TW201233734A - Diketopyrrolopyrrole pigment composition for color filter, coloring composition for color filter, and color filter - Google Patents
Diketopyrrolopyrrole pigment composition for color filter, coloring composition for color filter, and color filter Download PDFInfo
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/004—Diketopyrrolopyrrole dyes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0002—Grinding; Milling with solid grinding or milling assistants
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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
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0022—Wet grinding of pigments
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
- C09B67/0034—Mixtures of two or more pigments or dyes of the same type
- C09B67/0039—Mixtures of diketopyrrolopyrroles
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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
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
- C09B67/0041—Blends of pigments; Mixtured crystals; Solid solutions mixtures containing one azo dye
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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
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
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Abstract
Description
201233734 六、發明說明: 【發明所屬之技術領域】 本發明係關於一種彩色濾光片甩二酮基吡咯并吡咯 系顏料組成物、彩色濾光片用著色組成物、及使用該彩色 濾光片用著色組成物所形成之彩色濾光片。 【先前技術】 液晶顯示裝置係將2片偏光板挾住之液晶層,藉由控 制通過第1片偏光板之光的偏光度情形,控制通過第2片 • 偏光板之光量而進行顯示之顯示裝置,以使用扭轉向列(TN) 型液晶之型式為主流。藉由於此2片偏光板之間設置彩色 濾光片而可彩色顯示,近年,可使用於電視或個人電腦螢 幕,故對於彩色濾光片之高亮度化、高對比度化、高顏色 再現性之要求提高。 彩色濾光片係於玻璃等透明基板的表面使2種以上相 異色相之微細帶狀(strip)的濾光片區段平行或交叉配置 ^ 者,或使微細的濾光片區段以固定縱橫的配列配置者所構 成者。一般常由紅、綠、及藍3色的濾光片區段所形成, 此等各區段係例如數微米至數百微米般微細,而且,每一 色相以特定之排列整齊配置。 一般,在彩色液晶顯示裝置中係於彩色濾光片上藉由 蒸鍍或濺鍍形成用以驅動液晶之透明電極,進一步,於其 上形成用以使液晶朝一定方向配向之配向膜。為充分得到 此等透明電極及配向膜之性能,係在形成彩色濾光片之製 造步驟中,進行一般於200°C以上,較佳於230°C以上之高 323842 4 201233734 溫處理。因此’目前彩色濾光片之製造方法係以耐光性、 耐熱性優異之顏料作為著色劑,所謂顏料分散法的方法為 主流。 在顏料分散法中,紅色濾光片區段係一般使作為著色 劑之二_基料并*各系顏料、蒽酿系顏料、花系顏料或 二偶氮系顏料等耐光性及耐熱性優異的顏料單獨或組合使 用。 ' 二酮基吡咯并吡咯系顏料之中,c.i·顏料紅254係亮 度特別優異之顏料,故期望亮度更加提昇。又,近年,對 於彩色濾光片之高對比度化的要求亦強烈,因此,希望使 一酮基吡咯并吡咯系顏料之一次粒徑儘可能地微細化。 但,經微細化之二酮基吡咯并吡咯系顏料係因藉由其分子 間氫鍵而具有易結晶成長之性質,故在形成彩色濾光片時 之加熱步驟中引起結晶化,而有產生異物之問題。 另外,二酮基吡咯并吡咯系顏料係可藉由專利文獻i φ 及專利文獻2所揭示之製法(以下,稱為「琥珀酸酯合成法」) 而得到。 在專利文獻3中係揭示在琥珀酸酯合成法中,使用複 數種腈化合物作為原料而得到至少2種之構造相異的二酮 基°比°各并吡咯系顏料之混合物的方法。 在專利文獻4中係記載著將藉由使用複數種特定構造 式的腈化合物作為原料之琥珀酸酯合成法而得到之至少2 種的構造相異之二酮基吡咯并吡咯系顏料的混合物使用於 彩色濾光片。 323842 5 201233734 於專利文獻5及專利文獻6中係揭示一種彩色濾光片 用著色組成物,其係藉由使二酮基吡咯并吡咯系顏料(主要 是C. I.顏料紅254)、至少一個特定構造式之二芳基二酮基 吡咯并吡咯化合物、顏料衍生物合併使用,係高對比度且 抑制加熱步驟造成之結晶析出。201233734 VI. Description of the Invention: [Technical Field] The present invention relates to a color filter quinonedipyrrolopyrrole pigment composition, a coloring composition for a color filter, and the use of the color filter A color filter formed by coloring the composition. [Prior Art] The liquid crystal display device controls the display of the light passing through the second sheet of the polarizing plate by controlling the degree of polarization of the light passing through the first polarizing plate by sandwiching the liquid crystal layer of the two polarizing plates. The device is mainly in the form of using a twisted nematic (TN) type liquid crystal. Since the color filter is provided between the two polarizing plates, the color filter can be used for color display. In recent years, it can be used for a television or a personal computer screen, so that the color filter has high brightness, high contrast, and high color reproducibility. Request for improvement. The color filter is attached to a surface of a transparent substrate such as glass to arrange two or more thin-colored filter segments of a different color hue in parallel or in a crosswise manner, or to fix the fine filter segments. The vertical and horizontal arrangement of the configurator. It is generally formed of filter segments of three colors of red, green, and blue, and the segments are, for example, finely several micrometers to several hundreds of micrometers, and each of the hues is arranged neatly in a specific arrangement. Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed by vapor deposition or sputtering on a color filter, and further, an alignment film for aligning the liquid crystal in a certain direction is formed thereon. In order to sufficiently obtain the properties of the transparent electrode and the alignment film, in the production step of forming the color filter, the temperature is generally 203842 4 201233734, which is generally higher than 200 ° C, preferably 230 ° C or higher. Therefore, the current method for producing a color filter is a coloring agent which is excellent in light resistance and heat resistance, and the method of the pigment dispersion method is the mainstream. In the pigment dispersion method, the red filter segment is generally excellent in light resistance and heat resistance as a coloring agent and a pigment, a brewing pigment, an anthocyanin pigment, or a diazo pigment. The pigments are used singly or in combination. Among the diketopyrrolopyrrole pigments, c.i. Pigment Red 254 is a pigment which is particularly excellent in brightness, and therefore it is desired to further increase the brightness. Further, in recent years, there has been a strong demand for high contrast of color filters. Therefore, it is desirable to make the primary particle diameter of the monoketopyrrolopyrrole pigment as fine as possible. However, since the micronized diketopyrrolopyrrole pigment has a property of being easily crystallized by its intermolecular hydrogen bond, it causes crystallization in the heating step in forming a color filter, and is produced. The problem of foreign bodies. Further, the diketopyrrolopyrrole pigment can be obtained by the production method disclosed in Patent Document i φ and Patent Document 2 (hereinafter referred to as "succinate synthesis method"). Patent Document 3 discloses a method of obtaining a mixture of at least two diketone groups having different structural diketone ratios in a succinate synthesis method using a plurality of nitrile compounds as a raw material. Patent Document 4 describes a mixture of at least two diketo-pyrrolopyrrole pigments having different structures obtained by a succinate synthesis method using a nitrile compound having a plurality of specific structural formulas as a raw material. For color filters. 323842 5 201233734 discloses a coloring composition for a color filter by using a diketopyrrolopyrrole pigment (mainly CI Pigment Red 254), at least one specific structure, in Patent Document 5 and Patent Document 6. The bisaryldiketopyrrolopyrrole compound and the pigment derivative are used in combination to provide high contrast and suppress crystallization due to the heating step.
在專利文獻7中係揭示一種使用溴化二酮基吡咯并吡 咯顏料之彩色濾光片用著色組成物。又,於專利文獻8中 係記載著將溴化二酮基吡咯并吡咯系顏料組成物使用於彩 色遽光片。 [先前技術文獻] [專利文獻] 專利文獻1 專利文獻2 專利文獻3 專利文獻4 日本特開昭58-210084號公報 日本特開平07-90189號公報 日本特開昭61-120861號公報 日本特表2007-514798號公報Patent Document 7 discloses a coloring composition for a color filter using a brominated diketopyrrolopyrrole pigment. Further, Patent Document 8 describes the use of a brominated diketopyrrolopyrrole pigment composition for a color calendering sheet. [PRIOR ART DOCUMENT] [Patent Document] Patent Document 1 Patent Document 2 Patent Document 3 Patent Document 4 Japanese Laid-Open Patent Publication No. SHO-58-210084 Bulletin 2007-514798
專利文獻5 WO 2009/081930 號手冊 專利文獻6 :日本特開2009-149707號公報 專利文獻7:日本特開1999-231516號公報 專利文獻8 WO 2009/144115 號手冊 【發明内容】 本發明欲解決之課題在於提供一種彩色濾光片用二 酮基吡咯并吡咯系顏料組成物、彩色濾光片用著色組成 物、及使用此等之彩色濾光片,該彩色濾光片用二酮基吡 咯并吡咯系顏料組成物係亮度及對比度良好,即使藉由加 323842 6 201233734 熱步驟亦不易引起二_基吡咯并吡咯系顏料之結晶析出。 本發明之第1實施形態係關於一種彩色濾光片 基吡咯并吡咯系顏料組成物,係含有式(1)所示之二綱基吡 咯并吡咯顏料、以及式(A-2)所示之二酮基吡咯并吡咯顏料 的彩色濾光片用二酮基吡咯并吡咯系顏料組成物,其中, 式(A-2)所示之二酮基吡咯并吡咯顏料之含量,以二蜩基呪 咯并吡咯系顏料之合計質量作為基準,為i質量%至15 量% 〇Patent Document 5 WO 2009/081930, PCT Patent Application Publication No. JP-A-2009- 149 074, JP-A-1999- 231 516, JP-A-1999-231516, JP-A-2009-144115 A problem is to provide a diketopyrrolopyrrole pigment composition for a color filter, a coloring composition for a color filter, and a color filter using the same, and the color filter uses a diketopyrrole The pyrrole pigment composition has good brightness and contrast, and it is not easy to cause crystal precipitation of the di-p-pyrrolopyrrole pigment even by the thermal step of adding 323842 6 201233734. According to a first embodiment of the present invention, a color filter-based pyrrolopyrrole pigment composition comprising a di-n-propylpyrrolopyrrole pigment represented by formula (1) and a formula (A-2) A diketopyrrolopyrrole pigment composition for a color filter of a diketopyrrolopyrrole pigment, wherein the content of the diketopyrrolopyrrole pigment represented by the formula (A-2) is a dimercaptopurine The total mass of the pyrrole-based pigments is based on i mass% to 15% by weight.
BrBr
^ (1) 式(Α-2) Φ [式(Α-2)中, Α及Β分別獨立為氫原子、氟原子、碘原子、氰基、碳數i 至12之烷基、可具有取代基之苯基、—cf3、-or1、_SR2、 -N(R3)R4、-C00R5、-C0NH2、-C0NHR6、-C0N(R7)R8、-s〇2NH2、 -S〇2NHR9、或-S(M(R1D)R", R1至R11分別獨立為碳數1至12的烷基、可具有取代基之 苯基、或可具有取代基之芳烷基; 但A及B並不同時為氫原子] 又,第1實施形態係關於上述彩色遽光片用二酮基0比 323842 7 201233734 咯并吡咯系顏料組成物,其中,上述式(A_2)所示之二鲷 口比咯并〇比咯顏料為式(A-2-1)、式(A-2-2)、式(A-2-3)岑基 (A-2-4)之任一者; 2式^ (1) Formula (Α-2) Φ [In the formula (Α-2), Α and Β are independently a hydrogen atom, a fluorine atom, an iodine atom, a cyano group, an alkyl group having a carbon number of i to 12, and may have a substitution. Phenyl group, -cf3, -or1, _SR2, -N(R3)R4, -C00R5, -C0NH2, -C0NHR6, -C0N(R7)R8, -s〇2NH2, -S〇2NHR9, or -S( M(R1D)R", R1 to R11 are each independently an alkyl group having 1 to 12 carbon atoms, a phenyl group which may have a substituent, or an aralkyl group which may have a substituent; however, A and B are not simultaneously a hydrogen atom. Further, the first embodiment relates to a diketone group of the above-mentioned color calendering sheet 0 to 323842 7 201233734, a pyrrole pyrrole-based pigment composition, wherein the diterpene ratio of the above formula (A_2) is more than The pigment is any one of the formula (A-2-1), the formula (A-2-2), and the formula (A-2-3) sulfhydryl group (A-2-4);
[式(A-2-3)及式(A-2-4)中、 或可具有取代基 R6至R8分別獨立為碳數1至12的烧基 之苯基]。 又,第1實施形態係關於上述彩色遽光片用二嗣基吼 咯并吡咯系顏料組成物,其中,進一步含有c.顏料紅254 作為二酮基吡咯并吼咯系顏料。 又,第1實施形態係關於上述彩色遽光片用二嗣基吼 洛并㈣系顏料組成物’其中m叫并t各系顏 料之合計質1作為基準,式⑴所示之二酮基轉并^比咯顏 323842 8 201233734 料與C. I.顏料紅254之合計含量為85質量%至99質量%。 又,第1實施形態係關於上述彩色濾光片用二酮基吡 咯并吡咯系顏料組成物,其中,式(1)所示之二调基吡咯并 °比咯顏料與C. I.顏料紅254之質量比為20 : 80至99 : 1。 又’第1實施形態係關於上述彩色濾光片用二酮基吡 略并°比σ各糸顏料組成物’其中,進一步含有色素衍生物。 又’第2實施形態係關於一種彩色濾光片用二酮基吡 略并吡咯系顏料組成物,係含有式(1)所示之二酮基咣咯并 0比11各顏料、以及式(Β-2)所示之二綱基η比嘻并。比^各顏料的彩 色濾光片用二酮基吡咯并吡咯系顏料組成物,其中,式(1) 與式(Β-2)之質量比為97 : 3至85 : 15;[In the formula (A-2-3) and the formula (A-2-4), or a phenyl group which may have a substituent R6 to R8 each independently a carbon group of 1 to 12]. In addition, the first embodiment relates to a dimercapto fluorenylpyrrole pigment composition for a color calendering sheet, which further contains c. Pigment Red 254 as a diketopyrrolopyrrole pigment. In addition, in the first embodiment, the diketone group represented by the formula (1) is used as a reference for the total mass of the dimercapto pyrene (tetra) pigment composition for the color calender sheet And the total content of the 323842 8 201233734 material and the CI pigment red 254 is 85% by mass to 99% by mass. In addition, the first embodiment relates to a diketopyrrolopyrrole pigment composition for a color filter, wherein the quality of the dimethypyrrolopyrrole pigment and CI Pigment Red 254 represented by the formula (1) The ratio is 20: 80 to 99: 1. Further, the first embodiment relates to a diketopypyrrole ratio σ pigment composition of the above-mentioned color filter, which further contains a dye derivative. Further, the second embodiment relates to a diketopipyrrolopyrrole pigment composition for a color filter, which comprises a diketopoxime represented by the formula (1) and a pigment of 0 to 11 and a formula ( The two bases η shown in Β-2) are more than 嘻. The color filter of the pigments is a diketopyrrolopyrrole pigment composition, wherein the mass ratio of the formula (1) to the formula (Β-2) is 97:3 to 85:15;
BrBr
式(1) 式(B —2) [式(B-2)中, A及B分別獨立為氫原子、氟原子、氣原子、碘原子、氰 基、碳數1至12之烷基、可具有取代基之苯基、_CF3…〇Rl -SR2 > -N(R3)R4 ^ -C〇〇R5 , -c〇nh2 v -CONHR6 ^ -CGN(R7)R8 > -SO2NH2、-SO2NHR9、或-SC^j^R1。)!^11, R1至R11分別獨立為碳數i至12的炫基、可具有取代基之 323842 9 201233734 苯基、或可具有取代基之芳烷基; 但A及B並不同時為氫原子]。 又’第2實施形態係關於上述.彩色濾光片用二酮基吡 咯并吡咯系顏料組成物,其中,上述式(β_2)為式(6_2_丨)、 式(B-2-2)、式(B-2-3)、式(B-2-4)、式(B-2-5)、式(B-2-6) 或式(B-2-7)之任一者;Formula (1) Formula (B-2) [In the formula (B-2), A and B are each independently a hydrogen atom, a fluorine atom, a gas atom, an iodine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, and Phenyl group having a substituent, _CF3...〇Rl -SR2 > -N(R3)R4 ^ -C〇〇R5 , -c〇nh2 v -CONHR6 ^ -CGN(R7)R8 > -SO2NH2, -SO2NHR9, Or -SC^j^R1. ), ^11, R1 to R11 are each independently a thiol having a carbon number of i to 12, a phenyl 323842 9 201233734 phenyl group or a aryl group which may have a substituent; but A and B are not simultaneously hydrogen atom]. In the second embodiment, the diketoppyrrolopyrrole pigment composition for a color filter, wherein the formula (β_2) is a formula (6_2_丨), a formula (B-2-2), Any one of the formula (B-2-3), the formula (B-2-4), the formula (B-2-5), the formula (B-2-6) or the formula (B-2-7);
BrBr
式(B-2-1> ^ (B-2-2)式(B — 2 — 3) ίζ (Β- 2 -4)Formula (B-2-1> ^ (B-2-2) Formula (B — 2 — 3) ίζ (Β - 2 -4)
[式(Β-2-4)、式(Β-2-6)、及式(Β-2-7)中、 R至R分別獨立為碳數1至12的烧基、或可具有取代基 之苯基]。 ~ " 又,第2實施形態係關於上述彩色濾光片用二酮 基°比咯并吼咯系顏料組成物,其中,進一步含有色素衍生 323842 10 201233734 物。 又,第3實施形態係關於一種彩色濾光片用著色組成 物,係含有著色劑、黏合劑樹脂、及有機溶劑之著色組成 物,其中,著色劑含有第1實施形態之二酮基吡咯并吡咯 系顏料組成物。 又,第3實施形態係關於上述彩色濾光片用著色組成 物,其中,進一步含有光聚合性單體及/或光聚合起始劑。 又,第4實施形態係關於一種彩色濾光片用著色組成 • 物,係含有著色劑、黏合劑樹脂、及有機溶劑之著色組成 物,其中,著色劑為含有第2實施形態之二酮基°比咯并吡 p各系顏料組成物。 又,第4實施形態係關於上述彩色濾光片用著色組成 物,其中,進一步含有光聚合性單體及/或光聚合起始劑。 本發明之第5實施形態係關於一種彩色濾光片用著色 組成物,係含有顏料(A)、黏合劑樹脂(C-B)、與溶劑之彩 φ 色濾光片用著色組成物,其中,顏料(A)為含有式(1)所示 之顏料(A1),黏合劑樹脂(C-B)為含有鹼可溶性感光性樹脂 (C-B1)。 323842 11 201233734[In the formula (Β-2-4), the formula (Β-2-6), and the formula (Β-2-7), R to R are each independently a carbon group having 1 to 12 carbon atoms, or may have a substituent. Phenyl]. Further, the second embodiment relates to a diketone-pyrometric quinone pigment composition for a color filter, which further contains a pigment derivative 323842 10 201233734. In addition, the third embodiment relates to a coloring composition for a color filter, which comprises a coloring agent, a binder resin, and a coloring composition of an organic solvent, wherein the coloring agent contains the diketopyrrole of the first embodiment. Pyrrole pigment composition. In the third embodiment, the coloring composition for a color filter further contains a photopolymerizable monomer and/or a photopolymerization initiator. In addition, the fourth embodiment relates to a colored composition for a color filter, which comprises a coloring agent, a binder resin, and a coloring composition of an organic solvent, wherein the coloring agent contains the diketone group of the second embodiment. ° P-pyrazine p-series pigment composition. In the fourth embodiment, the coloring composition for a color filter further contains a photopolymerizable monomer and/or a photopolymerization initiator. According to a fifth aspect of the present invention, there is provided a coloring composition for a color filter comprising a pigment (A), a binder resin (CB), and a coloring composition for a color φ color filter of a solvent, wherein the pigment (A) is a pigment (A1) represented by the formula (1), and the binder resin (CB) is an alkali-soluble photosensitive resin (C-B1). 323842 11 201233734
Br 又,第5實施形態係關於上述彩色濾光片用μ 物,其中,顏料(A)進一步含有至少一種以上 者色級成 以外之二酮基吡咯并吡咯系顏料、偶氮系顏料/贫4(A1) 料、茈系顏料、啥°丫 _(quinacridone)系顏料 #飞系顏 酮(benz i m i dazo 1 one)系顏料、及喹啉系顏料所笨并咪唑 選出者。 一構成之砰中 又,第5實施形態係關於上述彩色據 物,其中’進-步含有乙醯笨系化合物、膦 ^且成 唑系化合物、及職系化合物所構成 二物、味 種以上之光聚合起始劑(C-D)。 的至少— 本發明之第6實施形態係關於 組成物,係、含有顏料(A)、黏合劑樹脂者色 色遽光片用著色組成物,其中,顏料(A)為含有、式二之彩 之顏料⑻’黏合為含有具有構成以= 至(D-b3)之樹脂(D-B1)。 bl) 323842 12 201233734Further, the fifth embodiment relates to the above-mentioned color filter for a color filter, wherein the pigment (A) further contains at least one of a diketopyrrolopyrrole pigment other than the color grade, and an azo pigment/lean 4 (A1) material, anthraquinone pigment, quinacridone pigment #benz imi dazo 1 one pigment, and quinoline pigment were selected as the imidazole. In a further embodiment, the fifth embodiment relates to the above-mentioned color data, wherein the method further comprises a second compound, a phosphine compound, an azole compound, and a grade compound. Photopolymerization initiator (CD). At least the sixth embodiment of the present invention relates to a composition, a coloring composition for a color-tone calender sheet containing a pigment (A) or a binder resin, wherein the pigment (A) is a color containing the formula 2 The pigment (8)' is bonded to contain a resin (D-B1) having a composition of = to (D-b3). Bl) 323842 12 201233734
BrBr
式(1) (D-bl)具有羧基之構成單元:2至60重量% (D-b2)具有式(D-2)或(D-3)所示之芳香族環基的構成單 元:2至80質量°/〇 (D-b3)具有式(D-4)或(D-5)所示之脂肪族環基的構成單 元:2至60質量°/〇(1) (D-bl) has a structural unit of a carboxyl group: 2 to 60% by weight (D-b2) a constituent unit having an aromatic ring group represented by the formula (D-2) or (D-3): 2 Component unit having an aliphatic ring group represented by formula (D-4) or (D-5) up to 80 mass%/〇(D-b3): 2 to 60 mass%/〇
式(D-2)Formula (D-2)
式(D- 3)Formula (D-3)
RR
[式(D-2)及式(D-3)中,R為氫原子、或可具有苯環之碳數 1至20的烷基;式(D-3)中之虛線部份係表示相鄰於苯環 且含有可具有取代基之一個以上的飽和或不飽和的雜環之 323842 13 201233734 ί哀狀構造][In the formula (D-2) and the formula (D-3), R is a hydrogen atom or an alkyl group having a benzene ring having 1 to 20 carbon atoms; and the dotted line in the formula (D-3) means a phase a benzene ring adjacent to a benzene ring and containing one or more saturated or unsaturated heterocyclic rings which may have a substituent 323842 13 201233734
又,第6實施形態係關於上述彩色濾光片用著色組成 物,其中,顏料(Α)進一步含有至少一種以上由顏料(Α1) 以外之二酮基吼咯并吡咯系顏料、偶氮系顏料、慧醌系顏 料、茈系顏料、喹吖酮系顏料、苯并咪唑酮系顏料、及喹 琳糸顏料所構成之群中選出者。 又,第6實施形態係關於上述彩色濾光片用著色組 成物,其中,進一步含有乙醯苯系化合物、膦系化合物、 咪唑系化合物、及肟酯系化合物所構成之群中選出的至少 一種以上之光聚合起始劑(D-D)。 本發明之第7實施形態係關於一種彩色濾光片,係具 備由上述彩色濾光片用著色組成物所形成之濾光片區段。 本案所揭示係與2011年1月28曰申請之曰本特願 2011- 15874號、2011年3月31日申請之日本特願 2011-76928號、2011年3月31日申請之日本特願 323842 14 201233734 2011-76929號、及2011年12月13日申請之日本特願 2011-271836號記載之主題相關,其等所揭示之内容係藉 由引用而援用於此。 【實施方式】 以下’詳細說明本發明之實施形態。In the coloring composition for a color filter, the pigment (Α) further contains at least one of a diketopyrrolopyrrole pigment other than the pigment (Α1), and an azo pigment. Among the groups of Huijing pigments, lanthanide pigments, quinophthalone pigments, benzimidazolone pigments, and quinoline pigments. In addition, the coloring composition for a color filter further contains at least one selected from the group consisting of an acetaminophen compound, a phosphine compound, an imidazole compound, and an oxime ester compound. The above photopolymerization initiator (DD). According to a seventh aspect of the invention, there is provided a color filter comprising a filter segment formed of the coloring composition for a color filter. The Japanese Patent Application No. 2011-76928, which was filed on January 28, 2011, and the Japanese Patent Application No. 323842, which was filed on March 31, 2011, was filed on January 31, 2011. The subject matter described in Japanese Patent Application No. 2011-271836, filed on Jan. 13, 2011, the entire disclosure of which is hereby incorporated by reference. [Embodiment] Hereinafter, embodiments of the present invention will be described in detail.
又,以下舉出之「c· L」意指彩色指數(C·丨.)。又, 表示為「(甲基)丙烯酸酯」、「(甲基)丙烯酸」或「(曱基) 丙稀醯胺」時,若無特別聲明,分別表示「丙烯酸酯及/ 或甲基丙烯酸酯」、「丙烯酸及/或曱基丙婦酸」、「丙烯醢胺 及/或甲基丙婦醯胺」。 [二_基吡咯并吡咯系顏料組成物] 首先,說明有關本發明之實施態樣的二酮基吡咯并吡 略系顏料組成物。 [第1實施形態] (二_基吡咯并吡咯系顏料組成物) 第1實施形態係-種彩色遽光片用二酮基鱗并祕 系顏料組成物,係含有下述式⑴所示之二喊鱗并^比洛 ^料、以及下述式(A-2)所示之特定雜二酮基鱗并吼洛顏 ^的彩色縣》用二酮基鱗并鱗系顏料組成物,下述 式(A—2)所示之特絲H叫并鱗㈣之含量,以二 ,基呢略并t各系顏料之合計質量作為基準 至15質量%。 ~貝里 323842 201233734 由使溴化二酮基°比咯并°比咯顏料(式(1))適用於彩色濾光 片,亮度會提高。進一步發現藉由使用含有於特定構造之 非對稱導入取代基之二酮基吡咯并吡咯顏料(式(A-2)(以 下,稱為「特定雜二酮基吡咯并吡咯顏料A」)之二酮基吡 咯并°比咯系顏料組成物,可得到不僅有高亮度亦有高對比 度且可抑制因加熱步驟造成之結晶析出的彩色濾光片。此 處所選定之特定雜二酮基吡咯并吡咯顏料A,由於對樹脂 成分相互作用小,故可有效率地覆蓋溴化二酮基吡咯并吡 ® 咯顏料之活性面,因可抑制加熱步驟所造成之顏料的熱凝 集,故可以少量之含量發揮高對比度化、及結晶析出抑制 效果。又,特定雜二酮基吼11 各并D比p各顏料A係色特性較至 今所知之結晶析出抑制劑更良好,亦可減少添加量,故無 損溴化二酮基《比咯并吼咯顏料之優異的亮度提昇效果。進 一步,二酮基吡咯并吡咯系顏料組成物係含有特定雜二酮 基吡咯并吡咯顏料A,故黏度安定性優異。 φ 依據第1實施態樣,可提供一種彩色濾光片用二酮基 吡咯并吡咯系顏料組成物,係亮度及對比度良好,即使藉 由加熱步驟亦不引起二酮基吡咯并吡咯系顏料之結晶析 出,再者,黏度安定性優異。 323842 16 201233734In addition, the following "c·L" means a color index (C·丨.). When it is expressed as "(meth) acrylate", "(meth) acrylate" or "(meth) acrylamide", unless otherwise stated, it means "acrylate" and / or methacrylate "Acrylic and/or mercapto-butanoic acid", "acrylamide" and/or methyl propyl amide. [Di-pyrrolopyrrole pigment composition] First, a diketopyrrolopyrrole pigment composition according to an embodiment of the present invention will be described. [First Embodiment] (di-p-pyrrolopyrrole pigment composition) The first embodiment is a diketone-based microparticle pigment composition for a color calendering sheet, which is represented by the following formula (1). The two ketone scales are combined with the ketones and the specific heterodiketones of the following formula (A-2). The content of the filament H shown in the above formula (A-2) is called the content of the scale (four), and the total mass of the pigments of the base and the base of each of the bases is 15% by mass. ~Berry 323842 201233734 Brightness is improved by applying a brominated diketone to a specific pigment (formula (1)) for a color filter. Further, it has been found that a diketopyrrolopyrrole pigment (formula (A-2) (hereinafter referred to as "specific heterodiketopyrrolopyrrole pigment A") having a substituent introduced in a specific structure is used. The ketopyrrolopyrazine pigment composition can obtain a color filter which not only has high brightness but also high contrast and can suppress crystal precipitation due to the heating step. The specific heterodiketopyrrolopyrrole selected here. Pigment A, because of the small interaction with the resin component, can effectively cover the active surface of the brominated diketopyrrolopyrrole pigment, and can inhibit the thermal agglomeration of the pigment caused by the heating step, so that a small amount can be contained. The high-contrast and crystallization-preventing effect are exhibited. Further, the specific heterodiketone oxime 11 is more excellent in D color than the pigmentation inhibitors of the pigments A, and the amount of addition can be reduced. Non-destructive brominated diketone-based "excellent brightness enhancement effect of pyrrole-pyrrole pigment. Further, the diketopyrrolopyrrole pigment composition contains a specific heterodiketopyrrolopyrrole pigment A Therefore, the viscosity stability is excellent. φ According to the first embodiment, a diketopyrrolopyrrole pigment composition for a color filter can be provided, which has good brightness and contrast, and does not cause a diketone group even by a heating step. The crystal of the pyrrolopyrrole pigment precipitates, and further, the viscosity stability is excellent. 323842 16 201233734
[式(A-2)中, A及B分別獨立為氫原子、氟原子、碘原子、氰基、碳數i 拳 至12之烷基、可具有取代基之苯基、-CF3、-Of、-SR2、 -N(R3)R4、-C00R5、-C0NH2、-C0NHR6、-C0N(R7)R8、-S〇2NH2、 -S〇2NHR9、或-SiMCR^R11, R1至R11分別獨立為碳數1至12的烷基、可具有取代基之 苯基、或可具有取代基之芳烷基; 但A及B並不同時為氫原子]。 上述碳數1至12之烧基可為直鍵狀,亦可為分枝狀, 鲁 具體上可舉例如曱基、乙基、丙基、異丙基、丁基、第二 丁基、第三丁基、戊基、己基、庚基、辛基、癸基、十二 碳基、1,5-二甲基己基、1,6-二甲基庚基、2-乙基己基等, 但不限定於此等。 可具有上述取代基之苯基可舉例如可具有碳數1至4 之烷基、三氟曱基、鹵原子、硝基、氰基、胺曱醯基、胺 磺醯基、碳數1至4之烷氧基等取代基之苯基。苯基係可 具有1個或二個以上此等取代基。更具體地可舉例如苯 基、對曱基苯基、4-第二丁基苯基、對硝基苯基、對甲氧 323842 17 201233734 基苯基、對氯苯基、2, 4-二氯笨基、3〜胺甲酿 但不限定於此等。 上述可具有取代基之芳絲係.可舉例如可具有碳數 1至4之燒基、:r惫甲美 占広 基、胺•基、:數心 芳产美心目^ 基等取代基之芳烧基。 ^基係可具有i個或二個以上此等之 可舉例如笨甲基、4_甲基苯甲基、 ^體地 帀备A埜田甘 4乐一丁基本曱基、4- M基本甲基、4噌絲甲基、2,4_ 限定於此等。 个T签寻,但不 效果之點,以式(A— 1 =’9從對比度及結晶析*抑制 2—3)、式(^卜心之^至8 上之烷基、或可具有取代 係、妷數4以 Λ對tb声*及蛀曰為佳。此等有效發揮高 _對比度化、及結晶析出抑制之理由,認㈣旁, 上之烧基的甲酿胺基(胺甲醯基)、苯基、第三^4以 的取代基所造成的立體障礙效果而可抑制賴之2龐大 又’具有甲醢胺基(胺曱醯基)、苯基 疑集。 二酮基— 各顏料仏特性 二:定雜 基鱗并祕㈣k❹ 4耗二明 323842 201233734[In the formula (A-2), A and B are each independently a hydrogen atom, a fluorine atom, an iodine atom, a cyano group, an alkyl group having a carbon number i to 12, a phenyl group which may have a substituent, -CF3, -Of , -SR2, -N(R3)R4, -C00R5, -C0NH2, -C0NHR6, -C0N(R7)R8, -S〇2NH2, -S〇2NHR9, or -SiMCR^R11, R1 to R11 are each independently carbon An alkyl group of 1 to 12, a phenyl group which may have a substituent, or an aralkyl group which may have a substituent; but A and B are not simultaneously a hydrogen atom]. The above-mentioned carbon number of 1 to 12 may be a straight bond or a branched form, and specifically, for example, an anthracene group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group, or a Tributyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, 1,5-dimethylhexyl, 1,6-dimethylheptyl, 2-ethylhexyl, etc., but It is not limited to this. The phenyl group which may have the above substituent may, for example, have an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a halogen atom, a nitro group, a cyano group, an amine fluorenyl group, an amine sulfonyl group, and a carbon number of 1 to A phenyl group of a substituent such as an alkoxy group. The phenyl group may have one or two or more such substituents. More specifically, for example, phenyl, p-nonylphenyl, 4-second butylphenyl, p-nitrophenyl, p-methoxy 323842 17 201233734 phenyl, p-chlorophenyl, 2, 4-di The chlorophenyl group and the glycerin group are not limited to these. The above-mentioned aromatic silk system which may have a substituent. For example, a substituent having a carbon number of 1 to 4, a pyridyl group, an amine group, a number of cores, and a substituent may be mentioned. Aromatic base. ^Base system may have i or more than one of these, such as stupid methyl, 4-methylbenzyl, ^ body preparation A Noda Gan 4 Le-butyl thiol, 4-M basic A The group, 4 fluorene methyl group, 2, 4_ are limited to these. T-sign, but not effective, by the formula (A-1 = '9 from the contrast and crystallization * inhibition 2-3), the formula (^ heart ^ to the alkyl group on 8, or can have a substitution The number of 妷, 妷 4 Λ Λ Λ t t t t t t t t 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The steric hindrance effect caused by the substituents of the phenyl group and the phenyl group and the third group can suppress the bulkiness of the ruthenium group and have a carbamide group (amine sulfhydryl group) and a phenyl group. Characteristics of each pigment 二 two: fixed heterobasic scales and secrets (four) k❹ 4 consumption two Ming 323842 201233734
[式(A-2-3)及式(A-2-4)中、 R6至R8分別獨立為碳數1至12的烷基、或可具有取代基 ^ 之苯基]。 將式(A-2)之特定雜二酮基吡咯并吡咯顏料A的具體 例舉例於以下,但不限定於此等。 323842 19 201233734[In the formula (A-2-3) and the formula (A-2-4), R6 to R8 each independently represent an alkyl group having 1 to 12 carbon atoms or a phenyl group which may have a substituent ^]. Specific examples of the specific heterodiketopyrrolopyrrole pigment A of the formula (A-2) are exemplified below, but are not limited thereto. 323842 19 201233734
323842 20 201233734323842 20 201233734
323842 21 201233734323842 21 201233734
323842 22 201233734323842 22 201233734
ClCl
ClCl
式(A- 2 - 1 5)Formula (A-2 - 1 5)
式(A — 2 _ 1 6)Formula (A - 2 _ 1 6)
ClCl
式(A- 2 - 1 7)Formula (A-2 - 1 7)
ClCl
式(A- 2 - 1 8) 顏料組成物之特徵在於:式(A_2)所示之特定雜二酮 ^比略并鱗顏料A的含量,以二并鱗顏料之 ,川跑丨5㈣之齡較佳係 質里枝H)質量%之範圍。若式(A_2)之特定雜二網基吼 323842 23 201233734 p各并°比。各顏料A的比率超出丨5質量%,雖然可得到結晶析 出抑制效果’但損及式(1)之填化二酮基α比洛并啦P各顏料優 異的亮度。另一方面’式(Α·~2)之特定雜二酮基吼洛并'^比嘻 顏料Α的比率未達1質量%時,高對比度化及結晶析出抑制 效果並不充分。結晶析出抑制效果不充分時,因在加熱步 驟於塗膜之表面析出結晶狀異物而引起光散射,引起亮度 及對比度比的降低。因此,藉由使用以上述比率含有特定 雜二酮基吡咯并吡咯顏料A之二酮基吡咯并吡咯系顏料組 參成物,而達成高壳度且高對比度,即使藉由加熱步驟亦可 抑制二酮基吡咯并咐•咯顏料之結晶析出。進一步可得到優 異之黏度安定性。 在無損其效果的範圍,顏料組成物亦可併用式(1)之 二酮基吡咯并吡咯顏料、及式(A-2)的特定雜二酮基吡咯并 11比洛顏料A以外之一觸基π比略并β比洛系顏料。且體上可舉 例如 C. I.顏料紅 254、255、264、272、C. I.顏料橘 71、 鲁 73或81等二酮基吡咯并吡咯系顏料,但不限定於此等。 讦併用之二酮基°比咯并吡咯系顏料,以C. I.顏料紅254為 #。C. I.顏料紅254為佳之理由係以琥珀酸二醋合成法製 造式(Α-2)的特定雜二酮基吡咯并吡咯顏料a時一般所含 有者’不易對式(1)之二酮基《比洛并β比洛顏料的優異之亮度 造成影響。 顏料組成物含有C. I.顏料紅254時,以二酮基π比略并 冰咯系顏料之合計重量作為基準(100質量%),較佳為式(1) 所示之二酮基吡咯并吡咯顏料與C. I.顏料紅254夕人^•丄人 < σ計含 323842 24 201233734 量為85質量%至99質量%。式(1)所示之二酮基°比洛并°比口各 顏料與C. I.顏料紅254之合計含量為未達85質量%時,有 時亮度提昇效果變少,多於99質量%時,由於特定雜二酮 基吡咯并°比咯顏料A之含量少,故有時無法充分得到對比 度比、結晶析出抑制效果。又,式(1)所示之二酮基π比11 各并 吡咯顏料與C. I.顏料紅254之質量比宜為20:80至99:1。 更佳係50 : 50至99 : 1。若式(1)所示之二酮基吡咯并吡 咯顏料與C. I.顏料紅254之合計中,式(1)所示之二酮基 擊 吡咯并吡咯顏料之含量為20質量%以上,亮度提昇效果 大,因而較佳。 又,就式(1)之二酮基吡咯并吡咯顏料、及式(Α-2)的 特定雜二酮基吡咯并吡咯顏料Α以外之二酮基吡咯并吡咯 系顏料而言,亦可使用後述之式(B-2)的特定雜二酮基吡咯 并吡咯顏料。此時,式(1)之二酮基吡咯并吡咯顏料與式 (B-2)的特定雜二酮基吡咯并吡咯顏料B之質量比宜為 ^ 97 : 3 至 85 : 15。 (二酮基吡咯并吡咯系顏料之製造法) 式(1)所示之二酮基吡咯并吡咯顏料係可使用國際公 開2009/144115號手冊等記載之公知的方法而得。 又,式(1)所示之二酮基吡咯并吡咯顏料係可以琥珀 酸二酯合成法製造。亦即,相對於琥珀酸二酯1莫耳,使 4-溴苯甲腈2莫耳在第三戊醇等惰性有機溶劑中,在鹼金 屬或鹼金屬烷氧化物的存在下,以80至110°C之高溫進行 縮合反應,生成二酮基°比p各并π比17各化合物的驗金屬鹽。繼 323842 25 201233734 而’對此二酮基吼略并0比哈化合物的驗金屬鹽,藉由使用 水、醇、酸等而質子化,可得到溴化二酮基吡咯并吡咯顏 料。此時,藉由在質子化之溫度、水、醇或酸的種類、比 率或量,可控制所得到之一次粒徑的大小。式⑴所示之二 酮基吡咯并吡咯顏料的製造方法係不限定於此方法。 式(A-2)之特定雜二酮基吡咯并吡咯顏料A係例如使 用文獻 Synth· C〇mmun_,1988, 18, 1213 及 Tetrahedr〇n, 58(2·)5547-舰記載之方法而進行合成。特㈣二嗣 Φ基°比咯并°比略顏料Α之製造方法並不限定於此方法。 又’式(A-2)之特定雜二酮基吡咯并吡咯顏料A係亦 可作為與C. I·顏料紅254之混合物而合成。此係在坡雖酸 二酯合成法中,可利用使用至少2種構造性相異之笨甲腈 化合物的方法(以下,稱為「琥珀酸二酯共合成法」^ 體上係在於W02009/081930號手冊記載之方法中,使所使 用之複數種苯甲腈化合物藉由從4_氣苯甲腈與下述式 • (A_3)所示之笨曱腈化合物選定,使式(A-2)的特定雜二酮 基吡咯并吡咯顏料A作為與αι.顏料紅254之混合物而製 造。 Ν〇Ηάβ 8 式(Α- 3> [式(A-3)中, A及B分別獨立為氫原子、氟原子、碘原子、氰基、碳數主 至12之烷基、可具有取代基之苯基、_CF3、_〇R】、_sr2、 323842 26 201233734 -N(R )R4、-COOR5、-CO·、-C0NHR6、_c〇N(R7)R8、_s〇2NH2、 -S〇2NHR9、或-StMClOR11, =至Rn分別獨立為碳數1至12的烷基、可具有取代基之 苯基、或可具有取代基之芳烧基; 但A及B並不同時為氫原子]。 石反數1至12的烷基、可具有取代基之苯基、或可具 有取代基之芳烷基係與上述之式(A_2)中的基相同。 顏料組成物可將式(1)所示之二酿I基η比洛并。比π各顏料 與特定雜二_基鱗并吼各顏料Α分別製造者加以混合而 使用又藉由琥珀酸二酯共合成法所合成之特定雜二_ 基吡咯并吡咯顏料Α與C. I.顏料紅254的混合物,進—步 與式(1)所示之二酮基吡咯并吡咯顏料混合而使用。此時係 於顏料載體中分散顏料前單純地混合,亦可藉鹽研磨處理 進行粉碎混合。 在顏料組成物中’式(1)所示之二酮基吼咯并。比咯顏 鲁料式(Α~2)之特定雜二酮基。比嘻并„比„各顏料a、及c. I. 顏料紅254之質量比係可使用TOF-MASS、FD-MASS、LC-MASS 或⑽R ’進行分析。或如日本特開平08-199085號公報所 揭不叙’使二酮基吡咯并吡咯系顏料組成物在四氫呋喃 中’與一第三丁基二碳酸酯及4-二甲基胺基吡啶進行室溫 撥摔轉換成所得到之可溶性的二_基各并化合物 後’亦可進行使用NMR、MASS或LC-MASS等分析。或亦可 將°比嘻并°比略環之NH基的氫,使用函化烷基等取代成烷 基’轉換成可溶性之二酮基吡咯并吡咯後進行上述分析。 323842 27 201233734 (色素衍生物) 以顏料組成物係以顏料結晶成長之抑制、以及顏料分 散性提昇為目的,可使用色素衍生物。可使用於顏料組成 物之色素衍生物,可舉例如二酮基吡咯并吡咯衍生物、苯 并異吲哚衍生物、蒽醌衍生物、二蒽醌衍生物、噻哄靛藍 (thiazineindigo)衍生物、偶氮色素衍生物、喹酞酮 (quinophthalone)衍生物、及喹吖酮(quinacrid〇ne)衍生 物等。色素衍生物之構造可例舉如下述式(4)所示之色素衍 生物,但不限定於此等。 P-Lm 式⑷ [式⑷中, P係二酮基吡咯并吡咯殘基、苯并異吲哚殘基、蒽醌衍生 物、二蒽醌殘基、噻畊靛藍殘基、偶氮色素殘基、喹酞酮 殘基、及喹吖酮殘基等。 m為1至4之整數, 隹 L分別獨立為-OH ; -SCbH、-c〇〇H、此等酸性基之1價至3 價的金屬鹽、烷基铵鹽;可具有取代基之酞醯亞胺甲基; 以下述式(a)、(b)、(c)、(d)、(e)、或(f)所示之基, 323842 28 201233734The pigment composition of the formula (A-2 - 18) is characterized in that the content of the specific heterodiketone represented by the formula (A_2) is slightly different from that of the squamous pigment A, and the age of the squama pigment is 5 (four). Preferably, the range of the quality of the branches is H). If the specific hetero-network of the formula (A_2) 323 323842 23 201233734 p is proportional to each other. When the ratio of the pigments A exceeds 5% by mass, the crystal precipitation suppressing effect can be obtained, but the brightness of each of the pigments of the filled diketone-α and the saponin of the formula (1) is deteriorated. On the other hand, when the ratio of the specific heterodikeke group of the formula (Α·~2) is less than 1% by mass, the effect of high contrast and inhibition of crystal precipitation is not sufficient. When the effect of suppressing the crystallization precipitation is insufficient, light scattering occurs due to precipitation of crystal foreign matter on the surface of the coating film in the heating step, resulting in a decrease in brightness and contrast ratio. Therefore, by using a diketopyrrolopyrrole pigment composition containing a specific heterodiketopyrrolopyrrole pigment A in the above ratio, high shelliness and high contrast can be achieved, even by a heating step. Crystallization of the diketopyrroloindole/argon pigment. Further excellent viscosity stability can be obtained. In the range in which the effect is not impaired, the pigment composition may be used in combination with a diketopyrrolopyrrole pigment of the formula (1) and a specific heterodiketopyrrolo 11 of the formula (A-2). The base π is slightly smaller than the beta pigment. Further, for example, C.I. Pigment Red 254, 255, 264, 272, C.I. Pigment Orange 71, and a diketopyrrolopyrrole pigment such as Ru 73 or 81 are not limited thereto. The diketone is used in combination with the pyrrole-based pigment, and C.I. Pigment Red 254 is #. The reason why CI Pigment Red 254 is better is to produce a specific heterodiketopyrrolopyrrole pigment of the formula (Α-2) by a succinic acid diacetate synthesis method, which is generally not suitable for the diketone group of the formula (1). The superior brightness of the bilo-β-pyrrol pigment affects. When the pigment composition contains CI Pigment Red 254, it is preferably a diketopyrrolopyrrole pigment represented by the formula (1) based on the total weight of the diketone π ratio and the icoric pigment (100% by mass). With CI Pigment Red 254 夕人^•丄人< σ计 containing 323842 24 201233734 The amount is 85% by mass to 99% by mass. When the total content of the diketone group and the CI pigment red 254 of the formula (1) is less than 85% by mass, the brightness enhancement effect may be less, and when it is more than 99% by mass, Since the specific heterodiketopyrrolopyrene has a smaller content than the azole pigment A, the contrast ratio and the crystal precipitation suppressing effect may not be sufficiently obtained. Further, the mass ratio of the diketone group π ratio of each of the pyrrole pigments represented by the formula (1) to the C.I. Pigment Red 254 is preferably from 20:80 to 99:1. Better system 50: 50 to 99: 1. In the total of the diketopyrrolopyrrole pigment represented by the formula (1) and the CI pigment red 254, the content of the diketoppyrrolopyrrole pigment represented by the formula (1) is 20% by mass or more, and the brightness enhancement effect is obtained. Large, so better. Further, a diketopyrrolopyrrole pigment of the formula (1) and a diketopyrrolopyrrole pigment other than the specific heterodiketopyrrolopyrrole pigment of the formula (Α-2) may also be used. A specific heterodiketopyrrolopyrrole pigment of the formula (B-2) described later. In this case, the mass ratio of the diketopyrrolopyrrole pigment of the formula (1) to the specific heterodiketopyrrolopyrrole pigment B of the formula (B-2) is preferably from ^97:3 to 85:15. (Production method of diketopyrrolopyrrole pigment) The diketopyrrolopyrrole pigment represented by the formula (1) can be obtained by a known method described in the handbook of International Publication No. 2009/144115. Further, the diketopyrrolopyrrole pigment represented by the formula (1) can be produced by a succinic acid diester synthesis method. That is, the 4-bromobenzonitrile 2 mole is in an inert organic solvent such as a third pentanol, in the presence of an alkali metal or an alkali metal alkoxide, in an amount of 80 to 100 mol of the succinic acid diester. The condensation reaction is carried out at a high temperature of 110 ° C to form a metal salt of each compound having a diketone ratio of p and a ratio of π to 17. Following the 323842 25 201233734, the metal salt of the diketo-based oxime-compound compound is protonated by using water, alcohol, acid or the like to obtain a brominated diketopyrrolopyrrole pigment. At this time, the size of the obtained primary particle diameter can be controlled by the type, ratio or amount of protonation temperature, water, alcohol or acid. The method for producing the diketopyrrolopyrrole pigment represented by the formula (1) is not limited to this method. The specific heterodiketopyrrolopyrrole pigment A of the formula (A-2) is carried out, for example, by the method described in Synth·C〇mmun_, 1988, 18, 1213 and Tetrahedr〇n, 58(2·)5547-ship. synthesis. The method for producing the (tetra) enthalpy Φ-based ratio and the specific pigment Α is not limited to this method. Further, the specific heterodiketopyrrolopyrrole pigment A of the formula (A-2) can also be synthesized as a mixture with C.I. Pigment Red 254. In the method of synthesizing acid diesters, it is possible to use a method using at least two structurally different carbonitrile compounds (hereinafter, referred to as "succinic acid diester co-synthesis method", which is based on W02009/ In the method described in the manual No. 081930, the plurality of benzonitrile compounds used are selected from the group consisting of 4_gasbenzonitrile and the abbreviated nitrile compound represented by the following formula (A_3) to give the formula (A-2). The specific heterodiketopyrrolopyrrole pigment A is produced as a mixture with αι. Pigment Red 254. Ν〇Ηάβ 8 Formula (Α-3) [In the formula (A-3), A and B are each independently hydrogen. Atom, fluorine atom, iodine atom, cyano group, alkyl group having a carbon number of 12, phenyl group which may have a substituent, _CF3, _〇R], _sr2, 323842 26 201233734 -N(R)R4, -COOR5, -CO·, -C0NHR6, _c〇N(R7)R8, _s〇2NH2, -S〇2NHR9, or -StMClOR11, = to Rn are each independently a C 1 to 12 alkyl group, a phenyl group which may have a substituent Or an aryl group which may have a substituent; but A and B are not simultaneously a hydrogen atom]. An alkyl group having an inverse number of 1 to 12, a phenyl group which may have a substituent, or may have a substituent The alkyl group is the same as the group in the above formula (A_2). The pigment composition may be a mixture of the two groups of the formula I (n), and the ratio of the pigments to the specific hetero-bases. The pigment Α is separately mixed by the manufacturer and used as a mixture of the specific hetero-dipyridylpyrrole pigment oxime synthesized by the succinic acid diester co-synthesis method, and the formula (1) is shown. The keto-pyrrolopyrrole pigment is used in combination, and is simply mixed before dispersing the pigment in the pigment carrier, or may be pulverized and mixed by a salt grinding treatment. In the pigment composition, the formula (1) Ketopyrrole. Specific pyridyl groups of the formula (Α~2). Compared with 嘻 and „ each pigment a, and c. I. Pigment red 254 mass ratio can use TOF- MASS, FD-MASS, LC-MASS or (10)R' is analyzed. Or, as disclosed in Japanese Laid-Open Patent Publication No. 08-199085, the composition of the diketopyrrolopyrrole pigment in tetrahydrofuran is combined with a third. Base dicarbonate and 4-dimethylaminopyridine are converted to the obtained soluble di-base each at room temperature After the compound, it can also be analyzed by NMR, MASS or LC-MASS, or the ratio of NH to ° can be compared with the hydrogen of the NH group, which is substituted with a functional alkyl group or the like to be converted into a soluble one. The above analysis is carried out after the diketopyrrolopyrrole. 323842 27 201233734 (Pigment Derivative) The pigment composition can be used for the purpose of suppressing the growth of the pigment crystal and improving the pigment dispersibility. The pigment derivative of the substance may, for example, be a diketopyrrolopyrrole derivative, a benzisoindole derivative, an anthracene derivative, a dioxane derivative, a thiazine indigo derivative, or an azo pigment derivative. , quinophthalone derivatives, quinocridine derivatives, and the like. The structure of the dye derivative is exemplified by the pigment derivative represented by the following formula (4), but is not limited thereto. P-Lm Formula (4) [In the formula (4), a P-based diketopyrrolopyrrole residue, a benzoisoindole residue, an anthracene derivative, a diterpene residue, a tidal indigo residue, an azo color residue a base, a quinacridone residue, a quinophthalone residue, and the like. m is an integer of 1 to 4, 隹L is independently -OH; -SCbH, -c〇〇H, a monovalent to trivalent metal salt or an alkylammonium salt of such an acidic group; may have a substituent a quinone imine methyl group; a group represented by the following formula (a), (b), (c), (d), (e), or (f), 323842 28 201233734
Rie •X~Y-(CH2)n^N; 式(a) R1y_^R19 -X-N N—R« R20、R21 式(b) R23 N=/ X 一 R2d 式(丨 ~Z-〇~R2s 式(d) X 為 ~S〇2~ 或直接鍵結,Rie •X~Y-(CH2)n^N; Formula (a) R1y_^R19 -XN N—R« R20, R21 Formula (b) R23 N=/ X A R2d Formula (丨~Z-〇~R2s (d) X is ~S〇2~ or direct bonding,
0-r2s -zO^nh 式(e) 式(f) -CO-' -CH2- ^ -CH2NHCOCH2-' -CH2NHS〇2CH5 Y為NH〜、-〇-、-S-、或直接鍵結, n為1至i〇之整數, R、R17分別獨立為氫原子、可具有取代基之碳數1至 ^的烧基、或可具有取代基之碳數2至30的烯基,R16與 R成為一體’必要時含有氮、氧、或硫原子,形成可具有 取代基之雜環。0-r2s -zO^nh Formula (e) Formula (f) -CO-' -CH2- ^ -CH2NHCOCH2-' -CH2NHS〇2CH5 Y is NH~, -〇-, -S-, or direct bonding, n An integer of 1 to i, R and R17 are each independently a hydrogen atom, a carbon group having 1 to 2 carbon atoms which may have a substituent, or an alkenyl group having 2 to 30 carbon atoms which may have a substituent, and R16 and R become The integral 'containing a nitrogen, oxygen, or sulfur atom as necessary to form a heterocyclic ring which may have a substituent.
Rl8 ' R19、R2°、R21及R22分別獨立為氫原子、可具有取 代基之碳數1至20的烷基、可具有取代基之碳數2至20 的烯基, R係式(a)或式(b)所示之取代基, R24係氯原子、-0H、烷氧基、式(a)或式(b)所示之取 代基, Z 為-C0NH---NHC0---S〇2NH-、或-NHS02-, R25係氫原子、-NH2、-NHC0CH3、-NHR26或式(c)所示之 取代基,此處,R26係可具有取代基之碳數1至20的炫基’ 323842 29 201233734 可具有取代基之碳數2至20的稀基。] 1價至3價之金屬可例舉如納、鉀、鎮、轉、鐵、或 紹等。又,燒基銨鹽可例舉如辛基胺、.月桂基胺、或硬脂 基胺等長鏈單烷基胺的銨鹽;或棕櫚基三曱基銨鹽、二月 桂基二甲基銨鹽、或二硬脂基二甲基銨鹽等4級烷基銨鹽。 可具有取代基之欧酿亞胺甲基、可具有取代基之烧 基、可具有取代基之烯基、或可具有取代基之雜環的取代 基,可例舉如鹵原子、硝基、氰基、胺曱醯基、N-取代胺 曱醯基、胺續醢基、N-取代胺續g藍基、碳數1至2〇之炫氧 基、碳數1至20之烧基硫基等,但不限定於此等。 色素衍生物係藉由在硫酸或發煙硫酸中加熱之項化 反應,硫酸中、與N-羥基曱基酞醯亞胺脫水縮合之酞醯亞 胺曱基化反應,使用氣磺酸與硫醯氣而氣磺化之後,使二 曱基胺基丙基胺等胺成分反應的磺醯胺化反應等公知的製 法來合成。 _ 用以形成上述式(a)、式(b)、及式(c)所示之取代基 所使用的胺成分,可例舉如二曱基胺、二乙基胺、曱基乙 基胺、M,N-乙基異丙基胺、N,N-乙基丙基胺、N,N-甲基丁 基胺、N,N-甲基異丁基胺、N,N-丁基乙基胺、N, N-第三丁 基乙基胺、二異丙基胺、二丙基胺、N, N-第二丁基丙基胺、 二丁基胺、二第二丁基胺、二異丁基胺、N,N-異丁基-第二 丁基胺、二戊基胺、二異戊基胺、二己基胺、二環己基胺、 二(2-乙基己基)胺、二辛基胺、N,N-曱基十八碳基胺、二 癸基胺、二烯丙基胺、N,N-乙基-1,2-二曱基丙基胺、N, N- 323842 30 201233734 甲基己基胺、二油基(oleyl)胺、二硬脂基胺、N, N-二甲基 胺基甲基胺、N,N-二甲基胺基乙基胺、N,N-二曱基胺基戊 基胺、N,N-二甲基胺基丁基胺、N,N-二乙基胺基乙基胺、 N,N-二乙基胺基丙基胺、N,N-二乙基胺基己基胺、N,N-二 乙基胺基丁基胺、N,N-二乙基胺基戊基胺、Ν,Ν-二丙基胺 基丁基胺、Ν,Ν-二丁基胺基丙基胺、Ν,Ν-二丁基胺基乙基 胺、Ν,Ν-二丁基胺基丁基胺、Ν,Ν-二異丁基胺基戊基胺、 Ν,Ν-甲基-月桂基胺基丙基胺、Ν,Ν-乙基-己基胺基乙基 ® 胺、Ν,Ν-二硬脂基胺基乙基胺、Ν,Ν-二油基胺基乙基胺、 Ν,Ν-二硬脂基胺基丁基胺、痕咬(piperidine)、2-曱基派 咬、3-曱基痕咬、4-甲基旅β定、2, 4-二甲基α底咬 (2, 4-lupetidine)、2, 6-二曱基旅淀、3, 5-二曱基〇底咬、 3-派唆曱醇、甲基嘛咬酸、異旅咬酸(isonipecotic acid)、異哌啶酸曱酯、異哌啶酸乙酯、2-哌啶乙醇、吡咯 咬(pyrrolidine)、3-經基°比嘻咬、N-胺基乙基派咬、N-鲁 胺基乙基-4-甲基哌啶、N-胺基乙基嗎啉、N-胺基丙基哌 啶、N-胺基丙基-2-甲基哌啶、N-丁基丙基-4-曱基哌啶、 N-胺基丙基嗎啉、N-甲基哌畊、N-丁基哌哄、N-甲基均哌 哄、1 -環戊基哌啡、1 -胺基-4 -甲基哌畊、1 -環戊基哌畊等, 但不限定於此等。 又,於偶氮色素導入取代基時,使取代基預先導入於 二偶氮成分或耦合劑成分,其後,藉由進行耦合反應而製 造偶氮色素衍生物。 色素衍生物之使用法’可例舉如使二酮基吡咯并吡咯 323842 31 201233734 ^料技成物分散於顏料麵中時與_ 混合之方 ^趟麵料製造時在水或有機溶劑%合處理之方法或添 =磨處Γ之方法。使色素街生物於顏料製造時在 =或有機溶射混合處理之方法或研磨處理時之Rl8 'R19, R2°, R21 and R22 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and R is a formula (a) Or a substituent represented by the formula (b), R24 is a chlorine atom, -OH, an alkoxy group, a substituent represented by the formula (a) or the formula (b), and Z is -C0NH---NHC0---S 〇2NH-, or -NHS02-, R25 is a hydrogen atom, -NH2, -NHCOCH3, -NHR26 or a substituent represented by the formula (c), where R26 is a substituent having a carbon number of 1 to 20 Base ' 323842 29 201233734 A dilute group having a carbon number of 2 to 20 which may have a substituent. The metal of 1 to 3 is exemplified by sodium, potassium, town, turn, iron, or sulphur. Further, the alkylamine salt may, for example, be an ammonium salt of a long-chain monoalkylamine such as octylamine, laurylamine or stearylamine; or palmityl-trimethylammonium salt or dilauryldimethyl A 4-alkylammonium salt such as an ammonium salt or a distearyldimethylammonium salt. The substituent of the urethane imino group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a heterocyclic ring which may have a substituent, and may, for example, be a halogen atom or a nitro group. A cyano group, an amine sulfhydryl group, an N-substituted amine fluorenyl group, an amine fluorenyl group, an N-substituted amine, a chloro group, a decyloxy group having a carbon number of 1 to 2 Å, and a pyridyl group having 1 to 20 carbon atoms. Base, etc., but is not limited to this. The pigment derivative is a mercaptosulfide and sulfur which is dehydrated and condensed with N-hydroxydecyl imine by sulfuric acid in a sulfuric acid or fuming sulfuric acid. After the sulfonation of the gas, the gas is synthesized by a known method such as a sulfoximation reaction in which an amine component such as dimercaptopropylamine is reacted. _ The amine component used to form the substituent represented by the above formula (a), formula (b), and formula (c) may, for example, be didecylamine, diethylamine or mercaptoethylamine. , M,N-ethylisopropylamine, N,N-ethylpropylamine, N,N-methylbutylamine, N,N-methylisobutylamine, N,N-butyl Base amine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N-second butylanamine, dibutylamine, di-tert-butylamine, Diisobutylamine, N,N-isobutyl-t-butylamine, dipentylamine, diisoamylamine, dihexylamine, dicyclohexylamine, di(2-ethylhexyl)amine, Dioctylamine, N,N-decyl octadecylamine, dimethylamine, diallylamine, N,N-ethyl-1,2-dimercaptopropylamine, N, N- 323842 30 201233734 Methylhexylamine, oleylamine, distearylamine, N,N-dimethylaminomethylamine, N,N-dimethylaminoethylamine, N, N-didecylaminopentylamine, N,N-dimethylaminobutylamine, N,N-diethylaminoethylamine, N,N-diethylaminopropylamine, N,N-diethylaminohexylamine, N,N-diethylaminobutylamine, N,N-diethylaminopentylamine, hydrazine, hydrazine-dipropylaminobutylamine, hydrazine, hydrazine-dibutylaminopropyl Amine, hydrazine, hydrazine-dibutylaminoethylamine, hydrazine, hydrazine-dibutylaminobutylamine, hydrazine, hydrazine-diisobutylaminopentylamine, hydrazine, hydrazine-methyl-lauric Aminopropylamine, hydrazine, hydrazine-ethyl-hexylaminoethylamine, hydrazine, hydrazine-distearate aminoethylamine, hydrazine, hydrazine-dioleylaminoethylamine, hydrazine , Ν-distearrylamidobutylamine, piperididine, 2-mercaptobite, 3-mercaptobite, 4-methylbendidine, 2,4-dimethyla Biting (2, 4-lupetidine), 2,6-diindenyl tour, 3, 5-dimercaptotrione bite, 3-p-sterol, methyl-bit acid, and isepipecotic acid ), Isopiperidic acid ester, Ethyl pipecolic acid ethyl ester, 2-piperidinyl alcohol, Pyrrolidine, 3-Phase ratio bite, N-Aminoethyl group bite, N-Dutamine Base ethyl-4-methylpiperidine, N-aminoethylmorpholine, N-aminopropyl piperidine, N-aminopropyl-2-methylpiperidine, N-butylpropyl- 4-mercaptopiperidine, N-aminopropylmorpholine, N-methylpiped, N-butylpiperidin, N-methylpiperidin, 1-cyclopentylpipenine, 1-amino-4-methylpiperidin, 1-cyclopentylpiped, etc., but not limited thereto . Further, when a substituent is introduced into the azo dye, the substituent is introduced into the diazo component or the couplant component in advance, and then the azo dye derivative is produced by a coupling reaction. The method of using the dye derivative can be exemplified by dispersing a diketopyrrolopyrrole 323842 31 201233734 material in a pigment surface and mixing it with water or an organic solvent at the time of manufacture of the fabric. The method or the method of adding the grind. The pigmented street organism is used in the production of pigments or in the method of organic spray mixing treatment or grinding treatment.
方法係顯現抑制二酮基鱗并鱗系顏^結晶成長的效 果期望由於發揮抑制結晶成長的效果,色素衍生物有效 地吸附於二酮基吡咯并吡咯系顏料之表面,而不會容易地 脫附。因此,色素衍生物之構造通常係具有與所使用之顏 料類似之化學構造者。從如此之理由,製造二辋基吡咯并 吡咯系顏料時,一般係具有二酮基吡咯并吡咯構造、噻啡 靛藍構造、苯并異吲哚構造、及喹吖鲷構造之色素衍生物 有效。 又’使用色素衍生物時,期望不會損及二鲥裊吡咯并 吡咯系顏料組成物之色調。從色相之觀點,宜使席呈現黃 色、撥色之二酮基吡咯并吡咯衍生物、笨并異吲嘧衍生物、 嘆口井競藍衍生物、偶氮色素衍生物或啥駄酮衍生物之使用。 色素衍生物之調配量,相對於二_基吼哈并冰咯系顏 料組成物1〇〇質量份,宜為0. 5至4〇質量份之範圈。更佳 係相對於二酮基吡咯并吡咯系顏料組成物1〇〇質耋份,為 3至35質量份之範圍。少於〇. 5質量份時,有時鱗晶成長 抑制效果不充分,多於4〇質量份時,有損二酮基吡咯并吡 11各系顏料之良好的色調。 以下,記载於二酮基吡咯并吡咯系顏料組成物所使用 之色素衍生物的具體例,但不限定於此等。 323842 32 201233734 (二酮基吡咯并吡咯衍生物的具體例) 二酮基吡咯并吡咯衍生物具體地可使用下述式(5)或 式(6)所示之化合物,但不限定於此等。The method exhibits an effect of inhibiting the growth of diketone scales and scaly crystals. It is expected that the pigment derivative is effectively adsorbed on the surface of the diketopyrrolopyrrole pigment without being easily removed. Attached. Therefore, the structure of the pigment derivative is usually a chemical construct similar to the pigment used. For this reason, when a dimercaptopyrrolopyrrole pigment is produced, it is generally effective to have a diketopyrrolopyrrole structure, a thiomorphin blue structure, a benzisoindene structure, and a quinone structure. Further, when a dye derivative is used, it is desirable not to impair the color tone of the dipyrrolopyrrole pigment composition. From the point of view of hue, it is advisable to present a yellow, dially-dyed diketopyrrolopyrrole derivative, a stupid iso-pyridinium derivative, a snorkeling blue derivative, an azo dye derivative or an anthrone derivative. Use. 5至四〇质量份的范围圈。 The amount of the pigment derivative, the amount of the composition of the second layer of the composition of the mass fraction of 0.5 to 4 parts by mass. More preferably, it is in the range of 3 to 35 parts by mass based on the diketopyrrolopyrrole pigment composition. When the amount is less than 5% by mass, the growth inhibition effect of the spherulite may be insufficient, and when it is more than 4 parts by mass, the good color tone of each of the diketopyrrolopyrrole pigments is impaired. Specific examples of the dye derivative used in the diketopyrrolopyrrole pigment composition are described below, but are not limited thereto. 323842 32 201233734 (Specific Example of Diketopyrrolopyrrole Derivative) The diketopyrrolopyrrole derivative may specifically be a compound represented by the following formula (5) or (6), but is not limited thereto. .
Lm 式(5)Lm type (5)
式(5-1) L= -COOH m=2 式(5-2) L = -S03H m=2 式(5-3) L = -S02NH2 m=2 式(5-4) l = —S02NH(CH2)2N(C2H5)2 m=2 式(5-5) L= -S02NH(CH2〉3N(CH3)2 m=2 式(5-6) L= -CH2NHCOCH2N(C4H9)2 m=2 式(5 - 7 ) L = -CH2NHCOCH2NH(CH2)2N(CH3)2 -m=2 式(5-8) L= -S02NH(CH2)3N(C2H5)2 m=2Formula (5-1) L= -COOH m=2 Formula (5-2) L = -S03H m=2 Formula (5-3) L = -S02NH2 m=2 Formula (5-4) l = —S02NH( CH2)2N(C2H5)2 m=2 Formula (5-5) L= -S02NH(CH2>3N(CH3)2 m=2 Formula (5-6) L= -CH2NHCOCH2N(C4H9)2 m=2 Formula ( 5 - 7 ) L = -CH2NHCOCH2NH(CH2)2N(CH3)2 -m=2 Formula (5-8) L= -S02NH(CH2)3N(C2H5)2 m=2
00
02 /"""\ 式(5·10) L= -s -N N-C2H5 m=2 N/ 323842 33 20123373402 /"""\ 式(5·10) L= -s -N N-C2H5 m=2 N/ 323842 33 201233734
式(6 -1 > 式(6-2> 式(6-3) 式(6-4) 式(6-5> 式(6 - 6〉 式(6-7) 式(6-8) 式(6-9) 式(6-10)Formula (6 -1 > Formula (6-2> Formula (6-3) Formula (6-4) Formula (6-5> Formula (6 - 6> Formula (6-7) Formula (6-8) Formula (6-9) Formula (6-10)
式(6) L = —SO3H m=2 L = 一 S02NH(CH2hN(C2Hsh L= 一 S〇2NH(CH2)3N(CH3)2 L= -CH2NHCOCH2N(C4H9)2 L= —CH2NHCOCH2NH(CH2)2N(CH3>2 0 II I rn=1 m=2 m=2 m—2 m=2Formula (6) L = -SO3H m=2 L = one S02NH(CH2hN(C2Hsh L= -S〇2NH(CH2)3N(CH3)2 L= -CH2NHCOCH2N(C4H9)2 L= —CH2NHCOCH2NH(CH2)2N( CH3>2 0 II I rn=1 m=2 m=2 m—2 m=2
0 〇2 〇 一S -N N-C2H5 m=2 2 5 -S02NH{CH2)2N(CH3)2 m=2 Φ (苯并異哚衍生物之具體例) 苯并異哚衍生物具體地可使用下述式(7)所示之化合 物,但不限定於此等。 34 323842 201233734 式(7) 式(7-1) L = —so2nhc3h6n(ch3)2 式(7-2) L = —S02NHC4H8N(CH3)2 式(7-3) L = —S02NHCH2N(CH3)2 式(7-4) L = —so2nhc2h4n(c2h5>2 式(7-5) L = —so2nhc2h4n(ch3)2 式(7-6) L = —so2nh(ch2>2n(ch3)(c2h5) 式(7-7) L = 一S02NH(CH2)2N(CH3)(n-C3H7) 式(7-8) L = —S02NH(CH2)3N(C2H5)2 式(7-9) L = —S02NH(CH2>3N(C4H9>2 式(7-10) L = —S02NH(CH2)4N(C2H5)2 式(7-1 1) L = —S02NH(CH)(CH3)(CH2)N(CH3)2 式(7-12) L = ——so2nh(ch2)(ch)(ch3>n(ch3)2 式(7-1 3> L = —302ΝΗ((:Η2)2Ν(ί·(:3Η7)2 式(7-14) L = —S02NH(CH2hN(C2H5)20 〇2 〇1 S -N N-C2H5 m=2 2 5 -S02NH{CH2)2N(CH3)2 m=2 Φ (Specific examples of benzindole derivatives) Benzoisoindole derivatives are specifically The compound represented by the following formula (7) is used, but is not limited thereto. 34 323842 201233734 Equation (7) Equation (7-1) L = —so2nhc3h6n(ch3)2 Equation (7-2) L = —S02NHC4H8N(CH3)2 Equation (7-3) L = —S02NHCH2N(CH3)2 (7-4) L = —so2nhc2h4n(c2h5>2 Equation (7-5) L = —so2nhc2h4n(ch3)2 Equation (7-6) L = —so2nh(ch2>2n(ch3)(c2h5) Equation (7 -7) L = a S02NH(CH2)2N(CH3)(n-C3H7) Formula (7-8) L = —S02NH(CH2)3N(C2H5)2 Formula (7-9) L = —S02NH(CH2>3N(C4H9>2 Formula (7-10) L = —S02NH(CH2)4N(C2H5)2 Formula (7-1 1) L = —S02NH(CH)(CH3)(CH2)N(CH3)2 Formula ( 7-12) L = ——so2nh(ch2)(ch)(ch3>n(ch3)2 Equation (7-1 3> L = —302ΝΗ((:Η2)2Ν(ί·(:3Η7)2 7-14) L = —S02NH(CH2hN(C2H5)2
(蒽醌衍生物之具體例) 蒽醌衍生物具體地可使用下述式(8)所示之化合物, 但不限定於此等。 35 323842 201233734(Specific Example of Anthracene Derivative) Specifically, the anthracene derivative may be a compound represented by the following formula (8), but is not limited thereto. 35 323842 201233734
式(8>Formula (8>
式(8-1> 式(8-2) 式(8-3) 式(8:4) 式(8-5) 式(8-6) 式(8-7) 式(8-8> 式(8-9〉 L= -OH L= -COOH L= -S03H L= 一 S02NH2 L = -S02NH(CH2)2N(C2H5)2 L= -S02NH(CH2)3N(CH3)2 L= -CH2NHCOCH2N(C4H9)2 L = -CH2NHCOCH2NH(CH2)2N(CH3>2 o 式(8-1 0)Formula (8-1> Formula (8-2) Formula (8-3) Formula (8:4) Formula (8-5) Formula (8-6) Formula (8-7) Formula (8-8 > Formula ( 8-9> L= -OH L= -COOH L= -S03H L=1 SO2NH2 L = -S02NH(CH2)2N(C2H5)2 L= -S02NH(CH2)3N(CH3)2 L= -CH2NHCOCH2N(C4H9 ) 2 L = -CH2NHCOCH2NH(CH2)2N(CH3>2 o Formula (8-1 0)
(二蒽醌衍生物之具體例)二蒽醌衍生物具體地可使用下述式(9)所示之化合 物,但不限定於此等。(Specific Example of Diterpene Derivative) The diterpene derivative may specifically be a compound represented by the following formula (9), but is not limited thereto.
36 323842 20123373436 323842 201233734
式(9)Formula (9)
式(9-1) L= -OH m=2 式(9-2) L= -COOH m=2 式(9-3) L= —S03H m=2 式(9-4) L = 一SO2NH2 m=2 式(9-5) L = -S02NH(CH2)2N(C2H5)2 m=2 式(9-6) L= -S02NH(CH2)3N(CH3)2 m=2 式(9-7) l= -ch2nhcoch2n(c4h9)2 m=2 式(9-8> L = 一CH2NHCOCH2NH(CH2)2N(CH3>2 式(9-9) L = -C2-N^l m=1 m=2 式(9-1 0) N-C2H5 m=2 (噻畊靛藍衍生物之具體例) 噻哄靛藍衍生物具體地可使用下述式(10)所示之化 合物,但不限定於此等。 37 323842 201233734Formula (9-1) L= -OH m=2 Formula (9-2) L= -COOH m=2 Formula (9-3) L= —S03H m=2 Formula (9-4) L = One SO2NH2 m =2 Formula (9-5) L = -S02NH(CH2)2N(C2H5)2 m=2 Formula (9-6) L= -S02NH(CH2)3N(CH3)2 m=2 Formula (9-7) l= -ch2nhcoch2n(c4h9)2 m=2 Formula (9-8> L = A CH2NHCOCH2NH(CH2)2N(CH3>2 Formula (9-9) L = -C2-N^lm=1 m=2 Formula ( 9-1 0) N-C2H5 m=2 (Specific example of the tidal indigo derivative) The compound represented by the following formula (10) can be specifically used as the thiazolidine derivative, but is not limited thereto. 201233734
式(10-1) L = -S02NH(CH2)3N(C2H5)2 m=2 式(10-2) l = -S02NH(CH2)3N{(CH2)3CH3}2 m=2 式(10-3> L = -S02NH(CH2)2N(C2H5)2 m=2 式(1 0-4> L = -S02N(CH3)2 m=2 式(10-5) L = -S02N(C4H9)2 m=2 式(1 0-6) L = -S02NH(CH2)3N(C2H5)(CH3) m=2 式(1 0-7) L = -S02NH(CH2)3N(CH3)2 m=2 式(1 0-8) L = -S02NH(CH2)2N(CH3)2 m=2 式(10-9> L = *S〇2—N N一CH3 m=2 (偶氮色素衍生物之具體例) 偶氮色素衍生物具體地可使用下述式(11)、式(12)、 式(13)所示之化合物,但不限定於此等。Formula (10-1) L = -S02NH(CH2)3N(C2H5)2 m=2 Formula (10-2) l = -S02NH(CH2)3N{(CH2)3CH3}2 m=2 Formula (10-3>) ; L = -S02NH(CH2)2N(C2H5)2 m=2 Formula (1 0-4> L = -S02N(CH3)2 m=2 Formula (10-5) L = -S02N(C4H9)2 m= 2 Formula (1 0-6) L = -S02NH(CH2)3N(C2H5)(CH3) m=2 Formula (1 0-7) L = -S02NH(CH2)3N(CH3)2 m=2 Formula (1 0-8) L = -S02NH(CH2)2N(CH3)2 m=2 Formula (10-9> L = *S〇2—NN-CH3 m=2 (Specific example of azo dye derivative) Azo Specific examples of the dye derivative include compounds represented by the following formulas (11), (12), and (13), but are not limited thereto.
38 323842 201233734 Η 。似38 323842 201233734 Η . like
式(1 1) 式(1 1-1) 式(1 1-2> 式(1卜3> 式(1卜4) 式(1 1 - 5 ) L1 = —OH L2= —NH(CH2)4N(C2H5)2 L'= -OH L2= —NH(CH2)3N(C 為)2 LU -NH(CH2)3N(C2H5)2 l2 = —nh(ch2)3n(c2hs)2 L1= —NH(CH2)2N(C3H7)2 l2=-NH(CH2)3N(C2H5)2 L2= -NH(CH2)sFormula (1 1) Formula (1 1-1) Formula (1 1-2 > Formula (1 Bu 3) Formula (1 Bu 4) Formula (1 1 - 5 ) L1 = —OH L2= —NH(CH2)4N (C2H5)2 L'= -OH L2=—NH(CH2)3N(C is)2 LU -NH(CH2)3N(C2H5)2 l2 = —nh(ch2)3n(c2hs)2 L1=—NH( CH2)2N(C3H7)2 l2=-NH(CH2)3N(C2H5)2 L2= -NH(CH2)s
L1 * 一OHL1 * one OH
式(1 1 - 6 ) CONH(CH2)2—~VcH3 -NH—^~~^-CONH(CH2)2— 式(1卜7) 式(1 1-8) -NH—^~^~CONH(CH2)2N(C2H4OH)2 CONH(CH2)2N(C2H4OH>2 -NH—^^-CONH(CH2)2N{CH(CH3)2}2 -NH—^^-CONH(CH2)2N{CH(CH3)2}2Formula (1 1 - 6 ) CONH(CH2)2 -~VcH3 -NH-^~~^-CONH(CH2)2 - Formula (1 Bu 7) Formula (1 1-8) -NH-^~^~CONH (CH2)2N(C2H4OH)2 CONH(CH2)2N(C2H4OH>2 -NH-^^-CONH(CH2)2N{CH(CH3)2}2 -NH-^^-CONH(CH2)2N{CH( CH3) 2} 2
式(1 1 -9 ) L1= -NH(CH2)2N(CH3)2 l2= -NH(CH2)2N(CH3)2 323842 39 201233734Formula (1 1 -9 ) L1= -NH(CH2)2N(CH3)2 l2= -NH(CH2)2N(CH3)2 323842 39 201233734
N=N_^Q_L2 NHCOCHCOCH3 式(12-1) L’ = —ch3 式(1 2-2> L1 = 一 CH3 式(12-3) L1 = 一 ch3 式(1 2-4) L1: -ch3 式(12-5) L1 = -och3 式(12-6> L1 = 一 och3 式(12-7> L1 = -och3 式(12-8) L1 = —och3 式(12-9) L1 = —N02 式(1 2-10) L1: —N02 式(12-1 1) L1: —N〇2 式(1 2-1 2) L1 = 一 N02 式(1 2) L2= -conh(ch2)2n(c2h5)2 L2= -conh(ch2>3n(c2hs)2 L2= -S02NH(CH2)2N(C2H5)2 L2= -S02NH(CH2)3N(C2H5)2 L2= -CONH(CH2)2N(C2H5)2 L2= -CONH(CH2)3N(CzHs)2 L 2 = —S02NH(CH2)2N(C2H5)2 L2= —S02NH(CH2)3N(C2H5)2 L2= —CONH(CH2)2N(C2Hs)2 L2= -CONH(CH2)3N(C2H5)2 l2= —S02NH(CH2)2N(C2H5)2N=N_^Q_L2 NHCOCHCOCH3 Formula (12-1) L' = —ch3 Formula (1 2-2> L1 = One CH3 Formula (12-3) L1 = One ch3 Formula (1 2-4) L1: -ch3 (12-5) L1 = -och3 Equation (12-6> L1 = one och3 Equation (12-7> L1 = -och3 Equation (12-8) L1 = —och3 Equation (12-9) L1 = —N02 (1 2-10) L1: —N02 Equation (12-1 1) L1: —N〇2 Equation (1 2-1 2) L1 = One N02 Equation (1 2) L2= -conh(ch2)2n(c2h5 ) 2 L2= -conh(ch2>3n(c2hs)2 L2= -S02NH(CH2)2N(C2H5)2 L2= -S02NH(CH2)3N(C2H5)2 L2= -CONH(CH2)2N(C2H5)2 L2= -CONH(CH2)3N(CzHs)2 L 2 = —S02NH(CH2)2N(C2H5)2 L2= —S02NH(CH2)3N(C2H5)2 L2= —CONH(CH2)2N(C2Hs)2 L2 = -CONH(CH2)3N(C2H5)2 l2= —S02NH(CH2)2N(C2H5)2
Lz= 一 S02NH(CH2)3N(C2H5>2 式(1 3) / /N=N^Q-L3 L1-^ >-nhcochcoch3 式(13-1) L1 = 一CH3 l2 = —ch3 l3 = -conh(ch2)2n(c2h5)2 式(13-2) L1: —CH3 l2 = 一 CH3 l3 = —conh(ch2>3n(c2h5)2 式(13-3) L1: 一 ch3 l2 = -ch3 L3= -S02NH(CH2)2N(C2Hs)2 式(13-4) L1 = -ch3 l2= —ch3 L3= -S02NH(CH2)3N(C2H5)2 式(13-5) L1 = -so3h l2 = 一N〇2 L3= —CONH(CH2)2N(C2H5)2 式(1 3 - 6) L1 = -S03H l2 = —N〇2 L3= -CONH(CH2)3N(C2H5)2 式(13-7) L1: —so3H l2 = —N〇2 L3= —S02NH(CH2)2N(C2H5)2 式(13-8) L1 = -S03H l2= 一 N02 L3= -S02NH(CH2)3N(C2H5)2Lz=一S02NH(CH2)3N(C2H5>2 Formula (1 3) / /N=N^Q-L3 L1-^ >-nhcochcoch3 Formula (13-1) L1 = One CH3 l2 = —ch3 l3 = - Conh(ch2)2n(c2h5)2 Formula (13-2) L1: —CH3 l2 = One CH3 l3 = —conh(ch2>3n(c2h5)2 Equation (13-3) L1: One ch3 l2 = -ch3 L3 = -S02NH(CH2)2N(C2Hs)2 Equation (13-4) L1 = -ch3 l2= —ch3 L3= -S02NH(CH2)3N(C2H5)2 Equation (13-5) L1 = -so3h l2 = one N〇2 L3=—CONH(CH2)2N(C2H5)2 Equation (1 3 - 6) L1 = -S03H l2 = —N〇2 L3= -CONH(CH2)3N(C2H5)2 Equation (13-7) L1: —so3H l2 = —N〇2 L3= —S02NH(CH2)2N(C2H5)2 Equation (13-8) L1 = -S03H l2= One N02 L3= -S02NH(CH2)3N(C2H5)2
(喹酞酮衍生物之具體例) 啥酜酮衍生物具體地可使用下述式(14-1)至式 40 323842 201233734 (14-13)所示之化合物,但不限定於此等。(Specific Example of Quinone Derivative) The anthrone derivative is specifically a compound represented by the following formula (14-1) to formula 40 323842 201233734 (14-13), but is not limited thereto.
CICI
(c2h5)2n(h2c)3hn(c2h5) 2n(h2c)3hn
41 323842 20123373441 323842 201233734
式(14-5) 式(14-6)Formula (14-5) Formula (14-6)
式 <14-7)Formula <14-7)
OC2H4N(C4H9)2 式(1 4-8)OC2H4N(C4H9)2 Formula (1 4-8)
OH NHCHOH NHCH
式(14-9>Formula (14-9>
c〇NH_<p^ ho3s/c〇NH_<p^ ho3s/
NHCH 323842 42 201233734NHCH 323842 42 201233734
ClCl
(喹吖酮衍生物之具體例) 喹吖酮衍生物具體地可使用下述式(15)所示之化合 物,但不限定於此等。 323842 43 201233734(Specific Example of Quinone Derivative) The compound of the following formula (15) can be specifically used as the quinophthalone derivative, but is not limited thereto. 323842 43 201233734
式(1 s) 式(15-1> 式(15-2> 式(1 S-3) 式(1 5-4) 式(1 5-5) 式(15-6) 式 <15-7)Formula (1 s) Formula (15-1 > Formula (15-2 > Formula (1 S-3) Formula (1 5-4) Formula (1 5-5) Formula (15-6) Formula <15-7 )
L =: —〇H ms2 L = -COOH m=2 L = —S03H m=2 La -so2nh(ch2)4叫CH3>2 L* -S02NH(CH2)2N(C2H5)2 m«2 L = 一 ch2nhcoch2ch2n(ch3>2 ms2 L* -ch2nhcoch2mhch2n(c2h5>2 m«2 ,Η2 L = -C mS=1 式(1 5-8) 0L =: —〇H ms2 L = -COOH m=2 L = —S03H m=2 La -so2nh(ch2)4 is called CH3>2 L* -S02NH(CH2)2N(C2H5)2 m«2 L = one Ch2nhcoch2ch2n(ch3>2 ms2 L* -ch2nhcoch2mhch2n(c2h5>2 m«2 ,Η2 L = -C mS=1 (1 5-8) 0
(顏料之平均一次粒徑)(average primary particle size of pigment)
或分=:ί樣的顏料組成物,以1粒徑非常微 [布寬度狹乍’也具有_之粒度分布為佳。藉由 日實施態樣之|貞料組成物之顺穿透型電子顯微鏡)曰所; =平均-次粒徑(體積平均粒徑)宜為5至Μ⑽之範隨 :小於5nm ’於有機溶劑中難以分散。又,若大於70⑽ …、法得到充分的對比度比。基於此種理由,較佳之範圍 40nm之範圍。藉由合成顏料、將其混合而形成顏对 組成物之階段’平均―:欠㈣t為上職圍時可直接使用 然而若非如此時’宜藉由鹽研磨處理等進行顏料之微細 323842 44 201233734 及整粒化。 (顏料之微細化) 含有第1實施態樣之二酮基π比咯并TJ比洛系顏料組成物 的顏料,以進行微細化而使用為佳,微細化方法係宜為雎 研磨處理❶ ‘ 鹽研磨處理係將顏料、水溶性無機鹽與水溶性有機、 劑之混合物使用捏合機、三混機、2根輥研磨機、3根輥石 磨機、球磨機、立式球磨機(attrit〇r)、砂磨機等現練機 —邊加熱一邊機械性混練後,藉水洗除去水溶性無機鹽婆 水溶性有機溶狀處理。水雜無機録發揮破碎助劑々 鹽研磨時利用無機鹽之高硬度而破碎顏料,藉^ 她®’引起結晶成長。因此,混練時係同時產 之破碎與結晶成長,依混練條 4 ’ 徑相異。 ^件則所付到之㈣的-次_ 藉由加熱促進結晶成長, 佳。加熱溫度未達35。(:時,未充^皿度為35至150°C』 粒子之形狀接近蚊形。另〜方:結晶成長,而劃 時,結晶成長進展過度,顏料熱溫度超過15代 磨處理之混缘時間從平銜恥人粒徑變大。又,鹽兩 刀布與鹽研磨處理所需要的 的沐, 買用之點’宜為2至24小暗 藉由使鹽研磨處理顏料時 、 粒徑非常微細,又,分布的寬=牛最適化’可得到-: 布之顏料。 寬度乍乍,具有㈣之粒度; 323842 又’使用於鹽研磨處理 之·水溶性無機鹽係可使用氣化 45 201233734 納、氯化鋇、氣化鉀、硫酸納等,然而,從價格之觀點, 宜使用氣化鋼(食鹽)。水溶性無機鹽係從處理效率與生產 效率之兩方面來看’相對於顏料⑽質量份宜使甩诱 至2000質量份’最宜使用期至12⑽質量份。 又,水溶性有機溶劑係用以濕潤顏料及水溶性無機鹽 t = t只要為溶解(混合)於水且實質上不溶解所使用 2無機鹽者即可,無特別限定。但,鹽研磨處理時溫度上 tit溶劑容易蒸發之狀態,故從安全性之觀點,宜為 沸點120 C以上之高沸點溶劑。 戊αΠ’可使用2甲氧基乙醇、2_丁氧基乙醇、2一(異 、2—(己基氧基)乙醇、二乙二醇、二乙二醇 I乙基醚、二乙二醇單丁基醚、三乙二醇 基醚、液狀之聚乙二醇、,乙-知早’ 丙醇、一石‘ _ 1甲虱基-2-丙醇、1-乙氧基—2— 、=-丙二醇、二丙二醇單甲基喊、二丙 乙㈣、 ^份之^二醇等。水溶性有機溶劑係相對於顏料二質 份。且用5至1000質量份,最宜使用50至500質量 研磨處理時為了提昇混練效率亦可 微細化及整粒化非常有效。在二— 但不限定3物Γ細化中’宜使用上述色素衍生物, 度,亦即相料 衍生物之使用量係不影響色調的程 範圍。對於顏料100質量份,宜為0.5JL40質量份的 又 323842 ’鹽研磨處理時係亦可依需要而添加樹脂 所使用 46 201233734 之樹脂的種類係無特別限^,可使用以天 然樹脂、合成樹月旨、天然樹脂㈣質之心ς脂、改質天 用之樹脂=在室溫為固體,且為水不雜2等。所使 -部分可☆於上料機溶劑。樹脂 ’更宜為 刪質量份’宜為5至200質量份的範圍。係相對於顏料 [第2實施形態] (二酮基吡咯并,各系顏料級成物) 第2實施態樣之彩色濾 料組成物,係含有下述式(1)之漠化各并,各系顏 與下述式(Β-2)所示之特定各顏料 = W“各系顏料組成物,,料的彩 與下述式(B-2)之質量比為9 下迷式⑴ 本發明人等累積精心研〜 .之範圏。 用之C. L顏料紅254(氣化二==果發現’取代以往所使 使溴化二酮基吡咯并D比咯粗 B比各顏料),藉由 片,亮度會提高。進—料’式⑴)適科彩色據光 此漠化二酮基鱗并.比 ^由使用以特定之比率含有 二酮基料并姆㈣(γ、]、㈣對稱地導入取代基之 基料并㈣顏料)(以下’稱為「特定雜二酮 對比产且可柚制卢^ i 料組成物,可得到高亮度、高 片。又 σ,,、、步驟所造成之結晶析出的彩色濾光 成物依ί:·ί Γ施’可提供-種彩色濾光片用顏料組 *獅其、、间儿度及阿對比度,即使藉由加熱争驟亦不引 起二嗣基鱗并鱗系顏料之結晶析出。 323842 47 201233734Or the fraction =: ί-like pigment composition, preferably having a particle size distribution with a very small particle size [cloth width narrowness]. By means of a daily implementation of the 贞 组成 组成 型 ; = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = It is difficult to disperse. Further, if it is larger than 70 (10) ..., the method obtains a sufficient contrast ratio. For this reason, a preferred range is 40 nm. By synthesizing pigments and mixing them to form a phase-to-construction stage 'average': when the (four) t is used for the upper occupation, it can be used directly. However, if it is not, the pigment should be finely polished by salt polishing, etc. 323842 44 201233734 and Whole granulation. (Purification of the pigment) The pigment containing the diketopyl π-pyro- and TJ-pyro pigment composition of the first embodiment is preferably used for refining, and the refining method is preferably 雎 grinding treatment ❶ ' The salt grinding treatment uses a kneader, a three-mixer, two roller mills, three roller mills, a ball mill, and a vertical ball mill (attrit〇r) for the mixture of the pigment, the water-soluble inorganic salt and the water-soluble organic agent. , sand mill and other training machines - while heating and mechanical mixing, by water to remove water-soluble inorganic salt water soluble organic solution treatment. The water-inorganic recording plays a role as a crushing aid. When the salt is ground, the high hardness of the inorganic salt is used to break the pigment, and the crystal is grown by the ®®. Therefore, during the kneading, the crushing and crystal growth at the same time are produced, and the diameter of the mixed strip is different. ^ The part that is paid (4) - times _ is promoted by heating to promote crystal growth. The heating temperature is less than 35. (: When the temperature is not 35 ° C to 150 ° C) The shape of the particles is close to the mosquito shape. The other side: the crystal grows, while the crystal growth progresses excessively, and the pigment heat temperature exceeds the 15th generation of the grinding. The time is larger from the size of the flat shame. In addition, the salt required for the two-knife cloth and the salt grinding treatment, the point of purchase 'is preferably 2 to 24 small dark, when the salt is ground to treat the pigment, the particle size Very fine, and the width of the distribution = the optimum of the cow 'is available -: the pigment of the cloth. The width is 乍乍, with the particle size of (4); 323842 'Used in salt grinding treatment · Water-soluble inorganic salt can be used for gasification 45 201233734 Nano, cesium chloride, potassium hydride, sodium sulphate, etc. However, from the price point of view, it is advisable to use gasified steel (salt). The water-soluble inorganic salt is in terms of both treatment efficiency and production efficiency. The pigment (10) part by mass is preferably tempered to 2000 parts by mass of 'the optimum period of use to 12 (10) parts by mass. Further, the water-soluble organic solvent is used for the wet pigment and the water-soluble inorganic salt t = t as long as it is dissolved (mixed) in water and Substantially does not dissolve the 2 inorganic salts used, no However, in the salt polishing treatment, the temperature of the tit solvent tends to evaporate, so from the viewpoint of safety, it is preferably a high boiling point solvent having a boiling point of 120 C or more. 戊αΠ' can be used with 2 methoxyethanol, 2_butyl Oxyethanol, 2 (iso), 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol I ethyl ether, diethylene glycol monobutyl ether, triethylene glycol ether, liquid Polyethylene glycol, B-known early 'propanol, one stone' _ 1 methyl ketone-2-propanol, 1-ethoxy-2, propylene glycol, dipropylene glycol monomethyl shrine, dipropylene B (tetra), ^ parts of diol, etc. The water-soluble organic solvent is based on the pigment component, and is used in an amount of 5 to 1000 parts by mass, preferably 50 to 500 mass, in order to improve the kneading efficiency. The granulation is very effective. In the second-but not limited to the refinement of the three substances, it is preferable to use the above-mentioned pigment derivative, and the degree, that is, the amount of the phase derivative used, does not affect the range of the color tone. For the pigment 100 parts by mass It should be 0.5JL 40 parts by mass and 323842 'salt grinding treatment can also be used if necessary to add resin 46 20123373 There are no special restrictions on the type of resin. The resin used in natural resin, synthetic tree, natural resin (four), and resin for daily use = solid at room temperature, and water is not mixed. The -part portion can be ☆ in the feeder solvent. The resin 'more preferably the mass part' is preferably in the range of 5 to 200 parts by mass. It is relative to the pigment [second embodiment] (diketopipyrrole, Each of the color filter compositions of the second embodiment contains the desertification of the following formula (1), and each of the lines and the specific formula shown by the following formula (Β-2) Pigment = W "The pigment composition of each series, the mass ratio of the color of the material to the following formula (B-2) is 9 (1) The inventors of the present invention have accumulated elaborate research. Using C. L Pigment Red 254 (gasification two == fruit found) instead of the conventionally used brominated diketopyrrolo D to be thicker than B), the brightness is improved by the sheet. The feed material 'formula (1)) is based on the light color of the diketone-based scale. The ratio is based on the use of a diketone base in a specific ratio and the (y) (y), (y), symmetrically introduced substituents. And (4) pigments) (hereinafter referred to as "specific heterodiketones comparatively produced and can be made from pomelo", which can obtain high brightness, high film, and σ,,,,,,,,,,,,,,,, Filtered by ί:·ί Γ 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 彩色 彩色 彩色 彩色 彩色 彩色 彩色 彩色 彩色 彩色 彩色 彩色 彩色 彩色 彩色 彩色 彩色 彩色 彩色 彩色 彩色 彩色 彩色 彩色 彩色 彩色 彩色 彩色 彩色Crystallization of pigments. 323842 47 201233734
BrBr
式(1) 式(B — 2) [式(B-2)中, A及B分別獨立為氫原子、氣原子、氣原子、峨原子、氮 基、碳數1至12之院基、可具有取代基之苯基、_叫、—⑽、 -SR2、-N(R3)R4、-C00R5、、C0NH2、_c〇nhr6、_c〇n(r7)r8、 -S〇2NH2、-S〇2NHR9、或-SO^R^R11, R1至R11分別獨立為碳數i至12的烷基、可具有取代基之 苯基、或可具有取代基之芳燒基; 但A及B並不同時為氫原子]。 上述碳數1至12之烷基可為直鏈狀,亦可為分枝狀, 具體上可例舉如甲基、乙基、丙基、異丙基、了基、第二 丁基、第二丁基、戊基、己基、庚基、辛基、癸基、十二 碳基、1,5-二曱基己基、1,6_二甲基庚基、2—乙基己基等, 但不限定於此等。 上述可具有取代基之苯基可例舉如可具有碳數1至4 之烧基、二氟甲基、鹵原子、石肖基、氛基、胺〒酿基、胺 磺醯基、碳數1至4之烷氧基等取代基之苯基。苯基可具 有1個或二個以上之此等取代基。更具體地可例舉如苯 323842 48 201233734 基、對曱基苯基、4-第三丁基苯基、對硝基苯基、對甲氧 基苯基、對氯苯基、2, 4-二氯苯基、3-胺甲醯基苯基等, 但不限定於此等。 上述可具有取代基之芳烷基可例舉如可具有碳數1至 4之烷基、三氟曱基、鹵原子、硝基、氰基、胺曱醯基、 胺磺醯基、碳數1至4之烷氧基等取代基之芳烷基。芳烷 基可具有1個或二個以上之此等取代基。更具體地可例舉 如苯甲基、4-曱基苯曱基、4-第三丁基苯甲基、4-曱氧基 • 苯曱基、4-硝基苯甲基、2, 4-二氯苯曱基等,但不限定於 此等。 將式(B-2)之特定雜二酮基吡咯并吡咯顏料B的具體 例舉例於以下。但不限定於此等。Formula (1) Formula (B-2) [In the formula (B-2), A and B are each independently a hydrogen atom, a gas atom, a gas atom, a helium atom, a nitrogen group, and a carbon number of 1 to 12, Phenyl group having a substituent, _call, -(10), -SR2, -N(R3)R4, -C00R5, C0NH2, _c〇nhr6, _c〇n(r7)r8, -S〇2NH2, -S〇2NHR9 Or -SO^R^R11, R1 to R11 are each independently an alkyl group having a carbon number of i to 12, a phenyl group which may have a substituent, or an aryl group which may have a substituent; but A and B are not simultaneously A hydrogen atom]. The alkyl group having 1 to 12 carbon atoms may be linear or branched, and specifically may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a benzyl group or a second butyl group. Dibutyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, 1,5-didecylhexyl, 1,6-dimethylheptyl, 2-ethylhexyl, etc., but It is not limited to this. The phenyl group which may have a substituent may, for example, be an alkyl group having a carbon number of 1 to 4, a difluoromethyl group, a halogen atom, a schlossyl group, an aryl group, an amine oxime group, an amine sulfonyl group, and a carbon number of 1 to A phenyl group of a substituent such as an alkoxy group. The phenyl group may have one or two or more such substituents. More specifically, for example, benzene 323842 48 201233734, p-nonylphenyl, 4-tert-butylphenyl, p-nitrophenyl, p-methoxyphenyl, p-chlorophenyl, 2, 4- Dichlorophenyl, 3-aminoformylphenyl, etc., but are not limited thereto. The above aralkyl group which may have a substituent may, for example, be an alkyl group having a carbon number of 1 to 4, a trifluoromethyl group, a halogen atom, a nitro group, a cyano group, an amine fluorenyl group, an amine sulfonyl group, or a carbon number. An aralkyl group having a substituent such as an alkoxy group of 1 to 4. The aralkyl group may have one or two or more such substituents. More specifically, it may, for example, be benzyl, 4-nonylphenyl fluorenyl, 4-tert-butylbenzyl, 4-decyloxybenzoyl, 4-nitrobenzyl, 2, 4 - Dichlorophenyl fluorenyl group or the like, but is not limited thereto. Specific examples of the specific heterodiketopyrrolopyrrole pigment B of the formula (B-2) are exemplified below. However, it is not limited to this.
323842 49 201233734323842 49 201233734
式(B--4a) 式(B — 2-4b> 式(B-2-4C)Formula (B--4a) Formula (B-2-4b> Formula (B-2-4C)
323842 50 201233734323842 50 201233734
323842 51 201233734323842 51 201233734
323842 52 201233734323842 52 201233734
於顏料組成物所使用的式(B-2)中,從色相、對比度、 及結晶析出抑制效果之點,以式(B-2-1)、式(B-2-2)、式 • (B—2_4a)、式(B-2-6b)、式(B-2—7)等為佳。 顏料組成物中之式(1)與式(B_2)的比率,就質量比為 97.3至85:15之範圍。若式之比率超過15質量%, 雖然可得到結晶析出抑制效果,但有損式⑴之優異的色 調此係起因於式⑴之漠化二酮基吼咯并η比嘻顏料色調優 於式(Β 2)之特疋雜二酮基0比略并〇比洛顏μ。另一方面, 式(Β 2)之比率未達3質量%時,高對比度化及結晶析出抑 制效果不充分。結晶析出抑制效果不充分時,在加熱步驟 因於塗膜的表面析出結晶狀異物而引起光散射,引起亮度 323842 53 201233734 及對比度比的降低。因此,藉由使用上述質量比範圍之二 @同基吼咯并吼咯系顏料組成物,達成高亮度且高對比度, 可抑制即使因加熱步驟造成之二酮基吡咯并唯咯顏料之龄 晶析出。 顏料組成物係在無損其效果之範圍,亦可併用式 之二酮基吡咯并吡咯顏料、及式(B—2)之特定雜二酮基吡咯 并吡咯顏料B以外的二酮基吡咯并吡咯系顏料。 又,就式(1)之二酮基吡咯并吡咯顏料、及式之 ^ 特定雜二酮基吡咯并吡咯顏料B以外的二酮基各并 系顏料而言’亦可使用前述式(A-2)的特定雜二酮基吨σ各并 °比洛顏料。此時’式(Α-2)所示之之特定雜二_基11比略并。比 咯顏料的含量,以二酮基°比咯并η比咯顏料之合計質量作為 基準,宜為1質量%至15質量%。 ' *''' (二酮基吼咯并吼咯系顏料之製造方法) 式(1)之溴化二酮基哺咯并吡咯顏料係可藉由與在第 馨 1實施態樣之方法同樣的方法來製造。 ' 式(Β-2)之特定雜二_基吼咯并吼咯顏料β係例如使 用文獻 Synth· Commun.,1988, 18, 1213 及In the formula (B-2) used for the pigment composition, the color phase, the contrast ratio, and the effect of suppressing the precipitation of crystals are expressed by the formula (B-2-1), the formula (B-2-2), and the formula (B). B-2_4a), formula (B-2-6b), formula (B-2-7), etc. are preferred. The ratio of the formula (1) to the formula (B_2) in the pigment composition is in the range of 97.3 to 85:15 by mass. When the ratio of the formula exceeds 15% by mass, the effect of suppressing the crystallization precipitation can be obtained, but the excellent color tone of the formula (1) is caused by the color tone of the diketone fluorenyl ytterbium ytterbium ytterbium ytterbium pigment of the formula (1) is superior to the formula ( Β 2) The special azetodione group 0 is slightly smaller than that of Luoyan. On the other hand, when the ratio of the formula (?2) is less than 3% by mass, the effect of high contrast and crystallization precipitation inhibition is insufficient. When the effect of suppressing the crystallization precipitation is insufficient, light scattering occurs due to precipitation of crystal foreign matter on the surface of the coating film in the heating step, and the luminance 323842 53 201233734 and the contrast ratio are lowered. Therefore, by using the above-mentioned mass ratio range of two @同基吼 吼 吼 系 颜料 pigment composition, high brightness and high contrast can be achieved, and the crystal of the diketopyrrolopyrole pigment can be suppressed even if it is caused by the heating step. Precipitate. The pigment composition may be used in combination with the diketopyrrolopyrrole pigment of the formula and the diketopyrrolopyrrole other than the specific heterodiketopyrrolopyrrole pigment B of the formula (B-2). It is a pigment. Further, in the case of the diketopyrrolopyrrole pigment of the formula (1) and the diketone-based pigment other than the specific heterodiketopyrrolopyrrole pigment B, the above formula (A- can also be used. 2) The specific heterodiketone ton σ each and the ratio of the pigment. At this time, the specific hetero-base 11 ratio shown by the formula (Α-2) is slightly shorter. The content of the specific conjugated pigment is preferably from 1% by mass to 15% by mass based on the total mass of the diketone ratio and the η ratio of the conjugated pigment. '*''' (Manufacturing method of diketopyrrolopyrrole pigment) The brominated diketone-based pyrrolepyrrole pigment of the formula (1) can be the same as the method of the first embodiment The way to manufacture. 'Specific heterozygous Β-pyrrolopyrrole pigment β of the formula (Β-2), for example, Synth· Commun., 1988, 18, 1213 and
Tetrahedron,58(2002)5547-5565 記載之方法進行人成 特定雜二酮基吡咯并吡咯顏料B之製造方法並不限定於此 方法。 又,可使式(1)之?臭化二酮基β比略并略顏料與式 (Β-2)之特定雜二酮基π比咯并吼11 各顏料Β同時作為微細之 顏料組成物而製造。此係在琥珀酸二酯合成法中,可利用 54 323842 201233734 使用至少2種構造相異之苯甲猜化合物的方法(以下,稱為 「號拍酸二酿共合成法」)。具體而言,於上述W0 2009/081930號手冊記載之方法中,使所使用之複數種笨 甲腈化合物藉由從4-氣笨甲腈與下述式(B_3)所示之苯甲 猜化合物選定,製造第2實施態樣之二嗣基吼洛并鱗系 顏料組成物。Tetrahedron, 58 (2002) 5547-5565 The method for producing a human hetero-diketopyrrolopyrrole pigment B is not limited to this method. Further, the odorous diketone group β of the formula (1) can be used as a fine pigment composition simultaneously with a specific heterodiketo group of the formula (Β-2). And manufacturing. In the succinic acid diester synthesis method, at least two methods of constructing a different benzoate compound (hereinafter, referred to as "the two-shot co-synthesis method") can be used by 54 323 842 201233734. Specifically, in the method described in the above-mentioned WO 2009/081930 manual, the plural kinds of carbonitrile compounds used are obtained from 4-benzoic carbonitrile and benzoic acid compound represented by the following formula (B-3). The composition of the second embodiment of the dimercapto ruthenium pigment was selected.
式(Β - 3〉 [式(Β-3)中, Α及Β分別獨立為氫原子、氟原子、氣原子、換原子、氰 基、碳數1至12之絲、可具有取代基之苯基、m -SR2 ^ -N(R3)R^ , -C00r5 , .c〇NH2 ^ _c〇nhr6 ^ _c〇n(r7)r8 ^ -S〇2NH2、-S〇2_9、或-S〇2N(Rl〇)Ru, R^RU分別獨立為碳數1至12的烧基、可具有取代基之 苯基、或可具有取代基之芳烷基; 但A及B並不同時為氫原子]。 碳數1至12的烷基、可具有取代基之苯基、或可具 有取代基之芳烷基係與上述式(B-2)中的基相同。 於第2實施態樣可使用之上述式(B-3)的苯曱腈化合 物之具體例舉例如下,但不限定於此等。 323842 55 201233734Formula (Β - 3> [In the formula (Β-3), Α and Β are independently a hydrogen atom, a fluorine atom, a gas atom, a substituted atom, a cyano group, a filament having a carbon number of 1 to 12, and a benzene having a substituent. Base, m -SR2 ^ -N(R3)R^ , -C00r5 , .c〇NH2 ^ _c〇nhr6 ^ _c〇n(r7)r8 ^ -S〇2NH2, -S〇2_9, or -S〇2N( R1)Ru, R^RU are each independently a carbon group having 1 to 12 carbon atoms, a phenyl group which may have a substituent, or an aralkyl group which may have a substituent; however, A and B are not simultaneously a hydrogen atom]. The alkyl group having 1 to 12 carbon atoms, the phenyl group which may have a substituent, or the aralkyl group which may have a substituent is the same as the group in the above formula (B-2). The above aspect can be used in the second embodiment. Specific examples of the benzoquinone compound of the formula (B-3) are as follows, but are not limited thereto. 323842 55 201233734
NC^〇 nchQ^- nch〇-CF3 式(B_3_l) 式(B_3_2> 式(B — 3 — 3)NC^〇 nchQ^- nch〇-CF3 Formula (B_3_l) Formula (B_3_2> Equation (B-3-3)
式(B-3 — 6C) ^ (B-3-6 d) 式(B-3 一 7) nc~~C3~°"~\ nc_^3~ci nc~^~^ 式(B-3-8)式(B-3-9)式(B-3-1 0)Formula (B-3-6C) ^ (B-3-6 d) Formula (B-3-7) nc~~C3~°"~\ nc_^3~ci nc~^~^ Formula (B-3 -8) Formula (B-3-9) (B-3-1 0)
式(B-3- 1 1) 參Formula (B-3- 1 1)
ncO-〇- nc~〇-^~ 式(B — 3 — 13> 式(B— 3 — 14)ncO-〇- nc~〇-^~ (B — 3 — 13> (B-3 – 14)
式(B-3 - 16) 式(B - 3-17〉 顏料組成物雖然可將分別製造的溴化二酮基吡咯并 ^、特疋的雜一酮基°比P各并π比a各B混合後形成,但就製 ^的容易度而言,則希望是以破舰二S旨共合成法同時製 造顏料組成物。如使用分別製造的化合物時,可在分散2 種顏料之前將其單純的混合,亦可藉由鹽研磨處理將其粉 201233734 碎混合 若藉由琥珀酸二酯共合成法製造式(1 )的溴化二酮基 吡咯并吡咯顏料與式(B-2)的特定雜二酮基吡咯并吡咯顏 料B之顏料組成物時,相對於丨莫耳珀酸二酯,使2莫耳 之4-溴苯f腈與式(B_3)的苯甲腈化合物之混合物反應。 此時’調整4-漠笨甲腈與式(B一3)的笨甲猜化合物之昆合 比(莫耳比),以使生成的二酮基吡咯并吡咯系顏料組成物 t的式⑴與式(B~2)之質量比成為97: 3至85至15。由 於反應&可因式(B-3)的苯甲腈化合物的種類而異,而改變 4_演苯甲腈與式(β'3)的笨甲腈化合物之混合比(莫耳 比)°為了將二酮基鱗并鱗系顏料組成物之質量比控制 =期望的範圍’4-絲甲腈與式(Β_3)的苯甲腈化合物之混 S比(莫耳比)大約在80 : 2〇至98至2的範圍内。又,在 2酸一酯共合成法中,雖然也可使!莫耳的琥賴二醋 其、相對的2莫耳式(B—3)的笨甲腈化合物岐應生成二酮 即’不含絲子的二時叫并t各顏 斗)但因其極為微量而幾乎盔影響。 =二醋共合成法中,:酸二嶋W化合物 ί反應比率,雖然相對於1莫耳的破㈣二酉旨,基本上使 2莫耳’但如使用苯甲猜化合物的量,相 玻贿二醋大、約過量25莫耳%左右時,可有效的提高Formula (B-3 - 16) Formula (B - 3-17) The pigment composition can be produced by separately producing a brominated diketopyrrazole and a hetero-keto group having a ratio of P to π and a B is formed after mixing, but in terms of ease of manufacture, it is desirable to simultaneously manufacture a pigment composition by a co-synthesis method of a ship. If a separately produced compound is used, it can be dispersed before the two pigments are dispersed. In simple mixing, the powder 201233734 may be mixed by salt grinding treatment. If the brominated diketopyrrolopyrrole pigment of formula (1) is produced by co-synthesis of succinic acid diester, and the formula (B-2) When a pigment composition of a specific heterodiketopyrrolopyrrole pigment B is reacted with a mixture of 2 moles of 4-bromobenzenefonitrile and a benzonitrile compound of the formula (B-3) with respect to the oximeperic acid diester At this time, 'adjust the 4-kun carbonitrile to the compound of the formula (B-3), and the molar ratio of the compound (mole ratio) to form the diketopyrrolopyrrole pigment composition t. (1) The mass ratio to the formula (B-2) is 97: 3 to 85 to 15. Since the reaction & may vary depending on the type of the benzonitrile compound of the formula (B-3), 4_ Mixing ratio of benzonitrile to a benzoic acid compound of the formula (β'3) (Mohr ratio) ° In order to control the mass ratio of the diketone scaled pigment composition = the desired range '4- The mixed S ratio (mole ratio) of the silk carbonitrile to the benzonitrile compound of the formula (Β_3) is in the range of about 80: 2 Torr to 98 to 2. Further, in the 2-acid monoester co-synthesis method, although Can make! Moer's aloe vinegar, the opposite 2 Mo's (B-3) stupid carbonitrile compound should form a diketone, ie 'no silky two-time call and t each fight" but It is almost helmeted because of its extremely small amount. = two vinegar co-synthesis method: acid diterpene W compound ί reaction ratio, although relative to 1 mole of broken (four) two 酉, basically make 2 moles 'but as the use of benzene to guess the amount of compound, phase glass When the bribe vinegar is large and the excess is about 25 mol%, it can be effectively improved.
藉由琥ίό酉夂一 g曰共合成法製造的顏料組成物中,漠化 二酮基鱗并鱗顏料與特定雜二喊鱗并料顏料B 323842 57 ϋ 201233734 之質畺 可以與第1實施態樣中的質量比之分析方法進 行相同的分析。 (色素衍生物) ^&第2替 、、I施態樣的顏料組成物中,可使用色素衍生物 以達成抑制顏料結晶成長,進而提高顏料分散性的目的。 色素何生物之例,可列舉如與第1實施態樣的色素衍生物 相同的色素竹生物。色素衍生物的適宜使用量,亦與第工 實施態樣相同。 ~ •(顏料的平均一次粒徑) 第2實施態樣的二酮基吨略并鱗系顏料板成物,宜 為-次粒,非常微細,同時具有狹窄的分布寬度、粒度分 布陡山肖。藉由TEM(穿透型電子顯微鏡)求得第2實施態樣 的二酮基t各并鱗系顏料組成物之平均—次粒徑(個數 平均粒徑),宜為5至70nm的範圍中。若小於—時,有 可能難以分散於有機溶劑中。又,若大於7〇nm時,有可能 鲁未能獲得充分的對比度比。基於此種理由,較佳的範圍是 1〇至4_。在以上述合成法製造二_基対并此略系顏料 乡且成物的階段中’雖然可在平均一次粒徑於上述範圍中時 直接使用,然而若非如此,則希望先行以鹽研磨處理等顏 料的微細化及整粒化。 (顏料的微細化) 含有第2實施態樣的二_基%„各并鱗系顏料組成物 之顏料,以使其微細化後使用為隹。微細化的方法宜為巴 研磨處理。鹽研磨處理’可進行與第(實施態樣相同的操 323842 58 201233734 作。 [彩色滤光片用著色組成物] 其次,說明本發明的實施態樣中之彩色濾光片用著色 組成物。 [第3實施態樣] (彩色濾光片用著色組成物) 第3實施態樣的彩色濾光片用著色組成物,含有第1 I 實施態樣的二酮基吡咯并吡咯系顏料組成物。第1實施態 樣的二明基β比略并比略系顏料組成物’可藉由與黏合劑樹 脂及有機溶劑一起併用,而作為著色組成物使用。又,亦 可併用第1實施態樣的二酮基吡咯并比略系顏料組成物以 外的著色劑。例如’亦可使用第2實施態樣的二酮基吡咯 并吡咯系顏料組成物。 (其他著色劑) 為調製色度等,第3實施態樣的著色組成物可在無損 • 及其效果的範圍,併用第1實施態樣的二酮基吡咯并吡咯 系顏料組成物以外的顏料或染料,可併用單獨丨種或2種 以上。 如併用一酮基η比洛并吼ρ各系顏料組成物以外的著色 劑時,在著色劑全部量中(1〇〇質量%),第丨實施態樣的二 酮基吡咯并吡咯系顏料組成物,宜為30質量%至1〇〇質量% 的範圍。以50質量%至100質量%的範圍較佳。如第i實施 態樣的二酮基吡咯并吡咯系顏料組成物少於30質量%時, 有可能使亮度的優異效果無法充分發揮。 323842 59 201233734 (黏合劑樹脂) 著色組成物中所含的黏合劑樹脂,可列舉如以往公知 的熱可塑性樹脂及熱硬化性樹脂。又,可使用第5實施態 樣中含有鹼可溶性感光性樹脂(C-B1)的黏合劑樹脂(C-B) 作為黏合劑樹脂,亦可使用含有具有第6實施態樣的構成 早元(D_bl)至(D_b3)之樹脂(D-B1)的黏合劑樹脂(D-B)。 熱可塑性樹脂可例舉如丙烯酸樹脂、丁路樹脂、笨乙 烯-順丁烯二酸共聚物、氣化聚乙烯樹脂、氯化聚丙烯樹 脂、聚氣乙烯樹脂、聚氣乙烯-醋酸乙烯樹脂共聚物、聚醋 酸乙烯、聚胺酯(urethane)系樹脂、聚酯樹脂、乙烯系樹 脂、醇酸(alkyd)樹脂、聚苯乙烯樹脂、聚醯胺樹脂、橡膠 系樹脂、環化橡膠系樹脂、纖維素類、聚乙烯(HDPE、LDPE)、 聚丁二烯及聚醯亞胺樹脂等。 在作為彩色濾光片用著色組成物使用時,宜為可見光 區域的400至700nm之全波長區域中的分光穿透率在8〇〇/〇 _ 以上的樹脂,並以95%以上的樹脂時較佳。又,在以鹼顯 像型著色阻劑的形態使用時,宜使用將含有酸性基的乙烯 性不飽和單體共聚合的鹼可溶性乙烯類樹脂。又,為了提 高光感度,亦可使用具有乙烯性不飽和活性雙鍵的能量線 硬化性樹脂。 將含有酸性基的乙烯性不飽和單體共聚合的驗可溶 性乙烯類樹脂,可例舉如具有羧基、磺酸基等酸性基的樹 脂。具體上,鹼可溶性樹脂可列舉如具有酸性基的丙烯酸 樹脂、烯烴/(無水)順丁烯二酸共聚物、苯乙烯/苯乙烯 323842 60 201233734 磺酸共聚物、乙烯/(甲基)丙烯酸共聚物,或異丁烯/(無水) 順丁烯二酸共聚物等。其中,以使用選自具有酸性基的丙 烯酸樹脂及苯乙烯/苯乙烯磺酸共聚物中的至少1種樹脂 為佳’尤其是具有酸性基的丙稀酸樹脂’以提焉耐熱性、 透明性’因而適用。 具有乙烯性不飽和活性雙鍵的能量線硬化性樹脂,可 使用的樹脂是在具有經基、叛基、胺基等反應性取代基的 高分子中,與具有異氰酸酯基、醛基、環氧基等反應性取 拳 代基的(甲基)丙烯酸基化合物或桂皮酸反應後,將(曱基) 丙烯醯基、苯乙烯基等光交聯性基導入該高分子内的樹 脂。又,也可使用一種使含有苯乙烯-順丁稀二酸折共聚物 或烯烴-順丁烯二酸酐共聚物等酸酐的高分子,藉由具 有(曱基)丙稀酸羥基烧酯等羥基的(曱基)丙烯酸化合物而 半酉旨化者。 兼具驗可溶性能與能量線硬化性能的熱可塑性樹 響 脂,也宜作為彩色濾光片用感光性著色組成物。 構成上述熱可塑性樹脂的單體,可列舉如以下的化合 物。例如,(曱基)丙烯酸曱酯、(曱基)丙烯酸乙醋、(曱基) 丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙稀酸正丁 酯、(甲基)丙烯酸異丁酯、(曱基)丙烯酸第三丁醋、(甲基) 丙烯酸2-乙基己酯、(曱基)丙烯酸環己酯、(曱基)丙稀酸 十八烧醋、(曱基)丙稀酸十一貌.醋、四氫11夫喃(曱基)丙稀 酸酯、(曱基)丙烯酸異莰酯、(甲基)丙烯酸笨酯、(曱基) 丙烯酸苯曱酯、(甲基)丙烯酸苯氧基乙酯、笨氧基二乙二 323842 61 201233734 醇(甲基)丙烯酸酯、甲氧基聚丙二醇(甲基)丙烯酸酯或乙 氧基聚乙二醇(曱基)丙烯酸酯等(甲基)丙烯酸酯類;或(甲 基)丙烯醯胺、N, N_二曱基(甲基)丙烯醯胺、N,N-二乙基(甲 基)丙稀酿胺、N-異丙基(甲基)丙烯醯胺、二丙酮(甲基) 丙稀醯胺或丙稀醢基嗎淋等(曱基)丙烯醯胺類;苯乙稀或 α-甲基苯乙烯等苯乙烯類;乙基乙烯醚、正丙基乙埽醚、 異丙基乙烯醚、正丁基乙烯醚或異丁基乙烯醚等乙烯醚 類、醋酸乙烯或丙酸乙烯等脂肪酸乙烯類。 龜 或環己基順丁稀二酿亞胺、苯基順丁埽二醯亞胺、曱 基順丁稀一酿亞胺、乙基順丁稀二酿亞胺、1,2-雙順丁烯 二醯亞胺乙烷、1,6-雙順丁烯二醯亞胺己烷、3-順丁烯二 醯亞胺丙酸、6, 7-亞甲基二氧基-4-甲基-3-順丁稀二醯亞 胺香豆素、4, 4’ -雙順丁烯二醯亞胺二苯基甲烷、雙(3_ 乙基-5-甲基-4-順丁烯二醞亞胺苯基)甲烷、ν,Ν,3_ 伸苯基二順丁烯二醯亞胺、N,N,_丨,4_伸苯基二順丁烯二 • 醯亞胺、N-(卜芘基)順丁烯二醯亞胺、N-(2, 4, 6-三氣笨基) 順丁烯二醯亞胺、N-(4-胺基苯基)順丁烯二醯亞胺、n_(4一 硝基苯基)順丁烯二醯亞胺、N_苯曱基順丁烯二醯亞胺、N_ 溴甲基-2, 3-二氣順丁烯二醯亞胺、琥珀醯亞胺基_3_順 丁烯二醯亞胺苯甲酸酯、N_琥珀醯亞胺基_3_順丁烯二醯亞 胺丙酸酯、N-號珀醯亞胺基_4-順丁烯二醯亞胺丁酸酯、卜 琥珀醯亞胺基順丁烯二醯亞胺己酸酯、N-[4-(2-苯并咪 唑)苯基]順丁烯二醯亞胺、9_順丁烯二醯亞胺吖啶等 取代順丁稀二醯亞胺類。 323842 62 201233734 作為熱硬化性樹脂,可例舉如環氧樹脂、笨代=聚氮 胺樹脂(benzoguanamine)、松香改質順丁烯二酸樹浐柃 香改質反丁烯二酸樹脂、三聚氰胺樹脂、尿素樹脂及酚 (phenol)樹脂等。其中’就提高耐熱性而言,以環氧樹脂、 三聚氰胺樹脂較適用。 黏合劑樹脂的質量平均分子量(Mw),為了使著色劑良 好分散,宜為5, 000至80, 000的範圍,以7, 〇〇〇至5〇 〇〇〇 的範圍時較佳。又,數目平均分子量(Mn)宜為2 5〇〇至 40, 000的範圍,Mw/Mn之值宜為10以下。 此處質量平均分子量(Mw)、數目平均分子量(Mn),是 使用東曹(Tosoh)股份有限公司製的凝膠滲透層析儀 「HLC-8120GPC」所測定的換算成苯乙烯之分子量,該層析 儀的分離管柱是4支直列連繫,填充劑是依序使用東曹股 份有限公司製的「TSK-GEL SUPER H5000」、「Η4000」、「Η3〇θ〇〇」 及「Η2000」’流動相是使用四氫呋喃。 如使用黏合劑樹脂作為彩色濾光片用組成物時,期望 能考量顏料吸附基及作用為顯像時的鹼可溶基的羧基、顏 料載體及作用為相對於溶劑的親和性基之脂肪族基及芳香 族基的平衡。就顏料分散性、顯像性及耐久性而言,宜使 用酸價20至300mgKOH/g的樹脂。如酸價未達2〇mgK〇H/g 時,將使相對於顯像液的溶解性變低,而難以形成微細的 圖案。如酸價超過300mgKOH/g時,有可能顯像而不留下微 細圖案。 相對於著色劑100質量份時,黏合劑樹脂可使用2〇 323842 63 201233734 至500質量份的量。如少於20質量份時,有可能使成膜性 及各種耐性不足,如多於500質量份時,有可能使顏料濃 度變低’無法顯現色特性。..... (有機溶劑)The pigment composition produced by the agglomeration method, the deserted diketone scaled scale pigment and the specific miscellaneous squash pigment B 323842 57 ϋ 201233734 can be compared with the first implementation The mass in the pattern is analyzed the same as the analytical method. (Pigment Derivative) ^& The pigment composition of the second and the first aspect of the pigment composition can be used for the purpose of suppressing the growth of the pigment crystal and further improving the pigment dispersibility. Examples of the pigments and organisms include the same pigment bamboos as the pigment derivatives of the first embodiment. The suitable amount of the pigment derivative used is also the same as that of the first embodiment. ~ • (average primary particle size of the pigment) The second embodiment of the diketone-based slightly squama pigmented sheet is preferably a sub-granule, very fine, and has a narrow distribution width and a fine particle size distribution. . The average-secondary particle diameter (number average particle diameter) of the diketone t squamous pigment composition of the second embodiment is determined by TEM (transmission electron microscope), preferably in the range of 5 to 70 nm. in. If it is less than - it may be difficult to disperse in an organic solvent. Also, if it is larger than 7 〇 nm, it may be impossible to obtain a sufficient contrast ratio. For this reason, the preferred range is from 1 〇 to 4 _. In the stage of producing the bismuth oxime by the above-mentioned synthesis method, and in the stage of the pigmentation, it is possible to use it directly when the average primary particle diameter is in the above range. However, if it is not, it is desirable to first perform salt polishing treatment or the like. The pigment is refined and granulated. (Refinement of Pigment) The pigment containing the bis-base% of each of the scaly pigment compositions of the second embodiment is used to make it fine and then used as a ruthenium. The method of miniaturization is preferably a bar grinding treatment. [Processing can be performed in the same manner as in the first embodiment (323842 58 201233734. [Coloring composition for color filter] Next, a coloring composition for a color filter in an embodiment of the present invention will be described. (3) (Coloring composition for color filter) The coloring composition for color filters of the third embodiment contains the diketopyrrolopyrrole pigment composition of the first embodiment. (1) The dibenzyl β ratio of the embodiment can be used as a coloring composition by using together with the binder resin and the organic solvent, and the second embodiment can be used in combination. The ketopyrrole is a coloring agent other than the pigment composition. For example, a diketopyrrolopyrrole pigment composition of the second embodiment can be used. (Other coloring agents) The coloring composition of the implementation can be In addition to the non-destructive and the range of the effect, the pigment or dye other than the diketopyrrolopyrrole pigment composition of the first embodiment may be used alone or in combination of two or more. When the coloring agent other than the pigment composition is used, the diketopyrrolopyrrole pigment composition of the second embodiment is preferably 30% by mass in the total amount of the coloring agent (1% by mass). The range of 1% by mass is preferably in the range of 50% by mass to 100% by mass. When the diketopyrrolopyrrole pigment composition of the i-th embodiment is less than 30% by mass, it is possible to cause brightness. 323842 59 201233734 (Binder Resin) The binder resin contained in the coloring composition may be a conventionally known thermoplastic resin or thermosetting resin. Further, in the fifth embodiment, the fifth embodiment can be used. Binder resin (CB) containing an alkali-soluble photosensitive resin (C-B1) As the binder resin, a resin (D-B1) containing the constituent elements (D_bl) to (D_b3) having the sixth embodiment can also be used. Adhesive resin (DB The thermoplastic resin may, for example, be an acrylic resin, a butadiene resin, a stupid ethylene-maleic acid copolymer, a vaporized polyethylene resin, a chlorinated polypropylene resin, a polystyrene resin, a polystyrene-vinyl acetate. Resin copolymer, polyvinyl acetate, urethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, Cellulose, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resin. When used as a coloring composition for color filters, it is preferably in the full-wavelength region of 400 to 700 nm in the visible light region. The resin having a spectral transmittance of 8 Å/Å or more is preferably 95% or more. Further, when it is used in the form of a base-developing coloring resist, an alkali-soluble vinyl-based resin obtained by copolymerizing an ethylenically unsaturated monomer having an acidic group is preferably used. Further, in order to improve the light sensitivity, an energy ray-curable resin having an ethylenically unsaturated active double bond may also be used. The soluble ethylene-based resin which copolymerizes the ethylenically unsaturated monomer containing an acidic group may, for example, be a resin having an acidic group such as a carboxyl group or a sulfonic acid group. Specifically, the alkali-soluble resin may, for example, be an acrylic resin having an acidic group, an olefin/(anhydrous) maleic acid copolymer, a styrene/styrene 323842 60 201233734 sulfonic acid copolymer, or an ethylene/(meth)acrylic acid copolymer. Or isobutylene / (anhydrous) copolymer of maleic acid and the like. Among them, it is preferable to use at least one resin selected from the group consisting of an acrylic resin having an acidic group and a styrene/styrenesulfonic acid copolymer, particularly an acrylic resin having an acidic group, to improve heat resistance and transparency. 'Therefore applicable. An energy ray-curable resin having an ethylenically unsaturated active double bond, which can be used in a polymer having a reactive substituent such as a thiol group, a thiol group, or an amine group, and having an isocyanate group, an aldehyde group, and an epoxy group. After reacting with a (meth)acrylic compound or cinnamic acid which is a reactive group, a photocrosslinkable group such as a (fluorenyl) acrylonitrile group or a styryl group is introduced into the polymer. Further, a polymer containing an acid anhydride such as a styrene-cis-butadiac dicarboxylic acid copolymer or an olefin-maleic anhydride copolymer may be used, and a hydroxyl group such as a hydroxyalkyl ester of (mercapto)acrylic acid ester may be used. (曱-based) acrylic compound and semi-defective. It is also a thermoplastic coloring agent that has both solubility and energy ray hardening properties, and is also suitable as a photosensitive coloring composition for color filters. The monomer constituting the above thermoplastic resin may, for example, be the following compound. For example, (mercapto) decyl acrylate, (mercapto) acrylate, (mercapto) n-propyl acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (methyl ) isobutyl acrylate, (butyl) acrylic acid, third butyl vinegar, (meth) acrylate 2-ethylhexyl acrylate, (decyl) hexyl hexyl acrylate, (mercapto) acrylic acid octagonal vinegar, ( Mercapto) acetic acid eleven appearance. vinegar, tetrahydro 11 furan (fluorenyl) acrylate, (decyl) isodecyl acrylate, (meth) acrylate, (fluorenyl) benzoquinone Ester, phenoxyethyl (meth) acrylate, phenyloxy diethylene 323842 61 201233734 alcohol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate or ethoxy polyethylene glycol ( (meth) acrylates such as acrylates; or (meth) acrylamide, N, N-dimercapto (meth) acrylamide, N, N-diethyl (methyl) propyl a thin amine, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide or acrylonitrile or the like (mercapto) acrylamide; Styrenes such as styrene or α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl ethoxylate, isopropyl vinyl ether, n-butyl vinyl ether or isobutyl vinyl ether, acetic acid A fatty acid such as ethylene or propionate ethylene. Turtle or cyclohexyl cis-butyl diimide, phenyl cis-butane quinone imine, fluorenyl-butyl butyl amide, ethyl cis-butyl diimide, 1,2-bis-butene Dimethyleneimine ethane, 1,6-bis-n-butylenediamine hexane, 3-m-butyleneimine propionic acid, 6,7-methylenedioxy-4-methyl- 3-cis-butyl diimide coumarin, 4, 4'-bis-s-methyleneimine diphenylmethane, bis(3_ethyl-5-methyl-4-s-butenylene) Amine phenyl)methane, ν, Ν, 3_phenylene dimethyleneimine, N,N,_丨,4_phenylene dimethylenebutene, N-(diphenyl) Maleimide, N-(2, 4, 6-tris), maleimide, N-(4-aminophenyl) maleimide, n_( 4-nitrophenyl) maleimide, N-phenylhydrazine, maleimide, N-bromomethyl-2,3-di-n-butyleneimide, amber Amine_3_maleimide benzoate, N_amber succinimide _3_succinimide propionate, N-type peryleneimine _4-cis Butylenediamine butyrate Substituted cis-butyl phthalate, N-[4-(2-benzimidazolyl)phenyl]butyleneimine, 9-m-butyleneimine acridine Amines. 323842 62 201233734 The thermosetting resin may, for example, be an epoxy resin, a benzoguanamine, a rosin-modified maleic acid, a musk-modified succinic acid resin, or a melamine. Resin, urea resin, phenol resin, and the like. Among them, epoxy resin and melamine resin are suitable for improving heat resistance. The mass average molecular weight (Mw) of the binder resin is preferably in the range of 5,000 to 80,000, and preferably in the range of 7, 〇〇〇 to 5 〇 in order to allow the colorant to be well dispersed. Further, the number average molecular weight (Mn) is preferably in the range of 25 to 40,000, and the value of Mw/Mn is preferably 10 or less. Here, the mass average molecular weight (Mw) and the number average molecular weight (Mn) are molecular weights converted to styrene measured by a gel permeation chromatography apparatus "HLC-8120GPC" manufactured by Tosoh Corporation. The separation column of the chromatograph is four in-line connections, and the filler is used in order to use "TSK-GEL SUPER H5000", "Η4000", "Η3〇θ〇〇" and "Η2000" manufactured by Tosoh Corporation. 'The mobile phase is tetrahydrofuran. When a binder resin is used as a composition for a color filter, it is desirable to consider a pigment adsorption group and an alkali-soluble carboxyl group at the time of development, a pigment carrier, and an aliphatic group acting as an affinity group with respect to a solvent. The balance between the base and the aromatic group. As the pigment dispersibility, developing property and durability, a resin having an acid value of 20 to 300 mgKOH/g is preferably used. If the acid value is less than 2 〇 mg K 〇 H / g, the solubility with respect to the developing liquid is lowered, and it is difficult to form a fine pattern. When the acid value exceeds 300 mgKOH/g, it is possible to develop without leaving a fine pattern. The binder resin may be used in an amount of 2 〇 323842 63 201233734 to 500 parts by mass relative to 100 parts by mass of the colorant. When the amount is less than 20 parts by mass, the film formability and various kinds of resistance may be insufficient. When the amount is more than 500 parts by mass, the pigment concentration may be lowered. ..... (Organic solvents)
為了使著色劑充分分散、浸透在著色劑載體中,易於 塗佈在玻璃基板等基板上,以形成厚度〇· 2至5em的乾燥 膜,而形成濾光片段(filter segment)係使著色組成物中 含有有機㈣。有機溶劑係考慮使著色組成物的塗佈性良 好’再加上著色組成物各成分的溶解性及安全性後選定。 有機溶劑的目的,切著色組成物調節成適度的濃 度’以形成均㈣厚㈣光片段,故相對於著色劑1〇〇質 量份時,宜使用500至4, 〇〇〇質量份的量。 (著色組成物的製法)In order to sufficiently disperse and impregnate the colorant in the colorant carrier, it is easy to apply on a substrate such as a glass substrate to form a dried film having a thickness of 〇 2 to 5 cm, and a filter segment is formed to form a coloring composition. Contains organic (4). The organic solvent is selected in order to improve the coatability of the colored composition, and the solubility and safety of each component of the colored composition are selected. For the purpose of the organic solvent, the cut coloring composition is adjusted to a moderate concentration to form a (four) thick (four) light segment, so that it is preferably used in an amount of 500 to 4 parts by mass relative to the mass of the coloring agent. (Method of making coloring composition)
者色組成物的是在上述勘合劑樹脂與有機溶劑形 的著色劑載體中’利用捏合機、2 _研磨機、3根槪研磨 機、球磨機、橫型砂磨機、縱型砂磨機、環孔型粒磨機 (annUlar、type beads miu)或立式球磨機等各種分散手 法使上述的一酉同基呢哈并D比嘻系顏料組成物微細分散而 製^ °又’也可使二_基^各并鱗系顏料組成物與其他 的者色劑等同時分散在著色劑載體上,形成著色組成物, 也可使其各別分散在著色劑載體上後混合形成。 (分散助劑) 繼 =散 323842 64 201233734 散=劑姆於防止分散後的著色劑之再凝聚的效果大,故利 、刀散助劑使著色劑分散在著色劑載體中而形成的著色組 成物’其對比度及黏度安定性良好。 在添加樹月曰型分散劑、界面活性劑時,相對於著色劑 10^質量份’分別宜為〇. i至55質量份,並以〇. i至45 質里伤較佳。如樹脂型分散劑、界面活性劑的調配量不到 〇.1質量份時,將不易獲得添加的效果,如調配量多於55 質直份時,有可能因過量的分散劑而影響分散。 (任意成分) 除了分散劑之外’著色組成物也可含有例如以下的成 分作為任意成分。任意成分的具體例係如後述。 (光聚合性單體及/或光聚合起始劑) 著色組成物在進一步添加光聚合性單體及/或光聚合 起始劑後,可作為感光性著色组成物使用。 感光性著色組成物中使用的光聚合性單體中,含有可 Φ 以紫外線或熱等硬化而生成透明樹脂的單體或寡聚物,此 等可單獨使用或混合2種以上使用。 相對於著色劑1〇〇質量份,單體的調配量宜為5至400 質量份’就光硬化性及顯像性而言以1 〇至3⑽質量份較佳。 使該組成物藉由紫外線照射而硬化後,應用光微影法 形成滤光片段時,除了光聚合起始劑以外,尚可調製成溶 劑顯像型或驗顯像型著色阻劑材的形態。 相對於感光性著色組成物中的著色劑1〇〇質量份,光 聚合起始劑宜為2至200質量份,就光硬化性及顯像性而 323842 65 201233734 言,以3至l5〇質量份較佳。 (增感劑) 感光性著色組成物中,可含有增感劑。. 相對於感光性組成物中含有的光聚合起始劑⑽質量 份’使用增感劑時的調配量宜為3至6〇質量份,就光硬化 性及顯像性而言,以5至50質量份較佳。 (多官能硫醇)The color composition is in the above-mentioned retanning agent resin and organic solvent-shaped coloring agent carrier, using a kneader, a 2_grinder, 3 mash grinders, a ball mill, a horizontal sand mill, a vertical sand mill, Various dispersing methods such as ring-type granule mill (annUlar, type beads miu) or vertical ball mill make the above-mentioned bismuth and D-type bismuth pigment composition finely dispersed to produce ^ ° and 'can also be two Each of the scaly pigment compositions is dispersed on the colorant carrier simultaneously with other colorants and the like to form a colored composition, which may be separately dispersed and dispersed on the colorant carrier to form a mixed composition. (Dispersing Aid) 继 散 323842 64 201233734 散=剂 The effect of re-agglomeration of the coloring agent after dispersing is large, so the coloring composition formed by the dispersing agent to disperse the coloring agent in the coloring agent carrier The object's contrast and viscosity stability is good. When the amount of the saponin-type dispersant or the surfactant is added, it is preferably from 0.1 to 55 parts by mass, and preferably from 〇. When the amount of the resin-type dispersant or the surfactant is less than 0.1 part by mass, the effect of addition is not easily obtained. For example, when the amount is more than 55 parts, the dispersion may be affected by an excessive amount of the dispersant. (Optional component) The coloring composition may contain, for example, the following components as optional components in addition to the dispersing agent. Specific examples of arbitrary components will be described later. (Photopolymerizable monomer and/or photopolymerization initiator) The coloring composition can be used as a photosensitive coloring composition after further adding a photopolymerizable monomer and/or a photopolymerization initiator. The photopolymerizable monomer to be used in the photosensitive coloring composition contains a monomer or an oligomer which can be cured by ultraviolet rays or heat to form a transparent resin. These may be used alone or in combination of two or more. The amount of the monomer is preferably from 5 to 400 parts by mass based on 1 part by mass of the colorant. It is preferably from 1 Torr to 3 (10) parts by mass in terms of photocurability and developability. After the composition is cured by ultraviolet irradiation, when the filter segment is formed by photolithography, it can be adjusted to be a solvent-developing type or a color-developing coloring resist material in addition to the photopolymerization initiator. form. The photopolymerization initiator is preferably 2 to 200 parts by mass with respect to 1 part by mass of the coloring agent in the photosensitive coloring composition, and is photohardenable and developable. 323842 65 201233734, 3 to 15 〇 mass Part is preferred. (Sensitizer) The photosensitive coloring composition may contain a sensitizer. The amount of the photopolymerization initiator (10 parts by mass) contained in the photosensitive composition is preferably 3 to 6 parts by mass in the case of using the sensitizer, and 5 to 6 in terms of photocurability and developability. 50 parts by mass is preferred. (multifunctional thiol)
感光性著色組成物可含有作用為連鎖移動劑的多官 能硫醇。、多官能硫醇宜為具有2個以上硫醇基的化合物。 以感光性著色組成物的全部固形分的質量為基準 (100質’多官能硫醇的含量宜為〇. i至3〇 ^量%,並 以i至20質量嫩佳。如多官能硫醇的含量未達〇. i質量% 時,無法充分獲得多官能硫醇的添加效果,如超過3〇質量 %時’有可能使感度過高反而使解像度降低。 [抗氧化劑] 著色組成物可含有抗氧化劑。因抗氧化劑可防止著色 組成物中所含的光聚合起始劑或熱硬化性化合物,受到熱 硬化或ITO退火(annealing)時的熱步驟之氧化而黃變,故 可提高塗賴穿透率。iUb ’可因含有抗氧化劑而防止加 熱步驟時的氧化而黃變後,獲得較高的塗膜穿透率。 以著色組成物的固形分質量為基準(1〇〇質量%)時,抗 氧化劑的含量是以0. 5至5· 〇質量%較佳,因其可使亮度、 感度良好。 (胺系化合物) 323842 66 201233734 合物著色組成物中可含有作用為還原溶存的氧之胺系化 (整平劑) 成物可使透明基板上的組成物之整平性變佳,著色組 (100V!添加整平劑。以著色組成物的全部質量為基準 %。1%)’整平劑的含量通常宜使用至5質量 % % 更化劑、硬化促進劑) 需要為I協助熱硬化性樹脂的硬化,在著色組成物中可依 質量=3有硬化劑、硬化促進劑。相對於熱硬化性樹脂100 发份,上述硬化促進劑的含量宜為0 01至15質量份。 /、他的添加劑成分) 安定為了使__黏度安定,著色組成物中可含有貯存 有石則又,為了提高與透明基板之間的密著性,也可含 夕燒麵合劑等密著提昇劑。 Μ色狀全部量為鮮(⑽f4%),貯存安定劑宜 0.1至ίο質量%。 %) 乂著色組成物的著色劑之全部量為基準(100質量 标密著提昇劑是使用0.01至10質量%,並宜為〇 買量%。 · 分=且’在以上躲意成分之外,也可含有後述任意成 壬一者。 (板大极子的去除) 32者色組成物宜以離心分離、燒結過濾膜或薄膜過濾膜 67 201233734 等過濾方式,將5以in以上的粗大粒子及混入的塵土去除, 該粗大粒子並宜為lvm以上,而以〇.5//m以上較佳。宜 使著色組成物如此的實質上不含〇. 5 μ m以上之粒子。並以 0. 3/z m以下較佳。 [第4實施態樣] (彩色濾光片用著色組成物) 第4實施態樣的彩色濾光片用著色組成物,含有第2 實施態樣的二酮基吡咯并吡咯系顏料組成物。第2實施態 樣的二酮基吡咯并吡咯系顏料組成物,因可與黏合劑樹脂 及有機溶劑併用而作為著色組成物使用。又,也可併用第 2實施態樣的二酮基吡咯并吡咯系顏料組成物以外的著色 劑。例如,也可使用第丨實施態樣的二酮基吡咯并吡咯系 顏料組成物。 (其他著色劑) 著色組成物可在無損其效果的範圍中,為了調整色 度,併用第2實施態樣的二酮基吡洛并吡咯系顏料組成物 以外的顏料或染料,可為單獨1種或併用2種以上。 如併用二酮基吡咯并吡咯系顏料組成物以外的著色 劑時,相對於著色劑全部量中(100質量%),第2實施態樣 的二_基吡咯并吡咯系顏料組成物宜為質量%至質 量% ’並以60質量%至100質量%較佳。如第2實施態樣的 二鋼基吡咯并吡咯系顏料組成物為4〇質量%以下時,可能 有無法充分發揮亮度與對比度的優異效果之情形。 (黏合劑樹脂) 323842 68 201233734 者色組成物中所含的黏合劑樹脂,可列舉如以往公知 的熱可塑性樹月曰及熱硬化性樹脂。黏合劑樹脂之例,可列 舉如與第3實施態樣中的黏合劑樹脂相同的黏合劑掛脂。 黏合劑樹脂的適宜使用量,也與第3實施態樣相同。 (有機溶劑) 為了使著色劑充分分散、浸透在著色劑載體中,易於 塗佈在玻璃基板等基板上’以形成厚度〇. 2至5/Zm的乾燥 膜後,而形成濾光片段,係使著色組成物中含有有機溶劑。 可與第3實施恐樣中的選定方法同樣的選定有機溶劑。有 機溶劑的適宜使用量,也與第3實施態樣相同。 (著色組成物的製法) 第4實施態樣的著色組成物,可以與第3實施態樣的 著色組成物的製法相同的製造方法製造。 (任意成分) 第4實施態樣的著色組成物中,可含有分散助劑、光 _ 聚合性單體及/或光聚合起始劑、增感劑、多官能硫醇、抗 氧化劑、胺系化合物、整平劑、硬化劑、硬化促進劑 他的添加劑等任意成分。至於此等任意成分的具體例,是 與第3實施態樣相同。又,適宜的例、適宜的使用量等也 與第3實施態樣相同。 (粗大粒子的去除) 第4實施態樣的著色組成物與第3實施態樣相同,宜 進行粗大粒子的去除。 [第5實施態樣] 323842 69 201233734 (彩色濾光片用著色組成物) 第5實施態樣的彩色濾光片用著色組成物,含有顏料 (A)、黏合劑樹脂(C-B)與溶劑,顏料(A)為含有式(1)所示 的顏料(A1),黏合劑樹脂(C-B)為含有鹼可溶性感光性樹脂 (C-B1)。第5實施態樣的彩色濾光片用著色組成物,可作 為感光性著色組成物使用。 本發明人等累積精心研究的結果發現使用含有溴化 二酮基吡咯并吡咯顏料(式(〇)與鹼可溶性感光性’樹脂的 • 著色組成物,取代以往使用的C. I.顏料紅254(氯化二酮基 吼咯并吼咯顏料),可得到具有高亮度、高對比度比,且已 抑制因加熱步驟的結晶析出而高精細的濾光片段之彩色濾 光片。 根據第5實施態樣,可提供高亮度、高對比度比的彩 色濾光片用著色組成物,其不僅不因加熱步驟而產生二酮 基°比11各并°比洛糸顏料的結晶析出,並且在形成感度或直線 φ 性等良好的濾光片段時必要的性能之平衡也優異。 (顏料(A)) 顏料(A)為含有式(1)所示的顏料(A1)。 《顏料(A1)》 323842 70 201233734The photosensitive coloring composition may contain a polyfunctional thiol which acts as a chain shifting agent. The polyfunctional thiol is preferably a compound having two or more thiol groups. Based on the mass of all the solid components of the photosensitive coloring composition (the content of the 100-mass polyfunctional thiol is preferably 〇. i to 3 〇 量 %, and is preferably from 1 to 20 by mass. Such as a polyfunctional thiol When the content is less than i% by mass, the effect of adding a polyfunctional thiol cannot be sufficiently obtained. For example, when it exceeds 3% by mass, it may cause the sensitivity to be too high and the resolution may be lowered. [Antioxidant] The coloring composition may contain Antioxidant. The anti-oxidant can prevent the photopolymerization initiator or the thermosetting compound contained in the coloring composition from being yellowed by the oxidation of the thermal step during the thermal hardening or ITO annealing, so that the coating can be improved. The penetration rate. iUb ' can be prevented from oxidizing and yellowing due to oxidation during the heating step, and a high coating film transmittance is obtained. Based on the solid content of the coloring composition (1 〇〇 mass %) The content of the antioxidant is preferably 0.5 to 5% by mass, because it is excellent in brightness and sensitivity. (Amine compound) 323842 66 201233734 The coloring composition of the composition may contain a solution for reductive dissolution. Oxygenation of oxygen The composition can improve the leveling property of the composition on the transparent substrate, and the coloring group (100V! Adding a leveling agent. Based on the total mass of the coloring composition, %. 1%) 'The content of the leveling agent is usually It is preferable to use 5% by mass of a curing agent or a curing accelerator. It is necessary to assist the curing of the thermosetting resin, and it is possible to have a curing agent or a curing accelerator depending on the mass of the coloring composition. The content of the above-mentioned hardening accelerator is preferably from 0 01 to 15 parts by mass based on 100 parts of the thermosetting resin. /, his additive component) stability In order to make __ viscosity stability, the coloring composition may contain stored stone, and in order to improve the adhesion with the transparent substrate, it may also be enhanced with the ceremonial mixture Agent. The total amount of the ochre is fresh ((10) f4%), and the storage stabilizer is preferably 0.1 to ίο% by mass. %) The total amount of the coloring agent of the 乂 coloring composition is based on the reference (100 mass-size adhesion enhancer is used in an amount of 0.01 to 10% by mass, and is preferably % by mass. · minutes = and 'outside the above-mentioned hiding ingredients Any one of the following may be included. (Removal of the plate-poles) The color composition of the 32-color composition is preferably a coarse particle of 5 or more by a centrifugal separation, a sintered filter membrane, or a membrane filtration membrane 67 201233734. And the mixed dust is removed, and the coarse particles are preferably lvm or more, and more preferably 〇.5//m or more. Preferably, the colored composition is substantially free of particles of μ 5 μ m or more. 3/zm or less. [Fourth embodiment] (Coloring composition for color filter) The coloring composition for a color filter according to the fourth embodiment contains the diketone group of the second embodiment. A pyrrolopyrrole-based pigment composition. The diketopyrrolopyrrole pigment composition of the second embodiment can be used as a coloring composition in combination with a binder resin and an organic solvent. Alternatively, the second embodiment can be used in combination. a form other than a diketopyrrolopyrrole pigment composition For example, a diketopyrrolopyrrole pigment composition of the second embodiment can also be used. (Other colorants) The coloring composition can be used in the range in which the effect is not impaired, in order to adjust the color, and the second color is used. When a pigment or a dye other than the diketopylpyrazole pyridin pigment composition of the embodiment is used, it may be used alone or in combination of two or more. When a coloring agent other than the diketopyrrolopyrrole pigment composition is used in combination, The di-based pyrrolopyrrole pigment composition of the second embodiment is preferably from 3% by mass to 9% by mass, and preferably from 60% by mass to 100% by mass, based on the total amount of the coloring agent (100% by mass). When the composition of the second steel-based pyrrolopyrrole pigment of the second embodiment is 4% by mass or less, there is a possibility that the excellent effect of brightness and contrast may not be sufficiently exhibited. (Binder resin) 323842 68 201233734 Color composition Examples of the binder resin contained in the resin include a conventionally known thermoplastic resin and a thermosetting resin. Examples of the binder resin include the same adhesive as the binder resin in the third embodiment. The binder is preferably used in the same manner as in the third embodiment. (Organic solvent) In order to sufficiently disperse and impregnate the colorant in the colorant carrier, it is easy to apply on a substrate such as a glass substrate. After forming a dried film having a thickness of 至2 to 5/Zm, a filter fragment is formed to contain an organic solvent in the colored composition. The organic solvent can be selected in the same manner as the selected method in the third embodiment. The amount of the suitable use is the same as that of the third embodiment. (Method for Producing Colored Composition) The colored composition of the fourth embodiment can be produced by the same manufacturing method as the method for producing the colored composition of the third embodiment. (Optional component) The coloring composition of the fourth embodiment may contain a dispersing aid, a photopolymerizable monomer, and/or a photopolymerization initiator, a sensitizer, a polyfunctional thiol, an antioxidant, and an amine system. Any component such as a compound, a leveling agent, a hardener, a hardening accelerator, and its additives. Specific examples of such arbitrary components are the same as in the third embodiment. Further, a suitable example, an appropriate amount of use, and the like are also the same as in the third embodiment. (Removal of coarse particles) The coloring composition of the fourth embodiment is the same as that of the third embodiment, and it is preferable to remove coarse particles. [Fifth Embodiment] 323842 69 201233734 (Coloring composition for color filter) The coloring composition for a color filter according to the fifth embodiment contains a pigment (A), a binder resin (CB), and a solvent. The pigment (A) is a pigment (A1) represented by the formula (1), and the binder resin (CB) is an alkali-soluble photosensitive resin (C-B1). The coloring composition for a color filter of the fifth embodiment can be used as a photosensitive coloring composition. As a result of intensive research by the inventors of the present invention, it has been found that a coloring composition containing a brominated diketopyrrolopyrrole pigment (a formula (〇) and an alkali-soluble photosensitive resin) is used instead of the previously used CI Pigment Red 254 (chlorinated). A diketone fluorenylpyrrole pigment) can obtain a color filter having a high luminance, a high contrast ratio, and suppressing a high-definition filter segment due to crystallization of a heating step. A coloring composition for a color filter having a high brightness and a high contrast ratio can be provided, which not only does not generate a diketone ratio of 11 by a heating step, but also forms a sensitivity or a straight line in the formation of a sensitivity or a straight line. It is also excellent in the balance of necessary properties such as a good filter fragment such as φ. (Pigment (A)) The pigment (A) contains the pigment (A1) represented by the formula (1). "Pigment (A1)" 323842 70 201233734
BrBr
Br 式(1)所示的顏料(A1)之溴化二酮基°比洛并吼洛顏 鲁 料’可由與第1實施態樣中的方法相同的方法製造。由於 使用式(1)所示的顏料(A1)’而得到相較於以往高亮度及高 對比度比的紅色著組成物。 又,可使用第1實施態樣中的二酮基吡咯并吡咯系顏 料組成物,也可使用2實施態樣中的二酮基吡咯并吡咯系 顏料組成物作為顏料(A)。 《其他的顏料》 φ 著色組成物也可併用顏料(A1)以外的顏料,作為此種 顏料’有機或無機顏料的單獨1種或併用2種以上。在顏 料之中,宜使用發色性高且耐熱性高的顏料,通常是使用 有機顏料。 作為可使用的有機顏料,可例舉如顏料(A1)以外的二 酮基吡咯并吡咯系顏料;偶氮、重氮、聚偶氮等偶氮系顏 料;鋼酞青、i化銅酞青、無金屬酞青等酞青系顏料;胺 基蒽醌、二胺基蒽醌、蒽嘧啶、黃蒽酮(flavanthrone)、 蒽_、茚酮、吼喃酮、紫蒽酮(violanthrone)等蒽自昆系顏 323842 71 201233734 料;喹吖啶酮系顏料;二噚畊系顏料;茈酮系顏料;花系 顏料;噻靛藍系顏料;異吲哚啉系顏料;吲哚啉蜩系顏料; 喹啉系顏料;士林(threne)系顏料;金屬錯物系顏料等。 在此等顏料之中,宜為含有選自顏料(A1)以外的二嗣 基°比p各并〇比哈系顏料、偶氮系顏料、蒽g昆系顏料、花系顏 料、喹吖啶酮系顏料、苯曱咪唑酮系顏料、喹啉系顏料所 形成之群組中的1種以上之顏料。此等顏料與顏料(A1)同 樣,可使紅色系顏料的調配比之調整的色調整變得容易, 並且此等的财光性或耐熱性優異。 又,作為無機顏料,可列舉硫酸鋇、鋅華、硫酸錯、 黃色鉛、鋅黃、暗紅色(紅色氧化鐵(皿))、鎘紅、海軍藍(群 青)、深藍(紺青)、氧化鉻綠、鈷綠、棕土、鈦黑、合成鐵 黑、氧化鈦、四氧化鐵等金屬氧化物粉、金屬硫化物粉、 金屬粉等。無機顏料可與有機顏料組合後使用,使其可一 面取得彩度與亮度的平衡,一面確保良好的塗佈性、感度、 _ 顯像性等。 如與紅色顏料或黃色顏料併用時,顏料(A)的合計1 〇〇 重量%中’式(1)所示的顏料(A1)之含量為40至1〇〇重量%, 並宜為50至100重量%,以60至1〇〇重量%更佳。此含量 的範圍,因可使式(1)所示的顏料(A1)之色特性充分顯現而 佳。 就可得充分的色再現性而言,在著色組成物的全部不 。揮發成分100重量%中,顏料(A)成分之含量較佳為1〇重量 %以上,更佳為15重量%以上,特佳為20重量%以上。又, 323842 72 201233734 就使著色組成物的安定性變佳而言,顏料(A)成分之含量較 佳為90重量%以下,更佳為80重量%以下,特佳為7〇重量 %以下。 在感光性著色組成物中,在不使耐熱性降低的範圍 内,也可含有染料用以調色。 《顏料的微細化》 顏料(A1)及其他的顏料宜微細化後使用。以在著色劑 载體中的分散良好而言,微細化後的顏料之一次粒徑宜為 20nm以上。又,由於可形成高對比度比的濾光片段,宜為 lOOnra以下。以25至85nm的範圍特佳。 同時,顏料的一次粒徑,可由顏料的TEM(穿透型電子 顯微鏡)之電子顯微鏡照片,以直接量測的方法進行一次粒 子的大小量測。具體上,是在量測各顏料的一次粒子之短 輛徑與長轴徑後,將其平均作為顏料粒子的粒徑。其次, 針對100個以上的顏料粒子,使各別粒子的體積近似於所 戈的粒位之立方體而求得平均體積,將具有此平均體積的 立方體之一邊的長度作為平均一次粒徑。 又,由此等微細化顏料的BET法求得的比表面積,宜 為60m2/g至130m2/g。若顏料(A)的比表面積小於下限值 時,有可能使彩色濾光片的亮度或對比度比降低。若比表 面積大於上限值時,有可能使顏料分散困難,而不易保持 作為著色組成物的安定性,難以確保流動性。其結果可能 使彩色濾光片的亮度或對比度比之特性降低。 控制顏料的比表面積之方式,有將顏料機械性的粉碎 323842 73 201233734 而控制比表面積的方法(稱為磨碎法)、將溶解於良容劑中 的顏料投入不良溶劑中後,析出期望之比表面積的顏料的 方法(稱為析出法)、及合成時製造期望之比表面積的顏料 的方法(稱為合成析出法)等。可依使用顏料的合成法或化 學性質等,針對各顏料選擇出適當的方法進行控制。控制 著色組成物中所含的顏料之比表面積的方法,也可使用上 述方法的任一種。 第5實施態樣中使用的顏料,宜使用磨碎法中的鹽研 磨處理以微細化,因使用這種的顏料,而可形成對比度比 高的濾光片段。鹽研磨處理是進行與上述二酮基吡咯并吡 略系顏料組成物中相同的方法。 (黏合劑樹脂(C-B)) 黏合劑樹脂(C-B)是分散顏料(A)的樹脂,其含有鹼可 溶性感光性樹脂(C-B1)。 《鹼可溶性感光性樹脂(C-B1)》 • 鹼可溶性感光性樹脂(C-B1),可舉出例如藉由以下所 示的(C-i)或(C-Bii)方法導入乙烯性不飽和雙鍵的樹脂。 < 方法(C-i)> 方法(C-i)係例如在具有環氧基的乙烯性不飽和單體 與其他的1種以上之單體共聚合而得的共聚物之側鏈環氧 基上’使具有乙稀性不飽和雙鍵的不飽和一元酸之緩基加 成反應,並且在生成的羥基上,使多元酸酐反應,導入乙 烯性不飽和雙鍵使其具有感光性樹脂的功能,且導入具有 鹼可溶性功能的羧基之方法。 323842 74 201233734 具有環氧基的乙烯性不飽和單體,可列舉例如(甲基) 丙烯酸縮水甘油酯、(甲基)丙烯酸甲基縮水甘油酯、(甲基) 丙烯酸2-環氧丙氧基乙醋、(甲基)丙烯酸3, 4-環氧基丁酯 及(曱基)丙烯酸3, 4-環氧基環己酯,此等單體可單獨使 用,也可2種以上併用。就接來的一步驟的與不飽和一元 酸之反應性而言,宜為(曱基)丙稀酸縮水甘油自旨。 不飽和一元酸可列舉如(曱基)丙烯酸、巴豆酸、鄰-、 間-、對-乙烯苯甲酸、(曱基)丙烯酸的α位鹵烷基、烷氧 ® 基、鹵素、确基、氰基取代物等單竣酸等,此等酸中,可 單獨使用,也可2種以上併用。 多元酸酐可列舉如四氩酞酸酐、酜酸酐、六氫酜酸 酐、琥珀酸酐、順丁烯二酸酐等,此等酸可單獨使用,也 可2種以上併用。羧基數的增加等,必要時可使用1, 2, 4-苯三曱酸酐等三羧酸酐,或使用苯均四酸二酐 (pyromelliticaciddianhydride)等四羧酸酐,將殘留的 φ 酸酐基加水分解等。又,使用具有乙烯性不飽和雙鍵的四 氫酞酸酐或順丁烯二酸酐作為多元酸酐時,更可增加乙烯 性不飽和雙鍵。 作為與方法(C-i)類似的方法,係例如在具有羧基的 乙烯性不飽和單體與其他的1種以上之單體共聚合而得的 共聚物之側鏈羧基的一部份,使具有環氧基的乙烯性不飽 和單體加成反應後,導入乙烯性不飽和雙鍵及敌基的方法。 < 方法(C-ii)> 方法(C-ii)係例如使用具有羥基的乙烯性不飽和單 323842 75 201233734 體,在與具有其他羧基的不飽和一元酸之單體或其他的單 體共聚合而得的共聚物之側鏈羥基上,使具有異氰酸酯基 的乙烯性不飽和單體之異氰酸酯基反應的方法。 具有羥基的乙烯性不飽和單體,可舉例如(甲基)丙烯 酸2-羥基乙酯、(曱基)丙烯酸2_或3_羥基丙酯、(曱基) 丙烯酸2-或3-或4-羥基丁酯、(曱基)丙烯酸甘油酯、或 環己烷二曱醇單(曱基)丙烯酸酯等(甲基)丙烯羥基烷酸 酯,此等單體可單獨使用,也可2種以上併用。又,也可 • 在上述(甲基)丙烯酸酯羥基烷上,使環氧乙烷、環氧丙烷 及/或環氧丁烷等加成聚合的聚醚單(甲基)丙烯酸酯或(聚) 7-戊内酯、(聚)ε-己内酯及/或(聚)12_羥基硬脂酸酯等 加成的(聚)酯單(甲基)丙烯酸酯。就塗膜異物的抑制而 吕,宜為(曱基)丙烯酸2-羥基乙酯或(曱基)丙烯酸甘油 酉旨。 具有異氰酸酯基的乙烯性不飽和單體,可列舉如 # 2-(甲基)丙烯醯基氧基乙基異氰酸酯,或1,卜雙[(曱基) 丙烯醯基氧基]乙基異氰酸酯等,但不侷限於此等單體, 也可2種以上併用。 鹼可溶性感光性樹脂(C-B1),可列舉如使用含有(甲 基)丙烯酸、巴豆酸、或α-氯丙烯酸等不飽和單羧酸、或 順丁烯二酸或反丁烯二酸等不飽和二羧酸等羧基,且具有 乙烯性不飽和雙鍵之單體而得的樹脂。作為鹼可溶性感光 性樹脂(C-B1)的前驅物之其他乙婦性不飽和單體,可列舉 如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸 323842 76 201233734 正丙醋、(曱基)丙稀酸異丙醋、(甲基)丙稀酸丁奶 丙稀酸異丁醋、(甲基)丙婦酸第二丁赌、曰:基) 三丁醋、(甲基)丙烯酸戊酉旨、(甲基)丙稀酸異戊酉旨丙=第 丙烯酸新戊酯、(曱基)丙烯酸第三戊酯、 、甲基) 曱基丁酸、(甲基)丙稀酸己酿、(甲基;丙烯 丙烯酸辛酯、(曱基)丙烯酸2~乙基己顆、 曰、甲基) 二烷酯、(曱基)丙烯酸十六烷酯、(甲基)丙丙烯酸十The brominated diketopyl group of the pigment (A1) represented by the formula (1) can be produced by the same method as the method of the first embodiment. By using the pigment (A1)' represented by the formula (1), a red composition having a higher luminance and a higher contrast ratio than that of the conventional one is obtained. Further, the diketopyrrolopyrrole pigment composition in the first embodiment can be used, and the diketopyrrolopyrrole pigment composition in the second embodiment can be used as the pigment (A). "Other pigments" φ The coloring composition may be used in combination with a pigment other than the pigment (A1), and may be used alone or in combination of two or more kinds of organic or inorganic pigments. Among the pigments, pigments having high color developability and high heat resistance are preferably used, and organic pigments are usually used. The organic pigment which can be used may, for example, be a diketopyrrolopyrrole pigment other than the pigment (A1); an azo pigment such as azo, diazo or polyazo; steel indigo, i-copper indigo Indigo-based pigments such as metal-free indigo; amine-based guanidine, diamine-based guanidine, pyrimidine, flavanthrone, 蒽_, fluorenone, fluorenone, violanthrone, etc. From Kunming 323842 71 201233734; quinacridone pigment; diterpene pigment; anthrone pigment; flower pigment; thiazolin pigment; isoporphyrin pigment; porphyrin lanthanide pigment; Quinoline pigments; threne pigments; metal miscellaneous pigments, and the like. Among these pigments, it is preferred to contain a diterpene ratio p selected from the group consisting of pigments (A1), and an antimony pigment, an azo pigment, a quinone pigment, an anthocyanin pigment, and a quinacridine. One or more pigments selected from the group consisting of ketone pigments, benzoimidazolone pigments, and quinoline pigments. These pigments are similar to the pigment (A1), and it is possible to easily adjust the color ratio of the red pigment to be adjusted, and is excellent in such good lightness or heat resistance. Further, examples of the inorganic pigment include barium sulfate, zinc oxide, sulfuric acid, yellow lead, zinc yellow, dark red (red iron oxide (dish)), cadmium red, navy blue (cyan), dark blue (indigo), and chromium oxide. Green, cobalt green, brown earth, titanium black, synthetic iron black, titanium oxide, iron oxide and other metal oxide powder, metal sulfide powder, metal powder and the like. Inorganic pigments can be used in combination with organic pigments to achieve a balance between saturation and brightness while ensuring good coatability, sensitivity, and photographic properties. When used in combination with a red pigment or a yellow pigment, the content of the pigment (A1) represented by the formula (1) in the total amount of the pigment (A) is 40 to 1% by weight, and preferably 50 to 100% by weight, more preferably 60 to 1% by weight. The range of this content is preferably such that the color characteristics of the pigment (A1) represented by the formula (1) are sufficiently exhibited. In terms of sufficient color reproducibility, all of the coloring compositions are not. The content of the pigment (A) component in 100% by weight of the volatile component is preferably 1% by weight or more, more preferably 15% by weight or more, and particularly preferably 20% by weight or more. Further, 323842 72 201233734, the content of the pigment (A) component is preferably 90% by weight or less, more preferably 80% by weight or less, and particularly preferably 7% by weight or less, in order to improve the stability of the coloring composition. In the photosensitive coloring composition, a dye may be contained for coloring in a range in which heat resistance is not lowered. <<Refinement of Pigment>> The pigment (A1) and other pigments should be used in a fine manner. The fine particle size of the finely divided pigment is preferably 20 nm or more in terms of good dispersion in the colorant carrier. Further, since a filter segment having a high contrast ratio can be formed, it is preferably 100 nm or less. It is particularly excellent in the range of 25 to 85 nm. At the same time, the primary particle diameter of the pigment can be measured by direct measurement by the electron micrograph of the TEM (transmissive electron microscope) of the pigment. Specifically, after measuring the short diameter and the major axis diameter of the primary particles of each pigment, the average is taken as the particle diameter of the pigment particles. Next, for 100 or more pigment particles, the volume of each particle is approximated to the cube of the grain position to obtain an average volume, and the length of one side of the cube having the average volume is taken as the average primary particle diameter. Further, the specific surface area determined by the BET method of the fine pigments is preferably from 60 m 2 /g to 130 m 2 /g. If the specific surface area of the pigment (A) is less than the lower limit value, the brightness or contrast ratio of the color filter may be lowered. When the specific surface area is larger than the upper limit value, it may be difficult to disperse the pigment, and it is difficult to maintain the stability as a coloring composition, and it is difficult to ensure fluidity. As a result, the brightness or contrast of the color filter may be degraded. In the method of controlling the specific surface area of the pigment, there is a method of controlling the specific surface area by mechanically pulverizing the pigment 323842 73 201233734 (referred to as a grinding method), and putting the pigment dissolved in the good-content agent into a poor solvent, and then depositing the desired A method of a pigment having a specific surface area (referred to as a precipitation method), a method of producing a pigment having a desired specific surface area during synthesis (referred to as a synthetic precipitation method), or the like. An appropriate method can be selected for each pigment to control according to the synthesis method or chemical properties of the pigment. Any of the above methods may be used as a method of controlling the specific surface area of the pigment contained in the colored composition. The pigment used in the fifth embodiment is preferably finely refined by a salt grinding treatment in a grinding method, and a filter having a high contrast ratio can be formed by using such a pigment. The salt grinding treatment is carried out in the same manner as in the above diketopyrrolopyran pigment composition. (Binder Resin (C-B)) The binder resin (C-B) is a resin which disperses the pigment (A) and contains an alkali-soluble photosensitive resin (C-B1). <<Alkali-soluble photosensitive resin (C-B1)>> The alkali-soluble photosensitive resin (C-B1) is, for example, introduced into the ethylenically unsaturated double by the (Ci) or (C-Bii) method shown below. The resin of the bond. <Method (Ci)> The method (Ci) is, for example, on a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group with one or more other monomers. a slow-radical addition reaction of an unsaturated monobasic acid having an ethylenically unsaturated double bond, and reacting a polybasic acid anhydride onto the generated hydroxyl group to introduce an ethylenically unsaturated double bond to have a function as a photosensitive resin, and A method of introducing a carboxyl group having an alkali-soluble function. 323842 74 201233734 Ethylene-containing unsaturated monomer having an epoxy group, for example, glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidyloxy (meth)acrylate Ethyl acetate, 3, 4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate, these monomers may be used singly or in combination of two or more. In view of the reactivity of the first step with the unsaturated monobasic acid, it is preferred that the (mercapto) acrylose glycidol be used. Examples of the unsaturated monobasic acid include (mercapto)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, an α-haloalkyl group of (mercapto)acrylic acid, an alkoxy group, a halogen, an exact group, For example, a monodecanoic acid such as a cyano substituent may be used alone or in combination of two or more. Examples of the polybasic acid anhydride include tetrahydrofurfuric anhydride, decanoic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. These acids may be used singly or in combination of two or more kinds. When the number of carboxyl groups is increased, if necessary, a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic anhydride such as pyromellitic aciddianhydride may be used, and the residual φ acid anhydride group may be hydrolyzed or the like. . Further, when tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bond can be further increased. A method similar to the method (Ci), for example, a part of a side chain carboxyl group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group with one or more other monomers, and having a ring A method of introducing an ethylenically unsaturated double bond and an ester group after an addition reaction of an ethylenically unsaturated monomer of an oxy group. <Method (C-ii)> The method (C-ii) is, for example, an ethylenically unsaturated single 323842 75 201233734 having a hydroxyl group, a monomer or other monomer having an unsaturated monobasic acid having another carboxyl group. A method of reacting an isocyanate group of an ethylenically unsaturated monomer having an isocyanate group on a side chain hydroxyl group of a copolymer obtained by copolymerization. The ethylenically unsaturated monomer having a hydroxyl group may, for example, be 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-(meth)acrylate. - (hydroxy) butyl acrylate, (meth) propylene hydroxy alkanoate such as cyclohexanedonol mono(indenyl) acrylate, these monomers may be used alone or in combination The above is used together. Further, it is also possible to add or polymerize a polyether mono(meth)acrylate or the like to ethylene oxide, propylene oxide, and/or butylene oxide on the above (meth) acrylate hydroxyalkane. An (poly)ester mono(meth)acrylate such as 7-valerolactone, (poly)ε-caprolactone and/or (poly)12-hydroxystearate. In the case of inhibition of the foreign matter of the coating film, it is preferably 2-hydroxyethyl (meth) acrylate or glycerin (mercapto) acrylate. Examples of the ethylenically unsaturated monomer having an isocyanate group include #2-(meth)acryloyloxyethyl isocyanate, or 1, bis[(indenyl)acrylenyloxy]ethyl isocyanate, and the like. However, it is not limited to these monomers, and two or more types may be used in combination. The alkali-soluble photosensitive resin (C-B1) may, for example, be an unsaturated monocarboxylic acid such as (meth)acrylic acid, crotonic acid or α-chloroacrylic acid, or maleic acid or fumaric acid. A resin obtained by a monomer having a carboxyl group such as an unsaturated dicarboxylic acid and having an ethylenically unsaturated double bond. Examples of the other ethylenically unsaturated monomer which is a precursor of the alkali-soluble photosensitive resin (C-B1) include methyl (meth)acrylate, ethyl (meth)acrylate, and (meth)acrylic acid 323842 76. 201233734 n-propyl vinegar, (mercapto) isopropyl isopropyl vinegar, (methyl) acrylic acid butyl milk, acrylic acid, isobutyl vinegar, (methyl) propylene glycol, second gambling, 曰: base) Vinegar, (meth)acrylic acid, (meth)acrylic acid, isoprene, propane = propenyl neopentyl acrylate, (p-butyl) methacrylate, methyl) mercaptobutyric acid, Methyl)acrylic acid, (methyl; octyl acrylate, 2-ethylhexyl acrylate, hydrazine, methyl) dialkyl ester, cetyl (meth) acrylate, ( Methyl)acrylic acid ten
(甲基)㈣酸異十八顏、(曱基)丙^環^十^鴨、 丙烯酸芳酯或(曱基)丙烯酸油酯等(甲基)丙烯甲基) (曱基)丙烯輯醋,對應目的可不侷限於此等^略或 選擇其他的乙烯性不飽和單體,也可併用2種=上’也可 就顏料分散性而言,宜為(曱基)—酸ϋ其中 酸乙醋。 W甲基)¾烯 臉可溶性感光性樹脂(C-B1)的重量平均分子 宜為 5, 000 至 100, 000 的範圍,以 5, 〇〇〇 至^ 〇〇〇 (^), 較佳,以5, 000至30, 000的範圍更佳。又,數平均=範, (Μη)宜為5, 000至50, 000的範圍,Mw/Mn之值宜為子以里 下。如鹼可溶性感光性樹脂(C_B1)的重量平均分子量 超過100,000時’因將使樹脂間的相互作用變強,而使L 色濾光片用著色組成物的黏度變高,以致難以操作。又, 如重量平均分子量(Mw)未達5,000時,可能使顯像性或對 於玻璃等基板的密著性降低。 就顏料的分散性、浸透性、顯像性及耐性而言,鹼可 溶性感光性樹脂(C-B1)的酸價宜為20至300KOH-mg/g。如 323842 77 201233734 酸價未達20KOH-mg/g時,將使對於顯像液的溶解性降低, 而變得難以形成微細圖案。如超過3〇〇K〇H_mg/g時,將無 法留住微細圖案。 在黏合劑樹脂(C-B)的合計1〇〇重量%中,鹼可溶性感 光性樹脂(C-B1)的含量宜為1〇至1〇〇重量%,並以2〇至 100重量%較佳,以40至100重量%更佳。只要使黏合劑樹 脂(C-B)中的驗可溶性感光性樹脂(c-βΐ)的含量為1〇重量 %以上,由於容易得到著色組成物的高亮度、高對比的效果 鲁因而較佳。 『其他的樹脂』 黏合劑樹脂(C-B) ’也可含有鹼可溶性感光性樹脂 (C-B1)以外的其他樹脂。作為其他的樹脂宜為可見光區域 的400至70〇nm之全波長區域中的穿透率在8〇%以上的樹 脂,並以95%以上的樹脂較佳。例如熱可塑性樹脂、熱硬 化性樹脂等’此等樹脂可單獨使用,也可將2種以上混合 後使用。 σ 熱可塑性樹脂可舉例如丁路樹醋、笨乙稀一順丁稀二 酸共聚物、氯化聚乙烯、氯化聚丙烯、聚氯乙烯、氯乙烯— 醋酸乙烯共聚物、聚醋酸乙烯、聚胺酯類樹脂、聚酯樹脂、 丙烯酸系樹脂、醇酸樹脂、聚苯乙烯、聚醯胺樹脂、橡膠 系樹脂、環化橡膠系樹脂、纖維素類、聚乙烯、聚丁二烯 及聚醯亞贿料。又,熱硬化轉脂可舉例如環氧樹月旨、 苯代三聚氰胺樹脂、松香改質順丁稀二酸樹脂、松香改質 反丁稀二_脂、三聚氰賴脂、尿素樹脂及麟脂等。 323842 78 201233734 川熱硬化性樹脂可舉例如苯代三聚氰胺樹脂、松香改質 脂丁烯一酸樹脂、松香改質反丁烯二酸樹脂、三聚氰胺樹 9尿素樹脂及酚樹脂等。 入益且,也可併用含有酸性基的乙烯性不飽和單體共聚 我成的驗可溶性樹脂。此種鹼可溶性樹脂可舉例如具有羧 a馱基等酸性基的樹脂。驗可溶性樹脂的具體例,可 、:如具有酸性基的丙烯酸樹脂、烯烴/(無水)順丁烯 烯1共忒物、苯乙烯/苯乙烯磺酸共聚物、乙烯/(甲基)丙 h久共聚物或異丁烯/(無水)順丁烯二酸共聚物等。其中, 2為選自具有酸性基的丙烯酸樹脂及笨乙烯/苯乙烯磺酸 ^物的至少1種樹脂,尤其適用具有酸性基的丙烯酸樹 9 ’因其耐熱性、透明性高。 脂相對於著色組成物中的顏料(Α)1〇0重量份,黏合劑樹 車交隹B)且使用至400重量份’以使用5〇至250重量份 (〉容劑) (c溶劑的使用是為了使顏料(A)充分分散在黏合劑樹脂 、B)中’使著色組成物塗佈在玻璃基板等基板上成為〇 2 =的乾燥膜厚,以容易形成濾光片段。作為溶劑宜為 有機溶劑。 ”、、 相對於顏料(A)100重量份,溶劑的含量宜使用8〇〇至 4’00〇重量份之量,使著色組成物調節至適宜的黏度後, 以形成均勻膜厚的濾光片段。 (¾光性著色組成物的製法) 323842 79 201233734 感光丨生著色組成物的製造係利用3根親研磨機、2根 輥研磨機砂磨機、捏揉機、立式球磨機等各種分散方式, 使顏料(A )較佳為與顏料分散劑一起,微細的分散在黏合劑 樹MC B)等色素載體及溶劑中,製成顏料分散體後,將光 聚合起始劑(C-D)、黏合劑樹脂(e_B)、絲合性化合物、 依情況需要的增感劑(C-E)、多官能硫醇、紫外線吸收劑、 禁止聚合劑、貯存安定劑、其他的成分混合在該顏料分散 體中,擾拌後可製造。又,含有2種以上的顏料之著色組 鲁成4勿的製it,是將各種顏料分散體各別微細分散在色素载 體及/或溶劑中的物質混合後,再混合光聚合起始劑(C D) 或光聚合性化合物,攪拌後可製造。 (顏料分散劑(C-C)) 在使顏料(A)分散在黏合劑樹脂(C_B)及/或溶劑中 時,可適宜的含有樹脂型顏料分散劑、色素衍生物、界面 活性劑等顏料分散劑(C-C)。因顏料分散劑(c_c)可使顏料 _ 的分散優異,防止分散後的顏料再凝聚之效果大,故使用 顏料分散劑(C-C)使顏料分散在黏合劑樹脂(C_B)及/或溶 劑中形成的著色組成物時,可得透明性優異的彩色濾光片。 尤其就著色組成物的安定性而言,著色組成物宜含有 酸性的樹脂型顏料分散劑。並且宜併用酸性的樹脂型顏料 分散劑與鹼性的色素衍生物,因不僅可使著色組成物的流 動性、安定性優異,也可得高亮度、高對比度比優異的濾 光片段。 相對於顏料(A)100重量份,顏料分散劑(c_c)可使用 323842 80 201233734 0. 1至40重量份,並宜使用0. 1至30重量份。 《樹脂型顏料分散劑、界面活性劑》 樹脂型顏料分散劑、界面活性劑之例係如後所述。 《色素衍生物》 色素衍生物可列舉如在有機顏料、蒽酷、α丫咬酮或三 畊中,導入鹼性取代基、酸性取代基或可具有取代基的酞 醯亞胺曱基形成的化合物。其結構是例如下述式(50)所示 的化合物,其中較佳為顏料衍生物。 P-Lm 式(50) [式(50)中, P :有機顏料殘基、蒽醌殘基、吖啶酮殘基或三畊殘 基 L:鹼性取代基、酸性取代基或可具有取代基的酞醯 亞胺甲基 m : 1至4的整數] 色素衍生物例如可使用日本特開昭63-305173號公 報、日本特公昭57-15620號公報、日本特公昭59-40172 號公報、日本特公昭63-17102號公報或日本特公平5-9469 號公報等中所記載之化合物,此等化合物可單獨使用,或 將2種以上混合後使用。 式(50)中,構成P的有機顏料殘基之有機顏料,可舉 例如二酮基吡咯并吡咯系顏料;偶氮、重氮、聚偶氮等偶 II系顏料;銅駄青、_化銅酜青、辞酜青、鹵化鋅酞青、 無金屬酞青等酞青系顏料;胺基蒽醌、二胺基二蒽醌、蒽 323842 81 201233734 喊咬、黃蒽酮、蒽酮、茚酮、°比喃酮、紫蒽酮等蒽賤系巧 料;喹吖啶酮系顏料;二噚畊系顏料;茈酮系顏料;托系 顏料;噻靛藍系顏料;異吲哚啉系顏料;異吲哚啉s同系麵 料;士林系顏料;喹啉系顏料;二噚畊系顏料;金屬錯物 系顏料等。 其中,並宜使用式(50)中L為鹼性取代基的可具 性取代基之色素衍生物。即使具有驗性取代基的色素彳彳& 聲 物不存在而不易分散的顏料時,也可藉由含有具有岭性取 代基的色素衍生物,而得到分散性、流動性、保存安定性 優”的顏料組成物。藉由酸性樹脂型分散劑與具有驗性取 代基之色素衍生物之相乘效果 ,可使顏料有效地分散,成 為μ動性、保存安定性優異的顏料組成物。 _在驗性取代基之中,宜使L為選自式(51)、(52)及(53) 所示的群組中的取代基。 式(S 1) 323842 82 201233734 R52 R53(methyl) (tetra) acid octadepene, (mercapto) propyl ring 十 10 ^ duck, aryl acrylate or (mercapto) acrylate oil (meth) propylene methyl) (fluorenyl) propylene vinegar The corresponding purpose may not be limited to such a selection or selection of other ethylenically unsaturated monomers, and may also be used in combination of two kinds of = upper or in terms of pigment dispersibility, preferably (mercapto)-acid hydrazine, wherein acid B vinegar. The weight average molecular weight of the W methyl) 3⁄4 olefin-soluble photosensitive resin (C-B1) is preferably in the range of 5,000 to 100,000, preferably 5, 〇〇〇 to ^ 〇〇〇 (^), preferably, It is better in the range of 5,000 to 30,000. Further, the number average = norm, (Μη) is preferably in the range of 5,000 to 50,000, and the value of Mw/Mn is preferably sub-input. When the weight average molecular weight of the alkali-soluble photosensitive resin (C_B1) exceeds 100,000, the viscosity of the coloring composition for the L color filter becomes high due to the strong interaction between the resins, so that it is difficult to handle. Further, when the weight average molecular weight (Mw) is less than 5,000, the developability or adhesion to a substrate such as glass may be lowered. The acid value of the alkali-soluble photosensitive resin (C-B1) is preferably from 20 to 300 KOH-mg/g in terms of dispersibility, permeability, developability and resistance of the pigment. When the acid value is less than 20 KOH-mg/g as in 323842 77 201233734, the solubility in the developing solution is lowered, and it becomes difficult to form a fine pattern. If it exceeds 3 〇〇K〇H_mg/g, the fine pattern will not be retained. The content of the alkali-soluble photosensitive resin (C-B1) is preferably from 1 to 1% by weight, and preferably from 2 to 100% by weight, based on 1% by weight of the total of the binder resin (CB). More preferably from 40 to 100% by weight. When the content of the soluble photosensitive resin (c-βΐ) in the binder resin (C-B) is 1% by weight or more, it is easy to obtain a high brightness and high contrast effect of the colored composition. "Other resin" The binder resin (C-B) ' may contain a resin other than the alkali-soluble photosensitive resin (C-B1). The other resin is preferably a resin having a transmittance of 8 % or more in the entire wavelength range of 400 to 70 Å in the visible light region, and preferably 95% or more. For example, a thermoplastic resin, a thermosetting resin, etc. may be used singly or in combination of two or more kinds. The σ thermoplastic resin may, for example, be a Bacillus vinegar, a stupid ethylene-succinic acid copolymer, a chlorinated polyethylene, a chlorinated polypropylene, a polyvinyl chloride, a vinyl chloride-vinyl acetate copolymer, or a polyvinyl acetate. Polyurethane resin, polyester resin, acrylic resin, alkyd resin, polystyrene, polyamide resin, rubber resin, cyclized rubber resin, cellulose, polyethylene, polybutadiene, and polyaluminum Bribe. Further, the thermosetting transesterification may, for example, be an epoxy resin, a benzoic melamine resin, a rosin-modified cis-butyl dibasic acid resin, a rosin-modified anti-butyl bis-lipid, a melamine lysine, a urea resin, and a lin. Fat and so on. 323842 78 201233734 The thermosetting resin may, for example, be a benzoic melamine resin, a rosin-modified fat-butene-acid resin, a rosin-modified fumaric acid resin, a melamine tree 9 urea resin or a phenol resin. In addition, it is also possible to use a combination of an ethylenically unsaturated monomer containing an acidic group to form a soluble resin. The alkali-soluble resin may, for example, be a resin having an acidic group such as a carboxy a fluorenyl group. Specific examples of the soluble resin may be, for example, an acrylic resin having an acidic group, an olefin/(anhydrous)-buteneene 1 conjugate, a styrene/styrenesulfonic acid copolymer, and an ethylene/(meth)-propyl group Long-term copolymer or isobutylene / (anhydrous) maleic acid copolymer and the like. Among them, 2 is at least one resin selected from the group consisting of an acrylic resin having an acidic group and a stupid ethylene/styrenesulfonic acid compound, and particularly, an acrylic tree 9' having an acidic group is used because of its high heat resistance and transparency. The fat is 1 〇 0 parts by weight relative to the pigment (Α) in the coloring composition, the binder is used to transfer B) and used to 400 parts by weight 'to use 5 〇 to 250 parts by weight (> 容) (c solvent It is used to sufficiently disperse the pigment (A) in the binder resin and B). The coating composition is applied to a substrate such as a glass substrate to have a dry film thickness of 〇2 = to easily form a filter segment. The solvent is preferably an organic solvent. With respect to 100 parts by weight of the pigment (A), the solvent is preferably used in an amount of from 8 Å to 4' 00 parts by weight to adjust the coloring composition to a suitable viscosity to form a uniform film thickness. Fragment. (3⁄4 Method for the preparation of a light-colored composition) 323842 79 201233734 The production of a photosensitive coloring composition is performed by using three pro-grinding machines, two roll grinders, a kneader, a vertical ball mill, and the like. In a preferred manner, the pigment (A) is preferably dispersed in a pigment carrier such as a binder tree MC B) and a solvent together with a pigment dispersant to form a pigment dispersion, and then a photopolymerization initiator (CD), A binder resin (e_B), a silk fibroin compound, a sensitizer (CE) as needed, a polyfunctional thiol, a UV absorber, a polymerization inhibitor, a storage stabilizer, and other components are mixed in the pigment dispersion. In addition, the coloring group containing two or more types of pigments is a mixture of two types of pigments, and is a mixture of various pigment dispersions dispersed in a pigment carrier and/or a solvent. Remixing photopolymerization initiator (CD Or a photopolymerizable compound which can be produced after stirring. (Pigment Dispersant (CC)) When the pigment (A) is dispersed in the binder resin (C_B) and/or a solvent, a resin type pigment dispersant may be suitably contained. A pigment dispersant (CC) such as a pigment derivative or a surfactant. The pigment dispersant (c) can be used because the pigment dispersant (c_c) is excellent in dispersion of the pigment_, and the effect of re-agglomeration of the pigment after dispersion is large. When the pigment is dispersed in the coloring composition formed by the binder resin (C_B) and/or the solvent, a color filter excellent in transparency can be obtained. Particularly, in terms of the stability of the coloring composition, the coloring composition preferably contains an acidity. A resin-based pigment dispersant is preferably used in combination with an acidic resin-based pigment dispersant and an alkaline pigment derivative, because it is excellent in fluidity and stability of the coloring composition, and also excellent in high brightness and high contrast ratio. 1至30重量份。 Resin type pigments. The pigment dispersing agent (c_c) may be used in an amount of 323842 80 201233734 0. 1 to 40 parts by weight, and preferably 0.1 to 30 parts by weight. dispersion , surfactants, examples of resin-based pigment dispersants and surfactants are described later. "Pigment Derivatives" Pigment derivatives can be cited, for example, in organic pigments, 蒽cool, α-bittone or three-plowing. A compound formed of a basic substituent, an acidic substituent or a hydrazinium group which may have a substituent, and its structure is, for example, a compound represented by the following formula (50), and among them, a pigment derivative is preferred. P-Lm Formula (50) [In the formula (50), P: an organic pigment residue, an anthracene residue, an acridone residue or a tri-farming residue L: a basic substituent, an acidic substituent or a hydrazine which may have a substituent醯iminomethyl m: an integer of 1 to 4] For example, JP-A-63-305173, JP-A-57-15620, JP-A-59-40172, and JP-A-2013 The compound described in the above-mentioned Japanese Patent Publication No. 5-17469, or the like, may be used alone or in combination of two or more. In the formula (50), the organic pigment constituting the organic pigment residue of P may, for example, be a diketopyrrolopyrrole pigment; an even II pigment such as azo, diazo or polyazo; copper indigo; Amaranth pigments such as copper phthalocyanine, eucalyptus green, zinc halide phthalocyanine, and metal-free indigo; amine hydrazine, diamino hydrazine, hydrazine 323842 81 201233734 shouting, flavonoids, fluorenone, anthraquinone Ketone, ° ketone, purpurone, etc.; quinacridone pigment; diterpene pigment; anthrone pigment; tray pigment; thiazolin pigment; isoporphyrin pigment Isoporphyrin s homologous fabric; Shilin pigment; quinoline pigment; dioxin pigment; metal miscellaneous pigment. Among them, it is preferred to use a dye derivative of the formula which is a basic substituent of L in the formula (50). Even if the dye enamel/amplifier having an inactive substituent does not exist in a pigment which is not easily dispersed, it is possible to obtain dispersibility, fluidity, and preservation stability by containing a pigment derivative having a ridge substituent. The pigment composition can be effectively dispersed by the synergistic effect of the acidic resin type dispersant and the dye derivative having an inert substituent, and becomes a pigment composition excellent in viability and storage stability. Among the inert substituents, L is preferably a substituent selected from the group consisting of the formulae (51), (52) and (53). Formula (S 1) 323842 82 201233734 R52 R53
XCH-0H -N \j-R56 \ /XCH-0H -N \j-R56 \ /
CH-CH (/54 R55CH-CH (/54 R55
式(5 2)Formula (5 2)
式(5 3) [式(51)至(53)中,] X 是-S〇2---CO-、-CH2---CH2NHCOCH2---CH2NHS〇2CH2-或 直接鍵結, Y是-NH---0-或直接鍵結, k是1至10的整數, Y1 是-NH---NR58-Z-NR59-或直接鍵結, R58及R59是分別獨立的氫鍵、可具有取代基的碳數1至36 之烷基、可具有取代基的碳數2至36之烯基或可具有取代 基的苯基, Z是可具有取代基的伸烷基或可具有取代基的伸芳基, R50、R51是分別獨立的氫原子、可具有取代基的碳數1至 30之烷基、可具有取代基的碳數2至30之烯基、或R5°與 R51成為一體且復含有氮、氧或硫原子的可具有取代基之雜 環, 323842 83 201233734 r52、r53、r54及R55是分別獨立的氫原子、可具有取代基的 碳數1至20之院基、可具有取代基的碳數2至20之稀基、 可具有取代基的碳數6至2〇之伸芳基, R56是氫原子、可具有取代基的碳數1至20之烷基、玎具 有取代基的碳數2至20之稀基, R57是上述式(51)所示的取代基或上述式(52)所示的取代 基, Q是羥基、烷氧基、上述式(51)所示的取代基或上述式(52) 鲁所示的取代基。] 用以形成式(51)至(53)所示的取代基時使用的胺成 分’可列舉如與第1實施態樣中的胺成分相同的胺成分。 可具有鹼性取代基的色素衍生物,可藉由各種的合成 途徑合成。例如’在有機顏料中導入式(54)至(57)所示的 取代基’與上述取代基反應後,使可形成式(51)至(53)所 示的取代基之上述胺成分,例如N,N-二曱基胺基丙基胺、 φ I曱基哌畊、二乙基胺或4-[4-羥基-6-[3-(二丁基胺基) 丙基胺基]-1, 3, 5-三啡-2-基胺基]苯胺等反應後可獲得。 式(54):-S〇2Cl 式(55):-C0C1 式(56):-CHNHCOCH2Cl 式(57):-CH2Cl 式(54)至(57)的取代基與上述胺成分反應時’也可使 部份的式(54)至(57)之取代基水解後,與使氣取代成羥基 的化合物混合。此時,式(54)及式(55)雖然可分別為磺酸 323842 84 201233734 ^幾^ &基但也均可就遊離酸的形態,也可為1至3價 的金屬或上述的單胺之鹽。 又’如有機顏料為偶氮系顏料時,預先將式(51)至(53) 所不的取代基導入重氮成分或耦合成分中,然後進行耦合 反應後,也可製造偶氮系顏料衍生物。 具有驗性取代基的三啡衍生物,可藉由各種的合成途 徑合成。例如’以三聚氣化氰為起使原料,在三聚氣化氰 的至少1個氣上形成式(51)至(53)所示的取代基的胺成分 反應’例如N,N_二甲基胺基丙基胺或M-曱基哌畊,接著使 三聚氯化氰的殘留氯與各種胺或醇反應後即得。 (任意成分) 除了顏料分散劑之外,第5實施態樣的著色組成物也 可含有例如以下的成分作為任意成分。任意成分的具體例 係如後述。 (光聚合起始劑(C-D)) φ 在感光性著色組成物中,可加入光聚合起始劑(C-D) 以調製成驗顯像型感光性著色組成物的型態,以使該組成 物受紫外線照射而硬化,以光蝕刻微影法形成濾光片段。 相對於顏料(A)l〇〇重量份,光聚合起始劑(C-D)的含 量宜為5至2〇〇重量份,就光硬化性及顯像性而言,以 至150重量份較佳。 (增感劑) 在感光性著色組成物中,可含有增感劑。 相對於感光性著色組成物中所含的光聚合起始劑 323842 85 201233734 (C-D)IOO重量份,增感劑的含量宜為3至6〇重量份’就 光硬化性及顯像性而言,以5至50重量份較佳。 (光聚合性化合物) 感光性著色組成物可含有光聚合性化合物。光聚合性 化合物中’含有可藉由紫外線或熱等而硬化生成樹脂的單 體或券聚物。 相對於顏料(A)100重量份,光聚合性化合物(C-C)的 含量宜為10至3〇〇重量份,就光硬化性及顯像性而言,以 _ 10至200重量份較佳。 (多官能硫醇) 感光性著色組成物可含有多官能硫醇(C-F)。多官能 硫醇是具有2個以上硫醇(SH)基的化合物。藉由將多官能 疏醇同時與上述的光聚合起始劑(C-D)使用,在光照射後的 自由基聚合過程中,因可作用為連鎖移動劑而產生不易受 到氧阻礙聚合的硫基自由基(thiyl radical),而可使所得 • 的感光性著色組成物成為高感度。尤其宜為SH結合在亞甲 基、伸乙基等脂肪族基上的多官能脂肪族硫醇。 相斟於顏料(A)l〇〇重量份,多官能硫醇的含量宜為 0.05至1〇〇重量份,並以1〇至5〇 〇重量份較佳。可因 使用重量份以上的多官能硫醇,而得較佳的耐顯像 性如使用1個硫醇⑽基的單官能硫醇時,並不能獲得 這樣的耐顯像性。 (紫外線°及收劑) 感光性著色組成物可含有紫外線吸收劑。因含有紫外 323842 86 201233734 線吸收劑,而可控制圖案的形狀與解像性。 相對於顏料(A)100重量份,紫外線吸收劑的含量為 0. 01至20重量份,並宜使用0. 05至10重量份的量。 可因使用0.01重量份以上的紫外線吸收劑,而得較 佳的解像度。 (禁止聚合劑) 感光性著色組成物可含有禁止聚合劑。因含有禁止聚 合劑,而可控制圖案的形狀與解像性。 • 相對於顏料(A)100重量份,禁止聚合劑的含量為0.01 至20重量份,並宜使用0. 05至10重量份的量。可因使用 0. 01重量份以上的禁止聚-合劑,而得較佳的解像度。 (貯存安定劑) 感光性著色組成物可含有貯存安定劑。因含有貯存安 定劑,而使組成物的經時黏度得以安定。 相對於顏料(A) 100重量份,貯存安定劑的含量為0. 01 φ 至20重量份,並宜使用0. 05至10重量份的量。可因使用 0. 01重量份以上的貯存安定劑,而提高著色組成物的經時 安定性。 (其他的添加劑) 在感光性著色組成物中,可含有矽烷耦合劑等密著提 昇劑,以提高與透明基板之間的密著性,或可作用為還原 溶存的氧之胺系化合物。 相對於顏料(A)100重量份,密著提昇劑為0. 01至10 重量份,並宜使用0.05至5重量份的量。 323842 87 201233734 曰— ^ 除了以上的任意成分之外,也可含有後述的任 思成分之任—者。 (粗大粒子的去除)Formula (5 3) [In the formulae (51) to (53),] X is -S〇2---CO-, -CH2---CH2NHCOCH2---CH2NHS〇2CH2- or direct bonding, Y is - NH---0- or direct bonding, k is an integer from 1 to 10, Y1 is -NH---NR58-Z-NR59- or a direct bond, and R58 and R59 are respectively independent hydrogen bonds and may have a substitution An alkyl group having 1 to 36 carbon atoms, an alkenyl group having 2 to 36 carbon atoms which may have a substituent or a phenyl group which may have a substituent, and Z is an alkylene group which may have a substituent or may have a substituent. An aryl group, R50 and R51 are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, or a combination of R5 and R51 a heterocyclic ring which may have a substituent containing a nitrogen, oxygen or sulfur atom, 323842 83 201233734 r52, r53, r54 and R55 are each independently a hydrogen atom, may have a substituent of a carbon number of 1 to 20, may have a substitution a dilute group having 2 to 20 carbon atoms, a aryl group having 6 to 2 carbon atoms which may have a substituent, R56 being a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a substituent having an anthracene a carbon number of 2 to 20, R57 is the above The substituent represented by the above formula (52) or the substituent represented by the above formula (52), wherein Q is a hydroxyl group, an alkoxy group, a substituent represented by the above formula (51) or a substituent represented by the above formula (52) . The amine component used in the formation of the substituents represented by the formulae (51) to (53) is exemplified by the same amine component as the amine component in the first embodiment. A pigment derivative which may have a basic substituent can be synthesized by various synthetic routes. For example, 'the substituents represented by the formulas (54) to (57) are introduced into the organic pigment to react with the above substituents, and the amine component which can form the substituents represented by the formulae (51) to (53), for example, N,N-didecylaminopropylamine, φ I hydrazine, diethylamine or 4-[4-hydroxy-6-[3-(dibutylamino)propylamino]- 1, 3, 5-tricyano-2-ylamino] aniline can be obtained after the reaction. Formula (54): -S〇2Cl Formula (55): -C0C1 Formula (56): -CHNHCOCH2Cl Formula (57): -CH2Cl When the substituent of the formula (54) to (57) is reacted with the above amine component, ' After the partial substituents of the formulae (54) to (57) are hydrolyzed, they are mixed with a compound which substitutes a gas for a hydroxyl group. In this case, the formula (54) and the formula (55) may be respectively a sulfonic acid 323842 84 201233734 ^ a few of the bases, but also in the form of a free acid, or a metal of 1 to 3 or the above-mentioned single Amine salt. Further, when the organic pigment is an azo-based pigment, a substituent derived from the formula (51) to (53) is introduced into a diazo component or a coupling component in advance, and then a coupling reaction is carried out to produce an azo-based pigment. Things. The trimorphine derivative having an inert substituent can be synthesized by various synthetic routes. For example, 'the reaction of an amine component forming a substituent represented by the formula (51) to (53) on at least one gas of a trimeric vaporized cyanide using a trimeric gasification cyanogen as a starting material', for example, N, N_ Methylaminopropylamine or M-mercaptopiped, followed by reaction of residual chlorine of cyanuric chloride with various amines or alcohols. (Optional component) The coloring composition of the fifth embodiment may contain, for example, the following components as an optional component, in addition to the pigment dispersant. Specific examples of the optional components will be described later. (Photopolymerization initiator (CD)) φ In the photosensitive coloring composition, a photopolymerization initiator (CD) may be added to prepare a pattern of the photosensitive coloring composition, so that the composition It is hardened by ultraviolet irradiation to form a filter segment by photolithography. The photopolymerization initiator (C-D) is preferably contained in an amount of 5 to 2 parts by weight based on the weight of the pigment (A), and preferably 150 parts by weight in terms of photocurability and developability. (Sensitizer) The photosensitive coloring composition may contain a sensitizer. The content of the sensitizer is preferably from 3 to 6 parts by weight based on the photopolymerization initiator 323842 85 201233734 (CD) 100 parts by weight in the photosensitive coloring composition, in terms of photocurability and development. It is preferably 5 to 50 parts by weight. (Photopolymerizable Compound) The photosensitive coloring composition may contain a photopolymerizable compound. The photopolymerizable compound contains a monomer or a valence polymer which can be cured by ultraviolet rays or heat to form a resin. The content of the photopolymerizable compound (C-C) is preferably 10 to 3 parts by weight based on 100 parts by weight of the pigment (A), and is preferably _10 to 200 parts by weight in terms of photocurability and developability. (Polyfunctional Mercaptan) The photosensitive coloring composition may contain a polyfunctional thiol (C-F). The polyfunctional thiol is a compound having two or more thiol (SH) groups. By using a polyfunctional alcoholic alcohol simultaneously with the above-mentioned photopolymerization initiator (CD), in the radical polymerization process after light irradiation, a sulfur-based free radical which is less susceptible to oxygen hindering polymerization can be produced by acting as a chain shifting agent. The thiyl radical can be made into a high sensitivity. Particularly preferred is a polyfunctional aliphatic thiol having SH bonded to an aliphatic group such as a methylene group or an ethyl group. The content of the polyfunctional thiol is preferably from 0.05 to 1 part by weight, and more preferably from 1 to 5 parts by weight, based on the weight of the pigment (A). When the monofunctional thiol having one thiol (10) group is used, it is possible to obtain such a development resistance by using a polyfunctional thiol having a weight or more. (Ultraviolet ray and charge) The photosensitive coloring composition may contain an ultraviolet absorber. The shape and resolution of the pattern can be controlled by the inclusion of UV 323842 86 201233734 line absorber. The amount of the ultraviolet absorber is from 0.01 to 20 parts by weight, and preferably from 0.05 to 10 parts by weight, based on 100 parts by weight of the pigment (A). A better resolution can be obtained by using 0.01 part by weight or more of the ultraviolet absorber. (Prohibition of Polymerization Agent) The photosensitive coloring composition may contain a polymerization inhibiting agent. The shape and resolution of the pattern can be controlled by the inclusion of a polymer inhibiting agent. The amount of the polymerization agent is from 0.01 to 20 parts by weight, and is preferably from 0.05 to 10 parts by weight, based on 100 parts by weight of the pigment (A). A preferred resolution can be obtained by using 0.01 parts by weight or more of the inhibiting polymerization agent. (Storage Stabilizer) The photosensitive coloring composition may contain a storage stabilizer. The composition's time-dependent viscosity is stabilized by the presence of a storage stabilizer. 0至10重量份的量。 The amount of the storage stabilizer is 0. 01 φ to 20 parts by weight, and preferably used in an amount of 0.05 to 10 parts by weight. The stability of the colored composition can be improved by using 0.01 parts by weight or more of the storage stabilizer. (Other additives) The photosensitive coloring composition may contain an adhesion promoter such as a decane coupling agent to improve the adhesion to the transparent substrate or to act as an amine compound which reduces the dissolved oxygen. The amount of the adhesion promoter is from 0.01 to 10 parts by weight, and preferably from 0.05 to 5 parts by weight, based on 100 parts by weight of the pigment (A). 323842 87 201233734 曰— ^ In addition to any of the above components, it may contain any of the components described below. (removal of coarse particles)
笛 G 貫施態樣的著色組成物也與第3實施態樣的著色 組成物相同’宜進行粗大粒子的去除。 [第6實施態樣] ;第實知態樣的彩色遽光片用著色組成物,是含有顏 # 二黏合劑樹脂(D-B)與溶劑的彩色濾光片用著色組成 」;(A)為含有式(Ο所示的顏料(A1),黏合劑樹脂(D-β) 為各有具有下述構成單元(D-bl)至(D-b3)的樹脂(D-bi)。 第6實細*態樣的彩色濾光片用著色組成物,可作為感光性 著色組成物使用。 本發明人等累積精心研究的結果發現使用含有溴化 二_基°比咯并吡咯顏料與具有特定構造的黏合劑樹脂之著 色組成物,取代以往使用的C. I.顏料紅254(氣化二酮基吡 馨 咯并吡咯顏料)時’可得具有高亮度、高對比度,且抑制因 加熱步驟而結晶析出的高精細的濾光片段之彩色濾光片。 根據第6實施態樣,可提供高亮度、高對比度比的彩 色濾光片用著色組成物,其不僅不會因加熱步驟而產生二 酮基°比洛并0比洛系顏料的綠晶析出,並且在作為感光性著 色組成物使用時,在形成感度或直線性等良好的濾光片段 時必要的性能之平衡也優異。 (顏料(A)) 顏料(A)是與第5實施態樣中的顏料(A)相同的顏料, 323842 88 201233734 可藉由與第5實施態樣中的製造方法相同的方法獲得。 由於將式(1)所示的顏料(A1)與樹脂(D-B1)組合後使 用,而可得比已往更高亮度及高對比度比的紅色著色組成 物。 第6實施態樣的著色組成物,也與第5實施態樣的著 色組成物相同,可併用顏料(A1)與其他的顏料,同時,宜 將顏料(A1)及其他的顏料微細化後使用。 (黏合劑樹脂(D-B )) 『樹脂(D-B)』 彩色濾光片用樹脂組成物中所含的黏合劑樹脂(D-B) 之特徵係含有具有下述構成單元(D-bl)至(D-b3)的樹脂 (D-B1)。 (D-B1)具有羧基的構成單元:2至60重量% (D-b2)具有式(D-2)或式(D-3)所示的芳香族環基之 構成單元:2至80重量% (D-b3)具有式(D-4)或式(D-5)所示的脂肪族環基之 構成單元:2至60重量°/〇 323842 89 201233734The coloring composition of the flute G is also the same as the coloring composition of the third embodiment. It is preferable to remove coarse particles. [Sixth embodiment] The coloring composition for a color light-receiving sheet of the practical aspect is a coloring composition for a color filter containing a pigment #2 binder resin (DB) and a solvent; (A) is The pigment (A1) and the binder resin (D-β) of the formula (?) are each a resin (D-bi) having the following structural units (D-bl) to (D-b3). The coloring composition of the fine color filter can be used as a photosensitive coloring composition. As a result of intensive research by the present inventors, it has been found that the use of a brominated bis-pyrrolopyrrole pigment and a specific structure are used. The coloring composition of the binder resin, in place of the conventional CI Pigment Red 254 (gasified diketopyrrolopyrrolopyrrole pigment), can have high brightness, high contrast, and inhibit crystal precipitation due to the heating step. A color filter of a high-definition filter segment. According to the sixth embodiment, a coloring composition for a color filter having a high luminance and a high contrast ratio can be provided, which not only does not generate a diketone group due to a heating step. °The green crystal of the pirox and the bismuth pigment is precipitated and is used as the photosensitivity When a coloring composition is used, it is excellent in balance of necessary performance when forming a good filter segment such as sensitivity or linearity. (Pigment (A)) Pigment (A) is a pigment in the fifth embodiment (A) The same pigment, 323842 88 201233734 can be obtained by the same method as the production method in the fifth embodiment. Since the pigment (A1) represented by the formula (1) is used in combination with the resin (D-B1), In addition, a red coloring composition having a higher brightness and a higher contrast ratio than in the past can be obtained. The coloring composition of the sixth embodiment is also the same as the coloring composition of the fifth embodiment, and the pigment (A1) and other pigments can be used in combination. At the same time, the pigment (A1) and other pigments should be refined and used. (Binder resin (DB)) "Resin (DB)" Adhesive resin (DB) contained in the resin composition for color filters. The feature is a resin (D-B1) having the following structural units (D-bl) to (D-b3). (D-B1) A constituent unit having a carboxyl group: 2 to 60% by weight (D-b2) A constituent unit having an aromatic ring group represented by formula (D-2) or formula (D-3): 2 to 80% by weight (D-b3) having a formula Constituent units of the aliphatic cyclic group D-4) or Formula (D-5) shown below: 2 to 60 wt. ° / square 323 842 89 201 233 734
式(D — 2〉Formula (D-2)
式(D - 3) [式(D-2)及(D-3)中,R是氫原子,或可具有苯環的碳 數1至20之烷基。式(D-3)中的虛_部份是表示鄰接於苯 環且含有可具有取代基的一個以上之飽和或不飽和的雜環 之環狀結構。]In the formulae (D-3) and (D-3), R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring. The imaginary moiety in the formula (D-3) is a cyclic structure which is adjacent to the benzene ring and contains one or more saturated or unsaturated heterocyclic rings which may have a substituent. ]
以下,依照構成單元(D-bl)、構成單元(D-b2)及構成 單元(D-b3)的順序說明。本實施態樣中,各構成單元的含 323842 90 201233734 有重 微各構成單元含在樹脂(D,)中的前驅物之重量 <構成單元(D-bl)>Hereinafter, the order of the constituent unit (D-bl), the constituent unit (D-b2), and the constituent unit (D-b3) will be described. In this embodiment, the 323842 90 201233734 of each constituent unit has a weight of the precursor contained in the resin (D,) of each constituent unit <constituting unit (D-bl)>
的J成早:(D Μ)具有羧基,顯像時作為鹼可溶性部位 Γ:二=合劑樹脂請的全部構成單元之重量為基 準’—績安定性Μ,構成單元(D-bl)為2至60 重量%。若未達2重量科,將使驗性顯像液造成的未曝光 部份1去除性不足,而致分散安定性,€、化。同時,若超過 60重星%夺將使對驗性顯像液的溶解速度變快,而甚至 溶解到曝光部份。 具有幾基的構成單元(D-bl)之前驅物,可列舉如含有 (甲基)丙烯酸、巴豆酸或α—氯化丙烯酸等不飽和單羧酸, 或順丁稀一酸或反丁烯二酸等不飽和二缓酸等缓基,且具 有乙烯性不飽和雙鍵的化合物等。又,也可使用以(甲基) 丙烯酸羥基烷酯等具有羥基的(甲基)两烯基化合物,使順 _ 丁稀二酸軒等不飽和二缓酸的酸酐半酯化者。其中,就聚 合性(控制分子量等的容易度)而言,以(甲基)丙烯酸較 佳,尤其以曱基丙烯酸最佳。此等化合物可單獨使用也 可併用2種以上。 即使是原料階段中含有羧基的前驅物,在藉由形成黏 合劑樹脂(D-B)的步驟使羧基轉化成酯鍵等時’也不符合構 成單元(D-bl)。 <構成單元(D-b2)> 構成單元(D-b2)具有式(D-2)或(D-3)所示的芳香族 323842 91 201233734 之環狀結構’具有作為相對於顏 劑形成的顏料組成物之親和性部位的功能::分散 的品質一 ㈣鮮,就顯像性_、光片段 。,構成早兀(D-b2)為20至80重量%。若未 組成於顏料或顏料與分散劑形成的顏料 光片^ 卩不足,而有無法獲得高品質的彩色渡 s、光片段之耐性惡化的問題;若超過8〇重旦 w 將使對於驗顯躲的轉速度變慢,拉長顯料間里° 色據光片的生產性惡化。 至彩 …使式(1)所示的顏料(A1)於結構中含有溴原 極率高於氯原子。因此,含有芳香放、'、子’其分 (D-b2),可望其冗電子系比氯化二心=構η成單元 (C. I.顏料紅254)可顯示較強的親和性等相^彳=咯顏料J is early: (D Μ) has a carboxyl group, and is used as an alkali-soluble site in development: 二: The weight of all constituent elements of the two-component resin is based on the benchmark's performance stability, and the constituent unit (D-bl) is 2 Up to 60% by weight. If it is less than 2 weights, it will make the unexposed part 1 caused by the testability liquid 1 depleted, and the dispersion stability will be reduced. At the same time, if more than 60% of the star weight will make the dissolution rate of the test imaging liquid faster, and even dissolve into the exposed portion. The precursor of the constituent unit (D-bl) having a few groups may, for example, contain an unsaturated monocarboxylic acid such as (meth)acrylic acid, crotonic acid or α-chlorinated acrylic acid, or a butyric acid or a reversed butene A compound having an ethylenic unsaturated double bond such as a diacid or a non-saturated acid such as a diacid or the like. Further, a (meth)dienyl compound having a hydroxyl group such as a hydroxyalkyl (meth)acrylate may be used, and an acid anhydride of an unsaturated dibasic acid such as cis-butadidic acid may be semi-esterified. Among them, in terms of polymerizability (easiness in controlling molecular weight and the like), (meth)acrylic acid is preferred, and thioglycolic acid is particularly preferred. These compounds may be used singly or in combination of two or more. Even the precursor containing a carboxyl group in the raw material stage does not conform to the constituent unit (D-bl) when the carboxyl group is converted into an ester bond or the like by the step of forming the binder resin (D-B). <Structural unit (D-b2)> The constituent unit (D-b2) has a cyclic structure of aromatic 323842 91 201233734 represented by formula (D-2) or (D-3) as having a relative pigment The function of the affinity part of the formed pigment composition: the quality of the dispersion is one (four) fresh, and the imaging _, the light fragment. The composition of early indica (D-b2) is 20 to 80% by weight. If the pigment light sheet which is not formed by the pigment or the pigment and the dispersant is insufficient, there is a problem that the high-quality color s and the light fragment are not deteriorated; if it exceeds 8 〇, the w will make the test The speed of hiding is slower, and the productivity of the light film is deteriorated. To the color, the pigment (A1) represented by the formula (1) contains a bromine atomic ratio higher than that of the chlorine atom in the structure. Therefore, it contains aromas, ', and 'subjects' (D-b2), and it is expected that the redundant electrons will show a stronger affinity than the chlorinated dicentric = conformal η unit (CI Pigment Red 254).彳=slip pigment
RR
式(D—2) [式(D-2)及式(D-3)中,R是氡原子戈可星 數1至2G之烧基。式(D-3)中的虛線 ,有笨環的碳 1伪疋表示隣接笨環 323842 201233734 且含有可具有取代基的一個以上飽和或不飽和的雜_ 曹 狀結構。] 衣之% 構成單元(D-b2)的前驅物,可列舉如笨乙烯、 基笨乙烯、二乙稀苯、茚、乙酿環烧烴、丙烯酸笨甲妒 曱基丙烯酸苯甲酯、雙酚Α二縮水甘油醚二(曱基)兩歸奶 酯、羥甲基化三聚氰胺的(甲基)丙烯酸酯等單體/寡聚物 或式(D-6)所示的乙烯性不飽和單體等。Formula (D-2) [In the formula (D-2) and the formula (D-3), R is a burnt group having a ruthenium atom of 1 to 2 G. The dotted line in the formula (D-3), which has a stupid ring carbon, 1 pseudo 疋 represents the adjacent stupid ring 323842 201233734 and contains one or more saturated or unsaturated hetero-cao structures which may have a substituent. % of clothing The precursor of the constituent unit (D-b2) may, for example, be stupid ethylene, base ethylene, diethyl benzene, hydrazine, ethylene ring-burning hydrocarbon, benzyl methacrylate acrylate, double Monomer/oligomer such as phenolphthalein diglycidyl ether di(indenyl) di-n-butyl ester, methylolated melamine (meth) acrylate or ethylenic unsaturated monomer represented by formula (D-6) Body and so on.
式(D-6) [式(D-6)中,R1是氫原子或曱基,R2是碳數2或3 的伸烷基,R3是可具有苯環的碳數1至20的烷基,n是1 至15的整數。] _ 式(D-6)所示的乙烯性不飽合單體,可舉例如第—卫 業製藥社製New Frontier CEA[E0改質甲盼丙稀酸g旨,ri · 氫原子、R2 :伸乙基、R3 :甲基,n=l或2]、NP-2[正-壬 基术氧基聚乙二醇丙烯酸醋,R1 :氳原子、R2 :伸乙基、 R3 :正壬基,n=2]、N-177E[正-壬基苯氧基聚乙二醇丙歸 酉夂酉旨’ R1 :氫原子、R2 :伸乙基、R3 :正壬基’ 16至17 ] 或PHE[丙烯酸苯氧乙酯,R1 :氫原子、R2 :伸乙基、R3 : 氧原子,n=l ]、Formula (D-6) [In the formula (D-6), R1 is a hydrogen atom or a fluorenyl group, R2 is an alkylene group having 2 or 3 carbon atoms, and R3 is an alkyl group having 1 to 20 carbon atoms which may have a benzene ring. , n is an integer from 1 to 15. _ The ethylene unsaturated monomer represented by the formula (D-6) is, for example, New Frontier CEA manufactured by Dai-ichi Pharmaceutical Co., Ltd. [E0 modified methotrexate g, ri · hydrogen atom, R2 : Ethyl, R3: methyl, n=l or 2], NP-2 [n-nonyl oxypolyethylene glycol acrylate, R1: 氲 atom, R2: ethyl, R3: 壬Base, n=2], N-177E [n-nonylphenoxy polyethylene glycol-propylation] R1: hydrogen atom, R2: ethyl group, R3: n-decyl group 16 to 17] Or PHE [phenoxyethyl acrylate, R1: hydrogen atom, R2: ethyl group, R3: oxygen atom, n = l],
Daicel公司製,IRR169[丙烯酸乙氧基化笨酯(E〇 323842 93 201233734 lmol),R1:氫原子、R2:伸乙基、R3:氫原子,n=l ]或Ebecry 1110[丙烯酸乙氧基化苯酯(£02111〇1),1^:氫原子、尺2: 伸乙基、R3 :氫原子,n=2 ]、 東亞合成公司製Aronix M-101A[酚E0改質(n = 2)丙 烯酸酯,R1 :氫原子、R2 :伸乙基、R3 :氫原子,n与2]、 ]\4-102[酚£〇改質(11%4)丙烯酸酯,1^:氫原子、1^:伸乙 基、R3 :氫原子,η与4]、Μ-110[對甲酚酚Ε0改質(η与1) 丙烯酸酯,R1 :氫原子、R2 :伸乙基、R3 :對曱酚基,η与 鲁 1]、Μ-111 [正壬基酚Ε0改質(η与1)丙烯酸酯,R1:氫原子、 R2 :伸乙基、R3 :正壬基,η与1]、Μ-113[正壬基酚Ε0改 質(η=?4)丙稀酸醋’R1:复原子、R2:伸乙基、R3:正壬基, η与4]或Μ-117[正壬基酚Ρ0改質(η与2. 5)丙烯酸酯,R1 : 氫原子、R .伸丙基、R3:正壬基,η%2.5]、 共榮公司製輕丙烯酸酯(light acrylate)P0-A[丙烯 酸苯氧基乙酯’ R1:氫原子、R2:伸乙基、R3:氫原子,n=l]、 ❿ P-200A[本氧基聚乙二醇丙婦酸醋,r1 :氫原子、r2 :伸乙 基、R3 :氫原子,η与2]、NP-4EA[壬基酚E0加成物丙烯酸 酯,R1:氫原子、R2:伸乙基、R3:正壬基,η-4]或ΝΡ-8ΕΑ[壬 基酚Ε0加成物丙烯酸酯,R1 :氫原子、R2 :伸乙基、R3 : 正壬基’ η与8]或輕酯(light ester)P0[甲基丙烯酸苯氧 基乙酯,R1 :甲基、R2 :伸丙基、R3 :氫原子,n=1 ]、 曰油公司製BlemmerANE-300[壬基苯氧基聚乙二醇丙 烯酸酯’ R1 :氫原子、R2 :伸乙基、f :正壬基,^与5]、 ΑΝΡ-300[壬基本氧基聚丙二醇丙婦酸醋,ri :氫原子、r2 : 323842 94 201233734 伸丙基、R3 :正壬基,η〜5]、43 ANEp_5〇〇[壬基苯氧基聚 乙二醇-聚丙二醇丙烯酸酯,Ri :氫原子、R2 :伸乙基及伸 丙基、R3 :正壬基,#5 + 5]、7〇 ANEp_5爾壬基.苯氧基 聚乙二醇-聚丙二醇丙烯酸酯,Ri :氫原子、R2 :伸乙基及 伸丙基、R3 :正壬基,n_9 + 3]、75 ANEp_6〇〇[壬基苯氧 基聚乙二醇-聚丙二醇丙烯酸酯,Rl :氫原子、R2:伸乙基 及伸丙基、R3:正壬基,η#5 + 2]、AAE-50 [苯氧基聚乙二 醇丙烯酸酯,Rl :氫原子、R2:伸乙基、R3:氫原子,η=1]、 _ ΑΑΕ-300[苯氧基聚乙二醇丙烯酸酯,Rl :氫原子、R2 :伸 乙基、R3 :氫原子,π〜5·5]、PAE-50[苯氧基聚乙二醇丙 烯酸酯’R1:甲基、R2:伸乙基、R3:氫原子,η=1]、ρΑΕ_1〇〇[笨 氧基聚乙二醇丙烯酸酯,Rl :甲基、R2 :伸乙基、R3 :氫原 子,n=2]或43PAPE-600B[苯氧基聚乙二醇-聚丙二醇丙烯 酸酯,R1 :甲基、R2 :伸乙基及伸丙基、R3 :氫原子,n%6 + 6]、 φ 新中村化學公司製NK ESTER AMP-10G[苯氧基乙二醇 丙烯酸酯(E0 lmol),R1 :氫原子、R2 :伸乙基、R3 :氫原 子’ n=l]、AMP-20G[苯氧基乙二醇丙烯酸酯(E〇 2mol),R1 : 氫原子、R2 :伸乙基、R3 :氫原子,η与2]、AMP-60G[苯氧 基乙二醇丙烯酸酯(Ε0 6mol),R1 :氫原子、R2 :伸乙基、 R ·氫原子,n*6]、PHE-1G[笨氧基乙二醇丙烯酸酯(E〇 lm〇l),R1 :甲基、R2 :伸乙基、R3 :氫原子,n=1]、 大阪有機化學公司製Biscoat# 192[丙烯酸笨氧基乙 醋’ R1 :氳原子、R2 :伸乙基、R3 :氫原子,n=l ]、或 323842 95 201233734 _曰本化藥製SR-339A[2-苯氧基乙二醇丙晞酸酯,β1 : 氫原子R .伸乙基、R3 :氫原子,n=l]或SR-504[乙氧基 化壬=丙歸酸g|,Rl :氫原子、R2:伸乙基、r3 :正壬基] 等仁並不侷限於此等化合物,同時,也可併用2種以上。 式(D 6)所不的乙烯性不飽和單體中,R3的烷基之碳數 為1至20 ’並以丨至1〇時較佳。烷基不僅只是直鏈狀烷 基’也可含衫枝狀⑥基及具轉環絲代制烧基。R3 的烧基之兔數為丨至1Q時’可使烧基成為障礙而抑制樹脂 彼此的接近’ it而促進對於樹脂顏料的吸附/配肖,如碳數 超過10時,將使烷基的立體障礙效果變高,甚至有妨礙到 對於苯環顏料的吸附/配向之傾向。此傾向會隨著R3的烧 基之碳鏈長度變長而變得明顯,如碳數超過20時,將使苯 %:的吸附/配向極端降低。具有R3所示的苯環之烷基,可 列舉如苯曱基、2-苯基(異)丙基等。可因增加一個側鏈苯 環,而更加改善溶劑親和性及顏料配向性,不只可提高分 散性,也可提高顯像性。 式(D-6)所示的乙烯性不飽和單體中,^宜為i至15 的整數。如η超過15時,將使親水性增加而使溶劑和的效 果變小,同時使乙烯系樹脂的黏度變高,也使使用此樹脂 的著色組成物之黏度變高,而可能影響到流動性。就溶劑 和而言,η是以1至4尤佳。 構成單元(D-b2)的前驅物,就與其他前驅物的共聚合 性而言,及顏料分散性而言,宜為α_曱基苯乙烯、丙烯酸 苯甲酯、甲基丙烯酸苯甲酯或式(D-6)所示的乙烯性不飽和 323842 96 201233734 上導入苯環後,因可使侧鏈苯 聚。並且,就 醋及/或甲基丙馳^t;,是哪吻 <構成單元(D-b3)> 脂:::::有:有^ 散劑形成的顏料組成物之親⑹目+於顏料或顏料與分 的疏水性部位之;於親和性躲,及㈣於驗顯像液 量為基準,就顯像二:树脂(D’)之全部構成單元的重 古,構成Hn 〜光片段的品質或分散安定性而 。構成早_-b3)為2至6〇重量%。如未達 = 料與分散劑形成的顏料組成物之親和 ㈣位不足’而有無法獲得高品質㈣光片段 : 色組成物的保存安定性惡化的問題也將因;: 部位不足而產生晝素部份的圖案剥離或缺陷的 超過6G重㈣時,將使溶解於驗顯像 卜又’拉長顯像時間而致彩色渡光片的生產性惡化。 構成單元(D_b3)在結構中具有的二環戊烧部位料 =科面結構,故可料於絲片段巾的分子相互凝聚、 狀態&供立體障礙D Λ 323842 97 201233734Made by Daicel, IRR169 [ethoxylated acrylate (E〇323842 93 201233734 lmol), R1: hydrogen atom, R2: ethyl, R3: hydrogen atom, n=l] or Ebecry 1110 [ethoxy acrylate Phenyl ester (£02111〇1), 1^: hydrogen atom, ruler 2: extended ethyl group, R3: hydrogen atom, n=2], Aronix M-101A manufactured by Toagosei Co., Ltd. [phenol E0 modified (n = 2) Acrylate, R1: hydrogen atom, R2: ethyl group, R3: hydrogen atom, n and 2], ]\4-102 [phenolic oxime (11% 4) acrylate, 1 ^: hydrogen atom, 1^: Ethyl, R3: hydrogen atom, η and 4], Μ-110 [p-cresol phenolphthalein 0 modified (η and 1) acrylate, R1: hydrogen atom, R2: ethyl, R3: pair Indophenol, η and Lu 1], Μ-111 [n-decylphenol oxime 0 (η and 1) acrylate, R1: hydrogen atom, R2: exoethyl, R3: n-decyl, η and 1] , Μ-113 [n-decyl phenolphthalein 0 modified (η = ? 4) acrylic vinegar 'R1: complex atom, R2: extended ethyl, R3: n-decyl, η and 4] or Μ-117 [正Nonylphenol Ρ0 modified (η and 2.5) acrylate, R1: hydrogen atom, R. propyl group, R3: n-decyl group, η% 2.5], light acrylate P0 -A[C Acid phenoxyethyl ester 'R1: hydrogen atom, R2: ethyl group, R3: hydrogen atom, n=l], ❿ P-200A [the present ethoxy polyethylene glycol acetoacetate, r1: hydrogen atom, R2: exoethyl, R3: hydrogen atom, η and 2], NP-4EA [nonylphenol E0 adduct acrylate, R1: hydrogen atom, R2: extended ethyl group, R3: n-decyl group, η-4 Or ΝΡ-8ΕΑ[nonylphenol oxime 0 adduct acrylate, R1: hydrogen atom, R2: exoethyl, R3: n-decyl' η and 8] or light ester P0 [benzoic acid benzene] Oxyethyl ester, R1: methyl group, R2: propyl group, R3: hydrogen atom, n=1], BlemmerANE-300 [mercaptophenoxy polyethylene glycol acrylate] R1: hydrogen atom , R2: exoethyl, f: n-decyl, ^ and 5], ΑΝΡ-300 [壬 basic oxypolypropylene glycol acetoacetate, ri: hydrogen atom, r2: 323842 94 201233734 propyl, R3: positive Sulfhydryl, η~5], 43 ANEp_5〇〇[Mercaptophenoxy polyethylene glycol-polypropylene glycol acrylate, Ri: hydrogen atom, R2: ethyl and propyl, R3: n-decyl, # 5 + 5], 7〇ANEp_5 alkenyl. phenoxy polyethylene glycol-polypropylene glycol acrylate, Ri: hydrogen atom, R2: extension And propyl, R3: n-decyl, n_9 + 3], 75 ANEp_6 〇〇 [mercaptophenoxy polyethylene glycol-polypropylene glycol acrylate, Rl: hydrogen atom, R2: extended ethyl and extended Base, R3: n-decyl group, η#5 + 2], AAE-50 [phenoxy polyethylene glycol acrylate, Rl: hydrogen atom, R2: ethyl group, R3: hydrogen atom, η=1], _ ΑΑΕ-300 [phenoxy polyethylene glycol acrylate, Rl: hydrogen atom, R2: ethyl group, R3: hydrogen atom, π~5·5], PAE-50 [phenoxy polyethylene glycol acrylic acid Ester 'R1: methyl, R2: ethyl, R3: hydrogen atom, η=1], ρΑΕ_1〇〇 [stupoxy polyethylene glycol acrylate, Rl: methyl, R2: ethyl, R3: Hydrogen atom, n=2] or 43PAPE-600B [phenoxy polyethylene glycol-polypropylene glycol acrylate, R1: methyl, R2: ethyl and propyl, R3: hydrogen atom, n% 6 + 6 φ NK ESTER AMP-10G [Phenoxyethylene glycol acrylate (E0 lmol), R1: hydrogen atom, R2: ethyl group, R3: hydrogen atom 'n=l], AMP- 20G [phenoxyethylene glycol acrylate (E〇2mol), R1: hydrogen atom, R2: extended ethyl group, R3: hydrogen atom, η and 2], AMP-60G [ Ethoxyethylene glycol acrylate (Ε6 6 mol), R1: hydrogen atom, R2: exoethyl, R·hydrogen atom, n*6], PHE-1G [stupoxy ethylene glycol acrylate (E〇lm〇) l), R1: methyl group, R2: ethyl group, R3: hydrogen atom, n=1], Biscoat# 192 [Acrylic acid acetoacetate] R1: 氲 atom, R2: ethyl , R3: hydrogen atom, n=l], or 323842 95 201233734 _ 曰 化 SR SR - - - - - - - - - - 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- a hydrogen atom, n=l] or SR-504 [ethoxylated oxime = alkanoic acid g|, Rl: a hydrogen atom, R2: an extended ethyl group, a r3: n-decyl group) is not limited to such a compound. At the same time, two or more types may be used in combination. In the ethylenically unsaturated monomer of the formula (D6), the alkyl group of R3 has a carbon number of from 1 to 20' and is preferably from 丨 to 1 Torr. The alkyl group is not only a linear alkyl group but also a hexagram 6 group and a spinning ring. When the number of rabbits of R3 is from 丨 to 1Q, 'the base can be made into an obstacle and the resin can be prevented from approaching each other'. It promotes the adsorption/distribution of the resin pigment. If the carbon number exceeds 10, the alkyl group will be made. The steric hindrance effect becomes high, and there is even a tendency to hinder the adsorption/alignment of the benzene ring pigment. This tendency becomes apparent as the length of the carbon chain of the alkyl group of R3 becomes longer. If the carbon number exceeds 20, the adsorption/alignment of benzene %: is extremely lowered. The alkyl group having a benzene ring represented by R3 may, for example, be a benzoinyl group or a 2-phenyl(iso)propyl group. The addition of a side chain benzene ring further improves solvent affinity and pigment alignment, which not only improves dispersibility but also improves development. In the ethylenically unsaturated monomer represented by the formula (D-6), it is preferably an integer of from i to 15. When η exceeds 15, the hydrophilicity is increased to reduce the effect of the solvent, and the viscosity of the vinyl resin is increased, and the viscosity of the colored composition using the resin is increased, which may affect the fluidity. . In terms of solvent and η, η is preferably from 1 to 4. The precursor of the constituent unit (D-b2) is preferably α-mercaptostyrene, benzyl acrylate or benzyl methacrylate in terms of copolymerization with other precursors and pigment dispersibility. Or after the introduction of the benzene ring on the ethylenically unsaturated 323842 96 201233734 represented by the formula (D-6), the side chain benzene can be aggregated. And, in the case of vinegar and/or methyl propyl ketone, which kiss <constituting unit (D-b3)> 脂::::: There are: a pigment composition formed by a powder (6) mesh + In the hydrophobic part of the pigment or pigment and the part; in the affinity hiding, and (4) on the basis of the test liquid amount, the image 2: the total composition of the resin (D') constitutes Hn ~ light The quality or dispersion stability of the fragments. The composition _-b3) is 2 to 6 〇 wt%. If the affinity of the pigment composition formed by the material and the dispersant is insufficient (four) is insufficient, the high quality (4) light fragment cannot be obtained: the problem of deterioration of the preservation stability of the color composition will also be caused by: When part of the pattern peeling or defect exceeds 6G weight (4), it will dissolve the test image and then lengthen the development time to deteriorate the productivity of the color light-emitting sheet. The constituent unit (D_b3) has a bicyclopentane burning site material in the structure = a mesa structure, so that the molecules of the silk segment towel can be coagulated, the state & steric obstacle D Λ 323842 97 201233734
(D-4)(D-4)
式(D-S) 構成單元(D-b3)的前驅物,可列舉如下述式戶斤 示的乙烯性不飽和單體或下述式(D_8)所示的乙烯 和單體。 見The precursor of the structural unit (D-b3) may, for example, be an ethylenically unsaturated monomer exemplified by the following formula or ethylene and a monomer represented by the following formula (D-8). see
°-r2^QD Ο 式(D-7)°-r2^QD Ο (D-7)
式(D-8) [式(D-7)及式(D-8)中,β _ E 7 9 -V' Q ΛΑ ^ a K 廣、子或甲基’ R2是破叙 2或3的伸録’Π1是〇至2的整數 疋炭數 323842 98 201233734 至於式(D-7)所示的乙烯性不飽和單體,可列舉例如 日立化成公司製的FancrylFA-513A[丙烯酸二環戊 酯,R丨:氫原子,R2 :無,m=〇]或FA_513M[丙烯酸二環戊 酯’ R1 :氫原子’ R2 :無’ m=0]等,但並不侷限於此等單 體,同時,也可2種以上併用。 至於式(D-8)所示的乙烯性不飽和單體,雖然可舉例 如 曰立化成公司製FancrylFA-511A[丙烯酸二環戊烯 • 酯,Rl :氫原子,R2 :無,m=0]、FA-512A[二環戊烯氧乙 基丙烯酸酯,R1 :氫原子,P :伸乙基,m=1]、fa_512m[甲 基丙烯酸二環戊烯氧基乙酯,Ri :曱基,R2 :伸乙基,m=1] 或FA-512MT[曱基丙烯酸二環戊烯氧基乙酯,Ri :甲基, R2 :伸乙基,m=l]等,但並不侷限於此等單體,同時,也 可2種以上併用。 <其他的構成單元> • 其他的構成單元是構成單元(D-bl)、構成單元(D-b2)、 構成單元(D-b3)以外的構成單元。 其他的構成單元之前驅物,可列舉例如(曱基)丙稀酸 甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(曱基) 丙烯酸異丙酯、(甲基)丙烯酸丁酯、(曱基)丙烯酸異丁酯、 (曱基)丙烯酸第二丁酯、(曱基)丙烯酸第三丁酯、(曱基) 丙烯酸戊酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸新戊酯、 (曱基)丙稀酸第二戊醋、(曱基)丙稀酸1 一甲基丁醋、(甲 基)丙烯酸己酯、(曱基)丙烯酸庚酯、(曱基)丙烯酸辛酯、 323842 99 201233734 (甲基)丙稀酸2-乙基己酯、(甲基)丙烯酸十二烷酯、(甲 基)丙烯酸十六烷酯、(甲基)丙烯酸十八烷酯、(曱基)丙烯 酸異十八烧酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸芳酯 或(甲基)丙烯酸油酯等(甲基)丙烯酸烷酯或(甲基)丙烯酸 芳酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2_羥基丙 酯、(甲基)丙烯酸万-羧基乙酯、聚乙二醇二(甲基)丙烯酸 酉曰、1,6-己二醇二(甲基)丙稀酸酯、三乙二醇二(甲基)丙 烯酸酯、三丙二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲 籲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、丨,6-己二醇二 縮水甘油醚二(甲基)丙烯酸酯、新戊二醇二縮水甘油醚二 (甲基)丙烯酸酯、二新戊四醇六(曱基)丙烯酸酯、(甲基) 丙烯酸異茨酯、酯丙烯酸酯、(曱基)丙烯酸環氧酯、胺酯 丙烯酸酯等各種丙烯酸酯或曱基丙烯酸酯,但不侷限於此 等單體,也可配合目的而選擇其他的乙烯性不飽和單體, 也可2種以上併用。 % 其他的乙烯性不飽和單體,可列舉例如四氫呋喃(甲 基)丙烯酸酯或具有3-曱基氧雜環丁烷(甲基)丙烯酸酯等 雜環式取代基的丙烯酸酯類; 曱氧基聚丙二醇(曱基)丙烯酸酯或乙氧基聚乙二醇 (甲基)丙烯酸酯等烷氧基聚烷二醇(甲基)丙烯酸酯類;或 (曱基)丙烯醯胺、N,N-二曱基(曱基)丙烯醯胺、n,N-二乙基(曱基)丙烯醯胺、N-異丙基(甲基)丙烯醯胺、二丙 酮(曱基)丙烯醯胺、丙烯醯基嗎啉、N—羥基曱基(甲基)丙 烯醯胺、N-乙烯曱醯胺等(曱基)丙烯醯胺類或丙烯腈等。 323842 100 201233734 同時,前述以外的構成單元之前驅物,可列舉例如: 乙基乙稀醚、正丙基乙烯喊、異两基乙稀鍵、正丁基 乙烯峻、異丁基乙_、經基乙基乙缚鱗、乙二醇二乙婦 酸、新戊四醇三乙烯趟等乙烯或醋酸乙稀醋或丙酸 乙浠s旨等脂肪酸乙烯@旨類。 再者,也可使用二曱基一2,2,-[氧基雙(亞曱基)]雙 -2-丙酸醋、二乙基一2,2’ _[氧基雙(亞甲基)]雙_2一丙酸 酉旨、二環己基-2,2’ -[氧基雙(亞甲基)]雙_2_丙酸醋、二 苯甲基-2, 2 -[氧基雙(亞甲基)]雙—2_丙酸醋等單體/寡 聚物。丙稀酸基構成單元以外的前述構成單元,也可與前 丙稀酸基構成單元併用。 <乙烯性不飽和雙鍵之導入> 又,為了藉由以下表示的方法(Μ)或導入乙 稀性不飽和雙鍵,也可使用具有環氧基的乙稀性不飽和單 體或具有經基的乙烯性不飽和單體。此等單體有可能因改 參質而形成其他的構成單元以外的構成單元,故最終還是期 望考篁構成單元(D-bl)、構成單元(D_b2)、構成單元(D_b3) 之重量比。 < 方法(D-i)> 方法(D-i)係例如在具有環氧基的乙烯性不飽和單體 與其他1種以上之乙烯性不飽和單體共聚合而得的共聚物 之侧鏈環氧基上,使具有乙烯性不飽和雙鍵的不飽和一元 酸之羧基加成反應,並且在生成的羥基上,使多元酸酐反 應,導入乙烯性不飽和雙鍵使其具有感光性樹脂的功能, 323842 101 201233734 且可導入具有驗可溶性功能的竣基之方法。 此步驟中使用的不飽和一元酸的幾基,因在對環氧基 的附加反應後將形成酯鍵,故不可成為樹脂(D_B1)的構成 單元(D-bl),而成為其他的構成單元;多元酸酐在與氫氧 基反應後因將形成羧基,故可成為樹脂(D_B1)的構成單元 (D-bl)。 具有環氧基的乙婦性不飽和雙鍵單體、不飽和一元酸 及多元酸酐之例,可列舉如與第5實施態樣中的乙烯性不 飽和雙鍵單體、不飽和一元酸及多元酸酐相同的乙烯性不 飽和單體、不飽和一元酸及多元酸肝。 與方法(D-i)類似的方法係例如在具有羧基的乙烯性 不飽和單體與其他1種以上之乙烯性不飽和單體共聚合而 得的共聚物的側鏈羧基的一部份上,使具有環氧基的乙烯 性不飽和單體加成反應後,導入乙烯性不飽和雙鍵及羧基 的方法。此時’只有相當於與環氧基加成反應中不能使用 % 的羧基之構成單元,符合樹脂(D-B1)的構成單元(D-bl)。 < 方法(D-ii)> ' 方法(D-ii)係使用具有羥基的乙烯性不飽和單體,在 與具有其他羧基之不飽和一元酸或其他乙烯性不飽和單體 共聚合而得的共聚物之侧鏈羥基上,使具有異氰酸酯基的 乙烯性不飽和單體之異氰酸酯基反應的方法。 具有羥基的乙烯性不飽和單體及具有異氰酸酯基的 乙烯性不飽和單體之例,可列舉如與第5實施態樣中具有 羥基的乙烯性不飽和單體及具有異氰酸酯基的乙烯性不飽 323842 102 201233734 和單體相同的具有羥基的乙烯性不飽和單體及具有異氰酸 酯基的乙烯性不飽和單體。 樹脂(D-B1)的重量平均分子量(Mw)宜為5 〇〇〇至 100, 000的範圍,以5, 〇〇〇至80, 000的範圍較佳,以5 〇〇〇 至30, 000的範圍更佳。又’數目平均分子量(Mn)宜為5,〇〇〇 至50,000的範圍,Mw/Mn之值宜為10以下。如樹脂(D_B1) 的重量平均分子量(Mw)超過1〇〇, 〇〇〇時,因將使樹脂間的 相互作用變強,而使彩色濾光片用著色組成物的黏度變 尚,以致難以操作。又,如重量平均分子量(Mw)未達5, 〇〇〇 時’可能使顯像性或對於玻璃等基板的密著性降低。 就成膜性及各耐性之良好而言,相對於式(丨)所示的 顏料(Al)100重量份,樹脂(D_B1)的含量宜使用3〇重量份 以上’就提高著色劑濃度、可顯現良好的色特性而言,宜 使用500重量份以下的量。並以使用50至25〇重量份的量 較佳。 • 《其他的樹脂》 著色組成物也可含有樹脂(D-B1)以外的其他樹脂。至 於其他的樹脂’宜為可見光區域的400至7〇〇nm之全波長 區域中的穿透率80%以上之樹脂,並以95%以上的樹脂較 佳。其他的樹脂中,包含熱可塑性樹脂、熱硬化性樹脂及 感光性樹脂’此等樹脂可單獨使用,也可混合2種以上使 用。樹脂之例可列舉如與第5實施態樣中的樹脂相同的樹 脂。 感光性樹脂可使用在具有羥基、羧基、胺基等反應性 323842 103 201233734 取代基的線狀高分子中,使具有異氰酸酯基、醛基、環氧 基專反應性取代基的(甲基)丙稀酸化合物或桂皮酸反應, 使(甲基)丙烯醯基、苯乙烯基等光交聯性基導入該線狀高. 分子中的樹脂。又’也可使用將含有苯乙烯_酸酐共聚物或 α-烯烴-酸酐共聚物等酸酐的線狀高分子,藉由具有(曱基) 丙烯酸羥基烧酯等羥基的(曱基)丙烯酸化合物半酯化而成 者。 (溶劑) 溶劑的使用是為了使顏料(Α)充分分散在黏合劑樹脂 (D-B)中,可使著色組成物塗佈在玻璃基板等基板上以成為 0.2至5em的乾燥膜厚,而容易形成濾光片段。溶劑宜為 有機溶劑。溶劑的適宜使用量,是與第5實施態樣中相同 (感光性著色組成物的製法) 第6實施態樣的著色組成物,可藉由與第5實施態樣 的著色組成物相同的製造方法製造。 ^ (任意成分) 在第6實施態樣的著色組成物中,可含有顏料分散劑 (D-C)、光聚合起始劑(Dh))、增感劑、光聚合性化合物、 多吕此硫醇、紫外線吸收劑、禁止聚合劑、貯存安定劑、 其他的添加劑等任意成分。此等任意成分的具體例係與第 5實施態樣相同。又,適宜的例、適宜的使用量等亦與 實施態樣相同。 (粗大粒子的去除) 第6實施態樣的著色組成物亦與第3實施態樣的著色 323842 104 201233734 組成物相同,宜進行粗大粒子的去除。 [溶劑、任意成分] 以下,表示上述彩色濾光片用著色組成物中使用的溶 劑及任意成分之具體例。 (其他著色劑(其他的顏料)) 著色組成物中使用的其他著色劑(其他的顏料),可列 舉例如 C. I.顏料紅 1、2、3、4、5、6、7、8、9、12、14、 15、16、17、2卜 22、23、3卜 32、37、38、4卜 47、48、 ® 48 :卜 48 : 2、48 : 3、48 : 4、49、49 :卜 49 : 2、50 : 1、 52 :卜 52 : 2 、 53 、 53 :卜 53 : 2 、 53 : 3 、 57 、 57 :卜 57 : 2、58 : 4、60、63、63 :卜 63 : 2、64、64 :卜 68、 69、8卜 81 :卜 81 : 2、81 : 3、81 : 4、83、88、90 : 1、 1(H 、 101 :卜 104 、 108 、 108 :卜 109 、 112 、 113 、 114 、 122 、 123 、 144 、 146 、 147 、 149 、 151 、 166 、 168 、 169 、 170 、 172 、 173 、 174 、 175 、 176 、 177 、 178 、 179 、 181 、 φ 184 、 185 、 187 、 188 、 190 、 192 、 193 、 194 、 200 、 202 、 206 、 207 、 208 、 209 、 210 、 214 、 215 、 216 、 217 、 220 、 22卜 223 、 224 、 226 、 227 、 228 、 240 、 230 、 231 、 232 、 233 、 235 、 236 、 237 、 238 、 239 、 242 、 243 、 245 、 246 、 247 、 249 、 250 、 251 、 253 、 254 、 255 、 264 、 255 、 256 、 257 、 258 、 259 、 260 、 262 、 263 、 264 、 265 、 266 、 267 、 268 、 269 、 270 、 271 、 272 、 273 、 274 、 275 、 276 、 277 、 278 、 279 、 280 、 281 、 282 、 283 、 284 、 285 、 286 或 287 等紅色顏料。紅色顏料可列舉如咕嘲(xanthene)系、單偶 323842 105 201233734 氮系(β比咬酮系、巴比妥酸(barbituric acid)系、金屬錯 合物系等)、二偶氮系、蒽醌系等。具體上,可列舉如C. I. 酸紅52、87、92、289、338等咕噸系酸性染料的造鹽化合 物等。此等顏料可單獨使用,也可將2種以上混合後使用。 例如可併用C. I.顏料橙1、2、5、13、16、17、19、 20、2卜 22、23、24、34、36、38、39、43、46、48、49、 51、55、59、6卜 62、64、65、67、68、69、70、71、72、 73、74、75、77、78或79等橙色顏料及/或C. I.顏料黃1、 Φ 1:卜2、3、4、5、6、9、10、12、13、14、15、16、17、 18、24、3卜 32、34、35、35 :卜 36、36 :卜 37、37 :卜 40、4卜 42、43、48、53、55、60、6卜 62、62 : 1、63、 65、73、74、75、77、8卜 83、87、93、94、95、97、98、 100、1(Π、104、105、106、108、109、110、1U、113、 114 、 115 、 116 、 117 、 118 、 119 、 120 、 123 、 126 、 127 、 127:卜 128、129、133、134、136、138、139、142、147、 • 148、150、15卜 152、153、154、155、156、157、158、 159 、 160 、 16卜 162 、 163 、 164 、 165 、 166 、 167 、 168 、 169 、 170 、 17卜 172 、 173 、 174 、 175 、 176 、 177 、 179 、 180 、 181 、 182 、 183 、 184 、 185 、 187 、 188 、 189 、 190 、 19卜 191 : 1、192、193、194、195、196、197、198、199、 200 、 202 、 203 、 204 、 205 、 206 、 207 、 208 、 213 、 214 、 218、219、220或221等黃色顏料。又,橙色染料及/或黃 色染料可列舉如喹啉系、單偶氮系(吡啶酮系、巴比妥酸 系、金屬錯合物系等)、二偶氮系、次曱基(methine)系等。 323842 106 201233734 此等顏料可單獨使用,也可將2種以上混合後使用。 此等顏料之中,適合併用的著色劑,可列舉如蒽醌系 顏料、單偶氮系、二偶氮系或咕噸系染料等。就亮度與對 比度而言,具體上,宜為C. I.顏料紅48 : 1、122、168、 176 、 177 、 185 、 202 、 206 、 207 、 209 、 224 、 242 、 254 、 C. I.顏料橙 38、7卜 C. I.顏料黃 83、117、129、138、139、 150、154、155、180、185及C. I.酸性紅52的造鹽化合物。 復以c.丨.顏料紅177、209、224、242或254 ; C. I.顏料黃 響 83、138、139、15◦或 180 更佳。 (有機溶劑) 著色組成物中使用的有機溶劑可列舉例如乳酸乙酯、 笨甲醇、1,2, 3-三氯丙烧、1,3-丁二醇、1,3-丁二醇、1,3- 丁二醇二醋酸酯、1,4-二噚烷、2-庚酮、2-甲基-1,3-丙二 醇、3, 5, 5-三甲基-2-環己婦-1-酮、3, 5, 5-三曱基環己酮、 3-乙氧基丙酸乙酯、3-甲基-i,3-丁二醇、3-甲氧基-3-甲 • 基一1_丁醇、醋酸3-曱氧基-3-曱基丁酯、3-曱氧基丁醇、 醋酸3-甲氧基丁酯、4-庚酮、間-二曱苯、間-二乙基苯、 間-二氯苯、N,N-二甲基乙醯胺、ν,Ν-二甲基甲醯胺、正丁 醇、正丁苯、醋酸正丙酯、Ν-甲基吡咯酮、鄰-二曱苯、鄰 -氣甲苯、鄰-二乙基苯、鄰_二氯苯、對-氯甲苯、對一二乙 基笨、第二丁基苯、第三丁基苯、丁内酯、異丁醇、異 苐酮、乙二醇二***、乙二醇二丁醚、乙二醇單異丙醚、 乙一醇單乙趟、乙二醇單乙趟醋酸酯、乙二醇單第三丁峻、 乙二醇單丁醚、乙二醇單丁醚醋酸酯、乙二醇單丙醚、乙 323842 107 201233734 一醇早己幽I、乙-酸留田Βϋί 乙一知早甲醚、乙二醇單曱醚醋酸酯、二異 1_、二乙二醇二***、二乙m二乙 丙喊、二乙二醇單乙峻_、二乙二醇單丁醚一乙」 醇單丁醚醋酸酯、-乙一、 一乙一 一乙一知早甲醚、環己醇、環己醇醋酸 酉曰、己酮、二丙二酿-田Formula (D-8) [In the formula (D-7) and (D-8), β _ E 7 9 -V' Q ΛΑ ^ a K broad, sub or methyl 'R2 is a breakaway 2 or 3伸 Π Π Π 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 323 , R丨: hydrogen atom, R2: none, m=〇] or FA_513M [dicyclopentanyl acrylate 'R1: hydrogen atom 'R2: no 'm=0], etc., but not limited to such monomers, Two or more types can also be used together. The ethylenically unsaturated monomer represented by the formula (D-8) may, for example, be Fancryl FA-511A manufactured by Sigma Chemicals Co., Ltd. [dicyclopentene acrylate], R1: hydrogen atom, R2: none, m=0. ], FA-512A [dicyclopentene oxyethyl acrylate, R1: hydrogen atom, P: exoethyl, m = 1], fa_512m [dicyclopentenyloxyethyl methacrylate, Ri: fluorenyl , R2: exoethyl, m = 1] or FA-512MT [dicyclopentenyloxyethyl decyl acrylate, Ri: methyl, R2: exoethyl, m = l], etc., but not limited These monomers may be used in combination of two or more kinds. <Other constituent units> • The other constituent units are constituent units other than the constituent unit (D-bl), the constituent unit (D-b2), and the constituent unit (D-b3). Other constituent unit precursors include, for example, (mercapto)methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (methyl) ) butyl acrylate, isobutyl (meth) acrylate, second butyl (meth) acrylate, tert-butyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate , (meth)acrylic acid neopentyl ester, (mercapto) acrylic acid second pentyl vinegar, (mercapto) acrylic acid 1 methyl butyl vinegar, (meth) hexyl acrylate, (decyl) acrylic acid Ester, octyl (meth) acrylate, 323842 99 201233734 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, (methyl Alkenyl (meth)acrylate such as octadecyl acrylate, isostearyl acrylate, cyclohexyl (meth) acrylate, aryl (meth) acrylate or (meth) acrylate Or aryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylate 2 _ Propyl propyl ester, 10,000-carboxyethyl (meth) acrylate, bismuth polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(methyl) acrylate, triethylene glycol (Meth) acrylate, tripropylene glycol di(meth) acrylate, trimethylolpropane tris(meth) acrylate, pentaerythritol tri(meth) acrylate, hydrazine, 6-hexanediol Diglycidyl ether di(meth) acrylate, neopentyl glycol diglycidyl ether di(meth) acrylate, dipentaerythritol hexa(indenyl) acrylate, (meth) isopropyl acrylate, Various acrylates or mercapto acrylates such as ester acrylate, (meth) acrylate epoxy ester, amine ester acrylate, etc., but are not limited to these monomers, and other ethylenically unsaturated monomers may be selected according to the purpose. , or two or more types can be used together. % Other ethylenically unsaturated monomers, for example, tetrahydrofuran (meth) acrylate or acrylate having a heterocyclic substituent such as 3-mercapto oxetane (meth) acrylate; Alkoxy polyalkylene glycol (meth) acrylates such as polypropylene glycol (mercapto) acrylate or ethoxypolyethylene glycol (meth) acrylate; or (mercapto) acrylamide, N, N-dimercapto(fluorenyl) acrylamide, n,N-diethyl(fluorenyl) acrylamide, N-isopropyl (meth) acrylamide, diacetone (fluorenyl) acrylamide And acryloyl morpholine, N-hydroxydecyl (meth) acrylamide, N-vinyl decylamine or the like (fluorenyl) acrylamide or acrylonitrile. 323842 100 201233734 Meanwhile, the precursor of the constituent unit other than the above may be, for example, ethyl ethyl ether, n-propyl vinyl, iso-ethylene di-ethyl, n-butyl vinyl, isobutyl b, and Ethyl ethyl sulphate, ethylene glycol diethoxylate, neopentyl alcohol, trivinyl hydrazine, etc., ethylene or ethyl acetate acetonate or acetoacetate s s. Further, dimercapto- 2,2,-[oxybis(indenyl)]bis-2-propionic acid vinegar, diethyl-2,2'-[oxybis(methylene) can also be used. )]Bis-2-propionic acid, dicyclohexyl-2,2'-[oxybis(methylene)]bis-2-propionic acid vinegar, diphenylmethyl-2,2-[oxyl Monomer/oligomer such as bis(methylene)]bis-2-propionic acid vinegar. The above-mentioned constituent unit other than the acrylic acid-constituting unit may be used in combination with the pre-acrylic acid group-constituting unit. <Importing of ethylenically unsaturated double bond> Further, in order to introduce an ethylenically unsaturated monomer having an epoxy group or a method of introducing an ethylenically unsaturated double bond, An ethylenically unsaturated monomer having a warp group. Since these monomers may form constituent units other than the constituent units due to the modification of the parameters, it is expected that the weight ratio of the constituent unit (D-bl), the constituent unit (D_b2), and the constituent unit (D_b3) is finally desired. <Method (Di)> The method (Di) is, for example, a side chain epoxy of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group with one or more other ethylenically unsaturated monomers. a carboxyl group addition reaction of an unsaturated monobasic acid having an ethylenically unsaturated double bond, and a polybasic acid anhydride is reacted on the produced hydroxyl group to introduce an ethylenically unsaturated double bond to have a function as a photosensitive resin. 323842 101 201233734 and a method of introducing a thiol group having a solubility function can be introduced. The group of the unsaturated monobasic acid used in this step does not become a constituent unit (D-bl) of the resin (D_B1) but becomes another constituent unit because an ester bond is formed after an additional reaction with the epoxy group. The polybasic acid anhydride forms a carboxyl group after the reaction with the hydroxyl group, and thus can be a constituent unit (D-bl) of the resin (D_B1). Examples of the ethylarene-unsaturated double bond monomer having an epoxy group, the unsaturated monobasic acid, and the polybasic acid anhydride include, for example, the ethylenically unsaturated double bond monomer and the unsaturated monobasic acid in the fifth embodiment. The same type of ethylenically unsaturated monomer, unsaturated monobasic acid and polyacid liver. A method similar to the method (Di) is, for example, a part of a side chain carboxyl group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group with one or more other ethylenically unsaturated monomers. A method of introducing an ethylenically unsaturated double bond and a carboxyl group after an ethylenically unsaturated monomer having an epoxy group is subjected to an addition reaction. At this time, only the constituent unit corresponding to the carboxyl group which cannot be used in the addition reaction with the epoxy group is satisfied, and the constituent unit (D-bl) of the resin (D-B1) is satisfied. <Method (D-ii)> 'Method (D-ii) uses an ethylenically unsaturated monomer having a hydroxyl group to copolymerize with an unsaturated monobasic acid or other ethylenically unsaturated monomer having another carboxyl group. A method of reacting an isocyanate group of an ethylenically unsaturated monomer having an isocyanate group on a side chain hydroxyl group of the obtained copolymer. Examples of the ethylenically unsaturated monomer having a hydroxyl group and the ethylenically unsaturated monomer having an isocyanate group include an ethylenically unsaturated monomer having a hydroxyl group in the fifth embodiment and an ethylenic group having an isocyanate group. 323842 102 201233734 The same ethylenically unsaturated monomer having a hydroxyl group and an ethylenically unsaturated monomer having an isocyanate group. The weight average molecular weight (Mw) of the resin (D-B1) is preferably in the range of 5 〇〇〇 to 100,000, preferably in the range of 5, 〇〇〇 to 80, 000, and 5 〇〇〇 to 30,000. The scope is better. Further, the number average molecular weight (Mn) is preferably in the range of 5, 〇〇〇 to 50,000, and the value of Mw/Mn is preferably 10 or less. When the weight average molecular weight (Mw) of the resin (D_B1) exceeds 1 Torr, the viscosity of the coloring composition for the color filter becomes too large, so that it is difficult to make the interaction between the resins stronger. operating. Further, if the weight average molecular weight (Mw) is less than 5, 〇〇〇 ' may cause deterioration in visibility or adhesion to a substrate such as glass. In order to improve the film formability and the respective resistances, the content of the resin (D_B1) is preferably 3 parts by weight or more with respect to 100 parts by weight of the pigment (Al) represented by the formula (丨), thereby increasing the concentration of the colorant. In order to exhibit good color characteristics, it is preferred to use an amount of 500 parts by weight or less. It is preferably used in an amount of 50 to 25 parts by weight. • "Other resin" The coloring composition may contain a resin other than the resin (D-B1). The other resin ' is preferably a resin having a transmittance of 80% or more in the entire wavelength range of 400 to 7 Å in the visible light region, and preferably 95% or more of the resin. Other resins include a thermoplastic resin, a thermosetting resin, and a photosensitive resin. These resins may be used singly or in combination of two or more kinds. Examples of the resin include the same resins as those in the fifth embodiment. The photosensitive resin can be used in a linear polymer having a reactive group of 323842 103 201233734 such as a hydroxyl group, a carboxyl group or an amine group, and a (meth) propyl group having an isocyanate group, an aldehyde group or an epoxy group-specific substituent. The dilute acid compound or cinnamic acid reacts to introduce a photocrosslinkable group such as a (meth) acrylonitrile group or a styryl group into the resin in the linear high molecular weight. Further, a linear polymer containing an acid anhydride such as a styrene-anhydride copolymer or an α-olefin-anhydride copolymer may be used, and a (fluorenyl)acrylic compound having a hydroxyl group such as a hydroxyalkyl ester of (fluorenyl) acrylate may be used. Esterified. (Solvent) The solvent is used in order to sufficiently disperse the pigment (Α) in the binder resin (DB), and the coloring composition can be applied onto a substrate such as a glass substrate to have a dry film thickness of 0.2 to 5 cm, which is easy to form. Filter the fragments. The solvent is preferably an organic solvent. The solvent is suitably used in the same manner as in the fifth embodiment (manufacturing method of the photosensitive coloring composition). The coloring composition of the sixth embodiment can be produced by the same coloring composition as the fifth embodiment. Method of manufacture. ^ (optional component) The coloring composition of the sixth embodiment may contain a pigment dispersant (DC), a photopolymerization initiator (Dh), a sensitizer, a photopolymerizable compound, and a thiol Any component such as a UV absorber, a polymerization inhibitor, a storage stabilizer, or other additives. Specific examples of such arbitrary components are the same as in the fifth embodiment. Further, suitable examples, suitable usage amounts, and the like are also the same as in the embodiment. (Removal of coarse particles) The coloring composition of the sixth embodiment is also the same as the coloring of the third embodiment 323842 104 201233734, and it is preferable to remove coarse particles. [Solvent, optional component] Hereinafter, specific examples of the solvent and optional components used in the coloring composition for a color filter described above will be described. (Other coloring agents (other pigments)) Other coloring agents (other pigments) used in the coloring composition include, for example, CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12 , 14, 15, 16, 17, 2, 22, 23, 3, 32, 37, 38, 4, 47, 48, ® 48: Bu 48: 2, 48: 3, 48: 4, 49, 49: 49 : 2, 50 : 1, 52 : Bu 52 : 2 , 53 , 53 : Bu 53 : 2 , 53 : 3 , 57 , 57 : Bu 57 : 2 , 58 : 4 , 60 , 63 , 63 : Bu 63 : 2, 64, 64: Bu 68, 69, 8 Bu 81: Bu 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 1 (H, 101: Bu 104, 108, 108: Bu 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, φ 184 , 185 , 187 , 188 , 190 , 192 , 193 , 194 , 200 , 202 , 206 , 207 , 208 , 209 , 210 , 214 , 215 , 216 , 217 , 220 , 22 , 223 , 224 , 226 , 227 , 228 , 240, 230, 231, 232, 233 , 235 , 236 , 237 , 238 , 239 , 242 , 243 , 245 , 246 , 247 , 249 , 250 , 251 , 253 , 254 , 255 , 264 , 255 , 256 , 257 , 258 , 259 , 260 , 262 , 263 , 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286 or 287 Pigment. The red pigment may be, for example, xanthene, monocouple 323842 105 201233734 nitrogen (beta ketone, barbituric acid, metal complex, etc.), diazo , 蒽醌, etc. Specific examples thereof include salt-forming compounds such as C. I. acid red 52, 87, 92, 289, and 338, which are acid dyes of xanthene-based acid dyes. These pigments may be used singly or in combination of two or more. For example, CI Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 2, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 51, 55 may be used in combination. 59, 6 Bu 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78 or 79 and other orange pigments and / or CI pigment yellow 1, Φ 1: Bu 2 3, 4, 5, 6, 9, 10, 12, 13, 14, 15, 16, 17, 18, 24, 3, 32, 34, 35, 35: Bu 36, 36: Bu 37, 37: Bu 40 4, 42, 43, 48, 53, 55, 60, 6 and 62, 62: 1, 63, 65, 73, 74, 75, 77, 8 and 83, 87, 93, 94, 95, 97, 98 , 100, 1 (Π, 104, 105, 106, 108, 109, 110, 1U, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 127: 128, 129, 133, 134, 136, 138, 139, 142, 147, • 148, 150, 15 152, 153, 154, 155, 156, 157, 158, 159, 160, 16 162, 163, 164, 165, 166 , 167, 168, 169, 170, 17 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 183, 184, 185, 18 7, 188, 189, 190, 19 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, 213, 214, a yellow pigment such as 218, 219, 220 or 221. Further, examples of the orange dye and/or the yellow dye include a quinoline type, a monoazo type (pyridone type, a barbituric acid type, a metal complex type, etc.). Diazo, methine, etc. 323842 106 201233734 These pigments may be used singly or in combination of two or more. Among these pigments, suitable coloring agents are exemplified by hydrazine. Anthraquinone pigment, monoazo, diazo or xanthene dye, etc. In terms of brightness and contrast, specifically, it is preferably CI Pigment Red 48: 1, 122, 168, 176, 177, 185, 202 , 206, 207, 209, 224, 242, 254, CI Pigment Orange 38, 7 Bu CI Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185 and CI Acid Red 52 Compound. Further, c. 丨. Pigment Red 177, 209, 224, 242 or 254; C. I. Pigment Yellow Ring 83, 138, 139, 15 ◦ or 180 is more preferable. (Organic solvent) Examples of the organic solvent used in the coloring composition include ethyl lactate, stupid methanol, 1,2,3-trichloropropane, 1,3-butanediol, and 1,3-butanediol. , 3-butanediol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3, 5, 5-trimethyl-2-cyclohexanyl- 1-ketone, 3, 5, 5-tridecylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-i, 3-butanediol, 3-methoxy-3-methyl Base 1-butanol, 3-decyloxy-3-mercaptobutyl acetate, 3-decyloxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-nonylbenzene, -diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, ν, Ν-dimethylformamide, n-butanol, n-butylbenzene, n-propyl acetate, Ν-甲Pyrrolidone, o-diphenylbenzene, o-gas toluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethyl stupid, t-butylbenzene, tert-butyl Benzene, butyrolactone, isobutanol, isoindolinone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl hydrazine, ethylene glycol monoacetic acid acetate, Ethylene glycol single third Ding Jun, ethylene glycol Monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene 323842 107 201233734 monool early chlorinated I, ethyl phthalate 留 乙 乙 知 早 early methyl ether, ethylene glycol monoterpene ether acetate , diiso-1_, diethylene glycol diethyl ether, diethylene glycol, ethylene glycol monoethylene glycol, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, -ethyl one, one B1, Yiyi, early methyl ether, cyclohexanol, cyclohexanol acetate, ketone, dipropylene, brewing
K口内知一甲醚、二丙二醇單甲醚醋酸酯、 丙二醇:::乙1二丙二醇單頂、二丙二醇單丙醚、二 早㈣、—丙酮醇、三醋酸甘油§旨、三丙二醇單丁 二醇單曱喊、丙二醇單二醋酸®旨、丙二醇苯韃、 醇單乙鱗、丙二醇單乙_醋酸醋、丙二醇單丁趟、丙 二醇單丙醚、丙二醇單甲趟、丙二醇單甲醚醋酸醋、丙二 醇早曱醚丙酸醋、苯甲醇、甲基異丁酮、甲基環己醇、醋 酸^戍®1、醋酸正丁自旨、醋酸異細旨、醋賴τ自旨、醋酸 丙酉曰、二讀®旨等。此等溶劑可單獨使用,必要時以任意 的比率混合2種以上後使用。 其中,就良好的著色劑之分散性、浸透性及著色組成 物的塗佈而言’宜使用乳酸乙料乳酸㈣類、丙二醇單 甲醚醋酸酯、丙二醇單***醋酸酯、乙二醇單曱醚醋酸酯、 乙一醇單***醋酸酯等二醇醋酸酯類、苯甲醇、二丙酮醇 等醇類或環己酮等酮類。 (樹脂型分散劑) 樹脂型分散劑具有可吸附在著色劑上的性質之顏料 親和性部位與具有與著色劑載體的相容性的部位,係作用 為吸附在著色劑上後,安定的分散在著色劑的著色劑載體 上的成分。樹脂型分散劑具體上可使用聚胺酯、聚丙烯酸 323842 108 201233734 酉旨等聚羧酸醋、不飽和聚醯胺、聚缓酸、聚緩酸(部份)胺 鹽、聚羧酸銨鹽、聚羧酸烷基胺鹽、聚矽氧烷、長鏈聚胺 基醯胺構酸鹽、含經基聚羧酸酯或此等的改質物、聚(低級 伸烧基亞胺)與具有遊離羧基的聚酯反應形成的醯胺或其 鹽等油性分散劑、(曱基)丙烯酸-苯乙烯共聚物、(曱基) 丙烯酸-(甲基)丙烯酸酯共聚物、苯乙烯-順丁烯二酸共聚 物、聚乙烯醇、聚乙烯吡咯酮等水溶性樹脂或水溶性高分 子化合物、聚酯系、改質聚丙酸酯系、環氧乙烧/環氧丙烧 ® 加成化合物、磷酸酯系等。雖然此等分散劑可單獨使用, 或將2種以上混合後使用,但不必然侷限於此等化合物。 市售的樹脂型分散劑可列舉如BYK Chemie Japan公 司製的 Disperbyk-101、103、107、108、110、111、112、 116、130、140、142、154、161、162、163、164、165、 166 、 167 、 168 、 170 、 17卜 174 、 180 、 181 、 182 、 183 、 184、185、190、2000、2001、2009、2010、2020、2025、 2050 、 2070 、 2095 、 2150 、 2155 、 2163 、 2164 或 Anti-Terra-U、203、204 ;或 BYK-P104、P104S、220S、 6919、21116、21324、21407、21715 等或 Lactimon、 Lactimon-WS 或 Bykumen 等;日本 Lubrizol 公司製的 SOLSPERSE-3000 、 9000 、 13000 、 13240 、 13650 、 13940 、 16000、17000、18000、20000、21000、24000、26000、27000、 28000、31845、32000、32500、32550、33500、32600、34750、 35100、36600、38500、41000、41090、53095、55000、56000、 76500 等;日本汽巴(Ciba Japan)公司製的 EFKA-46、47、 323842 109 201233734 48 、 452 、 4008 、 4009 、 4010 、 4015 、 4020 、 4047 、 4050 、 4055、4060、4080、4400、44(Π、4402、4403、4406、4408、 4300、4310、4320、4330、4340、450、45卜 453、4540、 4550、4560、4800、5010、5065、5066、5070、7500、7554、 1101、120、150、1501、1502、1503 等;楠本化成公司製 的 DISPARLON 3600Ν、DISPARLON 1850 ;味之素 Finetechno 公司製的 Ajisper-PAm、PB7U、PB82卜 PB822、PB824 等。此等製品可單獨使用,或將2種以上混合後使用。 ® 在此等製品中,較佳為具有酸性官能基的樹脂型顏料 分散劑之 BYK Chemie Japan 公司製的 Disperbyk-108、 110、11 卜 112、116、142、180、2000、2001 或日本 Lubrizol 公司製的 SOLSPERSE-3000、21000、26000、36600、41000 或日本汽巴公司製的EFKA-4401、4550或楠本化成公司製 的 DISPARLON 3600N、DISPARLON 1850 或味之素 Finetechno 公司製的Ajisper-PAlll等,但不侷限於此等製品。 φ (界面活性劑) 界面活性劑可列舉如十二烷基硫酸鈉、聚氧乙烯烷醚 硫酸鹽、十二烷苯磺酸鈉、苯乙烯-丙烯酸共聚物的鹼鹽、 硬脂酸鈉、烷基萘磺酸鈉、烷基二苯醚二磺酸鈉、十二烷 基硫酸單乙醇録、十二烧基硫酸三乙醇銨、硬脂酸單乙醇 胺、苯乙烯-丙烯酸共聚物的單乙醇胺、聚氧乙烯烧醚填酸 酯等陰離子性界面活性劑;聚氧基乙烯油醚、聚氧基乙烯 十二燒趟、聚氧基乙稀壬基苯趟、聚氧基乙埽烧醚填酸酯、 聚氧基乙烯山梨聚糖單硬脂酸酯、聚乙二醇單十二酸酯等 323842 110 201233734 非離子性界面活性劑;燒基四級敍鹽或此等的環氧乙院加 成物等陽離子性界面活性劑;烷基二曱基胺基醋酸甜菜鹼 等烷基甜菜鹼、烷基咪唑啉等兩性界面活性劑。.此.等界面 活性劑可獨使用,或將2種以上混合後使用,但未必侷限 於此等界面活性劑。 (光聚合性單體(光聚合性化合物)) 可藉由紫外線或熱等硬化而生成透明性樹脂的單體、 寡聚物’可列舉例如(曱基)丙烯酸甲酯、(曱基)丙烯酸乙 酯、(曱基)丙烯酸2-羥基乙酯、(曱基)丙烯酸2-羥基丙 酯、(甲基)丙烯酸環己酯、(曱基)丙烯酸羧基乙酯、聚 乙二醇二(曱基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸 酯、三乙二醇二(曱基)丙烯酸酯、三丙二醇二(曱基)丙烯 酸醋、三經曱基丙烷三(曱基)丙烯酸酯、新戊四醇三(甲基) 丙烯酸酯、1,6-己二醇二縮水甘油醚二(曱基)丙烯酸酯、 雙紛A二縮水甘油醚二(曱基)丙烯酸酯、新戊二醇二縮水 # 甘油醚二(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸 醋、二新戊四醇五(甲基)丙烯酸酯、(甲基)丙烯酸三環癸 醋、醋丙稀酸酯、羥曱基化三聚氰胺的(曱基)丙烯酸酯、(甲 基)丙稀酸環氧酯、胺酯丙烯酸酯等各種丙烯酸酯及曱基丙 烯酸酯、(曱基)丙烯酸、苯乙烯、醋酸乙烯酯、羥基乙基 乙烯醚、乙二醇二乙烯醚、新戊四醇三乙烯醚、(甲基)丙 稀酿胺、N一羥基曱基(曱基)丙烯醯胺、N-乙烯甲醯胺、丙 腈等’但未必侷限於此等化合物。此等光聚合性化合物可 獨使用’或必要時以任意比率將2種以上混合後使用。 323842 111 201233734 (光聚合起始劑) 光聚合起始劑可使用4-苯氧二氯乙醯苯、4-第三丁基 -二氯乙醯苯、二乙氧乙醯苯、1_(4-異丙基苯基)-2-羥基 -2-甲基丙烷-1-酮、1-羥基環己基苯基酮、2_曱基μ-ι^-(甲基硫基)本基]_2-嗎琳丙烧-嗣、2-(二甲基胺基)-2-[4-(曱基苯基)曱基]-卜[4-(4-嗎啉基)苯基]-1-丁酮或 2-苯甲基-2-二曱基胺基-1-(4-嗎琳苯基)-丁烧-1-酮等乙 酿苯類化合物;安息香、安息香甲醚、安息香***、安息 ® 香異丙醚或安息香二甲縮酮等安息香系化合物、二苯甲酮、 苯曱醯基苯曱酸、笨甲醯基苯曱酸曱酯、4-苯基二苯曱酮、 經基二苯曱酮、丙烯酸化二苯児酮、4-苯曱醯基-4,_甲基 二苯基硫化物或3,3’,4,4’ -四(第三丁基過氧羰基)二 本曱酮等二苯曱酮類化合物;β塞吨嗣(thioxanthone)、2-氣噻吨酮、2-曱基噻吨酮、異丙基噻吨酮、2, 4-二異丙基 嗟吨酮或2, 4-二乙基噻吨酮等噻吨酮系化合物;2, 4, 6-三 • 氣-s-三畊、2-苯基-4, 6-雙(三氯甲基)-s-三啡、2-(對- 甲氧基苯基)-4,6-雙(三氯曱基)-s-三畊、2-(對-曱苯基) 一4, 6-雙(三氯曱基)-s-三畊、2-胡椒基-4, 6-雙(三氣曱基) -3-三畊、2,4-雙(三氣曱基)-6-苯乙烯基-3-三畊、2-(萘 曱基-1-基)-4, 6-雙(三氯甲基)-s_三畊、2-(4-甲氧基萘曱 基一I-基)-4, 6-雙(三氣甲基)-s-三哄、2, 4-三氯甲基-(胡 椒基)-6-三畊或2, 4-三氯曱基-(4,-甲氧苯乙烯基)-6-三啡等三畊系化合物;乙酮、1-[9-乙基-6-(2-甲基苯曱醯 基)-9H-味唑基-3-基]-,1-(〇-乙醯肟)、1, 2-辛二酮,1-323842 112 201233734 [4-(苯硫基)-,2-(0-苯甲醯肟)]或;0-(乙醯基)-N-(l_ 苯基-2-侧氧基-2-(4’ -甲氧基-萘基)亞乙基)羥基胺等肟 酯類化合物;雙(2, 4, 6-三曱基苯甲醯基)苯基膦氧化物或 2, 4, 6-三曱基苯甲醯基二苯基膦氧化物等;9, 10-菲醌、莰 醌、乙基蒽醌等醌系化合物;硼酸酯系化合物;咔唑系化 合物;咪吐系化合物;或二茂鈦(t i tanocene)系化合物等。 此等光聚合起始劑可使用1種’或配合要求而以任意比率 將2種以上混合後使用。 在此等化合物之中,宜使含有選自乙醯苯系化合物、 膦系化合物、咪唾系化合物及两酯系化合物所形成之群組 中的至少1種以上的光聚合起始劑作為光聚合起始劑。也 因含有此等光聚合起始劑,而可使濾光片段的圖案形狀及 直線性更佳。 (增感劑) 增感劑可列舉如以查酮(chalcone)衍生物、二笨甲酿K mouth is known as monomethyl ether, dipropylene glycol monomethyl ether acetate, propylene glycol::: ethylene dipropylene glycol monotop, dipropylene glycol monopropyl ether, two early (four), - acetol, triacetin §, tripropylene glycol monobutyl Glycol singly, propylene glycol monodiacetate®, propylene glycol benzoquinone, alcohol monobutyl sulphate, propylene glycol monoethyl acetate vinegar, propylene glycol monobutyl hydrazine, propylene glycol monopropyl ether, propylene glycol monomethyl hydrazine, propylene glycol monomethyl ether acetate vinegar , propylene glycol, early oxime ether propionic acid vinegar, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, acetic acid 戍 1、 1, 1, acetic acid, butyl, acetaminophen, acetic acid, acetaminophen曰, Second Reading®, etc. These solvents may be used singly or in combination of two or more kinds at any ratio as necessary. Among them, in terms of good dispersibility, permeability, and coating of the coloring composition, it is preferable to use lactic acid ethyl lactic acid (IV), propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and ethylene glycol monoterpene. A diol acetate such as ether acetate or ethyl alcohol monoethyl ether acetate; an alcohol such as benzyl alcohol or diacetone alcohol or a ketone such as cyclohexanone. (Resin type dispersant) The resin type dispersant has a pigment affinity portion capable of adsorbing on a colorant and a portion having compatibility with a color carrier, and functions as a stable dispersion after being adsorbed on the colorant. A component on a colorant carrier of a colorant. The resin type dispersant may specifically be a polycarboxylate, a polyacrylic acid 323842 108 201233734, a polycarboxylic acid vinegar, an unsaturated polyamine, a poly-acid, a poly-acid (partial) amine salt, a polycarboxylate ammonium salt, a poly a carboxylic acid alkylamine salt, a polyoxyalkylene oxide, a long-chain polyamine guanamine compound, a trans-containing polycarboxylate or a modified substance thereof, a poly(lower alkylene imine), and a free carboxyl group An oily dispersant such as guanamine or a salt thereof formed by the reaction of a polyester, (mercapto)acrylic acid-styrene copolymer, (mercapto)acrylic acid-(meth)acrylate copolymer, styrene-maleic acid Water-soluble resin or water-soluble polymer compound such as copolymer, polyvinyl alcohol or polyvinylpyrrolidone, polyester-based, modified polypropionate-based, epoxidized/epoxypropane® addition compound, and phosphate ester system Wait. Although these dispersing agents may be used singly or in combination of two or more kinds, they are not necessarily limited to these compounds. Commercially available resin-type dispersing agents include Disperbyk-101, 103, 107, 108, 110, 111, 112, 116, 130, 140, 142, 154, 161, 162, 163, 164, which are manufactured by BYK Chemie Japan Co., Ltd. 165, 166, 167, 168, 170, 17 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti-Terra-U, 203, 204; or BYK-P104, P104S, 220S, 6919, 21116, 21324, 21407, 21715, etc. or Lactimon, Lactimon-WS or Bykumen, etc.; SOLSPERSE-made by Lubrizol, Japan 3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc.; EFKA-46, 47, 323842 109 201233734 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, manufactured by Ciba Japan Co., Ltd. 4055, 4060, 4080, 4400, 44 (Π, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 45, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc.; DISPARLON 3600Ν, DISPARLON 1850 made by Nanben Chemical Co., Ltd.; Ajisper-PAm, PB7U, PB82, PB822, PB824, etc. manufactured by Ajinomoto FineTech Co., Ltd. Used alone or in combination of two or more. ® Among these products, Disperbyk-108, 110, 11, 112, 116, 142, 180, 2000, 2001, manufactured by BYK Chemie Japan Co., Ltd., which is a resin-based pigment dispersant having an acidic functional group, or Lubrizol, Japan SOLKAPER-3000, 21000, 26000, 36600, 41000 or EFKA-4401, 4550 manufactured by Ciba, or DISPARLON 3600N, DISPARLON 1850, or Ajisper-PAlll manufactured by Ajinomoto FineTech Co., Ltd., but Not limited to such products. φ (surfactant) The surfactant may, for example, be sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, an alkali salt of a styrene-acrylic acid copolymer, sodium stearate, Sodium alkylnaphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanol of dodecyl sulfate, triethanolammonium dodecyl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer Anionic surfactant such as polyoxyethylene ether ether sulphonate; polyoxyethylene oleyl ether, polyoxyethylene decyl ruthenium, polyoxyethylene phenyl hydrazine, polyoxyethylene oxime ether Acid ester, polyoxyethylene sorbitan monostearate, polyethylene glycol monododecanoate, etc. 323842 110 201233734 Nonionic surfactant; burnt base four-salt salt or such epoxy a cationic surfactant such as an adduct; an amphoteric surfactant such as an alkylbetaine or an alkylimidazoline such as an alkyldidecylaminoacetate betaine. The surfactant may be used singly or in combination of two or more kinds, but it is not necessarily limited to such a surfactant. (Photopolymerizable monomer (photopolymerizable compound)) A monomer or oligomer which can be cured by ultraviolet light or heat to form a transparent resin, for example, (mercapto)methyl acrylate or (mercapto)acrylic acid Ethyl ester, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, carboxyethyl (meth) acrylate, polyethylene glycol bis (曱) Acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol bis(indenyl)acrylate, tripropylene glycol bis(indenyl)acrylic acid vinegar, tri-propyl mercaptopropane tris(曱) Acrylate, neopentyl alcohol tri(meth) acrylate, 1,6-hexanediol diglycidyl ether bis(indenyl) acrylate, bis-A diglycidyl ether bis(indenyl) acrylate , neopentyl glycol dihydrate # glyceryl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate vinegar, dipentaerythritol penta(meth)acrylate, (meth)acrylic acid癸 vinegar, vinegar acrylate, hydroxylated melamine (mercapto) acrylate, ( Various acrylates and mercaptoacrylates such as methyl acrylate epoxy esters and amine ester acrylates, (mercapto) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, Pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxyindenyl (decyl) acrylamide, N-vinylformamide, propionitrile, etc. 'but not necessarily limited to these compounds. These photopolymerizable compounds can be used alone or in combination of two or more kinds at any ratio as necessary. 323842 111 201233734 (Photopolymerization initiator) Photopolymerization initiator can be used 4-phenyl oxydichloro benzene benzene, 4-tert-butyl-dichloro ethane benzene, diethyl acetophenone benzene, 1 _ (4 -isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2 fluorenyl μ-ι^-(methylthio) benzyl]_2 -Mallin-propanone-oxime, 2-(dimethylamino)-2-[4-(nonylphenyl)indolyl]-bu [4-(4-morpholinyl)phenyl]-1- Butyl ketone compounds such as butanone or 2-benzyl-2-didecylamino-1-(4-morphinylphenyl)-butan-1-one; benzoin, benzoin methyl ether, benzoin ethyl ether, A benzoin compound such as benzoin or benzoin dimethyl ketal, benzophenone, benzoylbenzoic acid, benzoyl benzoyl phthalate, 4-phenyl benzophenone, Dibenzophenone, acrylated benzophenone, 4-phenylmercapto-4,-methyldiphenyl sulfide or 3,3',4,4'-tetra (t-butylperoxycarbonyl) Dibenzophenones such as diterpenoids; thioxanthone, 2-oxothione, 2-mercaptothioxanthone, isopropylthioxanthone, 2,4-diisopropyl Ketoxone Or a thioxanthone compound such as 2,4-diethylthioxanthone; 2, 4, 6-three • gas-s-three tillage, 2-phenyl-4,6-bis(trichloromethyl)- S-trimorphine, 2-(p-methoxyphenyl)-4,6-bis(trichloroindenyl)-s-trin, 2-(p-indolephenyl)-4,6-bis ( Trichloroindolyl)-s-three-plowing, 2-piperidin-4,6-bis(trioxanyl)-3-trinomethane, 2,4-bis(tris-methyl)-6-styryl -3-three tillage, 2-(naphthylfluorenyl-1-yl)-4,6-bis(trichloromethyl)-s_three tillage, 2-(4-methoxynaphthylquinone-I-group )-4,6-bis(trismethyl)-s-triterpene, 2,4-trichloromethyl-(piperidinyl)-6-three tillage or 2,4-trichloroindolyl-(4, 3-trimyl compound such as -methoxystyryl-6-trientin; ethyl ketone, 1-[9-ethyl-6-(2-methylphenylhydrazino)-9H-isoxazolyl-3- Base]-, 1-(〇-acetamidine), 1,2-octanedione, 1-323842 112 201233734 [4-(phenylthio)-, 2-(0-benzamide)] or; 2-(Ethyl)-N-(l-phenyl-2-oxo-2-(4'-methoxy-naphthyl)ethylidene) hydroxyamine and other oxime ester compounds; 4,6-trimercaptobenzylidene)phenylphosphine oxide or 2,4,6-trimercaptobenzamide Diphenylphosphine oxide, etc.; 9,10-phenanthrenequinone, anthracene, ethylhydrazine or the like anthraquinone compound; a borate ester compound; an oxazole compound; an oxime compound; or a titanocene ) a compound or the like. These photopolymerization initiators can be used in combination of two or more kinds at any ratio using one kind or combination. Among these compounds, at least one or more photopolymerization initiators containing a group selected from the group consisting of an acetophenone-based compound, a phosphine-based compound, an amino-salt compound, and a diester-based compound are preferably used as the light. Polymerization initiator. Also, since these photopolymerization initiators are contained, the pattern shape and linearity of the filter segments can be made better. (sensitizer) The sensitizer may, for example, be a chalcone derivative or a second stupid
丙酮(dibenzoylacetone)為代表的不飽和嗣類、笨甲美戈 樟腦醌(camphorquinone)等為代表的1,2~二酮衍生物、安A 1,2-dione derivative represented by acetone (dibenzoylacetone), which is represented by unsaturated steroids, camphorquinone, etc.
息香衍生物、苐衍生物、萘醌衍生物、蒽醌衍生物、 衍生物、噻噸(thioxanthene)衍生物、咕噸酮衍生物、嘆 噸酮衍生物、香豆素衍生物、酮香豆素衍生物、花青衍生 物、部花青(merocyanine)衍生物、氧雜菁(οχοη〇ι衍生物 等聚甲炔(polymethine)色素、吖啶(acridine)衍生物、〇丫 畊衍生物、噻吖畊衍生物、噚吖畊衍生物、吲哚啉衍生物 奠(azulene)衍生物、奠菁(azulenium)衍生物、方酸菁 323842 113 201233734 (squarylium)衍生物、卟琳(porphyrin)衍生物、四苯基卟 啉衍生物、三芳基甲烷衍生物、四苯甲卟吖畊衍生物、四 〇比哄°卜σ丫哄衍生物、欧青衍生物、四氣〇卜α丫哄 (tetraazaporphirazine)衍生物、四啥喔淋卟吖卩井衍生物、 萘花青衍生物、次萘花青衍生物、π比喃鏽(pyrylium)衍生 物、硫基°比喃鏽衍生物、四葉蘿芙靈(tetraphylline)衍生 物、輪稀(annulene)衍生物、螺旋β比喃衍生物、螺旋卩琴吖 哄衍生物、硫基螺旋11比喃衍生物、金屬芳醋烴錯合物、有 ® 機釕錯合物、或米歇爾酮(Michel le ketone)衍生物、聯ρ米 唾衍生物、α -醯氧酯、醯基膦氧化物、曱基苯基链醋酸、 苯甲基、9,10-菲醌、樟腦醌、乙基蒽醌、4, 4’ -二乙基異 酿紛(^8〇0111:1131〇?1^11〇116)、3,3’或4,4’-四(第三丁基 過氧羰基)二苯甲酮、4, 4’ -二乙基胺基二苯甲酮等。必要 時以任意比例使用2種以上的增感劑。 更具體而言,可列舉如大河原信等編著的「色素手冊」 φ (1986年’講談社)、大河原信等編著的「機能性色素的化 學」(1981年,CMC)、池森忠三朗等編著的「特殊機能材 料」(1986年,CMC)中所述之增感劑,但並不侷限於此等 化合物。又,其他也可含有顯示對於紫外線至近紅外線區 域之光可吸收的增感劑。 (多官能硫醇) 多官能硫醇可列舉例如己二硫醇、癸二硫醇、1,4- 丁 二醇雙硫基丙酸酯、1,4-丁二醇雙硫基甘油酸醋、乙二醇 雙硫基甘油酸酯、乙二醇雙硫基丙酸酯、三羥曱基丙烧三 323842 114 201233734 硫基甘油酸醋、三卿基丙燒三硫基丙酸醋、三"美乙 炫三(3-硫醇了酸自旨)、三鮮基时三⑶硫醇丁酸醋土)、 ^甲基城三(3-硫醇丙酸酯)、新細醇肆硫基甘油酸 S曰、新戍四醇肆硫基丙酸酯、新細醇肆(3_硫醇丙酸醋)、 二新戊四醇陸(3-硫醇丙酸酯)、三硫醇丙酸參(㈠基乙基) 異氰脲酸醋、1,4-二^基硫醇苯、2,4,6_三硫醇基土 畊、2-(Ν’Ν-二丁基胺基)_4,6_二硫醇基_s_三哄等。此等Aroma derivatives, anthraquinone derivatives, naphthoquinone derivatives, anthracene derivatives, derivatives, thioxanthene derivatives, xanthone derivatives, sinone derivatives, coumarin derivatives, ketones Bean derivatives, cyanine derivatives, melocyanine derivatives, oxyphthalocyanine (polymethine pigments such as οχοη〇ι derivatives, acridine derivatives, scorpion derivatives) , thiazolidine derivatives, sorghum derivatives, porphyrin derivatives, azulene derivatives, azulenium derivatives, squarylium 323842 113 201233734 (squarylium) derivatives, porphyrin Derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzidine derivatives, tetraterpene oxime σ 丫哄 derivatives, eucalyptus derivatives, tetragas 〇 丫哄 α丫哄(tetraazaporphirazine) derivative, tetraterpenoid derivative, naphthalocyanine derivative, hypophthalocyanine derivative, π-pyranium derivative, sulfur-based rust derivative, four-leaf Tetraphylline derivatives, annulene derivatives , a helical beta-pyran derivative, a helically-purine derivative, a sulfur-based helical 11-pyran derivative, a metal aromatic vinegar complex, a conjugated product, or a Michelle ketone Derivatives, hydrazine pi-salt derivatives, α-decyloxyesters, mercaptophosphine oxides, mercaptophenyl chain acetic acid, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylhydrazine, 4 , 4'-diethyl isosaccharide (^8〇0111:1131〇?1^11〇116), 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone And 4, 4'-diethylaminobenzophenone, etc., if necessary, two or more types of sensitizers are used in an arbitrary ratio. More specifically, the "Pigment Handbook" φ (produced by Ohara Shinto et al.) The sensitizer described in "Special Functional Materials" (1986, CMC), edited by "The Chemistry of Functional Pigments" (CMC, 1981, MIT, 1986) However, it is not limited to these compounds. Further, other sensitizers which exhibit light absorption from the ultraviolet to near-infrared region may be contained. (Polyfunctional thiols) Polyfunctional thiols may be used. Examples are hexanedithiol, decanedithiol, 1,4-butanediol dithiopropionate, 1,4-butanediol dithioglyceride, ethylene glycol dithioglyceride, Ethylene glycol dithiopropionate, trishydroxypropylpropane triglyceride 323842 114 201233734 thioglycerate glycerin, succinyl propyl trithiopropionate, three " Acid from the purpose), Sanshenji three (3) thiol butyrate vinegar), methyl group tris(3-thiol propionate), neosodium thioglycolate S曰, neodymidine Sodium thiopropionate, neodymium oxime (3_thiol propionate), dipentaerythritol (3-thiol propionate), trithiol propionate ((1)ylethyl) Cyanuric acid vinegar, 1,4-diyl mercaptan benzene, 2,4,6-trithiol-based soil, 2-(Ν'Ν-dibutylamino)_4,6-dithiol _s_三哄 and so on. Such
多官能硫醇可單獨使用!種’必要時可以任意比率將2以 上混合後使用。 (紫外線吸收劑) 紫外線吸收劑可列舉例如2—[4_[(2_羥基_3_(十二烷 及及十二烷基)氧基丙基)氧基]_2_羥基苯基]_4, 6—雙 (2’4-二甲基苯基)-1,3,5_三啡、2_(2—羥基一4_[1_辛基氧 基羰基乙氧基]苯基)-4, 6-雙(4-苯基苯基)_丨,3, 5_三畊等 羥基苯基三哄類;2-(5-曱基-2-羥基苯基)苯甲***、 2-(2H-苯甲基二唑-2-基)-4, 6-雙(1-甲基-1一苯基乙基)一 酚、2-(3-第三丁基-5-曱基-2-羥基苯基)-5—氣苯曱***等 本曱二嗤類,2, 4-二經基苯二曱_、2一經基_4_辛氧基苯二 甲酮、2,2’,4,4’ _四羥基苯甲二酮等苯二曱酮類;苯基 柳酸醋、對-第二丁基苯基柳酸醋等柳酸醋類;乙基_2_氰 基-3, 3 _ —本基丙烯酸醋等氛基丙稀酸醋類;2, 2, 6, 6- 四曱基哌啶-1-氡基(三丙酮-胺基氧基)、雙(2, 2, 6, 6-四甲基-4-哌啶基)-癸二酸酯、聚四丁基) 胺基]-1,3, 5-三畊-2, 4-二基][(2, 2, 6, 6-四曱基-4-哌啶 323842 115 201233734 基)胺基]等受阻胺類等。此等紫外線吸收劑可單獨使用i 種’必要時可以任意比率將2種以上混合後使用。 (禁止聚合劑) 禁止聚合劑可列舉例如甲基氫醌、第三丁基氫醌、 2, 5-二-第三丁基氫酿、4-苯酿^、4-甲氧基紛、4-甲氧基-1一 萘酴、第三丁基兒茶紛等衍生物及紛化合物;啡嗔哄、雙 -(1-二甲基苯甲基)啡噻畊、3, 7-二辛基啡噻哄等胺化合 物;二丁基二硫代胺甲酸銅、二乙基二硫代胺甲酸銅、二 ® 乙基二硫代胺曱酸錳、二苯基二硫代胺曱酸錳等銅及錳鹽 化合物,4-亞確基朌、N-亞确基二苯基胺、N-亞硝基環己 基羥基胺、N-亞硝基苯基羥基胺等亞硝基化合物及其銨或 鋁鹽等。此等禁止聚合劑可單獨使用1種,必要時可以任 意比率將2種以上混合後使用。 (抗氧化劑) 「抗氧化劑」只要是具有紫外線吸收功能、補足自由 • 基的功能或分解過氧化物的功能之化合物即可,具體上, 可使用受阻酚系、受阻胺系、磷系、硫系、笨甲***系、 二苯曱酮系、羥基胺系、柳酸酯系及三畊系的化合物作為 抗氧化劑,可使用已知的紫外線吸收劑、抗氧化劑等。此 專抗氧化劑可单獨使用1種,必要時可以任意比率將2種 以上混合後使用。 就可兼具塗膜的穿透率與感度而言,此等抗氧化劑之 中’宜為受阻酚系抗氧化劑、受阻胺系抗氧化劑、磷系抗 氧化劑或硫系抗氧化劑。同時,是以受阻酚系抗氧化劑、 323842 116 201233734 受阻胺系抗氧化劑或磷系抗氧化劑時較佳。 (胺系化合物) ▲胺系化合物可列舉如三乙醇胺、甲基二乙醇胺、三異 丙醇胺、4-二曱基胺基苯曱酸甲醋、4_二甲基胺基笨甲酸 乙酉曰4-—甲基胺基苯曱暖異戊g旨、2_二甲基胺基苯甲酸 乙酉曰、4-—曱基胺基苯甲酸2__乙己酯及N,N_二曱基對曱苯 胺等。此等胺系化合物可單獨使用i種,必要時可以任意 比率將2種以上混合後使用。 •(整平劑) 整平劑宜為主鏈上具有聚醚結構或聚酯結構的二甲 基聚石夕氧燒。主鏈上具有聚喊結構的二甲基聚石夕氧烧之具 體例"T列舉如東麗道康寧(T〇ray d〇w c〇rning)公司製的 FZ-2122、BYK chemie公司製的BYK_333等。主鏈上具有Multifunctional thiols can be used alone! If necessary, mix 2 or more at any ratio and use it. (Ultraviolet absorber) The ultraviolet absorber may, for example, be 2-[4_[(2_hydroxy_3_(dodecane and dodecyl)oxypropyl)oxy]_2-hydroxyphenyl]_4, 6 - bis(2'4-dimethylphenyl)-1,3,5-trimorphine, 2-(2-hydroxy-4-yl-[1-octyloxycarbonylethoxy]phenyl)-4,6- Bis(4-phenylphenyl)-indole, 3, 5_three tillage and other hydroxyphenyl triterpenoids; 2-(5-fluorenyl-2-hydroxyphenyl)benzotriazole, 2-(2H- Benzyldiazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl) monophenol, 2-(3-tert-butyl-5-fluorenyl-2-hydroxyl Phenyl)-5-gas benzotriazole and other diterpenoids, 2, 4-diphenyl benzoquinone _, 2-mono-based -4-xyoctyl phthalone, 2, 2', 4 , 4' _ tetrahydroxybenzoedione and other benzodiazepines; phenyl lauric acid vinegar, p-t-butylphenyl lauric acid vinegar and other vinegar vinegar; ethyl 2 - cyano-3, 3 _ — base acrylic vinegar and other aromatic acetonic acid; 2, 2, 6, 6-tetramethylene piperidin-1-yl (triacetone-aminooxy), double (2, 2, 6, 6-tetramethyl-4-piperidinyl)-sebacate, polytetrabutyl)amino]-1,3, 5-trinyl-2,4-diyl][(2, 2 , 6, 6- Yue-4-piperidinyl 323 842 115 201 233 734 yl) amino] hindered amine and the like. These ultraviolet absorbers can be used singly or in combination of two or more kinds at any ratio as necessary. (Polymering agent is prohibited) The polymerization inhibitor is exemplified by, for example, methylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydrogen, 4-benzene-branched, 4-methoxyl, 4 -Methoxy-1-naphthoquinone, tributyl catechin derivatives and compounds; morphine, bis-(1-dimethylbenzyl) thiophene, 3, 7-dioctine Amine compounds such as phenylethione; copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, manganese diphenyldithiocarbamate And other nitroso compounds such as copper and manganese salt compounds, 4-arylene, N-arylene diphenylamine, N-nitrosocyclohexylhydroxylamine, N-nitrosophenylhydroxylamine, and the like Ammonium or aluminum salts, etc. These non-polymerization agents may be used singly or in combination of two or more kinds in any ratio if necessary. (Antioxidant) The "antioxidant" may be a compound having a function of absorbing ultraviolet light, supplementing the function of a radical, or decomposing a peroxide. Specifically, a hindered phenol system, a hindered amine system, a phosphorus system, or a sulfur may be used. As the antioxidant, a known ultraviolet absorber, an antioxidant, or the like can be used as the antioxidant of the compound of the trimethoprim type, the benzophenone type, the hydroxylamine type, the salicylate type, and the tri-till type. This specific antioxidant can be used alone or in combination of two or more kinds at any ratio if necessary. In view of the transmittance and sensitivity of the coating film, the antioxidants are preferably hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants or sulfur-based antioxidants. At the same time, it is preferably a hindered phenol-based antioxidant, a 323842 116 201233734 hindered amine-based antioxidant or a phosphorus-based antioxidant. (Amine compound) ▲ The amine compound may, for example, be triethanolamine, methyldiethanolamine, triisopropanolamine, 4-didecylaminobenzoic acid methyl vinegar or 4-dimethylamino benzoic acid acetamidine 4-methylaminobenzoquinone warm isoamyl, 2-dimethylaminobenzoic acid ethyl acetophenone, 4-nonylaminobenzoic acid 2_-ethylhexyl ester and N,N-dimercaptopurine Aniline and the like. These amine compounds may be used singly or in combination of two or more kinds in any ratio as necessary. • (Leveling agent) The leveling agent should preferably be a dimethyl polyoxo-oxygenate having a polyether structure or a polyester structure in the main chain. A specific example of dimethyl polychlorite with a polyphonic structure in the main chain is exemplified by FZ-2122 manufactured by Toray ray d〇wc〇rning and BYK_333 manufactured by BYK Chemie. Wait. On the main chain
聚8曰尨構的二曱基聚矽氧烧之具體例,可列舉如MKSpecific examples of the polyfluorene-based polyfluorene-oxygen grouping can be exemplified as MK.
Chemie公司製的BYK_310、BYK-370等。也可併用主鏈上 鲁具有_結構的二甲基㈣氧烧與主鏈上具有聚醋結構的 二甲基聚矽氧烷。 作為整平劑特佳者,可使用分子内所有具有疏水基與 親水基的界面活性劑的一種’且即使不具有親水基對水之 /合解性小,而添加在著色組成物中時,可具有其表面張力 能偏低的特徵’並且不論表面張力能偏低與否對於玻璃基 板也有良好的濕潤性,並宜使用不因出現起泡而造成塗膜 的缺陷之添加量時可充分抑制靜電性的整平劑。具有此種 良好特性的整平劑,宜使用具有聚烷基氧化物單元的二甲 323842 117 201233734 基聚矽氧烷。作為聚環烯氧化物單元, 元、聚丙烯氧化物單元,二甲基聚砂氧燒^,氧化物單 乙烯氧化物單元與聚丙烯氧化物單^ τ同時具有聚 又’聚環軌化物單元與二曱基聚 態,可以是使聚環烯氧化物單元結合在_ 、、、σ σ形 nr仕一曱基聚矽氣 重複皁元上之錢型、結合在二ψ基聚錢㈣ 上的末端之末収質型、與二甲絲錢妓互重複結合 的直鏈狀W合型的任-種形態。具有聚環烯氧化物單 7G的二曱基㈣纽,在市面上已有東財料公司的製 品,例如 FZ-211G、FZ-2122、FZ-2130、FZ_2166、fz_2191、 FZ-2203、FZ-22G7 ’但並不侷限於等產品。整平劑可單獨 使用1種’必要時可以任意比率將2種以上混合後使用。 在整平劑中,也可補助性的加入陰離子性、陽離子 性、非離子性或兩性的界面活性劑。界面活性劑也可混合 2種以上後使用。可補助性加入整平劑中的陰離子性界面 活性劑,可列舉如聚氧乙烯烷醚硫酸鹽、十二烷基苯磺酸 鈉、苯乙烯-丙烯酸共聚物的鹼鹽、烷基萘磺酸鈉、烷基二 苯醚二磺酸鈉、十二烷基硫酸單乙醇胺、十二烷基硫酸三 乙醇胺、十二烧基硫酸銨、硬脂酸單乙醇胺、硬脂酸鈉、 十一烧基硫酸納、苯乙烯-丙烯酸共聚物的單乙醇胺、聚氧 乙烯烷醚磷酸酯等。 可補助性加入整平劑中的陽離子性界面活性劑,可列 舉如烷基四級銨鹽或此等的環氧乙烷加成物。可補助性加 入整平劑中的非離子性界面活性劑,可列舉如聚氧乙烯烷 323842 118 201233734 油醚、聚氧乙烯十二烷醚、聚氧乙烯壬基苯醚、聚氧乙烯 烧醚碌酸醋、聚氧乙稀山梨聚糖單硬脂酸醋、聚氧乙婦甘 油單十二烧醋等;可列舉如烷基二甲基胺基醋酸甜菜鹼、 烷基咪唑林兩性界面活性劑等,又,氟系或矽酮類的界面 活性劑。 (硬化劑、硬化促進劑) 作為硬化劑’酚系樹脂、胺系化合物、酸酐、活性g旨、 魏酸類化合物、磺酸類化合物等係有效者,但並不侷限於 •此等化合物’只要可與熱硬化性樹脂反應而得的生成物, 均可作為硬化劑使用。又,在此等硬化劑之中’宜為1分 子中具有2個以上酚性羥基的化合物、胺系硬化劑。作為 上述硬化促進劑,可使用例如胺化合物(例如,二氰二醯 胺、苯曱基二曱基胺、4-(二甲基胺基)-N,N-二曱基苯甲 胺、4-曱氧基-n,N-二曱基苯曱胺、4-曱基-N,N-二曱基苯 曱胺等)、四級銨鹽合物(例如,三乙基苯曱基氯化銨等)、 • 嵌段異氰酸酯化合物(例如,二曱基胺等)、咪唑衍生物二 環式脒化合物及其鹽(例如,咪唑、2-曱基咪唑、2-乙基咪 唑、2-乙基-4-曱基咪唑、2-苯基咪唑、4-苯基咪唑、卜 氰基乙基-2-苯基咪唑、i-(2-氰基乙基)-2-乙基-4-曱基咪 唑等)、磷化合物(例如,三苯基膦等)、胍胺(guanamine) 化合物(例如,三聚氰胺、脈胺、乙醢脈胺、本代二水氣胺 等)、S-三π井衍生物(例如,2, 4-二胺基甲基丙烯醯胺基 氧基乙基-S-三啡、2-乙烯基-2, 4-二胺基三嗪、2_乙烯 基-4, 6-二胺基_s_三畊/三聚氰酸加成物、2, 4-二胺基-6- 323842 119 201233734 曱基丙烯醯胺基氧基乙基-s-三畊/三聚氰酸加成物等) 等。此等硬化促進劑可單獨使用1種,也可2種以上併用。 (貯存安定劑) 貯存安定劑可列舉例如2,6-雙(1,1-二曱基乙基)-4-曱基酚、新戊四醇肆[3-(3,5-二-第三丁基-4-羥基苯基) 丙酸酯]、2,4-雙-(正辛基硫基)-6-(4-羥基-3, 5-二-第三 丁基苯胺)-1,3,5-三畊、第三丁基。比咯兒茶酚等受阻酚 類;四乙基膦、三乙基膦、四苯基膦等有機膦系;二曱基 ® 二硫代磷酸辞、二丙基二硫代磷酸辞、二丁基二硫代磷酸 鉬等亞磷酸鹽系;十二烷基硫化物、苯曱噻吩等硫系;苯 曱基三曱基氯化物、二乙基羥基胺等四級胺氯化物;乳酸、 草酸等有機酸及其甲醚等。此等貯存安定劑可單獨使用1 種,必要時可以任意比率將2種以上混合後使用。 (密著提昇劑) 密著提昇劑可列舉例如乙烯參(/5-曱氧基乙氧基)矽 φ 烷、乙烯基乙氧矽烷、乙烯基三曱氧矽烷等乙烯基矽烷類; T-曱基丙烯醯氧基丙烯三曱氧矽烷等(曱基)丙烯矽烷 類;点-(3, 4-環氧基環己基)乙基三甲氧矽烷、卢-(3,4-環氧基環己基)甲基三曱氧矽烷、点-(3, 4-環氧基環己基) 乙基三乙氧矽烷、卢-(3, 4-環氧基環己基)曱基三乙氧矽 烷、T-縮水甘油氧丙基曱氧矽烷等環氧矽烷;7-縮水甘 油氧丙基乙氧矽烷等環氧矽烷類;N-;8-(胺基乙基)r_胺 基丙基三甲氧矽烷、N-yS-(胺基乙基)T-胺基丙基三乙氧 矽烷、N-/3-(胺基乙基)τ-胺基丙基曱基二乙氧矽烷、r- 323842 120 201233734 胺基丙基三乙氧矽烷、胺基丙基三甲氧矽烷、N-苯基-r -胺基丙基三曱氧矽烷、Ν-苯基-r -胺基丙基三乙氧矽烷 等胺基矽烷類;r-硫醇丙基三曱氧矽烷、r-硫醇丙基三 乙氧矽烷等硫基矽烷類等矽烷耦合劑。此等密著提昇劑可 單獨使用1種,必要時可以任意比率將2種以上混合後使 用。 [彩色濾光片] 說明關於第7實施態樣的彩色濾光片。 •[第7實施態樣] (彩色濾光片) 第7實施態樣的彩色濾光片是使用上述的彩色濾光片 用著色組成物而形成。根據第7實施態樣可提供亮度、對 比度比優異的高精細彩色濾光片。第7實施態樣的彩色濾 光片,可使用於彩色液晶顯示器及彩色照相管元件等。 彩色濾光片具備紅色濾光片段、綠色濾光片段及藍色 φ 濾光片段。其中的紅色濾光片段,是由上述的著色組成物 形成。又,彩色濾光片也可具備洋紅色濾光片段、氰(cyano) 色濾光片段及黃色濾光片段。 彩色濾光片一般是在透明基板上具備上述濾光片段。 透明基板可使用鈉鹼石灰玻璃、低鹼硼矽酸玻璃、無鹼鋁 硼矽酸玻璃等玻璃板或聚碳酸酯、聚曱基丙烯酸甲酯、聚 對苯二曱酸乙二酯等樹脂板。又,也可在玻璃板或樹脂皮 的表面上,形成由氧化銦、氧化錫等形成的透明電極,用 於平板化後的液晶驅動。 323842 121 201233734 濾光片段的乾燥膜厚度宜為0. 2至10 ,以〇. 2至 5em較佳。在使塗膜乾燥時,也可使用減壓乾燥機、對流 烤箱(convection oven)、IR烤箱、加熱板等。 綠色濾光片段可使用含有綠色顏料與著色劑載體的 一般綠色著色組成物而形成。綠色顏料可使用例如C. I.顏 料綠 7、10、36、37 及 58 等。 又,綠色著色組成物也可併用黃色顏料或黃色染料。 可併用的黃色顏料可列舉如C.I.顏料黃1、2、3、4、5、6、 • 10、12、13、14、15、16、17、18、24、3卜 32、34、35、 35 : 1、36、36 :卜 37、37 : 1、40、42、43、53、55、60、 6卜 62、63、65、73、74、77、8卜 83、93、94、95、97、 98、100、1(U、104、106、108、109、110、113、114、115、 116 、 117 、 118 、 119 、 120 、 123 、 126 、 127 、 128 、 129 、 138 、 139 、 147 、 150 、 15卜 152 、 153 、 154 、 155 、 156 、 16卜 162、164、166、167、168、169、170、17卜 172、 173 、 174 、 175 、 176 、 177 、 179 、 180 、 18卜 182 、 185 、 187 、 188 、 193 、 194 、 198 、 199 、 213 、 214 、 218 、 219 、 220或221等黃色顏料。又,可併用的黃色染料,可列舉 如啥琳系、單偶氮系(咐咬酮系、巴比妥酸系、金屬錯合物 系等)、二偶氮系、次曱基系等。 藍色濾光片段可使用含有藍色顏料與著色劑載體的 一般藍色著色組成物而形成。藍色顏料可使用例如c. I.顏 料藍 15、15 :卜 15 : 2、15 : 3、15 : 4、15 : 6、16、22、 60、64等。又,藍色著色組成物中也可併用紫色顏料。可 323842 122 201233734 併用的紫色顏料可列Γ 夕』舉如C. I.顏料紫1、19、23、27、29、 e 乂2格37、4°、42、5〇等紫色顏料。又’也可使用呈現 ^或i色的驗_、酸性染料之造鹽化合物。在使用 =科時,以耐熱性與亮度而言,宜為㈣系染料。 (彩色遽光片的製造方法) 彩色濾光片可藉由印刷法或光蚀刻微影法製造。 =刷法形成濾光片段時,因只要將調製作為印刷油 成物重複進行印刷與乾燥即可圖案化,故作為 =色滤光片的製造法,是低成本且量產性優異。並且,由 圖案之印刷,印刷時滑度的微細 布毯上乾燥、固化的組成。=油墨不會在印刷的版上或 墨的流動性,也可調整分也可望在印刷機上控制油 若藉由絲關料_墨黏度。 上述溶劑顯像型或驗顯像型=光片段時,可將調製作為 佈在透明基板上,使_ =塗佈法、親塗法等塗佈方法塗 土板上使其乾無膜厚為〇2至 至5抑。必要時在乾燥的 ^ϋ*2 接觸狀態設置具有預透過與此麟觸或以非 去除未硬化部份以形成所要求等將顯像液噴霧後 二樣的重複操作後’即可製造彩色遽光片。並且,必3 :=加熱:促進著色阻劑材的聚合。藉夺 技術法’可製造比上述印刷法較高精度的彩色遽先片。 323842 123 201233734 然後’浸潰在溶#!麵顯像液巾,或財料將顯像 液喷霧後去除未硬化部份以形成期望的圖案後,即可形成 滤光片&。並且必要時可施予加熱,以促進顯像而形成的 滤光片段之聚合。藉由光餘刻微影技術法,可以製造精度 高於上述印刷法的濾光片段。 在顯像時,可使用碳酸鈉、氫氧化鈉等的水溶液作為 鹼顯像液,也可使用二甲基笨甲胺、三乙醇胺等有機鹼。 又,在顯像液中,也可添加消泡劑或界面活性劑。作為顯 •像處理方法,可適用淋浴顯像法、喷霧顯像法、浸潰顯像 法、覆液(pudd 1 e)顯像法等。 而且,為了提高紫外線曝光感度,也可在上述爹色阻 劑蜜佈乾燥後,藉由水溶性或鹼水溶性樹脂(例如聚乙烯醇 戒水溶性丙烯酸樹脂等)塗佈乾燥後形成防止因氧而造成 陴礙聚合的膜後,進行紫外線曝光。 彩色濾光片可藉由上述方法之外的電著法、轉印法等 φ 製造,可使用上述的著色組成物或感光性著色組成物的任 /方法。而且,電著法是利用已在基板上形成的透明導電 膜,藉由膠體粒子的電泳而在透明導電膜上電著形成各色 的濾光片段而製造彩色濾光片的方法。又,轉印法是預先 在剥離性的轉印基片表面上形成濾光片段,再使此據光片 段轉印到期望的基板上之方法。 上述的著色組成物可使用於任一方法,但,尤其是第 5及6的實施態樣的著組成物最適用於光蝕刻微影法。 在透明基板或反射基板上形成各色的濾光片段前,可 323^42 124 201233734 預先形成黑色矩陣。作為黑色矩陣可使用鉻或鉻/氧化鉻的 多層膜、氮化鈦等無機膜,或分散有遮光劑的樹脂膜,但 並不侷限於此等膜。又,也可在上述透明基板或反射基板 上預先形成薄膜電晶體(TFT),然後再形成各色的濾光片 段。並且在彩色濾光片上,必要時可形成保護膜、透明導 電膜、柱狀間隔片、液晶配向膜等。 彩色遽光片可使用密封劑而與基板對向貼合,使液晶 由设在密封部份的注入口注入後,將注入口密封,必要時 使偏光膜或位相差膜貼合在基板的外侧後,而製造液晶顯 示器。 這種液晶顯示器可使用於使用扭轉向列(t w i s t e d nematic(TN))、超級扭轉向列(STN)、面内切換(ips)、垂 直定向(VA)、光學補償彎曲(〇CB)等彩色濾光片而彩色化的 液晶顯示模式中。 [實施例]BYK_310, BYK-370, etc. manufactured by Chemie. It is also possible to use a dimethyl (tetra)oxy group having a _ structure in the main chain and a dimethyl polyoxyalkylene having a polyacetate structure in the main chain. As a particularly preferred leveling agent, one of all surfactants having a hydrophobic group and a hydrophilic group in the molecule can be used, and even if it does not have a hydrophilic group, it is small in water/complexity, and is added to the coloring composition. It can have a characteristic that its surface tension energy is low, and it has good wettability to the glass substrate regardless of whether the surface tension energy is low or not, and it is preferable to use it to sufficiently suppress the addition amount of the coating film which is not caused by the occurrence of foaming. An electrostatic leveling agent. For the leveling agent having such good characteristics, it is preferred to use dimethyl 323842 117 201233734-based polyoxyalkylene having a polyalkyl oxide unit. As a polycycloolefin oxide unit, a polysiloxane oxide unit, a dimethyl polyoxa oxide, an oxide monoethylene oxide unit and a polypropylene oxide mono τ have a poly-polycyclic ortho-organized unit The polymorphism with the diterpene group may be a combination of the polycycloolefin oxide unit on the _, , σ σ-shaped nr-based polyfluorene-repeating soap element, combined with the diterpene group (four) At the end of the end of the end, the type of the straight-chain W-type which is recombined with the dimethoate. A dimercapto (four) nucleus with polycycloolefin oxide single 7G, which has been manufactured by Dongcai Materials Co., Ltd., such as FZ-211G, FZ-2122, FZ-2130, FZ_2166, fz_2191, FZ-2203, FZ- 22G7 'but not limited to other products. One type of the leveling agent may be used singly. When necessary, two or more types may be used in combination at any ratio. In the leveling agent, an anionic, cationic, nonionic or amphoteric surfactant may also be added. The surfactant may be used in combination of two or more kinds. The anionic surfactant which can be added to the leveling agent can be supplemented, for example, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, alkylnaphthalenesulfonic acid Sodium, sodium alkyl diphenyl ether disulfonate, dodecyl sulfate monoethanolamine, dodecyl sulfate triethanolamine, dodecyl ammonium sulfate, stearic acid monoethanolamine, sodium stearate, eleven alkyl Sodium sulfate, styrene-acrylic acid copolymer monoethanolamine, polyoxyethylene alkyl ether phosphate, and the like. The cationic surfactant which can be added to the leveling agent can be supplemented, for example, an alkyl quaternary ammonium salt or an ethylene oxide adduct thereof. The nonionic surfactant which can be added to the leveling agent can be supplemented, for example, polyoxyethylene alkane 323842 118 201233734 oil ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene ether ether Sulphate, polyoxyethylene sorbitan monostearate, polyoxyethylene glycerol, single siu vinegar, etc.; for example, alkyl dimethylamino acetic acid betaine, alkyl imidazoline amphoteric interfacial activity A surfactant or the like, and a surfactant of a fluorine- or anthrone. (hardener, hardening accelerator) As a curing agent, a phenolic resin, an amine compound, an acid anhydride, an active g, a sulphate compound, a sulfonic acid compound, etc. are effective, but it is not limited to these compounds. The product obtained by the reaction with the thermosetting resin can be used as a curing agent. Further, among these curing agents, a compound having two or more phenolic hydroxyl groups and an amine curing agent in one molecule is preferable. As the hardening accelerator, for example, an amine compound (for example, dicyandiamide, benzoguanidinylamine, 4-(dimethylamino)-N,N-dimercaptobenzylamine, 4 can be used. - alkoxy-n,N-dimercaptobenzamine, 4-mercapto-N,N-dimercaptobenzamine, etc.), quaternary ammonium salt (for example, triethylphenylhydrazine chloride Ammonium, etc.), • Block isocyanate compounds (eg, dimethylamine, etc.), imidazole derivatives, bicyclic guanidine compounds, and salts thereof (eg, imidazole, 2-mercaptoimidazole, 2-ethylimidazole, 2- Ethyl-4-mercaptoimidazole, 2-phenylimidazole, 4-phenylimidazole, cyanoethyl-2-phenylimidazole, i-(2-cyanoethyl)-2-ethyl-4 - mercapto imidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, amide, acetaminophen, present dihydrate, etc.), S-three π well derivative (for example, 2, 4-diaminomethyl methacrylamidooxyethyl-S-trimorphine, 2-vinyl-2,4-diaminotriazine, 2-vinyl) 4, 6-diamino _s_three tillage / cyanuric acid adduct, 2, 4-diamino-6- 323842 119 20123 3734 mercapto acrylamide ethoxyethyl-s-three tillage / cyanuric acid adduct, etc.). These hardening accelerators may be used alone or in combination of two or more. (Storage stabilizer) The storage stabilizer may, for example, be 2,6-bis(1,1-didecylethyl)-4-nonylphenol, neopentyl quinone [3-(3,5-di- Tributyl-4-hydroxyphenyl)propionate], 2,4-bis-(n-octylthio)-6-(4-hydroxy-3, 5-di-t-butylaniline)-1 , 3,5-three tillage, third butyl. Hindered phenols such as catechol; organophosphines such as tetraethylphosphine, triethylphosphine, tetraphenylphosphine; dimercapto® dithiophosphoric acid, dipropyl dithiophosphoric acid, dibutyl a phosphite such as molybdenum dithiophosphate; a sulfur system such as dodecyl sulfide or benzoquinone; a quaternary amine chloride such as phenylmercaptotriyl chloride or diethylhydroxylamine; lactic acid or oxalic acid Such as organic acids and their methyl ethers. These storage stabilizers may be used singly or in combination of two or more kinds at any ratio if necessary. (Adhesive Lifting Agent) Examples of the adhesion promoting agent include vinyl decanes such as ethylene ginate (/5-decyloxyethoxy) 矽 φ alkane, vinyl ethoxy decane, and vinyl trioxoxane; T- Mercapto propylene oxy propylene trioxane oxane (mercapto) propylene decane; p-(3, 4-epoxycyclohexyl)ethyltrimethoxy decane, lutene (3,4-epoxy ring) Hexyl)methyltrioxoxane, p-(3,4-epoxycyclohexyl)ethyltriethoxydecane, lu-(3,4-epoxycyclohexyl)decyltriethoxydecane, T - an epoxy decane such as glycidyl oxypropyl oxoxane; an epoxy decane such as 7-glycidoxypropyl ethoxy hydride; N-; 8-(aminoethyl)r-aminopropyltrimethoxy decane , N-yS-(Aminoethyl)T-aminopropyltriethoxyoxane, N-/3-(Aminoethyl)t-aminopropylmercaptodiethoxyoxane, r-323842 120 201233734 Aminopropyl triethoxy decane, aminopropyl trimethoxy decane, N-phenyl-r-aminopropyl trioxoxane, fluorenyl-phenyl-r-aminopropyl triethoxy decane, etc. Amino decanes; r-thiol propyl trioxane, r-thiol propyl triethoxy hydrazine a decane coupling agent such as a thiodecane such as an alkane. These adhesion enhancers may be used singly or in combination of two or more kinds at any ratio if necessary. [Color Filter] A color filter according to the seventh embodiment will be described. [Seventh embodiment] (Color filter) The color filter of the seventh embodiment is formed by using the coloring composition for a color filter described above. According to the seventh embodiment, a high-definition color filter excellent in luminance and contrast ratio can be provided. The color filter of the seventh embodiment can be used for a color liquid crystal display, a color photographic tube element, or the like. The color filter has a red filter segment, a green filter segment, and a blue φ filter segment. The red filter segment is formed by the coloring composition described above. Further, the color filter may also have a magenta filter segment, a cyan (cyano) filter segment, and a yellow filter segment. The color filter generally has the above-described filter segments on a transparent substrate. The transparent substrate may be a glass plate such as soda lime glass, low alkali borosilicate glass or alkali-free aluminum boron borosilicate glass, or a resin plate such as polycarbonate, polymethyl methacrylate or polyethylene terephthalate. . Further, a transparent electrode made of indium oxide, tin oxide or the like may be formed on the surface of the glass plate or the resin skin to be used for liquid crystal driving after flattening. 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。. When the coating film is dried, a vacuum dryer, a convection oven, an IR oven, a heating plate, or the like can also be used. The green filter fragments can be formed using a generally green coloring composition comprising a green pigment and a colorant carrier. As the green pigment, for example, C.I. Pigment Green 7, 7, 36, 37, and 58 can be used. Further, a yellow pigment or a yellow dye may be used in combination with the green coloring composition. The yellow pigments which can be used together are, for example, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 3, 32, 34, 35, 35 : 1, 36, 36 : Bu 37, 37 : 1, 40, 42, 43, 53, 55, 60, 6 Bu 62, 63, 65, 73, 74, 77, 8 Bu 83, 93, 94, 95 , 97, 98, 100, 1 (U, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139 , 147, 150, 15 152, 153, 154, 155, 156, 16 162, 164, 166, 167, 168, 169, 170, 17 172, 173, 174, 175, 176, 177, 179, 180 , yellow pigment such as 18 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220 or 221. Further, a yellow dye which can be used in combination, for example, 啥琳系,单单An azo system (an acetophenone system, a barbituric acid system, a metal complex system, etc.), a diazo system, a sulfhydryl group, etc. A blue filter component can be used with a blue pigment and a colorant carrier. General blue coloring Formed as a composition. For blue pigment, for example, c. I. Pigment Blue 15, 15 : Bu 15 : 2, 15 : 3, 15 : 4, 15 : 6, 16, 22, 60, 64, etc. The purple pigment can also be used in combination with the coloring composition. The purple pigment which can be used in combination with 323842 122 201233734 can be listed as CI pigment purple 1, 19, 23, 27, 29, e 乂 2 grid 37, 4°, 42, 5 〇 and other purple pigments. Also 'can be used to show the ^ or i color test _, acid dye salt compound. When using = section, in terms of heat resistance and brightness, it should be (4) dye. Method for manufacturing light sheet) The color filter can be produced by a printing method or a photo-etching lithography method. When the filter is formed by a brush method, the pattern can be repeatedly printed and dried by using the preparation as a printing oil. Therefore, it is a manufacturing method of a color filter, which is excellent in low cost and high in mass productivity, and is a composition which is dried and solidified by a pattern printing and a fine cloth having a smoothness during printing. The fluidity of the plate or ink can also be adjusted. It is also expected to control the oil on the printing machine. When the above-mentioned solvent development type or inspection image type = light segment, the preparation may be performed on a transparent substrate, and the coating method such as coating method or affinity coating method may be applied to the soil plate to make it dry. The thickness is from 2 to 5. If necessary, in the dry state, the contact state is set to have a pre-transmission with the lining or to remove the uncured portion to form the desired repetitive operation of the developer. Light film. Also, it must be 3: = heating: promoting the polymerization of the colored resist material. The borrowing technology method can produce a color film with higher precision than the above printing method. 323842 123 201233734 Then, the filter & can be formed by dipping in a solution, or by removing the uncured portion of the liquid to form a desired pattern. Heating may be applied as necessary to promote polymerization of the filter segments formed by the development. By the optical lithography technique, it is possible to manufacture a filter segment having a higher precision than the above printing method. At the time of development, an aqueous solution of sodium carbonate or sodium hydroxide can be used as the alkali developing solution, and an organic base such as dimethylbenzamide or triethanolamine can also be used. Further, an antifoaming agent or a surfactant may be added to the developing solution. As a method of image processing, a shower development method, a spray development method, a dipping development method, a liquid coating (pudd 1 e) development method, or the like can be applied. Further, in order to increase the ultraviolet exposure sensitivity, after the above-mentioned enamel resist honey cloth is dried, it may be coated with a water-soluble or alkali water-soluble resin (for example, polyvinyl alcohol or water-soluble acrylic resin) to form an oxygen-preventing agent. After the film that hinders the polymerization is exposed, ultraviolet exposure is performed. The color filter can be produced by an electroforming method other than the above method, a transfer method, or the like, and any of the above-described coloring composition or photosensitive coloring composition can be used. Further, the electrophoresis method is a method of producing a color filter by electrophoresing a colloidal particle on a transparent conductive film to form a filter segment of each color by electrophoresis of a colloidal particle. Further, the transfer method is a method in which a filter segment is formed on the surface of a peelable transfer substrate in advance, and the light-receiving segment is transferred onto a desired substrate. The coloring composition described above can be used in any method, but in particular, the compositions of the fifth and sixth embodiments are most suitable for photolithography. Before forming a filter segment of each color on the transparent substrate or the reflective substrate, a black matrix may be formed in advance by 323^42 124 201233734. As the black matrix, a multilayer film of chromium or chromium/chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed can be used, but it is not limited to these films. Further, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then filter segments of respective colors may be formed. Further, on the color filter, a protective film, a transparent conductive film, a columnar spacer, a liquid crystal alignment film, or the like can be formed as necessary. The color glazing sheet can be bonded to the substrate by using a sealant, and the liquid crystal is injected from the injection port provided in the sealing portion, and the injection port is sealed. If necessary, the polarizing film or the retardation film is attached to the outside of the substrate. After that, a liquid crystal display is manufactured. Such a liquid crystal display can be used for color filtering using twisted nematic (TN), super twisted nematic (STN), in-plane switching (ips), vertical orientation (VA), optically compensated bending (〇CB), and the like. In the liquid crystal display mode in which the light is colored. [Examples]
、下雖然疋依照實施例為基礎說明本發明的實施態 樣,但是本發明並不侷限於此等範圍。 [實施例A] 份」及 使用 =特^的限制時,「份」及「%」是分別表示「質量 質量/0」。在製造顏料組成物、著色組成物時,是 衍生物。 (顏料的平均一次粒徑) 里·α·~3)的二綱基鱗并轉触物、式(7-1)的苯并 二“1何生物、式(8~5)的蒽崎生物及式(14-1)的姐酮 323842 125 201233734 依下述的方法測定(計算出)製造的顏料組成物之平 均一次粒徑。 顏料的平均一次粒徑是使用穿透型(TEM)電子顯微鏡 測定,由電子顯微鏡照片直接量測一次粒徑之大小的方 法。具體上,是在量測各顏料的一次粒子之短軸徑及長軸 徑後,將其平均作為顏料的平均一次粒徑。其次,針對100 個以上的顏料粒子,以近似於求得的粒徑之立方體求得各 粒子之體積(重量),將體積平均粒徑作為平均一次粒徑。 ® (黏合劑樹脂的質量平均分子量) 依照下述的方法,測定丙烯酸樹脂的質量平均分子 量。 又,丙烯酸樹脂的質量平均分子量(Mw)是利用TSKgel 管柱(東曹公司製)、配備RI檢測器的GPC(東曹公司製, HLC-8120GPC)測定,展開溶劑是使用THF,測定換算成聚 苯乙烯之質量平均分子量(Mw)。 φ 首先,說明實施例及參考例中使用的二酮基吡咯并吡 咯顏料、二酮基吡咯并吡咯系顏料組成物、其他的顏料、 黏合劑樹脂溶液,與綠色及藍色感光性著色組成物的製造 方法。 <二酮基吡咯并吡咯顏料的製造方法> (溴化二酮基吼咯并吼咯顏料式(1)) 於氮氣環境下,在附加迴流管的不銹鋼製反應容器内, 加入經分子篩脫水的第三戊醇200份及鈉-第三戊醇酸140 份,一邊攪拌一邊加熱至10 0 °c後,調製成醇酸醋溶液。 323842 126 201233734 另一方面,在玻璃製燒瓶中,加入琥泊酸二異丙酯88份、 4-溴苯甲腈153. 6份,一邊擾拌一邊加熱至9〇°C使其溶 解,調製成此等混合物的溶液。一邊將此混合物的加熱溶 液以2小時以一定的速度緩缓滴入在l〇〇°C加熱的上述醇 鹽溶液中,一邊激烈的攪拌。滴下結束後,在90°C繼續加 熱攪拌2小時,可得二酮基σ比咯并吼咯系化合物的鹼金屬 鹽。並且,在玻璃製附加内襯的反應容器中,加入曱醇600 份、水600份及醋酸304份,將其冷卻至-l〇°C。將此冷卻Although the embodiments of the present invention are described on the basis of the embodiments, the present invention is not limited to the scope. In the case of the "Example A] and the use of the limit of "Special", "Parts" and "%" indicate "Quality Quality / 0". In the case of producing a pigment composition or a coloring composition, it is a derivative. (average primary particle size of pigment) ··α·~3) of the two-grain scale and the touch substance, the benzo-2 of the formula (7-1), the organism of the formula (8~5) And the ketone of the formula (14-1) 323842 125 201233734 The average primary particle diameter of the produced pigment composition was measured (calculated) by the following method. The average primary particle diameter of the pigment was a transmission type (TEM) electron microscope. The method of directly measuring the size of the primary particle diameter by electron micrograph is specifically measured, and after measuring the short axis diameter and the major axis diameter of the primary particles of each pigment, the average is used as the average primary particle diameter of the pigment. Next, for 100 or more pigment particles, the volume (weight) of each particle is determined by a cube approximate to the obtained particle diameter, and the volume average particle diameter is taken as the average primary particle diameter. ® (mass average molecular weight of the binder resin) The mass average molecular weight of the acrylic resin is measured by the method described below. The mass average molecular weight (Mw) of the acrylic resin is a GPC (manufactured by Tosoh Corporation) equipped with a TSKgel column (manufactured by Tosoh Corporation) and equipped with an RI detector. HLC-8120GPC) determination The developing solvent is a mass average molecular weight (Mw) converted to polystyrene using THF. φ First, the diketopyrrolopyrrole pigment and the diketopyrrolopyrrole pigment composition used in the examples and the reference examples will be described. , other pigments, a binder resin solution, and a method for producing a green and blue photosensitive coloring composition. <Production method of diketopyrrolopyrrole pigment> (brominated diketopyrrolopyrrole pigment) Formula (1)) In a stainless steel reaction vessel equipped with a reflux tube, 200 parts of a third pentanol dehydrated by molecular sieves and 140 parts of sodium-third-pivalic acid were added under a nitrogen atmosphere, and heated to 10 0 while stirring. After the reaction, the solution was prepared into an alkyd solution. 323842 126 201233734 On the other hand, 88 parts of diisopropyl succinate and 156.6 parts of 4-bromobenzonitrile were added to the glass flask, while stirring The mixture was heated to 9 ° C to dissolve it, and a solution of the mixture was prepared. While the heated solution of the mixture was slowly dropped into the above alkoxide solution heated at 10 ° C for 2 hours, Intense stirring After the completion of the dropwise addition, heating and stirring were continued at 90 ° C for 2 hours to obtain an alkali metal salt of a diketo-based σ-pyrrolidine compound, and 600 parts of decyl alcohol was added to a glass-lined reaction vessel. 600 parts of water and 304 parts of acetic acid, which are cooled to -10 ° C. This is cooled
的混合物使用高速攪拌分散器,一邊使直徑8cm的剪切碟 (shear disk)以4000rpm回轉,一邊在其中少量的添加已 冷卻至75°C而預先得的τ二酮基吡咯并吡咯系化合物的驗 金屬鹽溶液。此時,一邊將甲醇、醋酸及水形成的混合物 冷卻’使其溫度持續保持在-5°C以下的溫度,且一邊調整 叫并t各系化合物的驗金屬鹽溶液之添加 速度,大概以120分鐘少量的添加。添加驗金屬鹽後,析 =色的結晶而生成紅色的懸濁液。接著,於代 將此膏狀物再分散冷卻至代之3 而得紅色膏狀物。 醇濃度大約_的懸雜後,於5。Μ財,形成甲 結晶轉移的粒子進行整粒及洗淨 ,3小時後’將伴隨 將所得的二酮基。叫并^各系化a者’以超過遽機過濾, 乾燥24小時,藉由粉碎得式⑴戶:物之水膏狀物以src 吡咯顏料150. 8份。 示的凑化二酮基吡咯并 (特定雜二酮基《比略并吡咯顏 323842 π Λ 式(Α-2-1)) 127 201233734 在反應容器1中加入宽= 弟二戊醇2 2 0份,一邊使其水浴 冷卻一邊加入60%NaH 32份% .. _.〇 知後’於90 C加熱攪拌。接著, 在反應容器2中’使第三戊醆】 ,φ ^ ,, X 醇 100 伤、由 Tetrahedron, 58(2002)5547至5565的方法合成的下述式(A i6)之化合 物85. 0伤及4氰基聯笨6〇. 9份加熱溶解,並以2小時將 此液滴入反應容器1中。使其於im:反應1M、時之後, 冷卻至6〇°C,一邊加入甲醇400份及醋酸50份,-邊進The mixture was subjected to a high-speed stirring disperser while rotating a shear disk having a diameter of 8 cm at 4000 rpm while adding a small amount of the previously added taudiolone pyrrolopyrrole compound which had been cooled to 75 ° C. Check the metal salt solution. At this time, while the mixture of methanol, acetic acid, and water is cooled, the temperature is maintained at a temperature of -5 ° C or lower, and the addition rate of the metal salt solution of each compound of the compound is adjusted to about 120. A small amount of additions in minutes. After the addition of the metal salt, a color crystal was formed to form a red suspension. Next, the paste was redispersed and cooled to a third to obtain a red paste. The alcohol concentration is about _ after the suspension, at 5. Fortunately, the particles which form the crystal transfer are granulated and washed, and after 3 hours, the obtained diketone group will accompany. 8份。 The src pyrrole pigment 150. 8 parts by squeezing the liquid paste of the formula (1). Shown the bis-ketopyrrolo (specific heterodiketone "Bigidopyrrole 323842 π Λ formula (Α-2-1)) 127 201233734 Adding width = dipentanol 2 2 0 in the reaction vessel 1 For the portion, while cooling the water bath, add 60% NaH 32% by weight.. _. Next, in the reaction vessel 2, the compound of the following formula (A i6) is synthesized by the method of 'the third pentacene 】, φ ^ , X alcohol 100, and Tetrahedron, 58 (2002) 5547 to 5565. Injury 4 cyano linkage 6 〇. 9 parts of heat dissolved, and dropped into the reaction vessel 1 in 2 hours. After im: reaction 1M, time, cooled to 6 ° C, while adding 400 parts of methanol and 50 parts of acetic acid, - edge into
行過遽及甲醇清洗,可得式(A_M)所㈣特定雜二嗣基吼 略并11比洛顏料A 88. 1份。After the hydrazine and methanol cleaning, the formula (A_M) (4) specific heterodioxyl sulphate and 11 pirule pigment A 88. 1 part.
(特定雜二酮基吡咯并吡咯嚭射A 合顋枓A式(A-2-2))(Specific heterodiketopyrrolopyrrole shot A combined with formula A (A-2-2))
除了將4-氰基聯笨6〇 · 9伤變更成4-三級丁基苯甲腈 54. 1份之外’其餘與特定雜- ΛΙ 一鲷基吡咯并吡咯顏料Α式 (A-2-1)的製造進行同樣操作 、作传到83. 9份的式(A-2-2) 所示之特定雜二酮基吡咯并吡咯顏料A。 (特定雜二喊鱗并t各顏料/—Μ⑼ 除了將4-氰基聯苯6〇 q n ^ hV U· 9份變更成N-丁基-4-氰基苯 醯胺68· 7伤之外’其餘盘輯令 ...9 ,、待疋雜二酮基吡咯并吡咯顏料Λ ^ 同樣操作’得·()份的式U-2-3a) 所示之特定雜二鲷基吡咯并吡咯顏料A。 323842 128 201233734 (特定雜二_基^比咯并啦咯顏料A式(A_2_3b)) 除了將4-氰基聯苯60. 9份變更成N-苯基-4-氰基苯 -篮月女75. 5伤之外,其餘與特定雜二酮基吨p各并^比.^各顏料a 式(A-2-1)的製造進行同樣操作,得到86. 9份的式(A—2_3b) 所示之特定雜二酮基吡咯并吼咯顏料A。 (特定雜二酮基^比咯并吼咯顏料A式(A_2_4a)) 除了將4-氰基聯苯60. 9份變更成N,N-二丁基-4-氰 φ基苯醯胺87.8份之外,其餘與特定雜二酮基吡咯并吡咯顏 料A式(A-2-1)的製造進行同樣操作,得到87.丨份的式 (A-2-4a)所不之特定雜二酮基吡咯并吡咯顏料a。 (特定雜二酮基吡咯并吡咯顏料A式(A_2—4b)) 除了將4-氰基聯苯6〇· 9份變更成N,N_二丁基_3_氰 基苯醯胺87. 8份之外,其餘與特定雜二酮基吡咯并吡咯顏 料A式(A-2-1)的製造進行同樣操作,得到83 8份的式 (A-2-4b)所示之特定雜二酮基吡咯并吡咯顏料A。 •(特定雜二酮基吡咯并吡咯顏料A式(A-2-9a)) 除了將4-氰基聯苯60. 9份變更成4_(辛基硫)_苯甲 腈84. 1伤之外’其餘與特定雜二酮基吡咯并吡咯顏料a式 (A-一2-1)的製造進行同樣操作,得到85 5份的式(A_2_ga) 所示之特定雜二酮基D比洛并吼?各顏料A。 (特定雜二酮基吡咯并吡咯顏料A s(a_2_8)) 除了將4_氰基聯苯60. 9份變更成4_(三氣f基)_苯 甲腈58. 1伤之外’其餘與特定雜二剩基b比洛并口比洛顏料a 式(A-2-1)的製造進行同樣操作,得到85 8份的式(A_2_8) 323842 129 201233734 所示之特定雜二嗣基t各并α比洛顏…。 〈二鲷基料并料系_組絲㈣造方法〉 (特定雜二_°叫并__混合物㈣-υ) 在附有回流管的不鱗鋼製反應容器中,氮氣環境下, 將經過分子篩脫水之第三戊醇2〇〇份,及第三戊氧基納140 伤加入邊授拌一邊在咖^加熱,調製成醇鹽溶液。 f 一方面,在玻璃製燒瓶中,將琥珀酸二異丙酯88份、4_ 籲氣苯曱腈101 5份及4_氰基聯苯ls. i份加入,一邊搜拌 -邊在9Gt加熱使其溶解,調製此等混合物的溶液。將此 混合物的加熱溶液,一邊激烈攪拌,一邊以2小時以一定 的速度緩慢地滴入至酬^加熱之上述醇鹽溶液中。滴下 、’、。束後,在90 C繼續加熱授拌2小時,得到二_基„比π各并 吡咯系化合物的鹼金屬鹽。再者,在玻璃製附有内襯之反 應容器中’加入曱醇6〇〇份、水6〇〇份及醋酸304份,冷 卻到-10°C。此經冷卻之混合物使用高速攪拌分散器,一邊 ® 使直瓜8cm之剪切碟以4〇〇〇rpm回轉,一邊在其中少量地 添加已冷卻到75°C的預先得到之二酮基吡咯并吡咯系化 合物的驗金屬鹽溶液。此時,一邊將甲醇、醋酸、及水所 成的混合物冷卻,使其溫度持續保持在_5。(:以下之溫度, 且一邊調整75°C的二酮基比洛并η比洛系化合物驗金屬鹽 溶液的添加速度’大概以120分鐘少量地添加。添加鹼金 屬鹽後’析出紅色的結晶而生成紅色的懸濁液。接著,將 得到之紅色懸濁液於5Ϊ以超過濾裝置洗淨後,過濾得到 紅色膏狀物。將此膏狀物再次分散到已冷卻至0°C之3500 323842 130 201233734 份甲醇中,形成甲醇濃度 小時,將伴隨結晶轉移❸4 9〇%的懸濁液,於5¾槐掉 、倉總心心/ 板子整粒及洗淨。接著’ 3 濾機過/慮,將得到之二酉同基 q起過 物,於8(TC乾燥24小時 各糸化5物的水⑼ 雜二酮基吡咯并吡咯顏:二卒侍到143. 6份气特 顏料紅254及式合物。有關得到 顏料A之含量,使用HPLC ^的特定雜二酮基如各各厂 ㈣-1)所示的特定雜二:基=析’。划^^ 別是90. 9質量%及9. !質量%。开如各顏料A之含量,分 (特定雜二_基鱗并_顏料混合物 除了將4-氰基聯笨15 、()) 13. 4份之外,其餘與特定雜二=更成4-第三丁基笨甲騰 丨)的製造進行同樣操作:得:含物 基吡咯开吡咯顏料混合物刀特弋雜二_ 紅254及式(终2)所_/此2)。有關得到之C· !声“明 •UA 2 2)所不的特定雜二酉同基 .顧料 之含量,使用HPLC定量分析時 I并比咯翱料a 所示的特定雜二酮基轉并„ . ·顏枓紅254與式(A—2一2) 9U質量級9.3質量%各顏料A之含量,分別是 (特定雜二·吨略并哎略顏料混合物3(r 二 =聯笨…份,變更成m 亂暴本(子)醯胺19. 3份 对顏科齡物1(R(M)的絲二祕祕并q 份之特定雜二并相觸作。得到142.9 得到之CU顏料红254及=料混合物3(RC_3)e有關 •顏科、.工254及式(A—2,所示的特定雜二嗣基 323842 131 201233734 0比ρ各并。比p各顏料A之含量,使用HPLC定量分析時,C. I.顏 料紅254與式(A-2-4a)所示的特定雜二酮基吡咯并吡咯顏 料A之含量,分別是90. 8質量%及9. 2質量%。 〈黏合劑樹脂溶液的製造方法〉 (丙烯酸樹脂溶液1的調製) 在可分離之4 口燒瓶中安裝溫度計、冷卻管、氮氣導 入管、滴下管及攪拌裝置的反應容器中,放入環己酮196 份,昇溫到80°C,反應容器内以氮氣取代後,藉由滴下管 • 以2小時,將37. 2份之曱基丙烯酸正丁酯、12. 9份曱基 丙烯酸2-羥基乙酯、12.0份曱基丙烯酸、20. 7份對異丙 苯基酚環氧乙烷改質丙烯酸酯(東亞合成(股)公司製 「八[〇^1\1^110」、1.1份的2,2’-偶氮雙異丁腈的混合物滴 下。滴下結束後,再繼續反應3小時,而得到丙烯酸樹脂 的溶液。冷卻到室溫後,將樹脂溶液約2份作為試樣,在 180°C加熱乾燥20分鐘後測定不揮發成分,在預先前合成 φ 的樹脂溶液中,添加曱氧基丙基醋酸酯,以使不揮發成分 變成20質量%方式調製丙烯酸樹脂溶液1。質量平均分子 量(Mw)是 26000。 (丙烯酸樹脂溶液2的調製) 在可分離4 口燒瓶中安裝有溫度計、冷卻管、氮氣導 入管、滴下管及攪拌裝置的反應容器中,放入環己酮207 份,昇溫到80°C,燒瓶内以氮氣取代後,由滴下管以2小 時將20份之甲基丙烯酸、20份的經對異丙苯基酚環氧乙 烷改質之丙烯酸酯(東亞合成(股)公司製「ARONIXM110」)、 323842 132 201233734 45份的甲基丙婦酸甲酉旨、85份的甲基丙 酯、及1· 33份的2’2’-偶氮雙異丁腈的混合物滴下: 滴下後,再繼續反應3小時,看得到共聚合物樹脂溶;束 其次,對得到的共聚合物溶液全量,—邊停止氮氣而注入 H、時之乾祕氣-邊難後,冷㈣室溫後,將6 的2-曱基丙烯醯氧基乙基異氰酸醋(昭和電工公司製々In addition to the 4-cyano-linked stupid 6〇·9 injury was changed to 4-tris-butylbenzonitrile 5.41 parts except for the rest and specific hetero- ΛΙ-mercaptopyrrolopyrrole pigments (A-2 The production of -1) was carried out in the same manner and carried out to 83.9 parts of the specific heterodiketopyrrolopyrrole pigment A represented by the formula (A-2-2). (Specific miscellaneous two shouting scales and t each pigment / - Μ (9) In addition to changing 4-cyanobiphenyl 6 〇 qn ^ hV U · 9 parts to N-butyl-4-cyanobenzoquinone 68 · 7 injuries 'The rest of the disc order...9, the doped diketopyrrolopyrrole pigment Λ ^ The same operation of the 'de() part of the formula U-2-3a) shows the specific heterodithiopyrrolopyrrole Pigment A. 323842 128 201233734 (Specific heterodi- _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 75. In addition to the injury, the rest is treated with the specific heterodiketone ton p and the ratio of each pigment a (A-2-1). The same operation is carried out to obtain 86. 9 parts of the formula (A-2_3b) The specific heterodiketopyrrolopyrrole pigment A shown. (Specific heterodiketone group pyrrolopyrrole pigment A formula (A_2_4a)) except that 4, 4-cyanobiphenyl 60.9 parts were changed to N, N-dibutyl-4-cyano-p-benzophenone 87.8 In the same manner as in the preparation of the specific heterodiketopyrrolopyrrole pigment A (A-2-1), the specific operation of the formula (A-2-4a) is obtained. Ketopyrrolopyrrole pigment a. (Specific heterodiketopyrrolopyrrole pigment A formula (A_2-4b)) except that 4-cyanobiphenyl 6 〇·9 parts was changed to N,N-dibutyl_3-cyanobenzoquinone 87. The same operation as the production of the specific heterodiketopyrrolopyrrole pigment A (A-2-1) was carried out in the same manner as in the case of 8 parts, to obtain 83 8 parts of the specific hetero group represented by the formula (A-2-4b). Ketopyrrolopyrrole pigment A. (1) (Specific heterodione-pyrrolopyrrole pigment A (A-2-9a)) In addition to the 4-cyanobiphenyl 60.9 parts changed to 4_ (octyl thio) benzoyl nitrile 84. 1 wounded The same procedure as in the production of the specific heterodiketopyrrolopyrrole pigment a (A-2-1) gives 85 5 parts of the specific heterodiketone D shown in the formula (A_2_ga).吼? Each pigment A. (Specific heterodiketopyrrolopyrrole pigment A s (a_2_8)) In addition to the 4 - cyanobiphenyl 60.9 parts changed to 4 _ (three gas f-based) _ benzonitrile 5. 1 injury The specific hetero-residue group b is subjected to the same operation as in the production of the formula of the sirloin pigment, a formula (A-2-1), to obtain 85 8 parts of the specific hetero-fluorenyl group t represented by the formula (A_2_8) 323842 129 201233734 and α 比洛颜... <Two bismuth base material doubling system _ group wire (four) manufacturing method> (specific miscellaneous _ ° _ _ _ mixture (four) - υ) In a non-scale steel reaction vessel with a return pipe, under nitrogen, will pass Molecular sieve dehydration of the third pentanol 2 parts, and the third pentamyl sodium 140 injury added to the side of the mixing while heating in the coffee, prepared into an alkoxide solution. f On the one hand, in a glass flask, 88 parts of diisopropyl succinate, 4 parts of 4_ benzophenone nitrile and 4 parts of 4-cyanobiphenyl ls. i were added, while mixing at 9 Gt It is dissolved to prepare a solution of these mixtures. The heated solution of the mixture was slowly added dropwise to the above-mentioned alkoxide solution heated at a constant rate for 2 hours while stirring vigorously. Drop, ',. After the bundle, the mixture was further heated and heated at 90 C for 2 hours to obtain an alkali metal salt of a bis-pi-pyrrolidine-based compound. Further, sterol 6 was added to a glass-lined reaction vessel. 6 parts of water, 30 parts of water and 304 parts of acetic acid, cooled to -10 ° C. This cooled mixture was spun using a high-speed stirring disperser, and the side of the straight melon was cut at 4 rpm. A metal salt solution of a previously obtained diketopyrrolopyrrole compound cooled to 75 ° C was added thereto in a small amount. At this time, a mixture of methanol, acetic acid, and water was cooled to maintain the temperature. Keeping at _5. (: The following temperature, and adjusting the addition rate of the diketopyrloate and η-Byro compound metal salt solution at 75 ° C) is added in a small amount for about 120 minutes. After adding the alkali metal salt 'The red crystal was precipitated to form a red suspension. Then, the obtained red suspension was washed with an ultrafiltration device at 5 Torr, and then filtered to obtain a red paste. The paste was again dispersed until it was cooled to 3500 323842 130 201233734 0°C In the case where the concentration of methanol is small, the suspension will be transferred with crystallization of ❸49%, and will be removed at 53⁄4, the whole heart/plate is granulated and washed. Then the '3 filter is over/under, and the second will be obtained. The same base q as a substance, at 8 (TC drying for 24 hours, each of the 5 substances of water (9) heterodiketopyrrolopyrrole: two strokes to 143.6 parts of the gas pigment red 254 and the formula.质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量质量%. Open as the content of each pigment A, the specific (different bis-base scale _ pigment mixture in addition to 4-cyano linkage 15 , ()) 13. 4 parts, the rest with the specific miscellaneous = = The manufacture of 4-t-butyl berylate is carried out in the same manner: Obtaining: the mixture of the pyrrole pyrrole pigment mixture is singularly mixed with two _ red 254 and the formula (final 2) _ / this 2). The specific miscellaneous diterpene of the C. sound "Ming UA 2 2" is not the same as the content of the material. When quantitatively analyzed by HPLC, I is more specific than the specific heterodikeke group shown by a. · Yan Yanhong 254 and (A-2 2) 9U quality grade 9.3 mass% of each pigment A content, respectively (specific miscellaneous ton ton slightly 哎 slightly pigment mixture 3 (r two = joint stupid ... part, changed to m chaos醯 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 RC_3)e related to • Yan Ke, gong 254 and formula (A-2, the specific heterodithiophene shown 323842 131 201233734 0 than ρ. The content of the specific heterodiketopyrrolopyrrole pigment A, which is represented by the formula (A-2-4a), is 90.8 mass%, respectively. And 9.2% by mass. <Method for Producing Binder Resin Solution> (Preparation of Acrylic Resin Solution 1) A cyclone is placed in a reaction vessel in which a thermometer, a cooling tube, a nitrogen introduction tube, a dropping tube, and a stirring device are attached to a separable 4-neck flask. 196份份为优选为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为为Ester, 12.0 parts of methacrylic acid, 20.7 parts of cumyl phenol oxirane modified acrylate (East Asia Synthetic Co., Ltd. "8 [〇^1\1^110", 1.1 parts of 2 , a mixture of 2'-azobisisobutyronitrile was dropped. After the completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was used as a sample at 180 °. After heating and drying for 20 minutes, the non-volatile component was measured, and acryloxypropyl acetate was added to the resin solution in which φ was previously synthesized, and the acrylic resin solution 1 was prepared so that the nonvolatile content became 20% by mass. Mass average molecular weight ( Mw) is 26000. (Acrylic resin dissolves Preparation of 2) In a separable 4-necked flask, a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen introduction tube, a dropping tube, and a stirring device was placed, and 207 parts of cyclohexanone was placed, and the temperature was raised to 80 ° C, and the inside of the flask was purged with nitrogen. After the substitution, 20 parts of methacrylic acid and 20 parts of isopropylidene phenol oxirane modified by a dropping tube for 2 hours (ARONIX M110 manufactured by Toagosei Co., Ltd.), 323842 132 201233734 45 parts of a mixture of methyl acetoacetate, 85 parts of methyl propyl ester, and 1 · 33 parts of 2'2'-azobisisobutyronitrile: After dripping, continue the reaction 3 In an hour, the copolymer resin is dissolved; the beam is second, and the total amount of the obtained copolymer solution is -, when the nitrogen gas is stopped, the H is injected, and the dry gas is secreted - after the difficulty, after the cold (four) room temperature, the 6 of the 2 - mercapto propylene oxiranyl ethyl isocyanate (made by Showa Denko)
Karen邏)、〇.()8份月桂酸二丁基錫、_環己酮的混入 物在m:以3小時滴下。將約2g樹脂溶液作為試樣,於口 職:加熱錢20分鐘後測定不揮發成分,在預先合成的 樹脂溶液中’添加環己綱,以將不揮發成分變成2〇質量% 方式調製丙烯酸樹脂溶液2。質量平均分子量(Mw)是 18000 。 〈綠色及藍色感光性著色組成物的製造方法〉 (綠色感光性著色組成物(GR-1)的調製)Karen Logic), 〇. () 8 parts of dibutyltin laurate, _cyclohexanone mixed in m: dripped in 3 hours. About 2 g of the resin solution was used as a sample, and the non-volatile component was measured after 20 minutes of heating, and the cyclohexyl group was added to the previously synthesized resin solution to prepare the acrylic resin by changing the nonvolatile content to 2% by mass. Solution 2. The mass average molecular weight (Mw) is 18,000. <Method for Producing Green and Blue Photosensitive Coloring Composition> (Preparation of Green Photosensitive Colored Composition (GR-1))
將下述之混合物以成為均勻的方式攪拌混合後,使用 直徑0.5mm的二氧化锆小球,以Eiger研磨機(EigerJapan 公司製「Mini model M-250 MKII」分散5小時後,以5. 0 β m的過濾膜過瀘、,製作綠色著色組成物1 (Gp_ 1)。 綠色顏料(C_ I.顏料綠36) 6 8份 黃色顏料(C. I.顏料黃150) 5. 2份 樹脂型分散劑(汽巴日本公司製「EFKA4300」)1.0份 丙稀酸樹脂溶液1 35. 0份 丙二醇單曱基醚醋酸酯 52. 0份 其次’將下述之混合物以成為均勻的方式攪拌混合 323842 133 201233734 後,以1 /z m的過;慮膜過濾,製作綠色感光性著色組成物 l(GR-l)。 42. 0 份 13. 2 份 綠色著色組成物l(GP-l) 丙烯酸樹脂溶液2 光聚合性單量體(東亞合成公司製「ARONIX M400」)2. 8份 光聚合始起劑(汽巴日本公司製「Irgacure_9〇7」)2. 〇份 增感劑(Hodogaya Chemical 公司製「εαβ-FI」 0. 4 份 乙二醇單甲基醚醋酸酯 39. 6份After the mixture was stirred and mixed in a uniform manner, a zirconia pellet having a diameter of 0.5 mm was used, and an Eiger mill ("Mini model M-250 MKII" manufactured by Eiger Japan Co., Ltd. was dispersed for 5 hours, and then 5.0. The filtration membrane of β m is passed through, and the green coloring composition 1 (Gp_ 1) is produced. Green pigment (C_I. Pigment Green 36) 6 8 parts of yellow pigment (CI Pigment Yellow 150) 5. 2 parts of resin type dispersant ( "EFKA4300" manufactured by Ciba Japan Co., Ltd.) 1.0 part of acrylic resin solution 1 30.5 parts of propylene glycol monodecyl ether acetate 50.2 parts secondly, the following mixture was stirred and mixed in a uniform manner 323842 133 201233734 1 /zm over; membrane filtration, green photosensitive coloring composition l (GR-l). 42. 0 parts 13. 2 parts of green coloring composition l (GP-l) acrylic resin solution 2 photopolymerization Separate single-body ("ARONIX M400" manufactured by Toagosei Co., Ltd.) 2. 8 parts of photopolymerization initiator ("Iggure_9〇7" manufactured by Ciba Japan Co., Ltd.) 2. Oxide sensitizer ("ααβ-" manufactured by Hodogaya Chemical Co., Ltd.份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份
(藍色感光性著色組成物l(BR-l)的調製) 將下述混合物以成為均勻的方式授拌混合後,使用直 徑0. 5顏的二氧化锆小球,以Eiger研磨機(Eiger日本公 司製「Mini model M-250 MKII」分散5小時後,以5. 〇 A m的過濾膜過濾,製作藍色著色組成物1 (bp-1)。 藍色顏料(C. I.顏料藍15 : 6) 7. 2份 紫色顏料(C. I.顏料紫23) 4. 8份 樹脂型分散劑(汽巴日本公司製「EFKA4300」) 1. 〇份 丙烯酸樹脂溶液1 35. 0份 丙二醇單甲基醚醋酸酯 52. 0份 其次,將下述組成之混合物以成為均勻的方式攪拌混 合後’以l//m的過濾膜過濾,製作藍色感光性著色組成物 l(BR-l)。 藍色著色組成物l(BP-l) 34. 0份 丙稀酸樹脂溶液2 15. 2份 光聚合性單體(東亞合成公司製「ARONIX M400」)3· 3份 323842 134 201233734 光聚合始起劑(汽巴日本公司製「Irgacure-907」)2. 0份 增感劑(Hodogaya Chemical 公司製「EAB-F1」 0. 4 份 乙二醇單曱基醚醋酸酯 45. 1份 [實施例1] (顏料組成物l(R-l)之製造) 將式(1)的溴化二酮基吡咯并吡咯顏料99. 0份、式 (A-2-1)的特定雜二酮基吡咯并吡咯顏料A 1. 0份、氣化鈉 1000份,及二乙二醇120份,放入不銹鋼製1加侖捏煉機 ® (井上製作所製)中,在60°C混練10小時。其次,將混煉 之混合物投入溫水中,一邊在約8 0 °C加熱,一邊擾拌1小 時作成膏狀物,過濾並水洗除去食鹽及二乙二醇後,在80 °C乾燥一晝夜,藉由粉碎得到96. 9份之二酮基吡咯并吡咯 系顏料組成物1 (R-1),平均一次粒子徑是37. Onm。 [實施例2] (顏料組成物2(R-2)之製造) φ 除了將式(1)的溴化二酮基吡咯并吡咯顏料99. 0份、 式(A-2-1)的特定雜二酮基吡咯并吡咯顏料A 1. 0份,變更 成式(1)的溴化二酮基吡咯并吡咯顏料97. 0份、式(A-2-1) 的特定雜二酮基吡咯并吡咯顏料A 3.0份之外,其餘與顏 料組成物l(R-l)的製造進行同樣操作,得到二酮基吡咯并 吡咯系顏料組成物2(R-2)96. 5份。平均一次粒子徑是 36. 8nm。 [實施例3] (顏料組成物3(R-3)之製造) 323842 135 201233734 除了將式(1)的溴化二酮基吡咯并吡咯顏料99. 0份、 式(Α-2-1)的特定雜二酮基吡咯并吡咯顏料A 1. 0份,變更 成式(1)的溴化二酮基吡咯并吡咯顏料9 5. 0份、式(A - 2 -1) 的特定雜二酮基吡咯并吡咯顏料A 5.0份之外,其餘與顏 料組成物l(R-l)的製造進行同樣操作,得到二酮基吡咯并 吡咯系顏料組成物3(R-3)97. 2份。平均一次粒子徑是 30.5nm。 [實施例4] •(顏料組成物4(R-4)之製造) 除了將式(1)的溴化二酮基吡咯并吡咯顏料99. 0份、 式(A-2-1)的特定雜二酮基吡咯并吡咯顏料A 1. 0份,變更 成式(1)的溴化二酮基吡咯并吡咯顏料90. 0份、式(A-2-1) 的特定雜二酮基吡咯并吡咯顏料A 10. 0份之外,其餘與顏 料組成物l(R-l)的製造進行同樣操作,得到二酮基吡咯并 吡咯系顏料組成物4(R-4)96. 9份。平均一次粒子徑是 • 28.5nm ° [實施例5] (顏料組成物5(R-5)之製造) 除了將式(1)的溴化二酮基吡咯并吡咯顏料99. 0份、 式(A-2-1)的特定雜二酮基吡咯并吡咯顏料A 1. 0份,變更 成式(1)的溴化二酮基吡咯并吡咯顏料85. 0份、式(A-2-1) 的特定雜二明基吡咯并吡咯顏料A 15. 0份之外,其餘與顏 料組成物l(R-l)的製造同進行樣操作,得到二酮基吡咯并 吡咯系顏料組成物5(R-5)97. 3份。平均一次粒子徑是 323842 136 201233734 29. 5nm。 [實施例6] (顏料組成物6(R-6)之製造) 除了將式(A-2-1)的特定雜二酮基吡咯并吡咯顏料A, 變更成式(A-2-2)的特定雜二酮基吡咯并吡咯顏料A之外, 其餘與顏料組成物3(R-3)的製造進行同樣操作,得到二酮 基吡咯并吡咯系顏料組成物6(R-6)98. 1份。平均一次粒子 徑是 29. 9nm。 籲[實施例7] (顏料組成物7(R-7)之製造) 除了將式(A-2-1)的特定雜二酮基吡令并吡咯顏料A, 變更成式(A-2-3a)的特定雜二酮基咐咯并吼咯顏料A之 外,其餘與顏料組成物3(R-3)的製造進行同樣操作,得到 二酮基吡咯并吡咯系顏料組成物7(R-7)98. 0份。平均一次 粒子徑是30. 7nm。 φ [實施例8] (顏料組成物8(R-8)之製造) 除了將式(A-2-1)的特定雜二酮基吡咯并吡咯顏料A, 變更成式(A-2-3b)的特定雜二酮基吡咯并吡咯顏料A之 外,其餘與顏料組成物3(R-3)的製造進行同樣操作,得到 二酮基吡咯并吡咯系顏料組成物8 (R - 8) 9 8. 4份。平均一次 粒子徑是31. 2nm。 [實施例9] (顏料組成物9(R-9)之製造) 323842 137 201233734 除了將式(A-2-1)的特定雜二酮基吡咯并吡咯顏料A, 變更成式(A-2-4a)的特定雜二酮基吡咯并吡咯顏料A之 外,其餘與顏料組成物3(R-3)的製造進行同樣之搡作,得 到二酮基吡咯并吡咯系顏料組成物9(R-9)97. 5份。平均一 次粒子徑是35. 4nm。 [實施例10] (顏料組成物10(R-10)之製造) 除了將式(A-2-1)的特定雜二酮基吡咯并吡咯顏料A, ® 變更成式(A-2-4b)的特定雜二鲷基β比p各并π比p各顏料A之 外,其餘與顏料組成物3(R-3)的製造進行同樣之操作,得 到二酮基吡咯并吡咯系顏料組成物10(R-10)96. 6份。平均 一次粒子徑是35. 8nm。 [實施例11] (顏料組成物ll(R-ll)之製造) 除了將式(A-2-1)的特定雜二酮基吡咯并吡咯顏料A, φ 變更成式(A-2-9a)的特定雜二酮基吡咯并吡咯顏料A之 外,其餘與顏料組成物3(R-3)的製造進行同樣之操作,得 到二酮基吡咯并吡咯系顏料組成物11 (R-ll)93. 9份。平均 一次粒子徑是32. 4nm。 [實施例12] (顏料組成物12(R-12)之製造) 除了將式(A-2-1)的特定雜二酮基吡咯并吡咯顏料A, 變更成式(A-2-8)的特定雜二酮基吡咯并吡咯顏料A之 外,其餘與顏料組成物3(R-3)的製造進行同樣之操作,得 323842 138 201233734 到二酮基吡咯并吡咯系顏料組成物12(R-12)95. 7份。平均 一次粒子徑是29. 8nm。 [實施例13] (顏料組成物13(R-13)之製造) 式(1)的溴化二酮基吡咯并吡咯顏料98. 〇份、市售的 c.i.顏料紅254(汽巴特別化學公司製「Irgaph〇r Red B-CF」1. 〇份、式(Α_2—ι)的特定雜二酮基吡咯并吡咯顏料 A 1.0份、氣化鈉1〇〇〇份,及二乙二醇12〇份,放入不銹 鋼製1加侖捏煉機(井上製作所製)中,在6(rc混練1〇小 時。其-人,將混煉之混合物投入溫水中,一邊在約加 熱一邊攪拌1小時作成膏狀物,過濾並水洗除去食鹽及二 乙二醇後’在80°C乾燥一晝夜,藉由粉碎得到96. 7份之 二酮基吡咯并吡咯系顏料組成物13(R-13),平均一次粒子 徑是 33. 2nm。 [實施例14] (顏料組成物14(R-l4)之製造) 除了將式(1)的溴化二酮基σ比略并°比洛顏料gg. 〇份、 市售的C· I·顏料紅254(汽巴特別化學公司製「Irgaphor RedB-CF」1.0份、與式(a_2-i)的特定雜二酮基吡咯并吡 p各顏料A 1 · 0伤,變更成式(1)的演化二綱基吨洛并π比洛顏 料80.0份、市售的C. I.顏料紅254(汽巴特別化學公司製 「Irgaphor RedB-CF」18.〇 份、與式(A-2—D的特定雜二 酮基吡咯并吡咯顏料A 2.0份之外,其餘與顏料組成物 13(R-13)的製造進行同樣操作’得到98. 3份之二酮基吡咯 323842 139 201233734 并吡咯系顏料組成物14(R-14),平均一次粒子徑是 30. 2nm 〇 [實施例15] (顏料組成物15(R-15)之製造) 除了將式(1)的溴化二酮基吡咯并吡咯顏料98. 0份、 市售的C. I.顏料紅254(汽巴特別化學公司製「Irgaphor RedB-CF」1. 0份、與式(A-2-1)的特定雜二酮基吡咯并吡 咯顏料A 1. 0份,變更成式(1)的溴化二酮基吡咯并吡咯顏 ® 料50. 0份、市售的C. I.顏料紅254 (汽巴特別化學公司製 「Irgaphor Red B-CF」45. 0 份、與式(A-2-1)的特定雜二 酮基吡咯并吡咯顏料A 5.0份之外,其餘與顏料組成物 13(R-13)的製造進行同樣操作,得到97. 0份之二酮基吡咯 并吡咯系顏料組成物15(R-15),平均一次粒子徑是 26.7nm。 [實施例16] •(顏料組成物16(R-16)之製造) 除了將式(1)的溴化二酮基吡咯并吡咯顏料98.0份、 市售的C. I.顏料紅254(汽巴特別化學公司製「Irgaphor Red B-CF」1.0份、與式(A-2-1)的特定雜二酮基吡咯并吡 咯顏料A 1. 0份,變更成式(1)的溴化二酮基吡咯并吡咯顏 料20. 0份、市售的C. I.顏料紅254 (汽巴特別化學公司 製「Irgaphor Red B-CF」72. 0 份、與式(A-2-1)的特定雜 二酮基吡咯并吡咯顏料A 8.0份之外,其餘與顏料組成物 13(R-13)的製造進行同樣操作,得到94. 8份之二酮基吡咯 323842 140 201233734 并吡咯系顏料組成物16(R-16),平均一次粒子徑是 28. Onm。 [實施例17] (顏料組成物17(R-17)之製造) 除了將式(1)的溴化二酮基吡咯并吡咯顏料98. 0份、 市售的C. I.顏料紅254(汽巴特別化學公司製「Irgaphor Red B-CF」1. 0份、與式(A-2-1)的特定雜二酮基°比咯并B比 咯顏料A 1. 0份,變更成式(1)的溴化二酮基吡咯并吡咯顏 ® 料20. 0份、市售的C. I.顏料紅254 (汽巴特別化學公司製 「Irgaphor Red B-CF」65. 0 份、與式(A-2-1)的特定雜二 酮基吡咯并吡咯顏料A 15.0份之外,其餘與顏料組成物 13(R-13)的製造進行同樣之操作,得到96. 2份之二酮基吡 咯并吡咯系顏料組成物17(R-17),平均一次粒子徑是 29. 3nm。 [實施例18] φ (顏料組成物18(R-18)之製造) 將式(1)的溴化二酮基吡咯并吡咯顏料80. 0份、特定 雜二酮基吡咯并吡咯顏料混合物1(RC-1)20. 0份、氯化鈉 1000份,及二乙二醇120份,放入不銹鋼製1加侖捏煉機 (井上製作所製)中,在60°C中混練10小時。其次,將混 煉之混合物投入溫水中,一邊在約80°C中加熱一邊攪拌1 小時作成膏狀物,過濾並水洗除去食鹽及二乙二醇後,在 80°C乾燥一晝夜,藉由粉碎得到96. 9份之二酮基吡咯并吡 咯系顏料組成物18(R-18),平均一次粒子徑是29. 2nm。 323842 141 201233734 [實施例19] (顏料組成物19(R-i9)之製造) 除了將特定雜二酮基吼哈并„比哈顏一 更成特定雜二酮基吡咯并吡咯顏料混合3物丨(叱、1) 外,其餘與顏料組成物180M8)的製造^务2(叱、2)之 到96. 1份之二酮基吼P各并姆系顏料組二同樣操作 平均一次粒子徑是30. 5nm。 ^ ^(Preparation of blue photosensitive coloring composition l (BR-1)) After mixing and mixing the following mixture in a uniform manner, a zirconium dioxide sphere having a diameter of 0.5 mm was used, and an Eiger mill (Eiger) was used. The "Mini model M-250 MKII" manufactured by Nippon Co., Ltd. was dispersed for 5 hours, and then filtered through a filtration membrane of 5. 〇A m to prepare a blue colored composition 1 (bp-1). Blue pigment (CI Pigment Blue 15: 6) 7. 2 parts of purple pigment (CI Pigment Violet 23) 4. 8 parts of resin type dispersant ("ACKA4300" manufactured by Ciba Japan) 1. Resin acrylic resin solution 1 30.5 parts of propylene glycol monomethyl ether acetate 52. 0 parts, the mixture of the following composition was stirred and mixed in a uniform manner, and then filtered through a filtration membrane of 1/m to prepare a blue photosensitive coloring composition 1 (BR-1). 1 (BP-1) 34. 0 parts of acrylic resin solution 2 15. 2 parts of photopolymerizable monomer ("ARONIX M400" manufactured by Toagosei Co., Ltd.) 3·3 parts 323842 134 201233734 Photopolymerization initiator (steam) "Irgacure-907" made by Ba Japan Co., Ltd. 2. 0 parts of sensitizer (EAB-F1, manufactured by Hodogaya Chemical Co., Ltd.) 0. 4 parts 1份 [Formula 1] (Production of the pigment composition l (Rl)) The brominated diketopyrrolopyrrole pigment of the formula (1): 99 parts, formula (A- 2-1) A specific heterodiketopyrrolopyrrole pigment A 1.0 part, 1000 parts of sodium vapor, and 120 parts of diethylene glycol, placed in a stainless steel 1 gallon kneader® (manufactured by Inoue Co., Ltd.) The mixture was kneaded at 60 ° C for 10 hours. Next, the kneaded mixture was poured into warm water, and heated at about 80 ° C, and then scrambled for 1 hour to form a paste, which was filtered and washed with water to remove salt and diethylene glycol. After drying at 80 ° C for one day and night, by pulverization, 96.9 parts of the diketopyrrolopyrrole pigment composition 1 (R-1) was obtained, and the average primary particle diameter was 37. Onm. [Example 2] ( Manufacture of the pigment composition 2 (R-2) φ In addition to the brominated diketopyrrolopyrrole pigment of the formula (1): 99 parts, the specific heterodiketopyrrolopyrene of the formula (A-2-1) Pyrrole pigment A 1. 0 parts, changed to the brominated diketopyrrolopyrrole pigment of formula (1) 97. 0 parts, the specific heterodiketopyrrolopyrrole pigment A of formula (A-2-1) 3.0 parts Other than the pigment composition l ( 5质量。 [Embodiment 3] (Pigment composition 3 ((Pigment composition 3) (Immediate primary particle diameter is 36. 8 nm. [Example 3] (Pigment composition 3 ( Manufacture of R-3) 323842 135 201233734 In addition to the brominated diketopyrrolopyrrole pigment of formula (1), 99. 0 parts, specific heterodiketopyrrolopyrrole pigment A of formula (Α-2-1) 1. 0 parts, changed to the brominated diketopyrrolopyrrole pigment of the formula (1), 9. 5 parts, of the specific heterodiketopyrrolopyrrole pigment A of the formula (A-2 -1), 5.0 parts 2份。 The same as the production of the pigment composition l (Rl) in the same manner to obtain a diketopyrrolopyrrole pigment composition 3 (R-3) 97.2 parts. The average primary particle diameter is 30.5 nm. [Example 4] • (Production of Pigment Composition 4 (R-4)) The specifics of the brominated diketopyrrolopyrrole pigment of the formula (1): 99 parts, formula (A-2-1) a part of the heterodione-pyrrolopyrrole pigment of the formula (1), and a specific heterodiketopyrrole of the formula (A-2-1). 9份。 The same as the production of the pigment composition l (Rl), the same procedure to obtain a diketopyrrolopyrrole pigment composition 4 (R-4) 96.9 parts. The average primary particle diameter is 28.5 nm ° [Example 5] (Production of Pigment Composition 5 (R-5)) In addition to the brominated diketopyrrolopyrrole pigment of the formula (1): 99 parts, formula ( A-2-1) a specific heterodiketopyrrolopyrrole pigment A 1. 0 parts, changed to a brominated diketopyrrolopyrrole pigment of formula (1) 85. 0 parts, formula (A-2-1 The same procedure as in the preparation of the pigment composition l (Rl) to obtain a diketopyrrolopyrrole pigment composition 5 (R-5) except for the specific heterodipypyrrolopyrrole pigment A of 15.1 parts ) 97. 3 copies. The average primary particle diameter is 323842 136 201233734 29. 5nm. [Example 6] (Production of Pigment Composition 6 (R-6)) The specific heterodiketopyrrolopyrrole pigment A of the formula (A-2-1) was changed to the formula (A-2-2). The same procedure as in the preparation of the pigment composition 3 (R-3) except for the specific heterodiketopyrrolopyrrole pigment A, to obtain a diketopyrrolopyrrole pigment composition 6 (R-6) 98. 1 serving. The average primary particle diameter is 29.9 nm. [Example 7] (Production of Pigment Composition 7 (R-7)) In addition to the specific heterodiketobenzopyrrole pigment A of the formula (A-2-1), it is changed to the formula (A-2- In the same manner as in the production of the pigment composition 3 (R-3) except for the specific heterodikedo-pyrrolopyrrole pigment A of 3a), a diketopyrrolopyrrole-based pigment composition 7 (R- 7) 98. 0 copies. 7纳米。 The average primary particle diameter is 30.7 nm. φ [Example 8] (Production of Pigment Composition 8 (R-8)) The specific heterodiketopyrrolopyrrole pigment A of the formula (A-2-1) was changed to the formula (A-2-3b). In the same manner as in the production of the pigment composition 3 (R-3) except for the specific heterodiketopyrrolopyrrole pigment A, a diketopyrrolopyrrole pigment composition 8 (R - 8) 9 was obtained. 8. 4 copies. 2纳米。 The average primary particle diameter is 31.2 nm. [Example 9] (Production of Pigment Composition 9 (R-9)) 323842 137 201233734 In addition to the specific heterodiketopyrrolopyrrole pigment A of the formula (A-2-1), the formula (A-2) was changed. In the same manner as in the production of the pigment composition 3 (R-3) except for the specific heterodiketopyrrolopyrrole pigment A of -4a), a diketopyrrolopyrrole pigment composition 9 (R) was obtained. -9) 97. 5 servings. The average primary particle diameter is 35.4 nm. [Example 10] (Production of Pigment Composition 10 (R-10)) The specific heterodiketopyrrolopyrrole pigment A, ® of the formula (A-2-1) was changed to the formula (A-2-4b). The specific heterodithiol β ratio is different from p and π is the same as the pigment A of each of P, and the same operation as in the production of the pigment composition 3 (R-3) is carried out to obtain a diketopyrrolopyrrole pigment composition. 10 (R-10) 96. 6 parts. The average primary particle diameter is 35.8 nm. [Example 11] (Production of Pigment Composition ll (R-ll)) In addition to the specific heterodiketopyrrolopyrrole pigment A of the formula (A-2-1), φ was changed to the formula (A-2-9a) The same operation as in the production of the pigment composition 3 (R-3) except for the specific heterodiketopyrrolopyrrole pigment A, to obtain a diketopyrrolopyrrole pigment composition 11 (R-ll) 93. 9 copies. 4纳米。 The average primary particle diameter is 32. 4nm. [Example 12] (Production of Pigment Composition 12 (R-12)) The specific heterodiketopyrrolopyrrole pigment A of the formula (A-2-1) was changed to the formula (A-2-8). The same operation as the preparation of the pigment composition 3 (R-3) except for the specific heterodiketopyrrolopyrrole pigment A was obtained, and 323842 138 201233734 to diketopyrrolopyrrole pigment composition 12 (R) was obtained. -12) 95. 7 copies. 8纳米。 The average primary particle diameter is 29. 8nm. [Example 13] (Production of Pigment Composition 13 (R-13)) Brominated diketopyrrolopyrrole pigment of the formula (1) 98. A commercially available ci Pigment Red 254 (Ciba Specialty Chemicals Co., Ltd.) "Irgaph〇r Red B-CF" 1. A 1.0 part of a specific heterodiketopyrrolopyrrole pigment A of the formula (Α_2-ι), 1 part of sodium gasification, and 12 parts of diethylene glycol The mixture was placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), and kneaded at 6 (rc for 1 hour). The mixture was poured into warm water while stirring, and stirred for about 1 hour while heating. After the paste, filtered and washed with water to remove salt and diethylene glycol, 'dry at 80 ° C for one day and night, by pulverization to obtain 96.7 parts of diketopyrrolopyrrole pigment composition 13 (R-13), The average primary particle diameter is 33. 2 nm. [Example 14] (Production of Pigment Composition 14 (R-1)) In addition to the brominated diketone σ ratio of the formula (1), the ratio of the pigment gg. 〇 And commercially available C·I·Pigment Red 254 (Irgaphor RedB-CF) made by Ciba Specialty Chemicals Co., Ltd. 1.0 part, and specific heterodiketopyrrolopypene pigment A 1 of formula (a_2-i) 0 injured, The evolution of the formula (1) is 20.0 parts per ton of lop-pyro-pyrazine pigment, and the commercially available CI pigment red 254 ("Irgaphor RedB-CF" manufactured by Ciba Specialty Chemicals Co., Ltd.). The same operation as the preparation of the pigment composition 13 (R-13) was carried out in the same manner as in the preparation of the specific heterodiketopyrrolopyrrole pigment A of -2 - D to obtain 98.3 parts of diketopyrrole 323842 139 201233734 And the pyrrole-based pigment composition 14 (R-14), the average primary particle diameter is 30. 2 nm 〇 [Example 15] (Production of Pigment Composition 15 (R-15)) In addition to the bromination of the formula (1) Ketopyrrolopyrrole pigment 98.0 parts, commercially available CI Pigment Red 254 (Irgaphor Red B-CF) made by Ciba Specialty Chemicals Co., Ltd. 1.0 part, and specific heterodiketone of formula (A-2-1) The pyridylpyrrole pigment A 1. 0 parts, changed to the brominated diketopyrrolopyrrole® material of the formula (1) 50. 0 parts, commercially available CI Pigment Red 254 (Irgaphor, Ciba Specialty Chemicals Co., Ltd. 45 parts of Red B-CF", and 5.0 parts of the specific heterodiketopyrrolopyrrole pigment A of the formula (A-2-1), the same as the production of the pigment composition 13 (R-13) operating, 97 parts of a diketopyrrolopyrrole pigment composition 15 (R-15) was obtained, and the average primary particle diameter was 26.7 nm. [Example 16] • (Production of Pigment Composition 16 (R-16)) In addition to 98.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1), commercially available CI Pigment Red 254 (Irgaphor Red B-CF, 1.0 part by Ciba Specialty Chemicals Co., Ltd., and Formula (A-2-) 1), a specific heterodione-pyrrolopyrrole pigment A 1. 0 parts, changed to a brominated diketopyrrolopyrrole pigment of the formula (1) 20.0 parts, a commercially available CI pigment red 254 (Ciba special 72.0 parts of "Irgaphor Red B-CF" manufactured by Chemical Co., Ltd., and 8.0 parts of the specific heterodiketopyrrolopyrrole pigment A of the formula (A-2-1), and the pigment composition 13 (R-13) The same procedure was carried out to obtain 94.8 parts of diketopyrrole 323842 140 201233734 and a pyrrole pigment composition 16 (R-16) having an average primary particle diameter of 28. Onm. [Example 17] (Production of Pigment Composition 17 (R-17)) In addition to the brominated diketopyrrolopyrrole pigment of the formula (1), 90.0 parts, commercially available CI Pigment Red 254 (Ciba Special) 1.0 part of "Irgaphor Red B-CF" manufactured by Chemical Co., Ltd., and the specific heterodiketone ratio of the formula (A-2-1), and the ratio of the B-pyrrome pigment A to the formula (1). 2 parts of brominated diketopyrrolopyrrole® material, commercially available CI Pigment Red 254 (Irgaphor Red B-CF, manufactured by Ciba Specialty Chemicals Co., Ltd.) 65.0 parts, and formula (A-2- 1) The diketone pyrrolopyrrole pigment is obtained in the same manner as in the preparation of the pigment composition 13 (R-13). The composition 17 (R-17), the average primary particle diameter was 29.3 nm. [Example 18] φ (Production of Pigment Composition 18 (R-18)) The brominated diketopyrrole of the formula (1) 0. 0 parts, a specific heterodiketopyrrolopyrrole pigment mixture 1 (RC-1) 20.0 parts, sodium chloride 1000 parts, and diethylene glycol 120 parts, put into a stainless steel 1 gallon kneading Machine (manufactured by Inoue Manufacturing Co., Ltd.), mixing at 60 ° C 10 Next, the kneaded mixture was poured into warm water, stirred while heating at about 80 ° C for 1 hour to form a paste, filtered and washed with water to remove salt and diethylene glycol, and dried at 80 ° C for a day and night. 9份。 By pulverization, 96.9 parts of the diketopyrrolopyrrole pigment composition 18 (R-18) was obtained, and the average primary particle diameter was 29.2 nm. 323842 141 201233734 [Example 19] (Pigment composition 19 (R) -i9) Manufacture) In addition to the specific heterodiketone-based haha and the specific heterodiketopyrrolopyrrole pigment mixed with three substances (叱, 1), the rest with the pigment composition 180M8) 5微米。 ^ ^ ^ ^ 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2
[實施例20] ’ (顏料組成物20(R-20)之製造) l) 除了將特定雜二酮基吡咯并吡11 各顏 變更成特定雜二酮基η比P各并U比哈顏料現八物~物1 ( Rc、 外’其餘與顏料組成物18(R~18)的製造進/ (叱*~3)之 得到9 5 · 4份之二酮基吡咯并吡咯系顏料缒仃同樣的操作 20(R-20),平均一次粒子徑是31· inm。成物 [實施例21] (顏料組成物21(R-21)之製造) 式 、式(7ί) ^ 12〇 將式(1)的溴化二酮基吡咯并吡咯顏料95 (A-2-1)之特定雜二酮基吡咯并吡咯顏料. 〇份 之色素衍生物5. 0份、氯化鈉1〇〇〇份,及—你 份,放入不銹鋼製1加侖捏煉機(井上製作二醇 C中混練1〇小時。其次,將混煉之混合物投入溫水中在: 邊在約80°C中加熱一邊攪拌1小時作成膏狀物,過濾並水 洗除去食鹽及二乙一醇後,在8〇。〇乾燥一畫夜,藉由粉碎 得到91. 8份之二酮基吡咯并吡咯系顏料組成物 323842 142 201233734 21(R-21),平均-次粒子徑是27·4⑽。 [實施例22] (顏料組成物22(R-22)之製造) 將式⑴的漠化二酮基^各并鱗顏料8〇 〇份市售 的C-L顏料紅254 (汽巴特別化學公司製^聊⑹μ B-CF」18.G份、式(A-2-1)之特定雜二酮基鱗并料顏 料A 2.0份、式(7-1)之色素衍生物5 〇份、氣化納誦 份,及二乙二醇120份,於人τ棘β〜, 赢 入不銹鋼製1加侖捏煉機(井上 •製作所製)中,在6〇t中混練1〇小時。其次,將混煉之混 合物投入溫水中,-邊在約8(rc中加熱一邊㈣i小時作 成膏狀物’韻並水洗除去食鹽及二乙二醇後,在啊乾 燥-晝夜,藉由粉碎得到91. 3份之二酮基料并料系顏 料組成物22(R-22),平均一次粒子徑是29. 。 [參考例1] * (顏料組成物23(R-23)之製造) # 除了將式⑴的臭化二酮基°比"各并°比口各顏料變更成市 售的C. I.顏料紅254(汽巴特別化學公司製「卜卿h〇rRed B-CF」之外,其餘與顏料組成物4(R_4)的製造進行同樣的 操作,得到96.0份之二酮基鱗并料系顏料組成物 23(R-23) ’平均一次粒子徑是3〇 9nme [參考例2] (顏料組成物24(R-24)之製造) 式⑴的漠化二_基鱗并如各顏料1〇〇〇份氣化 納1000份,及二乙二醇120份,玫入不_製i加命捏煉 323842 143 201233734 機(井上製作所製)中,在60°C中混練10小時。其次,將 已混煉之混合物投入溫水中,一邊在約8 0 °C中加熱一邊擾 拌1小時作成膏狀物,過爐、並水洗除去食鹽及二乙二醇 後,在80°C乾燥一畫夜,藉由粉碎得到96. 9份之二酮基 0比11 各并吨11各系顏料組成物24(R-24),平均一次粒子徑是 33. lnm。 [參考例3] (顏料組成物25(R-25)之製造) ® 除了將式(1)的溴化二酮基吡咯并吡咯顏料95. 0份, 及式(A-2-1)之特定雜二酮基吡咯并吡咯顏料A 5. 0份,變 更成式(1)的溴化二酮基吡咯并吡咯顏料70. 0份,及式 (A-2-1)之特定雜二酮基吡咯并吡咯顏料A 30.0份之外, 其餘與顏料組成物l(R-l)的製造進行同樣之操作,得到 98. 0份之二酮基D比17各并11比p各系顏料組成物25(R-25),平均 一次粒子徑是28. 6nm。 φ [參考例4] (顏料組成物26(R-26)之製造) 除了將式(1)的溴化二酮基吡咯并吡咯顏料98. 0份、 市售的C. I.顏料紅254(汽巴特別化學公司製「Irgaphor Red B-CF」1. 0份、式(A-2-1)的特定雜二酮基吡咯并吡咯 顏料A 1. 0份,變更成式(1)的溴化二酮基吡咯并吡咯顏料 15. 0份、市售的C. I.顏料紅254(汽巴特別化學公司製 「Irgaphor Red B-CF」65. 0 份、式(A-2-1)的特定雜二酮 基吡咯并吡咯顏料A 20.0份之外,其餘與顏料組成物 323842 144 201233734 13(R-13)的製造進行同樣之操作,得到95. 1份之二酮基吡 咯并吡咯系顏料組成物26(R-26),平均一次粒子徑是 29. 5nm。 [參考例5] (顏料組成物27(R-27)之製造) 除了將式(1)的溴化二酮基吡咯并吡咯顏料,變更成 市售的C. I.顏料紅254(汽巴特別化學公司製「Irgaphor RedB-CF」之外,其餘與顏料組成物24CR-24)的製造進行 ® 同樣之操作,得到98. 1份之二酮基D比洛并°比17各系顏料組成 物27(R-27),平均一次粒子徑是34. 9nm。 [參考例6] (顏料組成物28(R-28)之製造) 與日本特表2011-523433之實施例1016同樣的方法 合成,得到由式(1)的二酮基吡咯并吡咯顏料與下述式 (A-17)所成的顏料組成物28(R-28)。[Example 20] ' (Production of Pigment Composition 20 (R-20)) l) In addition to changing the specific heterodiketopyrrolopyrene 11 to a specific heterodiketone η ratio P and U Biha pigment Now eight objects ~ material 1 (Rc, outer 'the rest and pigment composition 18 (R~18) are made into / (叱*~3) to get 9 5 · 4 parts of diketopyrrolopyrrole pigment 缒仃The same operation 20 (R-20), the average primary particle diameter is 31·inm. The product [Example 21] (Production of Pigment Composition 21 (R-21)) Formula, Formula (7ί) ^ 12〇 (1) The specific heterodiketopyrrolopyrrole pigment of the brominated diketopyrrolopyrrole pigment 95 (A-2-1). The pigment derivative of the quinone portion 5. 0 parts, sodium chloride 1 〇〇〇 And, for your part, put into a stainless steel 1 gallon kneader (mixed in the broth C for 1 hour in the well. Secondly, put the mixture into the warm water: stir while heating at about 80 ° C After 1 hour, it was made into a paste, filtered and washed with water to remove salt and diethyl alcohol, and then dried at 8 Torr. After drying for one night, 91.8 parts of diketopyrrolopyrrole pigment composition 323842 142 201233734 21 (R-21) The average-secondary particle diameter is 27·4 (10). [Example 22] (Production of Pigment Composition 22 (R-22)) The desertified diketone group of the formula (1) and each of the scale pigments 8 parts of a commercially available CL Pigment Red 254 (manufactured by Ciba Specialty Chemicals Co., Ltd. (6) μ B-CF" 18.G, specific heterodiketone squash pigment A of formula (A-2-1) 2.0 parts, formula (7-1) The pigment derivative 5 〇 part, gasified 诵 诵 part, and diethylene glycol 120 parts, in the human τ β β ~, won the stainless steel 1 gallon kneader (Inoue • Manufacturing), at 6 〇t Mixing for 1 hour. Secondly, the mixture is mixed into warm water, and then dried at about 8 (heated in rc (four) for 1 hour to make a paste' rhyme and washed with water to remove salt and diethylene glycol, then dry - By day and night, 91.3 parts of the diketone base material was obtained by pulverization and the pigment composition 22 (R-22) was obtained, and the average primary particle diameter was 29. [Reference Example 1] * (Pigment composition 23 (R- 23) Manufactured by the change of the odorized diketone group of the formula (1) to the commercially available CI Pigment Red 254 ("Chuba Special Chemicals Co., Ltd." Other than -CF", the rest with pigment Production of Composition 4 (R_4) The same operation was carried out to obtain 96.0 parts of a diketone-based squash pigment composition 23 (R-23) 'The average primary particle diameter was 3 〇 9 nme [Reference Example 2] (Pigment composition) The manufacture of the product 24 (R-24)) The desertified bis-base scale of the formula (1) and 1000 parts of the gasification of each pigment, and 120 parts of the diethylene glycol, the rose into the Kneading 323842 143 201233734 machine (manufactured by Inoue Seisakusho Co., Ltd.), kneading at 60 ° C for 10 hours. Next, the kneaded mixture is poured into warm water, and stirred for about 1 hour while heating at about 80 ° C to form a paste. After drying and removing the salt and diethylene glycol, the mixture is dried at 80 ° C.纳米。 The average particle diameter is 33. lnm. The granules are obtained by pulverization. [Reference Example 3] (Production of Pigment Composition 25 (R-25)): In addition to the brominated diketopyrrolopyrrole pigment of the formula (1), 95. 0 parts, and the formula (A-2-1) The specific heterodione-pyrrolopyrrole pigment A 5. 0 parts, changed to the brominated diketopyrrolopyrrole pigment of the formula (1) 70. 0 parts, and the specific heterodione of the formula (A-2-1) The same operation as the preparation of the pigment composition l (R1) was carried out in the same manner as in the production of the pigment composition 1 (R1) to obtain 98.0 parts of diketone D to 17 and 11 to p of each pigment composition 25 6nm。 The average primary particle diameter is 28. 6nm. φ [Reference Example 4] (Production of Pigment Composition 26 (R-26)) In addition to the brominated diketopyrrolopyrrole pigment of the formula (1), 90.0 parts, commercially available CI Pigment Red 254 (Ciba "Irgaphor Red B-CF" manufactured by Special Chemicals Co., Ltd. 1.0 part, a specific heterodiketopyrrolopyrrole pigment A of formula (A-2-1), 1.0 part, changed to the brominated two of formula (1) a ketopyrrolopyrrole pigment of 1 part, a commercially available CI Pigment Red 254 ("Irgaphor Red B-CF" manufactured by Ciba Specialty Chemicals Co., Ltd. 65.0 parts, a specific heterodiketone of the formula (A-2-1) The same operation as in the manufacture of the pigment composition 323842 144 201233734 13 (R-13) was carried out to obtain 95. 1 part of a diketopyrrolopyrrole pigment composition 26 (except for 20.0 parts of the pyridylpyrrole pigment A). R-26), the average primary particle diameter is 29.5 nm [Reference Example 5] (Production of Pigment Composition 27 (R-27)) In addition to the brominated diketopyrrolopyrrole pigment of the formula (1), Manufactured in the same manner as in the manufacture of the chemically-produced CI Pigment Red 254 ("Irgaphor RedB-CF" manufactured by Ciba Specialty Chemicals Co., Ltd., and the other pigment composition 24CR-24) to obtain 98.1 parts of the diketone group. D The ratio of the average primary particle diameter is 34. 9 nm. [Reference Example 6] (Manufacture of Pigment Composition 28 (R-28)) and Japan Special Table 2011 The compound of Example 1016 of -523433 was synthesized in the same manner to obtain a pigment composition 28 (R-28) of the diketopyrrolopyrrole pigment of the formula (1) and the following formula (A-17).
式(A- 1 7) [參考例7] (顏料組成物29(R-29)之製造) 與日本特表2011-523433之實施例1039同樣的方法 323842 145 201233734 合成’得料式⑴的二_基„叫并顏料與下述式 (A-18)所成的顏料組成物29(R-29)。Formula (A-17) [Reference Example 7] (Production of Pigment Composition 29 (R-29)) The same method as Example 1039 of JP-A-2011-523433 323842 145 201233734 Synthesis of the second material of the formula (1) The pigment composition 29 (R-29) formed by the pigment and the following formula (A-18).
將所製造的顏料組成物1至29(R-1至29)的内容在表 A-1中表示。表1中記載的「PR254」是表示C. I·顏料紅 254的意思。 [表 A-1 ] &A- 1The contents of the pigment compositions 1 to 29 (R-1 to 29) to be produced are shown in Table A-1. "PR254" shown in Table 1 means C.I. Pigment Red 254. [Table A-1] &A- 1
顏料组成物 二W基吡略并吡咯系顏料 AP質Y比〒4 色责衍生换 舨料1 質量X 顏料2 質量X 孩料3 質璧X 實施例1 R-1 式⑴ 99 Λ ΪΑ-2- 1) 1 - — - - 實施例2 R-2 式⑴ 9 7 式(A-2-n 3 - — - - 實施例3 R-3 式(1) 9 5 式(Α-2- 1 1 5 - — - — 1Γ艳洌4 R-4 式⑴ 9 0 式(Α-2- 11 10 一 一 - 實旄例5 R-5 式⑴ 8S 式(A-2-li 1 5 一 — *· — 實旄例6 R-6 式⑴ 95 Κ (Α-2-2) 5 - _ - ' 貧施W 7 R-7 式⑴ 95 式(Α-2-3ίΐ) S 一 一 - - 實施W8 R-8 式⑴ 95 式(A-2-3hl 5 - 一 — ' 實施W9 R-9 式⑴ 9S 式(A- 2 - 4 a) 5 - - • * <施例1 0 R- 1 0 式⑴ 95 式(A- 2 -4 b) 5 - 一 - 實拢例1 1 R-1 1 式⑴ 95 式(A,2-9al 5 - 一 — — 贫旄W1 2 R- 1 2 式⑴ 9 5 式 CA-2-81 S - • — - 實施例1 3 R- 1 3 式⑴ 9 8 式(A-2 - η 1 PR 2 54 1 9 9:1 - 實旄例1 4 R-1 4 式⑴ ao Λ (Λ-2 - 1) 2 PR 2S4 18 8 2:18 - 贫施例1 5 R- 1 5 式⑴ 5 0 式(A* 2— η 5 PR 2 54 4 5 5 3:47 - 賁施例1 6 R-1 6 式⑴ 2 0 式(α-2-η 8 PR 2 5 4 7 2 2 2:78 實旄W1 7 R-1 7 式⑴ 2 0 式(A-2-η 15 PR 2 54 6 5 24:76 - 實施例1 8 R- 1 8 式⑴ 8 0 式(A-2- 1> 2 PR 2 54 18 " 82:18 實旄例1 9 R-1 9 式⑴ 80 式(A - 2-2> 2 PR 2 54 1 8 82:18 舍施例2 0 R 20 式⑴ 8 0 式(A- 2 -4 al 2 PR 2 54 18 8 2:18 — 實施例2 1 R-2 1 式⑴ 9 5 式 <A-2-l> 5 - - ^ (? - η 贫施例2 2 R-22 式⑴ 80 式 <A-2-l> 2 PR 254 18 8 2 : 1 R 五(7-η 參考例1 R-23 - - 式 <Α·2-1> 10 PR 254 9 0 麥蜍例2 R-24 式(1、 1 0 0 • 一 • - - - 參考例3 R-2 5 式⑴ 7 0 式 <Α-2-1> 3 0 - - — 拿考W4 R-26 式⑴ 15 ^ (A-2-n 2 0 PR 2 5 4 6 5 19:81 —_ 參考例5 R-27 - - - PR 254 1 0 0 - 參考例6 R- 2 8 式⑴ 8 2 一 一 式(A-1 7> 18 ~ 參考例7 R-29 式⑴ 11 - - 式(A-1 8) 8 9 [實施例23] 146 323842 201233734 (著色組成物1(R卜丨)之製作) ^下it之混合物攪拌混合成均勻後使用直徑5mm 氧化結J、球,以Eiger研磨機(Eiger日本公司製「ini model M-250 MKII」分散5小時後,以5, 〇 ”的過遽膜過 濾,製作著色組成物1(Rp i)。 二酮基吡咯并吡咯系顏料組成物1(R-1) 11. 0 份 色素衍生物式(14-1) 1.0份 丙烯酸樹脂溶液1 40. 0 份 丙二醇單甲醚醋酸酯 48. 0 份 [實施例24至44] (著色組成物2至22(RP-2至22)之製作) 除了將顏料組成物l(R-l)變更成在表A-2記載的顏料 組成物之外,其餘與著色組成物l(RP-l)進行同樣操作, 製作著色組成物2至22(RP-2至22)。 [實施例45] % (著色組成物23(RP-23)之製作) 將下述之混合物攪拌混合試圖使變成均勻後,使用直 徑0. 5mm的二氧化錘小球,以Eiger研磨機(Eiger日本公 司製「Mini model M-250 MKII」分散5小時後,以5. 0" m的過濾膜過濾,製作著色組成物23CRP-23)。 二_基吡咯并吡咯系顏料組成物2(R-2) 11.0份 色素衍生物式(6-3) 1.0份 樹脂型分散劑 6.0份 (Byk Chemie 公司製「BYK161」(30°/。溶液)) 323842 147 201233734 31.0 份 51. 0 份 丙烯酸樹脂溶液1 丙二醇單甲醚醋酸酯 [實施例46] (著色組成物24(RP-24)之製作) 將下述此合物授拌混合成均勻後,使用直徑〇. 5min的 二氧化鍅小球,以Eiger研磨機(Eiger日本公司製「MiniPigment composition two W-pyridolipid pyrrole pigment AP Y Y 〒 4 color derivative conversion material 1 mass X pigment 2 mass X child 3 quality 璧 X Example 1 R-1 Formula (1) 99 Λ ΪΑ-2 - 1) 1 - - - - Example 2 R-2 Formula (1) 9 7 Formula (A-2-n 3 - - - - Example 3 R-3 Formula (1) 9 5 Formula (Α-2- 1 1 5 - — - — 1Γ艳洌4 R-4 Formula (1) 9 0 Formula (Α-2- 11 10 一一 - Example 5 R-5 Formula (1) 8S Formula (A-2-li 1 5 I—*· — Example 6 R-6 Formula (1) 95 Κ (Α-2-2) 5 - _ - ' Poor W 7 R-7 Formula (1) 95 Formula (Α-2-3ίΐ) S One-one - Implement W8 R -8 Formula (1) 95 Formula (A-2-3hl 5 - I - ' Implement W9 R-9 Formula (1) 9S Formula (A- 2 - 4 a) 5 - - • * <Example 1 0 R- 1 0 (1) 95 Formula (A- 2 -4 b) 5 - A - Solid example 1 1 R-1 1 Formula (1) 95 Formula (A, 2-9al 5 - I - Barren W1 2 R- 1 2 Formula (1) 9 5 Formula CA-2-81 S - • - - Example 1 3 R- 1 3 Formula (1) 9 8 Formula (A-2 - η 1 PR 2 54 1 9 9:1 - Example 1 4 R-1 4 Formula (1) ao Λ (Λ-2 - 1) 2 PR 2S4 18 8 2:18 - Poor Example 1 5 R- 1 5 Formula (1) 5 0 Formula (A* 2 - η 5 PR 2 54 4 5 5 3:47 - Example 1 6 R-1 6 Formula (1) 2 0 Formula (α-2-η 8 PR 2 5 4 7 2 2 2:78 Real 旄W1 7 R-1 7 Formula (1) 2 0 Formula (A-2-η 15 PR 2 54 6 5 24:76 - Example 1 8 R- 1 8 Formula (1) 8 0 Formula (A-2- 1> 2 PR 2 54 18 " 82:18 Example 1 9 R-1 9 Formula (1) 80 Formula (A - 2-2 > 2 PR 2 54 1 8 82:18 Scenario 2 0 R 20 Formula (1) 8 0 Formula (A-2 - 4 al 2 PR 2 54 18 8 2:18 - Example 2 1 R-2 1 Formula (1) 9 5 Formula <A-2-l> 5 - - ^ (? - η Poor Example 2 2 R-22 Formula (1) 80 Formula <A-2-l> 2 PR 254 18 8 2 : 1 R 5 (7-η Reference Example 1 R-23 - - Formula <Α·2-1> 10 PR 254 9 0 Example 2 R-24 Type (1, 1 0 0 • One • - - - Reference Example 3 R-2 5 Formula (1) 7 0 Formula <Α-2-1> 3 0 - - — Take the test W4 R-26 Formula (1) 15 ^ (A-2-n 2 0 PR 2 5 4 6 5 19:81 —_ Reference Example 5 R-27 - - - PR 254 1 0 0 - Reference Example 6 R- 2 8 Equation (1) 8 2 Equation 1 (A-1 7> 18 ~ Reference Example 7 R-29 (1) 11 - - Formula (A-1 8) 8 9 [Example 23] 146 323842 201233734 (Production of coloring composition 1 (R 丨)) ^ Mix the mixture of it into a uniform and use straight The coloring composition 1 (Rp i) was prepared by filtering through a ruthenium membrane of an Eiger grinder ("i model M-250 MKII" manufactured by Eiger Japan Co., Ltd. for 5 hours and then 5, 〇"). . Diketopyrrolopyrrole pigment composition 1 (R-1) 11. 0 parts of pigment derivative formula (14-1) 1.0 part acrylic resin solution 1 40. 0 parts propylene glycol monomethyl ether acetate 48. 0 parts [ Examples 24 to 44] (Production of Colored Compositions 2 to 22 (RP-2 to 22)) In addition to changing the pigment composition 1 (R1) to the pigment composition described in Table A-2, Composition 1 (RP-1) was subjected to the same operation to prepare colored compositions 2 to 22 (RP-2 to 22). [Example 45] % (Production of the coloring composition 23 (RP-23)) The following mixture was stirred and mixed, and it was attempted to make it uniform, and a diameter of 0.5 mm of a dioxide ball was used, and an Eiger mill (Eiger) was used. The "Mini model M-250 MKII" manufactured by Nippon Co., Ltd. was dispersed for 5 hours, and then filtered through a filtration membrane of 5.0" m to prepare a colored composition 23CRP-23). Di-p-pyrrolopyrrole pigment composition 2 (R-2) 11.0 parts of pigment derivative Formula (6-3) 1.0 part of resin-type dispersant 6.0 parts ("BYK161" manufactured by Byk Chemie Co., Ltd. (30 ° / solution) 323842 147 201233734 31.0 parts 51.0 parts of acrylic resin solution 1 propylene glycol monomethyl ether acetate [Example 46] (Production of coloring composition 24 (RP-24)) The following compound was mixed and mixed to form a uniform , using a diameter of 〇. 5min of cerium oxide pellets, Eiger grinding machine ("Eiger Japan" "Mini
model M-250 MKII」分散5小時後,以5 0//ιη的過濾膜過 濾,製作著色組成物24(RP-24)。 二酮基吡咯并吡咯系顏料組成物2(R_2) 12. 0份 樹脂型分散劑 (味之素 FINETECHNO 公司製「Ajisper ΡΒ82ΐ」) 23· 0 份 61. 4 份 丙烯酸樹脂溶液1 丙二醇單曱醋酸酯 [參考例8至14] (著色組成物25至31(RP-25至31)之製作) 除了將顏料組成物1(ΙΜ)變更成在表A_2記載的顏 料組成物之外,其餘與著色組成物ΚΚΡΜ)進行同樣操 作’製作著色組成物25至31(RP-25至31)。 〈著色組成物之評估〉 (對比度測定基板的製作) 將實施例23至46、參考例8至14所得之著色組成4 在l〇〇mmxl〇〇mm、〇.7则1厚度的玻璃基板上,在c光 使膜厚塗佈成x=〇.64(),並加以乾燥。進—步,以咖^ 熱60分鐘可以得到紅色塗膜。 323842 148 201233734 (塗膜之對比度比評估) 有關塗膜之對比比的測定法說明。液晶裝置用背光單 元所放出之光,係通過偏光板而偏光,通過在玻璃基板上 塗佈著色組成物的乾燥塗膜,而到達偏光板。只要偏光板 與偏光板之偏光面為平行的話,光雖是透過偏光板,但在 偏光面為直行的情形,光是被偏光板遮斷。然而,藉由偏 光板當被偏光之光通過著色組成物的乾燥塗膜時,由於顏 • 料粒子產生散射等’當偏光面之一部分發生交錯時,偏光 板為平行之時穿透偏光板的光量會減少,偏光板為直行之 時一部分光穿透偏光板。將此穿透光當作在偏光板上的亮 度測疋’鼻出偏光板為平行之時的亮度,與直行時的亮度 之比(對比度比)。 (對比度比Μ平行時的亮度)/(直行時的亮度) 因此,由於塗膜中的顏料產生散射時,平行時的亮度 會下降,並且因為直行時的亮度會增加,故對比度比變成 % 下降。 同時’作為免度計者是使用色彩亮度計(T〇pC〇公司製 BM~ 5 A」)’作為偏光板者是使用偏光板(日東電工公司製 「NPF-G1220DUN」)。同時,在測定時,為了遮斷多餘的光, 在測定部分覆上開有lcm正方形孔洞的黑色遮罩。 〈黏度安定性評估〉 (初期黏度、經時增黏率的測定) 著色組成物的黏度是在調製著色組成物的當天,使用 E型黏度计(東機產業公司製「eld黏度計」),於2 5。〇測 323842 149 201233734 定初期黏度。於是,關於在40。(:靜置自調製著色組成物的 當天算起7天者,於使試樣溫度回到25〇c後,依據上述黏 度測定法,測定經時黏度,由下式求得經時增黏率。.. 經時增黏率=(經時黏度)/ (初期黏度)χ丨〇 〇 (0/〇) (初期黏度、經時增黏率的評估) 關於黏度安定性,係藉由經時增黏率來進行評估。σ 要經時增黏率在議以上未達酬的話,在實用上就有耐' _ I·生超過此範圍而會有降低黏度或增加黏度,將著色組成 物塗佈在玻璃基板時,在相同的塗佈條件則無法塗佈,在 生產性上會有問題。更佳的是在_以上未達110%之範圍。 〇.經時增黏率90%以上未達11〇% △、星β寺增黏率80%以上未達9〇%,或m乂上未達1贏 X.經時增黏率未達80%,或12〇%以上 323842 150 201233734 [表 A-2] 表A - 2 實典例2 3 實施例2 4 著色纽成軚 顏料粗成物 色素衍生铷 樹庙资分教射 評估結呆 對比度比 3 9 00 黏度安定性 0 RP-1 RP-2 R- 1 R- 2 式(1 4 - 1、 實Λ例2 5 實施树2 6 RP-3 RP-4 R-3 R _ 4 A v 1 4 — 1 ) 式(1 4 - 1、 式(1 4 — 1 > - 4 0 0 0 4 15 0 ο ο ο 實施例2 7 RP- 5 R-5 ^ (1 4-n 4 6 5 0 〇 2 8 RP-6 R-6 式 U 4- n — 4 0 5 0 〇 R P- 7 R-7 式(l 4-n _ 4 10 0 0 η地例3 0 R P- 8 R-8 式(1 4 - 1 i 4 10 0 〇 Τ綠例3 1 資施例3 2 R P- 9 RP-X 0 R-9 R - 1 0 式(i 4- n - 4 100 〇 實施例3 3 RP-1 i R-l 1 A 11 4 — 1 i 式(1 4 — 1 1 一 40 0 0 5 2 0 0 ο 〇 赏施例3 4 RP-1 2 R- 1 2 式 <1 4: ΰ 一 _ 3 7 0 0 〇 資施例3 〇 實秣树3 6 RP-1 3 RP- 1 4 R- 1 3 ^ (14-1¾ 40 0 0 0 實施例3 7 貧應例3 8 RP-1 5 RP-1 6 R-】S R- 1 6 瓦(1 4 —" 式(14 - η 式(1 4 - 1 > - 3 8 5 0 4 10 0 4 3 0 0 〇 〇 ο M «C>iH *9 實旄树4 0 RP- 1 7 RP-1 8 R-l 7 R- l 8 ^ (1 4 - η 式(1 4- η - 4 3 0 0 3 8 5 0 ο Ο 實祐例4 1 實施例4 2 RP- 1 9 RP-2 0 R-l 9 R- 2 0 式<i m - 3 7 5 0 〇 實妹例4 3 RP-2 1 R-2 1 Λ V 1 4 — 1 > 式 <ι 4-n 3 7 0 0 4 2 0 0 〇 〇 RP-2 2 R-2 2 式(1 4-η ......... ο η η 〇 實花W 4 5 RP-2 3 R-2 式(6-3) Β Υ Κ 1 6 1 3 3 5 0 〇 —_^碑>洌4 6 —麥考例8 — RP- 2 4 ~ RP-2 5 R-2 R-23 Ajisper P B fi 2 1 3400 3 3 0 0 〇 〇 參考例9 RP-26 R-24 2C (1 4-1> 3 η η 0 X 參考例1 0 RP- Z 7 R-2 5 式 <1 4- η S 9 S 0 X 參考例1 JI RP-2 8 R-2 6 式(1 4-1) __ 3 3 0 0 Δ 參考切1 2 參考例1 3 RP-2 9 R-27 式(1 4-1> — 2 15 0 X 參考例1 4 RP-3 1 R — 2 8 _ R-2 9 2: (1 4-1) _式及1 4-η = 2 5 3 0 C --- 2 3 0 0 Δ • <其他著色組成物的製作方法> (著色組成物32(RP-32)的製作) 將下述混合物攪拌混合成均勻後’使用直徑〇 5mnl的 一氧化錯小球’以Eiger研磨機(Eiger日本公司製「Mini model M-250 MKII」分散5小時後,以5. 0/zm的過濾膜過 濾,製作著色組成物32(RP-32)。 二蒽醌系顏料(PR177-1) 10. 8 份 色素衍生物 式(8-5) 1.2份 丙烯酸樹脂溶液1 40. 〇 份 151 323842 201233734 丙二醇單曱醚醋酸酯 48. 0 份 [實施例47] (感光性著色組成物l(RR-l)之製作彡. 將下述之混合物攪拌混合成均勻後,使用 1 // m的過 濾膜過濾,製作感光性著色組成物KRhi)。 著色組成物l(RP-l) 38. 4 份 著色組成物32(RP-32) 3· 6份 丙烯酸樹脂溶液2 13. 2 份 光聚合性單體(東亞合成公司製rAR〇NIX M4〇〇」 2. 8份 光聚合起始劑(汽巴曰本公司製rIrgacure_9〇7」 2.0份 增感劑(Hodogaya Chemical 公司製「EAB-F」 0.4份 乙二醇單甲醚醋酸酯 39. 6 份 [實施例48至72] (感光性著色組成物2至24(RR-2至24)之製作) 除了將著色組成物KRP-i)變更成著色組成物2至 φ 24(RP—2至24) ’同時,以使實施例47成為同樣色度的方 式調整著色組成物2至24(RP-2至24)與著色組成物32 (RP-32)的比率之外,其餘與實施例47進行同樣操作而製 作感光性著色組成物2至24(rr-2至24)。 [參考例15至21 ] (感光性著色組成物25至31 (RR-25至31)之製作) 除了將著色組成物KRP—U變更成著色組成物25至 31 (RP 25至31)’再者,以使實施例47成為同樣色度的方 式調整著色組成物25至31(RP-25至31)與著色組成"物32 323842 152 201233734 CRP-32)的比率之外’其餘與實施例47進行同樣操作可製 作感光性著色組成物25至31(RR-25至31)。 〈感光性著色組成物的評估〉 (色特性、對比度比(CR)評估) 將實施例47至72、參考例15至21所得之感光性著 色組成物’在100mm X 100mm、0. 7mm厚度的玻璃基板上, 於C光源中使膜厚成為χ=〇. 640,y=0· 328的方式而塗佈感 光性著色組成物’並加以乾燥後’使用超高壓水銀燈照射 ® 300mJ/cm2之紫外線。再者,於230°C加熱60分鐘可得到 紅色塗膜。之後’測定所得塗膜的亮度(γ )及對比度比(c R )。 同時’色度及亮度(Y)是以顯微分光光度計(〇lympus 光學公司製「OSP-SP200」)測定。 (塗膜表面的結晶析出評估) 將實施例47至72、參考例15至21所得之感光性著 色組成物’在100mm X 100顏、0· 7mm厚度的玻璃基板上, φ 於c光源中以使膜厚成為χ=〇· 640的方式塗佈感光性著色 組成物’並加以乾燥後,使用超高壓水銀燈照射300mJ/cm2 之紫外線。接著,於23(TC進行加熱處理60分鐘後,再重 複2次在240°C加熱處理60分鐘。加熱處理後的基板塗膜 表面以光學顯微鏡觀察,有無結晶析出是依據下述基準判 定。 ◎ : 230°C加熱處理6〇分鐘後,進一步在24(TC加熱處理 60分鐘後,及再進行24(TC加熱處理60分鐘亦無結晶析出 〇:230°C加熱處理6〇分鐘後,及再進行24(rCM熱處理 323842 153 201233734 60分鐘亦無結晶析出(第2次的24(rc加熱處理肋分鐘有 結晶析出) △:雖在230°C加熱處理60分鐘後沒有結晶析出,但進一 步240°C加熱處理60分鐘有結晶析出 X : 230°C加熱處理60分鐘後有結晶析出 [表 A-3]After the model M-250 MKII was dispersed for 5 hours, it was filtered through a filtration membrane of 50%, and a colored composition 24 (RP-24) was produced. Diketopyrrolopyrrole pigment composition 2 (R_2) 12.0 part resin type dispersant ("Ajisper ΡΒ82ΐ" manufactured by FINETECHNO Co., Ltd.) 23·0 parts 61. 4 parts acrylic resin solution 1 propylene glycol monoterpene acetic acid Ester [Reference Examples 8 to 14] (Production of Colored Compositions 25 to 31 (RP-25 to 31)) In addition to changing the pigment composition 1 (ΙΜ) to the pigment composition described in Table A-2, The composition ΚΚΡΜ) was subjected to the same operation to prepare colored compositions 25 to 31 (RP-25 to 31). <Evaluation of Coloring Composition> (Production of Contrast Measurement Substrate) The coloring compositions obtained in Examples 23 to 46 and Reference Examples 8 to 14 were 4 on a glass substrate having a thickness of 1 mm x 10 mm, 〇 7. The film thickness was applied to x = 〇.64 () in c light and dried. Into the step, to the coffee ^ heat for 60 minutes to get a red film. 323842 148 201233734 (Contrast Ratio Evaluation of Coating Film) Description of the measurement method for the contrast ratio of the coating film. The light emitted from the backlight unit for a liquid crystal device is polarized by a polarizing plate, and a dried coating film of a colored composition is applied onto a glass substrate to reach a polarizing plate. As long as the polarizing surfaces of the polarizing plate and the polarizing plate are parallel, although the light passes through the polarizing plate, when the polarizing surface is straight, the light is blocked by the polarizing plate. However, when the polarizing plate passes through the dried coating film of the coloring composition by the polarizing plate, scattering due to the pigment particles, etc., when one of the polarizing surfaces is staggered, the polarizing plate penetrates the polarizing plate when they are parallel. The amount of light is reduced, and a part of the light penetrates the polarizing plate when the polarizing plate is straight. This transmitted light is taken as the ratio of the brightness at the time when the nose-out polarizing plate is parallel and the brightness at the time of straight-line (contrast ratio). (Brightness when contrast is parallel to )) / (Brightness when going straight) Therefore, when the pigment in the coating film is scattered, the brightness in parallel is lowered, and since the brightness during straight running is increased, the contrast ratio becomes %. . At the same time, as a degree-free meter, a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as a polarizing plate. At the same time, in order to block the excess light during the measurement, a black mask having a square hole of 1 cm was placed on the measurement portion. <Viscosity stability evaluation> (Measurement of initial viscosity and time-increasing viscosity) The viscosity of the coloring composition is an E-type viscometer ("eld viscosity meter" manufactured by Toki Sangyo Co., Ltd.) on the day when the coloring composition is prepared. At 2 5 . Speculation 323842 149 201233734 Initial viscosity. So, about 40. (: After 7 days from the date of setting the self-modulating coloring composition, after the temperature of the sample is returned to 25 ° C, the viscosity is measured according to the above viscosity measurement method, and the time-increasing viscosity is obtained by the following formula. Time-dependent viscosity increase = (time-dependent viscosity) / (initial viscosity) χ丨〇〇 (0 / 〇) (Evaluation of initial viscosity, time-dependent viscosity increase) About viscosity stability, by time The viscosity increase rate is used for evaluation. σ If the time-increasing rate is not paid above, there is practical resistance to ' _ I·sheng beyond this range, there will be a decrease in viscosity or increase in viscosity, and the coloring composition will be coated. When it is coated on a glass substrate, it cannot be coated under the same coating conditions, and there is a problem in productivity. More preferably, it is less than 110% in the range of _. 〇. The viscosity increase rate over time is 90% or more. Up to 11〇% △, Star β Temple viscosity increase rate of 80% or more did not reach 9〇%, or m乂 did not reach 1 win X. The time-increasing viscosity rate did not reach 80%, or 12〇% or more 323842 150 201233734 [ Table A-2] Table A-2 Practical Example 2 3 Example 2 4 Coloring Newborns Pigment Pigment Pigment Derived Eucalyptus Temple Funding Assessment Evaluation Junction Contrast Ratio 3 9 00 Viscosity Stability 0 RP-1 RP-2 R- 1 R- 2 Formula (1 4 - 1 , Practical Example 2 5 Implementation Tree 2 6 RP-3 RP-4 R-3 R _ 4 A v 1 4 — 1 ) 1 4 - 1 , Formula (1 4 - 1 > - 4 0 0 0 4 15 0 ο ο ο Example 2 7 RP- 5 R-5 ^ (1 4-n 4 6 5 0 〇 2 8 RP-6 R-6 Formula U 4- n — 4 0 5 0 〇R P- 7 R-7 Formula (l 4-n _ 4 10 0 0 η Example 3 0 R P- 8 R-8 Formula (1 4 - 1 i 4 10 0 〇Τ Green Example 3 1 Example 3 2 R P- 9 RP-X 0 R-9 R - 1 0 Formula (i 4- n - 4 100 〇 Example 3 3 RP-1 i Rl 1 A 11 4 — 1 i Formula (1 4 — 1 1 1 40 0 0 5 2 0 0 ο 赏 赏 3 3 RP-1 2 R- 1 2 式 <1 4: ΰ 1 _ 3 7 0 0 〇 Example 3 〇 秣 3 3 6 RP-1 3 RP- 1 4 R- 1 3 ^ (14-13⁄4 40 0 0 0 Example 3 7 Poor Example 3 8 RP-1 5 RP-1 6 R- 】S R- 1 6 watts (1 4 -" (14 - η (1 4 - 1 > - 3 8 5 0 4 10 0 4 3 0 〇〇ο M «C> iH *9 旄Tree 4 0 RP- 1 7 RP-1 8 Rl 7 R- l 8 ^ (1 4 - η Formula (1 4- η - 4 3 0 0 3 8 5 0 ο 实 实 例 4 1 Example 4 2 RP - 1 9 RP-2 0 Rl 9 R- 2 0 Formula <im - 3 7 5 0 〇实妹例4 3 RP-2 1 R-2 1 Λ V 1 4 — 1 > Formula <ι 4-n 3 7 0 0 4 2 0 0 〇〇RP-2 2 R-2 2 Formula (1 4-η ......... ο η η 〇 花 W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W W RP-2 5 R-2 R-23 Ajisper PB fi 2 1 3400 3 3 0 0 〇〇Reference example 9 RP-26 R-24 2C (1 4-1) 3 η η 0 X Reference example 1 0 RP- Z 7 R-2 5 Formula <1 4- η S 9 S 0 X Reference example 1 JI RP-2 8 R-2 6 Formula (1 4-1) __ 3 3 0 0 Δ Reference cut 1 2 Reference example 1 3 RP-2 9 R-27 Formula (1 4-1) — 2 15 0 X Reference Example 1 4 RP-3 1 R — 2 8 _ R-2 9 2: (1 4-1) _Form and 1 4- η = 2 5 3 0 C --- 2 3 0 0 Δ • <Production method of other coloring composition> (Production of coloring composition 32 (RP-32)) After mixing and mixing the following mixture into a uniform After dispersing for 5 hours using an Eiger grinder ("Mini model M-250 MKII" manufactured by Eiger Japan Co., Ltd.) using a 〇5mnl diameter 〇5mnl filter, it was filtered through a 5.00/zm filter membrane to prepare a colored composition 32 ( RP-32). Diterpenoid pigment (PR177-1) 10. 8 parts of pigment derivative formula (8-5) 1.2 parts of acrylic resin solution 1 40. 151 151 323842 201233734 propylene glycol monoterpene ether acetate 48. 0 parts [Example 47 (Preparation of photosensitive coloring composition l (RR-1)) The following mixture was stirred and mixed to be uniform, and then filtered using a filtration membrane of 1 // m to prepare a photosensitive coloring composition KRhi). Coloring composition l (RP-1) 38. 4 parts of coloring composition 32 (RP-32) 3·6 parts of acrylic resin solution 2 13. 2 parts of photopolymerizable monomer (rAR〇NIX M4〇〇 manufactured by Toagosei Co., Ltd.) 2. 8 parts of photopolymerization initiator (rIrgacure_9〇7, manufactured by Ciba Barbine Co., Ltd.) 2.0 parts of sensitizer (EAB-F, manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts of ethylene glycol monomethyl ether acetate 39. 6 parts [Examples 48 to 72] (Production of photosensitive coloring compositions 2 to 24 (RR-2 to 24)) In addition to changing the coloring composition KRP-i) to the coloring composition 2 to φ 24 (RP-2 to 24) ' At the same time, except that the ratio of the coloring compositions 2 to 24 (RP-2 to 24) to the coloring composition 32 (RP-32) was adjusted in such a manner that Example 47 became the same chromaticity, the rest was carried out in the same manner as in Example 47. Photosensitive coloring compositions 2 to 24 (rr-2 to 24) were produced in the same manner. [Reference Examples 15 to 21] (Production of photosensitive coloring compositions 25 to 31 (RR-25 to 31)) In addition to coloring composition The substance KRP-U was changed to the coloring composition 25 to 31 (RP 25 to 31)'. Further, the coloring compositions 25 to 31 (RP-25 to 31) and the coloring composition were adjusted in such a manner that Example 47 became the same chromaticity. " The photosensitive coloring compositions 25 to 31 (RR-25 to 31) were produced in the same manner as in Example 47 except that the ratio of the material 32 323842 152 201233734 CRP-32) was carried out. <Evaluation of Photosensitive Coloring Composition> (Color characteristics, contrast ratio (CR) evaluation) The photosensitive coloring compositions obtained in Examples 47 to 72 and Reference Examples 15 to 21 were placed on a glass substrate having a thickness of 100 mm X 100 mm and 0.7 mm in a C light source. When the film thickness is χ=〇. 640, y=0·328, the photosensitive coloring composition is applied and dried, and the ultraviolet ray of 300 mJ/cm 2 is irradiated with an ultrahigh pressure mercury lamp. Further, it is heated at 230 ° C. A red coating film was obtained in 60 minutes. Then, the brightness (γ) and contrast ratio (c R ) of the obtained coating film were measured. Meanwhile, 'chromaticity and brightness (Y) are microscopic spectrophotometers (manufactured by 〇lympus Optics Co., Ltd.) Measurement of OSP-SP200") (Evaluation of crystal precipitation on the surface of the coating film) The photosensitive coloring compositions obtained in Examples 47 to 72 and Reference Examples 15 to 21 were placed on a glass substrate having a thickness of 100 mm X 100 and a thickness of 0.7 mm. , φ is applied to the c light source so that the film thickness becomes χ=〇·640 After the photosensitive coloring composition 'and dried, irradiated with ultraviolet rays using an ultrahigh pressure mercury lamp 300mJ / cm2 of. Subsequently, after heat treatment for 23 minutes at TC (TC), heat treatment was repeated twice at 240 ° C for 60 minutes. The surface of the substrate coating film after the heat treatment was observed by an optical microscope, and the presence or absence of crystal precipitation was determined according to the following criteria. : After heat treatment at 230 ° C for 6 minutes, further 24 (TC heat treatment for 60 minutes, and then 24 (TC heat treatment for 60 minutes, no crystal precipitation 〇: 230 ° C heat treatment for 6 〇 minutes, and then 24 (rCM heat treatment 323842 153 201233734 no crystal precipitation for 60 minutes (the second time 24 (the rc heat treatment rib minute crystal precipitation) △: no crystal precipitation after heat treatment at 230 ° C for 60 minutes, but further 240 ° C heat treatment for 60 minutes, crystal precipitation X: crystallization at 230 ° C for 60 minutes, crystal precipitation [Table A-3]
由表A-3的結果,於形成彩色濾光片中,於含有溴化 二酮基吡咯并吡咯顏料與特定雜二酮基吡咯并吡咯顏料A 之二_基料并鱗系顏料組成物中,使用特定雜二嗣基 吡咯并吡咯顏料A之含量,係將二酮基吡咯并吡咯系顏料 323842 154 201233734 的合計質量當作基準的1質量%至15質量%之二酮基此咯并 吼咯系顏料組成物的實施例,特別在亮度方面優異者’再 者有高的對比度,可以抑制因加熱步驟的二酮基吡哈并 咯系顏料之結晶析出。 〈彩色濾光片的製作〉 進行在彩色濾光片的製作中,使用的綠色感光性著色 組成物與藍色感光性著色組成物的製作。同時,有關紅色 是使用本實施例A的感光性著色組成物2(RR-2)。 ® 在玻璃基板上將黑色矩陣加工圖案,在該基板上以旋 轉塗佈法將感光性著色組成物2(RR-2)塗佈成x=〇. 640 ’ y=0. 328的膜厚而形成著色被膜。該被膜隔著光罩,使用 超高壓水銀燈照射300 mJ/cm2的紫外線。其次,藉由以0. 2 質量%的碳酸鈉水溶液所成的鹼顯像液喷霧顯像而除去未 曝光部分後’以離子交換水洗淨,將此基板在23(rc加熱 20分鐘,形成紅色濾光片段。藉由同樣的方法,分別塗# 鲁綠色感光性著色組成物KGR-1)成χ=〇. 300,y=〇. 600之勝 厚,塗佈藍色感光性著色組成物成χ=〇. 15〇, y=0.06G之膜厚,而分別形成綠色遽光片段、藍色滤光片 段,得到彩色濾光片。 ^ 藉由使用感光性著色組成物2(RR-2) ’可以製作高 度並且高對比,在加熱步驟中無結晶析出之彩色濾: [實施例B] 份」 在沒有特別限定下,「份」及 及「質量%」。在製造顏料組成物 」是分別表示「 、著色組成物時 質量 ,係 323842 155 201233734 使用作為色素衍生物的式(6-3)之二酮基吼π各并吡咯衍生 物、式(7-1)的苯并異吲哚衍生物、式(8_5)的蒽醌衍生物、 式(14-1)的喹酞酮衍生物。 (顏料的平均一次粒子徑) 藉由如下述的方法’測定(算出)製造的顏料組成物之 平均一次粒徑。 在顏料組成物的粉末中,加入丙二醇單甲基醚醋酸 酯,添加少量的作為樹脂型分散劑的Disperbyk_161,以 超音波處理1分鐘調製成測定用試料。將此試料藉由穿透 型(TEM)電子顯微鏡,拍射3張(3視野分)可以確認有ι〇〇 個以上顏料的一次粒子照片,分別自左上開始順序測定 100個的—次粒子之大小。具體而言’以⑽單位計測各顏 料-次粒子之短軸徑與長軸徑,將此之平均當作顏料粒子 的一次粒徑’作成以5nm為刻度合計3〇〇個之分佈,將已⑽ 刻度的中央值(例如6nm以上1〇nm以下的情形是如…當作 鲁,此等粒子之粒子徑,各粒子徑與以此數為基準“ 算,而算出個數平均粒子徑。 〈二酮基吡咯并吡咯系顏料組成物的製造方法〉 [實施例1 ] (顏料組成物l(R-l)之製造) 在附有回流管之不銹鋼製的反應容器中,於氮氣環产 下,加入以分子篩脫水的第三戊醇200份,及第三戊氧= 鈉140份,一邊攪拌一邊在100°C加熱,調製成醇鹽溶液。 另一方面,在玻璃製燒瓶中,加入琥珀醆二異丙酯肋份、 323842 156 201233734 4-溴化苯曱腈153.6份,一邊攪拌一邊加熱到90°C使其溶 解,調製成此等混合物的溶液。將此混合物的加熱溶液, 一邊激烈攪拌,一邊花2小時以一定速度緩慢濟下至在10 0 °(:加熱之上述醇鹽溶液中。結束滴下後,在90°C繼續加熱 擾拌2小時,得到二酮基°比略并°比D各系化合物的驗金屬 鹽。再者,在玻璃製附有内襯的反應器中,加入曱醇600 份、水600份、及醋酸304份,冷卻到-10°C。將此已冷卻 之混合物,使用高速授拌分散器,一邊使直徑8cm之剪切 ® 碟以4000 rpm回轉,一邊在其中,將冷卻到75°C預先得 到之二_基°比洛并°比洛系化合物的驗金屬鹽溶液,少量地 添加。此時,由曱醇、醋酸、及水所成的混合物之溫度持 續保持在-5°C以下之溫度,一邊冷卻,並且一邊調整75°C 的二酮基吡咯并吡咯系化合物鹼金屬鹽之添加速度,以大 概120分鐘少量地添加。添加鹼金屬鹽後,析出紅色的結 晶,而生成紅色的懸濁液。接著,將得到之紅色懸濁液於 φ 5°C,以超過濾裝置洗淨後,過濾得到紅色膏狀物。將此膏 狀物再次分散到已冷卻到0°C之3500份甲醇中,作成曱醇 濃度約為90%的懸濁液。接著於5°C攪拌3小時,將伴隨結 晶轉移之粒子進行整粒及洗淨。接著,以超過濾機過濾, 將得到之二酮基°比p各并°比洛系化合物的水膏狀物,於80°C 乾燥24小時,藉由粉碎,得到150. 8份式(1)之溴化二酮 基吡咯并吡咯顏料。 接著,在反應容器1中放入第三戊醇220份一邊以水 浴冷卻,一邊加入32份的60%NaH,在90°C加熱攪拌。其 323842 157 201233734 次,在反應容器2中,將100份之第三戊醇、根據 Tetrahedron, 58(2002) 5547 至 5565 的方法合成之下述 式(B-16)化合物99. 2份、及式(B4-1)的苯甲腈化合物 60. 9份加熱溶解,將此等花2小時滴入至反應容器1之 中。於120°C中反應10小時後,冷卻到60°C,由加入曱醇 400份及醋酸50份,進行過濾及曱醇洗淨,得到式(B-2-1) 所示87. 8份的特定雜二酮基吡咯并吡咯顏料B。From the results of Table A-3, in the formation of a color filter, in a bis-base squama pigment composition containing a brominated diketopyrrolopyrrole pigment and a specific heterodiketopyrrolopyrrole pigment A The content of the specific heterodithiopyrrolopyrrole pigment A is 1% by mass to 15% by mass of the diketone based on the total mass of the diketopyrrolopyrrole pigment 323842 154 201233734. In the examples of the bismuth pigment composition, particularly in terms of brightness, there is a high contrast ratio, and crystallization of the diketopipharbene pigment by the heating step can be suppressed. <Production of Color Filter> A green photosensitive coloring composition and a blue photosensitive coloring composition used in the production of a color filter were produced. Meanwhile, regarding the red color, the photosensitive coloring composition 2 (RR-2) of the present Example A was used. ® a black matrix processing pattern on a glass substrate, and the photosensitive coloring composition 2 (RR-2) was applied by spin coating on the substrate to a film thickness of x = 〇 640 ' y = 0.328 A colored film is formed. The film was irradiated with ultraviolet rays of 300 mJ/cm2 using an ultrahigh pressure mercury lamp through a mask. Next, after the unexposed portion was removed by spray development using an alkali developing solution of a 0.2% by mass aqueous solution of sodium carbonate, the substrate was washed with ion-exchanged water, and the substrate was heated at 23 (rc for 20 minutes, A red filter segment is formed. By the same method, #鲁绿色色性性组成物KGR-1) is separately formed into χ=〇. 300, y=〇. 600 wins thick, coated blue photosensitive coloring The composition was χ=〇. 15〇, y=0.06G, and a green calendering fragment and a blue filter fragment were respectively formed to obtain a color filter. ^ By using the photosensitive coloring composition 2 (RR-2) ', a color filter having a high height and high contrast and no crystal precipitation in the heating step can be produced: [Example B] Parts" Unless otherwise specified, "parts" And "% by mass". "In the production of the pigment composition" is a mass of the "coloring composition", which is 323842 155 201233734, which is a diketo oxime pi-pyrrole derivative of the formula (6-3) used as a pigment derivative, and the formula (7-1) a benzoisoindole derivative, an anthracene derivative of the formula (8-5), and a quinophthalone derivative of the formula (14-1). (Average primary particle diameter of the pigment) is determined by the following method ( The average primary particle diameter of the produced pigment composition was calculated. In the powder of the pigment composition, propylene glycol monomethyl ether acetate was added, and a small amount of Disperbyk_161 as a resin type dispersant was added, and the measurement was performed by ultrasonic treatment for 1 minute. Using the sample, the sample was photographed by a penetrating (TEM) electron microscope, and three shots (3 fields of view) were used to confirm the photo of the primary particles of the ι or more pigments, and 100 samples were sequentially measured from the upper left. The size of the secondary particles. Specifically, 'the short-axis diameter and the major-axis diameter of each pigment-secondary particle are measured in units of (10), and the average particle diameter of the pigment particles is averaged as the total particle diameter of 5 nm. Distribution, (10) The central value of the scale (for example, in the case of 6 nm or more and 1 〇 nm or less, the particle diameter of these particles, the particle diameter of each particle and the number of the particles are calculated as the reference, and the number average particle diameter is calculated. <Method for Producing Diketopyrrolopyrrole Pigment Composition> [Example 1] (Production of Pigment Composition l (Rl)) In a reaction vessel made of stainless steel with a reflux tube, under a nitrogen gas loop, 200 parts of a third pentanol dehydrated by a molecular sieve and 140 parts of a third pentoxide = sodium were added, and the mixture was heated at 100 ° C while stirring to prepare an alkoxide solution. On the other hand, amber was added to a glass flask. Diisopropyl ester rib, 323842 156 201233734 4-bromobenzonitrile 153.6 parts, heated to 90 ° C while stirring to dissolve, to prepare a solution of these mixtures. The heated solution of this mixture, while stirring vigorously While spending 2 hours at a certain speed, slowly lower to 10 ° (: heating the above alkoxide solution. After the end of the drop, continue heating at 90 ° C for 2 hours to obtain a diketone ° ratio and ° A metal salt than the compound of each D compound. In a glass-lined reactor, 600 parts of decyl alcohol, 600 parts of water, and 304 parts of acetic acid were added, and the mixture was cooled to -10 ° C. The cooled mixture was mixed using a high-speed mixer. The 8 cm diameter shearing plate was rotated at 4000 rpm, and the metal salt solution obtained by cooling to 75 ° C, which was previously obtained at 25 ° C, was added in small amount. , the temperature of the mixture of decyl alcohol, acetic acid, and water is maintained at a temperature below -5 ° C, while cooling, and adjusting the addition rate of the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C , added in a small amount of about 120 minutes. After the addition of the alkali metal salt, red crystals were precipitated to form a red suspension. Next, the obtained red suspension was washed at φ 5 ° C with an ultrafiltration device, and filtered to obtain a red paste. This paste was again dispersed in 3500 parts of methanol which had been cooled to 0 ° C to prepare a suspension having a decyl alcohol concentration of about 90%. Subsequently, the mixture was stirred at 5 ° C for 3 hours, and the particles accompanying the crystal transfer were granulated and washed. The aliquot of the ketone is obtained by the pulverization of the water-soluble paste of the ketone compound at a temperature of 80 ° C for 24 hours. a brominated diketopyrrolopyrrole pigment. Next, 220 parts of the third pentanol was placed in the reaction vessel 1, and the mixture was cooled in a water bath, and 32 parts of 60% NaH was added thereto, followed by heating and stirring at 90 °C. And a compound of the following formula (B-16), which is synthesized by the method of Tetrahedron, 58 (2002) 5547 to 5565, in a reaction vessel 2, 99. 2 parts, and 60 parts of the benzonitrile compound of the formula (B4-1) was dissolved by heating, and the mixture was dropped into the reaction vessel 1 for 2 hours. After the reaction was carried out at 120 ° C for 10 hours, and then cooled to 60 ° C, 400 parts of decyl alcohol and 50 parts of acetic acid were added for filtration and decyl alcohol washing to obtain 87. 8 parts of the formula (B-2-1). Specific heterodiketopyrrolopyrrole pigment B.
BrBr
式(B- 1 6) 進一步,將得到的式(1)之溴化二酮基吡咯并吡咯顏 料97. 0份、式(B-2-1)的特定雜二酮基吡咯并吡咯顏料B 3. 0份、氯化鈉1000份,及二乙二醇120份,放入不銹鋼 製1加侖捏煉機(井上製作所製)中,在60°C混練10小時。 ^ 其次,將混煉之混合物投入溫水中,一邊在約8 0 °C加熱, 一邊攪拌1小時作成膏狀物,過濾並水洗除去食鹽及二乙 二醇後,在80°C乾燥一畫夜,藉由粉碎得到96. 5份之二 酮基吡咯并吡咯系顏料組成物的顏料組成物l(R-l),平均 一次粒子徑是36. 8nm。 [實施例2] (顏料組成物2(R-2)之製造) 將顏料組成物1之製造中得到的式(1)之溴化二酮基 吡咯并吡咯顏料95. 0份、式(B-2-1)的特定雜二酮基吡咯 323842 158 201233734 并吡咯顏料B 5. 0份、氣化鈉1000份,及二乙二醇120 份,放入不銹鋼製1加侖捏煉機(井上製作所製)中,在60 °C混練10小時。其次,將混煉之混合物投入溫水中,一邊 在約80°C加熱,一邊攪拌1小時作成膏狀物,過濾並水洗 除去食鹽及二乙二醇後,在80°C乾燥一晝夜,藉由粉碎得 到97. 2份之二酮基吡咯并吡咯系顏料組成物的顏料組成 物2(R-2),平均一次粒子徑是30. 5nm。 [實施例3] ® (顏料組成物3(R-3)之製造) 除了將式(1)之溴化二酮基吡咯并吡咯顏料95. 0份、 及式(B-2-1)的特定雜二酮基π比D各并β比p各顏料B 5. 0份,變 更成式(1)之溴化二酮基吡咯并吡咯顏料90. 0份、及式 (B-2-1)的特定雜二酮基吡咯并吡咯顏料B 10.0份之外, 其餘的與顏料組成物2(R-2)的製造方法同樣進行,可以得 到96. 9份之二酮基吡咯并吡咯顏料組成物3(R-3),平均 ^ 一次粒子徑是26. 5nm。 [實施例4] (顏料組成物4(R-4)之製造) 除了將式(1)之溴化二酮基吡咯并吡咯顏料95. 0份、 及式(B-2-1)的特定雜二酮基吡咯并吡咯顏料B 5. 0份,變 更成式(1)之溴化二酮基吡咯并吡咯顏料85. 0份、及式 (B-2-1)的特定雜二酮基β比17各并B比洛顏料B 15.0份之外, 其餘的與顏料組成物2(R-2)的製造方法同樣進行,可以得 到97. 1份之二酮基吡咯并吡咯系顏料組成物的顏料組成 323842 159 201233734 物4(R-4),平均一次粒子徑是28. 5nm。 [實施例5] (顏料組成物5(R-5)之製造) 除了將式(B-3-1)的苯甲腈化合物60.2份,變更成式 (B-3-2)的笨甲腈化合物54. 2份之外,其餘的與顏料組成 物1 (R -1)中實施的特定雜二酮基吡咯并吡咯顏料B之製造 同樣進行,得到85. 2份之式(B-2-2)所示特定雜二酮基吡 洛并D比p各顏料B。 • 接著,式(1)之溴化二酮基吡咯并吡咯顏料95. 0份、 式(B-2-2)的特定雜二酮基D比洛并°比p各顏料B 5. 0份、氯化 鈉1000份,及二乙二醇120份,放入不銹鋼製1加侖捏煉 機(井上製作所製)中,在60°C混練10小時。其次,將混 煉之混合物投入溫水中,一邊在約80°C加熱一邊攪拌1小 時作成膏狀物,過濾並水洗除去食鹽及二乙二醇後,在80 °C乾燥一晝夜,藉由粉碎得到96. 2份之二酮基吡咯并吡咯 φ 系顏料組成物的顏料組成物5(R-5),平均一次粒子徑是 31. 6nm。 [實施例6] (顏料組成物6(R-6)之製造) 首先,除了將式(B-3-1)的苯甲腈化合物60.2份,變 更成式(B-3-3)的苯曱腈化合物58. 2份之外,其餘的與顏 料組成物l(R-l)中實施的特定雜二酮基吡咯并吡咯顏料B 之製造同樣進行,得到82. 2份之式(B-2-3)所示特定雜二 酮基吡咯并吡咯顏料B。 323842 160 201233734 接著,式(1)之溴化二酮基吡咯并吡咯顏料95. 0份、 式(Β-2-3)的特定雜二酮基吡咯并吡咯顏料Β 5. 0份、氯化 鈉1000份,及二乙二醇120份,放入不銹鋼製1加侖捏谏 機(井上製作所製)中,在60°C中混練10小時。其次,將 混煉之混合物投入溫水中,一邊在約8 0 °C加熱,一邊擾拌 1小時作成膏狀物,過濾並水洗除去食鹽及二乙二醇後, 在80°C乾燥一晝夜,藉由粉碎得到95. 9份之二酮基吡咯 并吡咯系顏料組成物的顏料組成物6(R-6),平均一次粒子 ® 徑是 34. 6nm。 [實施例7] (顏料組成物7(R-7)之製造) 除了將式(B-3-1)的苯甲腈化合物60. 2份,變更成式 (B-3-4a)的苯曱腈化合物84. 1份之外,其餘的與顏料組成 物l(R-l)中實施的特定雜二酮基吡咯并吡咯顏料B之製造 同樣進行,得到94. 1份之式(B-2-4a)所示特定雜二酮基吡 φ 咯并吡咯顏料B。 接著,式(1)之溴化二酮基吡咯并吡咯顏料95.0份、 式(B-2-4a)的特定雜二酮基吼17各并吼17各顏料B 5. 0份、氯 化鈉1000份,及二乙二醇120份,放入不銹鋼製1加侖捏 煉機(井上製作所製)中,在60°C混練10小時。其次,將 混煉之混合物投入溫水中,一邊在約80°C加熱,一邊授拌 1小時作成膏狀物,過濾並水洗除去食鹽及二乙二醇後, 在80°C乾燥一晝夜,藉由粉碎得到97. 9份之二酮基吡咯 并°比0各系顏料組成物的顏料組成物7(R-7),平均一次粒子 323842 161 201233734 徑是 28. 6nm。 [實施例8] (顏料組成物8(R-8)之製造) 除了將式(1)之溴化二酮基吡咯并吡咯顏料95. 0份、 及式(B-2-4a)的特定雜二酮基吡咯并吡咯顏料B 5. 0份變 更成式(1)之溴化二酮基吡咯并吡咯顏料85. 0份、及式 (B-2-4a)的特定雜二酮基吡咯并吡咯顏料B 15. 0份之外, 其餘的與顏料組成物7(R-7)之製造同樣進行,得到96. 1 ® 份之二酮基°比洛并°比洛系顏料組成物的顏料組成物8 (R-8),平均一次粒子徑是25. 5nm。 [實施例9] (顏料組成物9(R-9)之製造) 除了將式(B-3-1)的苯曱腈化合物60.2份,變更成式 (B-3-4b)的苯曱腈化合物71. 8份之外,其餘的與顏料組成 物l(R-l)中實施的特定雜二酮基吡咯并吡咯顏料B之製造 φ 同樣進行,得到79. 1份之式(B-2-4b)所示特定雜二酮基吡 咯并吡咯顏料B。 接著,式(1)之溴化二酮基吡咯并吡咯顏料95. 0份、 式(B-2-4b)的特定雜二酮基°比洛并。比洛顏料B 5.0份、氣 化鈉1000份,及二乙二醇120份,放入不銹鋼製1加侖捏 煉機(井上製作所製)中,在60°C混練10小時。其次,將 混煉之混合物投入溫水中,一邊在約8 0 °C加熱,一邊擾拌 1小時作成膏狀物,過濾並水洗除去食鹽及二乙二醇後, 在80°C乾燥一晝夜,藉由粉碎得到96. 5份之二酮基吡咯 323842 162 201233734 并吡咯系顏料組成物的顏料組成物9(r_9),平均一次粒子 徑是 31. 1 nm。 [實施例10] (顏料組成物HKR-10)之製造)Further, the obtained brominated diketopyrrolopyrrole pigment of the formula (1) is 97. 0 parts of the specific heterodiketopyrrolopyrrole pigment B of the formula (B-2-1). 3. 0 parts, 1000 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel one-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), and kneaded at 60 ° C for 10 hours. ^ Next, the kneaded mixture is poured into warm water, heated at about 80 ° C, stirred for 1 hour to form a paste, filtered and washed with water to remove salt and diethylene glycol, and dried at 80 ° C for one night. The average primary particle diameter is 36. 8 nm. The pigment particle composition l (Rl) of the composition of the ketone of the ketone. [Part 2] The brominated diketopyrrolopyrrole pigment of the formula (1) obtained in the production of the pigment composition 1 is 95. 0 parts, formula (B) -2-1) specific heterodiketopyrrole 323842 158 201233734 pyrrole pigment B 5. 0 parts, sodium vaporized 1000 parts, and diethylene glycol 120 parts, placed in a stainless steel 1 gallon kneader (Inoue Works In the system, knead at 60 ° C for 10 hours. Next, the kneaded mixture was poured into warm water, and while stirring at about 80 ° C, the mixture was stirred for 1 hour to prepare a paste, which was filtered and washed with water to remove salt and diethylene glycol, and then dried at 80 ° C for a day and night. 5nm。 The average particle diameter is 30. 5nm. The pigment particle composition 2 (R-2) having an average primary particle diameter of 30. 5nm. [Example 3] ® (Production of Pigment Composition 3 (R-3)), except that the brominated diketopyrrolopyrrole pigment of the formula (1) was 95. 0 parts, and the formula (B-2-1) 0份和式式式式式B(2), and the formula (B-2-1), the ketone diketopyrrolopyrrole pigment of the formula (1) is changed to 0. 0 parts, and the formula (B-2-1) And the other part is the same as the method for producing the pigment composition 2 (R-2), and 96.9 parts of the diketopyrrolopyrrole pigment is obtained. 5nm。 The average particle diameter is 26. 5nm. [Example 4] (Production of Pigment Composition 4 (R-4)) The specifics of the brominated diketopyrrolopyrrole pigment of the formula (1): 95 parts and the formula (B-2-1) a part of the heterodiketone pyrrolopyrrole pigment B 5. 0 parts, which is changed to a brominated diketopyrrolopyrrole pigment of the formula (1), 85. 0 parts, and a specific heterodione group of the formula (B-2-1) The same as the method for producing the pigment composition 2 (R-2), the same as the method for producing the pigment composition 2 (R-2), and a solution of 97. 1 part of the diketopyrrolopyrrole pigment composition is obtained. 5纳米。 The average particle diameter is 28. 5nm. [Example 5] (Production of Pigment Composition 5 (R-5)) In addition to 60.2 parts of the benzonitrile compound of the formula (B-3-1), it was changed to the carbonitrile of the formula (B-3-2). The formula (B-2-) is obtained in the same manner as in the production of the specific heterodiketopyrrolopyrrole pigment B which is carried out in the pigment composition 1 (R-1). 2) The specific heterodiketopylpolo D is shown as the pigment B of each p. • Next, the brominated diketopyrrolopyrrole pigment of the formula (1) is 95. 0 parts, the specific heterodiketone group D of the formula (B-2-2) is more than the ratio of the pigment b to each of the pigments B 5. 0 parts. 1000 parts of sodium chloride and 120 parts of diethylene glycol were placed in a stainless steel one-gallon kneader (manufactured by Inoue Co., Ltd.), and kneaded at 60 ° C for 10 hours. Next, the kneaded mixture was poured into warm water, stirred while heating at about 80 ° C for 1 hour to form a paste, filtered and washed with water to remove salt and diethylene glycol, and then dried at 80 ° C for a day and night by pulverization. 6纳米。 The pigment particle composition 5 (R-5) having an average primary particle diameter of 31.6 nm. [Example 6] (Production of Pigment Composition 6 (R-6)) First, except that 60.2 parts of the benzonitrile compound of the formula (B-3-1) was changed to benzene of the formula (B-3-3) 2份的式(B-2-2) The same as the production of the specific heterodiketopyrrolopyrrole pigment B carried out in the pigment composition l (Rl), the same is obtained. 3) The specific heterodiketopyrrolopyrrole pigment B shown. 323842 160 201233734 Next, the brominated diketopyrrolopyrrole pigment of the formula (1) is 95. 0 parts, the specific heterodiketopyrrolopyrrole pigment of the formula (Β-2-3) Β 0.5 part, chlorination 1000 parts of sodium and 120 parts of diethylene glycol were placed in a stainless steel one-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), and kneaded at 60 ° C for 10 hours. Next, the kneaded mixture was poured into warm water, and heated at about 80 ° C, and stirred for 1 hour to form a paste, filtered and washed with water to remove salt and diethylene glycol, and dried at 80 ° C for a day and night. 6纳米。 The granules having a particle size of 34.6 nm. [Example 7] (Production of Pigment Composition 7 (R-7)) A benzene of the formula (B-3-4a) was changed except that the benzonitrile compound of the formula (B-3-1) was 60. 2 parts. 5份的式(B-2-) The same as the production of the specific heterodiketopyrrolopyrrole pigment B carried out in the pigment composition l (Rl), the same as the production of 94.1 parts (B-2- 4a) shows the specific heterodiketopiperylpyrrolopyrrole pigment B. Next, 95.0 parts of the brominated diketopyrrolopyrrole pigment of the formula (1), the specific heterodiketopurine 17 of the formula (B-2-4a), and each of the pigments B 5. 0 parts, sodium chloride 1000 parts and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Co., Ltd.), and kneaded at 60 ° C for 10 hours. Next, the kneaded mixture was poured into warm water, and while heating at about 80 ° C, it was mixed for 1 hour to prepare a paste, filtered and washed with water to remove salt and diethylene glycol, and dried at 80 ° C for a day and night. 6纳米。 The granules were obtained by the pigment composition 7 (R-7), the average primary particles 323842 161 201233734 diameter was 28. 6nm. [Example 8] (Production of Pigment Composition 8 (R-8)) In addition to the specificity of the brominated diketopyrrolopyrrole pigment of the formula (1): 95 parts and the formula (B-2-4a) a heterodione-pyrrolopyrrole pigment B 5. 0 parts of a brominated diketopyrrolopyrrole pigment of the formula (1) 85. 0 parts, and a specific heterodiketopyrrole of the formula (B-2-4a) The same as the production of the pigment composition 7 (R-7), the same as the production of the pigment composition 7 (R-7), which gives 96. 1 ® parts of the diketone group and the ratio of the pyloric pigment to the composition of the pigment. 5纳米。 The average particle diameter is 25. 5nm. [Example 9] (Production of Pigment Composition 9 (R-9)) In addition to 60.2 parts of the benzoquinone compound of the formula (B-3-1), it was changed to the benzoquinone of the formula (B-3-4b). The same as the production of φ of the specific heterodiketopyrrolopyrrole pigment B carried out in the pigment composition l (Rl), the same as the compound 71. (part 1) (B-2-4b) The specific heterodiketopyrrolopyrrole pigment B is shown. Next, the brominated diketopyrrolopyrrole pigment of the formula (1) is 95. 0 parts, and the specific heterodiketone group of the formula (B-2-4b) is more than carbazide. 5.0 parts of Biro pigment B, 1000 parts of sodium carbonate, and 120 parts of diethylene glycol were placed in a stainless steel one-gallon kneader (manufactured by Inoue Co., Ltd.), and kneaded at 60 ° C for 10 hours. Next, the kneaded mixture was poured into warm water, and heated at about 80 ° C, and stirred for 1 hour to form a paste, filtered and washed with water to remove salt and diethylene glycol, and dried at 80 ° C for a day and night. 1微米。 By pulverization to obtain 96.5 parts of the diketopipyrrole 323842 162 201233734 and pyrrole pigment composition pigment composition 9 (r_9), the average primary particle diameter is 31.1 nm. [Example 10] (Production of Pigment Composition HKR-10)
除了將式(B-3-1)的苯甲腈化合物60.2份,變更成式 (B-3-5)的本曱腈化合物49. 7份之外,其餘的與顏料組成 物1 (R-1)中實施的特定雜二酮基β比洛并吼B各顏料B之製造 同樣進行,得到66. 9份之式(b-2-5)所示特定雜二酮基吡 咯并吡咯顏料B。 接著,式(1)之溴化二酮基吡咯并吡咯顏料95. 〇份、 式(B-2-5)的特定雜二酮基吡咯并吡咯顏料B 5. 〇份、氣化 鈉1000份,及二乙二醇12〇份,放入不銹鋼製丨加侖捏煉 機(井上製作所製)中,在60。(:混練10小時。其次,將混 煉之混合物投入溫水中,一邊在約8{rc加熱,—邊攪拌夏 小時作成膏狀物,過濾並水洗除去食鹽及二乙二醇後,在 8〇°C乾燥一晝夜,藉由粉碎得到97·5份之二_基吡咯并吡 咯系顏料組成物的顏料組成物10(R-10),平均一 * 是 33. lnm。 [實施例11] (顏料組成物ll(R-ll)之製造) 除了將式(B-3-1)的苯甲腈化合物6Q. 2份 (B=6b)的苯甲腈化合物亂9份之外,其餘的血顏料二 =實施的特定雜二酮基鱗并ntb —㈣之製 域同樣進行,得到9〇·7份之式(B_2_6b)所示料雜二嗣美 323842 163 201233734 吡咯并吡咯顏料B。 接著,式(1)之溴化二酮基吡咯并吡咯顏料95. 0份、 式(B-2-6b)的特定雜二酮基吡咯并吡咯顏料B 5. 0份、氯 化鈉1000份,及二乙二醇120份,放入不銹鋼製1加侖捏 煉機(井上製作所製)中,在60°C混練10小時。其次,將 混煉之混合物投入溫水中,一邊在約8 0 °C加熱,一邊擾拌 1小時作成膏狀物,過濾並水洗除去食鹽及二乙二醇後, 在80°C乾燥一晝夜,藉由粉碎得到98. 1份之二酮基吡咯 ® 并π比p各系顏料組成物的顏料組成物11 (R-11 ),平均一次粒 子徑是28. 9nm。 [實施例12] . (顏料組成物12(R-12)之製造) 除了將式(B-3-1)的苯曱腈化合物60. 2份,變更成式 (B-3-6c)的苯曱腈化合物75. 6份之外,其餘的與顏料組成 物l(R-l)中實施的特定雜二酮基吡咯并吡咯顏料B之製造 φ 同樣進行,得到100. 8份之式(B-2-6c)所示特定雜二酮基 吡咯并吡咯顏料B。 接著,式(1)之溴化二酮基吡咯并吡咯顏料95. 0份、 式(B-2-6c)的特定雜二酮基吡咯并吡咯顏料B 5. 0份、氯 化鈉1000份,及二乙二醇120份,放入不銹鋼製1加侖捏 煉機(井上製作所製)中,在60°C混練10小時。其次,將 混煉之混合物投入溫水中,一邊在約80°C加熱,一邊擾拌 1小時作成膏狀物,過濾並水洗除去食鹽及二乙二醇後, 在80°C乾燥一晝夜,藉由粉碎得到97. 4份之二酮基吡咯 323842 164 201233734 并β比ϋ各系顏料組成物的顏料組成物12 (R-12 ),平均一次粒 子徑是29. 8nm。 [實施例13] (顏料組成物13(R-13)之製造) 除了將式(B-3-1)的苯甲腈化合物60. 2份,變更成式 (B-3-7)的苯曱腈化合物87. 8份之外,其餘的與顏料組成 物l(R-l)中實施的特定雜二酮基吡咯并吡咯顏料B之製造 同樣進行,得到85. 2份之式(B-2-7)所示特定雜二酮基吡 籲0各并《比洛顏料B。 接著,式(1)之溴化二酮基吡咯并吡咯顏料95. 0份、 式(B-2-7)的特定雜二酮基吡咯并吡咯顏料B 5. 0份、氯化 鈉1000份,及二乙二醇120份,放入不銹鋼製1加侖捏煉 機(井上製作所製)中,在60°C混練10小時。其次,將混 煉之混合物投入溫水中,一邊在約80°C加熱,一邊擾拌1 小時作成膏狀物,過濾並水洗除去食鹽及二乙二醇後,在 φ 80°C乾燥一畫夜,藉由粉碎得到96. 3份之二酮基吡咯并吡 咯系顏料組成物的顏料組成物13(R-13),平均一次粒子徑 是 28. 2nm。 [實施例14] (顏料組成物14(R-14)之製造) 除了將式(1)之溴化二酮基吡咯并吡咯顏料95. 0份、 及式(B-2-7)的特定雜二酮基吡咯并吡咯顏料B 5. 0份、變 更成式(1)之溴化二酮基吡咯并吡咯顏料85. 0份、及式 (B-2-7)的特定雜二酮基吡咯并吡咯顏料B 15.0份之外, 323842 165 201233734 其餘的與顏料組成物13(R-13)之製造同樣進行,得到95. 1 份之二酮基吡咯并吡咯系顏料組成物的顏料組成物 14(R-14),平均一次粒子徑是26. 5nm。 [實施例15] (顏料組成物15(R-15)之製造) 除了將式(B-3-1)的苯甲腈化合物60.2份,變更成式 (B-3-8)的苯甲腈化合物50.0份之外,其餘的與顏料組成 物l(R-l)中實施的特定雜二酮基吡咯并吡咯顏料B之製造 • 同樣進行,得到64. 5份之式(B-2-8)所示特定雜二酮基吡 咯并吡咯顏料B。 接著,式(1)之溴化二酮基吡咯并吡咯顏料95. 0份、 式(B-2-8)的特定雜二酮基吡咯并吡咯顏料B 5.0份、氯化 鈉1000份,及二乙二醇120份,放入不銹鋼製1加侖捏煉 機(井上製作所製)中,在60°C混練10小時。其次,將混 煉之混合物投入溫水中,一邊在約80°C加熱一邊攪拌1小 φ 時作成膏狀物,過濾並水洗除去食鹽及二乙二醇後,在80 °C乾燥一晝夜,藉由粉碎得到97. 3份之二酮基吡咯并吡咯 顏料組成物15(R-15),平均一次粒子徑是34. 2nm。 [實施例16] (顏料組成物16(R-16)之製造) 附有回流管之不銹鋼製的反應容器中,於氮氣環境 下,加入以分子篩脫水的第三戊醇200份,及第三戊氧基 鈉140份,一邊攪拌一邊在100°C加熱,調製醇鹽溶液。 另一方面,在玻璃製燒瓶中,加入琥珀酸二異丙酯88份、 323842 166 201233734 4-溴化苯曱腈146. 0份及式(B-3-1)之苯曱腈化合物7. 6 份,一邊攪拌一邊在90°C加熱使其溶解,調製此等混合物 的溶液。將此混合物的加熱溶液,在100°C力σ熱之上·述醇 鹽溶液中,一邊激烈攪拌一邊花2小時以一定速度緩慢滴 下。結束滴下後,在90°C繼續加熱攪拌2小時,得到二酮 基吡咯并吡咯系化合物的鹼金屬鹽。又,在玻璃製附有内 襯的反應容器中,加入曱醇600份、水600份、及醋酸304 份,冷卻到-10°C。將此已冷卻之混合物,使用高速攪拌的 ® 分散器,一邊使直徑8cm之剪切碟以4000rpm回轉,一邊 在其中,將冷卻到75°C的先前得到的二酮基°比11 各并0比洛系 化合物的驗金屬鹽溶液,少量少量地添加。此時,由曱醇、 醋酸、及水所成的混合物溫度通常是試圖保持在-5°C以下 之溫度,一邊冷卻,並且一邊調整75°C的二酮基吡咯并吡 咯系化合物的鹼金屬鹽添加速度,花約120分鐘少量地添 加。添加驗金屬鹽後,會析出紅色的結晶,生成紅色的懸 φ 濁液。接著,將得到之紅色懸濁液於5°C以超過濾裝置洗 淨後,過濾、得到紅色膏狀物。將此膏狀物再次分散到已冷 卻到0°C之3500份曱醇中,作成曱醇濃度為約90°/◦的懸濁 液。接著於5°C攪拌3小時,將伴隨結晶轉移的粒子進行 整粒及洗淨。接著,以超過濾機過濾,將得到之二酮基吡 咯并吡咯系化合物的水膏狀物,於80°C乾燥24小時,藉 由粉碎,得到145. 8份的二酮基°比17各并°比11各系顏料組成物。 有關得到的二酮基°比11 各并D比咯顏料組成物中的式(1) 所示溴化二酮基吡咯并吡咯顏料及式(B-2-1)所示之特定 323842 167 201233734 雜二酮基吼洛并么轺 各顏枓β的含量,使用HPLC定量分析 時,式(1)所示漠化_ _ ^ _ 酮基吡咯并吡咯顏料與式(Β-2-1)所 各顏料β的質量比是龍m HPL曰C測錢件及保持時間是如以下。L定量之必要 &里線疋使用在製造顏料組成物⑽D中合成的式⑴之 廣化一酮基鱗并efcb略顏料及式(Β—η )之特㈣二嗣基 吡咯并吡咯顏料Β而作成。 癱裝置:曰本分光公司製Gulliver系列 檢出器:日本分光公司製UV~970檢出器 管柱 Waters a 司製 Symmetry ci8(5 // m,2· lram p xl50mm) 移動相A液:二甲基曱醯胺/水(1:1) 移動相B液.二甲基甲醯胺/水(97. 5 : 2. 5) 分配(B 液):47%〜(15 分鐘;分鐘)—1〇〇%—(25 分鐘)—100%In addition to 60.2 parts of the benzonitrile compound of the formula (B-3-1), it is changed to the indole nitrile compound of the formula (B-3-5) of 49. 7 parts, and the rest with the pigment composition 1 (R- 1) The specific heterodiketone group β is produced in the same manner as in the production of each of the pigments B, and 66.9 parts of the specific heterodiketopyrrolopyrrole pigment B represented by the formula (b-2-5) is obtained. . Next, the brominated diketopyrrolopyrrole pigment of the formula (1) 95. hydrazine, the specific heterodiketopyrrolopyrrole pigment B of the formula (B-2-5) 5. hydrazine, 1000 parts of sodium vaporized And 12 parts of diethylene glycol were placed in a stainless steel kneading kneader (manufactured by Inoue Seisakusho Co., Ltd.) at 60. (: kneading for 10 hours. Secondly, the kneaded mixture is put into warm water, and heated at about 8{rc, while stirring for summer hours to form a paste, filtered and washed with water to remove salt and diethylene glycol, at 8〇 After drying for a day and night, the pigment composition 10 (R-10) of 97. 5 parts of the bis-pyrrolopyrrole pigment composition was obtained by pulverization, and the average one was 33. lnm. [Example 11] Production of Pigment Composition ll (R-ll)) Except that the benzonitrile compound of the formula (B-3-1) 6Q. 2 parts (B=6b) of the benzonitrile compound is disordered, the rest of the blood Pigment 2 = the specific heterodiketone-based ntb-(4) domain was carried out in the same manner, and 9 〇·7 parts of the formula (B_2_6b) was obtained as the bismuth 323842 163 201233734 pyrrolopyrrole pigment B. (1) The brominated diketopyrrolopyrrole pigment 95. 0 parts, the specific heterodiketopyrrolopyrrole pigment B of the formula (B-2-6b) 5. 0 parts, 1000 parts of sodium chloride, and two 120 parts of ethylene glycol was placed in a stainless steel one-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), and kneaded at 60 ° C for 10 hours. Next, the kneaded mixture was poured into warm water. The ketone is obtained by heating at about 80 ° C, and stirring for 1 hour to form a paste. After filtering and washing with water to remove salt and diethylene glycol, drying at 80 ° C for one day and night, by pulverization, 98.1 parts of diketopyrrole is obtained. And the average primary particle diameter is 28.9%. [Example 12] (Production of Pigment Composition 12 (R-12)) In addition to the pigment composition 11 (R-11). 6 parts of the benzoquinone compound of the formula (B-3-1), changed to the benzoquinone compound of the formula (B-3-6c) 75. 6 parts, the rest with the pigment composition l (Rl The production of φ of the specific heterodiketopyrrolopyrrole pigment B carried out in the same manner is carried out, and 100. 8 parts of the specific heterodiketopyrrolopyrrole pigment B represented by the formula (B-2-6c) is obtained. (1) The brominated diketopyrrolopyrrole pigment 95. 0 parts, the specific heterodiketopyrrolopyrrole pigment B of the formula (B-2-6c) 5. 0 parts, 1000 parts of sodium chloride, and two 120 parts of ethylene glycol was placed in a stainless steel one-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), and kneaded at 60 ° C for 10 hours. Next, the kneaded mixture was poured into warm water and heated at about 80 ° C. Spoil 1 When it is made into a paste, filtered and washed with water to remove salt and diethylene glycol, dried at 80 ° C for one day and night, by pulverization to obtain 97. 4 parts of diketopyrrole 323842 164 201233734 and β specific pigment composition The pigment composition 12 (R-12) having an average primary particle diameter of 29.8 nm. [Example 13] (Production of Pigment Composition 13 (R-13)) In addition to the formula (B-3-1) 6 parts of benzonitrile compound, changed to the benzoquinone compound of formula (B-3-7) 87. 8 parts, the other specific heterodione pyrrole carried out in the pigment composition l (Rl) The production of the pyrrole pigment B was carried out in the same manner, and 85.2 parts of the specific heterodiketone group represented by the formula (B-2-7) and "Bilo pigment B" were obtained. Next, the brominated diketopyrrolopyrrole pigment of the formula (1) is 95. 0 parts, the specific heterodiketopyrrolopyrrole pigment B of the formula (B-2-7) is 5.0 parts, and the sodium chloride is 1000 parts. 120 parts of diethylene glycol and 120 parts of diethylene glycol were placed in a stainless steel one-gallon kneader (manufactured by Inoue Co., Ltd.), and kneaded at 60 ° C for 10 hours. Next, the kneaded mixture was poured into warm water, and heated at about 80 ° C, and stirred for 1 hour to form a paste, filtered and washed with water to remove salt and diethylene glycol, and dried at φ 80 ° C for one night. 2nm。 The pigment particle composition 13 (R-13) having an average primary particle diameter of 28. 2nm. [Example 14] (Production of Pigment Composition 14 (R-14)) In addition to the specificity of the brominated diketopyrrolopyrrole pigment of the formula (1): 95 parts and formula (B-2-7) a heterodione of the heterodiketopyrrolopyrrole pigment B 5. 0 parts, which is changed to a brominated diketopyrrolopyrrole pigment of the formula (1), 85. 0 parts, and a specific heterodione group of the formula (B-2-7) In the same manner as in the production of the pigment composition 13 (R-13), the pigment composition of the composition of the diketopyrrolopyrrole pigment composition was obtained in the same manner as in the production of the pyrrolopyrrole pigment B, 1 323. 5纳米。 The average primary particle diameter is 26. 5nm. [Example 15] (Production of Pigment Composition 15 (R-15)) In addition to 60.2 parts of the benzonitrile compound of the formula (B-3-1), the benzonitrile of the formula (B-3-8) was changed. 5份的式(B-2-8), except for the compound 50.0 parts, the same as the production of the specific heterodiketopyrrolopyrrole pigment B carried out in the pigment composition l (Rl). A specific heterodiketopyrrolopyrrole pigment B is shown. Next, the brominated diketopyrrolopyrrole pigment of the formula (1) is 95. 0 parts, 5.0 parts of the specific heterodiketopyrrolopyrrole pigment B of the formula (B-2-8), 1000 parts of sodium chloride, and 120 parts of diethylene glycol was placed in a stainless steel 1-gallon kneader (manufactured by Inoue Co., Ltd.), and kneaded at 60 ° C for 10 hours. Next, the kneaded mixture is poured into warm water, and while stirring at a temperature of about 80 ° C, a small φ is stirred to form a paste, which is filtered and washed with water to remove salt and diethylene glycol, and then dried at 80 ° C for a day and night. 2nm。 The granules were obtained by the smelting. [Example 16] (Production of Pigment Composition 16 (R-16)) In a reaction vessel made of stainless steel with a reflux tube, 200 parts of a third pentanol dehydrated by molecular sieves was added under a nitrogen atmosphere, and a third 140 parts of sodium pentoxide was heated at 100 ° C while stirring to prepare an alkoxide solution. On the other hand, in a glass flask, 88 parts of diisopropyl succinate, 323842 166 201233734 4-bromobenzonitrile 146. 0 parts and a benzoquinone compound of the formula (B-3-1) 7. Six parts were dissolved by heating at 90 ° C while stirring, and a solution of these mixtures was prepared. The heated solution of the mixture was slowly dripped at a constant rate for 2 hours while vigorously stirring at 100 °C under the force of σ heat in the alkoxide solution. After the completion of the dropwise addition, heating and stirring were continued at 90 ° C for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Further, 600 parts of decyl alcohol, 600 parts of water, and 304 parts of acetic acid were placed in a reaction vessel in which a glass was lined with a liner, and cooled to -10 °C. The cooled mixture was rotated at a speed of 4,000 rpm while using a high-speed stirring® disperser, while the previously obtained diketone ratio of 11 was cooled to 75 ° C. A metal salt solution of a bilo compound is added in small amounts in small amounts. At this time, the temperature of the mixture of decyl alcohol, acetic acid, and water is usually an alkali metal of a diketopyrrolopyrrole compound which is cooled while being adjusted to a temperature of -5 ° C or lower and adjusted at 75 ° C. The salt addition rate was added in small portions for about 120 minutes. When the metal salt is added, red crystals are precipitated to form a red suspended φ turbid liquid. Next, the obtained red suspension was washed with an ultrafiltration apparatus at 5 ° C, and then filtered to obtain a red paste. This paste was again dispersed in 3,500 parts of sterol which had been cooled to 0 ° C to prepare a suspension having a sterol concentration of about 90 ° / Torr. Then, the mixture was stirred at 5 ° C for 3 hours, and the particles accompanying the crystal transfer were granulated and washed. Then, the water-soluble paste of the diketopyrrolopyrrole compound was dried at 80 ° C for 24 hours, and pulverized to obtain 148.1 parts of diketone ratio of 17 each. And a ratio of 11 to each pigment composition. The brominated diketopyrrolopyrrole pigment represented by the formula (1) and the specific 323842 167 201233734 represented by the formula (B-2-1) in the obtained diketone group ratio 11 and D ratio. The content of hetero-ketone-based ruthenium and ruthenium ruthenium, and the quantitative analysis of the _ _ ^ _ ketopyrrolopyrrole pigment represented by formula (1) and the formula (Β-2-1) The mass ratio of each pigment β is a dragon m HPL 曰 C measuring piece and the holding time is as follows. The necessity of L quantification & 里 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋And made.瘫 device: Gulliver series detector manufactured by Sakamoto Shikotsu Co., Ltd.: UV-970 detector column made by Japan Spectrophotometer Waters a Division Symmetry ci8 (5 // m, 2· lram p xl50mm) Mobile phase A liquid: two Methyl decylamine / water (1:1) mobile phase B. dimethylformamide / water (97. 5: 2. 5) distribution (B solution): 47% ~ (15 minutes; minutes) - 1〇〇%—(25 minutes)—100%
波長:510nm φ 管柱溫度:35°C 流量:0. 3 mL/分鐘 試料注入量:5//L(溶解在N-甲基吡咯烷酮/28%CH3〇Na甲 醇溶液中) 上述式(1)保持時間:11. 9至12. 9分鐘 上述式(B-2-1)保持時間:13.2至14. 1分鐘 接著,將得到的二酮基吡咯并吡咯系顏料組成物 100. 0份、氣化鈉1〇〇〇份,及二乙二醇120份,放入不銹 鋼製1加侖捏煉機(井上製作所製)中,在60°C混練10小 323842 168 201233734 時。其次,將混煉之混合物投入溫水中,一邊在約8 0 °C加 熱一邊擾拌1小時作成膏狀物,過濾並水洗除去食鹽及二 乙二醇後,在80°C乾燥一晝夜,藉由粉碎得到97. 6份之 二酮基吡咯并吡咯系顏料組成物的顏料組成物 16(R-16),平均一次粒子徑是32. 2nm。 [實施例17] (顏料組成物17(R-17)之製造) 附有回流管之不銹鋼製的反應容器中,於氮氣環境 ® 下,加入以分子篩脫水的第三戊醇200份,及第三戊氧基 鈉140份,一邊攪拌一邊在100°C加熱,調製醇鹽溶液。 另一方面,在玻璃製燒瓶中,加入琥珀酸二異丙酯88份、 4-溴化苯曱腈146.0份及式(B-3-1)之苯曱腈化合物7.6 份,一邊攪拌一邊在90°C加熱使其溶解,調製此等混合物 的溶液。將此混合物的加熱溶液,一邊激烈攪拌一邊花2 小時以一定速度緩慢滴下在100°C加熱之上述醇鹽溶液 φ 中。結束滴下後,在90°C繼續加熱攪拌2小時,得到二酮 基吡咯并吡咯系化合物的鹼金屬鹽。又,在玻璃製附有内 襯的反應容器中,加入甲醇600份、水600份、及醋酸304 份,冷卻到-10°C。將此已冷卻之混合物,使用高速攪拌的 分散器,一邊使直徑8cm之剪切碟以400Orpm回轉,一邊 在其中,將冷卻到75°C預先得到之二酮基°比咯并吡咯系化 合物的鹼金屬鹽溶液,少量地添加。此時,由曱醇、醋酸、 及水所成的混合物溫度持續保持在-5°C以下之溫度,一邊 冷卻,並且一邊調整75°C的二酮基吡咯并吡咯系化合物的 323842 169 201233734 鹼金屬鹽添加速膚,的v 屬鹽後,析出έ由 刀鐘少量地添加。添加驗金 爲 、·工的結晶,生成紅色的懸濁液。接著,將 付到之紅色懸濁液於5,c以超過渡裝置洗淨後,過渡得到 =色:狀物。將此膏狀物再次分散到已冷卻到。。。之^⑽ 伤曱醇中,作成甲醇濃度約為_的懸濁液。接 =㈣3小時’將伴隨結晶轉移的粒子進行整粒及洗淨。5 接者’以超過滤、機過據,得到二酮基鱗并吼略系化 物。進一步將得到的紅色膏狀物再分散到 膏狀物添加,二=10:w^ m 搜拌卜卜時後,過觀淨,得到 -.㈣并料系化合物的水旋泥 °C乾燥24小時扒貧狀物在80 洛系顏料組2 碎、到154.8份二縣鱗并呢 與製造顏料組成物16(R_16)時同樣操 - ㈣并鱗顏料組成物令的式⑴所示填化有7一酮基 吡咯顏料及式(B-2-1)所示之特定雜 =比咯开 料B的含量,使用HPLC定量_ 2开=顏 料與式如,示特定雜二=: 轉顏料Β的質量比是94·8:5·2。 咏比各并 _ ^ ’將得到的二_基料并鱗系顏料組成物 化納10()()份’及二乙二醇烟 鋼製1加侖捏煉機(井上製作所製)中,在= 不銹 323842 時。其次’將混煉之混合物投入溫水中,一邊在:_加 170 201233734 熱一邊授拌卜J、時作成膏狀物,過遽並水洗除去食鹽及二 乙一醇後’在8『C乾燥一晝夜,藉由粉碎得到96. 6份之 -酮基比口各并口比略系顏料組成物的顏料組成物 17(R-17) ’平均—次粒子徑是27. 2nm。 [實施例18] (顏料組成物之製造) 附有回流管之不銹鋼製的反應容器中,於氮氣環境 下,加入以分子篩脫水的第三戊醇200份,及第三戊氧基 鈉140份’一邊攪拌一邊在loot:加熱,調製醇鹽溶液。 另一方面’在玻璃製燒瓶中,加入琥珀酸二異丙酯88份、 4-溴化苯甲腈146·〇份及式(B-3-1)之笨甲腈化合物7.6 伤,一邊擾拌一邊在90°C加熱使其溶解,調製此等混合物 的溶液。將此混合物的加熱溶液,一邊激烈攪拌一邊花2 小時,以一定速度緩慢滴下到l〇(rc加熱之上述醇鹽溶液 中。結束滴下後,在90°C繼續加熱攪拌2小時,得到二酮 鲁基°比17各并°比p各系化合物的驗金屬鹽。又,在玻璃製附有内 襯的反應容器中,加入曱醇600份、水600份、及醋酸304 份,冷卻到-10°C。將此已冷卻之混合物,使用高速攪拌的 分散器’一邊使直徑8cm之剪切碟以4000rpm回轉,一邊 在其中,將冷卻到75°C的先前得到之二g同基《比咯并ν»比咯系 化合物的驗金屬鹽溶液’少量地添加。此時,由曱醇、醋 酸、及水所成的混合物溫度持續保持在it:以下的溫度, 一邊冷卻,並且一邊調整75°C的二酮基°比洛并吼嘻系化合 物鹼金屬鹽的添加速度,約花120分鐘少量地添加。添加 323842 171 201233734 驗金屬鹽後,析出紅色的結晶,生成紅色的懸濁液。接著, 將得到之紅色的懸濁液於π,以超過渡農置洗淨後,過 滤得到紅色膏狀物。將此膏狀物再次分散到已冷卻到旳 之麵份甲醇中,作成甲醇濃度約為9〇%的懸濁液。接著 於授拌3小時,伴隨結晶轉移進行粒子整粒及洗淨。 接著’以超過濾機過渡,將得到二職^各并料系化入 物的紅色膏狀物,在8(TC乾燥24小時,藉由粉碎得到 伤一酮基吡咯并吡咯系顏料組成物。 . 與製造顏料組成物16(R-16)時同樣操作 二并鱗顏·成物中的式⑴所科化二酮基!:各綱并基 π顏料及奶-2-1)騎之較雜 料Β的含量,使用HPLC定量分析時,式⑴所各;顏 所示特定雜二"Μ: 比各顏枓6的質量比是94.5 : 5.5。 接著,將得到的二酮基吼w各并 之科異啊衍生物之色5 化鈉1000份,及二乙二醇12 物4.5伤、氣 煉機(井上製作所t:>t,t 冑㈣1加侖捏 混煉之混合物投Λ)二在,^ 小時作成膏狀物:水 阶乾燥一畫夜,藉由醇後,在 ::2成物的顏料組成物18 [實施例19] 323842 172 201233734 (顏料組成物19CR-19)之製造) 附有回流管之不銹鋼製反應容器中,於氮氣環境下, 加入以分子篩脫水的第三戊醇200份,及第三戊氧基鈉140 份,一邊攪拌一邊在100°C加熱,調製醇鹽溶液。另一方 面,在玻璃製燒瓶中,加入琥珀酸二異丙酯88份、4-溴化 苯甲腈138. 3份及式(B-3-1)之苯曱腈化合物15. 1份,一 邊攪拌一邊在90°C加熱使其溶解,調製此等混合物的溶 液。將此混合物的加熱溶液,一邊激烈授拌一邊花2小時, ® 以一定速度緩慢滴下到在100°C加熱之上述醇鹽溶液内。 結束滴下後,在90°C繼續加熱攪拌2小時,得到二酮基吡 咯并吡咯系化合物的鹼金屬鹽。.又,在玻璃製附有内襯的 反應容器中,加入曱醇600份、水600份、及醋酸304份, 冷卻到-10°C。將此已冷卻之混合物,使用高速攪拌的分散 器,一邊使直徑8cm之剪切碟以4000rpm回轉,一邊在其 中,將冷卻到75°C的先前得到的二酮基π比17各并^比11各系化合 ^ 物的鹼金屬鹽溶液,少量少量地添加。此時,由曱醇、醋 酸、及水所成的混合物溫度通常是試圖保持在-5°C以下之 溫度,一邊冷卻,並且一邊調整75°C的二酮基吡咯并吡咯 系化合物鹼金屬鹽的添加速度,約花120分鐘少量地添 加。添加驗金屬鹽後,會析出紅色的結晶,生成紅色的懸 濁液。接著,將得到之紅色懸濁液於5°C,以超過濾裝置 洗淨後,過渡得到紅色膏狀物。將此膏狀物再次分散到已 冷卻到0°C之3500份曱醇中,作成曱醇濃度約為90%的懸 濁液。接著於5°C攪拌3小時,將伴隨結晶轉移的粒子進 323842 173 201233734 行整粒及洗淨。接著,以超過濾機過濾,將得到之二酮美 吡咯并吡咯系化合物的紅色膏狀物,在8〇中乾燥24小時"·, 藉由粉碎得到145. 8份二酮基吡咯并吡咯系顏料組成物:。 與製造顏料組成物16(R-16)時同樣操作,有關二_美 吡咯并吡咯顏料組成物中的式(1)所示溴化二酮基吡咯并土 吡咯顏料及式(B-2-1)所示之特定雜二酮基吡咯并吡咯顏 料B的含量,使用HPIX定量分析時,式⑴所示演化二鋼 基吡咯并吡咯顏料與式(B-2-1)所示特定雜二酮基吡 ® 吼咯顏料B的質量比是88. 9 : 11. 1。 接著’將得到的二@同基鱗并鱗系顏料組成物 100· 〇份、氯化納1000份,及二乙二醇12〇份,放入 鋼製1加命捏煉機(井上製作所製)中,在6〇ΐ混練ι〇小 時。其次,將混煉之混合物投入溫水中,一邊在約耽力 熱-邊授拌H、時作㈣狀物,職並水洗除去食鹽及二1^ 乙二醇後’在8(TC乾燥一晝夜,藉由粉碎得到98」份之 馨^基鱗#轉系_組成物的㈣組成物 19CR-19), 平均一次粒子徑是28. 8nm。 [參考例1] (顏料組成物20(R-20)之製造) 將式(1)的漢化二酮基鱗并吨略顏料⑽.〇份、氯 2 1000务,及一乙二醇12〇份,放入不錄鋼製1加命* ,井上1作所製)中’在^混練10小時。其次,將 小物投人溫水+,—邊麵8Gt加熱—邊授伴1 ,、成膏狀物,卿並水洗除去食鹽及二乙二醇後,在 323842 174 201233734 份之二酮基β比洛并比 2 0 ) ’平均一次粒子徑 80°C乾燥一晝夜,藉由粉碎得到96.6 p各系顏料組成物之顏料組成物2〇 d 是 38. 9nm。 [參考例2] (顏料組成物21(R-21)之製造) 將式⑴的漠化二_基吼略并吡略顏料7〇 〇份、式 (B-2-1)之特定雜二酮基轉并鱗姉B 3q. q份氣化Wavelength: 510 nm φ Column temperature: 35 ° C Flow rate: 0.3 mL/min Sample injection amount: 5 / / L (dissolved in N-methylpyrrolidone / 28% CH3 〇 Na methanol solution) The above formula (1) 0份,气。 The first time (1), the gas composition of the above-mentioned formula (B-2-1), the retention time: 13.2 to 14. 1 minutes, the obtained diketopyrrolopyrrole pigment composition 100. 0 parts, gas 1 part of sodium and 120 parts of diethylene glycol were placed in a stainless steel 1 gallon kneader (manufactured by Inoue Co., Ltd.), and 10 small 323842 168 201233734 was kneaded at 60 °C. Next, the kneaded mixture was poured into warm water, and while stirring at about 80 ° C for 1 hour, it was made into a paste, filtered and washed with water to remove salt and diethylene glycol, and dried at 80 ° C for a day and night. 2nm。 The pigment particle composition 16 (R-16) having an average primary particle diameter of 32. 2nm. [Example 17] (Production of Pigment Composition 17 (R-17)) In a reaction vessel made of stainless steel with a reflux tube, 200 parts of a third pentanol dehydrated by molecular sieves was added under a nitrogen atmosphere®, and 140 parts of sodium tripentoxide was heated at 100 ° C while stirring to prepare an alkoxide solution. On the other hand, in a glass flask, 88 parts of diisopropyl succinate, 146.0 parts of 4-bromobenzonitrile, and 7.6 parts of a benzoquinone compound of the formula (B-3-1) were added, and while stirring, It was dissolved by heating at 90 ° C to prepare a solution of these mixtures. The heated solution of the mixture was slowly dripped at a constant rate for 2 hours at a constant rate in the above alkoxide solution φ heated at 100 °C. After the completion of the dropwise addition, heating and stirring were continued at 90 ° C for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Further, 600 parts of methanol, 600 parts of water, and 304 parts of acetic acid were placed in a reaction vessel made of a glass-lined liner, and the mixture was cooled to -10 °C. The cooled mixture was rotated at 400 rpm while using a high-speed stirring disperser, and the diketone-based ratio of the pyrrole-based compound which was previously obtained by cooling to 75 ° C was rotated at 400 rpm. An alkali metal salt solution is added in small amounts. At this time, the temperature of the mixture of decyl alcohol, acetic acid, and water is maintained at a temperature of -5 ° C or lower, and while cooling, and adjusting the ketone pyrrolopyrrole compound at 75 ° C, 323842 169 201233734 alkali After the metal salt is added to the skin, the v is a salt, and the precipitate is added in a small amount by a knife. Adding a gold test to the crystal of the work, a red suspension is formed. Next, the red suspension was washed at 5, c with a super-transition device, and then transitioned to obtain a color: The paste was again dispersed until it had cooled. . . In the (10) sputum alcohol, a suspension having a methanol concentration of about _ was prepared. Then, (4) 3 hours, the particles accompanying the crystal transfer were granulated and washed. 5 Receiver's ultra-filtered, machine-based, to obtain diketone scales and simplification of the system. Further, the obtained red paste is redispersed into the paste, and after the second=10:w^m is searched for the buck, the net is obtained, and the mixture of the compound is obtained. The hourly depleted matter is broken in the 80 color pigment group 2 to 154.8 parts in the second county scale and the same as in the manufacture of the pigment composition 16 (R_16) - (4) the scale pigment composition is filled with the formula (1) The content of the 7-ketopyrrole pigment and the specific impurity = the ratio of the bromide B represented by the formula (B-2-1) is quantified by HPLC _ 2 open = pigment and formula, for example, specific poly 2 =: transfer pigment Β The mass ratio is 94.8:5·2.咏 各 _ ^ ' _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Stainless 323842. Secondly, 'mix the mixture into warm water, while: _ add 170 201233734 heat while mixing the j, when made into a paste, after simmering and washing to remove salt and diethyl alcohol, 'dry at 8 C overnight 2纳米。 By pulverization to obtain a pigment composition 17 (R-17) 'average - secondary particle diameter is 27. 2nm. [Example 18] (Production of Pigment Composition) In a reaction vessel made of stainless steel with a reflux tube, 200 parts of a third pentanol dehydrated by a molecular sieve and 140 parts of a third sodium pentoxide were added under a nitrogen atmosphere. ' While stirring, luot: heat to prepare an alkoxide solution. On the other hand, in a glass flask, 88 parts of diisopropyl succinate, 146 parts of 4-bromobenzonitrile and benzoic nitrile compound 7.6 of formula (B-3-1) were added. The mixture was heated and dissolved at 90 ° C to prepare a solution of the mixtures. The heated solution of the mixture was stirred for 2 hours while stirring vigorously, and slowly dripped at a constant rate to the above alkoxide solution heated by rc. After the completion of the dropwise addition, heating and stirring were continued at 90 ° C for 2 hours to obtain a diketone. A metal salt of a compound of each of the ratios of 17 and a ratio of 17 to a compound of a p-series. In addition, 600 parts of methanol, 600 parts of water, and 304 parts of acetic acid are added to a glass-lined reaction vessel, and cooled to - 10 ° C. This cooled mixture, using a high-speed stirring disperser, while rotating a 8 cm diameter shearing disc at 4000 rpm, while cooling it to 75 ° C, the previously obtained two g of the same base Add a small amount of the metal salt solution of the oxo-r-based compound. In this case, the temperature of the mixture of decyl alcohol, acetic acid, and water is maintained at the temperature below it: while cooling, and adjusting 75 The addition rate of the diketone-based dioxo-based compound alkali metal salt at °C was added in a small amount for about 120 minutes. After the addition of 323842 171 201233734, the red salt was precipitated to form a red suspension. Then, will get The red suspension was washed at π, super-transitioned, and filtered to obtain a red paste. The paste was again dispersed in methanol which had been cooled to the surface of the crucible to give a methanol concentration of about 9 〇. % suspension. Then, after mixing for 3 hours, the particles were granulated and washed with crystal transfer. Then, by the transition of the ultra-filter, the red paste of the two jobs was obtained. The ketone-based pyrrolopyrrole pigment composition was obtained by pulverization at 8 (TC drying for 24 hours). The formula (1) in the same procedure as in the production of the pigment composition 16 (R-16) The content of the ketones of the ketones: the ketones of the ketones and the milk-2-1) are the contents of the girders of the cockroaches. : The mass ratio of each of the pigments is 64.5:5.5. Next, the obtained diketone oxime w is different from the color of the derivative, the color of the sodium salt is 1000 parts, and the diethylene glycol 12 is 4.5 wounds. Gas-making machine (Inoue Manufacturing Co., Ltd.: t, t t (four) 1 gallon kneading mixture mixture) 2, ^ hours into a paste: water level dry one night, After the alcohol, the pigment composition 18 in the composition of: 2 [Example 19] 323842 172 201233734 (pigment composition 19CR-19)) In a stainless steel reaction vessel with a reflux tube, under a nitrogen atmosphere 200 parts of a third pentanol dehydrated by molecular sieves and 140 parts of sodium p-pentoxide were added, and the mixture was heated at 100 ° C while stirring to prepare an alkoxide solution. On the other hand, in a glass flask, 88 parts of diisopropyl succinate, 138.3 parts of 4-bromobenzonitrile, and 15.1 parts of a benzoquinone compound of the formula (B-3-1) were added. The mixture was heated and dissolved at 90 ° C while stirring to prepare a solution of these mixtures. The heated solution of this mixture was allowed to stand for 2 hours while vigorously mixing, and the solution was slowly dropped to the above alkoxide solution heated at 100 ° C at a constant rate. After the completion of the dropwise addition, the mixture was further heated and stirred at 90 ° C for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Further, 600 parts of methanol, 600 parts of water, and 304 parts of acetic acid were placed in a glass-lined reaction vessel, and cooled to -10 °C. The cooled mixture was rotated at a speed of 4000 rpm while using a high-speed stirring disperser, while the previously obtained diketone π ratio of 17 was cooled to 75 ° C. The alkali metal salt solution of each of the 11 compounds was added in small amounts in small amounts. At this time, the temperature of the mixture of decyl alcohol, acetic acid, and water is usually an attempt to maintain the temperature below -5 ° C, while cooling, and while adjusting the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C The addition speed was added in a small amount for about 120 minutes. When a metal salt is added, red crystals are precipitated to form a red suspension. Next, the obtained red suspension was washed at 5 ° C with an ultrafiltration device to obtain a red paste. This paste was again dispersed in 3,500 parts of sterol which had been cooled to 0 ° C to prepare a suspension having a sterol concentration of about 90%. Subsequently, the mixture was stirred at 5 ° C for 3 hours, and the particles accompanying the crystallization transfer were granulated and washed in 323842 173 201233734. Then, the red paste of the diketope pyrrolopyrrolone compound was dried in 8 Torr for 24 hours, and 145. 8 parts of diketopyrrolopyrrole was obtained by filtration. Pigment composition: The brominated diketopyrrolopyrrole pigment of the formula (1) and the formula (B-2-) in the composition of the di-pyrrolidinopyrrole pigment are treated in the same manner as in the preparation of the pigment composition 16 (R-16). 1) The content of the specific heterodiketopyrrolopyrrole pigment B shown, when using HPIX quantitative analysis, the evolution of the steel-based pyrrolopyrrole pigment represented by formula (1) and the specific heteropoly shown in formula (B-2-1) The mass ratio of the ketopyrrole® fluorene pigment B is 88.9: 11.1. Then, 'the second granules of the squamous scales and the squamous pigments 100· 〇, 1000 parts of sodium chloride, and 12 parts of diethylene glycol were placed in a steel 1 simmering kneader (manufactured by Inoue Co., Ltd.) ), mixing 〇 〇 hours at 6 。. Next, the mixture of the mixture is put into warm water, and while the H-heat is being mixed, the (four) material is used, and the salt is washed and the salt is removed, and the ethylene glycol is removed. 8nm。 The averaging particle diameter is 28. 8nm. [Reference Example 1] (Production of Pigment Composition 20 (R-20)) The finished diketone of the formula (1) is a pigment (10). oxime, chlorine 2 1000, and monoethylene glycol 12 〇 In the case of the unrecorded steel 1 plus life*, the Inoue 1 is made in the middle of the 'mixing' for 10 hours. Secondly, the small object is poured into warm water +, - 8Gt heating on the side - while giving 1 , into a paste, and washed with water to remove salt and diethylene glycol, at 323842 174 201233734 parts of the diketone beta ratio The singularity of the pigment composition of the pigment composition of 96.6 p is 28.9 d is 38. 9 nm. [Reference Example 2] (Production of Pigment Composition 21 (R-21)) 7 parts of the desertified bismuth-pyridylpyrrolidine pigment of the formula (1), and the specific hetero formula of the formula (B-2-1) Keto group and scaly B 3q. q parts gasification
鈉1000份,及二乙二醇120份,放入尤凝^ 双入不銹鋼製1加侖捏煉 機(井上製作所製)中,在6(TC混練1〇小時。其次,將混 煉之混合物投入溫水中,一邊在約8rc加熱一邊攪拌二、 時作成膏狀物,减並水絲去切及二乙二醇後,在8〇 °c乾燥一晝夜,藉由粉碎得到95 8份夕_ m w 物之一酮基π比P各并π比略 系顏料組成物之顏料組成物21 (R-2 Ή,u 〇〇 ^ ’平均一次粒子徑是 28.4nm 〇 [參考例3 ] (顏料組成物22(R-22)之製造) 將式⑴㈣化二酮基鱗并t各顏料50』份、式 (B'2-l)之特定雜二_基轉并鱗轉 鈉1000份,及二乙二醇12〇份,姑λ 鼠化 ^ ^ ^ . 不銹鋼製1加命捏煉 在啊料ig㈣。其次,將混 ^之〜合射认溫水中,—邊在約咐加熱 B、作成膏狀物’過渡並水洗除去食鹽及 & °C乾燥-畫夜’藉由粉碎得到㈤份之:=後立在8[ 糸顏料組成物之顏料組成物22叫平均 323842 175 201233734 35. 4nm ° [參考例4;| (顏料組成物23(R-23)之製造)1000 parts of sodium and 120 parts of diethylene glycol were placed in a 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) made of stainless steel, and mixed at 6 (TC for 1 hour). Next, the mixture was mixed. In warm water, while stirring at about 8 rc, it is made into a paste. After the water is removed and cut into diethylene glycol, it is dried at 8 ° C for one day and night, and pulverized to obtain 95 8 times. One of the ketone groups π ratio P and π ratio of the pigment composition of the pigment composition 21 (R-2 Ή, u 〇〇 ^ 'the average primary particle diameter is 28.4 nm 〇 [Reference Example 3] (Pigment composition Production of 22(R-22)) The formula (1) (four) diketone ketone and t 50 pigments, the specific hetero-diyl group of the formula (B'2-l) is converted into 1000 parts of sodium, and two 12 二醇 diol, λ 鼠 rat ^ ^ ^. Stainless steel 1 life smelting in the material ig (four). Secondly, the mixture will be mixed into the warm water, - while heating in the 咐, B, into a paste The material 'transition and washing to remove salt and & °C dry-painting night' by pulverization to obtain (five) parts: = after standing at 8 [pigment pigment composition of pigment composition 22 called average 323842 175 201233734 35. 4nm [Reference Example. 4; | (a pigment composition 23 (R-23) of the manufactured)
將式(B-2-1)之特定雜二酮基吡咯并吡咯顏料b 80.0 伤、氣化鈉1000份,及二乙二醇110份,放入不銹鋼製i 力:侖捏煉機(井上製作所製)中,在赃混練1〇小時。其 夂’將混煉之混合物投入溫水中,一邊在約80。(:加熱一邊 攪拌1小時作成膏狀物,過濾並水洗除去食鹽及二乙二醇 在80 C乾燥一畫仪’藉由粉碎得到76. 8份之二酮基 比各并吡咯系顏料組成物之顏料組成物23(R-23),平均一 次粒子徑是39. 4nm。 [參考例5] (顏料組成物24(R-24)之製造) 將^⑴的漠化二酮基鱗并t各顏料7〇 〇份、式 之特絲二縣料并鱗顏㈣_份、氣化 機及二乙二醇120份’放入不镑鋼製1加余捏煉 =井上製作所製)中,在_混練心十其次,將混 時作2物投入溫水中’一邊在約㈣加熱-邊檀拌H、 ^成4物,喊並水洗除去錢及二乙二雜,在8〇 ^―晝夜,藉由粉碎得到95.8份之二酮基㈣并吼咯 %顏料組成物之顏料組成物__24),平均一次粒子徑是 仏 3nm。 [參考例6] (顏料組成物25(R-25)之製造) 323842 176 201233734 將市售的C. I·顏料紅254(汽巴特別化學公司製 「Irgaphor Red B-CF」100· 0 份、氯化鈉 1〇〇〇 份,及二 乙二醇120份,放入不銹鋼製ϊ加侖捏煉機.(井上製作所製) 中,在60 C混練10小時。其次,將混煉之混合物投入溫 水中,一邊在约8(TC加熱一邊攪拌1小時作成膏狀物,過 濾並水洗除去食鹽及二乙二醇後,在8〇〇c乾燥一晝夜,藉 由粉碎得到97. 8份之二酮基吡咯并吡咯系顏料組成物之 顏料組成物25(R-25),平均一次粒子徑是36. 3nm。 參[參考例7] (顏料組成物26(R-26)之製造) 將將市售的C. I.顏料紅254(汽巴特別化學公司製 「Irgaphor RedB-CF」90.0 份、式(Bn)之特定雜二酮 基吡咯并吡咯顏料B 10.0份、氣化鈉1〇〇〇份,及二乙二 醇120份’放入不銹鋼製1加侖捏煉機(井上製作所製)中, 在60°C混練10小時。其次,將混煉之混合物投入溫水中, • 一邊在約80°C加熱一邊攪拌1小時作成膏狀物,過濾並水 洗除去食鹽及二乙二醇後,在8〇°c乾燥一晝夜,藉由粉碎 得到9 5. 8份之二酮基吡咯并吡咯系顏料組成物之顏料組 成物26(R-26),平均一次粒子徑是31. 4nm。 將製造的顏料組成物1至26(R-1至26)的内容在表 B-1中表示。在表B-1中記載的「PR254」是指C I.顏料紅 254的意思。 323842 177 201233734 [表 B-l ] 表B-l 顏料 组成物 二《基吡咯并吡咯顏料 色素衍生物處理 平均-•次 粒子徑 (nm) 顏料1 質量比 顏料2 質量比 合成時 鹽研磨時 賁施例1 R-1 式⑴ 97 式(B - 2—1) 3 — — 36. 8 實施例2 R-2 式⑴ 95 式(B —2— 1) 5 — - 30. 5 實施例3 R-3 式⑴ 90 式(B — 2 —1) 10 — - 26· 5 實施例4 R-4 式⑴ 85 式(B—2— 1) 15 - - 28. 5 實施例5 R-5 式⑴ 95 式(B—2-2) 5 — - 31. 6 實施例6 R-6 式⑴ 95 式(B — 2 —3) 5 - - 34. 6 實施例7 R—7 式⑴ 95 式(B—2_4a) 5 一 — 28. 6 贫施例8 R-8 式⑴ 85 式(B_2—4a) 15 — - 25. 5 貧施例9 R-9 式⑴ 95 式(B — 2—4b) 5 - - 31. 1 實施例10 R-10 式⑴ 95 式(B — 2 —5) 5 — — 33. 1 實施例11 R-11 式⑴ 95 式(B_2_6b) 5 — — 28. 9 實施例12 R-12 式⑴ 95 式(B-2-6c) S — 一 29. 8 實施例13 R—13 式⑴ 95 式(B-2—7) 5 - — 28. 2 實施例14 R-14 式⑴ 85 式(B—2—7) 15 — — 26. 5 實施例15 R-15 式⑴ 95 式(B— 2-8> 5 - - 34. 2 實施W 16 R-16 式⑴ 94. 3 式(B_2— 1) 5. 7 - -F 32. 2 實施例17 R-17 式⑴ 94. 8 式(B— 2 -1) 5. 2 式(7—1) - 27. 2 贫施例18 R-18 式⑴ 94. 5 式(B—2- 0 5. 5 - 式(7 —1> 26. 2 實施例19 R-19 式⑴ 88. 9 式(Β—2— 1) 11. 1 — - 28. 8 參考例1 R-20 式⑴ 100 - — - - 38. 9 參考例2 R-21 式⑴ 70 式(Β—2 -1) 30 - - 28. 4 參考例3 R-22 式⑴ 50 式(Β—2-1) 50 - — 35. 4 參考例4 R-23 一 1 式(Β — 2_l)‘i 100 — — 39. 4 參考例5 R-24 式⑴ 70 式(B-2-4a) j 30 - - 27. 3 麥考例6 R-25 PR254 100 一 — 36. 3 參考例7 R-26 PR254 90 式(B—2 — 1) ί 10 — - 31. 4Injecting a specific heterodiketopyrrolopyrrole pigment b 80.0 of formula (B-2-1), 1000 parts of sodium vaporized, and 110 parts of diethylene glycol into a stainless steel i-force: lun kneader (inoue In the production system, I knead for 1 hour. Its 夂' is to mix the kneaded mixture into warm water, at about 80. (: stirring while heating for 1 hour to form a paste, filtering and washing to remove salt and diethylene glycol in a 80 C drying apparatus) by pulverization to obtain 76.8 parts of diketone ratio perpyrrole pigment composition The pigment composition 23 (R-23), the average primary particle diameter is 39. 4 nm. [Reference Example 5] (Production of Pigment Composition 24 (R-24)) The deserted diketone scale of ^(1) 7 parts of each pigment, the formula of the second county and the scales (four) _ parts, gasification machine and 120 parts of diethylene glycol 'into the non-pound steel 1 plus kneading = manufactured by Inoue Manufacturing Co., Ltd.) In the _ 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混 混By pulverizing, 95.8 parts of the diketone group (tetra) and the pigment composition of the pigment composition __24) were obtained, and the average primary particle diameter was 仏3 nm. [Reference Example 6] (Production of Pigment Composition 25 (R-25)) 323842 176 201233734 Commercially available C.I. Pigment Red 254 (Irgaphor Red B-CF, 100% by Ciba Specialty Chemicals Co., Ltd.) 1 part of sodium chloride and 120 parts of diethylene glycol were placed in a stainless steel kneading kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60 C for 10 hours. Secondly, the kneaded mixture was put into In the warm water, while stirring at a temperature of about 8 (TC) for 1 hour to form a paste, filtered and washed with water to remove salt and diethylene glycol, dried at 8 ° C for a day and night, by pulverization to obtain 97. The pigment composition of the ketopyrrolopyrrole pigment composition is 25 (R-25), and the average primary particle diameter is 36. 3 nm. Reference [Reference Example 7] (Production of Pigment Composition 26 (R-26)) Commercially available CI Pigment Red 254 (Irgaphor RedB-CF) made by Ciba Specialty Chemicals Co., Ltd. 90.0 parts, 10.0 parts of the specific heterodiketopyrrolopyrrole pigment B of the formula (Bn), and 1 part of sodium gasification. And 120 parts of diethylene glycol were placed in a stainless steel 1 gallon kneader (manufactured by Inoue Co., Ltd.) and kneaded at 60 ° C for 10 hours. Secondly, mixed The mixture was poured into warm water. The mixture was stirred for 1 hour while heating at about 80 ° C to form a paste. After filtering and washing with water to remove salt and diethylene glycol, it was dried at 8 ° C for one day and night, and pulverized to obtain 9 5 . The pigment composition 26 (R-26) of the bis-keto-pyrrolopyrrole pigment composition having an average primary particle diameter of 31. 4 nm. The pigment composition to be produced 1 to 26 (R-1 to 26) The content is shown in Table B-1. "PR254" described in Table B-1 means C I. Pigment Red 254. 323842 177 201233734 [Table Bl] Table B1 Pigment Composition II "Pyropyrrolopyrrole Pigment pigment derivative treatment average - • Secondary particle diameter (nm) Pigment 1 Mass ratio Pigment 2 Mass ratio Salt synthesis during synthesis 贲 Example 1 R-1 Formula (1) 97 Formula (B - 2 - 1) 3 - 36. 8 Example 2 R-2 Formula (1) 95 Formula (B-2 - 1) 5 - - 30. 5 Example 3 R-3 Formula (1) 90 Formula (B-2 - 1) 10 - - 26· 5 Example 4 R-4 Formula (1) 85 Formula (B-2 - 1) 15 - - 28. 5 Example 5 R-5 Formula (1) 95 Formula (B-2-2) 5 - - 31. 6 Example 6 R-6 Formula (1) 95 Formula (B-2 - 3) 5 - - 34. 6 Example 7 R—7 Formula (1) 95 Formula (B—2_4a) 5 I— 28. 6 Poor Example 8 R-8 Formula (1) 85 Formula (B_2—4a) 15 — - 25. 5 Poor Example 9 R-9 Formula (1) 95 Formula (B-2-4-b) 5 - - 31. 1 Example 10 R-10 Formula (1) 95 Formula (B-2-5) 5 — — 33. 1 Example 11 R-11 Formula (1) 95 Formula (B_2_6b 5 — — 28. 9 Example 12 R-12 Formula (1) 95 Formula (B-2-6c) S — A 29.8 Example 13 R—13 Formula (1) 95 Formula (B-2—7) 5 — — 28. 2 Example 14 R-14 Formula (1) 85 Formula (B-2-7) 15 — — 26. 5 Example 15 R-15 Formula (1) 95 Formula (B—2-8> 5 - - 34. 2 Implementation W 16 R-16 Formula (1) 94. 3 Formula (B_2-1) 5. 7 - -F 32. 2 Example 17 R-17 Formula (1) 94. 8 Formula (B-2 -1) 5. 2 Formula (7 —1) - 27. 2 Poor Example 18 R-18 Formula (1) 94. 5 Formula (B—2- 0 5. 5 - Formula (7-1) 26. 2 Example 19 R-19 Formula (1) 88. 9 Formula (Β—2—1) 11. 1 — - 28. 8 Reference Example 1 R-20 Formula (1) 100 - — - - 38. 9 Reference Example 2 R-21 Formula (1) 70 Formula (Β—2 -1) 30 - - 28. 4 Reference Example 3 R-22 Equation (1) 50 Equation (Β-2-1) 50 - - 35. 4 Reference Example 4 R-23 1 Formula (Β - 2_l) 'i 100 — — 39. 4 reference 5 R-24 Formula (1) 70 Formula (B-2-4a) j 30 - - 27. 3 Wheat test case 6 R-25 PR254 100 I— 36. 3 Reference Example 7 R-26 PR254 90 Formula (B-2 — 1) ί 10 — - 31. 4
<其他顏料的製造方法> (二蒽醌系顏料KPR177-1)的製造) 將二慧醌系顏料(C. I.顏料紅177)90. 0份、氯化鈉900 份,及二乙二醇110份,放入不銹鋼製1加侖捏煉機(井上 製作所製)中,在60°C混練10小時。其次,將混煉之混合 物投入溫水中,一邊在約80°C加熱一邊攪拌1小時作成膏 狀物,過濾並水洗除去食鹽及二乙二醇後,在80°C乾燥一 畫夜,藉由粉碎得到85.0份之二蒽醌系顏料KPR177-1), 178 323842 201233734 平均一次粒子徑是38. 2nm。 (偶氮系顏料1(ΡΠ50-1)的製造) 將偶氮系顏料(C. I.顏料黃150)90. 0份、氣化鈉900 份,及二乙二醇110份,放入不銹鋼製1加侖捏煉機(井上 製作所製)中,在6ITC混練10小時。其次,將混煉之混合 物投入溫水中,一邊在約80°c加熱一邊攪拌1小時作成膏 狀物,過濾並水洗除去食鹽及二乙二醇後,在80°C乾燥一<Production method of other pigments> (Production of diterpene pigment KPR177-1) 90. 0 parts of dimethicone pigment (CI Pigment Red 177), 900 parts of sodium chloride, and diethylene glycol 110 parts were placed in a stainless steel one-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), and kneaded at 60 ° C for 10 hours. Next, the kneaded mixture was poured into warm water, stirred while heating at about 80 ° C for 1 hour to form a paste, filtered and washed with water to remove salt and diethylene glycol, and then dried at 80 ° C for one night. 2nm。 The pulverization to obtain 85.0 parts of the diterpene pigment KPR177-1), 178 323842 201233734 average primary particle diameter is 38. 2nm. (Production of azo pigment 1 (ΡΠ50-1)) 90 parts of azo pigment (CI Pigment Yellow 150), 900 parts of sodium vaporate, and 110 parts of diethylene glycol were placed in a gallon of stainless steel. The kneader (manufactured by Inoue Works Co., Ltd.) was kneaded at 6 ITC for 10 hours. Next, the kneaded mixture was poured into warm water, stirred while heating at about 80 ° C for 1 hour to form a paste, filtered and washed with water to remove salt and diethylene glycol, and then dried at 80 ° C.
晝夜’藉由粉碎得到85. 0份之偶氮系顏料ΚΡΠ50-1), 平均一次粒子徑是26. 2nm。 〈黏合劑樹脂溶液的製造方法〉 (丙烯酸樹脂溶液1之調製) 在可分離之4 口燒瓶中安裝有溫度計、冷卻管、氮氣 $入管、滴下管及攪拌裝置的反應容器内,放入環己酮196 知’昇溫到80°c ’反應容器内以氮氣取代後,由滴下管以 —小時將3 7. 2份之甲基丙稀酸正丁自旨、12 · 9份甲基丙烯酸 ^羥基乙酯、12. 〇份甲基丙烯酸、2〇. 7份對異丙苯基酚環2nm。 The average primary particle diameter is 26. 2nm. <Method for Producing Binder Resin Solution> (Preparation of Acrylic Resin Solution 1) A separable 4-necked flask was equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube, and a stirring device in a reaction vessel. Ketone 196 Known 'heating to 80 ° C ' After the reaction vessel was replaced with nitrogen, 37.2 parts of methyl methacrylate was used for the hour-by-hour, and 12 9 parts of methacrylic acid was hydroxylated by the dropping tube. Ethyl ester, 12. 〇 methacrylic acid, 2 〇. 7 parts p-cumylphenol ring
M乙烷改質丙烯酸酯(東亞合成(股)公司製「ARONIX 」1. 1伤的2’ 2’ _偶氮雙異丁腈的混合物滴下。結束 /同下後,再繼續及廄 冷卻至卜〜 小時,而得到丙烯酸樹脂的溶液。 哉卜將樹脂溶液約2份作為試樣,在180°C加 成分,樹合成的樹脂溶液 %的方式調製…s旨’以使不揮發成分變成2〇質量 2_0製丙稀酸樹脂溶液1。重量平均分子量《W)是 323842 179 201233734 (丙烯酸樹脂溶液2的調製) 在可分離4 口燒瓶中安裝有溫度計、冷卻管、氮氣導 入管、滴下管及攪拌裝置的反應容器内,放入環己酮207 份,昇溫到80°C,反應容器内以氮氣取代後,由滴管費時 2小時將20份之曱基丙烯酸、20份的對異丙苯基酚環氧乙 烷改質丙烯酸酯(東亞合成(股)公司製「ARONIXM110」)、 45份的甲基丙烯酸甲酯、8. 5份的甲基丙烯酸2-羥基乙酯、 及1. 33份的2, 2’ -偶氮雙異丁腈的混合物滴下。結束滴下 ® 後,再繼續反應3小時,而得到共聚物樹脂溶液。其次, 對得到的共聚物溶液全量,停止氮氣一邊注入乾燥空氣一 邊攪拌1小時,冷卻到室溫後,將6. 5份的2-曱基丙烯醯 氧基乙基異氰酸酯(昭和電工公司製Karenz音譯)M01)、 0.08份月桂酸二丁基錫、26份環己酮的混合物在70°C花3 小時滴下。結束滴下後,再繼續反應1小時,而得到丙烯 酸樹脂的溶液。冷卻到室溫後,將樹脂溶液約2份作為試 φ 樣在180°C加熱乾燥20分鐘後測定不揮發成分,在先前合 成的樹脂溶液中添加環己酮,以使不揮發成分變成20質量 %的方式調製丙烯酸樹脂溶液2。重量平均分子量(Mw)是 18000 。 (黏合劑樹脂的重量平均分子量) 丙烯酸樹脂的重量平均分子量,係藉由GPC(凝膠滲透 層析分析儀)測定換算成聚苯乙烯的重量平均分子量。 〈使用二酮基吡咯并吡咯系顏料組成物的著色組成物之製 作方法〉 323842 180 201233734 [實施例20] (著色組成物l(RP-l)的製作) 將下述所示調配組成的混合物均.勻攪拌混合.,使用直 =〇.1咖的二氧化鍅小球,以pic〇MILL研磨機(淺田鐵工 公司製)分散8小時後,以的過遽膜過遽,製作著色 組成物l(RP-l)。 二酮基吡咯并吡咯系顏料組成物l(R-l) ii.o份Methane-modified acrylate (ARONIX) 1. 1 wound 2' 2' _ azobisisobutyronitrile mixture was dropped. After completion/same, continue and 廄 cooling to卜~hours, and a solution of the acrylic resin is obtained. About 2 parts of the resin solution is used as a sample, and the composition is added at 180 ° C, and the resin solution of the tree is prepared in a manner of ... to make the non-volatile component 2 〇Quality 2_0 acrylic acid resin solution 1. Weight average molecular weight "W" is 323842 179 201233734 (Preparation of acrylic resin solution 2) A thermometer, a cooling tube, a nitrogen introduction tube, a dropping tube, and the like are installed in a separable 4-necked flask. In the reaction vessel of the stirring device, 207 parts of cyclohexanone was placed, and the temperature was raised to 80 ° C. After the reaction vessel was replaced with nitrogen, 20 parts of mercaptoacrylic acid and 20 parts of p-cumene were taken from the dropping tube for 2 hours. a phenol epoxide modified acrylate ("ARONIX M110" manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 1.33 A mixture of 2,2'-azobisisobutyronitrile was dropped. After the completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin solution. Next, the total amount of the copolymer solution obtained was stirred for 1 hour while injecting dry air while cooling the nitrogen gas. After cooling to room temperature, 6.5 parts of 2-mercaptopropenyloxyethyl isocyanate (Karenz, Showa Denko) Transliteration) M01), a mixture of 0.08 parts of dibutyltin laurate and 26 parts of cyclohexanone was dropped at 70 ° C for 3 hours. After the completion of the dropwise addition, the reaction was further continued for 1 hour to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was dried as a test sample at 180 ° C for 20 minutes, and then the nonvolatile matter was measured, and cyclohexanone was added to the previously synthesized resin solution to change the nonvolatile content to 20 mass. The acrylic resin solution 2 is prepared in a % manner. The weight average molecular weight (Mw) is 18,000. (Weight average molecular weight of binder resin) The weight average molecular weight of the acrylic resin is measured by GPC (gel permeation chromatography analyzer) to determine the weight average molecular weight converted into polystyrene. <Method for Producing Colored Composition Using Diketopyrrolopyrrole Pigment Composition> 323842 180 201233734 [Example 20] (Production of Colored Composition 1 (RP-1)) A mixture of the following compositions was prepared. The mixture was uniformly stirred and mixed. Using a cerium oxide ball of straight = 〇.1 coffee, it was dispersed by a pic 〇MILL grinder (manufactured by Asada Iron Works Co., Ltd.) for 8 hours, and the ruthenium film was passed through to make a coloring composition. Object l (RP-l). Diketopyrrolopyrrole pigment composition l(R-l) ii.o
色素衍生物式(14-1) 1〇份 丙烯酸樹脂溶液1 40.0份 丙二醇單曱基醚醋酸酯 48.〇二 [實施例21至38] (著色組成物2至i9(RP-2至RP-19)之製作) 除了將顏料組成物1(R-D變更成在表B_2記載的顏料 =成物之外,其餘與著色組成物l(RP-l)進行同樣操作, 製作著色組成物2至19(RP-2至19)。 [實施例39] (著色組成物20(RP-20)之製作) 將下述所示調配組成之混合物均勻攪拌混合後,使用 直杈0. 1mm的二氧化鍅小球,以pico MILL研磨機分散8 小時後’以m的過濾膜過濾,製作著色組成物2〇(rp-2〇)。 二_基吡咯并吡咯系顏料組成物丨9(R_19) 11.0份 色素衍生物式(6-3) 1.0份 樹脂型分散劑(BykChemie公司製「BYK161」(30%溶液)6. 0份 丙烯酸樹脂溶液 31.0份 323842 181 201233734 丙二醇單曱醚醋酸酯 51.0份 [實施例40] (著色組成物21(RP-21)之製作) 將下述所示調配組成之混合物均勻擾拌混合後,使用 直徑0. 1mm的二氧化鍅小球,以PIC〇 MILL研磨機分散8 小時後’以5/zm的過濾膜過濾,製作著色組成物2KRP-21)。 二酮基°比咯并吡咯系顏料組成物19(R_19) 12. 0份 樹脂型分散劑(味之素Finetechno公司製「Ajisper PB821」3. 6份 零丙烯酸樹脂溶液1 23. 0份 丙二醇單甲醚醋酸酯 61.4份 [參考例8至14] (著色组成物22至28(RP-22至28)之製作) 除了將顏料組成物1(H)變更成在表B-2中記載的顏 料組成物之外,其餘與著色組成物IWP-D進行同樣操 作,製作著色組成物22至28(RP-22至28)。 323842 182 201233734 [表 B_2 ] 表B-2 著色组成物 顏料組成物 务施例20 RP-1 R-1 實施例21 RP-2 R-2 實施例22 RP-3 R—3 實施例23 RP-4 R~4 實施例24 RP-5 R-5 實施例25 RP-6 R-6 實施例26 RP-7 R-7 實施例27 RP-8 R-8 實施例28 RP-9 R-9 實施例29 RP-10 R…10 實施例30 RP-11 R-11 .實施例31 RP-12 R-12 實施例32 RP-13 R-13 實施例33 RP-14 R-14 實施例34 RP-15 R-15 實施例35 RP-16 R-16 實施例36 RP—17 R-17 實施例37 RP-18 R-18 實施例38 RP-19 R-19 實施例39 RP-20 R-19 實施例40 RP-21 R-19 參考例8 RP-22 R-20 參考例9 RP-23 R-21 參考例10 RP-24 R-22 參考例11 RP-25 R-23 參考例12 RP-26 R-24 參考例13 RP-27 R-25 參考例14 RP-28 R-26Pigment derivative formula (14-1) 1 part part acrylic resin solution 1 40.0 parts of propylene glycol monodecyl ether acetate 48. 〇2 [Examples 21 to 38] (Coloring compositions 2 to i9 (RP-2 to RP- (19) Production) The coloring composition 2 to 19 was produced in the same manner as in the coloring composition 1 (RP-1) except that the pigment composition 1 (RD was changed to the pigment = product described in Table B_2). 1mm的小鍅小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小The ball was dispersed by a pico MILL grinder for 8 hours, and then filtered through a filtration membrane of m to prepare a colored composition 2 (rp-2〇). Di-pyrrolopyrrole pigment composition 丨9 (R_19) 11.0 parts of a pigment Derivative formula (6-3) 1.0 part of resin type dispersant ("BYK161" (30% solution) manufactured by Byk Chemie Co., Ltd. 6. 0 parts of acrylic resin solution 31.0 parts 323842 181 201233734 propylene glycol monoterpene ether acetate 51.0 parts [Example 40 1mm的直径。 Using a mixture of 0. 1mm The cerium oxide pellets were dispersed in a PIC〇MILL mill for 8 hours and then filtered through a 5/zm filter membrane to prepare a colored composition 2KRP-21. Diketone-pyrolopyrrole pigment composition 19 (R_19) 12.0 parts of a resin type dispersant (Ajisper PB821 manufactured by Ajinomoto FineTech Co., Ltd.) 3. 6 parts of an acrylic resin solution 1 23. 0 parts of propylene glycol monomethyl ether acetate 61.4 parts [Reference Examples 8 to 14] (Coloring) Compositions 22 to 28 (Preparation of RP-22 to 28) The same procedure as in the coloring composition IWP-D except that the pigment composition 1 (H) was changed to the pigment composition described in Table B-2 Operation, coloring compositions 22 to 28 (RP-22 to 28) were produced. 323842 182 201233734 [Table B_2] Table B-2 Colored composition Pigment composition Example 20 RP-1 R-1 Example 21 RP-2 R-2 Example 22 RP-3 R-3 Example 23 RP-4 R~4 Example 24 RP-5 R-5 Example 25 RP-6 R-6 Example 26 RP-7 R-7 Example 27 RP-8 R-8 Example 28 RP-9 R-9 Example 29 RP-10 R...10 Example 30 RP-11 R-11. Example 31 RP-12 R-12 Example 32 RP-13 R-13 Example 33 RP-14 R-14 Example 34 RP-15 R-15 Real Example 35 RP-16 R-16 Example 36 RP-17 R-17 Example 37 RP-18 R-18 Example 38 RP-19 R-19 Example 39 RP-20 R-19 Example 40 RP-21 R-19 Reference Example 8 RP-22 R-20 Reference Example 9 RP-23 R-21 Reference Example 10 RP-24 R-22 Reference Example 11 RP-25 R-23 Reference Example 12 RP-26 R-24 Reference Example 13 RP-27 R-25 Reference Example 14 RP-28 R-26
〈其他著色組成物之製作方法〉 (著色組成物29(RP-29)之製作) 183 323842 201233734 將下述所示調配組成之混合物均勻撥拌混合後,使用 直徑0. lmm的二氧化錯小球’以PICO MILL研磨機分散8 小時後,以m的過濾膜過濾,製作著色組成物29(RP-29)。 一葱西昆系顏料(PR177-1) 10.8份 色素衍生物(8-5) 1.2份 丙烯酸樹脂溶液1 40. 0份 丙二醇單曱醚醋酸酯 48. 0份 (著色組成物30CYP-30)之製作) ® 將下述所示調配組成之混合物均勻擾拌混合後,使用 直徑0. lmm的二氧化銼小球,以PICO MILL研磨機分散8 小時後’以5ym的過濾膜過濾,製作著多組成物30(γρ-3〇)。 偶氮系顏料(ΡΥ150-1) 12.. 0份 樹脂型分散劑(Byk Chemie公司製「ΒΥΚ6919」(50%溶液)6.0份 丙稀酸樹脂溶液1 25 0份 丙二醇单甲_醋酸醋 57. 0份 φ 〈感光性著色組成物之製作方法〉 [實施例41] (感光性著色組成物之製作) 將下述之混合物攪拌混合成均勻後,使用m的過 濾膜過濾,製作感光性著色組成物KRRO。 著色組成物l(RP-l) 38. 2 份 著色組成物29(RP-29) 3. 8份 丙烯酸樹脂溶液2 13. 2 份 光聚合性單體(東亞合成公司製「Α_χ _〇」 2. 8份 323842 184 201233734 光聚合起始劑(汽巴日本公司製「Irgacure-907」2. 0份 增感劑(Hodogaya Chemical 公司製「EAB-F」0.4 份 丙二醇單曱醚醋酸酯 39. 6份 [實施例42至61] (感光性著色組成物2至21 (RR-2至21)之製作) 除了將著色組成物l(RP-l)變更成著色組成物2至21 (RP-2至21),又,將著色組成物2至21(RP-2至21)與著 色組成物29(RP-29)的比率變更(在全部著色組成物42份 ® 内變更比率)之外,其餘與實施例41進行同樣操作,可製 作感光性著色組成物2至21 (RP-2至21),同時,有關比 率的變更,在塗膜評估時,以C光源符合χ=〇. 64〇,y=〇. 328 之色度的方式,變更著色組成物2至21 (RP-2至21)與著 色組成物29(RP-29)的比率。 [參考例15至18、20、21] (感光性者色組成物22至25、27、28(RR-22至25、27、 φ 28)之製作) 除了將著色組成物l(RP-l)變更成著色組成物22至 25、27、28(RR-22 至 25、27、28),又,將著色組成物 22 至 25、27、28(RR-22 至 25、27、28)與著色組成物 29(rp_29) 的比率變更(在全部著色組成物42份内變更比率)之外,其 餘與實施例41進行同樣操作,可製作感光性著色組成物 22 至 25、27、28(RR-22 至 25、27、28)。並且,有關比率 變更係在塗膜評估時,以使C光源χ=〇. 640,y=〇. 328之色 度的方式變更著色組成物22至25、27、28(RP-22至25、 323842 185 201233734 27、28)與著色組成物29(RP-29)的比率。 [參考例19] (感光性著色組成物26CRR-26)之調製) 除了將著色組成物1(RP-1)變更成著色組成物% (RP-26)’將著色組成物29(Rp_29)變更成著色組成物 (YP-30),又,將著色組成物26(Rp〜26)與著色組成物3〇 (YP-30)的比率變更(在全部著色組成物42份内變更比率) 之外’其餘與實關41崎同樣操作,可製作感光性著色 組成物26(RR-26)。並且,有關比率的變更係塗膜評估時, 以C光源x=0. 640 ’ y=〇. 328之色度的方式變更著色組 26(RP-26)與著色組成物30(YP_3〇)的比率。 〈使用感光性著色組成物的塗膜製作與評估〉 使用所得之感光性著色組成物至 色塗膜,其色特性、對比度比、,而析出結晶的評估係 以下述方法進行。 在表B-3表示感光性著色組成物中的著色組成物之種 類及評估結果。 (塗膜的色特性評估) 在lOOramxlOOmm、0·7ιμ厚度的玻璃基板上,在c光源 中以使膜厚成為χ=〇· 640’y=〇. 328的方式塗佈感光性著色 組成物,乾燥後,使用超高壓水銀燈照射3〇〇mJ/cm2之紫外 線。再者,於230X:中加熱60分鐘可得到紅色塗膜。之後, 以顯微分光光度計(〇lympus光學公司製「〇Sp_Sp2〇〇」)測 定所得塗膜的亮度(Y)。並且,色度也同樣以顯微分光光度 323842 186 201233734 計(Olympus光學公司製「OSp-Sp2〇〇」)測定。 (塗膜的對比度比評估) 說明有關塗膜的對比度比之測定法。液晶顯示用背光 單元所放出之光,係通過偏光板而偏光,通過在玻璃基板 上塗佈著色組成物的乾燥塗膜,到達偏光板。只要偏光板 與偏光板之偏光面為平行的話,光雖然透過偏光板,但在 偏光面為直行時,光是被偏光板遮斷。然而,藉由偏光板 偏光之光通過著色組成物的乾燥塗膜時,由於顏料粒子而 發生散射等,當偏光面之一部分發生交錯時,偏光板為平 行之時透過偏光板的光量會減少,偏光板為直行之時一部 分透過偏光板。將此透過光作為在偏光板上的亮度測定, 算出偏光板為平行之時的亮度,與直行時的亮度之比(對比 度比)。 (對比度比)=(平行時的亮度)/ (直行時的亮度) 因此,由於塗膜中的顏料發生散射時,平行時的亮度 籲會下降’並且因為直行時的亮度會增加,故對比度比變成 下降。 並且,作為亮度計是使用色彩亮度計(Topco公司製 「BM-5A」),作為偏光板是使用偏光板(曰東電工公司製 「NPF-G 122GDM」。並且,測定時為了遮斷多餘的光,在 測定部分覆上開有lcm正方孔洞的黑色遮罩。X,在測定 對比度比+是使料色躲評估時同樣綠_的紅色塗 膜。 (塗膜表面的結晶析出評估) 323842 187 201233734 在100mm x 100mm、0.7mm厚度的破璃基板上,在C 光源中以使膜厚成為x=0. 640的方式塗佈感光性著色組成 物,乾燥後,使用超高壓水銀燈照射300mJ/cm2之紫外線。 接著於230°C進行加熱處理60分鐘後,再重複2次在240 °(:加熱處理60分鐘。加熱處理後的基板塗膜表面在光學顯 微鏡中觀察,有無結晶析出是依據下述基準來判定。 ◎ : 230°C加熱處理60分鐘後,進一步在240°C加熱處理 60分鐘後,及再進行240°C加熱處理60分鐘亦無結晶析出 ® 〇:230°C處理60分鐘加熱後,及再進行240°C加熱處理 60分鐘亦無結晶析出(第2次的240°C加熱處理60分鐘有 結晶析出) △:雖230°C加熱處理60分鐘後沒有結晶析出,但進一步 240°C加熱處理60分鐘有結晶析出 X : 230°C加熱處理60分鐘後有結晶析出Lmm的小氧化小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小小The ball was dispersed by a PICO MILL mill for 8 hours, and then filtered through a filtration membrane of m to prepare a colored composition 29 (RP-29). 1份(色色组成物30CYP-30), a portion of a pigment derivative (8177), a portion of a pigment derivative (8-5), 1.2 parts of an acrylic resin solution, 14.0 parts of propylene glycol monoterpene ether acetate. Manufactured ® The mixture of the following composition was evenly mixed and mixed, and then pulverized with a diameter of 0. lmm, and dispersed by a PICO MILL grinder for 8 hours, 'filtered with a 5 μm filter membrane to make more Composition 30 (γρ-3〇). Azo-based pigment (ΡΥ150-1) 12. 0 parts of resin type dispersant ("6919" (50% solution) made by Byk Chemie Co., Ltd. 6.0 parts of acrylic resin solution 1 25 0 parts of propylene glycol monomethyl acetate acetate 57. 0 parts φ <Method for producing photosensitive coloring composition> [Example 41] (Production of photosensitive coloring composition) The following mixture was stirred and mixed to be uniform, and then filtered using a filtration membrane of m to prepare a photosensitive coloring composition. KRRO. Coloring composition l (RP-1) 38. 2 parts of coloring composition 29 (RP-29) 3. 8 parts of acrylic resin solution 2 13. 2 parts of photopolymerizable monomer (made by Toagosei Co., Ltd. "Α_χ _ 〇" 2. 8 parts 323842 184 201233734 Photopolymerization initiator (Irgacure-907) made by Ciba Japan Co., Ltd. 2. 0 parts of sensitizer (EAB-F, manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts of propylene glycol monoterpene ether acetate 39. 6 parts [Examples 42 to 61] (Production of photosensitive coloring compositions 2 to 21 (RR-2 to 21)) except that the coloring composition 1 (RP-1) was changed to the coloring compositions 2 to 21 ( RP-2 to 21), in addition, the ratio of the coloring compositions 2 to 21 (RP-2 to 21) to the coloring composition 29 (RP-29) is changed (in all The photosensitive coloring compositions 2 to 21 (RP-2 to 21) were produced in the same manner as in Example 41 except that the color composition was changed to 42 parts in the color ratio, and the ratio was changed in the coating film. During the evaluation, the coloring composition 2 to 21 (RP-2 to 21) and the coloring composition 29 (RP-29) were changed in such a manner that the C light source conformed to the chromaticity of χ=〇. 64〇, y=〇.328. [Reference Example 15 to 18, 20, 21] (Preparation of photosensitive color compositions 22 to 25, 27, 28 (RR-22 to 25, 27, φ 28)) In addition to the coloring composition 1 (RP) -l) changed to coloring compositions 22 to 25, 27, 28 (RR-22 to 25, 27, 28), and further, colored compositions 22 to 25, 27, 28 (RR-22 to 25, 27, 28) The photosensitive coloring composition 22 to 25, 27, 28 can be produced in the same manner as in Example 41 except that the ratio of the coloring composition 29 (rp_29) is changed (the ratio is changed within 42 parts of all the coloring compositions). (RR-22 to 25, 27, 28). Moreover, when the film is evaluated, the coloring composition 22 is changed so that the C light source χ = 640 640, y = 328. 25, 27, 28 (RP-22 25, 323 842 185 201 233 734 27, 28) and the ratio of the coloring composition 29 (RP-29) of. [Reference Example 19] (Preparation of photosensitive coloring composition 26CRR-26) The coloring composition 29 (Rp_29) was changed except that the coloring composition 1 (RP-1) was changed to the coloring composition % (RP-26). In addition, the coloring composition (YP-30) is changed, and the ratio of the coloring composition 26 (Rp to 26) to the coloring composition 3 (YP-30) is changed (the ratio is changed within 42 parts of all the coloring compositions). The rest is operated in the same manner as Shisaka 41, and the photosensitive coloring composition 26 (RR-26) can be produced. Further, when the change of the ratio is the evaluation of the coating film, the coloring group 26 (RP-26) and the coloring composition 30 (YP_3〇) are changed so that the C light source x=0.640 'y=〇.328 is the chromaticity. ratio. <Preparation and Evaluation of Coating Film Using Photosensitive Colored Composition> Using the obtained photosensitive coloring composition to the color coating film, the color characteristics and the contrast ratio were evaluated, and the evaluation of the precipitated crystal was carried out by the following method. Table B-3 shows the types and evaluation results of the coloring composition in the photosensitive coloring composition. (Evaluation of color characteristics of the coating film) The photosensitive coloring composition was applied to the glass substrate having a thickness of 100 μm x 100 mm and 0·7 μm so that the film thickness became χ=〇·640′y=〇.328. After drying, an ultraviolet ray of 3 〇〇 mJ/cm 2 was irradiated with an ultrahigh pressure mercury lamp. Further, a red coating film was obtained by heating in 230X: for 60 minutes. Thereafter, the brightness (Y) of the obtained coating film was measured by a microspectrophotometer ("Sp_Sp2" manufactured by 〇lympus Optics Co., Ltd.). Further, the chromaticity was also measured by microscopic spectrophotometry 323842 186 201233734 ("OSp-Sp2" manufactured by Olympus Optical Co., Ltd.). (Evaluation of Contrast Ratio of Coating Film) Describes the measurement method regarding the contrast ratio of the coating film. The light emitted from the backlight unit for liquid crystal display is polarized by a polarizing plate, and a dried coating film of a colored composition is applied onto the glass substrate to reach the polarizing plate. As long as the polarizing surface of the polarizing plate and the polarizing plate are parallel, although the light passes through the polarizing plate, when the polarizing surface is straight, the light is blocked by the polarizing plate. However, when the polarized light is passed through the dried coating film of the coloring composition, scattering occurs due to the pigment particles, and when one of the polarizing surfaces is staggered, the amount of light transmitted through the polarizing plate is reduced when the polarizing plates are parallel. When the polarizing plate is straight, a part of the polarizing plate passes through the polarizing plate. This transmitted light was measured as the luminance on the polarizing plate, and the ratio of the luminance at the time when the polarizing plates were parallel and the luminance at the time of straight running (contrast ratio) was calculated. (contrast ratio) = (brightness in parallel) / (brightness in straight line) Therefore, since the pigment in the coating film is scattered, the brightness in parallel is lowered, and since the brightness during straightening increases, the contrast ratio Becomes a decline. In addition, a color luminance meter ("BM-5A" manufactured by Topco Co., Ltd.) is used as the luminance meter, and a polarizing plate ("NPF-G 122GDM" manufactured by Minto Electric Co., Ltd.) is used as the polarizing plate. The light is covered with a black mask with a 1 cm square hole in the measurement portion. X, the red color film is the same green color when the contrast ratio + is measured. (Evaluation of crystal precipitation on the surface of the coating film) 323842 187 201233734 On a glass substrate of 100 mm x 100 mm and 0.7 mm thickness, a photosensitive coloring composition is applied to a C light source so that the film thickness becomes x=0.640, and after drying, an ultrahigh pressure mercury lamp is used to irradiate 300 mJ/cm2. After the heat treatment was carried out at 230 ° C for 60 minutes, it was repeated twice at 240 ° (heat treatment for 60 minutes). The surface of the substrate coating film after the heat treatment was observed in an optical microscope, and the presence or absence of crystal precipitation was based on the following. ◎ : After heat treatment at 230 ° C for 60 minutes, further heat treatment at 240 ° C for 60 minutes, and further heat treatment at 240 ° C for 60 minutes without crystal precipitation ® 〇: 230 ° C treatment for 60 minutes heating And no further crystallization was carried out after further heating at 240 ° C for 60 minutes (the second 240 ° C heat treatment for 60 minutes showed crystal precipitation) △: no crystal precipitation after heat treatment at 230 ° C for 60 minutes, but further 240 ° C heat treatment for 60 minutes, crystal precipitation X: crystallization at 230 ° C for 60 minutes, crystal precipitation
323842 188 201233734 [表 B-3]323842 188 201233734 [Table B-3]
表B-3 著色组成物 著色组成物中的顏料分散體 評估结果 二明基吡咯并 吡咯系 调色用 亮度 (Y) 對比度比 結晶析出 實施例41 RR-1 RP-1 RP-29 21. 3 5400 0 實施例42 RR-2 RP-2 RP-29 21. 3 5600 〇 實施例43 RR-3 RP-3 RP-29 21. 0 6200 ◎ 實施例44 RR-4 RP-4 RP-29 20. 8 6200 ◎ 實施例45 RR-5 RP-5 RP-29 21. 2 5200 〇 實施例46 RR-6 RP-6 RP-29 21. 0 5000 〇 實施例47 RR-7 RP-7 RP-29 21. 0 6200 〇 實施例48 RR-8 RP-8 RP-29 20. 6 7000 ◎ 實施例49 RR-9 RP — 9 RP-29 21. 0 5500 〇 賞施例50 RR-10 RP-10 RP-29 21. 2 5100 〇 實施例51 RR-11 RP-11 RP-29 21. 2 5900 〇 實施例52 RR-12 RP-12 RP-29 21. 1 5500 〇 賁施例53 RR-13 RP-13 RP-29 21. 2 5800 ◎ 實施例54 RR-14 RP-14 RP-29 20. 6 6700 〇 實施例55 RR-15 RP-15 RP-29 21. 0 5000 Δ 實施例56 RR-16 RP-16 RP-29 21. 2 5700 | 〇 實施例57 RR-17 RP-17 RP-29 20. 9 6200 ◎ 實施例58 RR-18 RP-18 RP-29 20. 9 6300 ◎ 實施例59 RR-19 RP-19 RP-29 20. 9 6000 ◎ 實施例60 RR-20 RP-20 RP-29 20. 8 5800 〇 實施例61 RR-21 RP-21 RP-29 21. 3 5000 △ 參考例15 RR—22 RP-22 RP-29 21. 3 3200 X 參考例16 RR-23 RP-23 RP-29 20· 2 4900 ◎ 參考例17 RR-24 RP-24 RP-29 19. 9 3900 ◎ 參考例18 RR-25 RP — 25 RP-29 19. 0 2700 ◎ 參考例19 RR-26 RP — 26 YP-30 19. 9 4800 ◎ 參考例20 RR-27 RP-27 RP-29 20. 8 1100 X 參考例21 RR-28 RP-28 RP-29 20. 4 4200 △ 由表B-3的結果可知,於形成彩濾光片中,使用含有 將溴化二酮基吡咯并吡咯顏料與特定雜二酮基吡咯并吡咯 顏料B以特定比率(質量比97 : 3至85 : 15)之二酮基吡咯 并吡咯系顏料組成物的實施例,特別在亮度方面為優良, 再者,具有高對比可抑制因加熱步驟所造成之二酮基吡咯 并°比11各系顏料之結晶析出。 實施例43與參考例21的比較中,使用含有溴化二酮 189 323842 201233734 基吡咯并吡咯顏料與特定雜二酮基吡咯并吡咯顏料B之_ ’基吡咯并咣咯系顏料組成物的感光性著色組成物的於 果,係比以往利用含有C· I.顏料紅254之感光性著色1成 物有更高的亮度並且高對比’亦無結晶析出之問題。又 參考例15的不含有特定雜二酮基吡咯并吡咯顏科^之、臭化 二酮基吡咯并吡咯顏料,已知亮度雖優異,但鮮比低、盩 法抑制結晶析出。再者,由實施例42與實施例至4?、 及實施例49至53的結果,藉由使用特定雜二網基吡咯并 吡咯顏料B之效果,也可以確認與其種類有依存關係。开 實施例41至44、參考例15至18中,已知式^ 并'略顏料之含有比率 仁抑制結晶析出效果有變大的傾向。又,3 對比有最適點,若抑制特定雜 匕知關於 有比率的1 基岭并㈣顧料之含 十的话,可以取得亮度與對比的平衡。 合成=Γ2與實施例56,已知在以號_二醋共 料及特絲=域物,與在如㈡基鱗并鱗顏 理時心製=各弁鱗顏料Β分別合成的鹽研磨處 施例似料組成物,可得到同樣的效果。又,實 在實施例心ΓΓ比較中,也可以確認有同樣的效果。 化及結㈣知色物絲處理是有高對比度 〈彩色濾光片的製作〉 成:使用的綠色⑽ 323842 #色組成物的製作。並且,有關紅色是 190 201233734 使用本實施例B的感光性著色組成物16(RR_16)。 (綠色著色組成物1 (GP-1)的製作) 將下述所示調配組成之混合物擾拌混合均.勻後,使用 直徑0· 1mm的二氧化鍅小球,以PIC〇 MILL研磨機分散8 小時後,以5/zm的過濾犋過濾,製作綠色著色組成物1 (GP-1) 〇Table B-3 Evaluation of Pigment Dispersion in Coloring Composition Coloring Composition Results of Binding of Pyridylpyrrolopyrrole Color (Y) Contrast Ratio Crystallization Example 41 RR-1 RP-1 RP-29 21. 3 5400 0 Example 42 RR-2 RP-2 RP-29 21. 3 5600 〇 Example 43 RR-3 RP-3 RP-29 21. 0 6200 ◎ Example 44 RR-4 RP-4 RP-29 20. 8 6200 ◎ Example 45 RR-5 RP-5 RP-29 21. 2 5200 〇 Example 46 RR-6 RP-6 RP-29 21. 0 5000 〇 Example 47 RR-7 RP-7 RP-29 21. 0 6200 〇 Example 48 RR-8 RP-8 RP-29 20. 6 7000 ◎ Example 49 RR-9 RP — 9 RP-29 21. 0 5500 Appreciation Example 50 RR-10 RP-10 RP-29 21. 2 5100 〇 Example 51 RR-11 RP-11 RP-29 21. 2 5900 〇 Example 52 RR-12 RP-12 RP-29 21. 1 5500 〇贲 Example 53 RR-13 RP-13 RP -29 21. 2 5800 ◎ Example 54 RR-14 RP-14 RP-29 20. 6 6700 〇 Example 55 RR-15 RP-15 RP-29 21. 0 5000 Δ Example 56 RR-16 RP-16 RP-29 21. 2 5700 | 〇 Example 57 RR-17 RP-17 RP-29 20. 9 6200 ◎ Example 58 RR-18 RP-18 RP-29 20. 9 6300 ◎ Example 59 RR-19 RP -19 RP-29 20. 9 6000 ◎ Example 60 RR-20 RP-20 RP-29 20. 8 5800 〇 Example 61 RR-21 RP-21 RP-29 21. 3 5000 △ Reference Example 15 RR-22 RP-22 RP-29 21 3 3200 X Reference Example 16 RR-23 RP-23 RP-29 20· 2 4900 ◎ Reference Example 17 RR-24 RP-24 RP-29 19. 9 3900 ◎ Reference Example 18 RR-25 RP — 25 RP-29 19. 0 2700 ◎ Reference Example 19 RR-26 RP — 26 YP-30 19. 9 4800 ◎ Reference Example 20 RR-27 RP-27 RP-29 20. 8 1100 X Reference Example 21 RR-28 RP-28 RP- 29 20. 4 4200 △ It can be seen from the results of Table B-3 that in the formation of the color filter, the use of the brominated diketopyrrolopyrrole pigment and the specific heterodiketopyrrolopyrrole pigment B at a specific ratio ( Examples of the diketopipyrrolopyrrole pigment composition having a mass ratio of 97:3 to 85:15) are excellent in particular in terms of brightness, and further, high contrast suppresses diketopyrrole caused by the heating step And the ratio of the pigments of the 11 series of pigments precipitated. In a comparison of Example 43 with Reference Example 21, a photosensitive composition containing a brominated diketone 189 323842 201233734-based pyrrolopyrrole pigment and a specific heterodiketopyrrolopyrrole pigment B of a _ 'pyrrolopyrrole pigment composition was used. The result of the coloring composition is higher than that of the photosensitive coloring composition containing C·I. Pigment Red 254, and the high contrast is also not caused by crystal precipitation. Further, the odorized diketopyrrolopyrrole pigment which does not contain the specific heterodiketopyrrolopyrrolidinium of Example 15 is known to have excellent brightness, but has a low fresh ratio and suppresses crystallization. Further, from the results of Example 42 and Examples to 4?, and Examples 49 to 53, the effect of the specific hetero-dimethylpyrrolopyrrole pigment B was confirmed by the use of the specific hetero-network-based pyrrolopyrrole pigment B. In the examples 41 to 44 and the reference examples 15 to 18, the content ratio of the formula was slightly suppressed, and the effect of suppressing the crystallization of the kernel was increased. In addition, there is an optimum point for the comparison of 3, and if the specific impurity is suppressed, the balance of brightness and contrast can be obtained if there is a ratio of 1 base and (4). Synthetic = Γ 2 and Example 56, known as the salt granules synthesized by the number _ diacetate conjugate and the filth = domain, respectively, and the squama squama The same effect can be obtained by exemplifying the composition. Further, in the comparison of the heartbeats of the examples, it was confirmed that the same effect was obtained. (4) Knowing color silk processing is high contrast <Production of color filter> In: Green (10) 323842 #Color composition. Further, the red color is 190 201233734. The photosensitive coloring composition 16 (RR_16) of this Example B was used. (Preparation of green coloring composition 1 (GP-1)) The mixture of the following composition was mixed and mixed, and then dispersed, using a cerium oxide sphere having a diameter of 0·1 mm, dispersed by a PIC〇MILL mill. After 8 hours, it was filtered through a 5/zm filter to produce a green coloring composition 1 (GP-1).
綠色顏料(C. I.顏料綠36) 6. 8份 黃色顏料(C. I.顏料黃150) 5. 2份 樹脂型分散劑(汽巴日本公司製rEFKA43〇〇」) 1.0份 丙烯酸樹脂溶液1 35. 0 份 丙二醇單甲基醚醋酸酯 52. 0 份 (綠色感光性著色組成物1 (GR_ 1 )的調製) 將下述組成之混合物攪拌混合均勻後,以i μια的過 渡膜過濾’製作綠色感光性著色組成物1(GR_1;) 〇 綠色著色組成物1(GP-1) 42. 0 份 丙烯酸樹脂溶液2 13. 2 份 光聚合性單體(東亞合成公司製rAR〇NIX M40〇」) 2. 8份 光聚合始起劑(汽巴日本公司製「Irgacure-907」) 2. 0份 増感劑(Hodogaya Chemical 公司製「EAB-F1」 0.4份 乙二醇單曱基醚醋酸酯 39. 6 份 (藍色著色組成物l(BP-l)的調製) 將下述所示調配組成之混合物攪拌混合均勻後,使用 直徑〇. lmm的二氧化锆小球,以PICO MILL研磨機分散8 小時後’以5/zm的過濾膜過濾,製作藍色著色組成物1 323842 191 201233734 (ΒΡ-l)。 7. 2份 4. 8份 1. 0份 35. 〇 份 52. 〇 份 藍色顏料(C· I.顏料藍15 : 6) 紫色顏料(C. I.顏料紫23) 樹脂型分散劑(汽巴日本公司製「EFKA4300」) 丙烯酸樹脂溶液1 丙二醇單曱基醚醋酸酯 (藍色感光性著色組成物的調製)Green pigment (CI Pigment Green 36) 6. 8 parts of yellow pigment (CI Pigment Yellow 150) 5. 2 parts of resin type dispersant (rEFKA43〇〇 made by Ciba Japan) 1.0 part of acrylic resin solution 1 30.5 parts of propylene glycol Monomethyl ether acetate 52.0 parts (Preparation of green photosensitive coloring composition 1 (GR_ 1 )) A mixture of the following composition was stirred and mixed uniformly, and then filtered with a transition film of i μα to prepare a green photosensitive coloring composition. 1 (GR_1;) 〇Green coloring composition 1 (GP-1) 42. 0 parts of acrylic resin solution 2 13. 2 parts of photopolymerizable monomer (rAR〇NIX M40〇 manufactured by Toagosei Co., Ltd.) 2. 8 parts Photopolymerization initiator (Irgacure-907) manufactured by Ciba Japan Co., Ltd. 2. 0 parts of sensitizer (EAB-F1, manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts of ethylene glycol monodecyl ether acetate 39.6 parts ( Preparation of blue coloring composition l (BP-1) The mixture of the following composition was stirred and mixed uniformly, and then dispersed in a PICO MILL mill for 8 hours using a zirconia pellet having a diameter of 〇. Filtered with a 5/zm filter to produce a blue colored composition 1 323842 191 201233734 (ΒΡ-l) 7. 2 parts 4. 8 parts 1. 0 parts 35. 52 part 52. 蓝色part blue pigment (C·I. Pigment Blue 15 : 6) Purple pigment (CI Pigment Violet 23) Resin type dispersant ("EFKA4300" manufactured by Ciba Japan Co., Ltd.) Acrylic resin solution 1 Propylene glycol monodecyl ether acetate (modulation of blue photosensitive coloring composition)
將下述組成之混合物攪拌混合均勻後,以丨"^的過 濾膜過濾,製作藍色感光性著色組成物1(BR〇。 34· 〇 份 :l5. 2 份 3· 3份 0份 〇· 4份 藍色著色組成物l(BP-l) 丙烯酸樹脂溶液2 光聚合性單體(東亞合成公司製「Ar〇nIX M400」) 光聚合始起劑(汽巴日本公司製rIrgacure_9〇7」) 增感劑(Hodogaya Chemical 公司製「EAB-F1」 乙二醇單甲基醚醋酸酯 π,、 在玻璃基板上加工黑色矩陣圖案,在該基板上以旋轉 塗佈法將感光性著色組成物l6(RR_l6)以Χ=0 . 64〇,户〇 328 的膜厚的方式塗佈而形成著色被膜。該被膜隔著遮罩,使 用超高壓水銀燈照射3〇〇mJ/cm2的紫外線。其次,藉由以 0· 2重量%的碳酸鈉水溶液所成的鹼性顯像液噴霧顯像而除 去未曝光部分之後,以離子交換水洗淨,將此基板在23〇 C加熱20分鐘,形成紅色濾光片段。藉由同樣的方法,分 別塗佈綠色感光性著色組成物l(GR-l)成x=0. 300,y=0. 600 之膜厚’塗佈藍色感光性著色組成物KBR-丨)成χ=〇15〇, 323842 192 201233734 y=0. 060之膜厚,而形成綠色濾光片段、藍色濾光片段, 得到彩色濾光片。 藉由使用感光性著色組成物16(RR_i6),可以製作高 亮度並且高對比,在加熱步驟中無結晶析出之彩色濾光片。 [實施例C] " 實施例C中,在沒有特別限定下,「份」及「%」是分 別表示「質量份」及「質量%」。顏料的比表面積、顏料的 一次粒子徑、樹脂的重量平均分子量(Mw)、樹脂的酸價、 零塗膜的對比度比(CR)之測定方法如下所述。 (顏料的比表面積) 顏料粒子的比表面積,係藉由吸附氮氣之BET法求 得。並且,在測定中是使用自動蒸氣吸附量測定裝置(曰本 Bell 公司製「BELS0RP18」)。 (顏料的平均一次粒子徑) 顏料的平均一次粒子徑是由電子顯微鏡照片直接計 • 測一次粒子的大小之方法來測定。具體而言,計測各顏料 的一次粒子之短軸徑與長軸徑,將平均當作此顏料粒子的 粒徑。其次,關於1〇〇個以上的顏料粒子,將各粒子的體 積(重量)噔近似於求得之粒徑立方體的方式求得體積平均 粒徑當作平均一次粒徑。並且,電子顯微鏡是使用穿透型 (TEM)。 (樹脂的重量平均分子量(MW)) 使用TSKgel管柱(TOHSO公司製),裝備有R】檢出器 之GPCCT0HS0公司製’ HLC-8120GPC),使用THF作為展開 323842 193 201233734 溶劑,測定換算成聚苯乙烯的重量平均分子量(Mw)。 (樹脂的酸價) 在樹脂溶液0. 5至lg中’加入丙酮8〇mi及水10ml. 並攪拌均勻使其溶解,將〇· lm〇l/L之Κ0Η水溶液當作滴定 液,使用自動滴定裝置(「C0M_555」平沼產業製)來滴定, 測疋樹脂溶液的酸價。於是,由樹脂溶液的酸價與樹脂溶 液的固形分濃度,算出樹脂固形分的相當酸價。 (塗膜之對比度比) 由液晶顯示用背光單元所放出之光,係通過偏光板而 偏光’通過在玻璃基板上塗佈著色組成物的乾燥塗膜,到 達偏光板。只要偏光板與偏光板之偏光面為平行的話,光 雖是透過偏光板,但在偏光面為直行時,光是被偏光板遮 斷。然而,藉由偏光板在被偏光之光通過著色組成物的乾 燥塗膜時’由於顏料粒子而發生散射等,當偏光面之一部 分發生交錯時,偏光板為平行之時穿透偏光板的光量會減 少’偏光板為直行時一部分光會穿透偏光板。將此穿透光 作為在偏光板上的亮度,算出偏光板為平行之時的亮度, 與直行時的亮度之比(對比度比)。 (對比度比Μ平行時的亮度)/(直行時的亮度) 並且’作為亮度計係使用色彩輝度計(Topco公司製 「BM-5A」)’作為偏光板是使用偏光板(日東電工公司製 「NPF-G1220DUN」。並且,測定時為了遮斷多餘的光,在測 定部分覆上開有lcm正方孔洞的黑色遮罩。 在實施例前,說明有關在實施例及參考例使用的黏合 323842 194 201233734 樹脂(B)溶液、式(1)中所示顏料(A1、 、微細化顏料、顏料 分散體的製造方法。 〈黏合樹脂(B)溶液的製造方法〉 [驗可溶性感光性樹脂(B1-1)] 在具備溫度計、冷卻管、氮氣導入管滴下管及擾摔 裝置的可分離4 口燒觀中放入環己狗咖份,昇溫到8〇 。(:,燒瓶内以氮氣取代後,藉由滴下管費時2小時將18 份對異丙苯基酴環氧乙燒改質丙歸㈣(東亞合成(股)公 攀司製「麵IX M110」、10份之甲基μ酸苯甲醋、μ 份曱基丙稀酸縮水甘油醋、25份曱基㈣酸甲酿、2 〇份 的2, 2’-偶氮雙異丁腈的混合物滴下。滴下後,再於ι〇〇 °C反應3小時後,添加以50份環己陶溶解於1〇份偶氮雙 異丁腈之溶液’再於100°C繼續反應1小時。接著,將容 器内取代成空氣’將在9. 3份(縮水甘油基的當量)丙稀酸 中0.5份參二曱基胺基紛及0.1份氫g昆投入上述容器内, φ於120它持續反應6小時當變成固形分酸價為0.5時結束 反應’得到丙婦酸樹脂的溶液。再者,持續將四氫笨二酸 酐19· 5份(生成之羥基的當量)、三乙胺0 5份加入,在 120°C反應3. 5小時可得到丙烯酸樹脂的溶液。 冷卻到室溫後,將樹脂溶液約2g作為試樣在ΐ8〇ΐ加 熱乾燥20分鐘後,測定不揮發成分,在先前合成的樹脂溶 液中,試圖將不揮發成分變成20重量%而添加PGMEA,得 到驗性可溶性感光性樹脂(B1 -1)溶液。重量平均分子量(Mw) 是 19000 〇 323842 195 201233734 [丙烯酸樹脂溶液1] 在反應谷器中放入%己嗣370份’容器内一邊注入氮 氣一邊在80 C中加熱,在同溫度將20. 〇份甲基丙烯酸、 10.0份甲基丙烯酸甲酯、55.0份之甲基丙烯酸11正丁酯、 15. 0份2-輕基乙基曱基丙稀酸酷、4. 〇份2, 2, _偶氮雙異 丁腈的混合物花1小時滴下進行聚合反應。結束滴下後, 再繼續在8 0 C反應3小時後’添加以5 〇份環己g同溶解1 〇 份偶氮雙異丁腈之溶液,再於8(TC中繼續反應1小時,而 ®得到丙烯酸樹脂溶液。 冷卻到室溫後,將樹脂溶液約2g作為試樣在i8〇°C中 加熱乾燥20分鐘後測定不揮發成分,在先前合成的樹脂溶 液中,添加環己酮,試圖將不揮發成分變成2〇重量%而得 到丙烯酸樹脂溶液1。重量平均分子量(Mw)是4〇〇〇〇。 〈式(1)所示顏料(A1)的製造方法〉 首先,在附有回流管之不銹鋼製反應容器中,The mixture of the following composition was stirred and mixed uniformly, and then filtered through a filter membrane of 丨 " to prepare a blue photosensitive coloring composition 1 (BR 〇 34. 〇: 15: 2 parts 3 · 3 parts 0 parts 〇 - 4 parts of blue coloring composition 1 (BP-1) Acrylic resin solution 2 Photopolymerizable monomer ("Ar〇nIX M400" manufactured by Toagosei Co., Ltd.) Photopolymerization initiator (rIrgacure_9〇7, manufactured by Ciba Japan) A sensitizer ("EAB-F1" ethylene glycol monomethyl ether acetate π manufactured by Hodogaya Chemical Co., Ltd.), a black matrix pattern was processed on a glass substrate, and a photosensitive coloring composition was spin-coated on the substrate. L6 (RR_l6) is applied to form a colored film by the film thickness of 〇 . . . 〇 328. The film is irradiated with ultraviolet rays of 3 〇〇 mJ/cm 2 using an ultrahigh pressure mercury lamp through a mask. The unexposed portion was removed by spray development with an alkaline developing solution of 0.2% by weight aqueous sodium carbonate solution, and then washed with ion-exchanged water, and the substrate was heated at 23 ° C for 20 minutes to form a red color. Filtered fragments. By the same method, green photosensitive is applied separately The composition l (GR-1) was set to x=0. 300, y=0. 600 film thickness 'coated blue photosensitive coloring composition KBR-丨) into χ=〇15〇, 323842 192 201233734 y=0 The film thickness of 060 forms a green filter segment and a blue filter segment to obtain a color filter. By using the photosensitive coloring composition 16 (RR_i6), high brightness and high contrast can be produced, and heating is performed. In the step C, the "parts" and "%" represent "mass parts" and "% by mass", respectively. The specific surface area, the primary particle diameter of the pigment, the weight average molecular weight (Mw) of the resin, the acid value of the resin, and the contrast ratio (CR) of the zero coating film are measured as follows. (Specific surface area of the pigment) Ratio of the pigment particles The surface area was determined by the BET method of adsorbing nitrogen gas. In the measurement, an automatic vapor adsorption amount measuring device ("BELS0RP18" manufactured by Beckham Co., Ltd.) was used. (Average primary particle diameter of the pigment) Average primary particle of the pigment The diameter is directly measured by electron micrographs. Specifically, the short axis diameter and the major axis diameter of the primary particles of each pigment are measured, and the average is taken as the particle diameter of the pigment particles. Next, regarding one or more pigment particles, The volume average particle diameter was determined as the average primary particle diameter by approximating the volume (weight) of each particle to the obtained particle size cube, and the electron microscope was a transmission type (TEM). Molecular weight (MW)) A TSKgel column (manufactured by TOHSO Co., Ltd.) equipped with a R] detector GPCCT0HS0 company's "HLC-8120GPC" was used, and THF was used as a solvent for the development of 323842 193 201233734, and the weight average converted to polystyrene was measured. Molecular weight (Mw). (acid value of resin) In the resin solution 0.5 to lg 'add acetone 8 〇mi and water 10 ml. Stir and dissolve to dissolve, use 〇· lm〇l / L Κ 0 Η aqueous solution as a titrant, use automatic The titration device ("C0M_555", manufactured by Hiranuma Sangyo Co., Ltd.) was titrated to measure the acid value of the resin solution. Thus, the equivalent acid value of the resin solid content was calculated from the acid value of the resin solution and the solid content concentration of the resin solution. (Contrast Ratio of Coating Film) The light emitted from the liquid crystal display backlight unit is polarized by a polarizing plate. A dry coating film of a coloring composition is applied onto a glass substrate to reach a polarizing plate. As long as the polarizing surfaces of the polarizing plate and the polarizing plate are parallel, the light passes through the polarizing plate, but when the polarizing surface is straight, the light is blocked by the polarizing plate. However, when the polarized light passes through the dried coating film of the colored composition by the polarizing plate, 'scattering due to the pigment particles, etc., when one of the polarizing surfaces is staggered, the amount of light penetrating the polarizing plate when the polarizing plates are parallel Will reduce 'a part of the light will penetrate the polarizer when the polarizer is straight. This transmitted light was used as the luminance on the polarizing plate, and the ratio of the luminance at the time when the polarizing plates were parallel and the luminance at the time of straight running (contrast ratio) was calculated. (brightness when the contrast ratio is parallel) / (brightness when going straight) and "using a color luminance meter ("BM-5A" manufactured by Topco Corporation) as a brightness meter" is a polarizing plate (made by Nitto Denko Corporation) NPF-G1220DUN". In order to block excess light during measurement, a black mask with a 1cm square hole is placed on the measurement portion. Before the embodiment, the adhesions used in the examples and reference examples will be described. 323842 194 201233734 Resin (B) solution, pigment (A1, micronized pigment, and method for producing pigment dispersion). (Manufacturing method of binder resin (B) solution> [Soluble-sensitive resin (B1-1) )] Put a ring of dog food into a separable four-mouthed view with a thermometer, a cooling tube, a nitrogen inlet tube, and a spoiler, and heat up to 8 〇. (: After replacing the flask with nitrogen, borrow 18 parts of p-isopropylphenyl oxime Ethylene Ethylene was changed from the dropping tube to the time of 2 hours (4) (East Asia Synthetic (share) Pang Si "face IX M110", 10 parts of methyl acyl benzoate , μ part of thioglycolic acid glycidol vinegar, 25 A mixture of 2,2'-azobisisobutyronitrile of thiol (iv) acid and 2 parts of azobisisobutyronitrile was added dropwise. After dropping, it was further reacted at ι ° ° C for 3 hours, and then dissolved in 50 parts of cyclohexene. 1 〇 solution of azobisisobutyronitrile was further reacted at 100 ° C for 1 hour. Then, replacing the inside of the vessel with air 'will be 0.5 part of 9.3 parts (glycidyl equivalent) of acrylic acid The dinonylamino group and 0.1 part of hydrogen are put into the above container, and φ is continuously reacted for 6 hours at 120, and when it becomes a solid acid value of 0.5, the reaction is terminated to obtain a solution of the acrylic acid resin. 19 parts of tetrahydro succinic anhydride (equivalent of the resulting hydroxyl group), triethylamine 0 5 parts, and reacted at 120 ° C for 3.5 hours to obtain a solution of acrylic resin. After cooling to room temperature, the resin About 2 g of the solution was heated and dried for 20 minutes on a crucible, and the nonvolatile matter was measured. In the previously synthesized resin solution, PGMEA was added in an attempt to change the nonvolatile content to 20% by weight to obtain an insoluble soluble photosensitive resin ( B1 -1) solution. The weight average molecular weight (Mw) is 19000 〇323842 195 201233 734 [Acrylic Resin Solution 1] In a reaction vessel, 370 parts of % hexane was placed in a container, and while nitrogen gas was injected, it was heated in 80 C, and at the same temperature, 20. methacrylic acid, 10.0 parts of methacrylic acid was added. Ester, 55.0 parts of 11-butyl methacrylate, 15.0 parts of 2-light-ethyl decyl acrylate, 4. 〇 2, 2, _ azobisisobutyronitrile mixture for 1 hour The polymerization was carried out by dropping. After the completion of the dropwise addition, the reaction was further continued at 80 C for 3 hours, and then a solution of 1 part of azobisisobutyronitrile was dissolved in 5 parts of cyclohexan, and the reaction was continued at 8 (TC). 1 hour, while ® gets an acrylic resin solution. After cooling to room temperature, about 2 g of the resin solution was dried as a sample in i8 ° C for 20 minutes, and then the nonvolatile matter was measured. In the previously synthesized resin solution, cyclohexanone was added in an attempt to change the nonvolatile content into 2 The acrylic resin solution 1 was obtained by 5% by weight. The weight average molecular weight (Mw) is 4 Å. <Method for Producing Pigment (A1) Formula (1)> First, in a stainless steel reaction vessel with a return pipe,
環境下,力口入以分子篩脫水的第三戍醇份,及第三戊、 氧基納140份’-邊檀拌—邊在1Q『C加熱,調製醇鹽溶 液。另-方面’在玻璃製燒瓶中,加人伽酸二異丙酿⑽ 份、4-漠化苯曱腈153.6份,—邊攪拌—邊在啊加 其溶解,鋪此料合物的溶液。將料混合_加舞溶 液’-邊激烈攪拌’-邊費時2小時以—定速度緩慢地滴 到在ion:加熱之上述醇鹽溶液内。結束滴下後,在阶 繼續加熱猜2小時’得到二喊料并料系化合物的 驗金屬鹽。進-步,在坡璃製附有内襯的反應容器中,加 323842 196 201233734 入甲醇600份、水600份、及醋酸304份,冷卻到一 10°C。 將此已冷卻之混合物,使用高速攪拌的分散器,一邊使直 徑8cm之剪切碟以4〇〇〇rpm回轉,一邊在其中,將冷卻到 75 C的預先得到之二酮基吡咯并吡咯系化合物的鹼金屬鹽Under the environment, the third sterol fraction dehydrated by the molecular sieve and the third pentoxide and the sodium oxyhydroxide 140 parts of the side-side sandalwood were heated at 1Q and heated to prepare an alkoxide solution. On the other hand, in a glass flask, a solution of bismuth diacetate (10) and 153.6 parts of 4-dibenzoquinone were added, and while stirring, the solution of the conjugate was spread. The mixture was mixed with the dance solution and stirred vigorously for 2 hours at a constant rate to the above alkoxide solution heated in ion: heating. After the completion of the dropping, the heating was continued for 2 hours in the order to obtain the metal salt of the compound. In the step-by-step process, add 323842 196 201233734 to 600 parts of methanol, 600 parts of water, and 304 parts of acetic acid, and cool to a temperature of 10 °C. The cooled mixture was rotated at 4 rpm while using a high-speed stirring disperser, while the previously obtained diketopyrrolopyrrole cooled to 75 C was cooled therein. Alkali metal salt of compound
溶液,少量地添加。此時,由甲醇、醋酸、及水所成的混 合物溫度持續保持在-5°C以下之溫度,一邊冷卻,並且一 邊調整75 C的二嗣基^比洛并t各系化合物驗金屬鹽之添 加速度,約花120分鐘少量地添加。添加驗金屬鹽後,會 析出紅色的結晶’生成紅色的懸濁液。接著,將得到之紅 色懸濁液於韻裝置洗淨後,㈣㈣紅色膏狀 物。將此膏狀物再次分散到已冷卻到〇它之35〇〇份曱醇 中,作成甲醇濃度約為90%的懸濁液。接著,於5。〇攪拌3 小時,將伴隨結晶轉移的粒子進行整粒及洗淨'。接著,以 超過滤機萄,將得到二_基料并Μ系化合物的水膏 狀物,於8(TC乾燥24小時,藉由粉碎得到15〇· 8份式⑴ 所示顏料(A1)之溴化二酮基吡咯并吡咯顏料五。 [溴化二酮基吡咯并吡咯顏料(A1-1)] 將100.0份之漠化二酮基鱗并各顏料卜圆份 之氯化納,及二乙二醇12G份,放人不銹鋼^加余捏練 機(井上製作所製)中,在啊混練2小.其次,將混煉 之混合物投入溫水中,一邊在約8〇。厂Λ也 * 運們紙加熱-邊攪拌1小時 作成膏狀物,過濾並水洗除去食鹽及二乙二醇後在別。C 乾燥-畫夜,从粉碎制96.5份之式⑴料之漠化二 酮基鱗并鱗賴UH),平均—化子徑是65龍、比 323842 197 201233734 表面積是30m2/g。 [溴化二酮基吡咯并吡咯顏料(A1-2)] 100. 0份之漠化二酮基n比洛并11比洛顏料1、1000份之 氯化鈉,及120份之二乙二醇,放入不銹鋼製1加侖捏煉 機(井上製作所製)中,在60°C混練4小時。其次,將混煉 之混合物投入溫水中,一邊在約80°C加熱一邊攪拌1小時 作成膏狀物,過濾並水洗除去食鹽及二乙二醇後,在80°C 乾燥一畫夜,藉由粉碎得到96. 6份之溴化二酮基吡咯并吡 ® p各顏料(A1-2),平均一次粒子徑是55nm、比表面積是 45m2/g 〇 [溴化二酮基。比咯并吡咯顏料(A1 - 3 )] 將100. 0份之溴化二酮基吡咯并吡咯顏料1、1000份 之氣化鈉,及120份之二乙二醇,放入不銹鋼製1加侖捏 煉機(井上製作所製)中,在6(TC混練8小時。其次,將混 煉之混合物投入溫水中,一邊在約80°C加熱一邊攪拌1小 φ 時作成膏狀物,過濾並水洗除去食鹽及二乙二醇後,在80 °C乾燥一晝夜,藉由粉碎得到96. 5份之溴化二酮基吡咯并 吡咯顏料(A卜3),平均一次粒子徑是38nm、比表面積是 80m2/g ° [溴化二酮基°比咯并吼咯顏料(A1-4)] 將100. 0份之溴化二酮基吡咯并吡咯顏料1、1000份 之氣化鈉,及120份之二乙二醇,放入不銹鋼製1加侖捏 煉機(井上製作所製)中,在60°C混練12小時。其次,將 混煉之混合物投入溫水中,一邊在約80°C加熱一邊攪拌1 323842 198 201233734 小時作成膏狀物’過濾並水洗除去食鹽及二乙二醇後,在 80 C乾燥一晝夜,藉由粉碎得到96. 2份之溴化二酮基吡咯 并°比°各顏料(A1-4),平均-次粒子徑是3〇nm、比表面積是 120m2/g。 [溴化二酮基吡咯并吼咯顏料(A卜5)] 將100. 0份之溴化二酮基吡咯并吡咯顏料丨、1〇〇〇份 之氣化鈉,及12〇份之二乙二醇,放入不錄鋼製i加侖捏 _煉機(井上製作所製)中,在6(TC混練24小時。其次,將 混煉之混合物投入溫水中,一邊在約8(TC加熱一 邊攪拌1 小時作成膏狀物,過濾、並水洗除去食鹽及二乙二醇後,在 8〇 C乾燥一晝伏,藉由粉碎得到96. 2份之溴化二酮基^比咯 开吼略顏料(A1-5),平均一次粒子徑是19nm、比表面積是 180m2/g。 [溴化二酮基吡咯并吡咯顏料(A1_6)] 將100. 0份之溴化二酮基”比略并处^各顏料1 ' 1000份 鲁之氯化鈉、及120份之二乙二醇,放入不錄鋼製j加余捏 煉機(井上製作所製)中,在⑽它混練犯小時。其次,將 混煉之混合物投入溫水中,一邊在約got加熱一邊攪袢^ 】、時作成膏狀物,過濾並水洗除去食鹽及二乙二醇後,在 8〇 C乾燥一畫伏,藉由粉碎得到96· 2份之溴化二酮基„比咯 并吡咯顏料(A1_6),平均一次粒子徑是9⑽、比表面積是 270m2/g。 將已製造的溴化二酮基吡咯并吡咯顏料(A卜丨至6)的 内容表示在表C-1中。 323842 199 201233734 [表 C-l ] 表C-l 漠化二酮基吼洛并β比π各 顏料 A1-1 A1-2 A1-3 A1-4 A1-5 A1-6 混練時間(小時) 2 4 8 12 24 48 平均一次粒子徑(nm) 65 55 38 30 19 9 比表面積(m2/g) 30 45 80 120 180 270 〈顏料分散物之製造方法〉 φ [顏料分散物(P-1)] 將下述組成之混合物攪拌混合均勻後,使用直徑1mm 的二氧化結小球,以Eiger研磨機(Eiger日本公司製「Mini mode 1 M-250 MK11」分散5小時後,以5 // m的過遽膜過遽, 得到紅色顏料分散物(P-1)。 溴化二酮基吡咯并吡咯顏料(A1-1) 8. 78份 酸性樹脂型顏料分散劑 1. 74份 (Byk Chemie 日本公司製 BYK-111) ® 二酮基比洛并°比咯系顏料衍生物 2. 05份 衍生物1The solution was added in small amounts. At this time, the temperature of the mixture made of methanol, acetic acid, and water is continuously maintained at a temperature of -5 ° C or lower, while cooling, and while adjusting the metal salt of 75 C of the dimercapto group The addition speed was added in a small amount for about 120 minutes. When a metal salt is added, a red crystal precipitates to form a red suspension. Next, the obtained red suspension was washed in the rhyme apparatus, and (4) (iv) a red paste. This paste was again dispersed in 35 liters of sterol which had been cooled to 〇, to prepare a suspension having a methanol concentration of about 90%. Then, at 5. The crucible was stirred for 3 hours, and the particles accompanying the crystal transfer were granulated and washed. Next, an ultra-filter is used to obtain a water-based paste of a bis-base compound and a lanthanide compound, which is dried at 8 (TC for 24 hours, and 15 y·8 parts of the pigment (A1) represented by the formula (1) is obtained by pulverization. Brominated diketopyrrolopyrrole pigment 5. [BDE diketopyrrolopyrrole pigment (A1-1)] 100.0 parts of the deserted diketone scale and each pigment b of the sodium chloride, and two 12G of ethylene glycol, put in stainless steel ^ plus kneading machine (made by Inoue Manufacturing Co., Ltd.), mixing 2 small in the ah. Secondly, the mixture is mixed into warm water, while about 8 〇. The paper was heated - stirred for 1 hour to form a paste, filtered and washed with water to remove salt and diethylene glycol. After drying - painting night, 96.5 parts of the formula (1) of the deserted diketone scale was prepared. Scale 赖 UH), the average - chemical diameter is 65 dragons, than 323842 197 201233734 surface area is 30m2 / g. [Bromide diketopyrrolopyrrole pigment (A1-2)] 100. 0 parts of desertified diketone n is more than 11 moles of pigment, 1, 1000 parts of sodium chloride, and 120 parts of diethylene The alcohol was placed in a stainless steel one gallon kneader (manufactured by Inoue Co., Ltd.) and kneaded at 60 ° C for 4 hours. Next, the kneaded mixture was poured into warm water, stirred while heating at about 80 ° C for 1 hour to form a paste, filtered and washed with water to remove salt and diethylene glycol, and dried at 80 ° C for one night. 96.6 parts of each of the brominated diketopyrrolopyrrole p pigments (A1-2) having an average primary particle diameter of 55 nm and a specific surface area of 45 m 2 /g 〇 [brominated diketone group. More than arropyrrole pigment (A1 - 3 )] 100 parts of brominated diketopyrrolopyrrole pigment 1, 1000 parts of sodium sulphate, and 120 parts of diethylene glycol, 1 gallon in stainless steel In a kneading machine (manufactured by Inoue Seisakusho Co., Ltd.), 6 (TC was kneaded for 8 hours. Secondly, the kneaded mixture was poured into warm water, and while stirring at a temperature of about 80 ° C, a small φ was stirred to prepare a paste, which was filtered and washed. After removing salt and diethylene glycol, drying at 80 ° C for one day and night, by pulverization, 95.6 parts of brominated diketopyrrolopyrrole pigment (A b 3), the average primary particle diameter is 38 nm, specific surface area Is 80 m2 / g ° [brominated diketone ° pyrrole pigment (A1-4)] 100. 0 parts of brominated diketopyrrolopyrrole pigment 1, 1000 parts of sodium, and 120 The diethylene glycol was placed in a stainless steel one-gallon kneader (manufactured by Inoue Co., Ltd.) and kneaded at 60 ° C for 12 hours. Next, the kneaded mixture was poured into warm water while heating at about 80 ° C. Stir 1 323842 198 201233734 hours to make a paste 'filtered and washed to remove salt and diethylene glycol, then dry at 80 C for a day and night, From the pulverization, 96.2 parts of the brominated diketopyrrole were used to give a pigment (A1-4), and the average-secondary particle diameter was 3 〇 nm, and the specific surface area was 120 m 2 /g. [Dicarbonyl ketone bromide] And 吼 颜料 pigment (A 卜 5)] 100. 0 parts of brominated diketopyrrolopyrrole pigment 丨, 1 part of sodium hydride, and 12 parts of diethylene glycol, not put In a steel i-gallon kneading machine (manufactured by Inoue Seisakusho Co., Ltd.), it was kneaded at 6 (TC for 24 hours. Secondly, the kneaded mixture was poured into warm water, and stirred at about 8 (TC was heated for 1 hour to make a paste). After filtration, washing with water and removing the salt and diethylene glycol, drying at 100 ° C, and pulverizing to obtain 96.2 parts of the brominated diketone group to open the pigment (A1-5). The average primary particle diameter is 19 nm, and the specific surface area is 180 m 2 /g. [Bromide diketopyrrolopyrrole pigment (A1_6)] 100. 0 parts of brominated diketone group" is slightly mixed with each pigment 1 ' 1000 The sodium chloride and 120 parts of ethylene glycol are placed in a non-recorded steel j-plus kneader (manufactured by Inoue Seisakusho Co., Ltd.), and (10) it is mixed for hours. Secondly, the mixture will be mixed. Into warm water, while stirring, oh, heating, stirring, smashing, sifting, washing and removing salt and diethylene glycol, drying at 8 ° C, and pulverizing to obtain 96. 2 parts The brominated diketone pi-pyrrolopyrrole pigment (A1_6) has an average primary particle diameter of 9 (10) and a specific surface area of 270 m 2 /g. The produced brominated diketopyrrolopyrrole pigment (A 丨 to 6) The contents are shown in Table C-1. 323842 199 201233734 [Table C1] Table Cl Desertified diketone valence and β ratio π each pigment A1-1 A1-2 A1-3 A1-4 A1-5 A1-6 Mixing time (hours) 2 4 8 12 24 48 Average primary particle diameter (nm) 65 55 38 30 19 9 Specific surface area (m2/g) 30 45 80 120 180 270 <Method for producing pigment dispersion> φ [Pigment dispersion] (P-1)] After the mixture of the following composition was stirred and mixed uniformly, a disulfide pellet having a diameter of 1 mm was used, and after dispersing for 5 hours in an Eiger mill ("Mini mode 1 M-250 MK11" manufactured by Eiger Japan Co., Ltd.) The red pigment dispersion (P-1) was obtained by passing through a ruthenium film of 5 // m. Brominated diketopyrrolopyrrole pigment (A1-1) 8. 78 parts of acidic resin type pigment dispersant 1.74 parts (BYK-111 manufactured by Byk Chemie Japan) ® Diketopylbibilol ratio Derivatives 2. 05 derivatives 1
5· 83 份 丙烯酸樹脂溶液1 323842 200 201233734 81. 60 份 [顏料分散物(P-2)] 除了將演化二酮基β比咯并η比P各顏料(A 1 _ 1 )變更成漠 化一酮基《»比略并各顏料(ai-2)之外,其餘與紅色顏料分 散物(Ρ-1)同樣操作,得到紅色顏料分散物(Ρ_2)。 [顏料分散物(Ρ-3)] 除了將溴化二酮基V»比咯并吡咯顏料(八卜丨)變更成溴 化二酮基吡咯并吡咯顏料(Α卜3)之外’其餘與紅色顏料分 散物(Ρ-1)同樣操作,得到紅色顏料分散物(ρ_3)。 [顏料分散物(Ρ-4)] 除了將溴化二酮基吡咯并吡咯顏料(Ai-i)變更成溴 化二酮基啦咯并吡咯顏料(Α1-4)之外,其餘與紅色顏料分 散物(Ρ-1)同樣操作,得到紅色顏料分散物(p_R4)。 [顏料分散物(P-5)] 除了將溴化二酮基吡咯并吼咯顏料(A卜丨)變更成溴 Φ 化一晒基°比°各并吡咯顏料(A1-5)之外,其餘與紅色顏料分 散物(P_1)同樣操作,得到紅色顏料分散物(P-5) » [顏料分散物(P-6)] 除了將漠化二酮基吡咯并吡咯顏料(A1_i)變更成溴 化一綱基吼《各并。比咯顏料(M_6)之外,其餘與紅色顏料分 散物(P-1)同樣操作,得到紅色顏料分散物(p_6)。5· 83 parts of acrylic resin solution 1 323842 200 201233734 81. 60 parts [pigment dispersion (P-2)] In addition to changing the evolution of the diketone β to argon and η than the P pigment (A 1 _ 1 ) changed to desertification The monoketone "» is similar to the respective pigments (ai-2), and the rest is operated in the same manner as the red pigment dispersion (Ρ-1) to obtain a red pigment dispersion (Ρ_2). [Pigment Dispersion (Ρ-3)] In addition to changing the brominated diketone group V» than the pyrrole pyrrole pigment (Astragalus) to the brominated diketopyrrolopyrrole pigment (Α3) The red pigment dispersion (Ρ-1) was also operated to give a red pigment dispersion (ρ_3). [Pigment Dispersion (Ρ-4)] In addition to changing the brominated diketopyrrolopyrrole pigment (Ai-i) to the brominated diketopyrrolopyrrole pigment (Α1-4), the remaining red pigment The dispersion (Ρ-1) was operated in the same manner to obtain a red pigment dispersion (p_R4). [Pigment Dispersion (P-5)] In addition to changing the brominated diketopyrrolopyrrole pigment (A 丨) to a bromine Φ 一 基 基 ° ° ° 各 each pyrrole pigment (A1-5), The rest is treated in the same manner as the red pigment dispersion (P_1) to obtain a red pigment dispersion (P-5) » [Pigment dispersion (P-6)] In addition to changing the deserted diketopyrrolopyrrole pigment (A1_i) to bromine The first line of the syllabus The red pigment dispersion (p_6) was obtained in the same manner as the red pigment dispersion (P-1) except for the specific pigment (M_6).
[顏料分散物(P-7)J 除了將填化二酮基吡咯并吡咯顏料(八卜丨)變更成氯 化二綱基°比洛并吡咯顏料(C. I.顏料紅254;汽巴日本公司 323842 201 201233734 製「Irgaphor Red B-CF」)之外,其餘與紅色顏料分散物 (P-1)同樣操作,得到紅色顏料分散物(P-7)。 [顏料分散物(P-8)] 將下述之組成混合物攪拌混合均勻後,使用直徑1mm 的二氧化錯小球,以Eiger研磨機(Eiger日本公司製「Mini model M-250 MKII」分散5小時後,以5#πι的過濾膜過濾’ 得到顏料分散物(Ρ-8)。[Pigment Dispersion (P-7) J In addition to changing the filled diketopyrrolopyrrole pigment (Eight Buddhism) to a chlorinated bifido-pyrolopyrrole pigment (CI Pigment Red 254; Ciba Japan 323842 The red pigment dispersion (P-7) was obtained in the same manner as in the red pigment dispersion (P-1) except for "Irgaphor Red B-CF" manufactured by 201, 2012,734. [Pigment Dispersion (P-8)] After mixing and mixing the following composition mixture, an Eiger mill ("Mini model M-250 MKII" manufactured by Eiger Japan Co., Ltd.) was used as an Eiger mill using a diameter of 1 mm. After an hour, it was filtered with a 5#πι filter membrane to obtain a pigment dispersion (Ρ-8).
溴化二酮基吡咯并吡咯顏料(Α卜3) 6. 82份 蒽醌系顏料(C. I·顏料紅177) 1. 08份 (汽巴日本公司製「Cromophthal Red Α2Β」 鎳偶氮錯合物系顏料(C. I.顏料黃150) 0. 88份 (Lanxess 公司製 rE4GN」) 酸性樹脂型顏料分散劑 1. 74份 (日本 Lubrizol 公司製「s〇lsperse 21000」) 顏料衍生物1 2. 05份 衍生物1Brominated diketopyrrolopyrrole pigment (Α3) 6. 82 parts of anthraquinone pigment (C.I·Pigment Red 177) 1. 08 parts (Cromophthal Red Α2Β made by Ciba Japan) Nickel azo Compound pigment (CI Pigment Yellow 150) 0. 88 parts (rE4GN manufactured by Lanxess Co., Ltd.) 1. Resin-based pigment dispersant 1.74 parts ("s〇lsperse 21000" manufactured by Lubrizol Co., Ltd.) Pigment Derivative 1 2. 05 Derivative 1
5. 83 份 81.60 份 丙烯酸樹脂溶液1 環己酮 323842 202 201233734 [顏料分散物(P-9至20)] 除了變更成表C-2所示之顏料、顏料衍生物、及樹脂 型顏料分散劑之種類,及調配量之外,其餘與顏料分散物 (P-8)同樣操作,得到顏料分散物(P-9至20)。 [表 C-2 ] 表C-2 顏料分散體 顏料1 顏料2 顏料3 顏料衍生物 份 份 份 份 P—8 A1-3 6.82 PR177 1.08 PY150 0.88 衍生物1 2.05 P—9 A1 — 1 6.82 PR177 1.08 PY150 0.88 衍生物1 2.05 P-10 A1—2 6.82 PR177 1.08 PY150 0.88 衍生物1 2.05 P-11 A1-4 6.82 PR177 1.08 PY150 0.88 衍生物1 2.05 P—12 A1-5 6.82 PR177 1.08 PY150 0.88 衍生物1 2.05 P—13 A1-6 6.82 PR177 1.08 PY150 0.88 衍生物1 2.05 P-14 PR254 6.50 PR177 1.23 PY150 1.05 衍生物1 2.05 P-15 A1-3 7.07 P071 0.93 PY150 0.7B 衍生物1 2.05 P-16 A1-3 7.34 PR242 0J9 PY150 0.45 衍生物1 2.05 P-17 A1-3 6.79 PR179 1.09 PY150 0.90 2.05 P—18 A1-3 6.73 PR122 0.85 PY150 1.20 2.05 P —19 A1-3 6.75 1.10 PY180 0.93 衍生物4 2.05 P-20 A1—3 7.17 1.61 - 衍生物1 2.055. 83 parts 81.60 parts of acrylic resin solution 1 cyclohexanone 323842 202 201233734 [Pigment dispersion (P-9 to 20)] except for the pigments, pigment derivatives, and resin type pigment dispersants shown in Table C-2 The type of the mixture and the amount of the mixture were the same as those of the pigment dispersion (P-8) to obtain a pigment dispersion (P-9 to 20). [Table C-2] Table C-2 Pigment Dispersion Pigment 1 Pigment 2 Pigment 3 Pigment Derivative Parts Partition P-8 A1-3 6.82 PR177 1.08 PY150 0.88 Derivative 1 2.05 P—9 A1 — 1 6.82 PR177 1.08 PY150 0.88 Derivative 1 2.05 P-10 A1—2 6.82 PR177 1.08 PY150 0.88 Derivative 1 2.05 P-11 A1-4 6.82 PR177 1.08 PY150 0.88 Derivative 1 2.05 P—12 A1-5 6.82 PR177 1.08 PY150 0.88 Derivative 1 2.05 P-13 A1-6 6.82 PR177 1.08 PY150 0.88 Derivative 1 2.05 P-14 PR254 6.50 PR177 1.23 PY150 1.05 Derivative 1 2.05 P-15 A1-3 7.07 P071 0.93 PY150 0.7B Derivative 1 2.05 P-16 A1- 3 7.34 PR242 0J9 PY150 0.45 Derivative 1 2.05 P-17 A1-3 6.79 PR179 1.09 PY150 0.90 2.05 P-18 A1-3 6.73 PR122 0.85 PY150 1.20 2.05 P —19 A1-3 6.75 1.10 PY180 0.93 Derivative 4 2.05 P- 20 A1—3 7.17 1.61 - Derivatives 1 2.05
表C-2中之簡稱如下述。 〈顏料〉 φ PR254 :二酮基吡咯并吡咯系顏料C. I.顏料紅254;汽巴日 本公司製「Irgaphor Red B-CF」 P071 :二酮基吡咯并吡咯系顏料C. I.顏料橙71 ;汽巴日本 公司製「Irgazin DPP 0range398」 PR242 :偶氮系顏料C. I.顏料紅242 ; Clariant公司製 「N0V0PERM」 PR179:茈系顏料C. I.顏料紅179;大日本油墨化學工業(股) 公司製「Fastogen $uper MaroonPSK」 PR122 :喹吖酮系顏料C. I.顏料紅122 ; Clariant公司製 203 323842 201233734 「HOSTAPERM」 PY180 :苯并咪唑酮系顏料C. I.顏料黃180 ; Clariant公 司製「PV First Yellow HG」 PY138 :喹啉系顏料C. I.顏料黃180;BASF公司製「Paliotol Yellow K0960-HD」 〈顏料衍生物〉 衍生物2The abbreviations in Table C-2 are as follows. <Pigment> φ PR254 : Diketopyrrolopyrrole pigment CI Pigment Red 254; "Irgaphor Red B-CF" manufactured by Ciba Japan Co., Ltd. P071: Diketopyrrolopyrrole pigment CI Pigment Orange 71; Ciba Japan "Irgazin DPP 0range398" PR242: azo pigment CI Pigment Red 242; "N0V0PERM" manufactured by Clariant Co., Ltd. PR179: lanthanide pigment CI Pigment Red 179; Dainippon Ink Chemical Industry Co., Ltd. "Fastogen $uper MaroonPSK" PR122 : quinacridone pigment CI Pigment Red 122; 203 323842 201233734 "HOSTAPERM" PY180: benzimidazolone pigment CI Pigment Yellow 180; "PV First Yellow HG" manufactured by Clariant Co., Ltd. PY138: Quinoline pigment CI pigment Yellow 180; "Paliotol Yellow K0960-HD" manufactured by BASF Corporation <Pigment Derivatives> Derivatives 2
201233734 衍生物4201233734 Derivative 4
[實施例1] •(紅色著色組成物(DR-1)) 將下述組成混合物攪拌混合均勻後,以5 μ m的過濃 膜過濾’得到紅色著色組成物(DR-1)。 紅色顏料分散物(P-1) 40. 5份 鹼可溶性感光性樹脂(B1-1) 8. 6份 環己酮 50. 9份 [實施例2至6及參考例1] φ (紅色著色組成物(DR-2至7)) 除了將紅色顏料分散物(P-ι)變更成表C-3所示紅色 顏料分散物之外,其餘與紅色著色組成物(Dr_1)同樣操 作’得到紅色著色組成物(DR-2至7))。 [參考例2] (紅色著色組成物(DR-8)) 除了將鹼性可溶性感光性樹脂〈B丨_丨)變更成丙烯酸 樹脂溶液1之外,其餘與紅色著色組成物⑶^丨)同樣操 作,得到紅色著色組成物(DR-8)。 323842 205 201233734 [紅色著色組成物的評估] 關於得到之紅色著色組成物的色特性、對比度比(CR)、 及塗膜表面的結晶析出,以下述之方法評估。結果在表C-3 中表示。 (色特性、對比度比(CR)評估) 將付到之紅色著色組成物在10Omm X 10Omm、0. 7mm 厚度的玻璃基板上,在C光源以使膜厚成為x= 0. 644, y=0_340(正負〇.〇01以内)的方式塗佈,並在7〇。<:熱風烘 箱中乾燥20分鐘後,進一步於23〇它加熱6〇分鐘後得到 紅色塗膜。之後,測定得到之塗佈基板的亮度(γ),及對比 度比(CR)。 並且,色度及亮度(γ)是以顯微分光光度計(〇lympus 光學公司製「OSP-SP200」)測定。 (塗膜表面的結晶析出評估) 將在色特性、對比度比(CR)評估得到之基板,再重複[Example 1] (Red coloring composition (DR-1)) The following composition mixture was stirred and mixed uniformly, and then filtered through an over-concentrated membrane of 5 μm to obtain a red colored composition (DR-1). Red pigment dispersion (P-1) 40. 5 parts alkali-soluble photosensitive resin (B1-1) 8. 6 parts cyclohexanone 50. 9 parts [Examples 2 to 6 and Reference Example 1] φ (red coloring composition) (DR-2 to 7)) In addition to changing the red pigment dispersion (P-I) to the red pigment dispersion shown in Table C-3, the same operation as the red coloring composition (Dr_1) was performed to obtain red coloration. Composition (DR-2 to 7)). [Reference Example 2] (Red coloring composition (DR-8)) The same as the red coloring composition (3), except that the alkali-soluble photosensitive resin (B丨_丨) was changed to the acrylic resin solution 1. Operation gave a red colored composition (DR-8). 323842 205 201233734 [Evaluation of Red Colored Composition] The color characteristics, the contrast ratio (CR) of the obtained red colored composition, and the crystallization of the surface of the coating film were evaluated by the following methods. The results are shown in Table C-3. (Color characteristic, contrast ratio (CR) evaluation) The red colored composition was applied to a glass substrate having a thickness of 10Omm X 10Omm and 0.7 mm, and the C light source was used to make the film thickness x = 0. y = 0 340 It is applied in the way of the 正. <: After drying in a hot air oven for 20 minutes, it was further heated at 23 Torr for 6 minutes to obtain a red coating film. Thereafter, the brightness (γ) of the coated substrate and the contrast ratio (CR) were measured. Further, the chromaticity and the luminance (γ) were measured by a microspectrophotometer ("OSP-SP200" manufactured by 〇lympus Optics Co., Ltd.). (Evaluation of crystal precipitation on the surface of the coating film) The substrate obtained by evaluation of color characteristics and contrast ratio (CR) was repeated.
2次於240°C加熱處ί里60分鐘。加熱處理後的塗佈基板之 塗膜表面以光學顯微鏡觀察’依據下述基準列定有無於曰 析出。評估結果中,◎與〇是無結晶析出為良好 有結晶析出但使社沒有問題之程度,χ是因為結晶析出為 相當於無法使用的狀態。 ◎ : 23(TC加熱處理60分鐘後,進—步在2心加孰處理 60分鐘後,及再進行240°C加熱處理6〇分鐘亦心 〇賓c加熱處理6G分鐘後,及再進行 分知理亦無結晶析出(第2次的24『c加熱處理6〇分鐘有 323842 206 201233734 結晶析出) △:雖然在230°C加熱處理60分鐘後無結晶析出,但進一 步240°C加熱處理60分鐘有結晶析出 X : 230°C加熱處理60分鐘後有結晶析出 [表 C-3] 表C-32 times at 240 ° C heating ί 里 60 minutes. The surface of the coating film of the coated substrate after the heat treatment was observed by an optical microscope, and the presence or absence of precipitation was determined according to the following criteria. In the evaluation results, ◎ and 〇 are not crystallized, and the crystallization is good, but there is no problem in the crystallization, and the crystallization is because the crystallization is equivalent to an unusable state. ◎ : 23 (TC heat treatment for 60 minutes, after the step of 2 weeks of twisting treatment for 60 minutes, and then heat treatment at 240 ° C for 6 minutes, also after the heat treatment for 6G minutes, and then further It is also known that no crystals are precipitated (the second 24 "c heat treatment for 6 minutes has 323842 206 201233734 crystal precipitation" △: no crystal precipitation after heat treatment at 230 ° C for 60 minutes, but further 240 ° C heat treatment 60 Crystallization precipitated in minutes: Crystallization occurred after heat treatment at 230 ° C for 60 minutes [Table C-3] Table C-3
紅色 著色组成物 紅色 顏料分散體 亮度(Y) CR 結晶析出 實施例 1 DR-1 P-1 23.33 9000 ◎ 實施例 2 DR-2 P-2 23.27 12000 ◎ 實施例 3 DR-3 P-3 23.26 13000 ◎ 實施例 4 DR-4 P-4 23.23 12000 ◎ 實施例 5 DR-5 P-5 23.22 11000 ◎ 實施例 6 DR-6 P-6 23.23 9000 ◎ 參考例 1 DR-7 P-7 20.83 6000 X 參考例 2 DR-8 P-1 21.06 6000 XRed coloring composition Red pigment dispersion Brightness (Y) CR Crystal precipitation Example 1 DR-1 P-1 23.33 9000 ◎ Example 2 DR-2 P-2 23.27 12000 ◎ Example 3 DR-3 P-3 23.26 13000 ◎ Example 4 DR-4 P-4 23.23 12000 ◎ Example 5 DR-5 P-5 23.22 11000 ◎ Example 6 DR-6 P-6 23.23 9000 ◎ Reference Example 1 DR-7 P-7 20.83 6000 X Reference Example 2 DR-8 P-1 21.06 6000 X
含有式(1)所示之顏料(A1)與鹼可溶性感光性樹脂 (B1)之彩色過濾片用著色組成物,任一者皆為高亮度並且 高對比度比,即使在加熱步驟也不會產生二酿1基11比洛并0比 p各系顏料之結晶物析出而能得到良好之結果。 [實施例7至41、參考例3至5] (感光性著色組成物) 將在表C-4至C-9中所示組成、以調配量混合並攪拌 各材料,以1 # m的過濾膜過濾,得到感光性著色組成物。 323842 207 201233734 [表 C-4] 裹C 一 4 實施例7 實施例8 實施例9 實施例10 實施例11 實施洌*12 賞施洌13 RR-1 RR-2 RR—3 RR-4 RR-5 RR-6 RR-7 顏料分散逋 P-8 P-8 P-8 P-8 P-8 P-8 P-8 41.92 37.53 23.64 42.91 17.73 31.55 31.93 丙烯酸樹脂溶液1 14.85 15.25 35.09 18.60 28.27 28.70 27.33 鹼可溶性感光性樹脂(B1 — 1) 10.00 10.00 10.00 10.00 10.00 10.00 10.00 光聚合起始劑(D) D1 D1 01 D1 D1 D1 D1 0.52 0.53 0.45 0.50 0.95 0.85 0.67 D2 D2 D2 D4 D2 D2 0.13 0.45 0.25 0.20 0.30 0.10 D3 03 0.28 0.25 增感荆(E) E1 E2 0.25 0.05 光聚合性化合物 1.74 1.32 2.81 1.25 5.07 2.96 1.34 多官嫵硫醇(Π F1 0.60 紫外線吸收射(G〉 G1 0.28 有機溶射 30.97 35.24 27.28 25.99 37.18 25.⑽ 28.35 合計 100.00 100.00 100.00 100.00 100.00 100.00 100.00A coloring composition for a color filter containing the pigment (A1) represented by the formula (1) and the alkali-soluble photosensitive resin (B1), which is high in brightness and high in contrast ratio, does not occur even in a heating step Good results were obtained by precipitating the crystals of the pigments of the pigments of the two bases, 11 bases, and the like. [Examples 7 to 41, Reference Examples 3 to 5] (Photosensitive Coloring Composition) The compositions shown in Tables C-4 to C-9 were mixed and stirred in a blending amount, and filtered at 1 #m. The membrane was filtered to obtain a photosensitive coloring composition. 323842 207 201233734 [Table C-4] Wrap C-4 Embodiment 7 Example 8 Example 9 Example 10 Example 11 Implementation 洌*12 Reward 13 RR-1 RR-2 RR-3 RR-4 RR- 5 RR-6 RR-7 pigment dispersion 逋P-8 P-8 P-8 P-8 P-8 P-8 P-8 41.92 37.53 23.64 42.91 17.73 31.55 31.93 Acrylic resin solution 1 14.85 15.25 35.09 18.60 28.27 28.70 27.33 Alkali Soluble photosensitive resin (B1 - 1) 10.00 10.00 10.00 10.00 10.00 10.00 10.00 Photopolymerization initiator (D) D1 D1 01 D1 D1 D1 D1 0.52 0.53 0.45 0.50 0.95 0.85 0.67 D2 D2 D2 D4 D2 D2 0.13 0.45 0.25 0.20 0.30 0.10 D3 03 0.28 0.25 Sensitization (E) E1 E2 0.25 0.05 Photopolymerizable compound 1.74 1.32 2.81 1.25 5.07 2.96 1.34 Multi-manganese mercaptan (Π F1 0.60 UV absorption (G> G1 0.28 Organic spray 30.97 35.24 27.28 25.99 37.18 25 .(10) 28.35 Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00
[表 C-5 ] 表C-5 實施例14 實施例15 實施例16 實施例17 賁施例18 實施例19 賁施例20 RR-8 RR-9 RR-10 RR-11 RR-12 RR-13 RR-14 顏料分散逋 P-8 P-8 P-8 P»8 P-8 P-8 P-8 40.60 34.96 38.57 42.10 42.78 27.69 34.82 丙烯酸樹厢溶液1 tO.77 18.00 id.te 2.54 3.99 32.40 31.56 鹼可溶性感光性樹脂(B1—1) 10.00 10.00 10.00 10.00 10.00 10.00 10.00 光聚合起始劑(D) D3 D3 D3 D3 D3 Del D3 1.40 1.45 0.73 0.70 0.48 0.3» 0.21 D2 D5 D2 OZ 02 0.43 0.11 0.43 0.2» 0.09 D4 0.40 增感谢(E) E2 0.2t 光聚合性化合物 2.28 1.54 1.45 2.34 1.18 3.34 1.02 多官铤琉醇(F) F2 0.30 聚合禁止劑(H) HI H2 0.01 0.01 有機溶劑 34.73 34.05 29.64 42.21 40.74 25.70 22.00 合計 100.00 100.00 100.00 100.00 100.00 100.00 100.00 208 323842 201233734 [表 C-6 ] jfec-β 實施例21 賁施例22 實施例23 實施例24 賁施例25 賁施例26 實施例27 RR-15 RR-16 RR-17 RR-18 RR-19 RR-.20 RR-21 顏料分散想 P-8 P—8 P-8 P-8 P-8 P—8 P-8 24.46 20.13 37.11 21.13 21.44 26.98 42.79 丙烯酸樹脂溶液1 26.51 27.76 0.00 24.41 4.93 4.41 0.00 鹼可溶性感光性榭脂(B*( — 1) 10.00 to.oo 10.00 10.00 10.00 10.00 10.00 光聚合起始劑(D) D4 D4 D4 D4 D4 D4 D4 0.60 1.08 2.74 3.31 093 3.44 1.41 DS D5 D5 D5 D5 0.12 0.05 0.24 0.61 1.15 D3 0.17 增感劑(E> E1 E2 E1 1.03 0.15 0,09 先聚合性化合物 2.03 4.30 2.93 6.62 3.12 4.53 2.40 紫外線吸收劑(G) G2 0.10 聍藏安定射(J> J1 J2: 0.03 0.0:) 有機溶劑 36.25 36.68 46.19 34.14 58.61 50.55 42.25 合計 100.00 100.00 100.00 100.00 100.00 100.00 100.00[Table C-5] Table C-5 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 RR-8 RR-9 RR-10 RR-11 RR-12 RR- 13 RR-14 pigment dispersion 逋P-8 P-8 P-8 P»8 P-8 P-8 P-8 40.60 34.96 38.57 42.10 42.78 27.69 34.82 Acrylic tree solution 1 tO.77 18.00 id.te 2.54 3.99 32.40 31.56 Alkali-soluble photosensitive resin (B1—1) 10.00 10.00 10.00 10.00 10.00 10.00 10.00 Photopolymerization initiator (D) D3 D3 D3 D3 D3 Del D3 1.40 1.45 0.73 0.70 0.48 0.3» 0.21 D2 D5 D2 OZ 02 0.43 0.11 0.43 0.2 » 0.09 D4 0.40 增 Thanks (E) E2 0.2t photopolymerizable compound 2.28 1.54 1.45 2.34 1.18 3.34 1.02 poly-sterol (F) F2 0.30 polymerization inhibitor (H) HI H2 0.01 0.01 organic solvent 34.73 34.05 29.64 42.21 40.74 25.70 22.00 Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 208 323842 201233734 [Table C-6] jfec-β Example 21 Example 22 Example 23 Example 24 Example 25 Example 26 Example 27 RR-15 RR -16 RR-17 RR-18 RR-19 RR-.20 RR-21 Dispersion wanted P-8 P-8 P-8 P-8 P-8 P-8 P-8 24.46 20.13 37.11 21.13 21.44 26.98 42.79 Acrylic resin solution 1 26.51 27.76 0.00 24.41 4.93 4.41 0.00 Alkali-soluble photosensitive resin (B* ( — 1) 10.00 to.oo 10.00 10.00 10.00 10.00 10.00 Photopolymerization initiator (D) D4 D4 D4 D4 D4 D4 D4 0.60 1.08 2.74 3.31 093 3.44 1.41 DS D5 D5 D5 D5 0.12 0.05 0.24 0.61 1.15 D3 0.17 Sensitizer (E> E1 E2 E1 1.03 0.15 0,09 First polymerizable compound 2.03 4.30 2.93 6.62 3.12 4.53 2.40 UV absorber (G) G2 0.10 安藏安定射 (J> J1 J2: 0.03 0.0:) Organic solvent 36.25 36.68 46.19 34.14 58.61 50.55 42.25 Total 100.00 100.00 100.00 100.00 100.00 100.00 100.00
[表 C-7] 實施例2β 實施例29 實施例30 實施例31 實施例32 實施例33 實施例34 RR-22 RR-23 RR-24 RR-25 RR—26 RR-27 RR-28 顏料分散《 P-8 p-a P-8 P-9 P—10 P-11 P—12 43.14 35.73 35.26 41.92 41.92 41.92! 41.92 丙烯酸樹脂溶液1 3.55 1.02 0.00 14.85 14.85 14.85 14.85 鹼可溶性感光性樹脂【B1 — 1) 10.00 10.00 10.00 10.00 10.00 10.00 10.00 光聚合起始劑(D) 01 01 Dt 01 D1 D1 D1 1.62 1.44 0.94 0.52 0.52 0.52 0.52 D3 D3 0.40 0.24 增感荆(E) E2 0.40 光聚合诖化合物 2.68 1.60 1.28 1.74 1.74 1.74 1.74 多官铤硫醇(F) F2 F3 0.74 0.50 聚合禁止刑(H) 有機溶剖 38.21 49.47 51.78 30.97 30.97 30.97 30.97 合計 100.00 100.00 100.00 100.00 100.00 100.00 too.oo 209 323842 201233734 [表 C_8] 表C-8 實施例35 賁施例36 實施例37 貧施例38 賁施例39 實施例40 實施例41 RR-29 RR-30 RR-31 RR-32 RR-33 RR--34 RR-35 顏料分散《 P-13 P-15 P-16 P-17 P —18 P-19 P-20 41.92 41.92 41.92 41.92 41.92 41.52 41.92 丙烯酸樹脂溶液1 14.85 14.85 14.85 14.85 14.85 14.85 14.85 鹼可溶性感光性樹脂(B1 — 10.00 10.00 10.00 10.00 10.00 10.00 10.00 光聚合起始剤(D) D1 D1 D1 DY 01 D1 01 0.52 0.52 0.52 0.52 0.52 0.52 0.52 增感劑(E) 光聚合性化合物 1.74 1.74 1.74 1.74 1.74 1.74 1.74 多官逛硫醇(F) 聚合禁止劑〇〇 有機溶劑 30.97 30.97 30.97 30.97 30.97 30.<»7 30.97 合¥ 100.00 100.00 100.00 100.00 100.00 100.00 100.00[Table C-7] Example 2 β Example 29 Example 30 Example 31 Example 32 Example 33 Example 34 RR-22 RR-23 RR-24 RR-25 RR—26 RR-27 RR-28 Pigment dispersion P-8 pa P-8 P-9 P-10 P-11 P- 12 43.14 35.73 35.26 41.92 41.92 41.92! 41.92 Acrylic resin solution 1 3.55 1.02 0.00 14.85 14.85 14.85 14.85 Alkali-soluble photosensitive resin [B1 — 1) 10.00 10.00 10.00 10.00 10.00 10.00 10.00 Photopolymerization initiator (D) 01 01 Dt 01 D1 D1 D1 1.62 1.44 0.94 0.52 0.52 0.52 0.52 D3 D3 0.40 0.24 Sensitization (E) E2 0.40 Photopolymerization compound 2.68 1.60 1.28 1.74 1.74 1.74 1.74 Multi-manganese mercaptan (F) F2 F3 0.74 0.50 Polymerization prohibition (H) Organic dissolution profile 38.21 49.47 51.78 30.97 30.97 30.97 30.97 Total 100.00 100.00 100.00 100.00 100.00 100.00 too.oo 209 323842 201233734 [Table C_8] Table C-8 Example 35 Example 36 Example 37 Lean Example 38 Example 39 Example 40 Example 41 RR-29 RR-30 RR-31 RR-32 RR-33 RR--34 RR-35 Pigment Dispersion P -13 P-15 P-16 P-17 P —18 P-19 P-20 41.92 41.92 41.92 41.92 41.92 41.52 41.92 Acrylic resin solution 1 14.85 14.85 14.85 14.85 14.85 14.85 14.85 Alkali-soluble photosensitive resin (B1 — 10.00 10.00 10.00 10.00 10.00 10.00 10.00 Photopolymerization start 剤 (D) D1 D1 D1 DY 01 D1 01 0.52 0.52 0.52 0.52 0.52 0.52 0.52 Sensitizer (E) Photopolymerizable compound 1.74 1.74 1.74 1.74 1.74 1.74 1.74 Multi-functional thiol (F) Polymeric inhibitor 〇〇 Organic solvent 30.97 30.97 30.97 30.97 30.97 30.<»7 30.97 and ¥100.00 100.00 100.00 100.00 100.00 100.00 100.00
[表 C_9] 表C-9[Table C_9] Table C-9
參考例3 參考例4 參考例5 RR-36 RR-37 RR-38 顏料分散體 P-14 P-14 P-3 41.92 41.92 41.92 丙烯酸樹脂溶劑1 14.85 24.85 24.85 鹼可溶性感光性樹脂ΪΒ1 —1) 10.00 D1 D1 D1 0.52 0.52 0.52 光聚合起始劑(D) 增感劑(E) 光聚合性化合物 1.74 1.74 1.74 多官能硫醇(F) 聚合禁止劑(H) 有機溶劑 30.97 30.97 30.97 合計 100.00 100.00 ί 00.00 關於表C-4至C-9中之簡稱在以下表示。 〈光聚合起始劑(D)〉 210 323842 201233734 光聚合起始劑D1 : 2-曱基-l-[4-(甲基硫)苯基]-2-嗎啉呙 烧-1-_,(汽巴日本公司製「Irgacure 9〇7」) 光聚合起始劑D2 : 2-(二曱基胺基)-2-[(4-甲基笨基)曱 基]-l-[4-(4-嗎啉基)苯基]-ι_丁酮;(汽巴日本公司製 「Irgacure 379」) 光聚合起始劑D3 :乙烧-1-酮、i-[9-乙基-6-(2-曱基苯曱 醯基)-9H-咔唑-3-基]、1-(〇-乙醯肟);(汽巴曰本公司製 「Irgacure 0ΧΕ 02」) 光聚合起始劑D4: 2, 2,-雙(〇-氯苯基)-4, 5,4,,5,-四笨基 -1,2 -聯β米唾;(黑金化成公司製「聯味吐」) 光聚合起始劑D5 : 2, 4, 6-三曱基苯甲基-二苯基膦氧化合 物;(BASF 公司製「Lucirin ΤΡ0」) 〈增感劑〉 增感劑E1 : 2, 4-二乙基噻吨酮;(日本化藥公司製 「Kayacure DETX-S」) φ 增感劑£2:4,4’-雙(二乙基胺基)二苯曱酮;(11〇(1〇8&丫& Chemical工業公司製「EAB-F」) 〈光聚合性化合物〉 光聚合性化合物:二季戊四醇六丙烯酸酯;(東亞合成公司 製「A_X M-402」) 〈多官能硫醇〉 多官能硫醇F1 :三羥曱基乙烷參(3-酼基丁酸酯);(昭和 電工公司製「TEMB」) 多官能硫醇F2 :三羥甲基丙烷參(3-巯基丁酸酯);(昭和 323842 211 201233734 電工公司製「ΤΡΜΒ」) 多官能硫醇F3 :季戊四醇肆(3-巯基丙酸酯);(堺化學工 業公司製「PEMP」) 〈紫外線吸收劑〉 紫外線吸收劑Gl: 2-[4-[2-羥基-3-(十二烷基及十三烷基) 氧基丙基)氧基]-2-經基苯基]~4, 6-雙(2, 4-二曱基苯 基)-1,3, 5-三哄;(汽巴曰本公司製「TINUVIN 4〇〇」) φ 紫外線吸收劑G2:2-(2H-苯并***_2_基)_4,6_雙(1_甲基 -卜笨基乙基)酚;(汽巴日本公司製「TINUVIN 9〇〇」) 〈聚合禁止劑〉 聚合禁止劑HI . N-亞硝基苯基羥基胺鋁鹽;(和光純藥工 業公司製「Q-1301」) ' 聚合禁止劑H2 :甲基氫醌;(精工化學公司製「顧」) 〈貯藏安定劑〉 貯藏安定劑J1 : 2, 6一雙(1,1-二甲基乙基)-4-甲紛;(本州 # 化學工業公司製「BHT」) 貯藏安定劑J2 :三苯基膦;(北興化學工業公司製「τρρ 〈溶劑〉 j 有機溶劑:環己酮 [感光性著色組成物的評估] 關於得到之感光性著色組成物,將色特性、對比度比 (⑻、塗膜表面的結晶析出、感度、直線性、圖案形狀、 解像度、财顯像性、耐藥品性、經時安定性藉由下述之方 法評估。將結果在表(M0令表示。各評估結果中之判定, 323842 212 201233734 ◎是非常良好的程度,〇為良好的程度,△是使用上沒有 障礙的程度’ X是使用上為不好的程度。 (色特性、對比度比(CR)評估) 將付到之感光性著色組成物在1〇〇丽X 1〇〇丽、〇. 7匪 厚度的玻璃基板上,於後處理後,在C光源中以使膜厚成 為x=0.640,y=〇.328之方式塗佈,並在70°C的熱風烘箱 中乾燥20分鐘後,使用超高壓水銀燈,進行紫外線曝光累 計光量150mJ後,於23(TC加熱1小時後放置冷卻,得到 紅色塗膜。之後,測定得到塗佈基板的亮度(Y)及對比度比 (CR)。 並且色度及亮度(Y)是以顯微分光光度計(〇1 ympus 光學公司製「OSP-SP200」)測定。 (塗膜表面的結晶析出評估) 將在色特性、對比度比(CR)評估得到之基板,在260 C加熱1小時後放置冷卻。加熱處理後的塗佈基板之塗膜 • 表面以光學顯微鏡觀察,依據下述基準判定有無結晶析 出。評估結果中’ ◎沒有結晶析出為非常良好,◦是少量 結晶析出但為良好的程度,△是雖有結晶析出,但使用上 沒有問題的程度’X是因為有結晶析出為無法使用的程度。 ◎.結晶數為〇個 〇·結晶數為1個以上、未達10個 △•結晶數為10個以上、未達1〇〇個 X :結晶數為100個以上 (感度、直綠性、圖案形狀、解像度、耐顯像性、耐藥品性 323842 213 201233734 評估) 將得到之感光性著色組成物在100mm x 1 〇〇mm、〇. 7mm 厚度的破璃基板上塗佈後—在無塵烘箱中以7〇Pc加溫20 分鐘除去溶劑,得到約2//m的塗膜。接著,將此基板冷卻 到室溫後’使用超高壓水銀燈’隔著100寬(間距200 ym) 及25/ζιη寬(間距5〇μιη)條狀圖案的遮罩曝露在紫外線下。 之後’此基板使用23°C的碳酸鈉水溶液喷霧顯像之後,以 離子交換水洗淨、風乾,在無塵烘箱中以23〇t:加熱330 为I里。噴霧顯像係在各感光性著色組成物之塗膜中,以最 短時間進行沒有殘留顯像而可能形成圖案,將此當作適當 的顯像時間。 塗犋的膜厚是使用Dektak 3030(日本真空技術公司製) 來進行。 (感度評估)Reference Example 3 Reference Example 4 Reference Example 5 RR-36 RR-37 RR-38 Pigment dispersion P-14 P-14 P-3 41.92 41.92 41.92 Acrylic resin solvent 1. 14.85 24.85 24.85 Alkali-soluble photosensitive resin ΪΒ1 —1) 10.00 D1 D1 D1 0.52 0.52 0.52 Photopolymerization initiator (D) Sensitizer (E) Photopolymerizable compound 1.74 1.74 1.74 Polyfunctional thiol (F) Polymerization inhibitor (H) Organic solvent 30.97 30.97 30.97 Total 100.00 100.00 ί 00.00 The abbreviations in Tables C-4 to C-9 are indicated below. <Photopolymerization initiator (D)> 210 323842 201233734 Photopolymerization initiator D1: 2-mercapto-l-[4-(methylthio)phenyl]-2-morpholinium -1--, (Irgacure 9〇7, manufactured by Ciba Japan) Photopolymerization initiator D2: 2-(didecylamino)-2-[(4-methylphenyl)indolyl]-l-[4- (4-morpholinyl)phenyl]-ι-butanone; (Irgacure 379, manufactured by Ciba Japan Co., Ltd.) Photopolymerization initiator D3: Ethyl-1-ketone, i-[9-ethyl-6 -(2-mercaptobenzoyl)-9H-carbazol-3-yl], 1-(anthracene-ethene); ("Irgacure 0ΧΕ 02", manufactured by Ciba") Photopolymerization initiator D4: 2, 2,-bis(〇-chlorophenyl)-4, 5,4,,5,-tetraphenyl-1,2-linked beta-saliva; ("Golden Chemicals" company "Lianwei spit") Photopolymerization initiator D5 : 2, 4, 6-trimercaptobenzyl-diphenylphosphine oxide; ("Lucirin ΤΡ0" manufactured by BASF Corporation) <sensitizer> Sensitizer E1 : 2, 4- Diethylthioxanthone; (Kayacure DETX-S, manufactured by Nippon Kayaku Co., Ltd.) φ Sensitizer £2: 4,4'-bis(diethylamino)benzophenone; (11〇(1) EA8&丫& Chemical Industries, Inc. "EAB-F" <Photopolymerizable compound> Photopolymerizable compound: dipentaerythritol hexaacrylate; ("A_X M-402" manufactured by Toagosei Co., Ltd.) <Polyfunctional thiol> Polyfunctional thiol F1: Trihydroxy decyl ethane ginseng (3 - mercaptobutyrate) ("TEMB" by Showa Denko Co., Ltd.) Polyfunctional thiol F2: trimethylolpropane ginseng (3-mercaptobutyrate); (Showa 323842 211 201233734 "Electric company" "ΤΡΜΒ") Polyfunctional thiol F3: pentaerythritol lanthanum (3-mercaptopropionate); ("PEMP" manufactured by Sigma Chemical Industry Co., Ltd.) <UV absorber> UV absorber Gl: 2-[4-[2-hydroxy-3-( Dodecyl and tridecyl)oxypropyl)oxy]-2-ylphenyl]~4,6-bis(2,4-didecylphenyl)-1,3, 5-三哄;("Cumba 曰" company "TINUVIN 4〇〇") φ UV absorber G2: 2-(2H-benzotriazole_2_yl)_4,6_double (1_methyl-b stupid (ethylidene) phenol; ("CONUBA 9") manufactured by Ciba Japan Co., Ltd. <polymerization inhibitor> Polymerization inhibitor HI. N-nitrosophenylhydroxylamine aluminum salt; ("Wu Pure Chemical Industry Co., Ltd." -1301") ' Prohibition agent H2: methylhydroquinone; ("Gu" from Seiko Chemical Co., Ltd.) <Storage stabilizer> Storage stabilizer J1: 2, 6-double (1,1-dimethylethyl)-4-methyl ("BHT" manufactured by Chemical Industry Co., Ltd.) Storage stabilizer J2: Triphenylphosphine; ("Turkey Chemical Co., Ltd." "τρρ <solvent> j Organic solvent: cyclohexanone [evaluation of photosensitive coloring composition] The obtained photosensitive coloring composition has color characteristics and contrast ratio ((8), crystal precipitation on the surface of the coating film, sensitivity, linearity, pattern shape, resolution, financial imageability, chemical resistance, and stability over time) Methodological evaluation. The results are shown in the table (M0 order. The judgment in each evaluation result, 323842 212 201233734 ◎ is a very good degree, 〇 is a good degree, △ is the degree of use without obstacles 'X is used to a bad degree (Color characteristics, contrast ratio (CR) evaluation) The photosensitive coloring composition to be applied is on a glass substrate of 1 X X 〇〇 〇 〇 匪 匪 匪 匪 匪 匪 于 于 于 于 于 , , 在 在 在 在The film was applied in such a manner that the film thickness became x=0.640, y=〇.328, and dried in a hot air oven at 70° C. for 20 minutes, and then an ultrahigh pressure mercury lamp was used to carry out ultraviolet light exposure and the cumulative light amount was 150 mJ, at 23 ( After heating the TC for 1 hour, it was left to cool to obtain a red coating film. Thereafter, the brightness (Y) and the contrast ratio (CR) of the coated substrate were measured, and the chromaticity and brightness (Y) were microscopic spectrophotometers (〇1). Measurement by ympus Optics Co., Ltd. "OSP-SP200") (Evaluation of crystal precipitation on the surface of the coating film) The substrate obtained by evaluating the color characteristics and contrast ratio (CR) was heated at 260 C for 1 hour, and then left to cool. Coated substrate coating • Surface with light Under the microscope observation, the presence or absence of crystal precipitation was determined based on the following criteria. In the evaluation results, ◎ no crystal precipitation was very good, ◦ was a small amount of crystal precipitation but was good, and Δ was crystallized, but there was no problem in use. 'X is the extent to which crystal precipitation is unusable. ◎. The number of crystals is one. The number of crystals is one or more, and the number of crystals is less than ten. △ The number of crystals is 10 or more, and the number of crystals is less than one. X: The number of crystals is 100 or more (sensitivity, straight green color, pattern shape, resolution, development resistance, chemical resistance) 323842 213 201233734 evaluation) The photosensitive coloring composition obtained is 100 mm x 1 〇〇mm, 〇. 7 mm After coating on the thickness of the glass substrate, the solvent was removed by heating at 7 〇Pc for 20 minutes in a dust-free oven to obtain a coating film of about 2/m. Then, after cooling the substrate to room temperature, 'Ultra-high pressure was used. The mercury lamp is exposed to ultraviolet light through a mask of a strip pattern of 100 width (200 ym pitch) and 25/inch width (pitch 5 〇 μιη). After that, the substrate is sprayed with a sodium carbonate aqueous solution at 23 ° C. Ion exchange water Clean and air-dried, in a dust-free oven at 23〇t: heating 330 is I. Spray imaging is applied to the coating film of each photosensitive coloring composition, and the pattern can be formed without residual image development in the shortest time. This was taken as an appropriate development time. The film thickness of the coating was carried out using Dektak 3030 (manufactured by Nippon Vacuum Technology Co., Ltd.) (sensitivity evaluation)
測定藉由上述方法所形成之濾光片段之遮罩 部7刀的圖案膜厚’評估相對於塗佈後之膜厚成為·以上 之^曝光量。最小曝光量愈小,成為高感度良好的感光 性著色組成物。評估的等級如下述。 〇:未達50mJ/cm2 △ : 50mJ/cm2 以上、去、去,2 禾達 100mJ/cm2 X : 100mJ/cm2 以上 (直線性評估) ^關藉由上述方法所形成之㈣諸之1⑽_遮罩 刀、圖案如光學顯微鏡觀察並進行評估。評估的等 323842 214 201233734 級如下述。 〇:直線性良好 △:部分的直線性不良 X :直線性不良 (圖案形狀評估) 有關藉由上述方法所形成之濾光片段之100# m遮罩 部分的圖案剖面,使用電子顯微鏡觀察並進行評估。圖案 剖面是順錐體(taper)為良好。評估的等級如下述。 ®〇:剖面為順錐體形狀 X :剖面為逆錐體形狀 (解像性評估) 有關藉由上述方法所形成濾光片段之25/zm遮罩部分 的圖案,使用光學顯微鏡觀察並進行評估。評估的等級如 下述。解像性不良是指鄰接之直線圖案或是連接或是發生 缺陷。 φ ◎:解像性及直線性良好 〇:直線性方面略差但解像性良好 △:部分的解像性不良 X:解像性不良 (耐顯像性評估) 在喷霧顯像時以適當時間之2倍顯像,測定所形成的 濾光片段之100//m遮罩部分的圖案膜厚,與適當顯像時間 所形成的圖案膜厚相比較。評估的等級如下述。 ◎:膜厚差在20%以内 323842 215 201233734 〇:膜厚差大於20%,在40%以内 △:膜厚差大於40% X:以2倍顯像發生缺陷或剝落 (耐藥品性評估) 將藉由上述方法所形成濾光片段浸潰在N-甲基吡咯 烷酮溶液中30分鐘後,以離子交換水洗淨並風乾,有關 100 遮罩部分的圖案,使用光學顯微鏡觀察並進行評 估。評估的等級如下述。 $ ◎:外觀、色無變化’為良好 〇:雖一部分發生皺紋,但色無變化為良好 △:發生若干的色脫落 X :發生剝落或色脫落 (著色組成物的經時安定性評估) 關於得到之感光性著色組成物,測定初期及室溫1個 月後之黏度。算出相對於初期黏度之黏度增加情形而進行 φ 評估。評估的等級如下述。 (經時黏度變化率)=I [(初期黏度)-(經時黏度)]/(初期黏 度)丨 χ100«) ◎:黏度增加之比率為5%以下為良好 〇:黏度增加之比率為比5%大及10%以下 X :黏度增加之比率大於10% 323842 216 201233734 [表 C-lο] 裹 C-10 (評估1) 亮度Y (評诂2) 對比度 (評估3) 結晶析出 (評估4) 威度 (評估5) 直線性 (評估6) 囷案形狀 (評估7) 解像度. (評估8) 耐顯像性 (評估9) 耐槃品性 (評佑10) 經時安定性 實施例7 23.6 5300 〇 〇 ό 〇 〇 6 〇 實施例B 23.4 5200 〇 〇 〇 〇 η 〇 Θ 〇 f施例9 22.8 5000 〇 〇 〇 〇 〇 〇 ο 賞旄例10 23.0 4800 〇 0 〇 〇 〇 〇 實施例11 22.5 5200 & 〇 〇 〇 〇 〇 實施例12 22.4 5100 〇 _ 〇 〇 〇 〇 貧旄例13 22.4 5300 & 〇 〇 〇 〇 ❺ 〇 實施例14 22.6 4700 e 〇 〇 〇 〇 〇 〇 實施例15 22.1 4B00 〇 〇 〇 〇 Θ 〇 d V施例1β 22.fi 5000 & 〇 〇 〇 & 〇 & . 〇 V 施《1*7 22.2 5200 〇 〇 〇 〇 0 〇 & 〇 會铯例18 22.1 4900 〇 〇 〇 〇 ❻ 〇 ❺ 〇 Γ施例19 22.5 5400 & 〇 〇 〇 〇 〇 & 〇 r振例20 23.0 5300 & 〇 〇 〇 Θ 〇 & & 22.3 4600 & 〇 〇 〇 〇 〇 & & ir旄例22 22.4 4800 & 〇 〇 〇 & 〇 ❺ 〇 實施例23 22.S 4600 Θ 〇 〇 〇 & 〇 d 〇 V施例24 22.1 5100 ❺ 〇 〇 〇 & 〇 〇 實施例25 22.5 4700 ❺ 〇 〇 〇 ❾ 〇 〇 〇 實施例26 22Λ 4400 d 〇 〇 〇 〇 〇 實施例27 22.8 4600 d 〇 〇 〇 3 〇 〇 〇 ΓΛΜζβ 22,7 4800 Θ 〇 0 〇 〇 ❹ 〇 1「施例Ζ9 23.2 5000 & 〇 〇 〇 & 〇 〇 貧施例30 22.5 5100 Ο 〇 〇 〇 〇 〇 〇 If 施 Μ31 22.1 4700 <a ό 〇 〇 β 〇 〇 〇 霣施例32 22.8 5100 & 〇 〇 〇 & 〇 〇 〇 會施例33 22.7 5300 ά 〇 〇 〇 & 0 〇 〇 實施例34 22.3 5200 & 〇 〇 〇 & 〇 〇 〇 實施例35 22.2 4900 & 〇 〇 ' 〇 & 〇 〇 〇 寶施《3β 22.1 4d00 & 〇 〇 〇 & 〇 〇 〇 貧施例37 23.0 5100 〇 〇 〇 〇 & 〇 〇 〇 貧施例38 22.8 5000 & 〇 〇 〇 〇 〇 〇 〇 實施例39 22.3 5000 & 〇 〇 〇 ◎ 〇 〇 〇 會施例40 22.2 4900 动 〇 〇 〇 d 〇 〇 〇 1Γ柢例41 22.6 5100 & 〇 Q 〇 & 9 〇 〇 春考例3 18.0 2700 X 〇 5 〇 △ ό ά K 參七例4 18.4 3000 X 〇 厶 Δ X 〇 〇 〇 春去例5 18.0 2500 X 〇 Δ 〇 X S 厶 〇The pattern thickness of the mask portion 7 of the filter segment formed by the above method was measured, and the exposure amount with respect to the film thickness after coating was evaluated. The smaller the minimum exposure amount, the higher the sensitivity of the photosensitive coloring composition. The rating is as follows. 〇: less than 50mJ/cm2 △: 50mJ/cm2 or more, go, go, 2 Heda 100mJ/cm2 X: 100mJ/cm2 or more (straightness evaluation) ^Offer by the above method (4) 1(10)_ The mask and pattern are observed and evaluated by an optical microscope. The evaluation of 323842 214 201233734 is as follows. 〇: good linearity △: partial linearity defect X: poor linearity (pattern shape evaluation) The pattern cross section of the 100# m mask portion of the filter segment formed by the above method was observed using an electron microscope to evaluate. The pattern profile is good for the taper. The rating is as follows. ®〇: the profile is a forward cone shape X: the profile is an inverse cone shape (resolution evaluation) The pattern of the 25/zm mask portion of the filter segment formed by the above method is observed and performed using an optical microscope Evaluation. The rating is as follows. Poor resolution means that the adjacent straight line pattern is either connected or defective. φ ◎: Good resolution and linearity 〇: The linearity is slightly inferior, but the resolution is good. △: Part of the resolution is poor X: The resolution is poor (difference evaluation) In the case of spray development The pattern thickness of the 100//m mask portion of the formed filter segment was measured twice as long as the appropriate time, and compared with the pattern film thickness formed by the appropriate development time. The rating is as follows. ◎: film thickness difference is less than 20% 323842 215 201233734 〇: film thickness difference is more than 20%, within 40% △: film thickness difference is more than 40% X: defect or peeling occurs in 2 times imaging (anti-drug evaluation) The filter fragments formed by the above method were immersed in the N-methylpyrrolidone solution for 30 minutes, washed with ion-exchanged water and air-dried, and the pattern of the 100-mask portion was observed and evaluated using an optical microscope. The rating is as follows. $ ◎: No change in appearance and color' is good 〇: Although some wrinkles occur, the color does not change as good △: Several color detachments occur X: flaking or color detachment (evaluation of the stability of the coloring composition) The obtained photosensitive coloring composition was measured for viscosity at the initial stage and room temperature after one month. The φ evaluation was performed by calculating the increase in viscosity with respect to the initial viscosity. The rating is as follows. (Change rate of viscosity over time) = I [(initial viscosity) - (time-dependent viscosity)] / (initial viscosity) 丨χ 100 «) ◎: The ratio of viscosity increase is 5% or less is good 〇: the ratio of viscosity increase is ratio 5% large and 10% or less X: viscosity increase ratio is greater than 10% 323842 216 201233734 [Table C-lο] Wrap C-10 (Evaluation 1) Brightness Y (Evaluation 2) Contrast (Evaluation 3) Crystallization (Evaluation 4 ) Weighing (Evaluation 5) Straightness (Evaluation 6) Case shape (Evaluation 7) Resolution (Evaluation 8) Resistance to development (Evaluation 9) Durability (Evaluation 10) Time stability Example 7 23.6 5300 〇〇ό 〇〇6 〇Example B 23.4 5200 〇〇〇〇η 〇Θ 〇f Example 9 22.8 5000 〇〇〇〇〇〇ο Reward Example 10 23.0 4800 〇0 〇〇〇〇Example 11 22.5 5200 & 〇〇〇〇〇 Example 12 22.4 5100 〇 _ 〇〇〇〇 旄 Example 13 22.4 5300 & 〇〇〇〇❺ 〇 Example 14 22.6 4700 e 〇〇〇〇〇〇 Example 15 22.1 4B00 〇〇〇〇Θ 〇d V Example 1β 22.fi 5000 &〇〇〇&〇& . 〇V 1*7 22.2 5200 〇〇〇〇0 〇& 〇会铯例18 22.1 4900 〇〇〇〇❻ 〇ΓExample 19 22.5 5400 &〇〇〇〇〇& 〇r vibration example 20 23.0 5300 & 〇〇〇Θ 〇 &&& 22.3 4600 &&& ir example 22 22.4 4800 &amp& 〇❺ 〇 Example 23 22.S 4600 Θ 〇〇 〇& 〇d 〇V Example 24 22.1 5100 ❺ amp & 〇〇 Example 25 22.5 4700 ❺ 〇〇〇 〇〇〇 Example 26 22 Λ 4400 d 〇〇〇〇〇 Example 27 22.8 4600 d 〇〇〇3 〇〇〇ΓΛΜζβ 22,7 4800 Θ 〇〇❹0 〇〇❹ 〇1 “Example Ζ9 23.2 5000 &〇〇〇& Poorest Example 30 22.5 5100 Ο 〇〇〇〇〇〇If Μ31 22.1 4700 <a ό 〇〇β 〇〇〇霣Example 32 22.8 5100 &〇〇〇& 〇〇〇 施 Example 33 22.7 5300 ά 〇〇〇 & 0 〇〇 Example 34 22.3 5200 & ; 〇〇〇 & 〇〇〇 Example 35 22.2 4900 & 〇' 〇& 〇〇〇宝施《3β 22.1 4d00 &〇〇〇& 〇〇〇 施 37 37 23.0 5100 〇〇〇〇& 〇〇〇 施 38 38 22.8 5000 & 〇〇〇 〇〇〇〇Example 39 22.3 5000 & 〇〇〇 ◎ 〇〇〇 will apply 40 22.2 4900 〇〇〇 d 〇〇〇 1 41 Example 41 22.6 5100 & 〇Q 〇& 9 〇〇春考Example 3 18.0 2700 X 〇5 〇△ ό ά K Reference 7 cases 4 18.4 3000 X 〇厶Δ X 〇〇〇春去例5 18.0 2500 X 〇Δ 〇XS 厶〇
如表C-10所示,含有式(1)所示顏料(Al)與感光性樹 脂(B1)的彩色濾光片用著色組成物,在全部的評估得到高 φ 水準的評估結果。 (彩色濾光片的製造) 感光性著色組成物(RP-1)中,除了將顏料及顏料衍生 物的合計4. 54份,變更成在綠色感光性著色組成物是C. I. 顏料綠58/C.I.顏料黃150= 2.72份/1.82份,藍色感光性 著色組成物是C. I.顏料藍15 : 6/C. I.顏料紫23=3. 63份 /0.91份之外,其餘與顏料分散物(P-3)同樣調製顏料分散 物,再者將感光性著色組成物(RR-1)的顏料分散物變更成 各色顏料分散物,而得到彩色濾光片用綠色感光性著色組 217 323842 201233734 成物、彩色瀘、光片用藍色感光性著色組成物。 在lOOmmxlOOmin的玻璃基板上,以鑄模塗佈法將感光 性著色組成物(RR-1)塗佈成約2以m的厚度,在7〇〇c ^烘> 箱内以20分鐘除去溶劑使其乾燥。其次,使用曝光裝置藉 由紫外線進行條紋圖案曝光。曝光量累積量成為 lOOmJ/cm2。進一步,藉由由碳酸鈉水溶液所成的顯像液噴 霧顯像而除去未曝光部分之後,以離子交換水洗淨,將此 基板在230°C加熱30分鐘,形成線寬約50 am的紅色、廣& ® 片段。其次,藉由同樣的操作’在紅色濾光片段鄰接處~使 用綠色感光性著色組成物,形成綠色濾、光片段,其-欠,H 用藍色感光性著色組成物,形成藍色濾光片段,在同 璃基板上得到具備3色之濾光片段之彩色濾光片(> 使用以上之彩色濾光片用著色級成物時,可以製作具 有在廣色度範圍的色特性優良’耐熱性良好的紅@# 段之高精細的玻璃濾光片。 φ [實施例D] 實施例D中,「份」及「%」是分別表示「重量份」及 「重量%」。顏料的比表面積、顏料的一次粒子經、樹月t的 重量平均分子量(Mw)、樹脂的酸價、塗膜的對比度比(CR) 的測定方法是如以下所述。 (顏料的比表面積) 顏料粒子的比表面積係藉由氦1氣吸附之BET法 並且,在測定中是使用自動蒸氣吸附量測定裝置(日本 Bell 公司製「BELS0RP18」)。 323842 218 201233734 (顏料的平均一次粒子徑) 顏料的平均一次粒子徑是由電子顯微鏡照片直接計 測一次粒子的大小之方法測定。具體而言,計測各顏料的 一次粒子之短軸徑與長軸徑,將平均當作此顏料粒子的粒 控。其次’有關100個以上的顏料粒子,使各粒子的體積(重 置)近似於求到之粒徑立方體的方式求得體積平均粒徑當 作平均一次粒子徑。並且,電子顯微鏡是使用穿透型(TEm)。 (樹脂的重量平均分子量(Mw)) 使用TSKgel管柱(T0HS0公司製),裝備有ri檢出器 之GPC(T0HS0公司製,HLC-8120GPC),使用THF作為展開 溶劑測定聚苯乙烯換算的重量平均分子量(Mw)。 (樹脂的酸價) 在樹脂溶液0. 5至lg中,加入丙嗣8〇ml及水i〇mi 並授拌均勻使溶解,將〇. lmol/L之K0H水溶液當作滴定 液,使用自動滴定裝置(「C0M-555」平沼產業製)滴定,測 鲁定樹脂溶液的酸價。於是,由樹脂溶液的酸價與樹脂溶液 的固形分濃度’算出樹脂的固形分的相當酸價。 (塗膜之對比度比) 由液晶顯示用背光單元所放出之光,係通過偏光板而 偏光,通過在玻璃基板上塗佈著色組成物的乾燥塗膜,到 達偏光板。只要偏光板與偏光板之偏光面為平行的話光 雖是透過偏光板,但在偏光面為直行的情形 板遮斷。然而,藉由偏光板使被偏光之光通_== 的乾燥塗膜時,由於顏料粒子而發生散射等,當偏光面之 323842 219 201233734 一部分發生交錯時,偏光板為平行之時透過偏光板的光量 會減少,偏光板為直行之時一部分光會透過偏光板。將此 透過光當作在偏光板上的亮度測定,算出偏光板為平行之 時的亮度,與直行時的亮度之比(對比度比)。 (對比度比Μ平行時的亮度)/(直行時的亮度) 同時,作為凴度計係使用色彩亮度計(Το%。公司製 「BM-5A」),作為偏光板是使用偏光板(曰東電工公司製As shown in Table C-10, the coloring composition for the color filter containing the pigment (Al) represented by the formula (1) and the photosensitive resin (B1) was evaluated at a high φ level in all evaluations. (Production of color filter) In the photosensitive coloring composition (RP-1), the total amount of the pigment and the pigment derivative was changed to 4.54 parts, and the green photosensitive coloring composition was CI pigment green 58/CI. Pigment Yellow 150 = 2.72 parts / 1.82 parts, blue photosensitive coloring composition is CI Pigment Blue 15 : 6 / CI Pigment Violet 23 = 3. 63 parts / 0.91 parts, the rest with pigment dispersion (P-3) In the same manner, the pigment dispersion was prepared, and the pigment dispersion of the photosensitive coloring composition (RR-1) was changed to a pigment dispersion of each color to obtain a green photosensitive coloring group for color filters. 217 323842 201233734 The light sheet is colored with a blue photosensitive coloring composition. On a glass substrate of 100 mm x 100 min, the photosensitive coloring composition (RR-1) was applied by a die coating method to a thickness of about 2 m, and the solvent was removed in a 7 〇〇c ^ baking box for 20 minutes. dry. Next, the stripe pattern is exposed by ultraviolet rays using an exposure device. The cumulative amount of exposure becomes lOOmJ/cm2. Further, the unexposed portion was removed by spray development using a developing solution of sodium carbonate aqueous solution, and then washed with ion-exchanged water, and the substrate was heated at 230 ° C for 30 minutes to form a red line having a line width of about 50 am. , wide & ® clips. Next, by the same operation 'using a green photosensitive coloring composition adjacent to the red filter segment, a green filter, a light segment is formed, and the light is colored, and the blue photosensitive coloring composition is used to form a blue filter. A color filter is obtained by obtaining a color filter having a filter of three colors on a glass substrate (> when a coloring grade is used for the above color filter, a color having a wide color range can be produced. High-precision glass filter with excellent characteristics and good heat resistance. φ [Example D] In the example D, "parts" and "%" are "parts by weight" and "% by weight", respectively. The specific surface area of the pigment, the primary particle diameter of the pigment, the weight average molecular weight (Mw) of the tree t, the acid value of the resin, and the contrast ratio (CR) of the coating film are as follows. (Specific surface area of the pigment) The specific surface area of the pigment particles is a BET method by 氦1 gas adsorption, and an automatic vapor adsorption amount measuring device ("BELS0RP18" manufactured by Bell Co., Ltd.) is used in the measurement. 323842 218 201233734 (average primary particle diameter of the pigment) Pigment level The primary primary particle diameter is measured by directly measuring the size of the primary particles from an electron micrograph. Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment are measured, and the average is regarded as the grain control of the pigment particles. 'About 100 or more pigment particles, the volume average particle size is determined as the average primary particle diameter by making the volume (reset) of each particle approximate to the obtained particle size cube. Moreover, the electron microscope uses a penetrating type. (TEm) (weight average molecular weight (Mw) of resin) GPC (manufactured by TOHHS Co., Ltd.) equipped with a TSKgel column (manufactured by Toshiba Co., Ltd.), and GPC (HLC-8120GPC, manufactured by Toshiba Co., Ltd.) was used, and polystyrene was measured using THF as a developing solvent. The weight average molecular weight (Mw) in terms of ethylene. (Acid acid value of the resin) In the resin solution 0.5 to lg, add 〇8嗣ml and water i〇mi and mix and dissolve to dissolve, 〇. lmol/L The K0H aqueous solution is used as a titration solution, and is titrated by an automatic titrator ("C0M-555"). The acid value of the resin solution is measured. Thus, the acid value of the resin solution and the solid content of the resin solution are calculated. The solid content of the resin is equivalent to the acid value. (Contrast Ratio of Coating Film) The light emitted by the liquid crystal display backlight unit is polarized by a polarizing plate, and is applied to a glass substrate by applying a dried coating film of a coloring composition. Polarizing plate. As long as the polarizing surface of the polarizing plate and the polarizing plate are parallel, the light passes through the polarizing plate, but the plate is blocked when the polarizing surface is straight. However, the polarized light is passed through the polarizing plate _== When the coating film is dried, scattering occurs due to the pigment particles. When the 323842 219 201233734 part of the polarizing surface is interlaced, the amount of light transmitted through the polarizing plate decreases when the polarizing plate is parallel, and a part of the light passes through the polarizing plate when the polarizing plate is straight. board. This transmitted light was measured as the luminance on the polarizing plate, and the ratio of the luminance when the polarizing plates were parallel to the luminance at the time of straight running (contrast ratio) was calculated. (Brightness when the contrast ratio is parallel) / (Brightness when going straight) At the same time, a color luminance meter (Το%. "BM-5A" manufactured by the company) is used as the meter, and a polarizing plate is used as the polarizing plate. Electrician company
「腳-G122_N」。同時,測定時為了遮斷多於的光,在測 疋部分覆上開有1 cm正方孔洞的黑色遮罩 在實施例前,說明有關在實施例及參考例中使用的黏 者樹脂⑻驗、式⑴所示顏料(A1)、微細化顏料、顏料 分散體的製造方法。 <黏合劑樹脂(B)溶液的製造方法〉 [樹脂溶液(B1-1)] (階段1:樹脂主鏈之聚合) 於烤分離式之4 口燒瓶安裳有溫度計、冷卻管、乱氣 導入管、攪拌裝置之反應容器中加人丙二醇單甲細醋酸 。酉旨(PGMACMoo份,—邊於容器中注人氮氣…邊加熱至12〇 c’在同溫度下藉由滴入管費時2 5小時滴入苯乙稀瓜2 ^甲基丙烯酸縮水甘油酯35.5份、二燒戊稀甲基丙稀酸 :41. 0伤、及在此階段中之前驅物化合所需要的觸媒之偶 氮雙異T腈1.〇份的混合物,進躲合反應。 (階段2:對環氧基之聚合) ‘ 然後於燒㈣進行空氣置換,投人㈣酸17 〇份及 323842 220 201233734 在此階段中之前驅物的聚合所需之作為觸媒之參二 基曱基紛〇. 3份、及氫酉昆〇. 3份,在靴進行反應= 時,得到重量平分子量約12咖(以GPC測定)之樹鳴落、 ^投入之㈣酸細甲基丙烯酸縮水甘㈣誠 j 氧基末端進行⑽結,故於獅構造巾不產线基。畏 (階段3:對羥基之聚合) 一 v,加入四氫酞酸酐3〇.4份及在此階段"Foot-G122_N". At the same time, in order to block more light during the measurement, a black mask with a 1 cm square hole is placed on the test portion before the embodiment, and the adhesive resin (8) used in the examples and the reference examples is described. A method for producing a pigment (A1), a fine pigment, and a pigment dispersion represented by the formula (1). <Method for Producing Binder Resin (B) Solution> [Resin Solution (B1-1)] (Stage 1: Polymerization of Resin Main Chain) The 4-neck flask in the roasting type has a thermometer, a cooling tube, and a gas Add propylene glycol monomethyl acetate to the reaction vessel of the introduction tube and the stirring device. PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG PG Part, the second pentyl methacrylic acid: 41.0, and the mixture of the azobisiso-T nitrile required for the catalyst combination in the previous stage, the sputum mixture, into the dodge reaction. (Stage 2: Polymerization of epoxy groups) ' Then the air is replaced by burning (4), and the (4) acid is used for 17 parts and 323842 220 201233734. In this stage, the polymerization of the precursor is required as a catalyst. 3 parts, and hydrogen hydrazine. 3 parts, when the shoe is reacted =, the weight of the square molecular weight is about 12 coffee (measured by GPC), and the (tetra) acid fine methacrylic acid is obtained. Shrinking water (four) Cheng j oxy end of the (10) knot, so the lion construction towel does not produce line base. Fear (stage 3: polymerization of hydroxyl groups) a v, adding tetrahydrophthalic anhydride 3 〇. 4 parts and at this stage
合所需之作為觸媒之三乙就5份,在^ 應4小時。所加u 匕反 之2倾基的4:=:為_***開所產生 爷於樹脂構造中的羥基進行酯鍵結,s 者產生羧基末端。 另〜 (階段4:不揮發成分之調整) 40%而得到 添加丙二醇單甲基驗以使不揮發成分成為 樹脂溶液(B1-1)。 樹脂溶液(B1-1)中之構成單元的重量比係作 單元(D-bl)之四氫駄酸肝2丨.7重量%、作為構成單元 :本乙烯U.6重量%、作為構成單元(D_b3)之 2) 基丙稀酸醋·· 29.3重量%、作為其他構成單元之甲義 酸縮水甘㈣及於其縮水甘㈣末端_結 計37.4重量%。 之合 [樹脂溶液(Β1-2)] 使樹脂溶液(ΒΗ)之二環戊埽甲基丙稀酸酿形成為 :基丙婦酸二環戊婦酉旨以外’其餘係與樹脂溶液(ΒΗ)同 樣的方法而進行合成反應,得_脂歸.2)。 323842 221 201233734 [樹脂溶液(Bl-3)] 使樹脂溶液(B1-1)之二環戊烯曱基丙烯酸g旨形成為 曱基丙烯酸二環戊烯基氧基乙酯以外,其餘係與樹脂溶液 (B1 -1)同樣的方法而進行合成反應’得到樹脂溶液(b 1 一 3 ) [樹脂溶液(B1-4)] 於具備溫度計、冷卻管、氮氣導入管、滴入管及搜摔 裝置之分離式4 口燒瓶中加入PGMEA 370份,昇溫至8(rc , 於燒瓶内氮氣取代後,藉由滴入管費時2小時滴入對異丙 * 苯基酚環氧乙烷改質丙烯酸酯(東亞合成公司製Ar〇nix Ml 10) 18份、甲基丙烯酸苯甲酯1〇份、甲基丙烯酸縮水 甘油酯18.2份、曱基丙烯酸曱酯25份、及2, 2,_偶氣雙 異丁猜2.0份的混合物。滴入後’進一步,在1〇〇 °c反應3 小時後’添加使偶氮雙異丁腈1.0份溶解於環己酮5〇份 者’再以10 0 C持續反應1小時。繼而,於容器内置換成 空氣,丙烯酸9. 3份(環氧基當量)及參二甲基胺基酚〇 5 φ 份及氫酿〇.1份投入於上述容器内,以12(TC持續反應6 小時’固形分酸價成為0.5份時’使反應結束,得到兩稀 酸樹脂之溶液。進一步,繼續加入四氫酞酸酐丨9. 5份(所 生成之經基的當量)、二乙胺0. 5份,以12〇。(:持續反應& 5 小時,得到丙烯酸槪脂之溶液。 · 冷卻至室溫後,樹脂溶液約作為試樣,在18(rc加 熱乾燥20分鐘測定不揮發齡,於先前所合成之樹脂溶液 中添加PGMEA以使不揮發成分成為2〇重量%,而調製丙烯 酸樹脂溶液(BH)。重量平均分子量(Mw)為腳〇。 323842 222 201233734 [樹脂溶液(B1-5至15)及(B2-1至4)] 以與樹脂溶液(B1-1)同樣的方法進行樹脂溶液 至(B1-15)及(B2-1)至(B2至5)之調製。 亦即,樹脂溶液(B1-1)之製造方法中,使作為構成單 元(D-bl)至(D-b3)及其他構成單元之前驅物依表D—丨而取 代。於表中GMA-AA或GMA-MAA不存在之樹脂溶液時,係混 合全部之刖驅體,僅實施製造之階段1與階段4。表中, GMA-AA或GMA-MAA存在,進一步存在有τηΡΑ時,首先混 Φ 合GMA與構成單元(D-b2)、(D-b3)及其他之構成單元中除 去GMA-AA或GMA-MAA的前驅物而實施製造之階段1,繼 而,加入GMA之環氧當量的AA或MM作為前驅物而實施製 造之階段2,再加入THPA作為前驅物而實施製造之階段3、 階段4。表中,GMA-AA或GMA-MAA存在,THPA不存在時, 首先混合GMA與構成單元(D-bl)至(D-b3)及其他之構成單 元中除去GMA-AA或GMA-MAA的前驅物而實施製造之階段 φ 1 ’繼而’加入GMA之環氧當量的AA或MAA作為前驅物而 實施製造之階段2 ’進一步實施階段4。各階段所需要之觸 媒的份數係依在各階段混合之前驅物的合計份數之比例而 混合。 所得到之樹脂溶液(B1-1至15)及樹脂溶液(B2-1至 4)之組成及重量比表示於表D-1中。括弧内係表示樹脂固 形分中之構成單元重量比(重量%)。 323842 223 201233734 [表 D-l]The required three of the three as the catalyst are 5, and should be 4 hours. The addition of 匕 之 2 2 : : : : : : : : : : : : 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 Another ~ (stage 4: adjustment of non-volatile components) 40% was obtained by adding a propylene glycol monomethyl group to make a nonvolatile component into a resin solution (B1-1). The weight ratio of the constituent units in the resin solution (B1-1) is 2% by weight of the tetrahydrofurfuric acid liver of the unit (D-bl), and is a constituent unit: the present ethylene is U. 6 wt% as a constituent unit. (D_b3) 2) acrylic acid vinegar · 29.3 wt%, as the other constituent unit, the succinic acid (4) and the glycidyl (tetra) terminal _ knot 37.4% by weight. [Resin solution (Β1-2)] The dicyclopentanyl methyl acrylate of the resin solution (ΒΗ) is formed into a mixture of the following: the rest of the system and the resin solution (ΒΗ The same method is used for the synthesis reaction, and the result is _ lipid return. 2). 323842 221 201233734 [Resin solution (Bl-3)] The dicyclopentenyl methacrylate of the resin solution (B1-1) is formed into a dicyclopentenyloxyethyl methacrylate, and the rest is resin. The synthesis reaction is carried out in the same manner as the solution (B1 -1) to obtain a resin solution (b 1 to 3 ) [resin solution (B1-4)] provided with a thermometer, a cooling tube, a nitrogen introduction tube, a drip tube, and a search device. 370 parts of PGMEA was added to the separable 4-necked flask, and the temperature was raised to 8 (rc. After the nitrogen substitution in the flask, the isopropyl phenylphenol oxirane modified acrylate was added dropwise by dropping the tube for 2 hours. (Ar东亚nix Ml 10 manufactured by Toagosei Co., Ltd.) 18 parts, 1 part by weight of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of decyl methacrylate, and 2, 2, _ double pairs Isochao 2.0 parts of the mixture. After the instillation, 'further, after reacting for 3 hours at 1 °C, 'addition of 1.0 part of azobisisobutyronitrile to 5 parts of cyclohexanone' and then 10 0 C The reaction was continued for 1 hour. Then, the container was replaced with air, 9.3 parts of acrylic acid (epoxy equivalent) and dimethylamine. Phenolphthalein 5 φ parts and hydrogen hydrazine. 1 part was placed in the above-mentioned container, and 12 (TC was continuously reacted for 6 hours, when the solid content of the acid was 0.5 part), the reaction was completed, and a solution of the two dilute acid resins was obtained. Further, 5份。 The equivalent of the tetrahydrofuran anhydride 丨 9.5 parts (the equivalent of the formed base), diethylamine 0.5 parts, to 12 〇. (: continuous reaction & 5 hours, to obtain a solution of acrylic resin. After cooling to room temperature, the resin solution was used as a sample, and the non-volatile age was measured at 18 (rc heating and drying for 20 minutes), PGMEA was added to the previously synthesized resin solution to make the nonvolatile content 2% by weight, and acrylic acid was prepared. Resin solution (BH). The weight average molecular weight (Mw) is an ankle. 323842 222 201233734 [Resin solution (B1-5 to 15) and (B2-1 to 4)] In the same manner as the resin solution (B1-1) The resin solution is prepared to (B1-15) and (B2-1) to (B2 to 5). That is, in the method for producing the resin solution (B1-1), the constituent unit (D-bl) is used as D-b3) and other constituent units of the precursor are replaced by Table D-丨. Resins not present in the table GMA-AA or GMA-MAA In the case of solution, all of the ruthenium precursors are mixed, and only stage 1 and stage 4 of the production are carried out. In the table, GMA-AA or GMA-MAA is present, and when τηΡΑ is further present, the GMA and the constituent unit are first mixed (D- In the b2), (D-b3) and other constituent units, the precursor of GMA-AA or GMA-MAA is removed to carry out the stage 1 of the production, and then the epoxy equivalent of AA or MM of GMA is added as a precursor to manufacture. In stage 2, phase 3 and stage 4 of manufacturing are carried out by adding THPA as a precursor. In the table, GMA-AA or GMA-MAA is present. When THPA is not present, the precursors of GMA-AA or GMA-MAA are first mixed with GMA and constituent units (D-bl) to (D-b3) and other constituent units. The stage of manufacture φ 1 'and then the addition of AA or MAA of the epoxy equivalent of GMA as a precursor to the stage 2 of the manufacturing process is carried out. The number of catalysts required for each stage is mixed according to the proportion of the total number of parts of the precursor before mixing in each stage. The composition and weight ratio of the obtained resin solutions (B1-1 to 15) and resin solutions (B2-1 to 4) are shown in Table D-1. The brackets indicate the constituent unit weight ratio (% by weight) in the resin solid portion. 323842 223 201233734 [Table D-l]
蠡D-1 樹脂溶液名 «1成單元(bl)之 铕驅物 搆成筚元(b2)之 麻《物 搆成草元(b3)之甫 «物 其他構咸單无 構成單元 比合计 樹脂分 子量 溶埘名 不揮發成 分比串 Θ1-1 THPA(21.7 霣皇 St(11.6SJ|9«) DCPMA(29.3 重 置Η) GMA-AA(37.4ttftM) 100靈董% 12000 PGMAC 40霞置Η Θ1-2 THPA(21.7l*H) St(11.6 霣靈%> 7基丙燁酸二 環戍烯《(29.3 重董 GMA-AA(37.4^ftH〉 1001 置 Η 12500 PGMAC 40 靈·% B1-3 THPA(21.7MH) Stdldlft%) Τ基丙烯酸二 環戍烊氧基& 曲<29.3偷噩⑹ GMA-AA<37.4 貧量 10〇1量% 12800 PGMAC 40 霣 ft% B1-4 MAA(25 重·%) BzMAOOSftM) DCPMA(19.5 露 ft%) GMA-AA(27.5 重置 100戴貴% 19000 PGMAC 20重置% B1-6 THPACZfiM%) St(4 重 1%) DCPMA(25麓量知 GMA-AA(43 重 ft%) 100重置% 8000 PGMAC 40璽置妁 B1-6 1>^六(22重置紛 st(10l 置 DCPMA(24ftftM) GMA-AA(44 重置%) 100 竄 ΜΗ 9000 環己明 20重霣% B1-7 MAA(16U%) BzMA(09 重嫌 %) OCPMA(15 籯置 - lOOSft% 16000 PGMAC 40 創 Β1-Θ MAA(13 霣麗 %) BzMA(49ftK%) OCPMAdSflft%) OMA-MAA(23M%) lOOftM% 27000 PGMAC 40重·% B1-9 MAA(16Mft%) BzMA(S7 重 ft%) DCPMA(丨3重量%> QMA-MAACl4ftft%) 100黨量% 9000 PGMAC 40 麗 11% B1-10 MAA(,3 貢置 %} βιΜΑ(53 重最 Η) DCPMA<13XJ|%) GMA-MAA(21 賞量%> 100纛農% 27000 PGMAC 40鬣置% B1-11 MAA(57lfl;%) St(1〇S量%) DCPMAU3 震麗 GMA-MAA(13 重· βΜΑ(7 重·Η) 100戴量% 1S500 PGMAC 40 霣 B1-12 THPA(11.5 雪量 %) BzMA(11.5l ftM) OCPMA(S6lM%) GMA-AA(21 重量%) ιοοΧΜ% 14000 PGMAC 40重·% B1-13 MAA(42flft%) ΒζΜΑ<43 重最%> DCPMMl5SJt%> - UW重量96 15000 環已明 40 重 ft% B1-14 MAA(44 霣量%> SU7M%) OCPMA(49Sft%) - 100Μ% 21000 PGMAC 40重麗鉍 B1-15 MAA⑴露量%> BzMA(41 重 ftH〉 〇CPMA(45 黨騰 GMA-MAA(重悬 39〇 1001196 100500 PGMAC 40 霣·% Θ2-1 THPA(30.7ll%) St(16.4 重置%) 垂 GMA-AA(52.9 嫿嫌 %) 100貧纛% 11000 PGMAC 40重羹Μ B2—2 THPA(24.6 霣·軸) - DCPMA(33.1 霣 鸶%) ΟΜΑ-ΑΑ(42·3 麄置 100重蛋% 9500 PGMAC 40 重 1% BZ-3 - st(M.e 重羹%) DCPMA07.4S GMA-AAC47.8 重 ft%) 100戴最% 12000 PGMAC 40靈纛Η B2-4 MAA(32 重麗 %) BzMA《朗重ft%〉 - • 100重量% 18000 PGMAC 40籯纛% 表D-1中之構成單元的前驅物及構成單元之簡稱的說 明。 MAA:甲基丙烯酸 THPA :四氫酞酸酐(4-環己烯-1,2-二羧酸酐)蠡D-1 Resin solution name «1 into unit (bl) 铕 筚 constituting 筚 ( (b2) 麻 物 物 物 物 物 物 物 物 物 物 物 物 物 物 其他 其他 其他 其他 其他 其他 其他 其他 其他 其他 其他 其他Molecular weight dissolved non-volatile content ratio 1-1 THPA (21.7 霣皇St (11.6SJ|9«) DCPMA (29.3 reset Η) GMA-AA (37.4ttftM) 100 灵董% 12000 PGMAC 40 Xia Η Θ 1 -2 THPA(21.7l*H) St(11.6 霣灵%> 7-base propionate dicyclodecene" (29.3 heavy Dong GMA-AA (37.4^ftH> 1001 Η 12500 PGMAC 40 灵·% B1- 3 THPA (21.7MH) Stdldlft%) Hydrazinylbicyclononyloxy &曲<29.3 偷噩(6) GMA-AA<37.4 Poor 10〇1%% 12800 PGMAC 40 霣ft% B1-4 MAA( 25 weight ·%) BzMAOOSftM) DCPMA (19.5 ft%) GMA-AA (27.5 reset 100 wear expensive % 19000 PGMAC 20 reset % B1-6 THPACZfiM%) St (4 weight 1%) DCPMA (25 麓 know GMA-AA (43 ft%) 100 reset % 8000 PGMAC 40 妁 妁 B1-6 1>^ six (22 resets st (10l set DCPMA (24ftftM) GMA-AA (44 reset %) 100 窜ΜΗ 9000 环己明20重霣% B1-7 MAA(16U%) BzMA(09% suspected) OCPMA(15 籯置- lOO Sft% 16000 PGMAC 40 创Β1-Θ MAA(13 霣丽%) BzMA(49ftK%) OCPMAdSflft%) OMA-MAA(23M%) lOOftM% 27000 PGMAC 40 weight·% B1-9 MAA(16Mft%) BzMA(S7 Weight ft%) DCPMA (丨3wt%> QMA-MAACl4ftft%) 100 Party%% 9000 PGMAC 40 Li 11% B1-10 MAA(,3 tributary%} βιΜΑ(53 weight most) DCPMA<13XJ|% ) GMA-MAA (21% of the weight> 100% of the farmers 27000 PGMAC 40鬣% B1-11 MAA (57lfl;%) St (1〇S amount%) DCPMAU3 Zhenli GMA-MAA (13 weight · βΜΑ ( 7 重·Η) 100% of wear 1S500 PGMAC 40 霣B1-12 THPA (11.5 snow %) BzMA (11.5l ftM) OCPMA (S6lM%) GMA-AA (21% by weight) ιοοΧΜ% 14000 PGMAC 40%·% B1-13 MAA (42flft%) ΒζΜΑ<43 weight most %>DCPMMl5SJt%> - UW weight 96 15000 ring already clear 40 ft% B1-14 MAA (44 % quantity%> SU7M%) OCPMA (49Sft% ) - 100Μ% 21000 PGMAC 40 重丽铋B1-15 MAA(1)Exposure%> BzMA(41 重ftH> 〇CPMA(45 党腾GMA-MAA(Resuspension 39〇1001196 100500 PGMAC 40 霣·% Θ2-1 THPA (30.7ll%) St (16.4 reset %) 垂 GMA-AA (52.9 % %) 100% 1 11000 PGMAC 40羹Μ B2—2 THPA (24.6 霣·axis) - DCPMA (33.1 霣鸶%) ΟΜΑ-ΑΑ (42·3 100100 heavy egg% 9500 PGMAC 40 weight 1% BZ-3 - st (Me repeat %) DCPMA07.4S GMA-AAC47.8 weight ft%) 100 wear most % 12000 PGMAC 40 Ling B2-4 MAA (32%) BzMA "Large weight ft%" - • 100% by weight 18000 PGMAC 40% The abbreviations of the precursors and constituent units of the constituent units in Table D-1. MAA: methacrylic acid THPA: tetrahydrophthalic anhydride (4-cyclohexene-1,2-dicarboxylic anhydride)
BzMA ·.曱基丙烯酸苯曱酯 St:苯乙烯 224 323842 201233734 M110 :對異丙苯基酚環氧乙烷改質丙烯酸酯 DCPMA :曱基丙烯酸二環戊烯酯 GMA :甲基丙烯酸縮水甘油S旨 GMA-AA :於構成單元GMA加成反應丙烯酸並鍵結者 GMA-MAA:於構成單元GMA加成反應甲基丙烯酸並鍵結者 BMA :曱基丙烯酸正丁酯 [樹脂溶液(B2-5)之調製] 於反應容器中置入環己酮370份,一邊於容器中注入 • 氮氣一邊加熱至80°C,在同溫度費時1小時滴入甲基丙烯 酸20. 0份、甲基丙烯酸曱酯10. 0份、甲基丙烯酸正丁酯 55. 0份、曱基丙烯酸2-羥基乙酯15. 0份、2, 2’ -偶II雙 異丁腈4. 0份之混合物而進行聚合反應。滴入結束後,再 以80°C反應3小時後,添加使偶氮雙異丁腈1. 0份溶解於 環己酮50份者,進一步,以80°C持續反應1小時,得到 丙稀酸樹脂溶液。 φ 冷卻至室溫後,丙烯酸樹脂溶液約2g作為試樣,而 以180°C加熱乾燥20分並測定不揮發成分,於先前所合成 之丙烯酸樹脂溶液中添加環己酮以使不揮發成分成為20 重量%,而調製樹脂溶液(B2-5)。重量平均分子量(Mw)為 40000 。 <式(1)所示之顏料(A1)的製造方法> [溴化二酮基吡咯并吡咯顏料(A1-1)] 於安裝有回流管之不銹鋼製反應容器中,氮氣環境 下,加入經分子篩脫水之第三戊醇200份、及第三戊氧基 323842 225 201233734 鈉140份,一邊攪拌一邊加熱至100°C,調製醇鹽溶液。 另外,於玻璃製燒瓶中,加入琥珀酸二異丙酯88份、4-溴苯曱腈153. 6份,一邊攪拌一邊加熱至90°C使其溶解, 調製此等混合物的溶液。將此混合物之加熱溶液,一邊於 加熱至100°C的上述醇鹽溶液中激烈攪拌,一邊費時2小 時以一定的速度徐緩地滴入。滴入結束後,以90°C持續加 熱擾拌2小時,得到二酮基°比p各并β比σ各系化合物的鹼金屬 鹽。進一步,於附有玻璃製内襯的反應容器中,加入曱醇 ® 6 0 0份、水6 0 0份、及醋酸3 0 4份,冷卻至-10 °C。將此冷 卻的混合物使用高速攪拌分散器,使直徑8cm之剪切碟以 4000rpm旋轉,一邊於其中將冷卻至75°C之前,少量地添 加二酮基吼σ各并°比p各系化合物的驗金屬鹽溶液。此時,由 曱醇、醋酸、及水所構成之混合物的溫度持續保持於-5°C 以下之溫度,一邊冷卻,一邊調整75°C之二酮基吡咯并吡 咯系化合物的鹼金屬鹽添加的速度,大概經過120分而少 ^ 量地添加。添加驗金展鹽之後,析出紅色之結晶,生成紅 色的懸濁液。繼而,使所得到之紅色的懸濁液在5 °C以超 過遽裝置洗淨後,過濾、得到紅色膏狀物。使此膏狀物以冷 卻再分散於0°C之甲醇3500份,形成曱醇濃度約90%之懸 濁液,以5°C攪拌3小時,將伴隨結晶轉移之粒子進行整 粒及洗淨。繼而,以超過濾機濾別,使所得到之二酮基吡 咯并吡咯系化合物的水膏狀物以80°C乾燥24小時,藉粉 碎得到150.8份式(1)所示之顏料(A1)的溴化二酮基吡咯 并吡咯顏料。 323842 226 201233734 將所得到之溴化二酮基吡咯并吡咯顏料100. 0份、氯 化鈉1000份及二乙二醇120份倒入於不銹鋼製1加侖捏合 機(井上製作所製)中,以60°C混練8小時。其次,已混練 之混合物投入於溫水中,一邊加熱至約80°C —邊擾拌1小 時而形成膏狀物,進行過濾及水洗而除去食鹽及二乙二醇 後,以80°C乾燥一晝夜,藉由粉碎得到96. 5份式(1)所示 之溴化二酮基吡咯并吡咯顏料(A卜1)。平均一次粒徑為 38mm、比表面積為80m2/g。 •〈顏料分散ϋ之製造方法〉 [顏料分散體(P-1)] 將下述組成的混合物攪拌混合均勻後,使用直徑1mm 的二氧化錄珠粒,而以Eiger研磨機(Eiger Japan公司製 「Minimodel M-250 MKII」)分散5小時後,以5/z m之過 濾膜過濾,得到顏料分散體(P-1)。 溴化二酮基吡咯并吡咯顏料(A1-1) 8. 78份 φ 酸性樹脂型顏料分散劑 1.74份 (BYK Chemie Japan 公司製 BYK-111) 顏料衍生物1 2. 05份 323842 227 201233734 衍生物1BzMA ·. phenyl decyl acrylate St: styrene 224 323842 201233734 M110 : p-cumylphenol oxirane modified acrylate DCPMA: dicyclopentenyl acrylate GMA: glycidyl methacrylate S GMA-AA: Addition reaction in the constituent unit GMA Acrylic bond and bond GMA-MAA: Addition reaction methacrylic acid in the constituent unit GMA and bond BMA: n-butyl decyl acrylate [resin solution (B2-5 The methacrylate dimethyl methacrylate was added dropwise to the reaction vessel while immersing 370 parts of cyclohexanone in the reaction vessel while injecting nitrogen gas into the vessel to a temperature of 80 ° C. 0份的混合物进行进行进行。 0. 0 parts, n-butyl methacrylate 55.0 parts, 2-hydroxyethyl methacrylate 15.0 parts, 2, 2'- io II bisisobutyronitrile 4. 0 parts of the mixture for polymerization reaction. After the completion of the dropwise addition, the reaction was further carried out at 80 ° C for 3 hours, and then 1.0 part of azobisisobutyronitrile was dissolved in 50 parts of cyclohexanone, and further, the reaction was continued at 80 ° C for 1 hour to obtain propylene. Acid resin solution. After φ was cooled to room temperature, about 2 g of the acrylic resin solution was used as a sample, and dried at 180 ° C for 20 minutes, and the nonvolatile matter was measured, and cyclohexanone was added to the previously synthesized acrylic resin solution to make the nonvolatile matter 20% by weight, and the resin solution (B2-5) was prepared. The weight average molecular weight (Mw) was 40,000. <Production Method of Pigment (A1) Represented by Formula (1)> [Bromide Diketopyrrolopyrrole Pigment (A1-1)] In a stainless steel reaction vessel equipped with a reflux tube, under a nitrogen atmosphere, 200 parts of the third pentanol dehydrated by the molecular sieve and 140 parts of the third pentyloxy 323842 225 201233734 sodium were added, and the mixture was heated to 100 ° C while stirring to prepare an alkoxide solution. Further, 88 parts of diisopropyl succinate and 156.6 parts of 4-bromobenzonitrile were placed in a glass flask, and the mixture was heated to 90 ° C while stirring to dissolve, and a solution of these mixtures was prepared. The heated solution of the mixture was vigorously stirred at a constant rate for 2 hours while vigorously stirring in the above alkoxide solution heated to 100 °C. After the completion of the dropwise addition, the mixture was stirred at 90 ° C for 2 hours to obtain an alkali metal salt of a compound having a diketone ratio of p and a specific ratio of σ. Further, in a reaction vessel with a glass lining, sterol ® 600 parts, water 605 parts, and acetic acid 340 parts were added, and the mixture was cooled to -10 °C. The cooled mixture was rotated at a speed of 4000 rpm using a high-speed stirring disperser, and a small amount of diketone 吼σ was added to the mixture before the cooling to 75 ° C. Check the metal salt solution. In this case, the temperature of the mixture of decyl alcohol, acetic acid, and water is maintained at a temperature of -5 ° C or lower, and the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C is adjusted while cooling. The speed is about 120 points and less. After the gold deposit was added, red crystals were precipitated to form a red suspension. Then, the obtained red suspension was washed at 5 ° C in excess of the apparatus, and then filtered to obtain a red paste. The paste was cooled and redispersed in 3500 parts of methanol at 0 ° C to form a suspension having a decyl alcohol concentration of about 90%, and stirred at 5 ° C for 3 hours to granulate and wash the particles accompanying the crystal transfer. . Then, the water paste of the obtained diketopyrrolopyrrole compound was dried at 80 ° C for 24 hours by an ultrafilter, and 150.8 parts of the pigment (A1) represented by the formula (1) was obtained by pulverization. Brominated diketopyrrolopyrrole pigment. 323842 226 201233734 The obtained brominated diketopyrrolopyrrole pigment 100. 0 parts, 1000 parts of sodium chloride and 120 parts of diethylene glycol were poured into a stainless steel 1 gallon kneader (manufactured by Inoue Co., Ltd.) to Mix at 80 ° C for 8 hours. Next, the kneaded mixture was put into warm water and heated to about 80 ° C - while stirring for 1 hour to form a paste, which was filtered and washed with water to remove salt and diethylene glycol, and then dried at 80 ° C. By day and night, 95.6 parts of the brominated diketopyrrolopyrrole pigment (Ab) represented by the formula (1) was obtained by pulverization. The average primary particle diameter was 38 mm and the specific surface area was 80 m 2 /g. <Manufacturing method of pigment dispersion 〉> [Pigment dispersion (P-1)] A mixture of the following composition was stirred and mixed uniformly, and then an Eiger grinding machine (manufactured by Eiger Japan Co., Ltd.) was used. "Minimodel M-250 MKII" was dispersed for 5 hours, and then filtered through a 5/zm filtration membrane to obtain a pigment dispersion (P-1). Brominated diketopyrrolopyrrole pigment (A1-1) 8. 78 parts φ Acid resin type pigment dispersant 1.74 parts (BYK-111, manufactured by BYK Chemie Japan Co., Ltd.) Pigment derivative 1 2. 05 parts 323842 227 201233734 Derivative 1
樹脂溶液(B2-5) 環己酮Resin solution (B2-5) cyclohexanone
5. 83 份 81.60 份 [顏料分散體(P-2)] 除將溴化二酮基吡咯并吡咯顏料(A1-1)變更為氯化 二酮基吡咯并吡咯顏料(C. I.顏料紅254;汽巴日本公司製 「IrgaphorredB-CF」)以外,其餘係與顏料分散體(p-i) 同樣地而得到顏料分散體(P-2)。 [顏料分散體(P-3)] 將下述組成的混合物攪拌混合均勻後,使用直徑lmin 的一氧化錯珠粒,而以Eiger研磨機(Eiger Japan公司製 「Minimodel M-250 MKII」)分散5小時後,以5/zm之過 濾膜過濾,得到顏料分散體(p_3)。 溴化二i§j基吡咯并吡咯顏料(A1_i) 6. 82 份 蒽醌系顏料(c. I.顏料紅177) 1· 08 份 (斤巴日本公司製「Chromophtal redA2B」) 錄偶氮錯合物系顏料(C. I.顏料黃150 ) 0. 88 份 (Lanxcess 公司製「E4GN」) 323842 228 201233734 酸性樹脂型顏料分散劑 1. 74份 (日本 Lubrizol 公司製 Solsperse 21000 ) 顏料衍生物1 2. 05份 衍生物15. 83 parts 81.60 parts [Pigment dispersion (P-2)] In addition to changing the brominated diketopyrrolopyrrole pigment (A1-1) to chlorinated diketopyrrolopyrrole pigment (CI Pigment Red 254; steam A pigment dispersion (P-2) was obtained in the same manner as the pigment dispersion (pi) except for "Irgaphorred B-CF" manufactured by Babel Corporation. [Pigment Dispersion (P-3)] The mixture of the following composition was stirred and mixed uniformly, and then dispersed using an Eiger mill ("Minimodel M-250 MKII" manufactured by Eiger Japan Co., Ltd.) using a oxidized beads of a diameter of 1 min. After 5 hours, it was filtered through a 5/zm filtration membrane to obtain a pigment dispersion (p_3). Brominated di-jj-based pyrrolopyrrole pigment (A1_i) 6. 82 parts of anthraquinone pigment (c. I. Pigment Red 177) 1·08 parts ("Chromophtal red A2B" manufactured by KBA Japan) Compound pigment (CI Pigment Yellow 150) 0. 88 parts ("E4GN" manufactured by Lanxcess) 323842 228 201233734 Acid resin type pigment dispersant 1. 74 parts (Solsperse 21000, manufactured by Lubrizol, Japan) Pigment derivative 1 2. 05 Derivative 1
樹脂溶液(B2-5) 5. 83份 環己酮 81. 60份 [顏料分散體(P-4至10)] 除變更為表D-2所示之顏料、顏料衍生物、及樹脂型 顏料分散劑的種類、及調配量以外,其餘係與顏料分散體 φ (P-3)同樣地而得到顏料分散體(P-4至11)。 [表 D-2] 表D-2 顏料分散體 顏料1 顏料2 顏料3 顏料衍生物 份 份 份 份 P-3 A1 — 1 6.82 PR177 1.08 PY150 0.88 衍生物1 2.05 P-4 PR254 6.82 PR177 1.08 PY150 0.88 衍生物1 2.05 P-5 A1 ~1 6.82 P071 0.65 PY150 0.88 衍生物1 2.05 P-6 A1-1 6.82 PR242 0.60 PY150 0.88 衍生物1 2.05 P-7 A1 — 1 6.82 PR179 0.50 PY150 0.88 衍生物2 2.05 P—8 A1-1 6.82 PR122 0,55 PY150 0.86 衍生物3 2.05 P-9 A1-1 6.82 PR177 1.08 PY180 0.50 衍生物4 2.05 P-10 A1 —1 6.B2 PR177 1.08 PY138 0.55 衍生物1 2.05 229 323842 201233734 表D-2中之簡稱記載於下述。 <顏料> PR 254:二酮基吡咯并吡咯系顏料C. I.顏料紅254;汽巴日 本公司製「Irgaphor redB-CF」 P071:二酮基吡咯并吡咯系顏料C. I.顏料紅71 ;汽巴日本 公司製「Irgazin DPP orange398」 PR242:偶氮系顏料C. I.顏料紅242 ; Clariant公司製 「Novoperm」 0 PR 179:茈系顏料C. I.顏料紅179 ;大日本油墨化學工業 (股)製「Fastogen Super Maroon PSK」 PR 122:啥°丫酮系顏料C. I.顏料紅12;Clariant公司製 「HOSTPERM」 PY180 :苯并咪唑酮系顏料C. I.顏料黃180;Clariant公 司製「PV First Yellow HG」 PY138:喹啉系顏料C. I.顏料黃180; BASF公司製 φ 「Paliotol Yellow K0960-HD」 <顏料衍生物> 323842 230 201233734 衍生物2Resin solution (B2-5) 5. 83 parts of cyclohexanone 81. 60 parts [Pigment dispersion (P-4 to 10)] except for the pigments, pigment derivatives, and resin type pigments shown in Table D-2 A pigment dispersion (P-4 to 11) was obtained in the same manner as the pigment dispersion φ (P-3) except for the type of the dispersant and the blending amount. [Table D-2] Table D-2 Pigment Dispersion Pigment 1 Pigment 2 Pigment 3 Pigment Derivative Partition Part P-3 A1 — 1 6.82 PR177 1.08 PY150 0.88 Derivative 1 2.05 P-4 PR254 6.82 PR177 1.08 PY150 0.88 Derivative 1 2.05 P-5 A1 ~1 6.82 P071 0.65 PY150 0.88 Derivative 1 2.05 P-6 A1-1 6.82 PR242 0.60 PY150 0.88 Derivative 1 2.05 P-7 A1 — 1 6.82 PR179 0.50 PY150 0.88 Derivative 2 2.05 P —8 A1-1 6.82 PR122 0,55 PY150 0.86 Derivative 3 2.05 P-9 A1-1 6.82 PR177 1.08 PY180 0.50 Derivative 4 2.05 P-10 A1 —1 6.B2 PR177 1.08 PY138 0.55 Derivative 1 2.05 229 323842 201233734 The abbreviation in Table D-2 is described below. <Pigment> PR 254: Diketopyrrolopyrrole pigment CI Pigment Red 254; "Irgaphor redB-CF" manufactured by Ciba Japan Co., Ltd. P071: Diketopyrrolopyrrole pigment CI Pigment Red 71; Ciba Japan "Irgazin DPP orange398" manufactured by the company PR242: azo pigment CI Pigment Red 242; "Novoperm" manufactured by Clariant Co., Ltd. 0 PR 179: lanthanide pigment CI Pigment Red 179; Dainippon Ink Chemical Industry Co., Ltd. "Fastogen Super Maroon PSK" PR 122: 丫 丫 ketone pigment CI Pigment Red 12; "HOSTPERM" manufactured by Clariant PY180: benzimidazolone pigment CI Pigment Yellow 180; "PV First Yellow HG" manufactured by Clariant Co., Ltd. PY138: Quinoline pigment CI Pigment Yellow 180; φ "Paliotol Yellow K0960-HD" made by BASF <Pigment Derivatives> 323842 230 201233734 Derivative 2
φ 衍生物4 [實施例1] (紅色著色組成物(DR-1)) 將下述組成的混合物擾拌混合均勻後,以5 # m之過 323842 231 201233734 遽膜過滤,得到紅色著色組成物(DIM)。 紅色顏料分散體(P_R1) 樹脂溶液(B1-1) 40, 5 份 環己酉同 8· 6份 [實施例2至6及參考例^ 50. 9 份 (紅色著色組成物(J)R-2至γ )) 除將樹脂溶液(B卜i) 外’其餘係與紅色著色組 組成物(DR-2至7)。 [參考例2]φ derivative 4 [Example 1] (Red coloring composition (DR-1)) A mixture of the following composition was mixed and uniformly mixed, and then filtered through a membrane of 5 #m 323842 231 201233734 to obtain a red colored composition. (DIM). Red pigment dispersion (P_R1) Resin solution (B1-1) 40, 5 parts of cyclohexanthene with 8·6 parts [Examples 2 to 6 and reference examples ^ 50. 9 parts (red coloring composition (J) R- 2 to γ)) except for the resin solution (B i), the remaining lines were mixed with the red coloring group composition (DR-2 to 7). [Reference Example 2]
遵更為表D-2所示之樹脂溶液以 成物(D R -1)同樣做法而紅色著色 (紅色著色組成物(DR-8)) 除將紅色顏料分散體(P_R1)變更為紅色顏料分散體 (P-R2)以外’其餘係妹色著色組成物⑽―丨)同樣做法而 紅色著色組成物(DR-8)。 [紅色著色組成物之評估] 有關所得到之紅色著色組成物的色特性、對比度比 (CR)、及塗膜表面之結晶析出,以下述之方法評估。結果 表示於表D - 3。 (色特性、對比度比(CR)評估) 使所付到之紅色著色組成物塗佈於1 〇〇mmxl QQmm、 0.7mm厚的玻璃基板上,在c光源中以使膜厚成為χ=〇 644、 y=0.340(±0.001以内)的方式塗佈,以7(TC熱風烘箱乾燥 20分鐘後’進一步於230°C加熱60分鐘,得到紅色塗膜。 其後’測定所得到之塗佈基板的亮度(Y)及對比度比(CR)。 323842 232 201233734 並且,色度及亮度(Y)是以顯微分光光度計(Olympus 光學公司製「0SP- SP200」)測定。 (塗膜表面之結晶析出評估) 將在色特性、對比度比(CR)評估所得到之基板,進一 步重複2次於240°C加熱處理60分鐘。以光學顯微鏡觀察 加熱處理後之塗佈基板的塗膜表面,依據下述基準評估有 無結晶析出。在評估結果中,◎與〇係無結晶析出為良好, △係有結晶析出但使用上無問題的程度,X係由於結晶析出 ®相當於無法使用之狀態。 ◎ :230°C加熱處理60分鐘後,進一步在240°C加熱處理60 分鐘後,及再進行240°C加熱處理60分鐘,亦無結晶析出 〇:230°C加熱處理60分鐘後,進一步240°C加熱處理60 分鐘亦無結晶析出(第2次之240°C加熱處理60分鐘有結 晶析出) △ :23(TC加熱處理60分鐘無結晶析出,但進一步240°C加 φ 熱處理60分鐘有結晶析出 X: 230°C加熱處理60分鐘後有結晶析出 [表 D-3 ] 表D-3The resin solution shown in Table D-2 was colored red in the same manner as the product (DR-1) (red coloring composition (DR-8)) except that the red pigment dispersion (P_R1) was changed to red pigment dispersion. The red coloring composition (DR-8) is the same as the "other coloring composition (10) - 丨) other than the body (P-R2). [Evaluation of Red Colored Composition] The color characteristics, the contrast ratio (CR) of the obtained red colored composition, and the crystallization of the surface of the coating film were evaluated by the following methods. The results are shown in Table D-3. (Color property, contrast ratio (CR) evaluation) The red coloring composition was applied to a glass substrate of 1 mm×10×10 mm thick and 0.7 mm thick, and the film thickness was made to be χ=〇644 in the c light source. Applying y = 0.340 (within ± 0.001), and drying at 7 (TC hot air oven for 20 minutes) and further heating at 230 ° C for 60 minutes to obtain a red coating film. Thereafter, the obtained coated substrate was measured. Brightness (Y) and contrast ratio (CR) 323842 232 201233734 Further, chromaticity and luminance (Y) were measured by a microspectrophotometer ("0SP-SP200" manufactured by Olympus Optics Co., Ltd.). (Crystal precipitation on the surface of the coating film) Evaluation) The substrate obtained by evaluation of color characteristics and contrast ratio (CR) was further subjected to heat treatment at 240 ° C for 60 minutes twice. The surface of the coating film of the coated substrate after heat treatment was observed by an optical microscope, according to the following. The evaluation was carried out to determine whether or not crystals were precipitated. In the evaluation results, ◎ and lanthanide crystals were not precipitated well, △ was crystallized, but there was no problem in use, and X-based crystallization was equivalent to an unusable state. ◎ : 230 °C heat treatment 6 After 0 minutes, further heat treatment at 240 ° C for 60 minutes, and further heat treatment at 240 ° C for 60 minutes, no crystal precipitation 〇: heat treatment at 230 ° C for 60 minutes, and further heat treatment at 240 ° C for 60 minutes No crystal precipitation (the second 240 ° C heat treatment for 60 minutes, crystal precipitation) △: 23 (TC heating treatment for 60 minutes without crystal precipitation, but further 240 ° C plus φ heat treatment for 60 minutes, crystal precipitation X: 230 ° C Crystallization occurred after 60 minutes of heat treatment [Table D-3] Table D-3
參τ_色 著色组成物 红色 顏料分散體 樹脂溶液 亮度(Υ) CR 結晶析出 實施例 1 DR—1 Ρ-1 Β1-1 24.56 10330 ◎ 實施例 2 DR-2 Ρ-1 Β1-2 24.12 11000 ◎ 實施例 3 DR-3 Ρ-1 Β1-3 23.01 10550 ◎ 實施例 4 DR-4 Ρ—1 Β1 —4 23.78 10760 ◎ 實碜例 5 DR-5 Ρ-1 Β1-7 25.61 10620 ◎ 實施例 6 DR-6 Ρ—1 Β1-11 23.88 12020 ◎ 參考例 1 DR-7 Ρ—1 Β2-1 20.02 5390 X 參考例 2 DR-8 Ρ—2 Β1—1 20.96 5690 X 323842 233 201233734 含有式(1)所示之顏料(A1)與具有構成單元(D-bl)至 (D-b3)之樹脂(D-B1)的彩色濾光片用著色組成物任一者均 為高亮度且高對比度比,即使在加熱步驟亦不產生二酮基 吡咯并吡咯系顏料之結晶析出而能得到的良好結果。 [實施例7至31、參考例3至9] [感光性著色組成物(PR-1至32)) 以表D-4至10所示之組成、以調配量混合並攪拌各材料, 以l//m之過濾膜過濾,得到感光性著色組成物(PR-1至 32)。 [表 D-4] «0-4 實施例7 實施W 8 實施例9 實施例ΙΟ 賁施例11 RR-1 RR-2 RR-3 RR-4 RR-5 杈》名 丨重 林»名;重量% «m名:囂營% 树η名 ft% 材料名 重篇% 顏料分散體 P-3 ! 40.5 P-3 · 40.5 P-3 ! 40.5 P-3 40.5 P-3 40.5 榭脂溶液 B1-1 : 24.8 B1—2 J 24.8 B1 -3 ; 24.8 B1-4 24.8 B1-5 24.8 光聚合起始#I(D> D6 : 0.77 D6 ! 0.77 D6 ! 0.77 06 0.77 D6 0.77 增感射(ε> : : 先聚合性化合物(C) C1 : 5.25 C1 : S.25 C1 : 5.25 C1 5.25 C1 S.25 多官毖硫睁(F) · ί • 1 紫外線吸收谢(G) < 1 • 貯a安定剤(j〉 • 1 溶劑 PGMAC · 28.88 PGMAC ; 28.68 PGMAC i 28.68 PGMAC 28.68 PGMAC 28.68 合計 : 100 100: 100 100: 100 100 100 100 100 [表 D-5] >0-5 實施例12 f施例13 J*施例14 贫施例15 r施例16 RR-6 RR-7 RR-8 RR-9 RR-10 材料名 置量% 材名 霣置H 料料名 MM2L ggA__ mm% 顏料分散體 Ρ-3 40.5 P-3 40.5 P-3 40.5 P-3 40.S P-3 40.S 樹脂溶液 Β1-6 24.B B1-7 B卜10 Θ.6 16.2 B1-8 24.8 B1-9 24.8 B1-10 24.8 光聚合起始劑(D) DA 0.77 Οβ 0.77 D6 0.77 D6 0.77 D6 0.77 1先聚合性化合物(C) 1 C1______ 5.25 Cl 5.25 Cl 5^5 C1 5.25 C1 5.25 多官能葙薛(F> 紫外線吸收劑(G> 貯藏安定射ω) 溶$ PGMAC 28.ββ PGMAC 28.68 PGMAC 28.68 PGMAC 28.68 PGMAC 28.68 合計 i 100 1 i 1001 1 1 1001 II 1001 ί 100 234 323842 201233734 [表 D-6] 表D-β 實施例17 貫施例18 實施例19 實施例20 1★施例21 ~ RR-11 RR-12 RR—13 RR-14 IrR~15 料》名 tn isizUimmn xmiinimmn 1 ΏΕΕΠΏΗ 顏料分散體 P-3 :40.5 P-3 : 40.5 P-3 : 40.5 P-3 : 40.5 P-3 :40.5 * B1-9 ; β.4 B1-11 : 8.4 1 榭脂溶液 BT-11 ;24.8 B1-12 : 24.8 B1-11 : 8.4 B1-12 : 8.4 Bl-15 :24.8 • • Θ1-13 : 8 Bl-14 : β 光聚合起始劊(D> D6 • 0.77 D8 1 0.77 Οβ i 0.77 D6 ! 0.77 D6 • 0.77 Jfifl-KE) 1 : 1 1 : 1 1 : 1 El : 0.3 先裝合性化合物(C) IC1 ί 5.251 IC1 Ϊ 5.25i Cl : 5.25 lei ϊ 5^51 Cl ί 5.25 多官雉硫醇(F*) : 1 » * 丨 FI ! 1 紫外線吸收剤(G〉 1 » • j Q1 ί 0.22 貯藏安定谢(J) 1 • J1 ! 0.25 溶 IPGMAC :28.6BI IPGMAC : 28.661 PGMAC : 28.68 IPGMAC : 28.68! PGMAC ί 27.91 合計 1 ί 1001 I ί 1001 ? 100 1 ί 1001 1 i 1001 [表 D-7] *D-7 霄施例22 賁施例23 賞施例24 貲施例之5 實施例2β RR-16 RR —17 RR-18 RR 一 19 RR-20 lliUWM ;重置% 材料名 i重量% 封拉皂 z重量% 親料分散體 P-5 ί 35.6 P-6 ; 29.6 P-7 36.4 P-8 ;3β.4 P-9 3β.β 榭脂溶液 B1-1 ! is.e B1-1 ! 22.4 B1-1 18.9 B1-1 ! 36 B1-1 27.2 先聚合起始制(D) D1 : 0.75 D2 : 0.25 D3 0.63 D4 ! 1.22 DS 0.82 礒a劑(ε) Et ;0.25 E2 : 0 33 1 ί 1 1 : 1 光聚合性化合物(C) Cl j 4.4β C1 • 2.89 C1 5.53 IC1 5.551 Cl 4.35 1多官陡硫酵(F) ! 1 1 : 1 F1 0.63 F2______ 0.33 F3 0.51 紫外線致收制(〇> IG1 : 0.25! G2 0.25 貯ά安定剤(j> I ! I I ! I 溶费 1 IPGMAC ;39.341 IPGMAC :44.281 IPGMAC ;37.661 IPGMAC :20.5! PGMAC 28.32 合计 1 i 1001 I ! 1001 I ! 1001 1 ! 1001 1 i 1001Ττ_color coloring composition red pigment dispersion resin solution brightness (Υ) CR crystallization precipitation Example 1 DR-1 Ρ-1 Β1-1 24.56 10330 ◎ Example 2 DR-2 Ρ-1 Β1-2 24.12 11000 ◎ Example 3 DR-3 Ρ-1 Β1-3 23.01 10550 ◎ Example 4 DR-4 Ρ-1 Β1 -4 23.78 10760 ◎ Example 5 DR-5 Ρ-1 Β1-7 25.61 10620 ◎ Example 6 DR -6 Ρ—1 Β1-11 23.88 12020 ◎ Reference example 1 DR-7 Ρ—1 Β2-1 20.02 5390 X Reference example 2 DR-8 Ρ—2 Β1—1 20.96 5690 X 323842 233 201233734 Contains formula (1) Any of the coloring compositions for the color filter (A1) and the resin (D-B1) having the constituent units (D-bl) to (D-b3) are high in brightness and high in contrast ratio, even if Good results were obtained without precipitation of crystals of the diketopyrrolopyrrole pigment in the heating step. [Examples 7 to 31, Reference Examples 3 to 9] [Photosensitive coloring composition (PR-1 to 32)) The compositions shown in Tables D-4 to 10 were mixed and stirred in a blending amount to obtain The filter membrane of //m was filtered to obtain a photosensitive coloring composition (PR-1 to 32). [Table D-4] «0-4 Example 7 Implementation W 8 Example 9 Example 贲 Example 11 RR-1 RR-2 RR-3 RR-4 RR-5 杈》名丨重林» Name; Weight % «m name: 嚣营% tree η name ft% material name heavy weight % pigment dispersion P-3 ! 40.5 P-3 · 40.5 P-3 ! 40.5 P-3 40.5 P-3 40.5 blush solution B1- 1 : 24.8 B1—2 J 24.8 B1 -3 ; 24.8 B1-4 24.8 B1-5 24.8 Photopolymerization start #I(D> D6 : 0.77 D6 ! 0.77 D6 ! 0.77 06 0.77 D6 0.77 Sensitizing shot (ε > : : First polymerizable compound (C) C1 : 5.25 C1 : S.25 C1 : 5.25 C1 5.25 C1 S.25 Multi-manganese sulfonium (F) · ί • 1 UV absorption X (G) < 1 • Storage a stable剤(j> • 1 Solvent PGMAC · 28.88 PGMAC; 28.68 PGMAC i 28.68 PGMAC 28.68 PGMAC 28.68 Total: 100 100: 100 100: 100 100 100 100 100 [Table D-5] >0-5 Example 12 f Example 13 J*Example 14 Lean application 15 r Example 16 RR-6 RR-7 RR-8 RR-9 RR-10 Material Name Quantity % Material Name Setting H Material Name MM2L ggA__ mm% Pigment DispersionΡ -3 40.5 P-3 40.5 P-3 40.5 P-3 40.S P-3 40.S Resin solution Β1- 6 24.B B1-7 B Bu 10 Θ.6 16.2 B1-8 24.8 B1-9 24.8 B1-10 24.8 Photopolymerization initiator (D) DA 0.77 Οβ 0.77 D6 0.77 D6 0.77 D6 0.77 1 polymerizable compound ( C) 1 C1______ 5.25 Cl 5.25 Cl 5^5 C1 5.25 C1 5.25 Polyfunctional ( (F> UV Absorber (G> Storage Stabilization ω) Dissolved $ PGMAC 28.ββ PGMAC 28.68 PGMAC 28.68 PGMAC 28.68 PGMAC 28.68 Total i 100 1 i 1001 1 1 1001 II 1001 ί 100 234 323842 201233734 [Table D-6] Table D-β Example 17 Example 18 Example 19 Example 20 1 ★ Example 21 ~ RR-11 RR-12 RR— 13 RR-14 IrR~15 Material Name tn isizUimmn xmiinimmn 1 颜料 Pigment dispersion P-3 : 40.5 P-3 : 40.5 P-3 : 40.5 P-3 : 40.5 P-3 : 40.5 * B1-9 ; β. 4 B1-11 : 8.4 1 Rouge solution BT-11; 24.8 B1-12 : 24.8 B1-11 : 8.4 B1-12 : 8.4 Bl-15 : 24.8 • • Θ1-13 : 8 Bl-14 : β photopolymerization Start (D> D6 • 0.77 D8 1 0.77 Οβ i 0.77 D6 ! 0.77 D6 • 0.77 Jfifl-KE) 1 : 1 1 : 1 1 : 1 El : 0.3 Compound (C) IC1 ί 5.251 IC1 Ϊ 5.25i Cl : 5.25 lei ϊ 5^51 Cl ί 5.25 Multi-manganese thiol (F*) : 1 » * 丨FI ! 1 UV absorption 剤 (G > 1 » • j Q1 ί 0.22 Storage Ding Xie (J) 1 • J1 ! 0.25 Dissolved IPGMAC : 28.6BI IPGMAC : 28.661 PGMAC : 28.68 IPGMAC : 28.68! PGMAC ί 27.91 Total 1 ί 1001 I ί 1001 ? 100 1 ί 1001 1 i 1001 [Table D -7] *D-7 霄 Example 22 贲 Example 23 Reward Example 24 赀 Example 5 Example 2 β RR-16 RR —17 RR-18 RR -19 RR-20 lliUWM ; Reset % Material Name i % by weight Sealing soap z% by weight Proxies dispersion P-5 ί 35.6 P-6 ; 29.6 P-7 36.4 P-8 ; 3β.4 P-9 3β.β Rouge solution B1-1 ! is.e B1 -1 ! 22.4 B1-1 18.9 B1-1 ! 36 B1-1 27.2 First polymerization start system (D) D1 : 0.75 D2 : 0.25 D3 0.63 D4 ! 1.22 DS 0.82 礒a agent (ε) Et ; 0.25 E2 : 0 33 1 ί 1 1 : 1 Photopolymerizable compound (C) Cl j 4.4β C1 • 2.89 C1 5.53 IC1 5.551 Cl 4.35 1 Multi-dense sulphur fermentation (F) ! 1 1 : 1 F1 0.63 F2______ 0.33 F3 0.51 UV-induced System (〇> IG1: 0.25! G2 0.25 Storage stability (j > I ! I I ! I dissolution 1 IPGMAC ; 39.341 IPGMAC : 44.281 IPGMAC ; 37.661 IPGMAC : 20.5! PGMAC 28.32 Total 1 i 1001 I ! 1001 I ! 1001 1 ! 1001 1 i 1001
[表 D-8 ][Table D-8]
ap-Bap-B
T施例27 賁施例28 I實施例29 I 賁施例30 實施例31 RR-21 RR-22 RR-23 RR-24 RR 一 25 材料名 j重置耗 料》名 重量% +重量% 顏枓分散« P—10 :33.6 P-3 33.8 P-3 33.9 P-9 : 43.5 P-3 : 35.B Λ脂溶液 B1-1 :26.7 B1-1 33.1 Β1-Ί 27.6 B1-1 18.3 B1-1 :20.8 D6 ! 0.77 06 0.77 D6 0.77 D6 ! 0.77 D6 :0.77 增感劑(E> I : I I : I 丨: 1 ί : I E1 ! 0.55 电聚合性化合物(C) IC1 i 3.681 IC1 · 4.981 IC1 i 4.681 IC1 ! 4.02I C1 :4.62 多官矩硫择(F) : 1 I : I 1 • _ 1 F1 :Ο.ββ 紫外線吸收劑(G) IQ1 :0.271 IG2 : 0.291 , \ 1 聍ά安定制(J> I : I I : I J1 ;0.33 J2 ; 0.56 I 丨環己酮 :34.7β! IPGMAC : 27.061 PGMAC ! 32.72 PGMAC : 32.85 丨環己酮 :38.BI 合計 丨:1001 I : 1001 I : 1001 1 : 1001 I : 100! [表 D-9] 表D-9 I參考例3 [RR-26 I參考例4 IrR—27^ I參考例5 I參考例 IRR —2 I麥考例 IRR—5 30 顏料分散體 \asmm ί 40.5 P-3 ! 40.5 P-4 38.7 P-4 ! Γ 37.8 榭脂溶液 B2-1 24.8 Β2—2 24.8 B2-3 :24.8 B2-1 33 B2-2 27.9 光聚合起始剤(D) D6 0.77 D6 : 0.77 D6 j 0.77 D6 0.77 D6 · 0.77 增感剌(E) I 1 1 El 0.26 fc聚合性化合物(C) C1 5.25 C1 5.25 C1 :5.25 Cl 4.25 Cl 4.66 ί多官鉅琉酵(F) 1 紫外啟吸收制(G> 貯il安定荆(J> ί J1 0.25 溶劑 PGMAC 28.68 PGMAC : 28.68 環己酮I :28.68 PGMAC 23.02 PGMAC 28.62 合計 100 100 100 100 100 323842 235 201233734 [表 D_ 10 ] 表D-10 參考例 8 參考例 9 RR-31 RR—32 材料名 重置% 材料名 重量% 顏料分散體 ρ一 4 38.9 Ρ—4 34.7 S月旨溶族 Β2—3 30.1 日1一1 20.6 光聚合起始劑(D) D7 0.77 D6 0.77 增感ϋΕ) 光聚合性化合物(C) C1 3.36 多官能硫醇(F) 紫外線吸收劑(G) G1 0.46 貯藏安定劑(J) J2 0.33 溶劑 PGMAC 26.08 環己酮 43.93 合計- 100 100 表D-4至10中之簡稱表示於下。 <光聚合起始劑〇))> 光聚合起始劑D1.· 2-曱基-1-[4-(曱基硫)苯基]-2-嗎啉基 丙烧-1-酮(汽巴日本公司製「Irgacure 907」) 光聚合起始劑D2:2-(二甲基胺基)-2-[ (4-甲基苯基)曱 基]-l-[4-(4-嗎啉基)苯基]-1-丁酮(汽巴日本公司製 「Irgacure 379」) 光聚合起始劑D3:2, 4, 6-三曱基苯曱醯基-二苯基-氧化磷 (BASF 公司製「Lucilin ΤΡ0」) 光聚合起始劑04:2,2’-雙(〇-氯苯基)-4,5,4’,5’-四苯基-1,2’ -聯咪唑(黑金化成公司製「聯咪唑」) 光聚合起始劑D5: p-二曱基胺基乙醯苯(Daiki f ine公司製 「DMA」) 光聚合起始劑D6:乙烷-1-酮,l-[9-乙基-6-(2-甲基苯甲 323842 236 201233734 酿基)-9Η-α卡β坐-3-基],1-(鄰乙酿基肪) (汽巴日本公司製「Irgacure OXE02」) <增感劑> 增感劑E1: 2, 4-二乙基噻吨酮 (日本化藥公司製「Kayacure DETX-S」) 增感劑E2: 4,4’ -雙(二乙基胺基)二笨甲酮 (Hodogaya Chemical 工業公司製「EAB-F」) <光聚合性化合物> ® 光聚合性化合物Cl:二季戊四醇六丙烯酸酯 (東亞合成公司製「Aronix M-402」) <多官能硫醇> 多官能硫醇F1:三羥曱基乙烷參(3-酼基丁酸酯);(昭和電 工公司製「TEMB」) 多官能硫醇F2:三經甲基丙烧參(3-魏基丁酸酯);(昭和電 工公司製「TPMB」) φ 多官能硫醇F3:季戊四醇肆(3-巯基丙酸酯);(堺化學工業 公司製「PEMP」) <紫外線吸收劑> 紫外線吸收劑G1:2-[4-[(2-羥基-3-(十二烷基及十三烷 基)氧基丙基)氧基]-2-羥基苯基]-4, 6-雙(2, 4-二甲基笨 基)-1, 3, 5-三啡 (汽巴日本公司製「TINUVIN 400」) 紫外線吸收劑G2:2-(2H-苯并***-2-基)-4, 6-雙(1-曱基 -1-苯基乙基)酚;(汽巴日本公司製rTINUVIN 900」) 323842 237 201233734 <貯存安定劑> 貯存安定劑Jl:2, 6-雙(1,卜二曱基乙基)_4_甲基酚(本州 化學工業公司製「BHT」) 貯存安定劑J2:三苯基膦 (北興化學工業公司製「τρρ」) <溶劑> PGMAC:丙二醇單曱基醚醋酸醋 [感光性著色組成物之評估] 對於所得到之感光性著色組成物(pR_l至32),藉由 如下之方法評估色特性、對比度比(CR)、塗膜表面之結晶 析出、感度、直線性、圖案形狀、解像度、耐顯像性、耐 藥品性、經時安定性。結果表示於表D-ii中。在各評估結 果的判定,◎係非常良好的程度,〇係良好的程度,△係 不阻礙使用之程度,X係使用上不佳之程度。 (色特性、對比度比(CR)評估) 使所得到之紅色著色組成物塗佈於lOOmmxlOOmm、 0. 7mm厚的玻璃基板上,在c光源中後處理後以使膜厚成 為χ=0· 640、及y=0. 328的方式塗佈,以7(rc熱風烘箱乾 燥20分鐘後,使用超高壓水銀燈,以累積光量150mJ進行 紫外線曝光後,以23(TC加熱1小時而放置冷卻,得到紅 色塗膜°其後’測定所得到之塗佈基板的亮度(γ)及對比度 比(CR)。 並且’色度及亮度(Y)係以顯微分光光度計(〇lympus 光學公司製「OSP-SP200」)測定。 323842 238 201233734 (塗膜表面之結晶析出評估) 將以色特性、對比度比(CR)評估所得到之基板,進一 步在260°C加熱H、時而放置冷卻。以光.學顯微鏡觀察加 熱處理後之塗佈基板的塗膜表面’依據下述基準評估有無 結晶析出。在評估結果中,◎係無結晶析出為非常良好, 〇係有少量結晶析出但為良好的程度,△係有結晶析出但 使用上無問題的程度,X係由於無法結晶析出為無法使用的 程度。 ◎:結晶數為0個 〇:結晶數為1個以上、未達10個 △:結晶數為10個以上、未達100個 X :結晶數為100個以上 (感度、直線性、圖案形狀、解像度、耐顯像性、耐藥品性 評估) 使所得到之感光性著色組成物塗佈於1QQmm咖職、 春〇.7iim厚的玻璃基板上之後,在無塵烘箱中以7〇ΐ加溫2〇 分鐘而除去溶劑,得到約2# m之塗膜。然後,使此基板冷 卻至室溫後’使用超高壓水銀燈,隔著1〇〇/zm寬(間=2〇7〇 #m)及25/zm(間距50//m)條狀的遮罩而曝光於紫外線。其 後,於此基板使用23°C之碳酸鈉水溶液而喷塗顯像後,以 離子交換水洗淨並風乾,無塵烘箱中以23〇〇c加熱八 鐘。喷塗顯像係對於各感光性著色組成物的塗膜,無顯像 殘留而以可形成圖案的最短時間進行,以此作為適:顯 時間。 ‘ 323842 239 201233734 塗膜之膜厚係使用Dektak3_(日本真空技術公司製 而進行。 (感度評估) 二方法所形成之濾、光片段的ioo"m遮罩 最i曝^ Γ評估相對於塗佈後膜厚成為_以上之 光量愈小,成為高感度良好的感光性 者色、、且成# 估之等級係如下述。 〇:未達50mJ/cm2 △ : 50mJ/cm2 以上、未達 1〇〇mj/cm2 X: 100mJ/cm2 以上 (直線性評估) 有關藉由上述方法所形成之渡光片 部分之圖案,使用光學顯撒# Mm遮罩 級係如下述。先予.、、、頁微鏡觀察而進行評估。評估之等T Example 27 Example 28 I Example 29 I Example 30 Example 31 RR-21 RR-22 RR-23 RR-24 RR a 25 Material name j Reset consumption "Name weight % + weight %枓Dispersion « P-10 : 33.6 P-3 33.8 P-3 33.9 P-9 : 43.5 P-3 : 35.B blush solution B1-1 : 26.7 B1-1 33.1 Β 1-Ί 27.6 B1-1 18.3 B1- 1 : 20.8 D6 ! 0.77 06 0.77 D6 0.77 D6 ! 0.77 D6 : 0.77 Sensitizer (E> I : II : I 丨: 1 ί : I E1 ! 0.55 Electropolymerizable compound (C) IC1 i 3.681 IC1 · 4.981 IC1 i 4.681 IC1 ! 4.02I C1 :4.62 Multi-sense Moisture Selection (F) : 1 I : I 1 • _ 1 F1 : Ο.ββ UV Absorber (G) IQ1 :0.271 IG2 : 0.291 , \ 1 (J> I : II : I J1 ; 0.33 J2 ; 0.56 I 丨 Cyclohexanone: 34.7β! IPGMAC : 27.061 PGMAC ! 32.72 PGMAC : 32.85 Cyclohexanone: 38.BI Total 丨: 1001 I : 1001 I : 1001 1 : 1001 I : 100! [Table D-9] Table D-9 I Reference Example 3 [RR-26 I Reference Example 4 IrR-27^ I Reference Example 5 I Reference Example IRR — 2 I McGrade IRR-5 30 Pigment Dispersion\asmm ί 40.5 P-3 ! 40.5 P-4 38.7 P-4 ! Γ 37. 8 Rouge solution B2-1 24.8 Β2-2 24.8 B2-3 : 24.8 B2-1 33 B2-2 27.9 Photopolymerization start 剤 (D) D6 0.77 D6 : 0.77 D6 j 0.77 D6 0.77 D6 · 0.77 Sensitized 剌 ( E) I 1 1 El 0.26 fc polymerizable compound (C) C1 5.25 C1 5.25 C1 : 5.25 Cl 4.25 Cl 4.66 ί 官 琉 ( ( ( 紫外 紫外 紫外 紫外 紫外 紫外 紫外 紫外 紫外 紫外 紫外 紫外 紫外 紫外 紫外 紫外 紫外 紫外 紫外 紫外 紫外 紫外 紫外 紫外 紫外 紫外 紫外 紫外 ( ( ( J1 0.25 Solvent PGMAC 28.68 PGMAC : 28.68 Cyclohexanone I : 28.68 PGMAC 23.02 PGMAC 28.62 Total 100 100 100 100 100 323842 235 201233734 [Table D_ 10 ] Table D-10 Reference Example 8 Reference Example 9 RR-31 RR—32 Material Name Reset % Material Name Weight % Pigment Dispersion ρ - 4 38.9 Ρ - 4 34.7 S Month Solvent Β 2 - 3 30.1 Day 1 - 1 20.6 Photopolymerization Starter (D) D7 0.77 D6 0.77 Sensitization ϋΕ) Photopolymerization Compound (C) C1 3.36 Polyfunctional thiol (F) UV absorber (G) G1 0.46 Storage stabilizer (J) J2 0.33 Solvent PGMAC 26.08 Cyclohexanone 43.93 Total - 100 100 Tables D-4 to 10 Expressed below. <Photopolymerization initiator 〇))> Photopolymerization initiator D1.· 2-mercapto-1-[4-(indolylthio)phenyl]-2-morpholinylpropan-1-one ("Irgacure 907" manufactured by Ciba Japan Co., Ltd.) Photopolymerization initiator D2: 2-(dimethylamino)-2-[(4-methylphenyl)fluorenyl]-l-[4-(4 -morpholinyl)phenyl]-1-butanone ("Irgacure 379" manufactured by Ciba Japan Co., Ltd.) Photopolymerization initiator D3: 2, 4, 6-trimercaptophenyl-diphenyl-oxidation Phosphorus ("Lucilin ΤΡ0", manufactured by BASF Corporation) Photopolymerization initiator 04: 2,2'-bis(〇-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2' - Biimidazole ("Biimidazole" manufactured by Heijin Chemical Co., Ltd.) Photopolymerization initiator D5: p-didecylaminoethyl benzene ("DMA" manufactured by Daiki F ine Co., Ltd.) Photopolymerization initiator D6: ethane-1 -ketone, l-[9-ethyl-6-(2-methylbenzone 323842 236 201233734 brewing base)-9Η-α卡β坐-3-yl], 1-(o-ethylidene) (steam) "Irgacure OXE02" manufactured by Baline Co., Ltd. <sensitizer> Sensitizer E1: 2, 4-diethylthioxanthone (Kayacure DETX-S, manufactured by Nippon Kayaku Co., Ltd.) Sensitizer E2: 4 , 4'-bis(diethylamino)dibenzophenone (H "EAB-F" manufactured by Odogaya Chemical Co., Ltd. <Photopolymerizable compound> ® Photopolymerizable compound Cl: Dipentaerythritol hexaacrylate ("Aronix M-402" manufactured by Toagosei Co., Ltd.) <Multifunctional thiol> Polyfunctional thiol F1: trihydroxy decyl ethane ginate (3-mercaptobutyrate); ("TEMB" manufactured by Showa Denko Co., Ltd.) Polyfunctional thiol F2: trimethyl methacrylate (3-Wikidin) Acid ester); (TPMB) manufactured by Showa Denko Co., Ltd. φ Polyfunctional thiol F3: pentaerythritol lanthanum (3-mercaptopropionate); ("PEMP" manufactured by Sigma Chemical Industry Co., Ltd.) <Ultraviolet absorbing agent> Ultraviolet absorption Agent G1: 2-[4-[(2-hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis (2) , 4-dimethylphenyl)-1,3, 5-triphthol ("TINUVIN 400" manufactured by Ciba Japan) UV absorber G2: 2-(2H-benzotriazol-2-yl)-4 , 6-bis(1-mercapto-1-phenylethyl)phenol; (rTINUVIN 900, manufactured by Ciba Japan) 323842 237 201233734 <Storage stabilizer> Storage stabilizer Jl: 2, 6-double ( 1, di-diylethyl)_4_methylphenol (this "BHT" manufactured by Chemical Industry Co., Ltd. Storage stabilizer J2: Triphenylphosphine ("τρρ", manufactured by Kitagawa Chemical Co., Ltd.) <Solvent> PGMAC: Propylene glycol monodecyl ether acetate vinegar [Evaluation of photosensitive coloring composition] With respect to the obtained photosensitive colored composition (pR_1 to 32), color characteristics, contrast ratio (CR), crystal precipitation on the surface of the coating film, sensitivity, linearity, pattern shape, resolution, and image formation were evaluated by the following methods. Sex, chemical resistance, stability over time. The results are shown in Table D-ii. In the judgment of each evaluation result, ◎ is very good, the degree of lanthanism is good, △ is not inhibited from use, and X is not used to the extent. (Color property, contrast ratio (CR) evaluation) The obtained red coloring composition was applied onto a glass substrate of 100 mm×100 mm and 0.7 mm thick, and post-treated in a c light source so that the film thickness became χ=0·640. And y = 0.28, and dried in a 7 (rc hot air oven for 20 minutes, using an ultra-high pressure mercury lamp, ultraviolet light exposure at a cumulative light amount of 150 mJ, and then left at 23 (TC heating for 1 hour) to obtain a red color. After the coating film was measured, the brightness (γ) and the contrast ratio (CR) of the obtained coated substrate were measured. The 'chromaticity and brightness (Y) were measured by a microspectrophotometer ("OSP-" manufactured by 〇lympus Optics Co., Ltd. SP200") 323842 238 201233734 (Evaluation of crystal precipitation on the surface of the coating film) The substrate obtained by evaluation of the color characteristics and contrast ratio (CR) was further heated at 260 ° C, and then left to cool. The surface of the coating film of the coated substrate after the heat treatment was observed under the microscope. The presence or absence of crystal precipitation was evaluated according to the following criteria. In the evaluation results, no crystals were precipitated very well, and a small amount of crystals were precipitated in the lanthanum, but the degree of goodness was good. Have a knot The degree of crystallization is 0, and the number of crystals is 0 or less, and the number of crystals is less than 10, and the number of crystals is 10 or more. Less than 100 X: The number of crystals is 100 or more (sensitivity, linearity, pattern shape, resolution, development resistance, and chemical resistance). The obtained photosensitive coloring composition is applied to 1QQmm. After springing on a 7iim thick glass substrate, the solvent was removed by heating at 7 Torr for 2 Torr in a dust-free oven to obtain a coating film of about 2 # m. Then, after cooling the substrate to room temperature, 'use The ultra-high pressure mercury lamp is exposed to ultraviolet rays through a strip of 1 〇〇/zm width (between 2〇7〇#m) and 25/zm (pitch 50//m). Thereafter, the substrate is used. After spraying with a sodium carbonate aqueous solution at 23 ° C, it was washed with ion-exchanged water and air-dried, and heated in a dust-free oven at 23 ° C for eight minutes. The spray imaging system was applied to each photosensitive coloring composition. The film, without image retention, is carried out in the shortest time that can be patterned, as a suitable time: '323842 239 201233734 Film thickness of the coating film was carried out using Dektak3_ (manufactured by Nippon Vacuum Technology Co., Ltd. (sensitivity evaluation). The io"m mask of the filter and light fragments formed by the two methods is the most exposed. The smaller the amount of light becomes _ or more, the higher the sensitivity is, the higher the sensitivity is, and the rating is as follows. 〇: Less than 50mJ/cm2 △ : 50mJ/cm2 or more, less than 1〇〇mj /cm2 X: 100 mJ/cm2 or more (straightness evaluation) Regarding the pattern of the portion of the light-receiving sheet formed by the above method, the optical display is used as follows. The evaluation was performed by micro-mirror observation of ., , and page. Evaluation
〇:直線性良好 △:部分的直線性不良 X:直線性不良 (圖案形狀評估) V m遮罩 評估。圖 有關藉由上財法卿叙Μ諸的u :分之圖案的剖面’❹電子顯微鏡觀察而進 案剖面係順錐體為良好。評估之等級係如下述 〇:剖面為順錐狀形狀 X:剖面係逆錐狀形狀 (解像性評估) 323842 240 201233734 有關藉由上述方法所形成之濾光片段的心 为之圖案,使用光學顯微鏡觀察而進行評估。評估之。 係如下述。解像性不良是指鄰接之直線圖案為連接= 生缺陷。評估之等級係如下述。 5 ◎:解像性及直線性良好 〇:直線性方面略差,但解像性良好 △:部分解像性不良 X:解鄉性不良 (耐顯像性評估) 、嗔塗顯像時㈣當時間的2倍進行顯像,測定所形成 2光片段的議_遮罩部分之圖案膜厚’相較於以適當 ,員像時_像所形成的圖案膜厚。評估之等級係如下述。 ◎:膜厚差20%以内 〇:膜厚差大於20%,40%以内 △:膜厚差大於40% x:以2倍顯像產生缺陷或剝落 (耐藥品性評估) 將藉由上述方法所形成之濾光區段浸潰於N-曱基吡 各燒綱溶液30份鐘後’以離子交換水洗淨並風乾,對於 100以"1遮罩部分之圖案,使用光學顯微鏡觀察而進行評 估。評估之等級係如下述。 ◎.外觀、色無變化,為良好 〇:一部分產生皺紋,但色無變化、良好 △:產生若干顏色脫落 323842 241 201233734 χ:產生剝落或色脫落 (著色組成物之經時安定性評估) 對於所得到之感光性著色組成物,測定初期及室溫1 個月後之黏度,算出鄉對於初期黏度之黏度增加情形而進 行評估。評估之等級如下述。 (經時黏度變化率)=| [(初期黏度)-(經時黏度)]/(初期黏 度)|χ100«) ◎:黏度增加之比率大於5%以下為良好 〇:黏度增加之比率大於5%及10%以下 X:黏度增加之比率大於10% [表 D-l 1 ] 表 D-11 (評估1) 亮度Υ (評估2) 對比度 (評估3) 结晶析出 (评估4) 感度 (評估5) 直婊性 (評估6) 9索形狀 (評估7) 解像度 (評怙8) 耐顯像性 (評诂9) 耐第品性 (評估10) &時安定性 實施例7 23.6 5250 〇 〇 〇 ❺ © 〇 ο 實施例8 23.5 5060 9 0 〇 〇 d 〇 ο 實施例β 212 4980 9 〇 0 0 <9 0 ο 實施例10 23^ 5030 〇 0 〇 〇 〇 <9 0 ο 實旄例Ή 23.1 5170 0 0 〇 〇 〇 〇 〇 ο 實施例12 23.Β 5030 ❺ 〇 〇 〇 ❹ 〇 ο 實旄例13 24.8 4950 〇 〇 〇 〇 〇 〇 d ο 實旄例14 24.8 4810 〇 〇 〇 〇 〇 β Φ ο 賞旄例15 24.2 5110 0 0 0 0 〇 d ο 實铯例1β 24.2 4920 〇 〇 〇 〇 〇 〇 ο ο 實旄例17 23<3 5820 〇 〇 〇 〇 〇 ❺ ο 實施例18 23.5 5220 〇 0 〇 0 0 ο 賁施例19 24.4 5640 〇 〇 0 〇 〇 ο ο 實施例20 23.3 5460 〇 〇 〇 0 @ 實施例21 25.0 4890 〇 〇 〇 〇 ο 〇 ο ο 實硃例22 23.8 5070 ❺ 〇 0 0 〇 〇 ο ο 實脒例23 23.3 4740 〇 Ο ' 〇 〇 〇 ο ο 實施例24 24.0 5070 〇 〇 〇 〇 〇 〇 ο ο 實花例25 23.5 4930 〇 〇 0 0 〇 ο ο 實旄例2β 22.9 4Β20 ❸ 〇 〇 〇 〇 〇 ο ο 實滅例27 23.0 5120 ❹ 〇 〇 〇 〇 ❾ ο ο 實旄例28 23.6 4910 〇 0 〇 e & ο ο 實施例29 22.9 5290 ο 〇 〇 〇 Θ ⑪ ο ❹ 實旄例30 23.9 5020 〇 〇 〇 〇 ο 實施例31 23.Θ 4750 ❾ 〇 〇 0 ο ο 麥考例3 2Ζ2 4520 X 〇 〇 X 厶 〇 9 ο 麥考例4 21.0 4550 Δ 〇 〇 〇 〇 〇 Δ ο 參考例5 23.0 3290 Δ 〇 0 0 〇 〇 d X 麥考例6 20.8 4470 X 〇 Δ 厶 〇 ο ο 參考例7 20.0 4480 〇 〇 Δ 〇 〇 〇 厶 9 參考例8 20.7 3400 厶 Δ 厶 〇 〇 厶 ο ο 參考例9 21.7 4540 厶 X X X X X X ο〇: Good linearity △: Partial linearity defect X: Poor linearity (pattern shape evaluation) V m mask Evaluation. The cross-section of the cross-section is good by the electron microscopic observation of the section of the u: division pattern of the above-mentioned financial secretary. The rating is as follows: the cross section is a tapered shape X: the cross section is an inverse tapered shape (resolution evaluation) 323842 240 201233734 The pattern of the heart of the filter segment formed by the above method is used. Evaluation was performed by optical microscopy. Evaluation. It is as follows. A poor resolution means that the adjacent straight line pattern is a connection = a defect. The rating of the assessment is as follows. 5 ◎: Good resolution and linearity 〇: The linearity is slightly poor, but the resolution is good. △: Partial resolution is poor. X: Defectiveness of the hometown (difference assessment). When the smear is applied (4) When the development was performed twice as much as the time, the pattern thickness of the mask portion of the formed two-light portion was measured as compared with the pattern thickness of the pattern formed by the appropriate image. The rating of the assessment is as follows. ◎: film thickness difference within 20% 〇: film thickness difference is greater than 20%, within 40% △: film thickness difference is greater than 40% x: defect or flaking by 2 times imaging (anti-drug evaluation) will be by the above method The formed filter section was impregnated with N-mercaptopyrazine solution for 30 minutes, and then washed with ion-exchanged water and air-dried. For 100, the pattern of the mask portion was observed with an optical microscope. to evaluate. The rating of the assessment is as follows. ◎. Appearance, color, no change, good 〇: a part of wrinkles, but no change in color, good △: some color shedding 323842 241 201233734 χ: peeling or color shedding (evaluation of the stability of the coloring composition) The obtained photosensitive coloring composition was measured for viscosity at the initial stage and room temperature after one month, and the hometown was evaluated for the increase in viscosity of the initial viscosity. The rating is as follows. (Change rate of viscosity over time) =| [(Initial viscosity) - (time-dependent viscosity)] / (initial viscosity)|χ100«) ◎: The ratio of viscosity increase is more than 5% or less is good 〇: the ratio of viscosity increase is greater than 5 % and less than 10% X: The ratio of viscosity increase is greater than 10% [Table Dl 1 ] Table D-11 (Evaluation 1) Brightness Υ (Evaluation 2) Contrast (Evaluation 3) Crystallization (Evaluation 4) Sensitivity (Evaluation 5) Straight婊 (Evaluation 6) 9 Cable shape (Evaluation 7) Resolution (Evaluation 8) Resistance to imaging (Evaluation 9) Resistance to first product (Evaluation 10) & Stability Example 7 23.6 5250 〇〇〇❺ © 〇ο Example 8 23.5 5060 9 0 〇〇d 〇ο Example β 212 4980 9 〇0 0 <9 0 ο Example 10 23^ 5030 〇0 〇〇〇<9 0 ο Example Ή 23.1 5170 0 0 〇〇〇〇〇ο Example 12 23.Β 5030 ❺ 〇〇〇❹ 〇ο Example 13 24.8 4950 〇〇〇〇〇〇d ο Example 14 24.8 4810 〇〇〇〇〇β Φ ο 赏 Example 15 24.2 5110 0 0 0 0 〇d ο Example 1β 24.2 4920 〇〇〇〇〇〇ο ο Example 17 23<3 5820 〇〇〇〇〇❺ ο Embodiment 18 23.5 5220 〇0 〇0 0 ο 贲Example 19 24.4 5640 〇〇0 〇〇ο ο Example 20 23.3 5460 〇〇〇0 @Example 21 25.0 4890 〇〇〇〇ο 〇ο ο 22 23.8 5070 ❺ 〇0 0 〇〇ο ο Example 23 23.3 4740 〇Ο ' 〇〇〇ο ο Example 24 24.0 5070 〇〇〇〇〇〇ο ο Real flower example 25 23.5 4930 〇〇0 0 〇ο ο 实 Example 2β 22.9 4Β20 ❸ 〇〇〇〇〇ο ο 实例27 23.0 5120 ❹ 〇〇〇〇❾ ο ο 实例28 23.6 4910 〇0 〇e & ο ο Example 29 22.9 5290 ο 〇 〇〇Θ 11 ο ❹ Example 30 23.9 5020 〇〇〇〇ο Example 31 23.Θ 4750 ❾ 〇〇0 ο ο Mai test case 3 2Ζ2 4520 X 〇〇X 厶〇9 ο Mai test case 4 21.0 4550 Δ 〇〇〇〇〇Δ ο Reference Example 5 23.0 3290 Δ 〇0 0 〇〇d X Wheat test case 6 20.8 4470 X 〇Δ 厶〇ο ο Reference example 7 20.0 4480 〇〇Δ 〇〇〇厶9 Reference example 8 20.7 3400 厶Δ 厶〇〇厶ο ο Reference Example 9 21.7 4540 厶X X X X X X ο
242 323842 201233734 如表D-11所示,含有式(1)所示之顏料(A1)與具有構 成單元(D〜bl)至(D-b3)之樹脂(D-B1)的彩色濾光片用著色 組成物係在全部之評估得到高水準之評估結果.❶242 323842 201233734 As shown in Table D-11, a color filter containing the pigment (A1) represented by the formula (1) and the resin (D-B1) having the constituent units (D to bl) to (D-b3) The coloring composition is evaluated at all levels to obtain a high level of evaluation results.
亦即’在與顏料(A1)之組合中,在含有許多樹脂 之構成單元(Nbl)之構成中係對比度的提昇與經時安定性 的女疋化,在含有許多樹脂(D-b2)之構成甲係亮度之提昇 與耐藥品性之提昇,在含有許多樹脂(D-b3)之構成中係^ 看出可抑制在加熱步驟之顏料的結晶析出的結果、與抑制 解像度之效果的傾向,但若任—者構成單元滿足特定之含 有比,可得到具有高性能之感光性著色組成物1 =構成單元比,可得到高性能且均衡性良好之彩色渡 系二:==:乙_化合物、鱗 則感度、直線性、解析性更佳系化合物之任—者的組合, 其中,光聚合起始劑(D)為 - -6-(2-曱基笨甲醯基、元-卜明,1-[9-乙基 在感光性著色組成物中係進〜牛〜基]’「(Ο-乙醯基肟)’ 進一步含有多官能硫醇耐顯像性更優異。 顯像性更優異。 ?光性著色組成物中係於耐 又,進一步含有紫外線 係於解像性更優異。 吸收劑之感光性著色組成物中 劑之感光性著色組成物中 又,進一步,含有貯存安定 係於經時安定性更優異。 323842 243 201233734 另外,在參考例3至9的感光性著色組成物中係亮度 或對比度比亦低,在加熱步驟中之顏料的結晶析出或感度 為首之濾光片段的評估等無法得到全部為良好者。 (彩色濾光片之製造) 使感光性著色組成物(P R -1)中之顏料及顏料衍生物的 合計4. 39份,變更成在綠色感光性著色組成物中係C. I. 顏料綠58/C. I.顏料黃150=2. 63份以.76份,在藍色感光 性著色組成物中係C. I.顏料藍15:6/C. I.顏料紫23=3.51 ® 份/0. 88份以外,其餘係與顏料分散體(P-3)同樣地調製顏 料分散體,進一步,使感光性著色組成物(RR-1)之顏料分 散體變更成各色顏料分散體,得到彩色濾光片用綠色感光 性著色組成物、彩色濾光片用藍色感光性著色組成物。 於lOOmmxlOOmm之玻璃基板上以鑄模塗佈法塗佈感光性著 色組成物(RR-1)約m之厚度,在70°C之烘箱内以20分 鐘除去溶劑並乾燥。繼而,使用曝光裝置藉由紫外線進行 ^ 條紋圖案曝光。曝光量係100mJ/cm2。進一步,藉由碳酸 鈉水溶液所構成之顯像液進行喷塗顯像而除去未曝光部分 後,以離子交換水洗淨,以230°C加熱此基板30分鐘而形 成線寬約50 之紅色濾光片段。然後,藉同樣之操作, 於紅色濾光片段之相鄰處使用綠色感光性組成物而形成綠 色濾光片段,繼而,使用藍色感光性著色組成物而形成藍 色濾光片段,於同一玻璃基板上得到具備3色之濾光片段 的彩色濾光片。 若使用以上之彩色濾光片用著色組成物,可製造具有 323842 244 201233734 廣色度範圍的色特性優異,财熱性良好之紅色濾光片段的 尚精細之彩色遽光片。 產業上之利用可能性 若依本發明之實施態樣,提供一種亮度及對比度良好, 即使藉由加熱步驟亦不易引起二酮基吡咯并吡咯系顏料之 結晶析出的彩色濾光片用顏料組成物、著色組成物、及使 用此等之彩色濾光片。 【圖式簡單說明】 參無 【主要元件符號說明】 無That is, in the combination with the pigment (A1), in the constitution of a constituent unit (Nbl) containing a large number of resins, the contrast is improved and the stability over time is determined, and a plurality of resins (D-b2) are contained. In the structure containing a large amount of resin (D-b3), it is seen that the result of suppressing the crystallization of the pigment in the heating step and the effect of suppressing the resolution can be suppressed. However, if any of the constituent units satisfy a specific content ratio, a photosensitive coloring composition having a high performance of 1 = a constituent unit ratio can be obtained, and a high-performance and well-balanced color crossing system can be obtained: ==: B-compound The combination of the sensitivity, the linearity, and the analyticity of the compound, wherein the photopolymerization initiator (D) is - 6-(2-mercapto-carbenyl, meta-bumin 1-[9-ethyl is incorporated into the photosensitive coloring composition, and it is more excellent in the image-forming property of the polyfunctional thiol. Excellent. The light-colored coloring composition is resistant to, and further contains ultraviolet light in the solution. Further, the photosensitive coloring composition of the agent in the photosensitive coloring composition of the absorbent further contains a storage stability system and is more excellent in stability over time. 323842 243 201233734 In addition, the photosensitive materials in Reference Examples 3 to 9 The coloring composition has a low brightness or contrast ratio, and the evaluation of the crystallization of the pigment in the heating step or the evaluation of the filter element with the sensitivity first is not good. (Production of color filter) The total amount of the pigment and the pigment derivative in the coloring composition (PR-1) was 4.39 parts, and it was changed to CI pigment green 58/CI pigment yellow 150=2. 63 parts in the green photosensitive coloring composition. 76 parts, in the blue photosensitive coloring composition, CI Pigment Blue 15:6/CI Pigment Violet 23=3.51 ® parts/0. 88 parts, the other pigments were prepared in the same manner as the pigment dispersion (P-3) In the dispersion, the pigment dispersion of the photosensitive coloring composition (RR-1) is changed to a pigment dispersion of each color to obtain a green photosensitive coloring composition for a color filter, and the color filter is colored with blue color. Composition. at lO The photosensitive substrate (RR-1) was coated with a thickness of about m on a glass substrate of Omm x 1000 mm by a die coating method, and the solvent was removed in an oven at 70 ° C for 20 minutes and dried. Then, an ultraviolet light was used by an exposure device. The stripe pattern was exposed. The exposure amount was 100 mJ/cm 2 . Further, the unexposed portion was removed by spray imaging using a developing solution composed of an aqueous solution of sodium carbonate, and then washed with ion-exchanged water and heated at 230 ° C. The substrate is formed into a red filter segment having a line width of about 50 for 30 minutes. Then, by the same operation, a green photosensitive composition is formed adjacent to the red filter segment to form a green filter segment, and then, A blue color filter was formed using a blue photosensitive coloring composition, and a color filter having three color filter segments was obtained on the same glass substrate. When the coloring composition for a color filter described above is used, a fine color calender having a color filter characteristic of 323842 244 201233734 and a red filter having excellent color characteristics and good heat retention can be produced. INDUSTRIAL APPLICABILITY According to an embodiment of the present invention, there is provided a pigment composition for a color filter which is excellent in brightness and contrast, and which is less likely to cause crystal precipitation of a diketopyrrolopyrrole pigment by a heating step. , a coloring composition, and a color filter using the same. [Simple description of the diagram] References None [Main component symbol description] None
323842 245323842 245
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- 2012-01-27 KR KR1020187020266A patent/KR101942407B1/en active IP Right Grant
- 2012-01-27 KR KR1020187035854A patent/KR101971251B1/en active IP Right Grant
- 2012-01-27 CN CN201280006727.XA patent/CN103339536B/en active Active
- 2012-01-27 WO PCT/JP2012/051888 patent/WO2012102399A1/en active Application Filing
- 2012-01-27 KR KR1020137020929A patent/KR101920285B1/en active IP Right Grant
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TWI736632B (en) * | 2016-06-14 | 2021-08-21 | 南韓商東友精細化工有限公司 | Red colored photosensitive resin composition, color filter and display device having the same |
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TWI510561B (en) | 2015-12-01 |
KR20180083965A (en) | 2018-07-23 |
KR20180135982A (en) | 2018-12-21 |
WO2012102399A1 (en) | 2012-08-02 |
KR101942407B1 (en) | 2019-01-28 |
CN103339536A (en) | 2013-10-02 |
KR101971251B1 (en) | 2019-04-22 |
CN103339536B (en) | 2015-07-22 |
KR101920285B1 (en) | 2018-11-21 |
KR20140037818A (en) | 2014-03-27 |
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