ethyl ethyl ester, 3-mono-based (1^1,1-tripropenyloxymethyl)propane, 3-hydroxy-α, triconyl acryloxymethyl)propane The reactant formed by the reaction of a hydroxy compound. Further, as the ethylenic compound used in the present invention, for example, an acrylamide such as ethyl bis acrylamide or an allyl ester such as diallyl phthalate; ortho-benzoquinone; A vinyl group-containing compound or the like such as divinyl acetate. 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 radical of an 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. Therefore, two or more kinds of monomers may be used in combination. Further, if necessary, 97122823 75 200911930 may be used in combination with a polyfunctional monomer having no acid group as a monomer and a polyfunctional monomer having an acid group. The acid value of the polyfunctional monomer having an acid group is preferably 〇.丨4〇 mgKOH/g, particularly preferably 5 to 30 mgK0H/g. When the acid value of the polyfunctional monomer is too low, the development and dissolution characteristics are lowered. If it is too high, the production or handling becomes difficult and the photopolymerization performance is lowered, and the surface smoothness of the pixel and the like tend to be poor. 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, it is preferred to use an acid group as a general polyfunctional monomer. Adjust to the above range. In the present invention, a more preferable polyfunctional monomer having an acid group is commercially available as T01382 manufactured by Toagosei Co., Ltd., which is commercially available as dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate. A mixture of succinate as a main component. Other polyfunctional monomers other than the polyfunctional monomer may also be used in combination. In the present invention, the ethylene compound preferably has a molecular weight of 65 Å or less, preferably 550 or less, more preferably 400 or less, and a double bond equivalent of 150 or less, preferably 14 Å or less, more preferably 11 or more. 〇 The following. Further, the lower limit thereof is not particularly limited, and may be within the range in which the chemical structure of the addition polymerization can be obtained. Among the pixels which can reduce the "defects" of the pixels and form more excellent linearity, among these, a compound having a relatively small molecular weight and a small double bond equivalent is preferable. For example, a polymer having a molecular weight of 4 Å or less and a double bond equivalent of 110 or less, and an aliphatic polyhydroxy compound and an unsaturated carboxylic acid of 97,102,823, 76, 2009,119,130, and the like are preferred, and pentaerythritol IV is exemplified. Propionate, tetraol triacrylate, and the like. The sensitivity of the coloring composition of the colored calenders obtained by Yu Gu Gu ί ν 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二As such a 0, particularly preferred is dipentaerythritol tetrakis(meth)acrylate, dipentaerythritol or the like diacetate acrylate, dipentaerythritol hexa(methyl) acrylate acetonate A σ system by _ below and double bond when ^, the following (more preferably 11G or less) combination of ethylenic compounds: and! A composition having a good balance is preferred. The formulation of the poly-early body in the total solids of the colored composition of the invention is \i. The weight is 0% by weight or more, preferably 5% by weight or more, more preferably ^ or more, and usually 80% by weight or less, preferably 7% by weight or less. The weight% or less is particularly preferably 4% by weight or less. Further, the ratio of the phase to the material is usually 0% by weight or more, preferably 5% by weight, usually preferably 10% by weight or more, particularly preferably 20% by weight or more, and 2% to 〇0% by weight or less. Preferably, it is 1% by weight or less, more preferably 8 inches/6 or less. [2^3] Photopolymerization Initiator, Thermal Polymerization Initiator The coating film is cured, and the coloring composition of the present invention preferably contains at least one of the photopolymerization initiators. Among them, the method of hardening may be a method other than the method of using the above initiators. In the case where the colored composition of the present invention contains a resin component having an ethylenic double bond or contains an ethylenic compound as an upward-polymerizable monomer, it is preferred to contain a photopolymerization initiation system 97122823 77 200911930 and At least one of the thermal polymerization initiators, the photopolymerization initiation system has a function of directly absorbing light or causing a decomposition reaction or a degassing reaction by photo-sensitization, and generating a polymerization active radical, and the above-mentioned thermal polymerization initiator Polymerization of active radicals is produced by heat. [2-3-1] Photopolymerization initiator The photopolymerization initiator is usually used in the form of a mixture (additional polymerization) of an accelerator or the like. The photopolymerization initiating system has a function of directly absorbing light or causing a photolysis reaction to cause a decomposition reaction or a dehydrogenation reaction, and to generate a function of polymerizing active radicals. Examples of the photopolymerization initiator which is a component of the photopolymerization initiating component include, for example, Japanese Patent Laid-Open No. 59452396, JP-A-61-151197, and the like. Cene) a metallocene compound of the compound; or a hexaaryl derivative of the Japanese Patent Laid-Open No. 10_39503, a methyl allo-reading organism, an N=amine, an N-arylamino acid, an N-arylamine A radical active agent such as a sulfonate, a fluorene-aryl-α-amino acid ester, or an aminoalkyl ketone ketone compound; Japanese Patent Laid-Open No. Hei 2-6_67575, JP-A-2002-323762 An ester-based compound or the like is described in the publication of the Japanese Patent Publication No. 5(J). Specific examples of the photopolymerization initiator which can be used in the present invention are listed below. One kilogram of 2-(4-methoxyphenyl)_4,6-bis(trichloroindenyl)-tri-morphine, one-milk-n-butyl)-4,6-bis(trichloromethyl) , 2_(4_ethoxycyl)-4,6-bis(trioxanemethyl) are all ploughed, 2_(4_ethoxycarbonyl^97122823 78 200911930 base)-indole bis(trichloromethyl) All three talk about the equivalent of the methyl group of the three-speaking derivative; 々2-trichloromethyl-5 — (2, benzophenanthrene, hjm, two, methyl, methyl, 5-[10,000-(2' -benzofuranyl)vinyl]_j,3,4_σ, etc., di-salt, 2-trichloromethyl_5_[wan_(2, (6"-benzene and phoranyl))--1,3 , 4-oxadiazole, 2-trichloromethyl-5-furanyl q,3,4-oxadiazole-specific halomethylated sigma di-salt derivative; 2-«-chlorophenyl)-4 5_diphenylimidazole dimer, 2_(2,-chlorophenyl)-4,5-bis(3,_foxyphenyl)imidazole dimer, 2_(2,_fluorophenyl^-4 '5 - Diphenylimidazole dimer, 2-(2,-methoxyphenyl)-4,5-diphenyl imidazole dimer, (4'-methoxyphenyl)_4, 5_ Imidazole derivatives such as diphenylimidazole dimer; benzoin ether, benzoin phenyl ether, benzoin Anthracene, ether, ether, etc.; ^ 2-methyl hydrazine, 2-ethyl hydrazine, 2-tert-butyl fluorene, buckwheat and other hydrazine derivatives; " diphenyl ketone, Michler, s Ket〇ne, diethylaminodiphenyl ketone, 2-methyldiphenyl ketone, 3-methyldiphenyl ketone, 4-methyldiphenyl ketone, 2 a diphenyl group derivative such as diphenyl ketone, 4 bromodiphenyl ketone or 2 carboxydiphenyl ketone; 2' 2-dimethoxyoxy-2-phenylacetophenone, 2, 2 -diethoxyacetophenone, hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylacetone, hydroxy-1-indolylethyl-(p-isopropylphenyl) ketone,丨_丨_(p-dodecylphenyl) ketone, 2-mercapto-1-[4-(indolyl)phenyl]-2-indolyl propane-dione, M'l-trichloro Phenylethyl ke and other derivatives such as methyl-(p-butylphenyl) ketone; 97122823 79 200911930 0 thioxanthone, 2-ethyl sultonone, isopropyl beta ketoroate, 2- Thiophenone derivatives such as chlorothioxanthone, 2,4-dimercaptothioxanthone, 2,4-diethylthioxanthene, 2,4-diisopropylthioxanthone; p-dimethylamino Ethyl benzoate, a benzoic acid vinegar derivative such as ethyl diethylaminobenzoate; an acridine derivative such as 9-phenyl acridine or 9-(p-methoxyphenyl) acridine; 9, 10-dimethylbenzene And η non-speaking π non-speaking (phenazine) derivatives; benzopyrene S equivalent anthrone derivatives; " dicyclopentadienyl titanium dichloride, dicyclopentadienyl bisphenyl titanium Dicyclopentadienylbis-2,3,4,5,6-pentafluorobenzene-diyltitanium, dicyclopentadienylbis-2,3,5,6-tetrafluorophenyl-1-yl Titanium, dicyclopentadienyl bis-2,4,6-trifluorophenyl-1-yl titanium, dicyclopentadienyl-2,6-difluorophenyl-1-yl titanium, dicyclopentadiene Base-2,4-difluorobenzene-1-yl titanium, dimethylcyclopentadienylbis-2,3,4,5,6-pentafluorobenzene-1_yl titanium, dimercaptocyclopentane Alkenylbis-2,6-difluorophenyl-1-yltitanium, dicyclopentadienyl-2,6-di-fluoro-3-(pyrrole-bufyl)~phenyl-1-yltitanium, etc. Titanocene derivative; 2-mercapto-1-[4-(indolyl)phenyl]_2_indolyl propane-ketone, 2-benzyl-2-didecylamino-1-(4-indole Phenylphenyl)-butanone 2-benzyl- 2-dimethylamino-1-(4-morpholinylphenyl)butane-indole-ketone, ethyl 4-dimethylaminobenzoate, 4 -diamine Isoamyl benzoate, 4-diethylaminoacetophenone, 4-diaminophenylpropiophenone, 1,4-dimethylaminobenzoic acid 2-ethylhexyl ester, 2,5- Bis(4-diethylaminobenzylidene)cyclohexanone, 7-diethylamino _3_(4-diethylaminobenzimidyl)coumarin, 4-(diethylamino)chalcone, etc. "_Aminoalkylphenone compound; 97122823 80 200911930 1 [9-ethyl~6~(2-methylbenzhydryl)-9.Η·-carbazolyl] alkane 1 肟〇~acetic acid An oxime ester compound such as an ester or 1-(4-phenylaminophenylsulfonyl-phenyl)octane-nonanone oxime benzoate. The photopolymerization starting system for a substance is preferably an oxime ester compound which is represented by the following formula (1). ? /Vp/n (I) YC -XQ-p1 [In the formula (1), 'R represents a hydrogen atom, a carbon number of 2 (), a carbon number: 25 an alkenyl group, a carbon number of 3 to 2 The heteroaryl group of hydrazine or the heterogeneous carbon having a carbon number of 4 to 25 may have a substituent. Alternatively, R1 may form a ring with X or . An alkanoyl group having a carbon number of 2 to 20, an olefin group having a carbon number of 3 to 25, a carbon number, a ring (4) group of 8 or more, a aryl group (4) having a carbon number of 7 to 2, and a carbon number of 2 to 1 〇 = milk a aryloxycarbonyl group having a carbon number of 7 to 2 Å, a heteroaryl group having 2 to 2 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms or an alkylaminocarbonyl group having 2 to 2 carbon atoms. These may each have a substituent. # X表 A bivalent aromatic hydrocarbon group and/or an aromatic heterocyclic group in which two or more rings are not condensed by a substituent. γ represents an aromatic group which may have a substituent. The coloring composition for a color filter having a micronized pigment, in particular, a micronized brominated phthalocyanine pigment, is liable to cause extremely small foreign matter. Foreign matter 97122823 81 200911930 is observed after the coloring composition has been produced, and is also produced in the composition. It is clear from the results of the study that the origin of the foreign matter has a particularly close relationship. /, 九汆口 ~ Again, in the color filter, the coloring composition for the light film, the green color sensitivity to the light is the most difficult color. As one of the reasons, it is exemplified that the green pigment has a lower coloring power than the pigment of other colors, and thus the content of the pigment is inevitably high.乂 The maximum penetration wavelength of the green composition is about 53g (10), and the transmittance below 450 (10) is roughly close to 〇. In the use of photolithography: color: the production of light film is usually used as a high-pressure mercury lamp, * eight corresponding photopolymerization start-up, there is also the ability to harden from the ultraviolet part to the light near the sub- (10) The responder, but for green, light energy using a long wavelength portion can be cited. ..., / The sensitivity of the coloring composition is insufficient, and the rule is not obtained. In extreme cases, the hardenability of the coating film is poor, and the phenomenon of coating film is also caused. In addition, the 'color enamel sheet is coated when it is panelized: : 臈 臈', but if the film has low hardenability, it is usually used for: N-methylpyrrolidone (NMp) of Sword, which produces pigment °, In general, it is necessary to obtain a pigment containing micronized particles and a powder of one person. (4) Cyanine pigments and light for exposure; there is === difficult. 'The coloring composition for suppressing the generation of foreign matter, the coloring composition is very suitable: in the pairing agent, the photopolymerization initiator which is composed of the μ compound represented by the above formula (1) is constituted by 9710223 82 200911930 The above problem can be solved, and thus is preferable. In the above-mentioned month-deficient compound (1), Y_c(=〇)_x partially forms a light-absorbing portion 'fat structure portion: -c(-R1)=N-〇R2 portion forms a radical generating portion, > absorbance. YC (-Q)—X efficiently absorbs light and efficiently transfers the absorbed energy to the & structure portion, thereby achieving high sensitivity. In general, the light absorbing portion represented by the YC (-0)-X portion is added to the composition in a high concentration. In the case where the molecules are mutually bonded to each other, a plurality of molecules are formed in the appearance. The movement of a single molecule has a tendency to decrease in absorbance and absorption efficiency. Further, in the veterinary chemical CT article (I)' of the present invention, since the Y portion forms a bulky group, it is preferable because it can have a high absorbance even when it is added at a cerium concentration. Further, it is important that the YC(=〇)-X portion efficiently generates triplet energy for the generation of radicals in the 肟 structure, and in order to achieve efficient intramolecular energy transfer, it is important to make Y_c(= The _)_x portion is spatially as close as possible to the 肟 structure.
以上述通式(1 )所表示之化合物,因Y-C(=0)-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。 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 於與肟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 97122823 83 200911930 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、 窟(ChrySene)環、菲環、奠(咖、» ⑴orene)環 ' f naphthylene)環1 (indene)料由㈣族煙環所 構成之、%合象之基;來自D丫咬環、菲咬(伽細 壤、二苯并“(咖hene)it、㈣環、啡棘、二苯并〕 =(phenothlazine)環、啡啊(phen〇xazine)環、苯 噻哇(benz〇thiaZ〇le)環等由芳香族 構成之縮合環之基等。方曰…與方香族雜環所 該等均可具有任意之取代基。對於 於後加以敍述。 心之取代基」’ 以通式(I )所表示之化合物中,特佳 化:]與其縮合之環χ2所表示的結構之化合二In the compound represented by the above formula (1), since the YC(=0)-X moiety contains a diphenyl ketone structure having a high efficiency from a singlet state to a triplet state, or a structure similar thereto, it is possible to The absorbed light is efficiently converted into triplet energy. Further, the compound represented by the above formula (I) is a compound which is easily attached to the oxime structure by a spatial rotation of a diphenyl ketone structure or a structure similar thereto, and thus can be intramolecular. Perform efficient energy transfer and achieve higher sensitivity. In the formula (I), 'X' represents a group of a divalent aromatic hydrocarbon group and/or an aromatic heterocyclic group which may have a substituent and is condensed by two or more rings 97122823 83 200911930. Specific examples of X include, for example, a naphthalene ring, an anthracene ring, a ChrySene ring, a phenanthrene ring, a kiln, a (1) orene ring, and a ring of an indene. The base of the % conformation formed by the ring; from the D bite ring, the phenanthrene bite (gamma, dibenzo" (cahene), (four) ring, brown spine, dibenzo] = (phenothlazine) ring, a condensate ring composed of an aromatic group such as a phen〇xazine ring or a benz〇thiaZ〇le ring, etc., such as a aryl group and a fragrant heterocyclic ring, which may have any substitution. The following is a description of the structure of the compound represented by the formula (I), and the combination of the structure represented by the ring condensed with the ring 2
R2Ρ1 ο/ f NHC =中mY,與上述通式(I) 義相同。環γ2主的R R及 衣X表不與苯環縮合之 η 由2個以上搜邮姓丄 衣 了為早玉展 上衣所構成之縮合環。 X1之任一位詈。 核X可縮合 置本裱)(及與其縮合之 2 代基。] 〜娘X,進而可 97122823 84 200911930 以通式(1 )所表示之化合物,因苯環χ1可與— 一同形成二苯基酮結構或與其類似之結 高作:且自單重態至三重態的激發效率較高,因::較 作為通式⑴中之X’較佳為含有芳相雜環之Α 佳為於通式⑴中與苯環广縮合之環乂2為雜環 ’ 又’X通常為來自2〜4縮合環之2價基,就分子量變 =相對較小之方面而言,較佳為來自2或3縮合環之以賈 基’就容易適合組成物光硬化中所使用照射光之波長 面而3 ’更佳為來自3縮合環之2價基。 作為通式⑴中之X、以及於通式⑴中由苯Μ及環 所形成之結構,特佳為來自啼唾環之基。在X為來自咔 唑基之基的情形下,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。 :通式(I )中,R1表示氫原子、碳數卜2〇之燒基、碳 *〜25之烯基、碳數3〜2〇之雜芳基或者碳數4〜託之 雜芳院基’ β亥等烧基、烯基、雜芳基、雜芳烧基均可且有 取代基。藉由使R!成為此種基,與R1為苯基等之化ς物 相比’對光之敏感度變高。又,化合物之合成亦容易,因 此就工業生產之觀點而言亦較佳。 作為Rl之碳數1〜20之烧基,可舉出曱基、乙基、丙基、 丁基等’較佳為碳數卜^之烧基,更 烷基。 < 々作為R1之碳數2〜25之烯基,可舉出乙烯基、丙烯基 等車乂佳為丙烯基等石炭數3〜12之烯基,更佳為碳數2〜 97122823 85 200911930 5之婦基。 作為R1之礙數3〜20之雜芳基,可舉出:亞琉醯基、吱 喃基、㈣基、苯并㈣基、苯并科基等,較佳為碳數 3 15、更佳為碳數4〜1〇之雜芳基。 作為R1之碳數4〜25之雜芳烷基,可舉出:亞硫醯基曱 基、吱喃甲基"米唾基甲基、苯并嗟唾基甲基、苯并命坐 基甲基等’較佳為碳數4〜18、更佳為碳數4〜1()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 敍述。 作為R1,特佳為可具有取代基之烷基。其中,就製造的 谷易性方面而言,較佳為無取代之烧基。又,在如後述般 將以通式⑴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 取代胺基所取代之以,最佳乂醯基+乙酿氧基 胺基所取代之烷基。 於通式(I )中,R2表示碳數2〜2〇之烧醯基、碳數3〜 25之烯_、碳數4〜8之環紐基、碳數7〜2q之芳酿 基、碳數2〜10之烧氧幾基、碳數7〜20之芳氧幾基、碳 數2〜20之雜芳基、碳數3〜2〇之雜芳醯基、碳數2〜2〇 之烧基胺錢基,料㈣基、烯醯基、環㈣基、芳酿 基、烧㈣基、芳氧幾基、雜芳基、雜芳醯基、院基胺基 碳基均可具有取代基。藉由使R2成為此種基,*易於使月亏 部開裂’從而易於箱;^ 士 # &丄# 勿歹'm仔由於自由基之產生所導致之敏感度 97122823 86 200911930 的提昇。 作為R2之碳數2〜2G之㈣基,可舉出:乙醯基、丙酿 較佳為乙祕等碳數2〜12、更佳㈣ 作為R2之碳數3〜25之烯醯基,可 醯其笪,牛出丁烯醯基、丙烯 之:—基等碳數3〜12、更佳為碳… 甲碳其數4〜8之環炫酿基’可舉出環己基幾基、 r 土衣己基斂基、環戊基羰基等 數4〜8、更佳為俨把,7 佳為缞己基叛基寺碳 更佳為奴數4〜7之環烷醯基。 苯=之碳數7〜2〇之芳醢基,可舉出苯甲醯基、甲基 基、奈f醢基等’較佳為萘甲酿基等碳數7〜Μ、 更佳為奴數7〜1〇之芳醯基。 π炭數2〜10之炫氧幾基’可舉出甲氧幾基、乙 乳板基、丙氧㈣等,較佳以氧幾基等碳數2〜10 佳為碳數2〜8之烧氧羰基。 之,數7〜20之芳氧羰基,可舉出苯氧幾基、對 土 =基、萘氧幾基等,較佳為萘氧幾基等碳數7〜 15、更佳為碳數7〜1〇之芳氧羰基。 作為f之碳數2〜2。之雜芳基,可舉出噻吩基…比咯 暴、11比σ定基等,較佳為嗟吩某犛被赵9 2〜7之雜芳基。 "基專奴數2〜12、更佳為石炭數 :广碳數3〜2。之雜芳醯基,可舉出嗔吩幾基、吼 叛基、ϋ比㈣基等’較佳為嗟吩幾基等碳數5〜15、更 97122823 87 200911930 佳為碳數7〜10之雜芳醯基。 作為R2之碳數2〜20之烷基胺基羰基,可舉出咮啉基羰 基、二甲胺基羰基、曱胺基羰基等,較佳為二甲胺基羰基 等碳數2〜12、更佳為碳數2〜1〇之烷基胺基羰基。 上述各基中,就曝光敏感度方面而言,作為R2,較佳為 烷醯基、環烷醯基、芳醯基,更佳為烷醯基、芳醯基。 、再者,對作為R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(I)中,Y表示可具有取代基之芳香族基,更詳 =而έ,Y係來自芳香族烴環或芳香族雜環之丨價基,該 等均可具有取代基。再者,在γ為來自芳香族雜環之i價 基的It形下,可為i個以上之環縮合於苯基上而成之基, 亦可為1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 υ本基或芳香族雜環之部分與χ之一部分經由—基, 而形成二苯基鲖結構或與其類似之結構,因而較佳。 如上述叙,以通式(I )所表示之化合物,係二苯基 酮、口構或與其類似之結構#由分子内之空間性旋轉而容 易於與將結構部發生重叠之化合物,因此可在分 有放率的月b里轉移,並可達成更高的敏感度,因此較好。 在^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, 3一 位、3, 4-位及4, 5-位中所選擇的至少】處而成之2〜4縮 97122823 88 200911930 合環之基。又,縮合於y ^ 或者芳香族烴環及^苯基上之環,較佳為烴環, 面而言,縮合於香其族雜環。就量子產率較高之方 光波長範圍變寬之方面而二上之%較佳為烴環,又,就吸 作為Y之環,較佳為單^較佳為若香族環。 不變得過大之方面而言,二S3合環基,就分子量 特佳為單環及2縮合環基。再者,:二3縮合環基’ 環之基的情形ηΓ,吸# # Υ為來自3〜4縮合 廉價之光源,發生較長波長化,亦適應 作為Y之環的具體例,可舉 環、蒽環、窟環、菲产、1 來自苯環之基;來自萘 合環以上 & 、裱、第環、苊環、茚環等2縮 口%以上之芳香族烴環之其 命坐美、心m 吩基…比咬基"夫喃基、 白土 — ▲、以自5或6員芳香族雜環之基;或者來 ^丫 =、㈣環、二苯并“環K環、啡畊環、二 二抑井環、苯并嗟唾環、苯并令坐環等由芳香 夫、裱V、芳香族雜環所構成的縮合環之基。 作為γ之環基’特佳為苯基、萘基、嗟吩基"夫喃基及 2吡°疋基,就敏感度之方面而言,最佳為苯基、萘基及噢 吩基。 土 作為上述γ中之環基可具有之取代基,例如可舉出:甲 基、乙基、丙基等碳數丨〜別之烷基;甲硫基、乙硫基等 碳數1〜20之烷硫基;w_s〇3R(其中,R為曱基、乙基等 石反數1〜20之烷基)所表示之磺酸烷基酯基;戊氧基、己 氧基等碳數5〜20之烷氧基;環戊基、環己基等碳數5〜 97122823 89 200911930 2/之環烷基,·環戊氧基、環己氧基等碳數5〜2〇之環烧 氧基;咮啉基、哌啶基、吡咯啶基等原子數5〜2〇之環狀 胺基;二異丙胺基、二第三丁基胺基等碳數4〜2〇之二烷 基胺基;苯基、萘基等芳基;比啶基等雜芳基;苄基、苯 乙基等芳烷基;Cl、Br、I、F #鹵素原子;氧化四氫噻 吩基等。 該等之中,較佳為烧基、燒氧基、_S(hR、環狀胺基或 者一烷基胺基,就進一步提昇敏感度方面而言,特佬為環 狀胺基或二烧基胺基。 以通式(I )所表示之化合物中的特佳形態、即χ係來自 可具有取代基之咔唑環之基的化合物,係例如以下述通式 (BI )來表示。 [化 21]R2Ρ1 ο/ f NHC = medium mY, which is the same as the above formula (I). The R R of the ring γ2 main and the η which is not condensed with the benzene ring by the benzene ring are condensed by the two or more stencils. Any one of X1 is 詈. The nucleus X can be condensed and condensed (and the 2 aryl group condensed therewith). ~ Niang X, and further 97122823 84 200911930 The compound represented by the formula (1), because the benzene ring oxime 1 can form a diphenyl group together with The ketone structure or a similar structure is high: and the excitation efficiency from the singlet to the triplet is higher because: as the X' in the general formula (1), it is preferred to contain an aromatic heterocyclic ring. (1) The cyclic oxime 2 which is condensed with the benzene ring is a heterocyclic ring. The 'X' is usually a divalent group derived from a 2 to 4 condensed ring, and is preferably from 2 or 3 in terms of molecular weight change = relatively small. The condensed ring of Jaki' is easily adapted to the wavelength surface of the irradiation light used in the photohardening of the composition, and 3' is preferably a divalent group derived from the 3 condensed ring. As X in the formula (1), and in the formula (1) The structure formed by benzoquinone and a ring is particularly preferably a group derived from a sulfhydryl ring. In the case where X is a group derived from a carbazolyl group, it has not only the suitability for irradiation light at the time of exposure but also a strong skeleton. Therefore, in the formula (I), R1 represents a hydrogen atom, a carbon number of 2, an alkyl group of carbon * 25, A heteroaryl group having a number of 3 to 2 Å or a heterocyclic group of a carbon number of 4 to Torr can be substituted with an alkyl group, an alkenyl group, a heteroaryl group or a heteroaryl group. When it is such a base, it is more sensitive to light than a chemical compound in which R1 is a phenyl group, etc. Further, the synthesis of the compound is also easy, and therefore it is also preferable from the viewpoint of industrial production. Examples of the alkyl group of 1 to 20 include a mercapto group, an ethyl group, a propyl group, a butyl group, etc., which are preferably a carbon number, and a more alkyl group. < 々 as a carbon number of R1 2 to 25 Examples of the alkenyl group include a vinyl group, a propylene group, and the like, and an alkenyl group having a charcoal number of 3 to 12, such as a propylene group, and more preferably a carbon number of 2 to 97122823 85 200911930. Examples of the heteroaryl group of -20 include an anthracene group, a fluorenyl group, a (tetra) group, a benzo(tetra)yl group, a benzoacyl group, etc., preferably a carbon number of 3 15, more preferably a carbon number of 4 to 1. A heteroaryl group having 4 to 25 carbon atoms of R1, and examples thereof include a sulfinyl fluorenyl group, a fluorenylmethyl group, a benzyl group, a benzoxylmethyl group. , benzophenanylmethyl, etc. 'preferably carbon number 4~18 More preferably, it is a heterocyclic alkyl group having a carbon number of 4 to 1 (1). Further, each of the above groups may have a substituent. The substitution is described later. As R1, an alkyl group which may have a substituent is particularly preferred. In terms of the ease of production, it is preferably an unsubstituted calcining base. Further, in the case where a compound represented by the general formula (1) is used for a photopolymerizable composition as described later, From the viewpoint of the adhesion of the substrate, an alkyl group substituted with a substituted sulfhydryl group and an amino group substituted with an amine group is preferred. In the formula (I), R2 represents a decyl group having 2 to 2 carbon atoms, a olefin having 3 to 25 carbon atoms, a cyclononyl group having 4 to 8 carbon atoms, an aromatic aryl group having a carbon number of 7 to 2 q, and an aerobic group having a carbon number of 2 to 10. , an aryloxy group having a carbon number of 7 to 20, a heteroaryl group having a carbon number of 2 to 20, a heteroaryl fluorenyl group having a carbon number of 3 to 2 fluorene, an alkyl group having a carbon number of 2 to 2 fluorene, and a (4) group. The olefin group, the cyclo(tetra) group, the aryl group, the pyridyl group, the aryloxy group, the heteroaryl group, the heteroaryl fluorenyl group, and the anthranyl group-based carbon group may each have a substituent. By making R2 such a base, * is easy to crack the moon's deficiencies' and thus easy to box; ^ # ########################################################################### The (tetra) group having a carbon number of 2 to 2 G of R 2 may, for example, be an ethyl fluorenyl group or a propylene group having a carbon number of 2 to 12, more preferably (4) a carbon number of 3 to 25 as R 2 . It can be smashed, the beesulene-based, propylene:-based carbon number 3~12, more preferably carbon... The carbon ring number 4~8 ring bristles can be cited as cyclohexyl groups, r 衣 己 敛 base, cyclopentyl carbonyl, etc. 4~8, more preferably 俨, 7 缞 缞 基 叛 叛 叛 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺Benzene = a fluorenyl group having a carbon number of 7 to 2 Å, and examples thereof include a benzamidine group, a methyl group, a naphthyl group, etc., preferably a carbon number of 7 to Μ, more preferably a slave. Number 7 ~ 1 〇 醯 醯 。. The oxy-oxyl group of π carbon number 2 to 10 may be exemplified by a methoxy group, an ethyl silicate group, a propoxy group (tetra) or the like, and preferably a carbon number of 2 to 10 such as an oxygen group is preferably a carbon number of 2 to 8. Burning oxygen carbonyl. The aryloxycarbonyl group having a number of 7 to 20 may, for example, be a phenoxy group, a tertino group, a naphthyloxy group or the like, preferably a naphthooxy group or the like having a carbon number of 7 to 15, more preferably a carbon number of 7 ~1〇 of the aryloxycarbonyl group. The carbon number of f is 2 to 2. The heteroaryl group may, for example, be a thiophene group, a thief group, an eleventh sigma group or the like, and preferably a heteroaryl group of a porphin. "Based slave number 2~12, more preferably Carboniferous number: Wide carbon number 3~2. Examples of the heteroaryl group include a porphinyl group, a ruthenium group, a ruthenium group (tetra) group, etc., preferably a porphinyl group, such as a carbon number of 5 to 15, a further 97,712,823, 87, 2009,119,30, preferably a carbon number of 7 to 10 Heteroaryl group. The alkylaminocarbonyl group having 2 to 20 carbon atoms of R2 may, for example, be a porphyrinylcarbonyl group, a dimethylaminocarbonyl group or a decylaminocarbonyl group, and preferably a carbon number of 2 to 12 such as a dimethylaminocarbonyl group. More preferably, it is an alkylaminocarbonyl group having a carbon number of 2 to 1 fluorene. In the above respective groups, in terms of exposure sensitivity, R2 is preferably an alkano group, a cycloalkyl group or an aryl group, and more preferably an alkyl group or an aryl group. Further, the substitution of each of the above-mentioned groups as R is described later, and as the above-mentioned respective groups, it is particularly preferred that the substituents are not substituted. In the formula (I), Y represents an aromatic group which may have a substituent, and more specifically, and Y is derived from an aromatic hydrocarbon ring or an aromatic valence group of an aromatic heterocyclic ring, and these may have a substituent. Further, in the It form in which γ is an i-valent group derived from an aromatic heterocyclic ring, one or more rings may be condensed on the phenyl group, or one or more rings may be condensed to 5 or 6 The base of the heteroaryl group of the ring. The compound represented by the formula (I) is as described above, and a part of the fluorenyl or aromatic heterocyclic ring which γ has, and a part of the fluorene, form a diphenyl fluorene structure or the like by a group. Structure is therefore preferred. As described above, the compound represented by the formula (I), which is a diphenyl ketone, a mouth structure or a structure similar thereto, is easily sterically rotated in the molecule to be a compound which overlaps with the structure portion. It is better to transfer in the month b with the rate of release, and to achieve higher sensitivity. In the case where one or more rings are condensed to a phenyl group to form a condensed ring group, it is preferred that condensed from 1 to 3 of 5 or 6 membered rings to 2, 3, and 3 from the phenyl group. 4-bit and 4, 5-bit selected at least] 2~4 contracted 97102923 88 200911930 The base of the ring. Further, a ring condensed on the y ^ or aromatic hydrocarbon ring and the phenyl group is preferably a hydrocarbon ring, and is condensed to the alicyclic heterocyclic ring. The % of the light having a higher quantum yield is preferably a hydrocarbon ring, and is preferably a ring of Y, preferably a single ring. Insofar as it does not become too large, the two S3 ring-bonding groups are particularly preferably a monocyclic ring and a condensed ring group. Further, in the case of the base of the condensed ring group of the two condensed ring groups, η Γ, 吸## Υ is a light source which is condensed from 3 to 4, and is longer in wavelength, and is also suitable as a specific example of the ring of Y. , anthracene ring, cave ring, phenanthrene, 1 from the benzene ring; from the naphthalene ring above & 裱, 第, ring, 苊 ring, 茚 ring and other 2% of the aromatic hydrocarbon ring Beauty, heart m phenyl group... than bite base " fumonyl, clay- ▲, from 5 or 6 members of the aromatic heterocyclic ring; or ^ ^ =, (tetra) ring, dibenzo "ring K ring, a condensed ring composed of a fragrant ring, a fluorene ring, a benzo ring, a benzo ring, a benzo ring, or an aromatic heterocyclic ring, such as a cyclin ring, a benzo ring, and a ring. Phenyl, naphthyl, anthracenyl "fumyl and 2pyridinyl, and in terms of sensitivity, most preferred are phenyl, naphthyl and anthracenyl. Examples of the substituent which may be contained include a methyl group, an ethyl group, a propyl group, and the like, and an alkyl group having a carbon number of 1 to 20 such as a methylthio group or an ethylthio group; w_s〇3R; (where R is a thiol group a sulfonic acid alkyl ester group represented by an alkyl group such as an alkyl group having an inverse number of 1 to 20; a pentyloxy group such as a pentyloxy group or a hexyloxy group; a carbon number of 5 to 20; a carbon number such as a cyclopentyl group or a cyclohexyl group; 5~ 97122823 89 200911930 2/cycloalkyl, cyclopentyloxy, cyclohexyloxy and the like 5 to 2 ring of alkoxy groups; porphyrin group, piperidinyl group, pyrrolidinyl group and other atomic number 5 a cyclic amino group of ~2〇; a dialkylamino group having a carbon number of 4 to 2? such as a diisopropylamino group or a di-tert-butylamino group; an aryl group such as a phenyl group or a naphthyl group; An aralkyl group such as a benzyl group or a phenethyl group; a halogen atom such as a Cl, a Br, an I or a F group; a tetrahydrothiophenyl group; and the like. Among these, a pyridyl group, an alkoxy group, and a _S (hR, The cyclic amine group or the monoalkylamine group is particularly preferably a cyclic amine group or a dialkylamino group in terms of further improving sensitivity. A particularly preferred form of the compound represented by the formula (I), That is, a compound derived from a group of a carbazole ring which may have a substituent, for example, is represented by the following formula (BI).
RB R7 …w [式中U及Y與上述通式⑴中之Rm之含義 相同° R〜R分別獨立表示氫原子、或者自後述取代基群 Z中所選擇之基。]RB R7 ... w [wherein U and Y have the same meanings as Rm in the above formula (1). R to R each independently represent a hydrogen atom or a group selected from the substituent group Z described later. ]
作為上述通式(I)中之目士 k s L ’ λ可具有的取代基(通式(i)中 之苯環X1及與其縮合之Jf Υ2_τθι 、耶σ < % χ可具有的取代基)、通式 及κ可具有的取代基、以及通 97122823 200911930 式(m)中之r3〜r9 所選擇之基。 分別獨立可舉出自以下取代基群z中 [取代基群z] 〜可舉出.氟原子、氯原子、溴原子、碘原子等鹵素原子; I二基,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、 異丙基、正丁基、異丁基、第三丁基、戊基、第三戊基、 正己基正庚基、正辛基、第三辛基等碳數丨〜18之直鏈 或支鍵烧基;環丙基、環丁基、環戊基、環己基、金剛烧 基等碳數3〜18之環燒基,·乙烯基、丙婦基、己烯基等碳 數2 18之直鏈或者支鏈烯基;環戊埽基、環己烯基等碳 數3〜18之環烯基;甲氧基、乙氧基、正丙氧基、異丙氧 基、,丁氧基、第二丁氧基、第三丁氧基、正戊氧基、第 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、 ,戊硫基、第三戊硫基、正己硫基、正庚硫基、正辛硫基、 ^三辛硫基等碳數卜^之直鏈或支鏈烧硫L苯基、甲 苯基、二甲苯基、均三甲苯基等可經碳數6〜18之烷基取 代之芳基基、苯乙基等碳數7〜18之芳烧基;乙稀氧 基、丙烯氧基、己烯氧基等碳數2〜18之直鏈或支鏈稀氧 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;以-C〇R17所表示之醯基;羧基;以_〇c⑽“ 所表示之醯氧基;以-服1¾2。所表示之胺基;以— 97122823 91 200911930 所表示之醯胺基;以-nhcoor22所表示之胺曱酸酯基;以 -conr23r24所表示之胺曱醯基;u_c〇〇R25所表示之羧酸酯 基,以-S〇3NR26R27所表示之胺磺醯基;以_s〇3R28所表示之 磺酸酯基;2-噻吩基、2-吡啶基、呋喃基、噚唑基、苯并 唑基、噻唑基、苯并噻唑基、咮啉基、吡咯啶基、二氧 化四氫噻吩基等飽和或不飽和之芳香族雜環基;三曱基矽 烷基等三烷基矽烷基等。 土 再者,上述R17〜R28分別獨立表示氫原子、可經取代之 燒基、可經取代之烧醯可經取代之垸絲氧基、可經 取=之烯基、可經取代之芳基、或者可經取代之芳燒基二 该等之位置㈣並無特別限定,在具有複數 形下,取代基可相同亦可不同。 乂土的馆 ’複數個取代基可彼此鍵結形成環,所形成之 々可為飽和或不飽和之料族煙環或者芳香族雜環,環上 可進—步具有各取代基,取代基進而可形成環。 i 代^Γ)中’A9分別獨立為氫原子或者自上述取 選擇者’取代基群〇,較佳可舉出:可具 A之If、乙基等碳數1〜2°之烷基,可具有取代 土之本基寺石反數6〜2〇之芳 碳數3〜2〇之雜芳基,可;有取代基之^定基等 基,可且;碳數7〜18之芳烧 有取代基之三㈣錢基;特佳為燒基。 二;It式⑴中…具有之取代細式 佳者合的環χ2可具有之取代基)之較 〜、作為上述Κ3〜Κ9之較佳者相同。 97122823 92 200911930 作為R1可具有之取代基,較佳為以-NRl9R2()所表示之胺 基及芳基,作為R19及R2(),較佳為可經取代之烷醯基、可 經取代之烷基羰氧基。如前所述,因對組成物之密著性提 昇亦較有效’故特佳為N-乙醯基乙酿氧基胺基等以 -NR19R2°所表示之胺基。 本發明之以通式(I )所表示之化合物中,最佳為以下述 通式(Π )所表示之化合物。 [化 22] /OR2a Ο N 川、The substituent which the ketone ks L ' λ in the above formula (I) may have (the benzene ring X1 in the formula (i) and the condensed Jf Υ2_τθι, 耶σ < % χ may have a substituent) And a substituent which the formula and k may have, and a group selected by r3 to r9 in the formula (119) of the formula 9792823. Each of the substituent groups z in the following substituent group z may be a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a di-, nitro group, a cyano group, or an arbitrary Organic base and the like. Examples of the optional organic group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, third pentyl group, and n-hexyl-g-heptane. a straight or branched bond group having a carbon number of 丨18 or the like; a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group or the like having a carbon number of 3 to 18; a cyclic or branched alkenyl group having a carbon number of 2 18 such as a cycloalkyl group, a vinyl group, a propyl group or a hexenyl group; a cycloalkenyl group having 3 to 18 carbon atoms such as a cyclopentyl group or a cyclohexenyl group; Oxy, ethoxy, n-propoxy, isopropoxy, butoxy, second butoxy, tert-butoxy, n-pentyloxy, decyl, n-hexyloxy, n-heptyloxy a straight or branched alkoxy group having a carbon number of 1 to 18, such as a n-octyloxy group or a third octyloxy group; a thiol group, an ethylthio group, a n-propylthio group, an isopropylthio group, an n-butylthio group, a linear chain of carbon atoms such as a second butylthio group, a third butylthio group, a pentylthio group, a third pentylthio group, a n-hexylthio group, an n-heptylthio group, a n-octylthio group, a trioctylthio group, and the like Or branched-chain sulfur-burning L-phenyl, tolyl, xylyl, mesitylene, etc. a aryl group substituted with an alkyl group having 6 to 18 carbon atoms, an aryl group having 7 to 18 carbon atoms such as a phenethyl group; a linear chain having 2 to 18 carbon atoms such as an ethyleneoxy group, a propyleneoxy group or a hexenyloxy group; Or a branched diloxy group; a linear or branched alkenethio group having a carbon number of 2 to 18 such as an ethylenethio group, an acrylthio group or a hexenylthio group; a fluorenyl group represented by -C〇R17; a carboxyl group; 〇c(10)" represents a methoxy group; an amine group represented by -1⁄42.; an amidino group represented by -97122823 91 200911930; an amine phthalate group represented by -nhcoor22; represented by -conr23r24 Amine group; a carboxylate group represented by u_c〇〇R25, an amidoxime group represented by -S〇3NR26R27; a sulfonate group represented by _s〇3R28; 2-thienyl, 2 a saturated or unsaturated aromatic heterocyclic group such as pyridyl, furyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, porphyrinyl, pyrrolidinyl or tetrahydrothiophenyl; Further, the above-mentioned R17 to R28 each independently represent a hydrogen atom, a substitutable alkyl group, and a substituted calcined ruthenium which may be substituted. The position (4) of the oxy group, the alkenyl group which may be substituted, the aryl group which may be substituted, or the aryl group which may be substituted is not particularly limited, and in the plural form, the substituents may be the same or different. The plurality of substituents of the bauxite museum may be bonded to each other to form a ring, and the formed ruthenium may be a saturated or unsaturated group of tobacco rings or aromatic heterocyclic rings, and the ring may further have various substituents instead. The base may further form a ring. In the case of "i", "A9 is independently a hydrogen atom or a substituent of the above-mentioned substituents", preferably a carbon number of 1 such as If, an ethyl group, etc. The alkyl group of 2° may have a heteroaryl group having an aryl carbon number of 3 to 2 fluorene of 6~2〇, which may be substituted with a base of the earth, and may have a base such as a substituent, and may have a carbon number of 7 ~18 of the aromatic burned with a substituent of three (four) money base; especially good for the base. 2; It is the same as the preferred one of the above-mentioned Κ3 to Κ9 in the formula (1) which has the substitution ratio of the preferred ring. 97122823 92 200911930, as a substituent which R1 may have, preferably an amine group and an aryl group represented by -NRl9R2(), as R19 and R2(), preferably a substituted alkane group, which may be substituted Alkylcarbonyloxy. As described above, it is also effective to improve the adhesion of the composition. Therefore, it is preferably an amine group represented by -NR19R2° such as an N-acetyl group ethoxylated amine group. Among the compounds represented by the formula (I) of the present invention, the compound represented by the following formula (Π) is most preferred. [化22] /OR2a Ο N Chuan,
Ya—C—Xa~C—R1^ 式中,广表示碳數1〜3之烷基、或者以下述式(jja)所表 示之基。 [化 23] ch (Ha) R101〆 \r102 (式中,R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。) 反23表示碳數2〜4之烷醯基,r表示氮原子可經碳數1 〜4之炫基取代的2料絲。Γ表示可經㈣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醋系化 97122823 93 200911930 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。 [化 24]In the formula, the formula represents a group having a carbon number of 1 to 3 or a group represented by the following formula (jja). Ch (Ha) R101〆\r102 (wherein R and R1()2 each independently represent a hydrogen atom, a phenyl group or an N-ethenyl-N-acetoxyamino group.) A 2 to 4 alkyl alkane group, and r represents a 2-filament in which a nitrogen atom can be substituted with a condensed group having 1 to 4 carbon atoms. Γ represents a phenyl group which may be substituted by (iv) or a naphthyl group which may be substituted with a porphyrin group. The following is a exemplified embodiment of the best vinegar-based saponin 97122823 93 200911930 as the photopolymerization initiator of the present invention, 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. [Chem. 24]
97122823 94 200911930 [化 25]97122823 94 200911930 [Chem. 25]
97122823 95 200911930 [化 26]97122823 95 200911930 [Chem. 26]
97122823 96 200911930 [化 27]97122823 96 200911930 [Chem. 27]
97122823 97 200911930 [化 28]97122823 97 200911930 [Chem. 28]
97122823 98 200911930 [化 29]97122823 98 200911930 [Chem. 29]
0 翫公報、w〇2〇〇5/〇8〇337 號公 利特開2006-36750號公報等中記載之方法而合日本專 以上述通式⑴所表示之㈣系化合物,可^獨使用^ ,亦可併用2種以上。又,亦可將該等心旨系化 光聚合起始劑併用,視情況可藉由併用㈣待高敏 :為構成光聚合起始系成分之加速劑,例 ’N-一曱胺基苯甲酸乙g旨等N,N—二燒基胺 酿,2-疏基笨并嗔峻、2_#基苯并制 ^ :酉文烧基 化合物或者脂肪族多官能毓基化合物等。一雜環之巯基 該等其他光聚合起始劑或加速劑,可 π 種,亦可將2種以上混合❹。 ”】早獨使用1 97122823 99 200911930 ^考慮到化σ物所產生之自由基的種類,則較佳為併用 複數種光聚合起始劍,例如可舉出:以上述通式⑴所表 示之·旨系化合物與苯乙崎生物、^胺基炫基苯两系 化合物、或者噻噸酮衍生物之組合。在此情形下,作為苯 :酮,生物,例如較佳為2—甲基_卜[4_(甲硫基)苯 土]-2:咪啉基丙烷+酮;作為胺基烷基苯酮系化合 $,^义其佳為2-二曱胺基一 2_(4-甲基一节基)_卜(4 一味琳+ ::本基)丁烷+酮、"基I二甲胺基+(4-咮啉基苯 基)丁酮-1,作為噻噸酮衍生物,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 劑之合計量),係在本發明_光片用著色組成 物的、形分中,通常為G1〜4G重量%,較佳為〇卜 3〇重量%。若該調配比例顯著地低,則會導致對曝光光線 之破感度下降’反之㈣調配比例顯著地高,則未曝光部 分對顯影液之溶解性下降,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:曰本專利特開平[221 958號公報、特 開平4-21 9756 $公報中記載之二笨并α底喃色f,日本專 =特開平W襲3號公報、特时5 —289咖號公報中記 載之具有雜環之香豆素色素,日本專利特開平3_2397〇3 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 —丨924〇號公 97122823 100 200911930 報中記載之対亞甲基(pyrr〇methene)色素;其他可兴 出:日本專利特開日召47_2528號公報、特開昭⑹牛 號公報、特公昭45—37377號公報、特開昭48_84183號八 報、特開昭52-1 12681號公報、特開昭58_155〇3號公 特開昭60-88005號公報、特開昭59_564〇3號公報、 平2-69號公報、特開昭57—168〇88號公報、特開^ 5-1〇7761號公報、特開平5_21〇24〇號公報、特開平 4/288818號公報中記載之具有二烷基胺基苯骨架之色素 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, 4,一二乙胺基二苯基酮、 2-胺基二苯基酮、4-胺基二苯基酮、4, 4,_二胺基二苯基 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-(對二甲胺基苯基)苯并σ号唑、2_(對二 乙胺基苯基)苯并噚唑、2-(對二曱胺基苯基)苯并[4, 5]苯 并哼唑、2-(對二甲胺基笨基)苯并[6,7]苯并D号唑、2,5_ 雙(對二乙胺基苯基)1,3, 4-°号嗤、2-(對二曱胺基苯基)苯 并噻唑、2-(對二乙胺基苯基)笨并噻唑、2_(對二甲胺基 苯基)苯并咪唑、2-(對二乙胺基苯基)苯并咪唑、2, 5_雙 (對二乙胺基苯基)1,3, 4-噻二唑、(對二曱胺基笨基)„比 啶、(對二乙胺基苯基)α比啶、(對二曱胺基苯基)喹琳、(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笨基之化合物等。該等 97122823 101 200911930 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〇重量%以上,較佳為〇 2重 里%以上,更佳為〇 5重量%以上,又,通常為2〇重量% 以下,較佳為15重量%以下,更佳為丨〇重量%以下之範圍。 [2-3-2]熱聚合起始劑 作為本發明著色组成物中可含有之熱聚合起始劑之具 f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, 2,一 偶氮雙(2一甲基丁腈)、M,-偶氮雙(環己烯-1-甲腈)、 2’2/-偶氮雙(2’4一二曱基戊腈)、1一[(1-氰基_1_曱基乙基 偶氮]曱醯胺(2 —(胺曱醯基偶氮)異丁腈)、2, 2-偶氮雙{2- 甲基N-[l,i-雙(羥曱基)一2_羥乙基]丙醯胺}、2,2,一偶氮 雙[N-(2-丙烯基)_2_曱基丙酿胺]、2,2,_偶氮雙 丙稀基)-2-乙基丙醯胺]、2, 2, _偶氮雙[N_丁基_2_甲基丙 ㈣卜2’2’-偶氮雙(N_環己基_2_甲基丙酸胺)、2,2,_ 偶氮雙(二甲基―2-曱基丙酿胺)、2,2,-偶氮雙(二甲基_2_ 甲基丙酉夂酯)、2, 2’-偶氮雙(2, 4, 4-三曱基戊烯)等,該等 之中車父佳為2,2’—偶氮雙異丁猜、2, 2’-偶氮雙(2, 4-二甲 基戊腈)等。 一 τ 作為有機過氧化物,可舉出:過氧化苯甲醯、過氧化二 97122823 102 200911930 第一丁基、過氧化氯異丙苯 化二異丁酿、過氧化新癸T心:舉出:過氧 per〇xyne〇decan〇ate)、過山異丙本酯(Cumyl 二碳酸二異丙醋、過氧化二碳酸酸二正丙醋、過氧化 酸-1,U,3-四甲基丁醋 :::丁_、過氧化新癸 己基)醋、過氧化新癸酸+環己^酉夂二(4-第三丁基環 二碳酸二(2_乙氧基乙基)醋、過:化二甲上乙醋、過氧化 基)酯、過氧化新癸酸第三一反S夂一(2_乙基已 丁酯、過氧化新癸酸第-曰、、D乳化二石炭酸二甲氧基 過氧化特戊酸第 過虱化一正辛醯、過氧化二 土 ' 氧化2-乙基己酸_113卩^ —化二硬㈣、過 _(2 r其户航 J,3,3 —四甲基丁酯、2,5-二甲基-2,5_ 乙基己醯過氧基)己炫、過氧化2_ =過氧化專甲基苯甲酿)、過氧化2_乙基己酸^ -曰、輕化二苯甲酿、過氧化異丁酸第三丁醋、以― :第二丁基過氧基基環己院、丨,卜二(第三己基過 =,,基環己院、α二(第三己基過氧基) 衣兀_ ’ (第三丁基過氧基)環己烷、2, 2-二(4 4- =(一第三丁基過氧基)環己基)丙烧、過氧化異丙基單碳酸 己酉曰過氧化馬來酸第三丁醋、過氧化3, 5, 5 —三甲 基己酸第三J酯、過氧化月桂酸第三丁酯、2,5_二甲基 =,5-二(過氧化3_甲基苯曱醯基)己烷、過氧化異丙基單 ,酉文第一丁 Sa過氧化2-乙基己基單碳酸第三丁酯、過 乳化苯甲酸第三己酉旨、2, 5_二甲基_2, 5_二(苯甲醯過氧基) 97122823 103 200911930( 翫 、 、 、 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 2006 Two or more types may be used in combination. Further, these intentional photopolymerization initiators may be used in combination, and may be used in combination by (4) high sensitivity: an accelerator which constitutes a photopolymerization initiator component, for example, 'N-monoamidobenzoic acid B is intended to be N, N-dialkylamine, 2-succinyl and benzoic, 2_# benzoic acid: 酉 烧 烧 化合物 or aliphatic polyfunctional sulfhydryl compounds. A heterocyclic thiol group These other photopolymerization initiators or accelerators may be π or may be mixed with two or more kinds. In the case of the type of radical generated by the sigma, it is preferable to use a plurality of photopolymerization start swords in combination, and for example, it is represented by the above formula (1). A combination of a compound with a phenylacetic acid, an amino phenylbenzene compound, or a thioxanthone derivative. In this case, as a benzene: ketone, the organism is, for example, preferably 2-methyl-bu [ 4-(Methylthio)benzoic acid]-2: morpholinopropane + ketone; as an aminoalkyl phenone derivative, the compound is preferably a 2-diamine-based 2-(4-methyl moiety) Base)_Bu (4 Yi Lin + :: Benke) butane + ketone, " based I dimethylamino + (4- porphyrinylphenyl) butanone-1, as a thioxanthone derivative, Preferably, it is thioxanthone, 2,4-diethylthioxanthone, etc. 'The ratio of the above photopolymerization initiator components (i.e., the total amount of the photopolymerization initiator) is in the present invention. In the form of the coloring composition, it is usually G1 to 4 G% by weight, preferably 3% by weight. If the compounding ratio is remarkably low, the degree of damage to the exposure light is lowered. (Conversely, (4) When the proportion is remarkably high, the solubility of the unexposed portion to the developer is lowered, and the development is poor. In order to improve the sensitivity, the wavelength corresponding to the image exposure source may be blended in the photopolymerization initiator component as needed. As a sensitizing dye, the sensitizing dyes are described in Japanese Patent Application Laid-Open No. 221 958, No. 4-21 9756 The ketone of the coumarin having a heterocyclic ring, which is described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. 3-ketocoumarin compound, Japanese Patent Laid-Open No. 6-丨924〇 No. 97122823 100 200911930 The pyridinium (pyrr〇methene) pigment described in the report; Others can be found: Japanese Patent Special Day Call No. 47_2528, Special Kaikai (6) Bull Bulletin, Special Gong Sho 45-37377, Special Kaikai 48_84183, Eight Reports, Special Open No. 52-1 12681, and Special Kaikai No. 58_155〇3 60-88005, special opening 59_564〇3 Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A dye of a dialkylamino benzene skeleton, etc., and a preferred one of the sensitizing dyes is an amino group-containing sensitizing dye, and more preferably a compound having an amine group and a phenyl group in the same molecule. For example, 4'4-diaminoaminodiphenyl ketone, 4,4,diethylaminodiphenyl ketone, 2-aminodiphenyl ketone, 4-aminodiphenyl ketone, 4, a diphenyl ketone compound such as 4,-diaminodiphenyl ketone, 3,3-diaminodiphenyl ketone or 3,4-diaminodiphenyl ketone; 2-(p-dimethylamino) Phenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-diaminoaminophenyl)benzo[4,5]benzoxazole, 2-( P-Dimethylamino)benzo[6,7]benzo D-azole, 2,5-bis(p-diethylaminophenyl) 1,3,4-°, 2-(p-dioxin Aminophenyl)benzothiazole, 2-(p-diethylaminophenyl) benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2-(p-diethylaminobenzene) Benzimidazole, 2,5-bis(p-diethylaminophenyl) 1,3,4-thiadiazole, (p-diaminoalkyl), pyridine, (p-diethylaminobenzene) Alpha-pyridine, (p-diaminophenyl)quineline, (p-diethylaminophenyl)quinoline, (p-diaminophenyl)pyrimidine, (p-diethylaminophenyl) A compound containing a p-dialkylamino group and the like, such as a pyrimidine. The best of these 97122823 101 200911930 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 〇% by weight or more, preferably 〇2% by weight or more, more preferably 〇5% by weight or more, based on the total solid content of the colored composition. Further, it is usually 2% by weight or less, preferably 15% by weight or less, more preferably 5% by weight or less. [2-3-2] The thermal polymerization initiator is exemplified as the thermal polymerization initiator which can be contained in the coloring composition of the present invention, and examples thereof include an azo compound, an organic peroxide, and hydrogen peroxide. . Among these, an azo compound is suitably used. Examples of the azo compound include 2, 2, azobisisobutyronitrile, 2, 2, azobis(2-methylbutyronitrile), and M,-azobis(cyclohexene- 1-carbonitrile), 2'2/-azobis(2'4-didecyl valeronitrile), 1-[(1-cyano-1_mercaptoethylazo) decylamine (2 — (aminomercaptoazo)isobutyronitrile), 2,2-azobis{2-methylN-[l,i-bis(hydroxyindenyl)-2-hydroxyethyl]propanamine}, 2,2,-azobis[N-(2-propenyl)_2-mercaptopropanol], 2,2,-azobispropyl)-2-ethylpropanamide], 2, 2, _ azobis[N_butyl_2_methylpropane (tetra)b 2'2'-azobis(N_cyclohexyl-2-methylpropanoate), 2,2,_ azobis (Dimethyl-2-mercaptopropylamine), 2,2,-azobis(dimethyl-2-methylpropionate), 2,2'-azobis (2, 4, 4 - Tridecylpentene), etc. Among these, the car is preferably 2,2'-azobisisodin, 2,2'-azobis(2,4-dimethylvaleronitrile). One τ as an organic peroxide, which may be exemplified by benzammonium peroxide, oxidized two 97,102,823, 102, 2009,119,130, the first butyl group, the chloroperoxybenzene isopropylation, the oxidized neodymium T-heart: : Peroxy per 〇 xyne 〇 decan 〇 ate), isopropyl isopropyl ester (Cumyl diacetate diisopropyl vinegar, di-n-propyl acrylate, peroxyacid-1, U, 3-tetramethyl Butyl vinegar::: butyl _, peroxidic neodymium hexyl vinegar, peroxy neodecanoic acid + cyclohexyl bis(4-tert-butylcyclodicarbonate di(2-ethoxyethyl) vinegar, After: dimethyl acetate, peroxyl ester, peroxy neodecanoic acid, third anti-S 夂 one (2_ethyl butyl butyl ester, peroxy neodecanoic acid 曰 -, D emulsified di-carbolic acid Dimethoxyperoxidation of pivalic acid, bismuth, bismuth, bismuth peroxide, oxidized 2-ethylhexanoic acid, _113卩^, bis (four), _ (2 r, its household J, 3,3 -tetramethylbutyl ester, 2,5-dimethyl-2,5-ethylhexyl peroxy)hexidene, peroxidation 2_ = peroxymethyl bromide), peroxidation 2_ Ethylhexanoic acid ^ - 曰, lightened diphenyl brewing, peroxidic isobutyric acid third butyl vinegar —— :Second-butylperoxy-cyclohexyl, 丨, 卜二(Third hexyl-over =,, cycline, α-di(t-hexylperoxy) 兀 _ ' (third Peroxy)cyclohexane, 2,2-di(4-4-((t-butylperoxy)cyclohexyl)propane, isopropyl peroxydicarbonate hexanoic acid peroxide Third butan vinegar, 3, 5, 5 -trimethylhexanoic acid, third J ester, butyl laurate, 3,5-dimethyl =, 5 - 2 (peroxidized 3 - A Hexyl phenyl) hexane, isopropyl epoxide, bismuth, first butyl Sa, 2-ethylhexyl monocarbonate, tert-butyl ester, superemulsified benzoic acid, third hydrazine, 2, 5_ Dimethyl-2,5_bis(benzhydrylperoxy) 97122823 103 200911930
己烧、過毫#,A 虱化乙酸第三丁酯、2, 2_二(第二 丁烷、過氧仆贫田於松 、乐—丁基過氧基) 戍d第三丁醋、4,“二(第三丁基過氧基) 異丙苯、過氧:?三丁基過氧基異丙基)笨、過氧化二 、虱化二弟三己基、2, 5_二甲基 基過氧基)己烷、過氧化-第-丁其(弟三丁 2,5_ 、乳化一弟二丁基、過氣化氫對薄荷燒、 二異丙苯:過=第三丁基過氧基)己块+過氧化氣 丙苯、過氧化u’3’3—"四甲基丁基、過氧化氣異 虱弟二丁基、過氧化第三丁基二 基、2,3-二曱q “ 』丞一曱基矽烷 土 ,3-—本基丁烧、過氧化二(3~甲美笑 醯)與過氧化苯甲叫甲基苯甲醯)以及過氧化甲甲 之混合物等。 、孔化一本甲醯 再者,[2-3-1]項中所述之光聚合起始劑中, ::胺基烷基笨,系化合物等亦發揮熱聚合起始劑之作用° °因此’作為熱聚合起始劑’亦可使用自作為光聚合起 始劑之例而舉出例中所選擇的化合物。 该等熱聚合起始劑類可單獨使用1種,亦可併用2種 上。 /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’從而作為彩色濾、光片之财久性有時不足。 右過夕則熱收鈿之程度變大,從而有於熱硬化後產生 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3有比例較佳為0〜30重量%,特佳為〇〜2〇重量% 之範圍。 97122823 104 200911930 [2 - 2 - 4 ]界面活性劑 作為界面活性劑’可使用陰離子系 系、兩性界面活性劑等各種界面活性劑,作就對各::離子 成不良影響的可能性較低而言,較 =造 活性劑。作為界面活性劑之濃度範圍,系界面 量’通常為0.001重量%以上,較、^組成物 更佳為〇 m #日。/、 权佳马0.005重量%以上, 更隹為〇.〇1重^以上,最佳為〇 〇3重量% 常為10重量%以下,較佳為i重 ,、 曹暑以丁,曰杜& 更里/以下,更較佳為〇. 5 0下,取侄為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U 苯酚、鄰苯三酚、鄰苯二酚、2, 6-第三丁基-對甲酚、二 奈盼等。熱聚合抑制劑之調配量係相對於組成物之總固形 分,較佳為0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:鄰苯二甲酸二辛酯、鄰苯二 甲酸二(十二烷基)酯、三乙二醇二辛酸酯、鄰苯二曱酸二 甲基乙二酯(dimethylgiycol phthalate)、磷酸三曱苯 S旨、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10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,本發明之彩色濾光片用著色組成物,可藉由 105 97122823 200911930 向預先製備之顏料分散液中混合入其他成分而製備,又, 可將全部成分同時或依次混合。以下,以依照前者方法進 行製備之情形為例進行說明,但並不限定於此。 又本毛明之彩色濾光片用著色組成物,根據所應用之 衣私,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。 百先’分別秤取各特定量之顏料、分散劑及溶劑,於分 散處理步驟中使顏料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 C〇nditi〇ner)、 砂磨機(Sandgrinder)、球磨機、輕磨機、石磨機、喷射 磨機(jetmiU)、均質機等。藉由進行該分散處理而將色 材微粒化’因此可使著色組成物之塗佈特性提昇,並使势 品之彩色濾光片中之像素的穿透率提昇。 、 八”,進行分散處理時’如上所述,較佳為適當併用 为散树脂或分散助劑等。 在使用砂磨機進行分散處理的情形下,較佳為使用 至數顔直徑的玻璃珠或者氧化 . 溫唐,诵當执中i 疋1丁刀月文處理時之 组度通^又疋為0C以上,較佳為室溫以上 設定為lGGt以下’較佳為說以下之範圍。八吊 時間之適當時間係因顏料分散液的組成以及砂磨機= 的大=等而不同,因此必須進行適當調整。 破置 向藉由上述分散處理而獲得之顏料分散 劑、聚合性單體,視情況進一步混合入黏合劑樹 97122823 106 200911930 合起始系成分、以及除上述以外之成分等,而製成均勻的 分散溶液,藉此獲得著色组成物K,於分散處理步驟 及混合之各步驟中,會有微細的雜物混入,因此較佳為利 用過濾器等對所得顏料分散液進行過濾處理。 [4 ]彩色濾光片之製造 繼而,對本發明之彩色濾光片加以說明。 +本發明之衫色濾、光片之特徵為:於基板上具有使用上述 著色組成物而形成之像素。 [4-1]透明基板(支持體) 作為彩色濾光片之透明基板’若為透明且具有適度的強 度,則對其材質並無特別限定。作為材質,例如可舉出: 聚對苯二甲酸乙二料以旨系樹脂,聚丙烯、聚乙稀等聚 烯煙糸樹脂,聚碳_、聚甲基㈣酸以旨、 性樹脂製薄片;環氧樹脂、不飽和聚酷樹脂、聚(甲:) 丙烯酸系樹脂等熱硬化性樹脂薄片;或者各種 月ί之甲’就耐熱性之觀點而言,較佳為破璃或者耐熱_ 為了改良接著性等表面物性,視f要可對透明基板及军 色矩陣形成基板實施電暈放電處理、臭 …、 劑或胺基甲酸_脂等各種樹脂之薄偶合 明基板之厚度通常為G.G5mm以上,成處理等。透 又,通常為1〇mm以下,較佳為7咖二〇·^以上, 在進行各種樹脂之薄卿成處理的情 乾圍。又’ 0. 01 //in以上,較# A Q Μ V ,其膜厚通常為 佳為°.05 "以上’又,通常為10 97122823 107 200911930 # m以下,較佳為5 # m以下之範圍 [4-2]黑色矩陣 於上述透明基板上設置黑 色、綠色、藍色之像素圖像, 光片。 藉此可製造本發明之彩色遽 色矩陣係利用遮光金屬薄膜或黑色矩陣用感 色树脂組成物㈣成於透明基板上。作為遮光金 可使用金屬鉻,氧化鉻、氮化鉻等鉻化合物,_鎮之合 金等’可為將該等積層為複數層狀者。 ”、’’’、α 該等金屬遮光膜通常藉由雜法㈣成,在利用 阻劑形成膜狀之所需圖案之後,佶用牌 將硝酸⑽與過㈣ 或力S文加以混合而成之蝕刻液對鉻進行蝕刻,對其他 材料則使用對應於材料㈣刻液進行_,最後用專用剝 離劑將正型光阻劑剝離,藉此可形成黑色矩陣。 / 在此情形下,首先藉由蒸鍍或濺鍍法等於透明基板上形 成該等金屬或者金屬·金屬氧化物之薄膜。繼而,在該薄 膜上形成著色組成物之塗佈膜後,使用具有條形、鑲嵌 2、二角形等重複圖案之光罩,對塗佈膜進行曝光及顯 影,而形成光阻圖像。其後,對該塗佈膜實施蝕刻處理, 從而可形成黑色矩陣。 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’使用含有碳黑、石墨、鐵黑、苯胺黑、花青黑、鈦 黑等黑色色材之單獨一種或複數種,或者自無機或有機顏 97122823 108 200911930 料、染料中所適當選擇 里多“……藍色等混合而成之 …色色材的者色組成物,以與後述形m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 像素之形成方法係因所 同,如前所述,此處以使用 物之情形為例進行說明。 使用著色組成物之種類而不 光聚合性組成物作為著色組成 於設置有黑^矩陣之透明基板上塗佈紅色、綠色、藍色 中之-顏色的著色組成物’乾燥後於塗佈膜上重疊光 介隔該光罩進行圖料光、顯影,視需要進行熱硬化或光 硬化,、藉此形成像素。對紅色、綠色、藍色三種顏色之著 色組成物’分別進行該操作,從而可形成彩色濾光片圖像。 本發明之彩色滤光片用著色組成物,可用來製成紅色、 彔色藍色像素中之至少一種顏色之像素(光阻圖案)形成 用塗佈液,如前所H巾在闕耗像素形成用材料、 特別是含漠化鋅酜菁顏料之綠色像素形成用材料時,盆效 果•優點表現得最為顯著。 、> 形色濾光片用著色組成物之塗佈,可利用旋塗(叩inner) 法、線棒(wire-bar)塗法、流塗(fl〇wc〇at)法、模塗(Me 法、輥塗(roll c〇at)法、喷塗(spray c〇at)法等進 饤。其中’若利賴塗法則可大幅減少塗佈液的使用量, 並且全無在利用旋塗法時所附著之霧滴等的影響,進而可 抑制異物產生等,就以上综合觀點而言屬較佳。 右塗佈膜過厚則難以顯影,或者難以於液晶單元化步驟 97122823 109 200911930 中進行間隙調整。另— — 料濃度,而血法碩現 ’右塗佈膜過薄則難以提高顏 叩…凌顯現所需之 燥後之膜厚計,通f ㈣Μ之Μ,係以乾 上,更佳為"二ΓΓ以上’較佳為0.5_ 佳為以下更:上為,5又’通常為2…以下,較 [“]塗佈膜之乾燥更佳為5㈣以下之範圍。 為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⑽烘箱、對流㈣(⑶謂 ::;=行乾燥。通常,在預備乾燥後,進行再加熱而 預備乾燥之條件,可根據上述溶劑成分之㈣、所 乾,機之性能等作適t選擇。乾燥溫度及乾燥時間,可根 據4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4(rc以上,較佳為5(rc以上, 又’通#為8G c以下’較佳為7(rc以下之範圍;乾燥時 間通常為15秒以上,較佳為3〇秒以上,又,通常為5分 鐘以下,較佳為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5(rc以上,較佳為7(rc以上,又, 通常為200°C以下,較佳為16〇°c以下,特佳為13〇。〇以 下之範圍。又’乾無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1 〇分鐘 以下,其中較佳為5分鐘之範圍。乾燥溫度愈高則對透明 基板之接著性愈提高’但若乾燥溫度過高則黏合劑樹脂發 97122823 110 200911930 生分解:有時會誘發熱聚合而產生顯影不良。再者, 该,伟膜之乾燥步驟,可採用不提高溫度而於減厘 订乾耜之減壓乾燥法。 進 [4-5]曝光步驟 曝於著色組成物之塗佈膜上重疊負型矩陣圖 f ’;:隔錢罩圖案照射紫外線或可見光。此時為了防止 由^氧氣所造成之聚合障礙,視需要可於塗佈膜上形成聚 乙烯醇層等氧氣阻隔層後再進行曝光。 人 上述圖像曝光中所使用之光源,並無特別限^。作為光 源’例如可舉出:氣氣擦 … 且齒素燈、鎢絲燈、高壓水銀燈、 超同壓水銀燈、金屬鹵素燈、 碳弧燈、螢光燈等燈光、肩n 低壓水銀燈、 Α】·· 或氬離子雷射、YAG(Yttrium _咖Garnet,釔紹石榴石)雷射、準分子雷射 (Excimer Laser)、ϋ + μ 知 a 由射 射光源等。在昭射使用田特Ϊ二t雷射、半導體雷射等雷 學遽光I。 情形下’亦可利用光 [4-6]顯影步驟 明月之彩色遽光片,係利用上述光源對使用本發 者:佈膜進行圖像曝光後’使用有機溶劑或 =界面活性劑及驗性化合物之水溶液進行顯影,藉此可 於基板上形成圖像而製造。該水溶液中進而可含有有機溶 劑、緩衝劑、錯合劑、染料或者顏料。 斤:為鹼性化合物,例如可舉出:氫氧化鈉、氫氧化 氣氧化鐘、碳酸納、碳酸鉀、碳酸氫鈉、碳酸氣鉀、石夕酸 97122823 111 200911930 納、石夕酸鉀、偏石夕酸納、碟酸鈉、磷酸鉀、磷酸氫納、鱗 酸氫鉀、磷酸二氫鈉、磷酸-②知 卜卜 化入物· m μ- 氣氧化錢等無機驗性 化“勿,或者早.一或二乙醇胺、單.二或三甲 .二 或三乙胺、單或二異丙胺、正丁 _ 伸乙亞胺、乙二亞胺、四曱義气^ 或二異丙醇胺、 機鹼性化合物。 “飞乳化銨咖)、膽鹼等有 該等鹼性化合物可為2種以上之混合物。 作y性劑,例如可舉出:㈣乙婦 t乙稀烧基芳基醚類、聚氧乙烯烧基酿類、山梨醇酐烧: 酉曰類、單甘油酯烷基酯類等非 _ #辦^甘一 哥邪離子糸界面活性劑;烷基苯 :-夂:=烷基奈磧酸鹽類、烷基硫酸鹽類、烷基碏酸鹽 通、石頁基琥賴醋鹽類等陰離子性界面活性劑,·燒基甜试 鹼類,胺基酸類等兩性界面活性劑。 土木 /乍為有=容劑,例如可舉出··異丙醇、节醇、乙基赛璐 『、丁基赛路蘇、苯基赛璐蘇、丙二醇、二丙酮醇 二二:狀alC°hC)1)等。有機溶劑可單獨使用,亦可與 水;谷液併用而使用。己烧,过毫#, A decyl acetate third butyl ester, 2, 2 _ two (second butane, peroxygen lean field Yusong, Le-butyl peroxy) 戍d third vinegar, 4, "bis (tert-butylperoxy) cumene, peroxy: ? tributylperoxy isopropyl) stupid, peroxide 2, bismuth dihexyl, 2, 5 - dimethyl Base peroxy)hexane, peroxidation-di-buty (dimethoate 2,5_, emulsified di-dibutyl, per-hydrogenated hydrogen to peppermint, dicumyl: over = tert-butyl Peroxy) hexene block + peroxybenzene benzene, peroxy u'3'3 - " tetramethyl butyl, peroxy dioxin dibutyl, peroxybutyl butyl diyl, 2, 3-二曱q “ ” 丞 曱 曱 矽 矽 , , 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- a mixture or the like. Further, in the case of a photopolymerization initiator described in [2-3-1], the :aminoalkyl group, a compound or the like also functions as a thermal polymerization initiator. Therefore, 'as a thermal polymerization initiator' can also be used as an example of a photopolymerization initiator to exemplify the compound selected in the examples. These thermal polymerization initiators may be used alone or in combination of two or more. When the proportion of the thermal polymerization initiator in the colored resin composition is too small, the film hardening is insufficient, and the color durability of the color filter or the light sheet may be insufficient. On the right of the night, the degree of heat shrinkage becomes larger, which causes cracks and cracks after thermal hardening. Moreover, it is seen that the storage stability tends to decrease. Therefore, the proportion of the thermal polymerization initiator in 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. 97122823 104 200911930 [2 - 2 - 4 ] Surfactant As a surfactant, various surfactants such as an anionic system and an amphoteric surfactant can be used, and it is less likely to adversely affect each ion: Said, compared to the active agent. The concentration range of the surfactant is usually 0.001% by weight or more, and more preferably 〇 m #日. /, 权佳马 0.005 wt% or more, more 〇 〇 〇 1 ^ ^ above, preferably 〇〇 3 wt% often 10% by weight or less, preferably i weight, Cao Shu to Ding, Yu Du And the range of 0.3% by weight or less is taken. [2-2-5] Thermal polymerization inhibitor as a thermal polymerization inhibitor, for example, p-benzene phenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, two Nai Pan and so on. The blending amount of the thermal polymerization inhibitor is preferably in the range of 0% by weight or more and 3% by weight or less based on the total solid content of the composition. [2-2-6] Plasticizer as a plasticizer, for example, dioctyl phthalate, di(dodecyl) phthalate, triethylene glycol dicaprylate, ortho Dimethylgiline dimethylate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetin, and the like. The compounding amount of the plasticizer is preferably in the range of usually 10% by weight or less based on the total solid content of the composition. [3] Preparation of Colored Composition Next, a method of preparing the colored composition of the present invention will be described. As described above, the coloring composition for a color filter of the present invention can be prepared by mixing other components into a previously prepared pigment dispersion by 105 97122823 200911930, and all the components can be mixed simultaneously or sequentially. Hereinafter, the case where the preparation is carried out according to the former method will be described as an example, but the invention is not limited thereto. Further, the coloring composition for the color filter of the present invention may be photocurable (photopolymerizable) or thermally polymerizable depending on the clothing to be used. Hereinafter, the case of a photopolymerizable composition (hereinafter referred to as "photoresist") will be described as an example. However, the present invention is not limited thereto. Each of the pigments, dispersants, and solvents is weighed in a predetermined amount, and the pigment dispersion is prepared by dispersing the pigment in a dispersion treatment step. In this dispersion treatment step, 'can be used: Paint C〇nditi〇ner, sand grinder, ball mill, light mill, stone mill, jet mill U, homogenizer, etc. . By performing the dispersion treatment, the color material is micronized. Therefore, the coating property of the coloring composition can be improved, and the transmittance of the pixel in the color filter of the potential product can be improved. , 八", when performing the dispersion treatment, as described above, it is preferably used as a bulk resin or a dispersion aid, etc. In the case of dispersion treatment using a sand mill, it is preferred to use glass beads of several diameters. Or oxidation. Wen Tang, when the i 执 执 丁 丁 丁 丁 丁 丁 丁 丁 丁 丁 丁 丁 丁 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ The appropriate time for the sling time varies depending on the composition of the pigment dispersion liquid and the size of the sand mill = the like, and therefore must be appropriately adjusted. The pigment dispersant and the polymerizable monomer obtained by the above dispersion treatment are broken. Further mixing into the binder tree 97122923 106 200911930, together with the starting component, and components other than the above, to form a uniform dispersion solution, thereby obtaining the colored composition K, in the steps of the dispersion treatment step and mixing In the case where fine impurities are mixed, it is preferred to filter the obtained pigment dispersion liquid by a filter or the like. [4] Production of Color Filters Next, Color Filters of the Present Invention The shirt color filter and the light sheet of the present invention are characterized in that they have pixels formed on the substrate using the above colored composition. [4-1] Transparent substrate (support) A transparent substrate as a color filter 'The material is not particularly limited as long as it is transparent and has a moderate strength. Examples of the material include polyethylene terephthalate for resin, polypropylene and polyethylene. Anthraquinone resin, polycarbo_, polymethyl (tetra) acid, thin film made of resin, epoxy resin, unsaturated polycarbonate, poly(methyl:) acrylic resin, etc.; or various months From the viewpoint of heat resistance, it is preferably glass-breaking or heat-resistant. In order to improve surface properties such as adhesion, it is necessary to perform corona discharge treatment, odor, or agent on a transparent substrate and a military matrix forming substrate. The thickness of the thin coupling substrate of various resins such as carbamic acid-lipid is usually G.G5 mm or more, and is formed into a treatment or the like. The thickness is usually 1 mm or less, preferably 7 Å or more. The thinness of the resin is processed into a dry circumference. ' 0. 01 // above, compared to # AQ Μ V , the film thickness is usually preferably °.05 "above' again, usually 10 97122823 107 200911930 # m below, preferably below 5 # m [4-2] The black matrix is provided with black, green, and blue pixel images and light sheets on the transparent substrate. Thereby, the color enamel matrix of the present invention can be manufactured by using a light-shielding metal film or a black matrix color-sensitive resin. The composition (4) is formed on a transparent substrate. As the light-shielding gold, a chromium compound such as metal chromium, chromium oxide or chromium nitride may be used, and an alloy such as _zhen may be a layer of these layers. ", '' , α, the metal light-shielding film is usually formed by the hybrid method (four), after using the resist to form the desired pattern of the film, the card is used to mix the nitric acid (10) with the (four) or force S text to form an etchant to the chromium The etching is performed, and for other materials, the etching is performed using the corresponding material (4), and finally the positive photoresist is peeled off with a special stripping agent, whereby a black matrix can be formed. / In this case, first, a film of the metal or metal/metal oxide is formed on the transparent substrate by evaporation or sputtering. Then, after a coating film of a coloring composition is formed on the film, a coating film having a repeating pattern such as a strip shape, a mosaic shape, or a square shape is used to expose and develop the coating film to form a photoresist image. Thereafter, the coating film is subjected to an etching treatment to form a black matrix. 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, 'use one or more kinds of black color materials containing carbon black, graphite, iron black, aniline black, cyanine black, titanium black, or the like, or choose from the inorganic or organic pigment 97102223 108 200911930 materials and dyes. "...a color composition of a color material, such as a mixture of blue and the like, can form a black matrix in the same manner as the method of m green and blue pixels described later. [4-3] Pixel formation of pixels The formation method is the same as described above, and the case of using the article will be described as an example. The type of the coloring composition is used instead of the photopolymerizable composition as a coloring composition coated on a transparent substrate provided with a black matrix. In the red, green, and blue colors, the coloring composition of the color is dried, and the light is superimposed on the coating film to separate the light, and the light is developed, and if necessary, heat hardening or light hardening is performed, thereby forming pixels. The coloring composition of the three colors of red, green, and blue colors is separately performed to form a color filter image. The coloring composition for a color filter of the present invention can be used for making a coating liquid for forming a pixel (resist pattern) of at least one of red and blue blue pixels, such as a material for forming a consumable pixel, particularly a green pixel containing a desertified zinc phthalocyanine pigment. When forming a material, the pot effect and the advantage are most prominent. · > The color filter is coated with the coloring composition by spin coating (wire-bar) method, wire-bar coating method, Flow coating (fl〇wc〇at) method, die coating (Me method, roll coating (roll c〇at) method, spray (spray c〇at) method, etc., where 'Ruo Lilai coating method can be greatly reduced The amount of the coating liquid to be used is not affected by the mist or the like adhered by the spin coating method, and it is also possible to suppress the generation of foreign matter, etc., which is preferable from the above viewpoint. Development, or difficult to adjust the gap in the liquid crystal unitization step 97122923 109 200911930. Another - material concentration, and the blood method is too thin, the right coating film is too thin, it is difficult to improve the appearance of the film Thick gauge, pass f (four) Μ Μ, is to dry, better for " Preferably, 0.5_ is preferably the following: upper, 5 and 'usually 2... or less, more preferably 5 (four) or less than the drying of the ["] coating film. Coating for forming the substrate on the substrate Drying of the film, preferably using a hot plate, infrared (10) oven, convection (4) ((3) said::; drying; usually, after pre-drying, reheating to prepare for drying, according to the above solvent components (4) The drying temperature and the drying time can be selected according to the type of the four components and the performance of the dryer to be used. Specifically, the drying temperature is usually 4 (rc or more, Preferably, it is 5 (rc or more, and 'pass# is 8 G c or less' is preferably 7 (the range of rc or less; the drying time is usually 15 seconds or longer, preferably 3 sec or more, and usually 5 minutes or less). Preferably, it is in the range of 3 minutes or less. The temperature condition for reheating and drying is preferably a temperature higher than the preliminary drying temperature. Specifically, it is usually 5 (rc or more, preferably 7 (rc or more, and usually 200 ° C or lower, preferably 16). 〇°c or less, especially preferably 13〇. 〇 The following range. 'Dry no time depends on the heating temperature' but usually 10 seconds or more', preferably 15 seconds or more, and usually 1 minute In the following, it is preferably in the range of 5 minutes. The higher the drying temperature, the higher the adhesion to the transparent substrate is. 'But if the drying temperature is too high, the binder resin is 97102823 110 200911930 Biodegradation: sometimes thermal polymerization is induced. The development process is poor. Further, the drying step of the film may be carried out by a vacuum drying method in which the temperature is not increased, and the drying step is performed on the coating film of the coloring composition. Overlapping the negative matrix diagram f ';: The spacer cover pattern is irradiated with ultraviolet light or visible light. In order to prevent the polymerization barrier caused by the oxygen gas, an oxygen barrier layer such as a polyvinyl alcohol layer may be formed on the coating film as needed. Exposure. People above picture The light source used in the exposure is not particularly limited. As the light source, for example, a gas scrub can be used, and a tooth lamp, a tungsten lamp, a high pressure mercury lamp, a super pressure mercury lamp, a metal halide lamp, a carbon arc lamp, Fluorescent lights, shoulders, n low-pressure mercury lamps, Α ···· or argon-ion lasers, YAG (Yttrium _ Gar Garnet, 钇 garnet) laser, Excimer Laser, ϋ + μ know a In the case of a ray, a light source such as a ray, a semiconductor laser, or the like, can be used in the case of the ray, and a color ray film of the moon can be used in the case of the light [4-6] development step. By using the above-mentioned light source, after image exposure using the film of the present invention, "developing with an aqueous solution of an organic solvent or a surfactant and an organic compound, an image can be formed on the substrate, and the aqueous solution is further produced. It may contain an organic solvent, a buffer, a complexing agent, a dye or a pigment. King: It is a basic compound, and examples thereof include sodium hydroxide, oxidized gas oxidation clock, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, and potassium carbonate. , 夕夕酸97122823 111 20091 1930 nano, potassium astragalate, sodium sulphate, sodium sulphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen citrate, sodium dihydrogen phosphate, phosphoric acid - 2 ibbs, m μ- gas oxidation Inorganic verification of money, etc. "Do not, or early. One or two ethanolamine, mono. di or trimethyl. di or triethylamine, mono or diisopropylamine, n-butyl iodide, ethylenediimide, tetraterpene义^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ Epoxy Ether, Ethylene Oxide Ether, Sorbitan, Scallop, Ethyl Alcohol, Ethyl Alcohol, Ethyl Alcohol Ethyl Ester Alkylbenzene:-夂:=alkylnaphthalate, alkyl sulfate, alkyl citrate, sulphate, etc., anionic surfactant, · burnt sweet Test alkaloids, amino acid and other amphoteric surfactants. The soil/乍 is a volumetric agent, and examples thereof include isopropyl alcohol, stilbene, ethyl cyanohydrin, butyl sirlo, phenyl cyanidin, propylene glycol, and diacetone alcohol. °hC) 1) and so on. The organic solvent may be used singly or in combination with water or gluten.
顯影處理之條件# I 以卜^㈣㈣,Wit常為1(TG 以上,其t較佳為〗5ΐ以上,更 常為501C以下,其’’’、 上’又’通Conditions for development processing # I 卜^(4)(4), Wit is often 1 (TG or more, t is preferably ΐ5ΐ or more, more usually 501C or less, and ’’’’’’’’’’’’’’
之範圍。顯影方法可採乂〜以下’更佳為40t^T 題与夺扣立士 知用次次顯影法、噴霧顯影法、刷子 '·,頁办法、起θ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 97122823 112 200911930 處理條件,溫度通常在1〇〇〇c以上、較佳為15〇它以上, 又,通常為280°c以下、較佳為25(TC以下之範圍内選擇, 日jr間在5分鐘以上、6〇分鐘以下之範圍内選擇。經過該 等「系列步驟,而完成單色之圖案化圖像形成。依序反覆 J行該步驟,將黑色、紅色、綠色、藍色圖案化,而形成 衫色濾、光片。再者,該等四色之圖案化之順序,並 於上述順序。 疋 “再者’本發明之彩色遽光片係除上述製造方法外,亦可 =2 i將含有聚醯亞胺系樹脂作為黏合劑樹脂之著色組 ^於基板上,再利用蝕刻法形成像素之方法來f 二又:,丨可舉出:(2)使用本發明之著色組成物作為著色 ΐ,或m用刷機於透明基板上直接形成像素圖像之方 ':、、責”二用本發明之著色組成物作為電鍍液,使基板 色在形成特定圖案的1το電極上析出著 组,可舉出··⑷將㈣有本發明著色 組成物之缚膜貼附於透明其 香巴 光、顯影,形成像素圖像其剝離,進行圖像曝 色組成物作為著色油=利用 或(5)使用本發明之著 方法等。彩色濟光月^ t墨列印機形成像素圖像之 組成物之二根據彩—著色 [4-8]透明電極之形成 ιτο等透明二::慮:片’係在原有狀態下於像素上形成 等零件的-部分,機:顯示器、液晶顯示裝置 -為了k面表面平滑性或耐久性,視需 97122823 113 200911930 要亦可於像素上设置聚酿胺、聚酿亞胺等表塗層。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) 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 色濾'光片上形成配向膜,再將間隔件散布於該配向膜上, 然後與對向基板相貼合而形成液晶單^,再將液晶注入至 所形成之液晶單元中,並與對向電極接線而完成。配向膜 較佳為聚醯亞胺等樹腊膜。配向膜之形成通常採用凹版印 刷法及/或柔版印刷法,將g己向膜之厚度設絲⑽。 利用熱燒成進行配向膜之硬化處理後,藉由紫外線照射或 使用研磨布之處理進行表面處理,加工成可調整液晶之斜 度的表面狀態。 間隔件可使用與對向基板的間隙(卿)相對應之尺寸 者,通吊為2〜8 # m者。亦可利用光微影法於彩色 濾光片基板上形成透明樹脂膜的感光性間隔件(ps,ph〇t〇 spacer) ’將其代替間隔件而活用。作為對向基板,通常 :使用陣列基板’特佳為TFT(thin fUm加心咖, 薄膜電晶體)基板。 與對向基板貼合之間隙,因液晶顯示裝置之用途而不 同’通常在2㈣以上' 8 "以下之範圍内選擇。與對 向基板貼合後’利用環氧樹脂等密封材料將液晶注入口以 外的部分加以密封。藉自uv照射及/或加熱使密封材料硬 97122823 114 200911930 化,從而將液晶單元周邊密封。 周邊經禮、封之液晶單元,在切斷成面板單位後,於真空 室内形成減壓狀態,將上述液晶注入口浸潰於液晶中,然 後使室内漏氣,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1 χ 1 〇 2 pa以上、較佳為1X1 〇_3 %以 上,又,通常為lxl(T pa以下、較佳為lxl〇-6 Pa以下之 範圍。又,較佳為在減壓時對液晶單元進行加溫,加溫溫 度通常為3(TC以上、較佳為50t以上,又,通常為1〇〇 C以下、較佳為9 〇。〇以下之範圍。 減壓時之加溫保持時間通常設為丨〇分鐘以上、6〇分鐘 以下之乾圍,其後浸潰於液晶中。注入有液晶之液晶單元 係藉由使UV硬化樹脂硬化而將液晶注入口密封,完成液 晶顯示裝置(面板)。 液aa之種類並热特別限制,為芳香族系、脂肪族系、多 %狀化合物等習知之液晶,且可為溶致型液晶 licund crystal)、熱致型液晶(therm〇tr〇pic Hquid 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 Hquid crystal)等,可為任一者。 [6 ]有機EL顯示器 在使用本發明之彩色濾、光片製作有機EL顯示器的情形 下’例如’如@ 1所不’首先製作於透明支持基板】〇上 形成有樹脂黑色㈣(未圖示)而成之本發明之彩色濾、光 97122823 115 200911930 片’上述樹脂黑色矩陣設置於像素2()(其巾,像素別中 月之著色組成物而形成者)以及 40,腺古_、 隔有機保護層30及無機氧化膜 :機發光體500積層於該彩色濾光片上,夢此可势 作有機EL元件。 猎此了衣 ^為有機發光體5〇〇之積層方法,可舉出:於彩色滤光 面逐次形成透明陽極5〇、電洞注入層51、電洞傳輸 二,、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5G0貼合於無機氧 化膜40上之方法等。使用如此製作之有機EL元件1 〇〇, 藉由例如「有機EL顯示器」(0hm公司,2〇〇4年8月2〇 日^丁’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EL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乩 器。 [實施例] 、’k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0 再者,實施例1〜4及比較例丨〜2係使用C· L色素綠 %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. L 色素紅254等紅色顏料作為顏料之例。 97122823 116 200911930 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(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」(相當於本申請案說明書中之[2 — 1 — 1 ]樹 月曰以下稱為[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 (V )所表示化合物作為必需部分的單體成分進行聚合而 成之共聚物、即「(曱基)丙烯酸系樹脂( 案說明書中之㈣樹脂。以下,稱為㈣接= 為黏合劑樹脂之例。 實施例21〜29係進而使用肟酯系化合物作為光聚合起 始劑(光聚合起始系成分)之例。 實施例30〜36係進而使用芳香族羧酸系化合物之例。 [合成例1 :溴化鋅酞菁之合成] 以鄰苯二曱腈(phthalodinitrile)及氯化鋅為原料,製 造鋅酞菁。所獲得鋅酞菁之卜氯萘溶液,在600〜70〇 nm 處有光吸收。 至於鹵化’係將%醢乳3,1重量份、無水氯化铭3 7重 量份、氣化鈉0.46重量份、鋅酞菁1重量份於4〇〇c下混 合,再滴加溴4.4重量份。於80。(:下反應15小時,其後 將反應混合物投入水中,使溴化鋅酞菁粗顏料析出。將該 水性漿料過滤’用8 0 C之熱水進行清洗,於g 〇 下使其 97122823 117 200911930 乾而獲得u重量份之經精製之漠化鋅駄 向雙腕型捏合齡加人上述溴㈣ :、經粉碎的氯化鈉12重量份、二乙二醇18重量份置 及—甲苯0.09重量份’於7(rc下混練1〇小時 取出置於8G°C之水1GG重量份中,擾拌i小時後,、 過遽、熱水清洗、乾燥、粉碎,而獲得漠化鋅駄菁顏料二 根據質量分析之齒素含量分析可知,所獲得之 菁顏料係平均組成為ZnPcBri4C12(Pc:酞菁),i分子中” 均含有14個溴原子者。又,用穿透型電子顯微鏡(日立: 作所公司製造之「H-9_UHR」)所敎之—次粒徑 : 值為 0. 023 # m。 g 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 粒子像,根據該像測定一次粒徑’求出單個平均值(平^ 粒徑)。 [合成例2 :分散劑A,之合成] 除不將共聚物中之胺基(二曱胺基)進行四級化以外,依 照曰本專利特開平卜22 9 014號公報之實施例i,合成具 有三級胺基之曱基丙烯酸系A-B嵌段共聚物。 所獲得共聚物之重量平均分子量為9〇〇〇,胺價為121 mgKOH/g,酸價為〇 mgK0H/g。又,B —嵌段中之「側鏈上 具有胺基之重複單元」係以下述式(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u 97122823 118 200911930 莫耳%。 [化 31]The scope. The development method can be carried out by any of the following methods: more preferably 40 t ^ T and Snaps, a secondary development method, a spray development method, a brush method, a page method, and a θ wave development method. [4~7] Thermal hardening treatment The developed color filter is subjected to heat hardening treatment. At this time, the temperature is 9710223 112 200911930, and the temperature is usually 1 〇〇〇 c or more, preferably 15 Å or more, and usually 280 ° C or less, preferably 25 (TC or less). The date jr is selected within a range of 5 minutes or more and 6 minutes or less. After the "series steps, the monochromatic patterned image formation is completed. The steps are repeated in sequence, and the steps are black, red, green, The blue pattern is formed to form a shirt color filter and a light sheet. Further, the order of patterning of the four colors is in the above order. 疋 "Further" the color light-receiving sheet of the present invention is in addition to the above manufacturing method. It is also possible to use a polyimine-based resin as a coloring group of a binder resin on a substrate, and then to form a pixel by etching, and then: (2) use the present The coloring composition of the invention is used as a coloring crucible, or m is formed by directly forming a pixel image on a transparent substrate by a brush. The coloring composition of the present invention is used as a plating solution to make the substrate color form a specific pattern. 1τοThe group is deposited on the electrode, which can be cited. (4) attaching the binding film having the colored composition of the present invention to transparent scented light, developing, forming a pixel image, peeling off, and performing image coloring composition as a coloring oil = utilizing or (5) using the present invention Method, etc. Color Jiguang month ^ t ink printer to form a pixel image of the second component according to color - coloring [4-8] transparent electrode formation ιτο and other transparent two:: consideration: the film 'in the original state Forming a part of the part on the pixel, the machine: display, liquid crystal display device - for k-surface smoothness or durability, as needed, 97122923 113 200911930 can also be set on the pixel, such as polyamine, polyaniline, etc. In addition, in the case of a planar alignment type driving method (IPS mode), some of them do not form a transparent electrode. [5] Liquid crystal display device (panel) Next, the liquid crystal display device (panel) of the present invention The manufacturing method is described. In the liquid crystal display device of the present invention, an alignment film is usually formed on the color filter 's optical sheet of the present invention, and the spacer is spread on the alignment film, and then bonded to the opposite substrate. Forming a liquid crystal unit, and then injecting the liquid crystal into the formed liquid crystal cell and completing the wiring with the counter electrode. The alignment film is preferably a wax film such as polyimide, and the alignment film is usually formed by gravure printing method. / or flexographic printing method, the thickness of the film has been set to (10). After the hardening treatment of the alignment film by thermal baking, the surface treatment is performed by ultraviolet irradiation or treatment using a polishing cloth, and processed into an adjustable liquid crystal. The surface state of the slope. The spacer can be used in the size corresponding to the gap of the opposite substrate, and can be lifted to 2 to 8 # m. It can also be formed on the color filter substrate by photolithography. The photosensitive spacer (ps, ph〇t〇 spacer) of the transparent resin film is used in place of the spacer. As the counter substrate, generally, an array substrate is used, and a TFT (thin fUm, thin film transistor) substrate is particularly preferable. The gap to be bonded to the counter substrate is different depending on the use of the liquid crystal display device, and is usually selected within the range of 2 (four) or more. After bonding to the opposite substrate, a portion other than the liquid crystal injection port is sealed with a sealing material such as an epoxy resin. The sealing material is hardened by UV irradiation and/or heating to seal the periphery of the liquid crystal cell. After the liquid crystal unit is cut and formed into a panel unit, a vacuum state is formed in the vacuum chamber, the liquid crystal injection port is immersed in the liquid crystal, and then the chamber is leaked to inject the liquid crystal into the liquid crystal cell. . The degree of pressure reduction in the liquid crystal cell is usually 1 χ 1 〇 2 Pa or more, preferably 1×1 〇 _ 3% or more, and is usually lxl (T Pa or less, preferably lxl 〇 -6 Pa or less). Further, it is preferable to heat the liquid crystal cell at the time of pressure reduction, and the heating temperature is usually 3 (TC or more, preferably 50 t or more, and usually 1 〇〇 C or less, preferably 9 〇. The temperature holding time at the time of pressure reduction is usually set to a dry circumference of 丨〇 minute or more and 6 〇 minutes or less, and then immersed in the liquid crystal. The liquid crystal cell in which the liquid crystal is injected is cured by curing the UV hardening resin. The liquid crystal injection port is sealed to complete the liquid crystal display device (panel). The type of the liquid aa is particularly limited, and is a conventional liquid crystal such as an aromatic system, an aliphatic system, or a poly-type compound, and may be a lyotropic liquid crystal licund crystal. Any of thermochromic liquid crystals, such as nematic liquid crystals, smectic liquid crystals, and the like. Cholesterol-like liquid crystal (ch〇lesteric Hquid crystal), etc. [6] In the case of using an organic EL display using the color filter or the optical sheet of the present invention, the organic EL display is formed, for example, on a transparent support substrate, such as @1, and is formed with a resin black (4). (not shown) the color filter of the present invention, light 97122923 115 200911930 piece 'The resin black matrix is set in the pixel 2 (), the towel, the color forming composition of the moon, and 40, gland Ancient _, the organic protective layer 30 and the inorganic oxide film: the illuminant 500 is laminated on the color filter, and it is expected to be an organic EL element. The method of layering the organic light illuminator 5 A method of sequentially forming a transparent anode 5, a hole injection layer 51, a hole transmission 2, a light-emitting layer 53, an electron injection layer 54, and a cathode 55 on a color filter surface; or forming a substrate on another substrate The organic light-emitting device 5G0 is bonded to the inorganic oxide film 40, etc. The organic EL device 1 thus produced is used, for example, by "organic EL display" (0hm company, 2, 4, August 2) Day ^ Ding's time as Jing Shi, Anda thousand waves An organic EL display can be produced by the method described in the above, etc. Further, the color filter of the present invention can be applied to an organic EL display of a passive driving method or an organic driving device of an active driving method. [Embodiment] The present invention will be described more specifically with reference to the production examples, examples, and comparative examples. However, the present invention is not limited to the following examples as long as the points are not exceeded. ~4 and Comparative Example 22 are examples in which C·L pigment green % is used as a pigment, and Examples 5 to 36 and Comparative Examples 3 to 7 are examples in which a zinc bromide phthalocyanine pigment is used as a pigment, and Examples 37 to 43 are used. A red pigment such as c. L Pigment Red 254 is used as an example of the pigment. 97122823 116 200911930 In these examples, Examples 7 to 15 and Comparative Examples 5 to 6 further use "a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, a resin obtained by adding an unsaturated monobasic acid to at least a part of an epoxy group of the copolymer, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of a hydroxyl group produced by the addition reaction" (Equivalent to [2 - 1 - 1 ] tree moon 曰 hereinafter referred to as [2 -1 -1 ] resin) in the specification of the present application as an example of a binder resin. In the examples 16 to 20 and the comparative example 7, a copolymer obtained by polymerizing a monomer component having a compound represented by the above formula (V) as an essential component, that is, a "(fluorenyl) acrylic resin ( (4) Resin in the specification. Hereinafter, it is referred to as (4) connection = an example of a binder resin. Examples 21 to 29 are further examples in which an oxime ester compound is used as a photopolymerization initiator (photopolymerization initiation component). Examples of Examples 30 to 36 are further examples of using an aromatic carboxylic acid compound. [Synthesis Example 1: Synthesis of zinc bromide phthalocyanine] Zinc phthalocyanine was produced using phthalodinitrile and zinc chloride as raw materials. The obtained phthalocyanine solution of zinc phthalocyanine has light absorption at 600 to 70 〇 nm. As for the halogenated 'system, 3 parts by weight of the milk, 3 parts by weight of anhydrous chlorinated salt, and 0.46 parts by weight of sodium gasification. 1 part by weight of zinc phthalocyanine was mixed at 4 ° C, and 4.4 parts by weight of bromine was added dropwise thereto at 80 ° (: 15 hours under reaction, after which the reaction mixture was put into water to make zinc bromide phthalocyanine crude pigment Precipitate. Filter the aqueous slurry 'washed with 80 C hot water, g Next, make 97122823 117 200911930 dry and obtain u parts by weight of refined desertified zinc lanthanum to the double wrist type kneading age to add the above bromine (4): 12 parts by weight of crushed sodium chloride, 18 parts by weight of diethylene glycol And - 0.09 parts by weight of toluene was taken out in 1 cc under rc for 1 hour, taken out in 1 GG parts by weight of water at 8 G ° C, after being scrambled for 1 hour, washed with hydrazine, hot water, dried, pulverized, and obtained. According to the analysis of the dentin content of the mass spectrometry zinc phthalocyanine pigment 2, the average composition of the obtained cyanine pigments is ZnPcBri4C12 (Pc: phthalocyanine), and all of the i molecules contain 14 bromine atoms. Transmissive electron microscope (Hitachi: "H-9_UHR" manufactured by the company) - Secondary particle size: Value is 0. 023 # m. g Furthermore, the average-minor particle size of the pigment is based on the pigment. Ultrasonic dispersion was carried out in chloroform, and the dispersed droplets were applied to a grid attached to the rubber film, dried, and a particle image of the pigment was observed by a transmission electron microscope (TEM), and the image was measured based on the image. A single average value (flat diameter) was determined for the particle size. [Synthesis Example 2: Dispersant A, Synthesis] In addition to the quaternization of the amine group (diammonium group) in the copolymer, the sulfhydryl group having a tertiary amino group is synthesized in accordance with Example i of the Japanese Patent Laid-Open Publication No. 22 9 014 Acrylic AB block copolymer. The obtained copolymer has a weight average molecular weight of 9 Å, an amine value of 121 mg KOH/g, and an acid value of 〇mgK0H/g. Further, the B-block is on the side chain. The repeating unit having an amine group is a structure represented by the following formula (a), and the ratio of the repeating unit represented by the following formula (b) in the A-block is u 97122823 118 200911930 mol%. [化31]
(a) 再者,藉由以下方法測定胺價及酸價。 [胺價之測定] 用 將 於100 mL燒杯中精確秤取入0.5〜1>5 50 mL乙酸溶解。使用具備pH電極之自g二政劑, 0‘1 mol/L之HCL〇4乙酸溶液對該溶液進定装置, 滴定pH曲線的拐點作為滴定終點,根據丁:滴定。 胺價[mgK0H/g]=(56lxV)/(WxS) 式衣出胺價。 (其中’ W為分散劑試料旦 量[mL],S為分散劑試料里g],V為滴定終點之滴定 叶之固形分濃度[wt%]。) 97122823 119 200911930 [合成例3 :分散劑c之合成] 將重里平均分子量約為5〇〇〇之聚乙烯亞胺5〇重量份、 η=5之聚己内酯40重量份、及硬脂酸6重量份、與丙二 酉予單甲醚乙酸酯300重量份混合,於氮氣環境中於15〇。〇 下攪拌3小時。如此合成之分散劑c之胺價為54 mgKOH/g,酸價為丨 〇 mgK〇H/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 單甲醚乙酸酯400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9〇它。 另一方面,向單體槽中加入2, 2,-[氧基雙(亞甲基)]雙 -2-丙酸二甲酯30重量份、甲基丙烯酸6〇重量份、甲基 丙嫦酸環己酯11 〇重量份、過氧化2_乙基己酸第三丁酯 5. 2重量份、丙二醇單甲醚乙酸酯4〇重量份,向鏈轉移 劑槽中加入正十二烧基硫醇5.2重量份、丙二醇單曱醚乙 酸酯27重量份,將反應槽之溫度穩定於9(rc,然後自單 體槽及鏈轉移劑槽開始滴加反應物,使之開始聚合。一面 將溫度保持於90°C—面分別以135分鐘進行滴加,滴加 結束60分後’開始升溫使反應槽達到1丨。 維持11 0°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,向反應槽中加入甲基丙烯酸環氧丙酯39 6重 量份、2, 2’-亞曱基雙(4_曱基-6—第三丁基苯酚)〇4重量 份、三乙胺0.8重量份,並直接於11(rc反應9小時。 97122823 120 200911930 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i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 單甲醚乙酸酯400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 〇。〇。 另一方面,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、甲基丙烯酸重量份、曱基 丙烯酸苄酯110重量份、過氧化2-乙基己酸第三丁酯5.2 重里伤、丙一醇單甲_乙酸g旨4 〇重量份,向鏈轉移劑槽 中加入正十二烷基硫醇5.2重量份、丙二醇單曱醚乙酸酯 27重量份’將反應槽之溫度穩定於9〇〇c,然後自單體槽 及鏈轉移劑槽開始滴加反應物’使之開始聚合。一面將溫 度保持於90°C—面分別以135分鐘進行滴加,滴加結束 ⑼分後’開始升溫使反應槽達到U(rc。 維持1UTC達3小時後,將氣體導入管安裝在分離式燒 瓶上,開始進行氧氣/氮氣= 5/95(v/v)混合氣體之吹泡。 繼而’向反應槽中加入甲基丙烯酸環氧丙酯39. 6重量 份、2, 2,-亞甲基雙(4_曱基-6-第三丁基苯酚)〇· 4重量 份、二乙胺0. 8重量份,並直接於11 〇。(: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。 σ 97122823 121 200911930 [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甲醚乙酸酯145重 里伤加以攪拌,升溫至12〇°C。向其中滴加苯乙烯20重 1伤、曱基丙烯酸環氧丙酯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12(TC下繼續攪拌2小時。繼而,將反應 谷窃内變更置換為空氣,向丙埽酸27重量份中投入參(二 曱胺基曱基)苯酚〇· 7重量份及對苯二酚〇12重量份,於 12 0 C下連續反應6小時。其後,加入四氫鄰苯二甲酸酐 (THPA)52重量份、三乙胺〇· 7重量份,於12(Γ(:下反應 3. 5小時。 如此獲得之黏合劑樹脂F之藉由GPC法所測定的經聚笨 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曱醚乙酸酯35重量份、卜 甲氧基-2-丙醇8. 8重量份、偶氮系聚合起始劑(和光純藥 公司製造之「V-59」)1· 5重量份,於氮氣環境中升溫至 80〇C。 以2小時向其中滴加甲基丙烯酸苄酯9. 5重量份、甲基 丙烯酸甲酯6.5重量份、甲基丙烯酸2-羥基乙酯3.5重 量份、以及甲基丙烯酸1〇· 7重量份,進而攪拌4小時, 而獲得聚合反應液。 向該聚合反應液中添加丙二醇單甲醚乙酸酯25.5重量 份、對甲氧基苯酚〇. 重量份、三苯基膦〇. 3重量份, 97122823 122 200911930 使其溶解。繼❿,滴加丙稀酸(3 士環氧基環己基)〒醋 α5ί4#^85ΐ:τ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Gpc法所測定之聚合平 均分子量,、經聚苯乙烯換算為18〇〇〇。又,藉纟中和滴定 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)甲酯向羧基之導入率為66%。 [合成例8 :黏合劑樹脂η之合成] 將具有三環癸烧骨架之單丙稀酸醋(日立化成公司製造 之FA 513Μ」)1〇重1份、甲基丙稀酸環己酯復5重量 份、甲基丙烯酸曱酉旨3.〇重量份、以及曱基丙烯酸43. 5 重量份溶解於丙二醇單甲_乙酸醋15〇重量份中,於氣氣 環境中加入偶氮雙異丁腈h25重量份,於8〇〇c下反應7 小時。 如此獲待之黏合劑樹脂H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72〇〇,酸價為84。 [合成例9 :黏合劑樹脂丨之合成] 面進行氮氣置換一面將丙二醇單曱醚乙酸酯145重 =伤加以攪拌,升溫至丨2〇°c。向其中滴加苯乙烯丨〇重 ϊ =、甲基丙烯酸環氧丙酯85 2重量份以及具有三環癸 烷月木之單丙烯酸酯(日立化成公司製造之「FA_513M」)66 重里伤,以及以3小時滴加2, 2,-偶氮雙-2-曱基丁腈9. 00 重量份,進而於9〇。〇下繼續攪拌2小時。 97122823 123 200911930 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(二曱胺基甲基)苯酚〇.7重量份以及對 苯二盼0. 12重量份’於i〇〇°C下連續反應12小時。 其後,加入四氫鄰苯二曱酸酐(ΤΗΡΑ)56· 2重量份、以 及三乙胺0.7重量份,於1〇〇。〇下反應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 乙烯換算之重量平均分子量Mw約為6000,酸價為90 mgKOH/g。 [合成例1 0 :黏合劑樹脂j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120X:。 向其中滴加甲基丙烯酸苄酯30重量份、甲基丙烯酸環 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9〇 °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(二曱胺基甲基)苯酚〇7重量份以及對 苯二酚0.12重量份,於10(rc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、三乙胺〇 7 重量份,於10(TC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14〇〇〇,酸價為 mgKOH/g。 97122823 124 200911930 [合成例11 :黏合劑樹脂κ之合成] 以與合成例9中所獲得樹脂" 甲其岛祕缺與> ^ J <方式,將苯乙烯、 西旨(土日立化成以及具有三環癸燒骨架之單丙稀酸 =立化成公司製造之「FA侧」)進行聚合。 重量份中投入參(二甲胺…向丙稀酸43.2 装ID 切G.7重量份以及對 本-盼G.12重讀,於⑽。口連續反應a 力^四氣鄰笨二甲酸肝⑽Α)5〇·2重量价、三乙胺〇? 重罝份,於loot下反應3. 5小時。 =此獲得之黏合劑樹脂κ之藉由咖法所载的經聚苯 烯換异之重量平均分子量⑽約為8_,酸價為78 mgKOH/g。 [合成例12 :黏合劑樹脂L之合成] 曰面進行氮氣置換一面將丙二醇單甲醚乙酸酯145重 加以攪掉,升溫至120。〇。向其中滴加苯乙烯10重 里伤、甲基丙烯酸環氧丙酯115.2重量份、以及具有三環 ^烧骨架之單丙烯酸酯(日立化成公司製造之 FA 513Μ」)46重量份。繼而,以3小時滴加2, 2’ _偶氮 雙2-甲基丁腈7·47重量份,進而於9〇。匸下繼續攪拌2 /J、時。 繼而’將反應容器内變更置換為空氣,於丙烯酸58. 3 重里份中投入參(二曱胺基甲基)苯酚0 7重量份以及對 苯一酚0. 12重量份,於1 〇〇。〇下連續反應i 2小時。其後, 加入四氫鄰笨二曱酸酐(THPA)57 2重量份、三乙胺〇7 97122823 125 200911930 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 乙烯換算之重量平均分子量Mw約為咖 為^ mgKOH/g。 員為 1〇〇 [合成例13 :黏合劑樹脂μ之合成] 以與合成例9中所獲得樹脂I相同之方式,— 甲基丙烯酸環氧丙酉旨' 以及具有三環癸燒骨酸 酯(曰立化成公司製造之「FA_513Mj )進行聚人 :而,將反應容器内變更置換為空氣,丁於“酸43 2 重里份中投入參(二甲胺基甲基)苯酚〇 苯二酚0. 12重量份,於10(rc下遠缽. 里伤以及對 於剛C下連續反應12小時。1後, 加入琥珀酸酐30·〗重量份、三乙 ,、交 。。下反應3.5小時。 …重讀’於⑽ 如此獲得之黏合劑樹脂M之藉由Gpr、土 & t mgK0H/g。 %子里MW約為咖,酸價為81 [合成例14 :黏合劑樹脂n之合成] ASS例9所獲得樹脂1相同之方式,將苯乙浠、甲 二立二^^旨、以及具有三環癸燒骨架之單丙稀酸函旨 (日立化成公司製造之「FA-513M」)進行聚入 反容器内變更置換為空氣‘丙烯酸43.2 二(二甲胺基甲基)笨· °.7重量份以及對 ’於靴下連續反應12小時。其後, 本偏三甲酸酐69.2重量份、三乙胺0.7重量份,於 97122823 126 200911930 100°c下反應3. 5小時。 如此獲得之黏合劑樹脂Μ + — w㈣由gpc法所測定的經聚苯 mg_/g。 〃子* Μ» '約為謂,酸價為79 [合成例15 :黏合劑樹脂ρ之合成] 將:二醇單,乙酸酿…重量份加入至4 口燒瓶 ’面進㈣乳吹泡—面升溫至85t。以4小時向盆 ::加將甲基丙烯酸节_96δ重量份、甲基丙稀酸/ 重讀、以及2,2、偶氮雙異丁腈4.93重量份溶解於丙 二®子単甲醚乙酸醋96.5重量份中而成者。 、丙 士滴加結束後,在將反應液保持於阶下進q掉 化,其後停止氮氣吹泡,升溫至i⑽。c並料^小時。 如此獲得之黏合劑樹脂P之藉由哪法所測 乙烯換算之重量平约分孚θ 1 、、工艰本 mg_/g。 !^刀子1為15_,酸價為180 [合成例16 :黏合劑樹脂Q之合成] 將:二醇單甲醚乙酸酷114〇重量份加入至4 口燒瓶 2 —面進行氮氣吹泡-面升溫至阶。以4小時向並 ::加將甲基丙烯酸如6·8重量份、甲基丙烯酸33二 -二ί甲以及2’2 _偶氮雙異丁腈9.85重量份溶解於丙 一知早甲醚乙酸酯96.5重量份中而成者。 士滴加結束後,在將反應液保持於85。〇下進而攪拌2 時’其後停止氮氣吹泡,升溫至i⑽。Cii_ 2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 97122823 127 200911930 乙烯換异之重量平均分子量為8刪,酸價為⑺呢腦 [合成例17 :黏合劑樹脂R之合成] 將具有三環癸燒骨架之單两稀酸醋(日立化成公司製造 之「FA-513M」)l〇重量份、甲基丙烯酸苄酯62 〇重量份、 以及甲基丙烯酸28.〇重量份溶解於丙二醇單甲鍵乙酸醋 150重里伤中於氮氣環境中加入偶氮雙異丁腈〇 65重 量份,於80°C下反應7小時。 · 如此獲得之黏合劑樹脂R之藉由GPC法所測定的經聚苯 ㈣換算之重量平均分子量Mw約為17刚,藉由中和滴 定法所測定之酸價為10 2。 [合成例18 :黏合劑樹脂s之合成] 將丙二醇單曱鱗乙酸醋114重量份加入至4 口燒瓶中, 一面進行氮氣吹泡一面升溫至85〇c ^以4小時向其中滴 加將曱基丙烯酸苄酯114重量份、甲基丙烯酸26重量份、 2, 2’-偶氮雙異丁腈99重量份溶解於丙二醇單曱崎乙酸 酯96重量份中而成者。 滴加後,在將反應液保持於85〇c下進而攪拌2小時, 其後停止&氣吹泡’升溫至⑽。c並㈣M、時。向其中 加入四乙基氣化銨〇·7重量份,於8(rc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_丨_曱酯 16重I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8(rc下攪拌3〇小時,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、 97122823 128 200911930 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)中之甲基丙 稀酉欠麦更為丙烯酸以外’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1〇1 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)中之甲基丙 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800^ 酸價為102 mgKOH/g之聚合物溶液。 [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. 〇15 “ m的C. I.色素綠36、及2. 93重量份之平均一次粒徑為 0.025 //m的c. I.色素黃15〇、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_丨中記載之各種 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中記載之各種黏合劑樹脂經固形分換算3·26重量 份,與直徑為0.5 ram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,表中之所謂「溶 97122823 129 200911930 劑」,係與「綠色顏料分散液」中所含之溶劑不同,為另 外調配者。 [表1] 表-1 分散劑之種類/胺價 黏合劑樹脂 著色組成物之評價 黏度變化 溶解時間 對比度 實施例1 AV121 E 〇 〇 6096 實施例2 AV121 D 〇 〇 6023 實施例3 AV121 F Δ 〇 5780 實施例4 AV121 G 〇 〇 5820 比較例1 B’MO E X 無法評價 無法評價 比較例2 C/10 E X 無法評價 無法評價 表中,分散劑A’及分散劑C分別係上述合成例2及3 中獲得之化合物,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](a) Further, the amine value and the acid value were determined by the following methods. [Measurement of amine price] Dissolve accurately by taking 0.5 to 1 > 5 50 mL of acetic acid in a 100 mL beaker. The solution was set up using a pH electrode from g bis-agent, 0 '1 mol/L of HCL 〇 4 acetic acid solution, and the inflection point of the pH curve was titrated as the titration end point, according to D: titration. The amine price [mgK0H/g] = (56lxV) / (WxS). (Where 'W is the dispersant sample amount [mL], S is the dispersant sample g], and V is the solid concentration [wt%] of the titration leaf at the end of the titration.) 97122823 119 200911930 [Synthesis Example 3: Dispersant Synthesis of c] 5 parts by weight of polyethyleneimine having an average molecular weight of about 5 Å, 40 parts by weight of polycaprolactone having η=5, and 6 parts by weight of stearic acid, and propylenediacetate 300 parts by weight of methyl ether acetate was mixed and placed at 15 Torr in a nitrogen atmosphere. Stir under 3 for 3 hours. The amine valence of the dispersant c thus synthesized was 54 mgKOH/g, and the acid value was 丨 〇 mgK〇H/g. [Synthesis Example 4: Synthesis of the binder resin d] A separation flask equipped with a cooling tube was prepared as a reaction vessel, and 400 parts by weight of propylene glycol monomethyl ether acetate was added thereto, and after nitrogen substitution, the mixture was heated with an oil bath while stirring. The temperature of the reaction vessel was raised to 9 Torr. On the other hand, 30 parts by weight of 2,2,-[oxybis(methylene)]bis-2-propionic acid dimethyl ester, 6 parts by weight of methacrylic acid, and methyl propyl hydrazine are added to the monomer tank. 11 parts by weight of acid cyclohexyl ester, 5.2 parts by weight of tert-butyl peroxy 2-ethylhexanoate, 4 parts by weight of propylene glycol monomethyl ether acetate, and adding n-dodecane to the chain transfer agent tank 5.2 parts by weight of thiol and 27 parts by weight of propylene glycol monoterpene ether acetate, the temperature of the reaction vessel was stabilized at 9 (rc, and then the reactant was added dropwise from the monomer tank and the chain transfer agent tank to start polymerization. While maintaining the temperature at 90 ° C - the surface was added dropwise at 135 minutes, and after the end of the dropwise addition for 60 minutes, the temperature was raised to bring the reaction tank to 1 Torr. After maintaining the temperature at 10 ° C for 3 hours, the gas introduction tube was installed. On the separable flask, bubble blowing of an oxygen/nitrogen = 5/95 (v/v) mixed gas was started. Then, 36 parts by weight of glycidyl methacrylate was added to the reaction vessel, 2, 2'- 4 parts by weight of fluorenyl bis(4-fluorenyl-6-tert-butylphenol), 0.8 parts by weight of triethylamine, and reacted directly at 11 (rc reaction for 9 hours. 97122823 120 200911930 After cooling to room temperature, a polymer solution having a weight average molecular weight of 8000 and an acid value of i〇1 mgK0H/g as measured by a GPC method was obtained. [Synthesis Example 5··Binder Resin E Synthesis] A separation flask equipped with a cooling tube was prepared as a reaction vessel, and 400 parts by weight of propylene glycol monomethyl ether acetate was added thereto, and after nitrogen substitution, the mixture was heated with an oil bath while stirring, and the temperature of the reaction vessel was raised to 9 Torr. On the other hand, 30 parts by weight of 2,2,-[oxybis(methylene)]bis-2-propionic acid dinonyl ester, methacrylic acid by weight, benzyl methacrylate is added to the monomer tank. 110 parts by weight of ester, butyl peroxy 2-ethylhexanoate 5.2 heavy wound, propanol monomethyl-acetic acid g, 4 parts by weight, adding n-dodecyl mercaptan to the chain transfer agent tank 5.2 Parts by weight, propylene glycol monoterpene ether acetate, 27 parts by weight 'stabilize the temperature of the reaction tank at 9 〇〇c, then start to add the reactants from the monomer tank and the chain transfer agent tank to start polymerization. Keep at 90 ° C - the surface is added dropwise at 135 minutes, and the end of the drop (9) is followed by 'starting The temperature of the reaction vessel reached U (rc. After maintaining 1 UTC for 3 hours, the gas introduction tube was mounted on a separate flask, and bubble blowing of an oxygen/nitrogen = 5/95 (v/v) mixed gas was started. 3重量份,2,2,-methylenebis(4-fluorenyl-6-t-butylphenol)〇·4 parts by weight, diethylamine 0 was added to the reaction vessel. 8 parts by weight, and directly at 11 Torr. (: 9 hours under reaction. Cooling to room temperature', the polystyrene-converted weight average molecular weight determined by the GPC method was 8000, and the acid value was 103 mgKOH/g. The polymer solution. σ 97122823 121 200911930 [Synthesis Example 6. Synthesis of Adhesive Resin f] The propylene glycol monomethyl ether acetate 145 was repeatedly wound while stirring with nitrogen, and the mixture was stirred and heated to 12 ° C. To the mixture, 82 parts by weight of styrene, 57 parts by weight of glycidyl methacrylate, and 82 parts by weight of a monoacrylate having a tricyclodecane skeleton ("FA-513M" manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto. 12 (Stirring was continued for 2 hours at TC. Then, the reaction was changed to air, and 7 parts by weight of propionate was added to the bis(diamine fluorenyl) phenolphthalein · 7 parts by weight and hydroquinone. 12 parts by weight of hydrazine was continuously reacted at 12 0 C for 6 hours. Thereafter, 52 parts by weight of tetrahydrophthalic anhydride (THPA) and 7 parts by weight of triethylamine hydrazine were added to react at 12 (Γ:: 3. 5 hours. The weight average molecular weight MW of the binder resin F thus obtained by the GPC method is about 15,000. [Synthesis Example 7: Synthesis of binder resin G] To the reaction vessel 35 parts by weight of propylene glycol monoterpene ether acetate, 8.8 parts by weight of methoxy-propanol, and an azo polymerization initiator ("V-59" manufactured by Wako Pure Chemical Industries, Ltd.) 1·5 5重量份, 份份份份份份份份份份份份份份份份份份6.5 parts by weight of methyl methacrylate, 3.5 parts by weight of 2-hydroxyethyl methacrylate, and 1 part by weight of methacrylic acid, and further stirred for 4 hours to obtain a polymerization reaction liquid. Propylene glycol monomethyl ether acetate 25.5 parts by weight, p-methoxyphenol oxime. Parts by weight, triphenylphosphine hydrazine. 3 parts by weight, 97122823 122 200911930 to dissolve it. Following hydrazine, dropwise addition of acrylic acid (3 gram ring) Oxycyclohexyl) hydrazine vinegar α5ί4#^85ΐ: τ reaction for 24 hours' to obtain a resin solution having an ethylenically unsaturated group in the side chain. The average molecular weight of the binder resin G thus obtained measured by the Gpc method It is converted to polystyrene by 18 〇〇〇. Further, the acid value measured by the neutralization titration method is 50. Further, according to the acid value before and after the reaction, acrylic acid (3,4-epoxycyclohexyl group) is known. The synthesis rate of the methyl ester to the carboxyl group is 66%. [Synthesis Example 8: Synthesis of the binder resin η] The monoacrylic acid vinegar having a tricyclic smoldering skeleton (FA 513 制造 manufactured by Hitachi Chemical Co., Ltd.) 1 part, 5 parts by weight of cyclohexyl methacrylate, methyl The olefinic acid is used in an amount of 3 parts by weight, and 4 parts by weight of methacrylic acid is dissolved in 15 parts by weight of propylene glycol monomethyl acetate, and 25 parts by weight of azobisisobutyronitrile is added to the gas atmosphere. The reaction was carried out for 7 hours at 8 ° C. The weight average molecular weight Mw of the binder resin H thus determined by the Gpc method was about 72 Å, and the acid value was 84. [Synthesis Example 9: Synthesis of binder resin ]] The surface was subjected to nitrogen substitution, and propylene glycol monoterpene ether acetate 145 weight = injury was stirred and heated to 丨 2 ° ° C. To the mixture, styrene oxime ϊ 、, 85 2 parts by weight of glycidyl methacrylate, and a monoacrylate having a tricyclodecane moon ("FA_513M" manufactured by Hitachi Chemical Co., Ltd.) were severely wounded, and 00 parts by weight of 2,2,-azobis-2-mercaptobutyronitrile was added dropwise over 3 hours, and further to 9 Torr. Stirring was continued for 2 hours under the armpits. And the amount of benzodiazepines is 0. 12 parts by weight of the bismuth phthalate. The reaction was continued for 12 hours at 〇 ° C. Thereafter, 56. 2 parts by weight of tetrahydrophthalic anhydride (ΤΗΡΑ) and 0.7 parts by weight of triethylamine were added at 1 Torr. The underarm reaction was 3.5 hours. The polystyrene-equivalent weight average molecular weight Mw of the binder resin I thus obtained, as measured by the GPC method, was about 6,000, and the acid value was 90 mgKOH/g. [Synthesis Example 10: Synthesis of binder resin j] 145 parts by weight of propylene glycol monomethyl ether acetate was stirred while being purged with nitrogen, and the temperature was raised to 120X:. 30 parts by weight of benzyl methacrylate, 85.2 parts by weight of oxypropyl methacrylate, and 46 parts by weight of a monoacrylate ("FA-513m" manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton were added dropwise thereto. Further, 7.47 parts by weight of 2,2'-azobis-2-mercaptobutyronitrile was added dropwise over 3 hours, and stirring was continued at 9 ° C for 2 hours. Then, the inside of the reaction vessel was changed to air, and 7 parts by weight of ginseng (diaminomethyl) phenolphthalein and 0.12 parts by weight of hydroquinone were added to 43 2 parts by weight of acrylic acid, and the reaction was continued at 10 (rc). After 12 hours, 50.2 parts by weight of tetrahydrophthalic anhydride (THPA) and 7 parts by weight of triethylamine hydrazine were added, and the reaction was carried out at 10 (TC) for 3.5 hours. The binder resin thus obtained was used by Gpc. The polystyrene-equivalent weight average molecular weight Mw measured by the method is about 14 Å, and the acid value is mgKOH/g. 97122823 124 200911930 [Synthesis Example 11: Synthesis of binder resin κ] Acquired the resin "Kakijima's secrets and > ^ J < method, the styrene, the West (the Hitachi Chemical and the mono-acrylic acid with the tricyclic smoldering skeleton = the "FA side" made by the company The polymerization is carried out. The ginseng is added to the parts by weight (dimethylamine is added to the acrylic acid 43.2, the ID is cut, G.7 parts by weight, and the original-looking G.12 is re-read, at (10). The continuous reaction of the mouth is a force ^ four gas neighboring two Formic acid liver (10) Α) 5 〇 2 weight, triethylamine 〇 罝 罝 , , loo loo loo loo loo loo loo loo loo loo loo loo The binder resin κ has a weight average molecular weight (10) of about 8 Å and an acid value of 78 mg KOH/g by the polyphenylene exchanged by the coffee method. [Synthesis Example 12: Synthesis of binder resin L] While replacing the nitrogen gas, propylene glycol monomethyl ether acetate 145 was repeatedly stirred and heated to 120 ° C. To this was added dropwise 10 parts of styrene, 115.2 parts by weight of glycidyl methacrylate, and having a tricyclic ring. 46 parts by weight of a single acrylate (FA 513 制造 manufactured by Hitachi Chemical Co., Ltd.), and then added 2,2'-azobis 2-methylbutyronitrile to 7.47 parts by weight over 3 hours, and further to 9 〇 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续 继续Phenol 0. 12 parts by weight in 1 Torr. Continuous reaction i for 2 hours under the enthalpy. Thereafter, 4 parts by weight of tetrahydro-o-succinic anhydride (THPA) was added, and triethylamine 〇 7 97122823 125 200911930 parts by weight ' The reaction was carried out at 100 ° C for 3.5 hours. The binder resin L thus obtained was determined by the GPC method. The olefin-converted weight average molecular weight Mw is about 2 mg KOH/g. The composition is 1 〇〇 [Synthesis Example 13: Synthesis of binder resin μ] In the same manner as the resin I obtained in Synthesis Example 9, -methyl group Acrylic propylene acrylate and 'tricyclic strontium oleate (FA_513Mj manufactured by 曰立化成公司) are used for aggregation: instead, the reaction vessel is changed to air and diced in "acid 43 2 aliquots" The ginseng (dimethylaminomethyl) phenol hydroquinone was added in an amount of 0.12 parts by weight, and was subjected to a continuous reaction at 12 ° for 12 hours. After 1st, 30 parts by weight of succinic anhydride, triethyl, and cross were added. . The reaction was carried out for 3.5 hours. ...rereading '(10) The binder resin M thus obtained is obtained by Gpr, soil & t mgK0H/g. % MW is about coffee, and the acid value is 81 [Synthesis Example 14: Synthesis of binder resin n] The same method as the resin 1 obtained in ASS Example 9 is carried out in the same manner as in the case of phenelzine, acetonitrile, and The mono-acrylic acid of the tricyclic teriyaki skeleton ("FA-513M" manufactured by Hitachi Chemical Co., Ltd.) was changed into air in the anti-tank and replaced with air 'acrylic acid 43.2 bis(dimethylaminomethyl) stupid · °. 7 parts by weight and continuous reaction for 12 hours under the boot. 5小时。 After the reaction, the reaction was carried out at a pressure of 3.592 126 126 200911930 at 100 ° C for 3.5 hours. The binder resin Μ + - w (d) thus obtained was polyphenylene mg_/g as determined by the gpc method. 〃子* Μ» 'About, the acid value is 79 [Synthesis Example 15: Synthesis of binder resin ρ] Place: diol, acetic acid, ... part by weight, add to the 4-neck flask 'face (four) milk blowing - The surface temperature is raised to 85t. 4 hours to the basin:: add methacrylic acid _96 δ parts by weight, methyl acrylate / read, and 2, 2, azobisisobutyronitrile 4.93 parts by weight in the propylene carbonate methyl ether The vinegar is made up of 96.5 parts by weight. After the completion of the dropwise addition of the solvent, the reaction solution was kept under the step and then dropped, and then the nitrogen bubble was stopped, and the temperature was raised to i (10). c and then ^ hours. The weight of the binder resin P thus obtained is determined by the method of ethylene, and the weight of the ethylene is approximately θ 1 , and the labor is mg_/g. ! ^Knife 1 is 15_, and the acid value is 180 [Synthesis Example 16: Synthesis of Binder Resin Q] Add: 114 parts by weight of diol monomethyl ether acetate to the 4-neck flask 2 for nitrogen blowing - surface heating To the order. 4 hours to the:: plus methacrylic acid such as 6.8 parts by weight, methacrylic acid 33 di- 2, and 2'2 azo azobisisobutyronitrile 9.85 parts by weight dissolved in propyl mycohol The acetate was formed in 96.5 parts by weight. After the completion of the dropwise addition, the reaction solution was maintained at 85. When the crucible was further stirred for 2', the nitrogen blowing was stopped, and the temperature was raised to i (10). Cii_ 2 hours. The thus obtained binder resin Q is determined by the Gpc method. The polystyrene 97122923 127 200911930 ethylene has a weight average molecular weight of 8 and the acid value is (7) brain [Synthesis Example 17: Synthesis of binder resin R a single dilute acid vinegar ("FA-513M" manufactured by Hitachi Chemical Co., Ltd.) having a tricyclic teriyaki skeleton, a weight fraction of benzyl methacrylate, 62 parts by weight of benzyl methacrylate, and 28. parts by weight of methacrylic acid. After dissolving in 150 weights of propylene glycol monomethyl acetate, 65 parts by weight of azobisisobutyronitrile was added to the nitrogen atmosphere, and the reaction was carried out at 80 ° C for 7 hours. The weight average molecular weight Mw of the polyphenylene (IV) converted by the GPC method thus obtained is about 17, and the acid value measured by the neutralization titration method is 10 2 . [Synthesis Example 18: Synthesis of binder resin s] 114 parts by weight of propylene glycol monoterpene acetate vinegar was placed in a 4-necked flask, and the temperature was raised to 85 〇c while nitrogen gas was bubbled, and 曱 was added thereto in 4 hours. 114 parts by weight of benzyl acrylate, 26 parts by weight of methacrylic acid, and 99 parts by weight of 2,2'-azobisisobutyronitrile were dissolved in 96 parts by weight of propylene glycol monoterpene acetate. After the dropwise addition, the reaction solution was further stirred at 85 ° C for 2 hours, and then the temperature of the & gas bubble was stopped to (10). c and (four) M, hour. To this was added 7 parts by weight of tetraethylammonium hydride, and the mixture was stirred at 8 (rc) to dissolve, and then 16 gram of acrylic acid _3,4-epoxycyclohexyl-indole oxime was added dropwise over 1 hour. I part, a solution of 24 parts by weight of propylene glycol monomethyl ether acetate. The mixture was stirred at 8 (rc for 3 hours) to obtain a polystyrene-converted weight average determined by the Gpc method. Molecular weight: 97122823 128 200911930 A polymer solution having an acid value of 90 mgKOH/g [Synthesis Example 19: Synthesis of binder resin D1] In addition to the methyl propylene in the above Synthesis Example 3 (synthesis of binder resin D)酉 麦 麦 more than acrylic acid 'synthesis under the same conditions as in Synthesis Example 3' to obtain a polymer solution having a weight average molecular weight of 8,200 and an acid value of 1〇1 mgKOH/g. [Synthesis Example 20: Adhesive resin Synthesis of E1] The synthesis was carried out under the same conditions 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. Polymerization with an average molecular weight of 800^ and an acid value of 102 mgKOH/g [1] Examples 1 to 4 and Comparative Examples 1 to 2: Examples of use of CI Pigment Green 36. [Preparation of coloring composition] The average primary particle diameter of 6.85 parts by weight of the pigment was 〇. 15" CI pigment green 36, and 2.93 parts by weight of c. I. pigment yellow 15 平均, propylene glycol monomethyl ether acetate as a solvent, 60.00 parts by weight In the table of the dispersing agent, each of the dispersing agents described in the above-mentioned enthalpy is converted into a solid content of 1 > 96 parts by weight, and each of the various binder resins described in Table 1 as a dispersion resin is converted into a solid fraction of 3.26 parts by weight, and has a diameter of 0.5. 225 parts by weight of ram zirconia beads were filled together in a stainless steel container, and a green pigment dispersion liquid was prepared by dispersing a paint shaker for 6 hours. Then, the components described in Table-2 were mixed in the obtained green color. In the pigment dispersion liquid, a coloring composition is prepared. Further, the so-called "solvent 97102223 129 200911930 agent" in the table is different from the solvent contained in the "green pigment dispersion liquid", and is a blender. [Table 1] Table-1 Types of Dispersants / Amine Price Adhesives Lipid coloring composition evaluation viscosity change dissolution time contrast Example 1 AV121 E 〇〇 6096 Example 2 AV121 D 〇〇 6023 Example 3 AV121 F Δ 〇 5780 Example 4 AV121 G 〇〇 5820 Comparative Example 1 B'MO EX Unevaluable evaluation was not possible. Comparative Example 2 C/10 EX Unevaluable evaluation The dispersant A' and the dispersant C were the compounds obtained in the above Synthesis Examples 2 and 3, respectively, and the dispersant B' was 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]
97122823 130 200911930 [表2] 表-2 成分之種類 成分之詳細内容 調配量(重 *----- 顏料分散液 溶 #1 丙二醇單甲醚乙酸酯 一37· 09〜~~ —-勢合劑樹脂 -追加與表-1中所記載者相同者 _2·2(Ρ^ 眾合性單體 二季戊四醇六丙烯酸酯 5.66 ~ 尤本:合起始系忐合1 - 2-疏基苯并售°坐 尤參σ起始系成分2 光裝合起始系成合:¾ 對二甲胺基苯甲酸 Χ46~~~^ 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 >谷解時間、以及對比度。測定方法分別記載如下,測定結 果不於表-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r 」,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)。 比較14日間之黏度變化率,將未滿4%者記為〇,將4% 以上未滿10%者記為△,將1〇%以上者記為χ。 其結果示於表-1。 [溶解時間之測定] 分別將上述實施例及比較例中所得著色組成物旋塗於 蒸鍍有鉻之玻璃基板上,以8(TC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,以使所獲得乾燥塗佈膜達到 色座標為〇· 600之膜厚。 利用高壓水銀燈通過光罩圖案以60 mJ/cm2對所得乾燥 97122823 131 200911930 塗佈膜進行曝光後,使用0 04 影液溫度_,以。.…二:二_ =燥塗佈膜溶解而露出基板面為止之 色組成物之溶解時間」。 | 者 對於各實施例及比較例中所得著 間,將未滿1GG秒者記為〇,將100秒以上未時 為△’將12°以上者記為X。其結果示於表]: [對比度之測定] 述較例中所獲得之著色組成物,以與上 進二二相同之方式’於透明玻璃基板上 進订疑塗及預烤。除了不介隘# m n ^ - 1 s d, 先罩圖案以外,以與上述[溶 解π間之測疋]項中相同之方式 進行曝光,並在與上述[溶解 二獲仔之乾無塗佈膜 氣進行乾燥。用充为置的水進行清洗後,以潔淨空 於23(TC供箱中對所得乾燥塗佈膜進行分鐘 烤左:製成著色樹脂膜。所得著色樹脂膜之膜厚為… m著色此,製成於透明㈣基板上具㈣色樹脂膜之 圖2(a)及⑻均係用以說明測定著色板 正交穿透光之色度的方法之模式圖。 板:4先二(a)所不’在所得著色板(以下稱為「著色 板34」)之兩側重疊偏本^ 35之偏光軸相互平=二3及自35:咖 之狀心下’自一側偏光板35側照射 97122823 132 200911930 背光源37之光36,使用色彩亮度計T0PC0N TECHN0H0USE 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 ’使用色彩亮度計32 ’以與上述Lp相同之方式,測97122823 130 200911930 [Table 2] Table-2 Ingredients of ingredients The content of the ingredients (weight *----- pigment dispersion solution #1 propylene glycol monomethyl ether acetate - 37 · 09 ~ ~ ~ - potential Mixture resin - added the same as those described in Table-1. 2·2 (Ρ^ The merging monomer dipentaerythritol hexaacrylate 5.66 ~ Ebene: the starting system is combined with 1-2-3 thiophene benzo ° 坐 尤 尤 σ σ 系 系 成分 2 光 光 光 光 光 光 光 光 光 : : : : : : : : : : : : : : : : : : ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ 46~~~^ For the measurement, the viscosity change, the coloring resin film, the gluten solution time, and the contrast ratio are as follows. The measurement results are as follows. The measurement results are not shown in Table-1. [Viscosity change of the coloring composition] E type manufactured by Toki Sangyo Co., Ltd. The viscosity meter r", the coloring composition obtained in the above examples and comparative examples were measured, respectively, after the production (preparation), and the viscosity after standing for 2 weeks in a thermostat at 23 ° C (20 rpm) Comparing the change rate of viscosity during the 14th period, the person who is less than 4% is recorded as 〇, and the person who is more than 4% less than 10% is recorded as △, The results are shown in Table 1. The results are shown in Table 1. [Measurement of Dissolution Time] The colored compositions obtained in the above Examples and Comparative Examples were spin-coated on a glass substrate on which chromium was deposited, to 8 (The hot plate of TC was prebaked for 3 minutes to prepare a dry coating film. Further, the number of rotations at the time of spin coating was adjusted so that the obtained dried coating film reached a film thickness of 〇·600. The high-pressure mercury lamp is exposed to the obtained dried 97102923 131 200911930 coating film at 60 mJ/cm 2 through a reticle pattern, and then used to dissolve the substrate surface by using the 0 04 liquid temperature _, .... The dissolution time of the color composition of the present invention is as follows: For each of the examples and the comparative examples, the one that is less than 1 GG seconds is denoted as 〇, and the time that is less than 100 seconds or longer is Δ', and 12 degrees or more is recorded as X. The results are shown in the table]: [Determination of Contrast] The coloring composition obtained in the comparative example was prepared on the transparent glass substrate in the same manner as the above method.介隘# mn ^ - 1 sd, before the cover pattern, in comparison with the above [dissolved π In the same way as in the item, the exposure is carried out, and after drying with the above-mentioned [dissolved and dried smear-free film gas, after washing with the water, it is clean and empty at 23 (the TC is supplied to the tank) The dried coating film is baked for a minute to make a colored resin film. The film thickness of the obtained colored resin film is... m is colored, and the (four) color resin film formed on the transparent (four) substrate is shown in Fig. 2 (a) and (8). A schematic diagram for explaining a method of measuring the chromaticity of the orthogonally transmitted light of the colored plate. Plate: 4 first two (a) does not 'on both sides of the resulting colored plate (hereinafter referred to as "colored plate 34") overlaps the polarized axis of the ^ 35 horizontally = two 3 and from 35: the heart of the coffee 'From the side of the polarizing plate 35 side, 97122823 132 200911930 Backlight 37 light 36, using the "BM-5A" 32 manufactured by the color luminance meter T0PC0N TECHN0H0USE, the light transmitted through the other polarizing plate 33 is measured under the condition of 2° field of view. The brightness 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 luminance meter 32'. In the same way as Lp above,
定透過另一偏光板33之光的亮度Lc(正交穿透光的亮 度)。 U 再者’貪光源3 7係使用具有如圖3所示之發光光譜者。 該光s晋之測定’係使用Konica Minolta製造之分光放射 亮度計CS-1 000A,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rND Filter _4」進行 測定,並進行計算。 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1(: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12 8 〇 〇。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 用例。 [顏料分散液之製備] 使用合成例1中獲得之溴化鋅酞菁7. 24重量份、以及 97122823 133 200911930 2. 54重量份之C.1.色素黃150,將作為溶剩之 p乙《 6G.00重量份、作為分散劑之表〜 各種成分經固形分換算〗.96重 屺载之 之矣?中々讲*私人w 以及作為分散樹脂 之表-3中嗽黏合劑樹脂經以固形 份,與直徑為〇.5_之氧化錯珠225重量份 器中;藉由塗料振動機分散“、時備 分散液τ、υ、ν及说。 [表3] 表-3The brightness Lc of the light transmitted through the other polarizing plate 33 (the brightness of the orthogonal penetrating light). U again, the greedy light source 7 7 uses a luminescence spectrum as shown in FIG. The measurement of the light ray is performed using a spectroradiometer CS-1 000A manufactured by Konica Minolta, and a filter rND Filter _4 manufactured by Kenko Co., Ltd. for the purpose of controlling the amount of light and making the measurement easy. Calculation. 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 brightness Lp of the parallel penetrating light and the brightness 1 of the orthogonal penetrating light by the formula Lp/Lc. Further, basic glass was used instead of each. The blank test value when the color plates of the examples and the comparative examples were measured was 12 8 〇〇. 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 use of zinc bromide phthalocyanine pigments [Preparation of pigment dispersion liquid] The zinc bromide phthalocyanine obtained in Synthesis Example 1 was used. And 9712823 133 200911930 2. 54 parts by weight of C.1. Pigment Yellow 150, will be used as the remaining p "6G.00 parts by weight, as a dispersant table ~ various components by solid fraction conversion〗 96屺 之 矣 々 々 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人 私人Machine dispersion ", time dispersion τ, υ, ν and said. [Table 3] Table-3
t施例5 ---顏料 -—----— 分散劑_ 樹脂 顏料分散液 實施例6 合成例1中所獲得之 渙化鋅酞菁 D Τ 比較例3 A Ε U 比較例4 B 「 D V ---~~-J C -—IZJ W 其中’表-3中之分散劑A及β係以下化合物。 [刀政劑A·畢克化學公司製造之分散劑6919」] 其係甲基丙烯酸系AB嵌段共聚物。胺價為121 mgKOH/g,酸價為丨mgK〇H/g以下。 B瓜I又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,以下遂式㈦ 所表示之重複單元在A叙段中之比例為丨 [化 33] ' 97122823 134 200911930t Example 5 ---Pigment------ Dispersant_ Resin Pigment Dispersion Example 6 Zinc Antimonide Phthalocyanine D 合成 obtained in Synthesis Example 1 Comparative Example 3 A Ε U Comparative Example 4 B " DV ---~~-JC -—IZJ W The following dispersants A and β are the following compounds. [Knife Chemical A. Dispersant 6919 by BYK Chemical Co., Ltd.] It is an AB block copolymer. The amine value was 121 mgKOH/g, and the acid value was 丨mgK〇H/g or less. Approximately 100 mol% of the repeating unit having a functional group containing a nitrogen atom contained in B melon I is a structure represented by the following formula (a), and further, the repeating unit represented by the following formula (7) is described in The ratio in the paragraph is 丨[化33] ' 97122823 134 200911930
h3c (a) (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] H3C~N+-CH3H3c (a) (b) [Dispersant B: "Disperbyk 2000" manufactured by BYK Chemical Co., Ltd.] It is composed of a solvophilic A block and a B block having a functional group containing a nitrogen atom. Acrylic AB block copolymer. The functional group (adsorbing group) containing a nitrogen atom is mainly the following structure, [Chem. 34] H3C~N+-CH3
ci- 胺價約為10mgKOH/g,且主鏈為甲基丙烯酸之嵌段共 聚物。 97122823 135 200911930 [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日後之黏度(均為20 rpm)。結果示於表-4。 [表4 ] 表-4 顏料 分散液 黏度(mPa· s) 剛製備後 7曰後 實施例5 T 13. 2 13. 3 實施例6 U 12. 8 13.0 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 =顏料分散液中4 2%以下’相對於此,於不使用本發明 分π散劑之比較例3及4之顏料分散液中為1〇〇%以上。 [著色組成物之製備] ::他成分混合於上述各顏料分散液中,而製備表_5 不之著色組成物。再者,表_5之「溶劑1」及 =」均與顏料分散液中所含之溶劑不同,而為另外調配 [表5 ]The ci-amine has a valence of about 10 mg KOH/g and the main chain is a block copolymer of methacrylic acid. 97122823 135 200911930 [Viscosity Change of Pigment Dispersion] For the pigment dispersions T, U, V, and W obtained in Examples 5 to 6 and Comparative Examples 3 to 4, an E-type viscometer manufactured by Toki Sangyo Co., Ltd. was used. RE-80L"" measures the viscosity immediately after preparation and the viscosity after 7 days of standing in a 23 ° C thermostat (both 20 rpm). The results are shown in Table-4. [Table 4] Table-4 Pigment Dispersion Viscosity (mPa·s) Immediately after 7 制备 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 in the case of Examples 5 and 6 = 4 2% or less of the pigment dispersion liquid, 'relative to this, without using the present invention. The powder dispersion liquid of Comparative Examples 3 and 4 of the powder was 1% by weight or more. [Preparation of Colored Composition]: The ingredients were mixed in each of the above pigment dispersions to prepare a colored composition of Table _5. Furthermore, the "solvent 1" and =" of Table _5 are different from the solvent contained in the pigment dispersion, and are additionally formulated [Table 5].
97122823 136 200911930 黏合劑樹脂 黏合劑樹脂F 2.94 聚合性單體 二季戊四醇六丙稀酸δ旨 3.63 光聚合起始系成分1 2,2’ -雙(鄰氯笨基)-4,4’,5,5’ -四茉某-丨.2’ -聯咪唑 0.38 光聚合起始系成分2 4,4,-雙-二乙胺基二苯基酮 0.19 光聚合起始糸成分3 2-巯基苯并噻唑 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贿見方、厚度〇. 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.6〇o之膜厚。 、繼=,利用2 kW高壓水銀燈,以300 mJ/cm2之曝光量 面曝光處理。其後,使用ο·1重量%碳酸鈉水溶液, 壓進C度23〇C下進行顯影。繼而,“ 3 kg/Cm2之水 化處理,秒喷射水洗處理,於23〇t下進行30分鐘熱硬 上具有成著色樹脂膜。如此’製成於透明玻璃基板 香色樹脂膜之著色板。 之Γ:比:著色板之對比度。測定方法與上述[1] -6。 &測疋]項中所記載者相同。測定結果示於表 [表6] 表-6 ---—- 對比度〜 .實施例5 8630 ' _實施例fi 8600 比較例3 6830 _比較例4 7510 97122823 137 200911930 綜合表~4及矣β 施例5〜6之著多έ之'°果可知’使用本發明分散劑之實 比,分散穩定性二成物且滿 [2-2]實施例7叫 較间對比度’其有用性極高。 例。 15及比較例5〜6:使用[2-h]樹脂之 [顏料分散液之製備] 除了使用黏合劑樹脂E作為分散樹脂 料分散液V相同之方上迷顔 式’衣備綠色顏料分散液X。(苴用 於後述之比較例5。) ^ [著色組成物之製備]97122823 136 200911930 Adhesive Resin Adhesive Resin F 2.94 Polymeric monomer Dipentaerythritol Hexaacrylic acid δ 3.63 Photopolymerization initiating component 1 2,2' -Bis(o-chlorophenyl)-4,4',5 , 5'-tetramos-丨.2'-biimidazole 0.38 photopolymerization starting component 2 4,4,-bis-diethylaminodiphenyl ketone 0.19 photopolymerization starting enthalpy component 3 2-mercaptobenzene And thiazole 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 a glass substrate having a thickness of 7 7 mm using a spin coater. ("AN100" manufactured by Asahi Glass Co., Ltd.), and then 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 == o.6 〇o. , followed by =, using a 2 kW high pressure mercury lamp, exposed exposure of 300 mJ / cm2. Thereafter, development was carried out by using a 0.2% by weight aqueous sodium carbonate solution and pressing C at 23 °C. Then, "3 kg/cm2 of hydration treatment, a second spray water washing treatment, and a colored resin film on a thermosetting sheet for 30 minutes at 23 Torr, such a swatch made of a scented resin film on a transparent glass substrate. Γ 比: ratio: contrast of the colored plate. The measurement method is the same as that described in the above [1] -6. & 疋]. The measurement results are shown in the table [Table 6] Table -6 ----- Contrast ~. Example 5 8630 ' _ Example fi 8600 Comparative Example 3 6830 _ Comparative Example 4 7510 97122823 137 200911930 Synthesis Table ~4 and 矣β Example 5~6 έ ' ' ' ' ' ' ' ' ' ' The actual ratio of the agent, the dispersion stability of the second product and the full [2-2] Example 7 is called the contrast ratio 'is extremely useful. Example 15 and Comparative Examples 5 to 6: using [2-h] resin [Preparation of Pigment Dispersion] In addition to the use of the binder resin E as the dispersion resin dispersion V, the same type of "green pigment dispersion X" was used. (苴 used in Comparative Example 5 described later.) ^ [Coloring Preparation of composition]
1以表-7所示之比例,將上述顏料分散液τ(其中,於比 較例5中為顏料分散液χ,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χ之使用 量(含量),* 2(比較例6)為顏料分散液γ之使用量。 97122823 138 09200 比紗^ 57.78 ‘ 25. 9; 8.00 2.94 3.63 〇 0.38 2 0.38 0.76 <=3 比車交例5 57.78*' 25.93 8.00 1 2.94 CO CO cd 0.38 2 〇 0.38 0. 76 CZ5 實施例15 57.78 25.93 8.00 〇* 2.94 3. 63 CZ5 〇〇 CO 05 T—1 〇〇 CO CZ5 0.76 實施例14 57.78 25.93 8.00 Oh 2. 94 〇 丨 3.63 0.38 05 ί "H 〇 CO CO CZ5 0. 76 S CZ5 實施例13 57.78 25.93 8.00 1—Η 2.94 <Z5 3.63 0.38 2 0〇 CO CO C=5 <3> 實施例12 57.78 25.93 8.00 2.94 3.63 0.38 2 〇* 0.38 0.76 C5 實施例11 〇〇 〇· 卜· LO 25.93 8.00 1 2.94 1 I 3.63 I 〇 0.38 02 r—Η 0.38 0.76 〇· 實施例10 57.78 25.93 8.00 1 2.94 1 | 3.63 | 〇 〇〇 CO <3? CD I H cri 0.38 CO CD 實施例9 57.78 25.93 8.00 1 2.94 3.63 CD OO CO <〇 ⑦ —H O· OO CO Ο 0.76 〇 實施例8 I I 57.78 I 25.93 g 〇〇 1 2.94 1 I 3.63 I 〇 OO CO 〇· 05 1 ' < 0.38 0.76 <=> L實施例7丨 57.78 25.93 8.00 1—H ί 2.94 1 CO CO CO 〇 OO CO C5 0.19 CO CO o 1 I 0.76 CZ) 成分 丙二醇單甲醚乙酸酯 ! 3-乙氧基丙酸乙酯 樹脂^«類 調配量 二季戊四醇六丙烯酸画旨 i季戊四醇四丙稀酸 2, 2’ -(鄰氣苯基)-4,4’,5,5’ -四苯 基聯咪唑 4,4’ -雙-二乙胺基二苯基酮 卜錄苯并奮垒 cja ¥ Λ Λ Y塔 τ ® 蝴硪 F-475(氟系界面活性劑,大曰本 油墨化學工業公司製造) 顏料錄液Ί 丨溶劑1 1 丨溶劑2 | 黏合劑档f脂 聚合1·生單體 光聚合起始 糸成分1 光聚合起始 系成分2 iz U 界面活性劑 6ει sszn卜 6 200911930 [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_ 疋將實施例7〜15及比較例5〜6中所獲得之著色 物 、x •於2 3 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「?曰後 之黏度與「製備丨日後」之黏度的差相對於「製備1曰 後」之黏度的比例來表示。 [表8] 表-81 The pigment dispersion liquid τ (wherein the pigment dispersion liquid in Comparative Example 5, the pigment dispersion liquid W in Comparative Example 6), the solvent, the binder resin, and the polymerizability 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 a monomer, a photopolymerization initiator component, and a surfactant. Further, the value in Table _7 is the content (parts by weight) ° and 'Table-7' * 1 (Comparative Example 5) is the amount (content) of the pigment dispersion liquid, and * 2 (Comparative Example 6) is The amount of the pigment dispersion γ used. 97122823 138 09200 Specific yarn ^ 57.78 ' 25. 9; 8.00 2.94 3.63 〇0.38 2 0.38 0.76 <=3 than car example 5 57.78*' 25.93 8.00 1 2.94 CO CO cd 0.38 2 〇0.38 0. 76 CZ5 Example 15 57.78 25.93 8.00 〇* 2.94 3. 63 CZ5 〇〇CO 05 T-1 〇〇CO CZ5 0.76 Example 14 57.78 25.93 8.00 Oh 2. 94 〇丨3.63 0.38 05 ί "H 〇CO CO CZ5 0. 76 S CZ5 Implementation Example 13 57.78 25.93 8.00 1—Η 2.94 <Z5 3.63 0.38 2 0〇CO CO C=5 <3> Example 12 57.78 25.93 8.00 2.94 3.63 0.38 2 〇* 0.38 0.76 C5 Example 11 〇〇〇· 卜· LO 25.93 8.00 1 2.94 1 I 3.63 I 〇0.38 02 r—Η 0.38 0.76 〇· Example 10 57.78 25.93 8.00 1 2.94 1 | 3.63 | 〇〇〇CO <3? CD IH cri 0.38 CO CD Example 9 57.78 25.93 8.00 1 2.94 3.63 CD OO CO <〇7 —HO· OO CO Ο 0.76 〇Example 8 II 57.78 I 25.93 g 〇〇1 2.94 1 I 3.63 I 〇OO CO 〇· 05 1 ' < 0.38 0.76 <= > L Example 7丨57.78 25.93 8.00 1—H ί 2.94 1 CO CO CO 〇OO CO C5 0.19 CO CO o 1 I 0.76 CZ) Composition Propylene glycol monomethyl ether acetate! 3-ethoxypropionate ethyl ester resin ^«-type compounded dipentaerythritol hexa-acrylic acid i-pentaerythritol tetraacrylic acid 2, 2' - (o-phenyl)-4,4 ',5,5'-Tetraphenylbiimidazole 4,4'-bis-diethylaminodiphenyl ketone benzophene cja ¥ Λ Λ Y tower τ ® butterfly F-475 (fluorine interface Active agent, manufactured by Otsuka Ink Chemical Industry Co., Ltd.) Pigment recording liquid 丨 Solvent 1 1 丨 Solvent 2 | Adhesive file f Fat polymerization 1. Raw monomer photopolymerization initiation 糸 component 1 Photopolymerization initiation component 2 iz U-surfactant 6ει ssznb 6 200911930 [Viscosity change of coloring composition] - Coloring matter obtained in Examples 7 to 15 and Comparative Examples 5 to 6 using an E-type viscometer "RE_" manufactured by Toki Sangyo Co., Ltd. , x • The viscosity (20 rpm) after storage for 1 day at 2 3 C, and after 7 days in a 35 ° C thermostat. 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 of the "after the crucible" and the viscosity of the "preparation after the preparation" to the viscosity after the "preparation of 1". [Table 8] Table-8
根據表-8,對在35°c下靜置7曰後之黏度變化率(黏 度增加率)比較可知’使用[2-1-1]樹脂之實施例?〜13 之著色纽成物’黏度下降、或者只有丨%以下之黏度增 加’與使用其他黏合劑樹脂之實施例14及15之著色組 97122823 140 200911930 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2代 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曰者、以及 •於23°C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]相同之方式’測定對比度。結果示於表-9。 [表9] 表~9 _對比廑 _7曰後 12曰後 ~ _ 8448 8363 ~ 7091 6449 _ 7041 6774According to Table-8, the viscosity change rate (viscosity increase rate) after standing at 35 ° C for 7 比较 was compared. 'Example of using [2-1-1] resin? The color retention of ~13 is reduced, or only the viscosity increase of less than 丨% is higher than that of the color set of Examples 14 and 15 using other adhesive resins, 97122823 140 200911930. On the other hand, it has been found that Comparative Examples 4 and 5 which do not use the dispersing agent of the present invention are not suitable for producing a color filter because they are rapidly cured. [Measurement of Contrast] The coloring compositions obtained in Examples 7, 14, and 15 were stored in the next generation for one day, and the colored composition was used in the same manner as in [Measurement of Contrast] of [2_1;] above. The way, made into a swatch. Further, 'the coloring compositions obtained in Examples 7, 14, and 15 are separately stored at 23 ° C for 7 、, and • stored at 23 ° C for 12 days, and the same is used. The method is made into a swatch. The contrast was measured in the same manner as in the above [2-1] [Measurement of Contrast]. The results are shown in Table-9. [Table 9] Table ~9 _Comparative 廑 _7 曰 After 12 ~ ~ _ 8448 8363 ~ 7091 6449 _ 7041 6774
_實施例 實施例1 4 15 8303 8280" 8〇1? 根據表-9可知,使用「9〗 έθ , ., t 定用1樹脂之實施例7之著色 組成物’與使用其他達 ^ δ劑樹脂之實施例14及15之著 色組成物相比,可更县& u ^ ^ 「 丈長期地維持高對比度,故更佳。 L /合解日•間之測定] 97122823 141 200911930 =施:8〜15中所獲得之著色組成物分別旋塗於装 :有鉻:玻璃基板上,以說之加熱板進行3分鐘預烘 烤,^成乾燥塗佈臈。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卜〇. 6〇〇之膜厚、。 繼而,利用高壓水銀燈通過寬度5〇、县^ 之直線狀光罩圖案,以6〇 j 2 又 _ 後使;°·。4韻氧化卸水溶液心 胍度咖),以壓力㈣㈣進行嘴霧顯影。 七將未曝光部分之著色組成物完全溶解於顯影液中而 示於表_1()。 k者色、,且成物之溶解時間。結果 [直線狀圖案之缺陷之測定] 使用貫施例8〜]^由&成π 「、々初* 中所獲传之者色組成物,以盥上述 [>谷解時間之測定]相同 ,、上这 上形成乾燥塗佈膜,介隖 圾瑀基板 ± 隔先罩圖案進行曝光及顯影。再 :將顯獨設為上述[溶解時 溶解時間的2倍。 〜」T r/r判疋之 :影後’用充分量的水清洗,然 其後,於23(TC之忸π 士 & ^ ^ ^ 宴t 之烘相中進行3〇分鐘後烘烤,而形成由 耆色树月曰膜所構成之直飨 1.8 左右。 直線狀圖案。者色樹脂膜之臈厚為 使用光學顯微鏡 案’對線邊緣的凹 再現性而重複2次 、1 〇倍放大率觀察1 〇條直線狀圖 處加以計數,作為缺陷數。為了確認 ’求出平均值。結果示於表-1 〇。 97122823 142 200911930 再者’將直線狀 圖5。 [表 10] 圖案之代表例之顯微鏡觀察圖表示於 表_ 10EXAMPLES Example 1 4 15 8303 8280" 8〇1? According to Table-9, the coloring composition of Example 7 using '9〗 έ θ, ., t was used, and other δ agents were used. Compared with the colored compositions of Examples 14 and 15 of the resin, it is more desirable to maintain a high contrast ratio for a long time & u ^ ^ "There is better. L / Reconciliation Day / Determination" 97122823 141 200911930 = Shi: The colored compositions obtained in 8 to 15 were respectively spin-coated on a chrome-plated glass substrate, and the hot plate was pre-baked for 3 minutes to form a dry coated crucible. Further, when the spin coating was adjusted The rotation speed is such that the obtained dry coating film reaches the color coordinate mark as the thickness of the film. Then, the high-pressure mercury lamp is used to pass the linear mask pattern of the width 5〇, the county ^, to 6〇j 2 again_ After the time; °·.4 rhyme oxidizing the aqueous solution, the pressure is developed by the pressure (4) (4). The coloring composition of the unexposed part is completely dissolved in the developing solution and is shown in Table_1(). Color, and the dissolution time of the product. Results [Determination of defects in linear patterns] Using Example 8~]^ & π ", 々 * * 中 中 * * * * * * * 々 々 々 々 々 々 々 々 々 々 々 々 々 々 々 々 々 々 々 々 々 々 々 々 々 々 々 & & & & & & & & & & The mask pattern is used for exposure and development. Again: the above is set to the above [2 times the dissolution time during dissolution. ~"T r/r is judged: after the shadow, 'wash with a sufficient amount of water, then, 23 (TC TC π 士 ± & ^ ^ ^ ^ feast t in the baking phase for 3 minutes after baking, and formed by the 耆 color tree moon 曰 film composed of about 1.8 。. Straight pattern. The thickness of the film was counted twice in the optical microscope using the concave reproducibility of the line edge, and the magnification was observed by 1 〇 magnification. The number of defects was counted as the number of defects. The results are shown in Table-1. 97122823 142 200911930 Furthermore, 'the straight line is shown in Fig. 5. [Table 10] A microscopic observation of a representative example of the pattern is shown in Table _ 10
根據表、10可知,使用含有[2+ 及15相比,溶觫s W树知之貫施例14 又,可知1 ㈣Trn生更佳° n"T ° ’ 3有「分子量為400以下、且雙鍵當量為 110以下i之务人此,去L、 又况田里苟 352’雙鍵“或 醇四丙稀_。分子量為 、田里為88)作為聚合性單體 色組成物,直線狀圖案之缺 ^ 、者 良好直線性之圖案。㈣數特別少,從而獲得具有 [2-3]實施例16〜2〇及比較例7 黏合劑樹脂之例 車乂例7.使用[H-2]樹脂作為 [顏料分散液之製備] :了使用黏合劑樹脂R作為分散樹脂以外,以與 顏料慮T相同之方式’製 於後述比較例7。) 刀戚狄ϊ匕、使用 97122823 143 200911930 [著色組成物之製備] 如表-11所示,將久山 ,各成分加以混合,而制, 物。於(其中,於實妒 I備著色la成 只苑例16〜20中使用鈕』, 风 於比較例7中使用顏社、顏料分散液T, τ從用顯科分散液γ 〇 脂D」等之表述,意指「 ^ 11中’「分散樹 脂」。 用黏合劑樹脂D作為分散樹 顏 再者、’表'U中之「溶劑L及「溶劑2」,表示 料分散液」中所含之溶劑 3 川M外’重新調配之溶劑。 97122823 144 200911930 11—|丨< 〔II <〕 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 Ce; 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-髄基苯并噻唑 2-曱基-1~[4-(曱硫基)苯基]-2-p未淋基丙炫-1-酮 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* | 實施例18 分散劑A 分散樹脂D r Η W 實施例17 分散劑A 分散樹脂D τ' i 實施例16 分散劑A 分散樹脂D ω (重量 份) 57.78 | 25.93 I 〇 CD 〇〇 寸 oi CO CD CO 〇〇 CO 〇 CZ> 〇〇 CO CD CO 〇 〇 成分之種類 顏料分散液 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 们-essu6 200911930 [溶解時間之測定] 物吏用^例16〜20及比較例7中所獲得之著色么且放 :’以^上述之[溶解時間之測定〕項中 ,’敎者色纽成物之溶解時間。其中,使 之直線狀光罩圖案,使該光罩 冤又25 "並加以固定,進行曝:罩二案f基板之間距離為150 _12。 & $仃曝先。洛解時間之測定結果示於表 [直線狀圖案之缺陷之測定] 使用實施例16〜20及比較例7 物’以與上述⑽]之[直線狀圖案之缺陷之測定 1= 方式’測定缺陷數。為了確認再現性而重複上= 均值。結果示於表_12。 複2-人’未出平 [表 12]According to Tables and Tables 10, it can be seen that the use of [2+ and 15 compared to the solution of the 觫 觫 树 树 又 又 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 14 The key equivalent is 110 or less. In this case, go to L, and then the 田 352' double bond "or alcohol tetrapropyl _". The molecular weight is, and the field is 88) as a polymerizable monomer color composition, the lack of a linear pattern, and a pattern of good linearity. (4) The number is particularly small, thereby obtaining a ruthenium having [2-3] Examples 16 to 2 and Comparative Example 7 adhesive resin. 7. Using [H-2] resin as [Preparation of pigment dispersion]: In addition to the binder resin R, the binder resin R was used in the same manner as the pigment T, and was produced in Comparative Example 7 described later. ) 戚 戚 ϊ匕 ϊ匕 使用 使用 122 122 122 122 122 122 122 122 122 122 122 122 122 122 122 122 122 122 122 122 122 122 122 122 122 122 122 122 122 122 122 122 122 122 122 122 In the case of (in the case of the actual coloring, I used the button in the case of 16 to 20), the wind used in the comparative example 7 to use Yanshe, the pigment dispersion T, and the τ from the use of the koji dispersion γ 〇 D The expression "etc." means "dispersion resin" in the "^11". The binder resin D is used as the dispersion of the tree, and the "solvent L and the solvent 2" in the 'Table' U indicate the dispersion of the material. Solvent containing solvent 3 Re-dissolved solvent. 97122823 144 200911930 11—|丨< [II <] Details of the composition Comparative Example 7 Dispersant A Dispersing Resin R Propylene Glycol Monomethyl Ether Acetate 3-B Ethyl oxypropionate Ce; dipentaerythritol hexaacrylate 2, 2'-bis(o-phenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole 4, 4 '-Bis-diethylaminodiphenyl ketone 2-mercaptobenzothiazole 2-mercapto-1~[4-(indolyl)phenyl]-2-p unleaved thiol-1-one Fluorine-based surfactant "F-475" manufactured by Otsuka Ink Chemical Industry Co., Ltd. Example 20 Dispersant A Dispersing Resin D CU Example 19 Dispersant A Dispersing Resin D Ο* | Example 18 Dispersant A Dispersing Resin D r Η W Example 17 Dispersant A Dispersing Resin D τ' i Example 16 Dispersant A Dispersing Resin D ω (parts by weight) 57.78 | 25.93 I 〇CD 〇〇 inch oi CO CD CO 〇〇CO 〇CZ> 〇〇CO CD CO 〇〇 component type pigment dispersion solvent 2 binder resin polymerizable monomer photopolymerization starting component 1 photopolymerization initiator component 2 photopolymerization initiator component 3 photopolymerization initiator component 4 surfactants - Essu6 200911930 [Determination of dissolution time] The color of the material obtained in the examples 16 to 20 and the comparative example 7 is placed and placed: 'In the above-mentioned [measurement of dissolution time], the 'color of the color' The dissolution time, in which the linear mask pattern is made, the mask is again fixed and exposed, and the distance between the substrates of the mask and the case f is 150 _12. & The measurement results of the solution time are shown in the table [Measurement of Defects in Straight Line Patterns] Using Examples 16 to 20 and Comparative Example 7 to measure the number of defects with [Measurement of defects in linear patterns 1 = mode] of (10) above Repeat the above = mean value to confirm reproducibility. The results are shown in the table _ 12. Complex 2-person's not flat [Table 12]
根據表一^之結果可明瞭,使用[2 + 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 案。 _ [2-4]實施例21〜29:使㈣g旨系化合物作為光聚合起始 97122823 146 200911930 劑之例。 [著色組成物之製備] 將 57. 78 夤 θ、 酸酯25.93夤:伤、之上述顏料分散液Τ、丙二醇單甲醚乙 而其他成八*份、3-乙氧基丙酸乙_ UG重量份、進 再者,2 ”乂混合’而製備表_13所示之著色組成物。 劑a、b、J3中之、光聚合起始系成分5〜8(㈣系起始 及d),勿別為以下化合物。 L 化 35]From the results of Table I, it is understood that the coloring compositions of Examples 16 to 20 using [2 + 2] resins have a shorter dissolution time and better developability. Further, it can be seen that since the defects of the pattern are small, a better linearity can be obtained. _ [2-4] Examples 21 to 29: Examples of the (iv) g-based compound as a photopolymerization initiator 97122823 146 200911930. [Preparation of coloring composition] 57.78 夤θ, acid ester 25.93 夤: the above pigment dispersion Τ, propylene glycol monomethyl ether B and other 八*份, 3-ethoxypropionic acid B _ UG The color composition shown in Table _13 is prepared by adding 2 parts by weight and mixing. In the agents a, b, and J3, the photopolymerization initiation component 5 to 8 ((4) is the starting and d) , do not be the following compounds. L 35]
(特酸系起始劑a) [化 36](Special acid initiator) a [Chemical 36]
97122823 147 200911930 (肟酯系起始劑b) [化 37]97122823 147 200911930 (an oxime ester starter b) [Chem. 37]
(肟酯系起始劑c) [化 38](肟 ester based initiator c) [Chem. 38]
(月亏醋系起始劑d :汽巴精化(Ciba Specialty Chemicals)公司製造之「Irgacure OXE02」) 97122823 148 200911930 εΙ-礤 〔coI<〕 實施例2£ Μ 2. 94 CO CD CO 卜 寸· 05 d r Ή 寸* 1 < 1 1 1 〇 實施例28 e- 2. 94 3. 63 〇 S CI5 實施例27 e-h 2. 94 3.63 〇 CO 1 1 〇 1 1 1 1 (NI <〇 實施例26 e- 2.94 3.63 卜 寸· ο 寸 Η 1 1 1 1 C<1 C5 CZ5 實施例25 e-· 2. 94 CQ CO CO 1 1 1 CO oi 1 1 CN1 r-H 1 S CZ5 實施例24 E-^ 2.94 1 3.63 1 1 1 1 1 1 I 一 C<1 C3 <〇 實施例23 2.94 3.63 I 1 1 1 1 1 LO CO 1 03 C=5 c=5 實施例22 2.94 3.63 1 1 1 1 1 〇 卜· 1 1 03 <=) ο 實施例21 6- 2.94 3.63 | 1 1 1 1 〇 卜· 1 1 1 oa ο <〇 成分 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 基聯咪唑 4, 4’ -雙-二乙胺基二苯基酮 2-毓基苯并噻唑 2-曱基-1-[4-(曱硫基)苯基]-2_σ未 啉基丙烷-1-酮 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 s ” ϊ Η ±1 齋 ^ i 5 ^ LO (i. 成分之種類 1黏合劑樹脂| 1聚合性單體1 光聚合起始 系成分1 光聚合起始 糸成分2 光聚合起始 糸成分3 光聚合起始 糸成分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 糸成分8 界面活性劑(Monthly vinegar-based initiator d: "Irgacure OXE02" manufactured by Ciba Specialty Chemicals Co., Ltd.) 97122823 148 200911930 εΙ-礤[coI<] Example 2 £ Μ 2. 94 CO CD CO · 05 dr 寸 inch* 1 < 1 1 1 〇 Example 28 e- 2. 94 3. 63 〇S CI5 Example 27 eh 2. 94 3.63 〇CO 1 1 〇1 1 1 1 (NI <〇implementation Example 26 e- 2.94 3.63 Bu inch · ο inch Η 1 1 1 1 C<1 C5 CZ5 Example 25 e-· 2. 94 CQ CO CO 1 1 1 CO oi 1 1 CN1 rH 1 S CZ5 Example 24 E- ^ 2.94 1 3.63 1 1 1 1 1 1 I - C < 1 C3 <〇 Example 23 2.94 3.63 I 1 1 1 1 1 LO CO 1 03 C=5 c=5 Example 22 2.94 3.63 1 1 1 1 1 ·卜·1 1 03 <=) ο Example 21 6- 2.94 3.63 | 1 1 1 1 ·卜·1 1 1 oa ο <〇 component pigment dispersion binder resin F dipentaerythritol hexaacrylate 2, 2 '-(o-phenyl)-4,4',5,5'-tetraphenylbiimidazole 4,4'-bis-diethylaminodiphenyl ketone 2-mercaptobenzothiazole 2-mercapto -1-[4-(indolyl)phenyl]-2_σ-nonylpropan-1-one ketone ester ester starter a oxime ester Starting agent b oxime ester-based initiator c oxime ester-based initiator ds ” ϊ Η ±1 斋 ^ i 5 ^ LO (i. Component type 1 binder resin | 1 polymerizable monomer 1 photopolymerization initiation system Component 1 Photopolymerization initiation enthalpy component 2 Photopolymerization initiation enthalpy component 3 Photopolymerization initiation enthalpy component 4 Photopolymerization initiation component 5 Photopolymerization initiation component 6 Photopolymerization initiation component 7 Photopolymerization initiation enthalpy component 8 surfactants
6寸I 200911930 [溶解時間之測定] 使用實施例21〜29中所獲得之著 ^述[2 — 3]之[溶解時間之測定]項相同之方式, 其中,所製成之乾燥塗佈: 厚為2.5㈣左右。溶解時間之測定結果示於表 [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 結果不於表—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 (迅)製備後於23°C下靜置1曰者、以及 (匕)於23力下靜置1日後,於35。〇: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8〇°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4。 再者’於表-14中’〇意指無異物,〇△意指異物 97122823 150 200911930 為5個以下’ △意指異物為6個以上。 [NMP耐性] 將以與上述[異物評價]中之(诅)相同之方式形成 有乾餘塗佈膜的玻璃基板’設置於加入有曱基吡略 °疋酮(NMP)之試樣瓶中,以使其長度的一半浸潰於n〜 曱基吡咯啶酮(NMP)中,並加蓋,於23。〇下靜置3〇 分鐘。 將基板取出後,進行水洗,並吹壓縮空氣進行乾燥。 、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。 其結果不於表—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。NMp非浸潰部分 ‘:之表面變粗經,或者雖然不明顯但仍可判明浸潰 部分/非浸潰部分之邊界。 △:於表面上可見明顯的析出物,可明確地判明歷 浸潰部分/非浸潰部分之邊界線。 97122823 151 200911930 〔H嵴〕 實施例29 CO od CNl oo 〇 <3 〇 <1 實施例28 E-h 05 〇6 oa 〇 〇 < 實施例27 Csl od 03 LO 〇 〇 < 實施例26 I 31.3 I 寸 <3 <1 <3 〇 |實施例25 I E-< LO 寸· CO 寸 C<1 〇 〇 〇 實施例24 e-· 〇) ai C<i LO oa 〇 〇 〇 實施例23 | ◦ CO CO LO oa 〇 〇 〇 實施例22 | CO 寸* CO LO 03 〇 〇 〇 實施例21 CO CD Cvl LO C<1 〇 〇 〇 實施例 顏料分散液 線寬(#m) 溶解時間(秒) 1曰後 7日後 NMP耐性 異物評價 essu6 200911930 根據表-14之結果可知,使用職系化合物作為光聚合 起始系成分(光聚合起始劑)之實施例21〜25,與使用其 他光聚合起始劑之實施例26〜29相比較,並未產生異 物,NMP耐性亦優異。又,併用肪醋系化合物與苯乙嗣衍 生物作為光聚合起始系成分之實施例25,與其他實施例 相比,雖然光聚合起始系成分之總含量相同或者較少,卻 顯不更高敏感度(可獲得線寬較粗之圖案)。 [2-5]實施例30〜36 :使用芳香族羧酸系化合物之例。 於10.55重里伤之顏料分散液τ中,加入丙二醇單曱酿 乙酸酯5. 96重量份、〇. 42重量份之黏合劑樹脂E、汽巴 精化a司製造之光聚合起始劑「I rgacure 」(化學 、’、。構參照上述[2 _ 5 ]中之「月亏g旨系起始劑d」)以及汽巴精 化公司製造之「Irgacure 907」(2_曱基甲硫基) 笨基]-2-咮啉基丙烷-卜酮)各010重量份、作為聚合性 單體之季戊四醇四丙烯酸酯〇· 77重量份(其中,僅於實施 例36中為〇.86重量份),進而表_16中所記載之芳香族 幾酸系化合物(或者與其進行比較之化合物)〇. 〇85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_丨5所示。 97122823 153 200911930 [表 15] 表-15 化合物No. 結構式 商品名或化合物名 1 0 共榮社化學公司製造之 [H0A-MPL] 2 >5 鄰苯二甲酸單曱酯 (Aldrich公司製造) 3 °νΡ HO 1 〇入。 ο" 鄰苯二甲酸單苄酯 (Aldrich公司製造) 4 Ο 0 共榮社化學公司製造之 「LIGHT ACRYLATE Η0Α-ΗΗ」 5 °v9 —〇 I Λ 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日者, 154 97122823 200911930 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-8〇l」,分 別對實施例30〜36中所得、並以上述(v )或(yi)之方 法靜置後的著色組成物之黏度(2〇 rpm)進行測定。再 者’表-16中之「黏度變化率」’係以「進而35。匸、6 曰後」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®案之缺陷之測定]項相同之方式進行測定。再 =,對於各實施例之(v)及⑷之各著色组成物,各測 定2次,求出平均值。測定結果示於表_丨6。 [線寬之測定] 對實施例30〜36中所獲得、並以上述(v)或(vi)之 方法加以靜置後的菩备4 ’ 便的者色組成物,分別以與上述[2-4]之 [線寬之測定1相闾$ 士 π, 」相U之方式進行測定。結果 6。 [6-4]溶解時間之測定 各 方30〜36中所獲得、並以上述(V)或⑷之 f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1 j 、 、 同之方式進行測定。結果示於表 -1 b 〇 97122823 155 200911930 〔91 <〕 實施例36 1 4. 40 5.91 CO 一 CO CO § ι^Η CO 〇 〇> r-H LO CD CD 實施例35 化合物6 4.32 ! 5 LO CO T*"H CO § oo LO 卜 r-H CO CO Ο) οα 导 實施例34 化合物5 4. 59 LO 1-Η CO CO 寸· CO CO CO 00 CO 1-―1 CO (XI LO cd OO 呀 實施例33 i化合物4 T-4 r-Η 呀· 5.43 1-H CO CO CO s 00 1-H CO 32.1 05 LO oi 實施例32 化合物3 4. 20 LO 〇> -3.6 oo 1-H CO CT3 CO <NI i 1 LO LO T-H 實施例31 化合物2 4.17 LO d> 05 oi 1 S CO CM_ CO CO LO C^l in CO (N1 實施例30 化合物1 1_ 4. 05 LO 〇 CD CO LO CO LTD 32.1 co r-Η CO LO 寸· 1-H CO 芳香族羧酸系化合物 23°C、1 曰後(mPa· s) 1 進而 35°C、6 曰後(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°C、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) 9- 200911930 f:據表—16可知’含有芳香族羧酸系化合物之實施例3〇 〜32,與不含該化合物之實施例3…比,黏度二 ^更高’溶解時間更短(顯影性優異)且溶解性不經時= 又,可知線寬之經時性減少(敏感度之經時性下降) 更少,缺陷之經時性增加亦較少。 [3 ]貫施例3 7〜4 3 : Γ ϊ a * 4d · u I.色素紅254等使用例。 [顏料分散液之製備] (1) P. R. 254顏料分散液之製備 細乍為紅色顏料之8·5〇重量份之C I•色素紅254、 =分散齊"經固形分換算6·23重量份、合成 一 办刀換异2. 83重量份、作為溶劑之丙 ::早f鍵乙酸醋50.16重量份,與直徑〇.5 _之氧化 錯珠225重量份一(si it * e 刀门填充至不鏽鋼容器中,藉由塗料振動 機。進饤6小時分散,而製備U.254顏料分散液。 (2) P· R. 177/P· Y. 15〇顏料分散液之製備 將作為紅色顏料之22.4〇重量份之CI•色素紅⑺、作 為上色顏料之5.60重量份之C I.色素黃γΐ5〇、畢克化學 j製造之分散劑「Dlsperbyk2謝」經固形分換算848 旦里伤口成例18中獲得之樹脂s經固形分換算&⑽重 里伤以及作為溶劑之丙二醇單甲酸乙酸自旨工57. 66重量 與直徑0.5 mm之氧化結珠675重量份一同填充至不 鐵鋼容器中’藉由塗料振動機進行“、時分散 P.R.177/P.Y.150顏料分散液。 有 [著色組成物之製備] 97122823 157 200911930 於上述P.R· 254顏料分散液3.87重量份、以及上述 P. R. 177/P. Y. 150顏料分散液4. 15重量份中,加入丙__ 醇單曱醚乙酸酯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「IrgacureOXE02」(化學結構參照上述[2_5]中之 「肟酯系起始劑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-(甲硫其) 苯基]-2-咮啉基丙烷-1-酮)〇. 〇7重量份、大日本油墨公司 製造之界面活性劑「F475」0· 〇〇3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中為〇.78重量份),進而表_17中^己载之 方香族羧酸系化合物(或者與其進行比較之化合物)〇.⑽ 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 與其進仃比較之化合物),分別如上述表_丨5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日者、以及 、)將(v )進而於3 5。〇之恆溫槽中靜置6日者, 刀別進仃以下之評價。結果示於表-17。 [組成物之黏度變化] 對東機產業公司製造之E型黏度計「RE-80L」,分另, 對貫施例37〜/1Q山- 加以靜置後的^所獲得、並以上述(V)或㈤之方沒 者色組成物之黏度(2〇 rpm)進行測定。月 97122823 158 200911930 者,表-17中之「黏度變化率」,係以「進而35°C、6曰 後」之黏度與「23°C、1日後」之黏度的差相對於「23t、 1曰後」之黏度的比例來表示。測定結果示於表-17。 97122823 159 200911930 卜 i 實施例43 1 〇〇 呀· CO T-Η LO cd 實施例42 化合物6 LO 却’ 5. 04 oo 實施例41 化合物5 4. 77 05 Η LO oo oo 實施例40 L_ 化合物4 CO 〇〇 〇〇 LO 03 <3Ϊ> 實施例39 [化合物3 4.53 CO 實施例38 |化合物2 1 4. 55 4. 50 -1.1 實施例37 化合物1 4. 68 4.62 1-1.3 1 芳香族羧酸系化合物 23°C、1 曰後(mPa· s) 進而 35°C、6 曰後(mPa· s) 黏度變化率00 黏度變化 091 200911930 根據表-17可知,含有芳香族羧酸系化合物之實施例37 〜39,與不含該化合物之實施例4〇〜43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 二本專利申請案(特願2007-196441 )、2008年2月6 J申 凊之日本專利申請案(特願2008-026120)、2008年2月 13曰申明之曰本專利申請案(特願2〇〇8_〇31884)、別⑽ 年4月7日申請之日本專利申請案(特願2〇〇8 —〇99以7)、 =^年5月3G日中請之日本專利中請案(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) 本I明务揮如下之有用效果,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麵 W微粒化之㈣分散’結果可製造高穿透率、高對比 低膜厚的彩色遽光片之顏料分散液及著色組成物。 ⑵特別是可提供達成了在以綠色像素之高亮度化為目 的而使㈣化㈣菁綠色顏料時所存在之問題、即兼具高 對比度與分散穩定性的顏料分散液及彩色滤光片用著色 組成物。 ⑻可提供具有以下等優點之彩色濾光片著色組成物: 97122823 161 200911930 $顯影液之溶解性良好、於顯影步驟巾可在特定時間内顯 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。6 inch I 200911930 [Measurement of dissolution time] The same manner as in [Measurement of dissolution time] of [2 - 3] obtained in Examples 21 to 29 was used, wherein dry coating was prepared: The thickness is about 2.5 (four). The measurement results of the dissolution time are shown in the table. [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 result is not shown in Table-14. [Evaluation of foreign matter] The coloring compositions obtained in Examples 21 to 29 were each placed at a temperature of 23 ° C after being rapidly prepared, and (匕) were allowed to stand under a force of 23 for 1 day. 35. 〇: The 6-inch thermostat is stored in a glass substrate of 5 cm square (AN100 manufactured by Asahi Glass Co., Ltd.), heated at 8 °C for 3 minutes, and exposed at 60 mJ/cm2. Dry the coated film. 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 4. Further, 'in Table-14' means no foreign matter, and 〇△ means foreign matter 97122823 150 200911930 is 5 or less' Δ means 6 or more foreign substances. [NMP resistance] A glass substrate having a dry coating film formed in the same manner as in (foreign matter evaluation) described above was placed in a sample bottle to which decylpyrrolidone (NMP) was added. , so that half of its length is immersed in n~pyridylpyrrolidone (NMP) and capped at 23. Leave it under your arm for 3 minutes. After the substrate was taken out, it was washed with water, and compressed air was blown and dried. 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 result is not in Table-14. Further, the surface state of the observed portion was evaluated in Table_14 in the following manner.无. No difference from the impregnation part of NMP, the surface is smooth 〇 △: a small amount of precipitates are visible on the surface. NMp non-impregnated part ‘: The surface becomes rough, or although it is not obvious, the boundary of the impregnated/non-impregnated part can still be determined. △: Obvious precipitates were observed on the surface, and the boundary line of the submerged/non-impregnated portion was clearly discriminated. 97122823 151 200911930 [H嵴] Example 29 CO od CNl oo 〇<3 〇<1 Example 28 Eh 05 〇6 oa 〇〇< Example 27 Csl od 03 LO 〇〇< Example 26 I 31.3 I inch <3 <1 <3 〇|Example 25 I E-< LO inch · CO inch C<1 〇〇〇Example 24 e-· 〇) ai C<i LO oa 〇〇〇Implementation Example 23 | ◦ CO CO LO oa 〇〇〇 Example 22 | CO Inch * CO LO 03 〇〇〇 Example 21 CO CD Cvl LO C<1 〇〇〇 Example Pigment Dispersion Line Width (#m) Dissolution Time (seconds) NMP resistance foreign matter evaluation after 7 days essu6 200911930 According to the results of Table-14, Examples 21 to 25 using a grade compound as a photopolymerization initiator component (photopolymerization initiator), and other In comparison with Examples 26 to 29 of the photopolymerization initiator, no foreign matter was generated, and NMP resistance was also excellent. Further, in Example 25 in which a fatty vinegar-based compound and a phenethyl hydrazine derivative were used as a photopolymerization initiator component, the total content of the photopolymerization initiator component was the same or less than that of the other examples, but it was not observed. Higher sensitivity (a pattern with a thicker line width). [2-5] Examples 30 to 36: Examples in which an aromatic carboxylic acid compound is used. In the pigment dispersion τ of 10.55 heavy wounds, propylene glycol monobromide acetate was added in an amount of 5.96 parts by weight, 42. 42 parts by weight of the binder resin E, and the photopolymerization initiator manufactured by Ciba Specialty Chemicals Division A" "Irgacure" (Chemical, ', ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, ) 基 ] ] ] ] ] ] 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 86 Further, the aromatic acid-based compound (or a compound thereof) described in Table 16 was further prepared to have a coloring composition of 85 parts by weight. Further, the aromatic carboxylic acid-based compounds (and the compounds to be compared therewith) used in the examples are shown in Table _5 below. 97122823 153 200911930 [Table 15] Table-15 Compound No. Structural formula or compound name 1 0 [H0A-MPL] 2 >5 Monodecyl phthalate (manufactured by Aldrich) manufactured by Kyoeisha Chemical Co., Ltd. 3 °νΡ HO 1 Loading. ο" Monobenzyl phthalate (made by Aldrich) 4 Ο 0 "LIGHT ACRYLATE Η0Α-ΗΗ" manufactured by Kyoeisha Chemical Co., Ltd. 5 °v9 —〇I 二 Dimethyl phthalate (Manufactured by Aldrich) 6 "H0A-MS", manufactured by Kyoeisha Chemical Co., Ltd. [Evaluation of coloring composition] After the coloring composition (v) obtained in Examples 30 to 36 was prepared and allowed to stand at 23 ° C for one day, And (vi) that the (v) was further allowed to stand in a thermostat at 35 ° C for 6 days, and 154 97122823 200911930 was subjected to the following evaluations. The results are shown in Table_16. [Viscosity change of the composition] The E-type viscometer "re-8〇l" manufactured by Toki Sangyo Co., Ltd. was used, and the results obtained in Examples 30 to 36 were respectively allowed to stand by the above method (v) or (yi). The viscosity of the subsequent colored composition (2 rpm) was measured. In addition, the "viscosity change rate" in Table-16 is the difference between the viscosity of "further after 35. 匸, 6 曰" and the viscosity of "23 ° C, 1 day later" relative to "the rest at 23 C" The ratio of the viscosity after 1 day is expressed. The results of the measurements are shown in Table-16. [Measurement of Defects in Straight Line Pattern] The coloring compositions obtained in Examples 30 to 36 and allowed to stand by the above method (v) or (vi) are respectively [straight to the above [2_2] The measurement of the defects in the case of the case is measured in the same manner. Further, each of the colored compositions of (v) and (4) of each of the examples was measured twice, and the average value was determined. The measurement results are shown in Table _丨6. [Measurement of line width] The color compositions of the radix 4' obtained in Examples 30 to 36 and which were left to stand by the method of the above (v) or (vi) were respectively -4] The measurement of [line width measurement 1 phase 闾 $ 士, ” phase U is performed. Result 6. [6-4] The dissolution time is determined by the coloring composition obtained in each of 30 to 36 and resting on the above (V) or (4) f, respectively, and the dissolution time of [2-3] above. The measurement 1 j , and the same method were used for the measurement. The results are shown in Table-1 b 〇97122823 155 200911930 [91 <] Example 36 1 4. 40 5.91 CO-CO CO § ι^Η CO 〇〇> rH LO CD CD Example 35 Compound 6 4.32 ! 5 LO CO T*"H CO § oo LO 卜rH CO CO Ο) οα Introduction Example 34 Compound 5 4. 59 LO 1-Η CO CO Inch · CO CO CO 00 CO 1-―1 CO (XI LO cd OO 呀Example 33 i Compound 4 T-4 r-Η 呀· 5.43 1-H CO CO CO s 00 1-H CO 32.1 05 LO oi Example 32 Compound 3 4. 20 LO 〇> -3.6 oo 1-H CO CT3 CO < NI i 1 LO LO TH Example 31 Compound 2 4.17 LO d > 05 oi 1 S CO CM_ CO CO LO C^l in CO (N1 Example 30 Compound 1 1_ 4. 05 LO 〇CD CO LO CO LTD 32.1 co r-Η CO LO inch · 1-H CO Aromatic carboxylic acid compound 23 ° C, after 1 曰 (mPa· s) 1 Further 35 ° C, after 6 曰 (mPa· s) Viscosity change rate 23 °C, 35°C after 1 day, 23°C after 6 days, 35°C after 1 day, 23°C after 6 days, 35°C after 1 day, and viscosity change after 6 days (seconds) Line width (" m) Defects (a) 9- 200911930 f: According to Table-16, 'containing aromatic carboxyl Examples 3 to 32 of the compound, compared with Example 3, which does not contain the compound, the viscosity is higher, the dissolution time is shorter (excellent developability), and the solubility is not longer = again, the line width is known. The decrease in time (the decrease in sensitivity over time) is less, and the lapse of time is less. [3] Example 3 7~4 3 : Γ ϊ a * 4d · u I. Pigment Red 254 [Example of use] [Preparation of pigment dispersion] (1) Preparation of PR 254 pigment dispersion Fine 乍 is 8·5 〇 of red pigment, CI• Pigment Red 254, = scattered " · 23 parts by weight, a synthetic knife-changing difference 2. 83 parts by weight, as solvent C:: early f-key vinegar 50.16 parts by weight, and diameter 〇.5 _ oxidized wrong beads 225 parts by weight (si it * e The knife door is filled into a stainless steel container by means of a paint shaker. The dispersion was allowed to stand for 6 hours to prepare a U.254 pigment dispersion. (2) P·R. 177/P·Y. Preparation of 15〇 pigment dispersion liquid as 22.4 parts by weight of red pigment, • Pigment Red (7), as a coloring pigment, 5.60 parts by weight of C I. Pigment Yellow ΐ ΐ 〇 〇 毕 毕 毕 D 「 「 「 「 「 「 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 848 57. 66 parts by weight and 675 parts by weight of oxidized beads having a diameter of 0.5 mm were filled into a non-ferrous steel container. 'When the paint shaker was used, the PR177/PY150 pigment dispersion was dispersed. And the propylene glycol monoterpene ether acetate 5.63 parts by weight of the above-mentioned PR 177/PY 150 pigment dispersion 4.15 parts by weight The resin F obtained in Synthesis Example 6 was converted into a photopolymerization initiator "Irgacure OXE02" manufactured by Ciba Specialty Chemicals Co., Ltd. according to the solid content conversion (the chemical structure is referred to the "Oxyl Ester" in the above [2_5]. Agent d") 0. 05 parts by weight, Ciba Specialty Chemicals Co., Ltd. Photopolymerization initiator "Irgacure 907" (2-mercapto-1-[4-(methylthio)phenyl]-2-indolyl propan-1-one) 制造. 〇 7 parts by weight, large The surfactant "F475" manufactured by Nippon Ink Co., Ltd. is 0.3 parts by weight, and "T01382", which is a polymerizable monomer, is 0.70 parts by weight of "T01382" (wherein only 实施.78 weight in Example 43) The red coloring composition was prepared by further adding a compound of the aromatic carboxylic acid compound (or a compound thereof) contained in Table _17 to (10) parts by weight. Further, the aromatic carboxylic acid-based compound (and the compound which is compared with the ruthenium compound) used in each of the examples are shown in Table _5, respectively. [Evaluation of coloring composition] The coloring composition (v) obtained in each of Examples 37 to 43 was prepared and allowed to stand at 23 ° C for one day, and (v) further to 3 5 . If you leave it in the constant temperature bath for 6 days, the knife will not be evaluated. The results are shown in Table-17. [Viscosity change of the composition] The E-type viscometer "RE-80L" manufactured by Toki Sangyo Co., Ltd. is obtained by the above-mentioned method 37~/1Q mountain - after being placed, and the above ( The viscosity (2 rpm) of the color composition of the V) or (5) was measured. In the case of the month 9712823 158 200911930, the "viscosity change rate" in Table-17 is the difference between the viscosity of "further after 35 ° C, 6 曰" and the viscosity of "23 ° C, 1 day later" relative to "23t, 1 The ratio of the viscosity of the "after" is expressed. The measurement results are shown in Table-17. 97122823 159 200911930 卜 i Example 43 1 Oops · CO T-Η LO cd Example 42 Compound 6 LO However ' 5. 04 oo Example 41 Compound 5 4. 77 05 Η LO oo oo Example 40 L_ Compound 4 CO 〇〇〇〇LO 03 <3Ϊ> Example 39 [Compound 3 4.53 CO Example 38 | Compound 2 1 4. 55 4. 50 - 1.1 Example 37 Compound 1 4. 68 4.62 1-1.3 1 Aromatic carboxy Acid compound 23 ° C, 1 曰 (mPa · s) and further 35 ° C, 6 曰 (mPa · s) viscosity change rate 00 viscosity change 091 200911930 According to Table-17, it contains an aromatic carboxylic acid compound Examples 37 to 39 showed less increase in viscosity over time than in Examples 4 to 43 without the compound, and the viscosity stability was higher. 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 June 21, 2007 (Japanese Patent Application No. 2007-163914), and two patent applications filed on July 27, 2007 (Japanese Patent Application No. 2007-196441), February 2008 6 J. Japanese Patent Application (Japanese Patent Application No. 2008-026120), February 13th, 2008, and the application for this patent application (Special Wish 2〇〇8_〇31884), and (7) April 7th Japanese Patent Application (Special Wish 2〇〇8-〇99 to 7), =^ Japanese Patent Application in May 3G, Japan (Special Wish 2〇〇8-143372), citing its contents As a reference. (Industrial Applicability) This is a useful effect of the following, and its industrial use value is extremely large. (1) It is possible to provide a pigment dispersion having a high transmittance, a high contrast and a low film thickness, and a coloring composition, by providing a small amount of addition amount to efficiently atomize the surface of the surface. Things. (2) In particular, it is possible to provide a pigment dispersion liquid and a color filter which have a high contrast ratio and a dispersion stability for the purpose of imparting (4) a cyanine green pigment for the purpose of increasing the luminance of green pixels. Coloring composition. (8) A color filter coloring composition having the following advantages can be provided: 97122823 161 200911930 $The developer has good solubility, and can be developed in a specific time in the developing step; no colored resin remains on the non-image portion on the substrate. The undissolved matter of the 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.
⑷使用上述彩色濾光片用著色組成物 質彩色濾光片。 ^DD 晋提供使用了上述彩色濾光片之高品f液晶顯示裝 置及有機EL顯示器。 衣 【圖式簡單說明】 表示具備本發明之彩色遽光片的有機EL元件之 一例的剖面概略圖。 τ < 穿===以說明於實施例中測定著色板之平行 色度的方法之模式圖。 色系色度圖之色度座標(二象素的奶表 ,用之背光光源的發光光譜之/ μ心對比度時所使 圖4係表示顯示實施例中測 之特性的光譜之圖。 十比度時所使用偏光板 圖5係用顯微鏡觀察實施 狀圖案(像素)之代表例之圖。(a)=缺陷所使用之直線 為缺陷數為57之圖案,(c)為缺人為無缺陷之圖案’㈦ 【主要元件符號說明】 、㈢數為1〇〇以上之圖案。 10 透明支持基板 20 像素 97122823 162 200911930 30 有機保護層 32 色彩亮度計 33、35 偏光板 34 著色板 36 光 37 背光源 40 無機氧化膜 50 透明陽極 51 電洞注入層 52 電洞傳輸層 53 發光層 54 電子注入層 55 陰極 100 有機EL元件 500 有機發光體 97122823 163(4) A coloring composition color filter is used for the color filter described above. ^DD Jin provides high-quality f liquid crystal display devices and organic EL displays using the above color filters. [Brief Description of the Drawings] A schematic cross-sectional view showing an example of an organic EL device including the color light-emitting sheet of the present invention. τ < Wear === to illustrate a schematic diagram of a method of determining the parallel chromaticity of the colored plate in the examples. The chromaticity coordinates of the color chromaticity diagram (a two-pixel milk meter, the illuminance spectrum of the backlight source/μ-heart contrast ratio is used to make a graph showing the spectrum of the characteristics measured in the examples. FIG. 5 is a diagram showing a representative example of an embodiment pattern (pixel) observed by a microscope. (a) = the line used for the defect is a pattern having a defect number of 57, and (c) is a defect-free one. Pattern '(7) [Main component symbol description], (3) Number is 1〇〇 or more. 10 Transparent support substrate 20 pixels 97102923 162 200911930 30 Organic protective layer 32 Color brightness meter 33, 35 Polarizer 34 Coloring plate 36 Light 37 Backlight 40 Inorganic oxide film 50 Transparent anode 51 Hole injection layer 52 Hole transport layer 53 Light-emitting layer 54 Electron injection layer 55 Cathode 100 Organic EL element 500 Organic light-emitting body 97122823 163
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JP2007-196441 | 2007-07-27 | ||
JP2008026120A JP5320760B2 (en) | 2007-07-27 | 2008-02-06 | Coloring composition for color filter, color filter, and liquid crystal display device |
JP2008-026120 | 2008-02-06 | ||
JP2008031884A JP4407758B2 (en) | 2007-07-27 | 2008-02-13 | Pigment dispersion, coloring composition for color filter, color filter, and liquid crystal display device |
JP2008-031884 | 2008-02-13 | ||
JP2008099747 | 2008-04-07 | ||
JP2008-099747 | 2008-04-07 | ||
JP2008-143372 | 2008-05-30 | ||
JP2008143372A JP2009052020A (en) | 2007-07-27 | 2008-05-30 | Pigment dispersion, coloring composition for use in color filter, color filter, liquid crystal display unit, and organic el display |
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- 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 (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI500710B (en) * | 2008-06-30 | 2015-09-21 | Sanyo Color Works | Pigment dispersions for color filters |
TWI470036B (en) * | 2009-03-26 | 2015-01-21 | Fujifilm Corp | Pigment dispersion, colored curable composition, color filter and method of manufacturing the same |
TWI486334B (en) * | 2009-09-14 | 2015-06-01 | Fujifilm Corp | Photopolymerizable composition, color filter and method of producing the same, solid-state image pick-up device, liquid crystal display, planographic printing plate, and novel compound |
TWI595055B (en) * | 2012-06-20 | 2017-08-11 | 阪田油墨股份有限公司 | A green colored composition for a color filter |
US10921708B2 (en) | 2015-12-08 | 2021-02-16 | Fujifilm Corporation | Radiation-sensitive resin composition, cured film, pattern forming method, solid-state imaging device, and image display device |
TWI731895B (en) * | 2015-12-08 | 2021-07-01 | 日商富士軟片股份有限公司 | Radiation-sensitive resin composition, cured film, pattern forming method, solid-state imaging device, and image display device |
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 |
TW201037041A (en) | 2010-10-16 |
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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