TW201917175A - Azo pigment, coloring material for color filter, coloring composition for color filter, and color filter having high brightness and contrast and high tinting strength - Google Patents
Azo pigment, coloring material for color filter, coloring composition for color filter, and color filter having high brightness and contrast and high tinting strength Download PDFInfo
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- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- G03F7/004—Photosensitive materials
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- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
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- 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
本發明係關於一種彩色濾光片用著色劑、著色組成物、以及使用該著色組成物形成之彩色濾光片,該彩色濾光片用著色劑用於製造彩色液晶顯示裝置及彩色固體攝像元件等所使用之彩色濾光片。 The present invention relates to a colorant for a color filter, a coloring composition, and a color filter formed using the coloring composition. The colorant for a color filter is used for manufacturing a color liquid crystal display device and a color solid-state imaging element. The color filters used.
液晶顯示裝置係藉由使夾於2片偏光板之間的液晶層控制通過第1片偏光板之光的偏光程度,並調控通過第2片偏光板的光量,而進行顯示之顯示裝置。液晶顯示裝置中,使用扭轉向列(TN;Twisted Nematic)型液晶之類型成為主流。作為其他具代表性之液晶顯示裝置之方式,有將一對電極設置於單側基板上而對與基板平行之方向施加電場的面內切換(IPS;In Plane Switching)方式、使具有負介電各向異性之向列液晶進行垂直配向的垂直配向(VA;Vertical Alignment)方式、以及使單軸性相位差膜之光軸相互正交而進行光學補償的光學補償彎曲(OCB;Optically Compensated Bend)方式等,且各個方式均得到實用化。 The liquid crystal display device is a display device that displays a liquid crystal layer sandwiched between two polarizing plates to control the degree of polarization of light passing through the first polarizing plate and regulate the amount of light passing through the second polarizing plate. In a liquid crystal display device, a type using Twisted Nematic (TN) liquid crystal has become the mainstream. Other representative liquid crystal display devices include an in-plane switching (IPS) method in which a pair of electrodes are provided on a single-sided substrate and an electric field is applied in a direction parallel to the substrate. Vertical alignment (VA; Vertical Alignment) method for anisotropic nematic liquid crystals, and optically compensated bends (OCB; Optically Compensated Bend) for optical compensation by orthogonalizing the optical axes of uniaxial retardation films to each other Methods, etc., and each method has been put into practical use.
液晶顯示裝置可藉由在2片偏光板之間設置彩色濾光片而實現彩色顯示。近年來,由於彩色濾光片逐漸用於電視或電腦監視器等,故而對於彩色濾光片之高對比度化、高亮度化之要求不斷提高。 The liquid crystal display device can realize color display by providing a color filter between two polarizing plates. In recent years, since color filters are gradually used in televisions, computer monitors, etc., the requirements for high contrast and high brightness of color filters have been increasing.
彩色濾光片由以下之彩色濾光片構成:於玻璃等透明基板的表面將2種以上之不同色相之微細的帶(條紋)狀的濾光片段平行或交叉地配置而成之彩色濾光片、或者將微細的濾光片段以縱橫固定之排列配置而成之彩色濾光片。濾光片段微細達數微米至數百微米,而且按各色相以預定的排列整齊地配置。 The color filter is composed of the following color filters: a color filter in which two or more fine band (striped) filter segments of two or more different colors are arranged on the surface of a transparent substrate such as glass in parallel or crosswise Light filters, or color filters in which fine filter segments are arranged in a fixed horizontal and vertical arrangement. The filter segments are as fine as several micrometers to hundreds of micrometers, and are arranged neatly in a predetermined arrangement for each hue.
一般而言,彩色液晶顯示裝置中,於彩色濾光片上藉由蒸鍍或濺鍍而形成有透明電極,用以使液晶驅動,進而於該透明電極上形成有配向膜,用以使液晶沿固定方向配向。為了充分地獲得該等透明電極及配向膜的性能,必須於一般為200℃以上、較佳為230℃以上之高溫下形成該等透明電極及配向膜。因此,目前,作為彩色濾光片的製造方法,被稱作顏料分散法之方法成為主流,該方法係以耐光性、耐熱性優異之顏料作為著色劑。 Generally, in a color liquid crystal display device, a transparent electrode is formed on a color filter by evaporation or sputtering to drive the liquid crystal, and an alignment film is formed on the transparent electrode to make the liquid crystal Orientation in a fixed direction. In order to fully obtain the performance of the transparent electrodes and alignment films, the transparent electrodes and alignment films must be formed at a high temperature of generally 200 ° C or higher, preferably 230 ° C or higher. Therefore, currently, as a method for manufacturing a color filter, a method called a pigment dispersion method has become mainstream, and this method uses a pigment having excellent light resistance and heat resistance as a colorant.
作為對彩色濾光片所要求之品質項目,可列舉亮度及對比率。若使用對比率低之彩色濾光片,則會使液晶所控制之偏光程度混亂,在必須遮斷光時(OFF狀態)發生漏光,或者在必須使光透過時(ON狀態)發生透過光衰減,從而導致畫面模糊。因此,為了實現高品質的液晶顯示裝置,高對比度化不可或缺。 Examples of quality items required for color filters include brightness and contrast ratio. If a color filter with a low contrast ratio is used, the degree of polarization controlled by the liquid crystal will be confusing, light leakage will occur when light must be blocked (OFF state), or transmitted light attenuation will occur when light must be transmitted (ON state). , Resulting in blurred images. Therefore, in order to realize a high-quality liquid crystal display device, high contrast is indispensable.
另外,若使用亮度低之彩色濾光片,則光的透過率低,因此成為昏暗的畫面,為了獲得明亮的畫面,必須增多作為光源之背光的數量。因此,就抑制消耗電力之增大之觀點而言,彩色濾光片之高亮度化成為趨勢。進而,由於如上所述般逐漸將彩色液晶裝置用於電視或電腦監視器等,故而對於彩色濾光片之高亮度化、高對比度化、並且高可靠性之要求亦變高。 In addition, if a color filter with a low brightness is used, the light transmittance is low, so it becomes a dim picture. In order to obtain a bright picture, the number of backlights used as a light source must be increased. Therefore, from the viewpoint of suppressing an increase in power consumption, it is a trend to increase the brightness of color filters. Furthermore, since color liquid crystal devices are gradually used in televisions, computer monitors, and the like as described above, the requirements for high brightness, high contrast, and high reliability of color filters have also increased.
對於作為彩色濾光片基板之三原色(紅、綠、藍;RGB)之一的紅色濾光片段,一般單獨或組合使用二酮基吡咯并吡咯顏料、蒽醌顏料或苝顏料等耐光性及耐熱性優異之顏料作為著色劑。 For red filter segments that are one of the three primary colors (red, green, blue; RGB) of a color filter substrate, diketopyrrolopyrrole pigments, anthraquinone pigments, and perylene pigments are generally used alone or in combination. A pigment having excellent heat resistance is used as a colorant.
於上述顏料種之中,就亮度之觀點而言,使用作為二酮基吡咯并吡咯顏料之C.I.顏料紅254作為主顏料,就對比率之觀點而言,使用作為蒽醌顏料之C.I.顏料紅177作為主顏料。其中,由於C.I.顏料紅177的分光透過率低於C.I.顏料紅254,分光形狀亦不良,故而隨著添加C.I.顏料紅177,有引起亮度降低之缺點。因此,期望開發出亮度優異之C.I.顏料紅177代替材料。 Among the above pigment types, CI Pigment Red 254, which is a diketopyrrolopyrrole pigment, is used as the main pigment from the viewpoint of brightness, and CI Pigment Red 177, which is an anthraquinone pigment, is used from the viewpoint of contrast. As the main pigment. Among them, the spectral transmittance of C.I. Pigment Red 177 is lower than that of C.I. Pigment Red 254, and the spectral shape is also poor. Therefore, the addition of C.I. Pigment Red 177 has the disadvantage of causing a decrease in brightness. Therefore, it is desirable to develop C.I. Pigment Red 177, which is excellent in brightness, as an alternative material.
近年來,為了實現高亮度化、高著色力,提出有使用以C.I.顏料紅269為代表之偶氮顏料或專利文獻3中所記載之雙偶氮顏料作為主顏料。然而,由於該顏料對於溶劑之親和性、或顏料表面的酸性度等係與C.I.顏料紅254或C.I.顏料紅177等不同,故而亦有分散性、流動性、保存穩定性差,進而耐熱性、 耐光性亦差之缺點,無法獲得具有實用性之彩色濾光片。另外,如C.I.顏料紅269之類的偶氮顏料有時存在因向鄰接的他色濾光片段之顏色轉移導致亮度降低之問題,對移染性有高要求。 In recent years, in order to achieve high brightness and high tinting power, it has been proposed to use an azo pigment represented by C.I. Pigment Red 269 or a disazo pigment described in Patent Document 3 as a main pigment. However, the pigment's affinity for solvents, or the acidity of the pigment surface is different from CI Pigment Red 254 or CI Pigment Red 177, etc., so it also has poor dispersibility, flowability, and poor storage stability, and further has heat resistance and light resistance. It is also disadvantageous in that it cannot obtain a practical color filter. In addition, azo pigments such as C.I. Pigment Red 269 sometimes have a problem of reduced brightness due to color transfer to adjacent other color filter segments, and have high requirements for migration properties.
於專利文獻1至專利文獻3中,為了謀求紅色濾光片段的亮度進一步提高,提出有使用C.I.顏料紅177、C.I.顏料紅269及專利文獻3中所記載之雙偶氮顏料作為主顏料。然而,專利文獻1至專利文獻3之方法無法獲得充分的亮度,需要進一步改善。 In Patent Documents 1 to 3, in order to further improve the brightness of the red filter segment, it is proposed to use C.I. Pigment Red 177, C.I. Pigment Red 269, and the disazo pigment described in Patent Document 3 as the main pigment. However, the methods of Patent Documents 1 to 3 cannot obtain sufficient brightness, and further improvement is required.
[先前技術文獻] [Prior technical literature]
[專利文獻] [Patent Literature]
專利文獻1:日本專利特開2008-304521號公報。 Patent Document 1: Japanese Patent Laid-Open No. 2008-304521.
專利文獻2:日本專利特表2007-533802號公報。 Patent Document 2: Japanese Patent Publication No. 2007-533802.
專利文獻3:日本專利特開2014-160160號公報。 Patent Document 3: Japanese Patent Laid-Open No. 2014-160160.
本發明之目的在於提供一種彩色濾光片用著色組成物,不僅耐熱性、耐光性等堅牢性優異,塗膜異物少,保存穩定性良好,為低移染性,而且亮度及對比度高,表現相同顏色時膜厚變薄。 The object of the present invention is to provide a colored composition for a color filter, which not only has excellent fastness properties such as heat resistance and light resistance, has few foreign matter on the coating film, has good storage stability, has low migration, but also has high brightness and contrast, and exhibits high performance. The film thickness becomes thinner for the same color.
本發明者等人反覆進行努力研究,結果發現,藉由將具有某種特定結構之偶氮顏料用於彩色濾光片用著色劑,可解決上 述之課題,從而完成本發明。 The inventors of the present invention have conducted diligent research, and as a result, have found that the use of an azo pigment having a specific structure in a colorant for a color filter can solve the above-mentioned problems and complete the present invention.
亦即,本發明之實施態樣係關於一種偶氮顏料,由下述通式(1)或通式(2)所表示之化合物所構成。 That is, an embodiment of the present invention relates to an azo pigment composed of a compound represented by the following general formula (1) or general formula (2).
[通式(1)中,R1表示鹵素原子、可具有取代基之烷基、可具有取代基之烷氧基、或可具有取代基之芳氧基。R2及R3分別獨立地表示氫原子、可具有取代基之烷基、或可具有取代基之苯基。 [In the general formula (1), R 1 represents a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent. R 2 and R 3 each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent.
X1至X4分別獨立地表示氫原子、可具有取代基之烷基、可具有取代基之烷氧基、羥基、氰基、硝基、羧基、磺基、或鹵素原子] X 1 to X 4 each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a sulfo group, or a halogen atom]
[通式(2)中,R4表示鹵素原子、可具有取代基之烷基、可具有取代基之烷氧基、或可具有取代基之芳氧基。R5及R6分別獨立地表示氫原子、可具有取代基之烷基、或可具有取代基之苯基。 [In the general formula (2), R 4 represents a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent. R 5 and R 6 each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent.
X5至X12分別獨立地表示氫原子、可具有取代基之烷基、可具有取代基之烷氧基、羥基、氰基、硝基、或鹵素原子。A表示直接鍵結、或2價連結基。前述2價連結基為可具有取代基之伸烷基、-O-、-S-、-CO-、-SO2-、-COO-、-CONH-、或-SO2NH-] X 5 to X 12 each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a hydroxyl group, a cyano group, a nitro group, or a halogen atom. A represents a direct bond or a divalent linking group. The divalent linking group which may have substituent group of alkylene, -O -, - S -, - CO -, - SO 2 -, - COO -, - CONH-, or -SO 2 NH-]
另外,本發明之實施態樣係關於一種彩色濾光片用著色劑,包含前述偶氮顏料。 Moreover, the aspect of this invention is a coloring agent for color filters containing the said azo pigment.
另外,本發明之實施態樣係關於一種彩色濾光片用著色組成物,至少含有著色劑及黏合劑樹脂,且前述著色劑為前述彩色濾光片用著色劑。 An embodiment of the present invention relates to a coloring composition for a color filter, which contains at least a coloring agent and a binder resin, and the coloring agent is the coloring agent for the color filter.
另外,本發明之實施態樣係關於前述彩色濾光片用著色組成物,其進而含有具有酸性取代基之樹脂型分散劑。 Moreover, the aspect of this invention is the said coloring composition for color filters which further contains the resin-type dispersing agent which has an acidic substituent.
另外,本發明之實施態樣係關於前述彩色濾光片用著色組成物,其中,前述具有酸性取代基之樹脂型分散劑為具有芳香族羧基之樹脂型分散劑。 An embodiment of the present invention relates to the coloring composition for a color filter, wherein the resin-based dispersant having an acidic substituent is a resin-based dispersant having an aromatic carboxyl group.
另外,本發明之實施態樣係關於前述彩色濾光片用著色組成物,其進而含有色素衍生物,且該色素衍生物包含具有鹼性取代基之色素衍生物。 Moreover, the aspect of this invention is the said coloring composition for color filters which further contains a pigment derivative, and this pigment derivative contains the pigment derivative which has a basic substituent.
另外,本發明之實施態樣係關於前述彩色濾光片用著色組成物,其中,前述著色劑進而包含選自由C.I.顏料紅254、C.I.顏料紅242、C.I.顏料黃138、C.I.顏料黃139、C.I.顏料黃150、 下述通式(3)所表示之黃色顏料及溴化二酮基吡咯并吡咯顏料所組成之群組中的至少一種。 An embodiment of the present invention relates to the coloring composition for a color filter, wherein the colorant further comprises a member selected from the group consisting of CI Pigment Red 254, CI Pigment Red 242, CI Pigment Yellow 138, CI Pigment Yellow 139, and CI. Pigment yellow 150, at least one of the group consisting of a yellow pigment represented by the following general formula (3) and a brominated diketopyrrolopyrrole pigment.
[通式(3)中,Z1至Z13分別獨立地表示氫原子、鹵素原子、可具有取代基之烷基、可具有取代基之烷氧基、可具有取代基之芳基、-SO3H、-COOH、及該等酸性基之1價至3價之金屬鹽、烷基銨鹽、可具有取代基之鄰苯二甲醯亞胺甲基、或可具有取代基之胺磺醯基。 [In the general formula (3), Z 1 to Z 13 each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, -SO 3 H, -COOH, and monovalent to trivalent metal salts of these acidic groups, alkyl ammonium salts, phthalimide imide methyl groups which may have a substituent, or sulfamidines which may have a substituent base.
Z1至Z4及/或Z10至Z13中的鄰接的基也可成為一體而形成可具有取代基之芳香環] The adjacent groups in Z 1 to Z 4 and / or Z 10 to Z 13 may be integrated to form an aromatic ring which may have a substituent.]
另外,本發明之實施態樣係關於前述彩色濾光片用著色組成物,其進而含有光聚合性單體。 Moreover, the aspect of this invention is the said coloring composition for color filters which further contains a photopolymerizable monomer.
另外,本發明之實施態樣係關於一種彩色濾光片,於基板上具備濾光片段,該濾光片段由前述彩色濾光片用著色組成物所形成。 In addition, an embodiment of the present invention relates to a color filter having a filter segment on a substrate, the filter segment being formed of the coloring composition for a color filter.
根據本發明,所具有之優異效果為:可提供一種彩色濾光片用著色組成物及彩色濾光片,該彩色濾光片用著色組成物不 僅耐熱性、耐光性等堅牢性優異,塗膜異物少,保存穩定性良好,為低移染性,而且亮度及對比度高,表現相同顏色時膜厚變薄。 According to the present invention, an excellent effect is that a coloring composition for a color filter and a color filter can be provided. The coloring composition for a color filter is excellent in not only fastness such as heat resistance and light resistance, but also a coating film. Few foreign matter, good storage stability, low migration, high brightness and contrast, thin film thickness when the same color is expressed.
以下,詳細地說明本發明。再者,本說明書中,於表述為「(甲基)丙烯醯基」、「(甲基)丙烯酸基」、「(甲基)丙烯酸」、「(甲基)丙烯酸酯」、或「(甲基)丙烯醯胺」之情形時,只要無特別說明,則分別表示「丙烯醯基及/或甲基丙烯醯基」、「丙烯酸基及/或甲基丙烯酸基」、「丙烯酸及/或甲基丙烯酸」、「丙烯酸酯及/或甲基丙烯酸酯」、或「丙烯醯胺及/或甲基丙烯醯胺」。另外,本說明書中所列舉之「C.I.」意指色指數(C.I.)。 Hereinafter, the present invention will be described in detail. In addition, in this specification, it is expressed as "(meth) acrylfluorenyl", "(meth) acryl", "(meth) acryl", "(meth) acrylate", or "(formyl In the case of "methacryl)", unless otherwise specified, it means "acryl and / or methacryl", respectively, "acryl and / or methacryl", "acryl and / or methyl "Methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamine". In addition, "C.I." listed in this specification means a color index (C.I.).
<偶氮顏料> <Azo pigment>
首先,對本發明之由通式(1)或通式(2)所表示之化合物所構成之偶氮顏料進行說明。再者,本說明書中,有時將「由通式(1)或通式(2)所表示之化合物所構成之偶氮顏料」簡記為「顏料」,將「彩色濾光片用著色劑」簡記為「著色劑」而進行說明。 First, the azo pigment which consists of the compound represented by General formula (1) or General formula (2) of this invention is demonstrated. In addition, in this specification, "the azo pigment composed of a compound represented by general formula (1) or general formula (2)" may be abbreviated as "pigment" and "colorant for color filters" The description is simply referred to as "colorant".
通式(1)中,R1表示鹵素原子、可具有取代基之烷基、可具有取代基之烷氧基、或可具有取代基之芳氧基。R2及R3分別獨立地表示氫原子、可具有取代基之烷基、或可具有取代基之苯基。 In the general formula (1), R 1 represents a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent. R 2 and R 3 each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent.
X1至X4分別獨立地表示氫原子、可具有取代基之烷基、可具有取代基之烷氧基、羥基、氰基、硝基、羧基、磺基、或鹵素原子。 X 1 to X 4 each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a sulfo group, or a halogen atom.
再者,通式(1)中分別存在多個之R1、R2及R3各者相互可相同亦可不同。 Furthermore, each of a plurality of R 1 , R 2, and R 3 in the general formula (1) may be the same as or different from each other.
R1中,作為「鹵素原子」,可列舉:氟、溴、氯、碘,該等之中,較佳為氯。 Examples of the "halogen atom" in R 1 include fluorine, bromine, chlorine, and iodine. Among these, chlorine is preferred.
R1中,作為「可具有取代基之烷基」,可列舉:甲基、乙基、正丙基、異丙基、正丁基、第三丁基、異丁基、第三戊基、2-乙基己基、硬脂基、氯甲基、三氯甲基、三氟甲基、2-甲氧基乙基、2-氯乙基、2-硝基乙基、環戊基、環己基、二甲基環己基等,該等之中,較佳為甲基、三氟甲基。 Examples of the "alkyl group which may have a substituent" in R 1 include methyl, ethyl, n-propyl, isopropyl, n-butyl, third butyl, isobutyl, third pentyl, 2-ethylhexyl, stearyl, chloromethyl, trichloromethyl, trifluoromethyl, 2-methoxyethyl, 2-chloroethyl, 2-nitroethyl, cyclopentyl, cyclo Hexyl, dimethylcyclohexyl, etc. Among these, methyl and trifluoromethyl are preferred.
R1中,作為「可具有取代基之烷氧基」,可列舉:甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、正辛氧基、2-乙基己氧基、三氟甲氧基、環己氧基、硬脂氧基、2-(二乙基胺基)乙氧基等,該等之中,較佳為甲氧基、三氟甲氧基,其中,尤佳為甲氧基。 Examples of the "alkoxy group which may have a substituent" in R 1 include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, n-octyloxy, and 2-ethyl Hexyloxy, trifluoromethoxy, cyclohexyloxy, stearyloxy, 2- (diethylamino) ethoxy, etc. Among these, methoxy and trifluoromethyl are preferred Of these, methoxy is particularly preferred.
R1中,作為「可具有取代基之芳氧基」,可列舉:苯氧基、 萘氧基、4-甲基苯氧基、3,5-氯苯氧基、4-氯-2-甲基苯氧基、4-第三丁基苯氧基、4-甲氧基苯氧基、4-二乙基胺基苯氧基、4-硝基苯氧基等,該等之中,較佳為苯氧基。 In R 1 , examples of the "aryloxy group which may have a substituent" include phenoxy, naphthyloxy, 4-methylphenoxy, 3,5-chlorophenoxy, and 4-chloro-2- Methylphenoxy, 4-tert-butylphenoxy, 4-methoxyphenoxy, 4-diethylaminophenoxy, 4-nitrophenoxy, etc., among these, Phenoxy is preferred.
R2及R3中,作為「可具有取代基之烷基」,可列舉:甲基、乙基、正丙基、異丙基、正丁基、第三丁基、異丁基、第三戊基、2-乙基己基、硬脂基、氯甲基、三氯甲基、三氟甲基、2-甲氧基乙基、2-羥基乙基、2-氯乙基、2-硝基乙基、環戊基、環己基、二甲基環己基等,較佳為甲基、乙基、正丙基、異丙基、正丁基、第三丁基、異丁基、2-羥基乙基。 Examples of the "alkyl group which may have a substituent" in R 2 and R 3 include methyl, ethyl, n-propyl, isopropyl, n-butyl, third butyl, isobutyl, and third Amyl, 2-ethylhexyl, stearyl, chloromethyl, trichloromethyl, trifluoromethyl, 2-methoxyethyl, 2-hydroxyethyl, 2-chloroethyl, 2-nitro Ethyl, cyclopentyl, cyclohexyl, dimethylcyclohexyl, etc., preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, third butyl, isobutyl, 2- Hydroxyethyl.
R2及R3中,作為「可具有取代基之苯基」之取代基,可列舉:R1中的鹵素原子、可具有取代基之烷基、可具有取代基之烷氧基、及可具有取代基之芳氧基,除該等以外,亦可列舉:羥基、胺基、-NR7R8、磺基、-SO2NR9R10、-COOR11、-CONR12R13、硝基、氰基。 Examples of the substituent of the "phenyl group which may have a substituent" in R 2 and R 3 include a halogen atom in R 1 , an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and In addition to the aryloxy group having a substituent, a hydroxyl group, an amine group, -NR 7 R 8 , a sulfo group, -SO 2 NR 9 R 10 , -COOR 11 , -CONR 12 R 13 , nitrate, etc. can also be mentioned. And cyano.
前述R7至R13分別獨立地表示氫原子、可具有取代基之烷基,作為「可具有取代基之烷基」,較佳為經胺基、單烷基胺基、或二烷基胺基取代之烷基。 The aforementioned R 7 to R 13 each independently represent a hydrogen atom and an alkyl group which may have a substituent, and as the "alkyl group which may have a substituent", an amino group, a monoalkylamino group, or a dialkylamine is preferred. Substituted alkyl.
X1至X4中,作為「可具有取代基之烷基」,與R1中的「可具有取代基之烷基」的含義相同,較佳為甲基、乙基、三氟甲基。 X 1 to X 4 is, as "the alkyl group may have a substituent" for R 1 in "the alkyl group may have a substituent group" meaning the same, preferably methyl, ethyl, trifluoromethyl.
X1至X4中,作為「可具有取代基之烷氧基」,與R1中的「可 具有取代基之烷氧基」的含義相同。 X 1 to X 4 is, as "the group may have a substituent alkoxy", and in R 1 'may have a substituent group of alkoxy group "meaning the same.
通式(2)中,R4表示鹵素原子、可具有取代基之烷基、可具有取代基之烷氧基、或可具有取代基之芳氧基。R5及R6分別獨立地表示氫原子、可具有取代基之烷基、或可具有取代基之苯基。 In the general formula (2), R 4 represents a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent. R 5 and R 6 each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent.
X5至X12分別獨立地表示氫原子、可具有取代基之烷基、可具有取代基之烷氧基、羥基、氰基、硝基、或鹵素原子。A表示直接鍵結、或2價連結基。前述2價連結基為可具有取代基之伸烷基、-O-、-S-、-CO-、-SO2-、-COO-、-CONH-、或-SO2NH-。 X 5 to X 12 each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a hydroxyl group, a cyano group, a nitro group, or a halogen atom. A represents a direct bond or a divalent linking group. The divalent linking group which may have substituent group of alkylene, -O -, - S -, - CO -, - SO 2 -, - COO -, - CONH-, or -SO 2 NH-.
再者,通式(2)中分別存在多個之R4、R5及R6之各者相互可相同亦可不同。 Furthermore, each of a plurality of R 4 , R 5, and R 6 in the general formula (2) may be the same as or different from each other.
R4中,「鹵素原子」、「可具有取代基之烷基」、「可具有取代基之烷氧基」、及「可具有取代基之芳氧基」與R1中的「鹵素原子」、「可具有取代基之烷基」、「可具有取代基之烷氧基」、及「可具有取代基之芳氧基」的含義相同。 In R 4 , "halogen atom", "alkyl group which may have substituent", "alkoxy group which may have substituent", and "aryloxy group which may have substituent" and "halogen atom" in R 1 "Alkyl which may have a substituent", "Alkoxy which may have a substituent", and "Aryloxy which may have a substituent" have the same meaning.
R5及R6中,「可具有取代基之烷基」、「可具有取代基之苯基」與R2及R3中的「可具有取代基之烷基」、「可具有取代基之苯基」的含義相同。 In R 5 and R 6 , "alkyl group which may have a substituent", "phenyl group which may have a substituent" and "alkyl group which may have a substituent" in R 2 and R 3 , and "alkyl group which may have a substituent""Phenyl" has the same meaning.
X5至X12中,作為「可具有取代基之烷基」、「可具有取代基之烷氧基」,與R1中的「可具有取代基之烷基」、「可具有取代基之烷氧基」的含義相同。 In X 5 to X 12 , the "alkyl group which may have a substituent", the "alkoxy group which may have a substituent", and the "alkyl group which may have a substituent" and "the group which may have a substituent" in R 1 "Alkoxy" has the same meaning.
A中,作為可具有取代基之伸烷基,可列舉:亞甲基、伸乙基、正伸丙基、正伸丁基、正伸己基、正伸庚基、正伸辛基、正伸十二烷基,作為取代基,可列舉R1所表示之「可具有取代基之烷基」。 In A, examples of the alkylene group which may have a substituent include methylene, ethylene, n-propylene, n-butylene, n-hexyl, n-heptyl, n-octyl, and n-dodecyl. Examples of the substituent include "an alkyl group which may have a substituent" represented by R 1 .
作為通式(2)中的A,較佳為可具有取代基之伸烷基、-O-、-S-、-CO-、-SO2-,其中,尤佳為-SO2-。 General formula (2) as A, preferred is a group may have a substituent of alkylene, -O -, - S -, - CO -, - SO 2 -, wherein, particularly preferably -SO 2 -.
<彩色濾光片用著色劑> <Colorant for color filters>
本發明之彩色濾光片用著色劑包含由通式(1)或通式(2)所表示之化合物所構成之偶氮顏料。本發明之彩色濾光片用著色劑中,為了調整色度等,亦可在無損本發明之效果之範圍內,併用上述通式(1)或通式(2)所表示之化合物以外之顏料或染料等其他著色劑。該等顏料、染料可單獨使用或視需要以任意之比率混合2種以上而使用。 The colorant for a color filter of the present invention contains an azo pigment composed of a compound represented by the general formula (1) or the general formula (2). In the colorant for a color filter of the present invention, in order to adjust the chromaticity and the like, a pigment other than the compound represented by the general formula (1) or the general formula (2) may be used within a range that does not impair the effect of the present invention. Or dyes and other colorants. These pigments and dyes can be used alone or as a mixture of two or more kinds at an arbitrary ratio as needed.
作為其他著色劑,例如可列舉:C.I.顏料紅7、14、41、48:1、48:2、48:3、48:4、57:1、81、81:1、81:2、81:3、 81:4、122、146、168、169、176、177、178、179、184、185、187、200、202、208、210、242、246、254、255、264、269、270、272、273、274,276、277、278、279、280、281、282、283、284、285、286、或287等紅色顏料。作為紅色染料,可列舉:二苯并吡喃染料、偶氮(吡啶酮系、巴比妥酸系等)染料、雙偶氮染料、蒽醌染料、次甲基染料等。另外,亦可為將該等染料進行色澱化而成之色澱顏料、磺酸或羧酸等具有酸性基之酸性染料之無機鹽、酸性染料與含氮化合物之成鹽化合物、酸性染料之磺醯胺化合物等形態。 Examples of other colorants include CI Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 242, 246, 254, 255, 264, 269, 270, Red pigments such as 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, or 287. Examples of the red dye include dibenzopyran dyes, azo (pyridone-based, barbituric acid-based) dyes, bisazo dyes, anthraquinone dyes, and methine dyes. In addition, it may be a lake pigment obtained by lake-forming these dyes, an inorganic salt of an acidic dye having an acidic group such as a sulfonic acid or a carboxylic acid, a salt-forming compound of an acidic dye and a nitrogen-containing compound, or an acidic dye. Forms of sulfonamide.
另外,可併用C.I.顏料橙43、71、或73等橙色顏料及/或C.I.顏料黃1、2、3、4、5、6、10、12、13、14、15、16、17、18、24、31、32、34、35、35:1、36、36:1、37、37:1、40、42、43、53、55、60、61、62、63、65、73、74、77、81、83、93、94、95、97、98、100、101、104、106、108、109、110、113、114、115、116、117、118、119、120、123、126、127、128、129、138、139、147、150、151、152、153、154、155、156、161、162、164、166、167、168、169、170、171、172、173、174、175、176、177、179、180、181、182、185、187、188、193、194、198、199、213、214、218、219、220、221或下述通式(3)所表示之黃色顏料。另外,作為橙色染料及/或黃色染料,可列舉:喹啉系、偶氮系(吡啶酮系、巴比妥酸系、金屬錯合物系等)、雙偶氮系、次甲基系等。 In addition, orange pigments such as CI Pigment Orange 43, 71, or 73 and / or CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, 221 or the following general formula (3) Yellow pigment. Examples of the orange dye and / or yellow dye include quinoline-based, azo-based (pyridone-based, barbituric acid-based, and metal complex-based), diazo-based, and methine-based. .
關於所併用之著色劑中較佳的著色劑,就耐熱性、耐光性等堅牢性及色度區域之觀點而言,可列舉:偶氮系、萘酚偶氮 系、二酮基吡咯并吡咯系、蒽醌系、喹酞酮系、及苝系之色素。具體而言,可列舉:C.I.顏料紅269、177、254、242、C.I.顏料黃138、139、150、185、下述通式(3)所表示之黃色顏料、及溴化二酮基吡咯并吡咯顏料。 Among the preferred colorants used in combination, from the viewpoints of fastness such as heat resistance and light resistance and the chromaticity range, azo-based, naphtholazo-based, diketopyrrolopyrrole Based, anthraquinone based, quinophthalone based, and fluorene based pigments. Specific examples include CI Pigment Red 269, 177, 254, 242, CI Pigment Yellow 138, 139, 150, 185, a yellow pigment represented by the following general formula (3), and brominated diketopyrrolopyrrole Pyrrole pigment.
尤其是,就亮度及著色力之觀點而言,進而較佳為C.I.顏料紅254、242、C.I.顏料黃138、139、150、下述通式(3)所表示之黃色顏料、及溴化二酮基吡咯并吡咯顏料。 In particular, from the viewpoints of brightness and color strength, CI Pigment Red 254, 242, CI Pigment Yellow 138, 139, and 150, a yellow pigment represented by the following general formula (3), and bromide Ketopyrrolopyrrole pigments.
[通式(3)中,Z1至Z13分別獨立地表示氫原子、鹵素原子、可具有取代基之烷基、可具有取代基之烷氧基、可具有取代基之芳基、-SO3H、-COOH、及該等酸性基之1價至3價之金屬鹽、烷基銨鹽、可具有取代基之鄰苯二甲醯亞胺甲基、或可具有取代基之胺磺醯基。 [In the general formula (3), Z 1 to Z 13 each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, -SO 3 H, -COOH, and monovalent to trivalent metal salts of these acidic groups, alkyl ammonium salts, phthalimidoimine methyl groups which may have a substituent, or sulfamoniums which may have a substituent base.
Z1至Z4及/或Z10至Z13中的鄰接的基也可成為一體而形成可具有取代基之芳香環。 Adjacent groups in Z 1 to Z 4 and / or Z 10 to Z 13 may be integrated to form an aromatic ring which may have a substituent.
此處,作為鹵素原子,可列舉:氟、氯、溴、碘。 Here, examples of the halogen atom include fluorine, chlorine, bromine, and iodine.
另外,作為可具有取代基之烷基,可列舉:甲基、乙基、丙基、異丙基、丁基、異丁基、第三丁基、新戊基、正己基、 正辛基、硬脂基、2-乙基己基等直鏈或支鏈烷基,此外,亦可列舉:三氯甲基、三氟甲基、2,2,2-三氟乙基、2,2-二溴乙基、2,2,3,3-四氟丙基、2-乙氧基乙基、2-丁氧基乙基、2-硝基丙基、苄基、4-甲基苄基、4-第三丁基苄基、4-甲氧基苄基、4-硝基苄基、2,4-二氯苄基等具有取代基之烷基。 Examples of the alkyl group which may have a substituent include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, third butyl, neopentyl, n-hexyl, n-octyl, Linear or branched alkyl groups such as stearyl, 2-ethylhexyl, and other examples include trichloromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2,2-di Bromoethyl, 2,2,3,3-tetrafluoropropyl, 2-ethoxyethyl, 2-butoxyethyl, 2-nitropropyl, benzyl, 4-methylbenzyl, An alkyl group having a substituent, such as 4-tert-butylbenzyl, 4-methoxybenzyl, 4-nitrobenzyl, 2,4-dichlorobenzyl, and the like.
另外,作為可具有取代基之烷氧基,可列舉:甲氧基、乙氧基、丙氧基、異丙氧基、正丁氧基、異丁氧基、第三丁氧基、新戊氧基、2,3-二甲基-3-戊氧基、正己氧基、正辛氧基、硬脂氧基、2-乙基己氧基等直鏈或支鏈烷氧基,此外,亦可列舉:三氯甲氧基、三氟甲氧基、2,2,2-三氟乙氧基、2,2,3,3-四氟丙氧基、2,2-二-三氟甲基丙氧基、2-乙氧基乙氧基、2-丁氧基乙氧基、2-硝基丙氧基、苄氧基等具有取代基之烷氧基。 Examples of the alkoxy group which may have a substituent include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a third butoxy group, and neopentyl. Straight or branched chain alkoxy groups such as oxy, 2,3-dimethyl-3-pentoxy, n-hexyloxy, n-octyloxy, stearyloxy, 2-ethylhexyloxy, etc. Can also be listed: trichloromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 2,2,3,3-tetrafluoropropoxy, 2,2-di-trifluoro Alkoxy groups having a substituent such as methylpropoxy, 2-ethoxyethoxy, 2-butoxyethoxy, 2-nitropropoxy, and benzyloxy.
另外,作為可具有取代基之芳基,可列舉:苯基、萘基、蒽基等芳基,此外,亦可列舉:對甲基苯基、對溴苯基、對硝基苯基、對甲氧基苯基、2,4-二氯苯基、五氟苯基、2-胺基苯基、2-甲基-4-氯苯基、4-羥基-1-萘基、6-甲基-2-萘基、4,5,8-三氯-2-萘基、蒽醌基、2-胺基蒽醌基等具有取代基之芳基。 Examples of the aryl group which may have a substituent include aryl groups such as phenyl, naphthyl, and anthracenyl, and p-methylphenyl, p-bromophenyl, p-nitrophenyl, and p-phenyl Methoxyphenyl, 2,4-dichlorophenyl, pentafluorophenyl, 2-aminophenyl, 2-methyl-4-chlorophenyl, 4-hydroxy-1-naphthyl, 6-methyl Aryl groups having substituents, such as phenyl-2-naphthyl, 4,5,8-trichloro-2-naphthyl, anthraquinone, and 2-aminoanthraquinone.
另外,作為酸性基,可列舉:-SO3H、-COOH,作為該等酸性基之1價至3價之金屬鹽,可列舉:鈉鹽、鉀鹽、鎂鹽、鈣鹽、鐵鹽、鋁鹽等。另外,作為酸性基之烷基銨鹽,可列舉:辛基胺、月桂基胺、硬脂基胺等長鏈單烷基胺之銨鹽、棕櫚基三甲基銨、二月桂基二甲基銨、二硬脂基二甲基銨鹽等四級烷基銨鹽。 Examples of the acidic group include -SO 3 H and -COOH. Examples of the monovalent to trivalent metal salt of the acidic group include sodium salt, potassium salt, magnesium salt, calcium salt, iron salt, Aluminum salts, etc. Examples of the alkylammonium salt of an acidic group include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine, and stearylamine, palmityl trimethylammonium, and dilauryldimethyl Tertiary alkylammonium salts such as ammonium and distearyldimethylammonium salts.
作為可具有取代基之鄰苯二甲醯亞胺甲基(C6H4(CO)2N-CH2-)、及可具有取代基之胺磺醯基(H2NSO2-)中的「取代基」,可列舉:上述之鹵素原子、可具有取代基之烷基、可具有取代基之烷氧基、可具有取代基之芳基等。 Among the phthalimidoiminomethyl groups which may have a substituent (C 6 H 4 (CO) 2 N-CH 2- ), and the aminesulfonyl groups (H 2 NSO 2- ) which may have a substituent Examples of the "substituent" include the above-mentioned halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and an aryl group which may have a substituent.
通式(3)之Z1至Z4及/或Z10至Z13中的鄰接的基亦可成為一體而形成可具有取代基之芳香環。此處所謂之芳香環,可列舉烴芳香環及雜芳香環,作為烴芳香環,可列舉:苯環、萘環、蒽環、菲環等,另外,作為雜芳香環,可列舉:吡啶環、吡嗪環、吡咯環、喹啉環、喹噁啉環、呋喃環、苯并呋喃環、噻吩環、苯并噻吩環、噁唑環、噻唑環、咪唑環、吡唑環、吲哚環、咔唑環等。 Adjacent groups in Z 1 to Z 4 and / or Z 10 to Z 13 in the general formula (3) may be integrated to form an aromatic ring which may have a substituent. Examples of the aromatic ring include a hydrocarbon aromatic ring and a heteroaromatic ring. Examples of the hydrocarbon aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Examples of the heteroaromatic ring include a pyridine ring. , Pyrazine ring, pyrrole ring, quinoline ring, quinoxaline ring, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, oxazole ring, thiazole ring, imidazole ring, pyrazole ring, indole ring Carbazole ring.
作為本發明之彩色濾光片用著色劑中所使用之通式(3)所表示之黃色顏料的具體例,可列舉下述所示之喹酞酮化合物(a)至喹酞酮化合物(r)等,但本發明並不限定於該等。另外,本發明中所使用之喹酞酮化合物例如可藉由日本專利公報2930774號記載之方法而製造,但本發明並不限定於該等。 Specific examples of the yellow pigment represented by the general formula (3) used in the colorant for a color filter of the present invention include the quinophthalone compound (a) to the quinophthalone compound (r) shown below. ), Etc., but the present invention is not limited to these. The quinophthalone compound used in the present invention can be produced, for example, by the method described in Japanese Patent Publication No. 2930774, but the present invention is not limited to these.
喹酞酮化合物(q) 喹酞酮化合物(r)
作為可併用之染料,較佳為呈現紅色、紫色,且具有油溶性染料、酸性染料、直接染料、鹼性染料之任一形態之染料。 As the dye that can be used in combination, a dye that exhibits red and purple colors and has any form of an oil-soluble dye, an acid dye, a direct dye, or a basic dye is preferable.
該等之中,由於色相優異,故而較佳為使用二苯并吡喃系油溶性染料、二苯并吡喃系鹼性染料、二苯并吡喃系酸性染料。另外,亦可為將該等染料進行色澱化而成之色澱顏料、磺酸或羧酸等具有酸性基之酸性染料之無機鹽、酸性染料與含氮化合物之成鹽化合物、酸性染料之磺醯胺化合物等形態。 Among these, a dibenzopyran-based oil-soluble dye, a dibenzopyran-based basic dye, and a dibenzopyran-based acid dye are preferably used because of their excellent hue. In addition, it may be a lake pigment obtained by lake-forming these dyes, an inorganic salt of an acidic dye having an acidic group such as a sulfonic acid or a carboxylic acid, a salt-forming compound of an acidic dye and a nitrogen-containing compound, or an acidic dye. Forms of sulfonamide.
作为二苯并吡喃系油溶性染料,可列举:C.I.溶劑紅35、C.I.溶劑紅36、C.I.溶劑紅42、C.I.溶劑紅43、C.I.溶劑紅44、C.I.溶劑紅45、C.I.溶劑紅46、C.I.溶劑紅47、C.I.溶劑紅48、C.I.溶劑紅49、C.I.溶劑紅72、C.I.溶劑紅73、C.I.溶劑紅109、C.I.溶劑紅140、C.I.溶劑紅141、C.I.溶劑紅237、C.I.溶劑紅246、C.I.溶劑紫2、C.I.溶劑紫10等。其中,更佳為作為顯色性高之玫瑰紅系油溶性染料之C.I.溶劑紅35、C.I.溶劑紅36、C.I.溶劑紅49、C.I.溶劑紅109、C.I.溶劑紅237、C.I.溶劑紅246、C.I.溶劑紫2。 Examples of the dibenzopyran-based oil-soluble dyes include CI solvent red 35, CI solvent red 36, CI solvent red 42, CI solvent red 43, CI solvent red 44, CI solvent red 45, CI solvent red 46, and CI. Solvent Red 47, CI Solvent Red 48, CI Solvent Red 49, CI Solvent Red 72, CI Solvent Red 73, CI Solvent Red 109, CI Solvent Red 140, CI Solvent Red 141, CI Solvent Red 237, CI Solvent Red 246, CI Solvent Violet 2, CI Solvent Violet 10 and the like. Among them, CI Solvent Red 35, CI Solvent Red 36, CI Solvent Red 49, CI Solvent Red 109, CI Solvent Red 237, CI Solvent Red 246, and CI Solvent are more preferred as a rose red oil-soluble dye with high color rendering properties. Purple 2.
作為二苯并吡喃系鹼性染料,可列舉:C.I.鹼性紅1(玫瑰紅6GCP)、8(玫瑰紅G)、C.I.鹼性紫10(玫瑰紅B)等。其中,就顯色性優異之方面而言,較佳為使用C.I.鹼性紅1、C.I.鹼性紫10。 Examples of the dibenzopyran-based basic dyes include C.I. Basic Red 1 (Rose Red 6GCP), 8 (Rose Red G), C.I. Basic Violet 10 (Rose Red B), and the like. Among these, C.I. Basic Red 1 and C.I. Basic Violet 10 are preferably used in terms of excellent color rendering properties.
作為二苯并吡喃系酸性染料,較佳為使用C.I.酸性紅51(赤藻紅(食用紅色3號))、C.I.酸性紅52(酸性玫瑰紅)、C.I.酸性紅87(曙紅G(食用紅色103號))、C.I.酸性紅92(酸性夾竹桃紅PB(食用紅色104號))、C.I.酸性紅289、C.I.酸性紅388、孟加拉玫瑰紅B(食用紅色5號)、酸性玫瑰紅G、C.I.酸性紫9。 As the dibenzopyran-based acid dye, it is preferable to use CI Acid Red 51 (Red Algae Red (Edible Red No. 3)), CI Acid Red 52 (Acid Red Rose), CI Acid Red 87 (Eosin G (edible) Red No. 103)), CI Acid Red 92 (Acid Oleander PB (Edible Red No. 104)), CI Acid Red 289, CI Acid Red 388, Bengal Rose Red B (Edible Red No. 5), Acid Rose Red G, CI Acid Violet 9.
其中,就耐熱性、耐光性之方面而言,更佳為使用作為二苯并吡喃系酸性染料之C.I.酸性紅87、C.I.酸性紅92、C.I.酸性紅388、或者作為玫瑰紅系酸性染料之C.I.酸性紅52(酸性玫瑰紅)、C.I.酸性紅289、酸性玫瑰紅G、C.I.酸性紫9。 Among them, in terms of heat resistance and light resistance, it is more preferable to use CI acid red 87, CI acid red 92, CI acid red 388, or rose red acid dye as dibenzopyran acid dyes. CI acid red 52 (acid rose red), CI acid red 289, acid rose red G, CI acid violet 9.
該等染料中,尤其是就顯色性、耐熱性、耐光性優異之方面而言,最佳為使用作為玫瑰紅系酸性染料之C.I.酸性紅52。 Among these dyes, C.I. Acid Red 52, which is a rose red-based acid dye, is particularly preferably used in terms of excellent color rendering properties, heat resistance, and light resistance.
於與上述之紅色顏料或黃色顏料、橙色顏料、染料併用之情形時,上述通式(1)或通式(2)所表示之化合物的含量於著色劑之合計100質量%中為10質量%至90質量%,較佳為20質量%至80質量%。於上述通式(1)或通式(2)所表示之化合物的含量為10質量%以下之情形時,無法充分地發揮出亮度或著色力優異之效果。 When the red pigment, yellow pigment, orange pigment, and dye are used in combination, the content of the compound represented by the general formula (1) or the general formula (2) is 10% by mass based on 100% by mass of the total amount of the colorant. It is 90% by mass, preferably 20% by mass to 80% by mass. When the content of the compound represented by the general formula (1) or the general formula (2) is 10% by mass or less, the effect of excellent brightness and coloring power cannot be sufficiently exhibited.
<顏料的平均一次粒徑> <Average primary particle size of pigment>
藉由以下之方法,測定(算出)顏料的平均一次粒徑。 The average primary particle diameter of the pigment was measured (calculated) by the following method.
於顏料之粉末中添加丙二醇單甲醚乙酸酯,添加少量之Disperbyk-161作為樹脂型分散劑,利用超音波洗淨機分散1分鐘,製備測定用試樣。針對該試樣,藉由穿透式電子顯微鏡(日本電子公司製造之「JEM-1200EX」),拍攝可確認100個以上之顏料的一次粒子之照片3張(3視野量),分別自左上依序測定100個 一次粒子的大小。具體而言,以nm單位量測各個顏料的一次粒子的短軸徑及長軸徑,將該短軸徑及長軸徑之平均當作該顏料的一次粒徑,以每5nm為刻度製成合計300個之分佈,將以每5nm為刻度之中央值(例如於6nm以上且10nm以下之情形時為8nm)近似為該等粒子的粒徑,基於各個粒徑及其數量進行計算,藉此算出個數平均粒徑。 To the powder of the pigment, propylene glycol monomethyl ether acetate was added, and a small amount of Disperbyk-161 was added as a resin-based dispersant, and dispersed in an ultrasonic cleaner for 1 minute to prepare a sample for measurement. With respect to this sample, three photographs (three fields of view) of primary particles of 100 or more pigments can be taken with a transmission electron microscope ("JEM-1200EX" manufactured by Japan Electronics Co., Ltd.). The size of 100 primary particles was measured sequentially. Specifically, the short-axis diameter and the long-axis diameter of the primary particles of each pigment are measured in nm units, and the average of the short-axis diameter and the long-axis diameter is regarded as the primary particle diameter of the pigment. The distribution of a total of 300 particles is approximated by the central value of each 5 nm scale (for example, 8 nm in the case of more than 6 nm and less than 10 nm) as the particle size of these particles, and is calculated based on each particle size and number. The number average particle diameter was calculated.
<著色劑之微細化> <Miniaturization of colorants>
本發明中所使用之顏料可進行微細化而使用。對於包含上述通式(1)或通式(2)所表示之化合物之顏料,亦較佳為進行微細化而使用。微細化方法並無特別限定,例如可使用濕式磨碎、乾式磨碎、溶解析出法之任一者,可如本發明中所例示般進行作為濕式磨碎之1種之利用捏合機法之鹽磨(salt milling)處理。 The pigment used in the present invention can be used in a finer form. The pigment containing the compound represented by the general formula (1) or the general formula (2) is also preferably used for miniaturization. The method of miniaturization is not particularly limited, and for example, any one of wet grinding, dry grinding, and dissolution can be used, and a kneader method as one of the wet grinding can be performed as exemplified in the present invention. Salt milling.
關於經微細化之顏料的一次粒徑,就於著色劑載體中的分散良好而言,較佳為20nm以上。另外,就可形成對比率高之濾光片段而言,較佳為100nm以下。尤佳的範圍為25nm至85nm之範圍。 The primary particle diameter of the finely-refined pigment is preferably 20 nm or more in terms of good dispersion in the colorant carrier. In addition, in order to form a filter segment having a high contrast ratio, it is preferably 100 nm or less. A particularly preferred range is a range from 25 nm to 85 nm.
所謂鹽磨處理,係指以下之處理,亦即,將顏料、水溶性無機鹽及水溶性有機溶劑之混合物,使用捏合機、三元混合機、雙輥研磨機、三輥研磨機、球磨機、磨碎機、砂磨機等混練機,一面進行加熱一面進行機械混練後,藉由水洗而將水溶性無機鹽及水溶性有機溶劑去除。水溶性無機鹽係作為破碎助劑發揮作用,在鹽磨時利用無機鹽的高硬度而將顏料破碎。藉由將對顏料進行鹽磨處理時的條件最佳化,可獲得一次粒徑非常微 細,且分佈之範圍窄,具有陡峭的粒度分佈之顏料。 The so-called salt milling treatment refers to the following processing, that is, using a kneader, a ternary mixer, a two-roller mill, a three-roller mill, a ball mill, a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent, After kneading machines such as attritors and sand mills perform mechanical kneading while heating, water-soluble inorganic salts and water-soluble organic solvents are removed by washing with water. The water-soluble inorganic salt system functions as a crushing aid, and uses a high hardness of the inorganic salt to crush the pigment during salt milling. By optimizing the conditions when the pigment is subjected to salt milling, a pigment having a very fine primary particle size, a narrow distribution range, and a steep particle size distribution can be obtained.
作為水溶性無機鹽,可使用氯化鈉、氯化鋇、氯化鉀、硫酸鈉等,就價格之方面而言,較佳為使用氯化鈉(食鹽)。就處理效率及生產效率之兩方面而言,水溶性無機鹽相對於著色劑100質量份,較佳為使用50質量份至2000質量份,最佳為使用300質量份至1000質量份。 As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate, and the like can be used. In terms of price, sodium chloride (table salt) is preferably used. In terms of both processing efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 parts by mass to 2000 parts by mass with respect to 100 parts by mass of the colorant, and most preferably used in an amount of 300 parts by mass to 1,000 parts by mass.
水溶性有機溶劑發揮將顏料及水溶性無機鹽濕潤之作用,只要為溶解(混和)於水且不會將所使用之無機鹽實質上溶解之溶劑,則並無特別限定。但是,由於在鹽磨時溫度上升,成為溶劑容易蒸發之狀態,故而就安全性之方面而言,較佳為沸點120℃以上之高沸點溶劑。例如,可使用2-甲氧基乙醇、2-丁氧基乙醇、2-(異戊氧基)乙醇、2-(己氧基)乙醇、二乙二醇、二乙二醇單***、二乙二醇單丁醚、三乙二醇、三乙二醇單甲醚、液狀之聚乙二醇、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、二丙二醇、二丙二醇單甲醚、二丙二醇單***、液狀之聚丙二醇等。水溶性有機溶劑相對於著色劑100質量份,較佳為使用5質量份至1000質量份,最佳為使用50質量份至500質量份。 The water-soluble organic solvent exhibits the function of moistening the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it is a solvent that dissolves (mixes) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling, and the solvent easily evaporates, a high-boiling point solvent having a boiling point of 120 ° C. or higher is preferred in terms of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentoxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, two Ethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, Dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, and the like. The water-soluble organic solvent is preferably used in an amount of 5 to 1,000 parts by mass, and most preferably used in an amount of 50 to 500 parts by mass, with respect to 100 parts by mass of the colorant.
對顏料進行鹽磨處理時,亦可視需要添加樹脂。所使用之樹脂的種類並無特別限定,可使用天然樹脂、改質天然樹脂、合成樹脂、經天然樹脂改質之合成樹脂等。所使用之樹脂較佳為於室溫下為固體且不溶於水,且進而較佳為一部分可溶於上述有機溶劑。樹脂的使用量相對於著色劑100質量份,較佳為5質量份至200質量份之範圍。 When the pigment is subjected to salt milling, a resin can also be added as needed. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is preferably solid at room temperature and insoluble in water, and further preferably a part of the resin soluble in the organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by mass based on 100 parts by mass of the colorant.
另外,對顏料進行鹽磨處理時,亦可視需要添加後述之色素衍生物。所使用之色素衍生物的結構並無特別限定,可列舉於有機顏料、蒽醌、吖啶酮或三嗪中導入有鹼性取代基、酸性取代基、或可具有取代基之鄰苯二甲醯亞胺甲基之化合物。該等可單獨使用或混合2種以上而使用。 In addition, when the pigment is subjected to salt milling, a pigment derivative described later may be added as necessary. The structure of the pigment derivative to be used is not particularly limited, and examples thereof include an organic pigment, anthraquinone, acridone, or triazine, in which a basic substituent, an acidic substituent, or phthalate which may have a substituent is introduced. A compound of iminomethyl. These can be used individually or in mixture of 2 or more types.
該等色素衍生物的使用量相對於著色劑100質量份,較佳為2質量份至30質量份,最佳為5質量份至20質量份。 The use amount of these pigment derivatives is preferably 2 parts by mass to 30 parts by mass, and most preferably 5 parts by mass to 20 parts by mass with respect to 100 parts by mass of the colorant.
<彩色濾光片用著色組成物> <Coloring composition for color filter>
本發明之彩色濾光片用著色組成物除前述所說明之著色劑以外,由黏合劑樹脂構成。 The coloring composition for a color filter of the present invention is composed of a binder resin in addition to the coloring agent described above.
<黏合劑樹脂> <Binder Resin>
黏合劑樹脂係使著色劑分散、染色、或滲透之樹脂,可列舉熱塑性樹脂等。另外,於以鹼顯影型著色阻劑材料之形態使用之情形時,較佳為使用使含酸性基之乙烯性不飽和單體進行共聚而成之鹼可溶性乙烯系樹脂。另外,進而為了提高光感度,亦可使用具有乙烯性不飽和雙鍵之活性能量線硬化性樹脂。 The binder resin is a resin that disperses, dyes, or penetrates a colorant, and examples thereof include thermoplastic resins. In the case of using it in the form of an alkali-developing coloring resist material, it is preferable to use an alkali-soluble vinyl resin obtained by copolymerizing an ethylenically unsaturated monomer containing an acidic group. In addition, in order to improve the light sensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond may be used.
尤其是藉由將側鏈上具有乙烯性不飽和雙鍵之活性能量線硬化性樹脂用於鹼顯影型著色阻劑材料,而在利用活性能量線進行曝光而形成塗膜時,藉由使樹脂進行三維交聯而將著色劑固定,耐熱性變得良好,可抑制著色劑之因熱所致之褪色(分光特性之惡化)。另外,於顯影步驟中亦具有抑制著色劑成分之凝 聚、析出之效果。 In particular, an active energy ray-curable resin having an ethylenically unsaturated double bond in a side chain is used for an alkali-developing coloring resist material, and when an active energy ray is used to form a coating film, the resin is made by By performing three-dimensional crosslinking to fix the colorant, the heat resistance becomes good, and the colorant's discoloration (deterioration of the spectral characteristics) due to heat can be suppressed. In addition, the development step also has the effect of suppressing aggregation and precipitation of colorant components.
作為黏合劑樹脂,較佳為於可見光區域之400nm至700nm之全波長區域中之分光透過率較佳為80%以上、更佳為95%以上之樹脂。 As the binder resin, a resin having a spectral transmittance in a full wavelength range of 400 nm to 700 nm in the visible light region is preferably 80% or more, and more preferably 95% or more.
為了使著色劑較佳地分散,黏合劑樹脂的重量平均分子量(Mw)較佳為10,000至100,000之範圍,更佳為10,000至80,000之範圍。另外,數量平均分子量(Mn)較佳為5,000至50,000之範圍,Mw/Mn之值較佳為10以下。 In order to disperse the colorant better, the weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, and more preferably in the range of 10,000 to 80,000. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.
於將黏合劑樹脂用於彩色濾光片用感光性著色組成物之情形時,作為著色劑吸附基及顯影時的鹼可溶基發揮作用之羧基、作為對著色劑載體及溶劑之親和性基發揮作用之脂肪族基及芳香族基之平衡對於著色劑的分散性、滲透性、顯影性、進而耐久性而言重要,較佳為使用酸值20mgKOH/g至300mgKOH/g之樹脂。若酸值未達20mgKOH/g,則對於顯影液之溶解性差,難以形成微細圖案。若超過300mgKOH/g,則微細圖案無法殘留。 When a binder resin is used for the photosensitive coloring composition for color filters, a carboxyl group which functions as a coloring agent adsorption group and an alkali-soluble group during development, and an affinity group for a colorant carrier and a solvent The balance between the functioning aliphatic group and aromatic group is important for the dispersibility, permeability, developability, and further durability of the colorant. It is preferable to use a resin having an acid value of 20 mgKOH / g to 300 mgKOH / g. If the acid value is less than 20 mgKOH / g, the solubility in the developer is poor, and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, a fine pattern cannot remain.
關於黏合劑樹脂,就成膜性及各種耐性良好而言,相對於著色劑的總質量100質量份,較佳為以20質量份以上之量使用,就著色劑濃度高,可表現出良好的色特性而言,較佳為以1000質量份以下之量使用。 As for the binder resin, in terms of good film-forming properties and various resistances, it is preferably used in an amount of 20 parts by mass or more based on 100 parts by mass of the total mass of the colorant. As the concentration of the colorant is high, it can exhibit good properties. In terms of color characteristics, it is preferably used in an amount of 1,000 parts by mass or less.
作為黏合劑樹脂中所使用之熱塑性樹脂,例如可列舉:丙 烯酸樹脂、丁醛樹脂、苯乙烯-順丁烯二酸共聚物、氯化聚乙烯、氯化聚丙烯、聚氯乙烯、氯乙烯-乙酸乙烯酯共聚物、聚乙酸乙烯酯、聚胺基甲酸酯系樹脂、聚酯樹脂、乙烯系樹脂、醇酸樹脂、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(High Density Polyethylene,高密度聚乙烯)、LDPE(Low Density Polyethylene,低密度聚乙烯))、聚丁二烯、及聚醯亞胺樹脂等。其中,較佳為使用丙烯酸樹脂。 Examples of the thermoplastic resin used in the binder resin include acrylic resin, butyraldehyde resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, and vinyl chloride- Vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber system Resin, cellulose, polyethylene (HDPE (High Density Polyethylene, high density polyethylene), LDPE (Low Density Polyethylene, low density polyethylene)), polybutadiene, and polyimide resin. Among these, an acrylic resin is preferably used.
作為使含酸性基之乙烯性不飽和單體進行共聚而成之乙烯系鹼可溶性樹脂,例如可列舉:具有羧基、碸基等酸性基之樹脂。 Examples of the ethylene-based alkali-soluble resin obtained by copolymerizing an ethylenically unsaturated monomer containing an acidic group include resins having an acidic group such as a carboxyl group and a fluorenyl group.
作為鹼可溶性樹脂,具體而言,可列舉:具有酸性基之丙烯酸樹脂、α-烯烴/順丁烯二酸(酐)共聚物、苯乙烯/苯乙烯磺酸共聚物、乙烯/(甲基)丙烯酸共聚物、或異丁烯/順丁烯二酸(酐)共聚物等。其中,選自具有酸性基之丙烯酸樹脂、及苯乙烯/苯乙烯磺酸共聚物中的至少1種樹脂、尤其是具有酸性基之丙烯酸樹脂因耐熱性、透明性高而可較佳地使用。 Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / maleic acid (anhydride) copolymer, a styrene / styrene sulfonic acid copolymer, and ethylene / (methyl). Acrylic acid copolymer, isobutylene / maleic acid (anhydride) copolymer, etc. Among them, at least one resin selected from the group consisting of an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, and particularly an acrylic resin having an acidic group is preferably used because of its high heat resistance and high transparency.
作為具有乙烯性不飽和雙鍵之活性能量線硬化性樹脂,例如可列舉藉由以下所示之(i)或(ii)之方法而導入有不飽和乙烯性雙鍵之樹脂。 Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins having an unsaturated ethylenic double bond introduced by the method (i) or (ii) shown below.
[方法(i)] [Method (i)]
作為方法(i),例如有以下之方法:使具有環氧基之不飽和乙烯性單體、與其他1種以上之單體進行共聚,藉此獲得共聚物,使所獲得之共聚物的側鏈環氧基、與具有不飽和乙烯性雙 鍵之不飽和一元酸的羧基進行加成反應,進而使所生成之羥基、與多元酸酐進行反應,從而導入不飽和乙烯性雙鍵及羧基。 As the method (i), for example, there is a method in which an unsaturated ethylenic monomer having an epoxy group is copolymerized with one or more other monomers to obtain a copolymer, and a side of the obtained copolymer is obtained. The chain epoxy group is added to a carboxyl group of an unsaturated monobasic acid having an unsaturated ethylenic double bond, and the generated hydroxyl group is reacted with a polybasic acid anhydride to introduce an unsaturated ethylenic double bond and a carboxyl group.
作為具有環氧基之不飽和乙烯性單體,例如可列舉:(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-縮水甘油氧基乙酯、(甲基)丙烯酸3,4環氧丁酯、及(甲基)丙烯酸3,4環氧環己酯,該等可單獨使用,亦可併用2種以上。就與下一步驟之不飽和一元酸之反應性之觀點而言,較佳為(甲基)丙烯酸縮水甘油酯。 Examples of the unsaturated ethylenic monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and 2-glycidyloxyethyl (meth) acrylate. , 3,4 epoxybutyl (meth) acrylate, and 3,4 epoxycyclohexyl (meth) acrylate. These can be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.
作為不飽和一元酸,可列舉:(甲基)丙烯酸、丁烯酸、鄰、間、對乙烯基苯甲酸、(甲基)丙烯酸之α位鹵烷基、烷氧基、鹵基、硝基、氰基取代物等單羧酸等,該等可單獨使用,亦可併用2種以上。 Examples of the unsaturated monobasic acid include (meth) acrylic acid, butenoic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl group of (meth) acrylic acid, alkoxy group, halo group, and nitro group. Monocarboxylic acids, such as cyano substituents, etc., may be used alone or in combination of two or more.
作為多元酸酐,可列舉:四氫鄰苯二甲酸酐、鄰苯二甲酸酐、六氫鄰苯二甲酸酐、琥珀酸酐、順丁烯二酸酐等,該等可單獨使用,亦可併用2種以上。亦可增加羧基的數量等,視需要使用偏苯三甲酸酐等三羧酸酐,或使用均苯四甲酸二酐等四羧酸二酐,而將殘留之酐基進行水解等。另外,若使用具有不飽和乙烯性雙鍵之四氫鄰苯二甲酸酐或顺丁烯二酸酐作為多元酸酐,則可進而增加不飽和乙烯性雙鍵。 Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc. These may be used alone or in combination of two types. the above. The number of carboxyl groups may be increased. If necessary, tricarboxylic anhydride such as trimellitic anhydride or tetracarboxylic dianhydride such as pyromellitic dianhydride may be used to hydrolyze the remaining anhydride groups. In addition, if tetrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the unsaturated ethylenic double bond can be further increased.
作為方法(i)的類似的方法,例如有以下之方法:使具有羧基之不飽和乙烯性單體、與其他1種以上之單體進行共聚,藉此獲得共聚物,使所獲得之共聚物的側鏈羧基的一部分、與具 有環氧基之不飽和乙烯性單體進行加成反應,從而導入不飽和乙烯性雙鍵及羧基。 As a similar method to the method (i), for example, there is a method in which an unsaturated ethylenic monomer having a carboxyl group is copolymerized with one or more other monomers to obtain a copolymer, and the obtained copolymer is obtained. A part of the side chain carboxyl group is added to an unsaturated ethylenic monomer having an epoxy group to introduce an unsaturated ethylenic double bond and a carboxyl group.
[方法(ii)] [Method (ii)]
作為方法(ii),有以下之方法:使用具有羥基之不飽和乙烯性單體,與其他具有羧基之不飽和一元酸之單體或其他單體進行共聚,藉此獲得共聚物,使所獲得之共聚物的側鏈羥基、與具有異氰酸酯基之不飽和乙烯性單體的異氰酸酯基進行反應。 As the method (ii), there is a method of using a unsaturated ethylenic monomer having a hydroxyl group and copolymerizing another unsaturated monobasic acid monomer or other monomer having a carboxyl group, thereby obtaining a copolymer, and obtaining the obtained copolymer. The copolymer has a side chain hydroxyl group that reacts with an isocyanate group of an unsaturated ethylenic monomer having an isocyanate group.
作為具有羥基之不飽和乙烯性單體,可列舉:(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-或3-羥基丙酯、(甲基)丙烯酸2-或3-或4-羥基丁酯、(甲基)丙烯酸縮水甘油酯、或環己烷二甲醇單(甲基)丙烯酸酯等(甲基)丙烯酸羥基烷基酯類,該等可單獨使用,亦可併用2種以上。另外,亦可使用對上述(甲基)丙烯酸羥基烷基酯加成聚合環氧乙烷、環氧丙烷、及/或環氧丁烷等而成之聚醚單(甲基)丙烯酸酯,或加成(聚)γ-戊內酯、(聚)ε-己內酯、及/或(聚)12-羥基硬脂酸等而成之(聚)酯單(甲基)丙烯酸酯。就抑制塗膜異物之觀點而言,較佳為(甲基)丙烯酸2-羥基乙酯、或(甲基)丙烯酸縮水甘油酯。 Examples of the unsaturated ethylenic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or (meth) acrylate, or 4-hydroxybutyl (meth) acrylate, glycidyl (meth) acrylate, or hydroxyalkyl (meth) acrylates such as cyclohexanedimethanol mono (meth) acrylate, these can be used alone or in combination. 2 More than that. In addition, a polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the hydroxyalkyl (meth) acrylate may be used, or (Poly) ester mono (meth) acrylate obtained by addition of (poly) γ-valerolactone, (poly) ε-caprolactone, and / or (poly) 12-hydroxystearic acid. From a viewpoint of suppressing a coating film foreign body, 2-hydroxyethyl (meth) acrylate or glycidyl (meth) acrylate is preferable.
作為具有異氰酸酯基之不飽和乙烯性單體,可列舉異氰酸2-(甲基)丙烯醯氧基乙酯、或異氰酸1,1-雙[(甲基)丙烯醯氧基]乙酯等,但並不限定於該等,亦可併用2種以上。 Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloxyethyl isocyanate and 1,1-bis [(meth) acryloxy] ethyl isocyanate. Esters are not limited to these, and two or more kinds may be used in combination.
<有機溶劑> <Organic solvent>
本發明之著色組成物,基於容易使著色劑充分地分散、滲 透於著色劑載體中,以乾燥膜厚成為0.2μm至5μm之方式塗佈於玻璃基板等基板上而形成濾光片段的目的,可含有有機溶劑。關於有機溶劑,除著色組成物的塗佈性良好以外,亦考慮著色組成物各成分的溶解性、進而安全性而選定。 The coloring composition of the present invention is based on the purpose of easily dispersing the colorant sufficiently and penetrating into the colorant carrier, and coating the substrate on a substrate such as a glass substrate with a dry film thickness of 0.2 to 5 μm to form a filter segment. May contain organic solvents. The organic solvent is selected in consideration of the solubility and further the safety of each component of the coloring composition in addition to the good coatability of the coloring composition.
作為有機溶劑,例如可列舉:1,2,3-三氯丙烷、1-甲氧基-2-丙醇、乳酸乙酯、1,3-丁二醇、1,3-丁二醇二乙酸酯、1,4-二噁烷、2-庚酮、2-甲基-1,3-丙二醇、3,5,5-三甲基-2-環己烯-1-酮、3,3,5-三甲基環己酮、3-乙氧基丙酸乙酯、3-甲基-1,3-丁二醇、3-甲氧基-3-甲基-1-丁醇、乙酸3-甲氧基-3-甲基丁酯、3-甲氧基丁醇、乙酸3-甲氧基丁酯、4-庚酮、間二甲苯、間二乙基苯、間二氯苯、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、正丁醇、正丁基苯、乙酸正丙酯、N-甲基吡咯啶酮、鄰二甲苯、鄰氯甲苯、鄰二乙基苯、鄰二氯苯、對氯甲苯、對二乙基苯、第二丁基苯、第三丁基苯、γ-丁內酯、異丁醇、異佛爾酮、乙二醇二***、乙二醇二丁醚、乙二醇單異丙醚、乙二醇單***、乙二醇單***乙酸酯、乙二醇單第三丁醚、乙二醇單丁醚、乙二醇單丁醚乙酸酯、乙二醇單丙醚、乙二醇單己醚、乙二醇單甲醚、乙二醇單甲醚乙酸酯、二異丁基酮、二乙二醇二***、二乙二醇二甲醚、二乙二醇單異丙醚、二乙二醇單***乙酸酯、二乙二醇單丁醚、二乙二醇單丁醚乙酸酯、二乙二醇單甲醚、環己醇、環己醇乙酸酯、環己酮、二丙二醇二甲醚、二丙二醇甲醚乙酸酯、二丙二醇單***、二丙二醇單丁醚、二丙二醇單丙醚、二丙二醇單甲醚、雙丙酮醇、甘油三乙酸酯、三丙二醇單丁醚、三丙二醇單甲醚、丙二醇二乙酸酯、丙二醇苯醚、丙二醇單***、丙二醇單***乙酸酯、丙二醇單丁醚、丙二醇單丙醚、丙 二醇單甲醚、丙二醇單甲醚乙酸酯、丙二醇單甲醚丙酸酯、苄醇、甲基異丁基酮、甲基環己醇、乙酸正戊酯、乙酸正丁酯、乙酸異戊酯、乙酸異丁酯、乙酸丙酯、二元酸酯等。該等溶劑可單獨使用或視需要以任意之比率混合2種以上而使用。 Examples of the organic solvent include 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, and 1,3-butanediol diethyl. Acid ester, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexene-1-one, 3,3 , 5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, acetic acid 3-methoxy-3-methylbutyl, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butanol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chloro Toluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, second butylbenzene, third butylbenzene, γ-butyrolactone, isobutanol, isophorone, Ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether Ether, glycol monobutyl ether acetate, glycol monopropyl ether, glycol mono Hexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, Diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexyl Ketones, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, glycerol triacetate, triacetate Propylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether Ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-pentyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, acetic acid Propyl esters, dibasic acid esters, etc. These solvents can be used singly or as a mixture of two or more kinds at any ratio as needed.
溶劑可以相對於著色組成物中的著色劑100質量份,為100質量份至10000質量份、較佳為500質量份至5000質量份之量使用。 The solvent may be used in an amount of 100 parts by mass to 10,000 parts by mass, preferably 500 parts by mass to 5000 parts by mass, with respect to 100 parts by mass of the coloring agent in the coloring composition.
<光聚合性單體> <Photopolymerizable monomer>
本發明之著色組成物中可添加之光聚合性單體中,包含藉由紫外線或熱等硬化而生成透明樹脂之單體或低聚物。 The photopolymerizable monomer that can be added to the coloring composition of the present invention includes a monomer or oligomer that generates a transparent resin by curing with ultraviolet rays or heat.
作為藉由紫外線或熱等硬化而生成透明樹脂之單體、低聚物,例如可列舉:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸β-羧基乙酯、聚乙二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、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(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、1,6-己二醇二縮水甘油醚二(甲基)丙烯酸酯、雙酚A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、二季戊四醇六(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、(甲基)丙烯酸三環癸酯、酯丙烯酸酯、羥甲基化三聚氰胺之(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、丙烯酸胺基甲酸酯等各種丙烯酸酯及甲基丙烯酸酯、(甲基)丙烯酸、苯乙烯、乙酸乙烯酯、羥 基乙基乙烯醚、乙二醇二乙烯醚、季戊四醇三乙烯醚、(甲基)丙烯醯胺、N-羥基甲基(甲基)丙烯醯胺、N-乙烯基甲醯胺、丙烯腈等,但未必限定於該等。該等光聚合性化合物可單獨使用1種或視需要以任意之比率混合2種以上而使用。 Examples of monomers and oligomers that generate a transparent resin by curing with ultraviolet rays or heat include methyl (meth) acrylate, ethyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. , 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanedi Alcohol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (methyl) Acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol Diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecyl (meth) acrylate, ester acrylate, methylolation Various methacrylates such as (meth) acrylates, epoxy (meth) acrylates, acrylic urethanes, and methacrylates, (Meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acryl Amine, N-vinylformamide, acrylonitrile, and the like are not necessarily limited to these. These photopolymerizable compounds can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.
光聚合性單體的含量相對於著色劑100質量份,較佳為5質量份至500質量份,就光硬化性及顯影性之觀點而言,更佳為10質量份至400質量份。 The content of the photopolymerizable monomer is preferably 5 parts by mass to 500 parts by mass with respect to 100 parts by mass of the colorant, and more preferably 10 parts by mass to 400 parts by mass in terms of photocurability and developability.
<光聚合起始劑> <Photopolymerization initiator>
可於本發明之著色組成物中添加光聚合起始劑而以溶劑顯影型或鹼顯影型感光性著色組成物之形態製備,以藉由紫外線照射使該組成物硬化,藉由光微影法形成濾光片段。 A photopolymerization initiator can be added to the coloring composition of the present invention to prepare it in the form of a solvent-developing type or an alkali-developing type photosensitive coloring composition, and the composition is hardened by ultraviolet irradiation, and a photolithography method A filter segment is formed.
作為光聚合起始劑,可使用4-苯氧基二氯苯乙酮、4-第三丁基二氯苯乙酮、二乙氧基苯乙酮、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-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基丙烷-1-酮、2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎啉基)苯基]-1-丁酮、或2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁烷-1-酮等苯乙酮系化合物;安息香、安息香甲醚、安息香***、安息香異丙醚、或二苯乙二酮二甲基縮酮等安息香系化合物;二苯甲酮、苯甲醯基苯甲酸、苯甲醯基苯甲酸甲酯、4-苯基二苯甲酮、羥基二苯甲酮、丙烯酸化二苯甲酮、4-苯甲醯基-4'-甲基二苯基硫醚、或3,3',4,4'-四(第三丁基過氧化羰基)二苯甲酮等二苯甲酮系化合物;噻噸酮、2-氯噻噸酮、2-甲基噻噸酮、異丙基噻噸酮、2,4-二異丙基噻噸酮、或2,4-二乙 基噻噸酮等噻噸酮系化合物;2,4,6-三氯均三嗪、2-苯基-4,6-雙(三氯甲基)均三嗪、2-(對甲氧基苯基)-4,6-雙(三氯甲基)均三嗪、2-(對甲苯基)-4,6-雙(三氯甲基)均三嗪、2-向日葵基-4,6-雙(三氯甲基)均三嗪、2,4-雙(三氯甲基)-6-苯乙烯基均三嗪、2-(萘-1-基)-4,6-雙(三氯甲基)均三嗪、2-(4-甲氧基-萘-1-基)-4,6-雙(三氯甲基)均三嗪、2,4-三氯甲基-(向日葵基)-6-三嗪、或2,4-三氯甲基-(4'-甲氧基苯乙烯基)-6-三嗪等三嗪系化合物;1,2-辛二酮,1-[4-(苯硫基)-2-(O-苯甲醯基肟)]、或O-(乙醯基)-N-(1-苯基-2-側氧基-2-(4'-甲氧基-萘基)亞乙基)羥基胺等肟酯系化合物;雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、或2,4,6-三甲基苯甲醯基二苯基氧化膦等膦系化合物;9,10-菲醌、樟腦醌、乙基蒽醌等醌系化合物;硼酸鹽系化合物;咔唑系化合物;咪唑系化合物;或者二茂鈦系化合物等。該等光聚合起始劑可單獨使用1種或視需要以任意之比率混合2種以上而使用。 As the photopolymerization initiator, 4-phenoxydichloroacetophenone, 4-tert-butyldichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) can be used. ) -2-hydroxy-2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinylpropane -1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone Or acetophenone compounds such as 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butane-1-one; benzoin, benzoin methyl ether, benzoin ether, benzoin Benzoin compounds such as isopropyl ether, or diacetophenone dimethyl ketal; benzophenone, benzophenethylbenzoic acid, methyl benzylbenzoate, 4-phenylbenzophenone, Hydroxybenzophenone, acrylated benzophenone, 4-benzylidene-4'-methyldiphenylsulfide, or 3,3 ', 4,4'-tetrakis (third butyl peroxide (Carbonyl) benzophenone-based compounds such as benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone Ketones, or thioxanthone compounds such as 2,4-diethylthioxanthone; 2,4,6-trichloro Triazine, 2-phenyl-4,6-bis (trichloromethyl) himetriazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) himetriazine, 2 -(P-tolyl) -4,6-bis (trichloromethyl) mesatriazine, 2-sunfloweryl-4,6-bis (trichloromethyl) mesatriazine, 2,4-bis (trichloro) (Methyl) -6-styryl-triazine, 2- (naphthalen-1-yl) -4,6-bis (trichloromethyl) -triazine, 2- (4-methoxy-naphthalene-1 -Yl) -4,6-bis (trichloromethyl) mesatriazine, 2,4-trichloromethyl- (sunfloweryl) -6-triazine, or 2,4-trichloromethyl- (4 '-Methoxystyryl) -6-triazine and other triazine compounds; 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzylidene oxime) ], Or oxime ester compounds such as O- (ethenyl) -N- (1-phenyl-2- pendantoxy-2- (4'-methoxy-naphthyl) ethylene) hydroxylamine; Phosphine-based compounds such as bis (2,4,6-trimethylbenzylidene) phenylphosphine oxide, or 2,4,6-trimethylbenzylidenediphenylphosphine oxide; 9,10-phenanthrene Quinone compounds such as quinone, camphorquinone, and ethyl anthraquinone; borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds. These photopolymerization initiators may be used individually by 1 type, and may mix and use 2 or more types by arbitrary ratios as needed.
光聚合起始劑含量相對於著色劑100質量份,較佳為1質量份至500質量份,就光硬化性及顯影性之觀點而言,更佳為5質量份至400質量份。 The content of the photopolymerization initiator is preferably 1 to 500 parts by mass based on 100 parts by mass of the colorant, and more preferably 5 to 400 parts by mass from the viewpoint of photocurability and developability.
<增感劑> <Sensitizer>
進而,本發明之彩色濾光片用著色組成物中可含有增感劑。 Furthermore, the coloring composition for color filters of this invention may contain a sensitizer.
作為增感劑,可列舉:以查耳酮衍生物或二亞苄基丙酮等為代表之不飽和酮類、以苯偶醯或樟腦醌等為代表之1,2-二酮衍生物、安息香衍生物、茀衍生物、萘醌衍生物、蒽醌衍生物、二苯并吡喃(xanthene)衍生物、硫雜蒽(thioxanthene)衍生物、氧葱酮(xanthone)衍生物、噻噸酮(thioxanthone)衍生物、香豆素衍 生物、酮基香豆素衍生物、花青衍生物、部花青衍生物、氧喏衍生物等聚次甲基色素、吖啶衍生物、吖嗪衍生物、噻嗪衍生物、噁嗪衍生物、吲哚啉衍生物、薁衍生物、薁鎓衍生物、方酸鎓衍生物、卟啉衍生物、四苯基卟啉衍生物、三芳基甲烷衍生物、四苯并卟啉衍生物、四吡嗪并紫菜嗪衍生物、酞菁衍生物、四氮雜紫菜嗪衍生物、四喹噁啉并紫菜嗪衍生物、萘酚菁衍生物、亞酞菁衍生物、吡喃鎓衍生物、噻喃鎓衍生物、新西蘭雞蛋果青苷(tetraphyllin)衍生物、輪烯衍生物、螺吡喃衍生物、螺噁嗪衍生物、硫代螺吡喃衍生物、金屬芳烴錯合物、有機釕錯合物、米其勒酮衍生物等。該等增感劑可單獨使用1種或視需要以任意之比率混合2種以上而使用。 Examples of the sensitizer include unsaturated ketones represented by chalcone derivatives or dibenzylideneacetone, 1,2-dione derivatives represented by benzophenone or camphorquinone, and benzoin. Derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone ( thioxanthone) derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, and oxazolate derivatives, such as polymethine pigments, acridine derivatives, and azine derivatives , Thiazine derivative, oxazine derivative, indolinoline derivative, osmium derivative, osmium derivative, squarium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative , Tetrabenzoporphyrin derivative, Tetrapyrazino-porphyrazine derivative, Phthalocyanine derivative, Tetraazaporphyrazine derivative, Tetraquinoxaline porphyrazine derivative, Naphthol cyanine derivative, Subphthalocyanine Derivatives, pyranium derivatives, thiananium derivatives, New Zealand eggplant tetraphyllin derivatives, Rotene derivatives, spiropyran derivatives, spiroxazine derivatives, thiospiropyran derivatives, metal aromatic hydrocarbon complexes, organic ruthenium complexes, Michelinone derivatives, and the like. These sensitizers can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.
進而,作為具體例,可列舉:大河原信等人編著之「色素手冊」(1986年、講談社)、大河原信等人編著之「功能性色素之化學」(1981年、CMC)、池森忠三朗等人編著之「特殊功能材料」(1986年、CMC)中所記載之增感劑,但並不限定於該等。另外,此外亦可含有對紫外至近紅外區域之光顯示吸收之增感劑。 Furthermore, as specific examples, the "Color Handbook" (1986, Kodansha) by Ogawara Shinzo and others, the "Chemistry of Functional Pigments" (1981, CMC) by Ogawara Shinzo, and others Sensitizers described in "Special Functional Materials" (1986, CMC) by the author, but are not limited to these. In addition, it may contain a sensitizer that shows absorption of light in the ultraviolet to near-infrared region.
上述增感劑中,作為尤佳的增感劑,可列舉:噻噸酮衍生物、米其勒酮衍生物、咔唑衍生物。進而,具體而言,可使用2,4-二乙基噻噸酮、2-氯噻噸酮、2,4-二氯噻噸酮、2-異丙基噻噸酮、4-異丙基噻噸酮、1-氯-4-丙氧基噻噸酮、4,4'-雙(二甲基胺基)二苯甲酮、4,4'-雙(二乙基胺基)二苯甲酮、4,4'-雙(乙基甲基胺基)二苯甲酮、N-乙基咔唑、3-苯甲醯基-N-乙基咔唑、3,6-二苯甲醯基-N-乙基咔唑等。 Among the above sensitizers, particularly preferred sensitizers include thioxanthone derivatives, Michelinone derivatives, and carbazole derivatives. Further specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropyl can be used. Thioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) diphenyl Methanone, 4,4'-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzyl-N-ethylcarbazole, 3,6-benzophenone Fluorenyl-N-ethylcarbazole and the like.
增感劑的含量相對於著色組成物中所含之光聚合起始劑100質量份,較佳為3質量份至60質量份,就光硬化性、顯影性之觀點而言,更佳為5質量份至50質量份。 The content of the sensitizer is preferably 3 to 60 parts by mass based on 100 parts by mass of the photopolymerization initiator contained in the coloring composition, and more preferably 5 in terms of photohardenability and developability. Part by mass to 50 parts by mass.
<多官能硫醇> <Polyfunctional thiol>
本發明之彩色濾光片用著色組成物可含有多官能硫醇。多官能硫醇係具有2個以上之硫醇(SH)基之化合物。多官能硫醇藉由與上述之光聚合起始劑一起使用,而於光照射後的自由基聚合過程中,作為鏈轉移劑發揮作用,產生不易受到因氧所致之聚合阻礙之硫自由基(thiyl radical),因此所獲得之彩色濾光片用著色組成物成為高感度。尤佳為SH基鍵結於亞甲基、伸乙基等脂肪族基之多官能脂肪族硫醇。 The coloring composition for color filters of the present invention may contain a polyfunctional thiol. The polyfunctional thiol is a compound having two or more thiol (SH) groups. The polyfunctional thiol is used together with the aforementioned photopolymerization initiator, and functions as a chain transfer agent in the radical polymerization process after light irradiation, generating sulfur radicals which are not easily hindered by the polymerization caused by oxygen. (thiyl radical), the coloring composition for a color filter thus obtained has high sensitivity. Particularly preferred is a polyfunctional aliphatic thiol having an SH group bonded to an aliphatic group such as methylene or ethylene.
作為多官能硫醇,例如可列舉:己烷二硫醇、癸烷二硫醇、1,4-丁二醇雙硫代丙酸酯、1,4-丁二醇雙硫代乙醇酸酯、乙二醇雙硫代乙醇酸酯、乙二醇雙硫代丙酸酯、三羥甲基丙烷三硫代乙醇酸酯、三羥甲基丙烷三硫代丙酸酯、三羥甲基乙烷三(3-巰基丁酸酯)、三羥甲基丙烷三(3-巰基丁酸酯)、三羥甲基丙烷三(3-巰基丙酸酯)、季戊四醇四硫代乙醇酸酯、季戊四醇四硫代丙酸酯、季戊四醇四(3-巰基丙酸酯)、二季戊四醇六(3-巰基丙酸酯)、三巰基丙酸三(2-羥基乙基)異氰尿酸酯、1,4-二甲基巰基苯、2,4,6-三巰基均三嗪、2-(N,N-二丁基胺基)-4,6-二巰基均三嗪等。該等多官能硫醇可單獨使用1種或視需要以任意之比率混合2種以上而使用。 Examples of the polyfunctional thiol include hexanedithiol, decane dithiol, 1,4-butanediol dithiopropionate, 1,4-butanediol dithiopropionate, Ethylene glycol dithioglycolate, ethylene glycol dithiopropionate, trimethylolpropane trithioglycolate, trimethylolpropane trithiopropionate, trimethylolethane Tris (3-mercaptobutyrate), trimethylolpropane tri (3-mercaptobutyrate), trimethylolpropane tri (3-mercaptopropionate), pentaerythritol tetrathioglycolate, pentaerythritol tetra Thiopropionate, pentaerythritol tetra (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), trimercaptopropionate tri (2-hydroxyethyl) isocyanurate, 1,4 -Dimethyl mercaptobenzene, 2,4,6-trimercapto-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-triazine, and the like. These polyfunctional thiols can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.
多官能硫醇的含量相對於著色劑100質量份,較佳為0.05 質量份至100質量份,更佳為1.0質量份至50.0質量份。 The content of the polyfunctional thiol is preferably from 0.05 to 100 parts by mass, and more preferably from 1.0 to 50.0 parts by mass based on 100 parts by mass of the colorant.
藉由使用0.05質量份以上之多官能硫醇,可獲得更良好的耐顯影性。於使用硫醇(SH)基為1個之單官能硫醇之情形時,無法獲得此種耐顯影性之提高。 By using a polyfunctional thiol in an amount of 0.05 parts by mass or more, better development resistance can be obtained. When a monofunctional thiol having one thiol (SH) group is used, such an improvement in development resistance cannot be obtained.
<調平劑> <Leveling agent>
本發明之著色組成物中,較佳為添加調平劑,以使透明基板上的組成物的調平性良好。作為調平劑,較佳為主鏈上具有聚醚結構或聚酯結構之二甲基矽氧烷。作為主鏈上具有聚醚結構之二甲基矽氧烷的具體例,可列舉:Dow Corning Toray公司製造之FZ-2122、BYK-Chemie公司製造之BYK-333等。作為主鏈上具有聚酯結構之二甲基矽氧烷的具體例,可列舉:BYK-Chemie公司製造之BYK-310、BYK-370等。主鏈上具有聚醚結構之二甲基矽氧烷、與主鏈上具有聚酯結構之二甲基矽氧烷亦可併用。調平劑的含量通常相對於著色組成物的總質量100質量份,較佳為使用0.003質量份至1.0質量份。 In the coloring composition of the present invention, it is preferable to add a leveling agent so that the leveling property of the composition on the transparent substrate is good. As a leveling agent, dimethylsiloxane having a polyether structure or a polyester structure on the main chain is preferred. Specific examples of the dimethylsiloxane having a polyether structure on the main chain include FZ-2122 manufactured by Dow Corning Toray, BYK-333 manufactured by BYK-Chemie, and the like. Specific examples of the dimethylsiloxane having a polyester structure on the main chain include BYK-310 and BYK-370 manufactured by BYK-Chemie. A dimethylsiloxane having a polyether structure on the main chain and a dimethylsiloxane having a polyester structure on the main chain can also be used in combination. The content of the leveling agent is usually 100 parts by mass with respect to the total mass of the coloring composition, and preferably 0.003 to 1.0 part by mass.
作為尤佳的調平劑,係分子內具有疏水基及親水基之所謂界面活性劑的一種,且具有以下之特徵:儘管具有親水基,但對於水之溶解性小,於添加至著色組成物之情形時,該調平劑的表面張力降低能力低。調平劑進而有用的是儘管表面張力降低能力低,但對玻璃板之潤濕性良好之調平劑,可較佳地使用於因起泡所致之塗膜缺陷不出現之添加量下可充分地抑制帶電性之調平劑。作為具有此種較佳特性之調平劑,可較佳地使用具有聚環氧烷單元之二甲基聚矽氧烷。作為聚環氧烷單元,有聚環氧乙烷單元、聚環氧丙烷單元,二甲基聚矽氧烷亦可一併 具有聚環氧乙烷單元及聚環氧丙烷單元。 As a particularly good leveling agent, it is a type of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, and has the following characteristics: Although it has a hydrophilic group, it has little solubility in water and is added to a coloring composition In this case, the surface tension reducing ability of the leveling agent is low. The leveling agent is further useful as a leveling agent with good wettability to the glass plate despite its low surface tension reducing ability. It can be preferably used in an amount where the coating film defects caused by foaming do not appear. Leveling agent that fully suppresses chargeability. As the leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyethylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit. The dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.
另外,聚環氧烷單元與二甲基聚矽氧烷之鍵結形態可為聚環氧烷單元鍵結於二甲基聚矽氧烷的重複單元中的側鏈型、鍵結於二甲基聚矽氧烷的末端的末端改質型、與二甲基聚矽氧烷交替地重複鍵結的直鏈狀嵌段共聚物型之任一種。具有聚環氧烷單元之二甲基聚矽氧烷係由Dow Corning Toray股份有限公司在市場上銷售,例如可列舉:FZ-2110、FZ-2122、FZ-2130、FZ-2166、FZ-2191、FZ-2203、FZ-2207,但並不限定於該等。 In addition, the bonding form of the polyalkylene oxide unit and the dimethyl polysiloxane may be a side chain type in which the polyalkylene oxide unit is bonded to the repeating unit of the dimethyl polysiloxane, and the dimethyl polysiloxane is bonded to the dimethyl polysiloxane. Either a terminally modified type of the end of the base polysiloxane, or a linear block copolymer type which is repeatedly and repeatedly bonded to dimethyl polysiloxane. The dimethyl polysiloxane having a polyalkylene oxide unit is marketed by Dow Corning Toray Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191 , FZ-2203, FZ-2207, but not limited to these.
調平劑中,亦可輔助性地添加陰離子性、陽離子性、非離子性、或兩性之界面活性劑。界面活性劑亦可混合2種以上而使用。作為輔助性地添加至調平劑中之陰離子性界面活性劑,可列舉:聚氧乙烯烷基醚硫酸鹽、十二烷基苯磺酸鈉、苯乙烯-丙烯酸共聚物之鹼鹽、烷基萘磺酸鈉、烷基二苯醚二磺酸鈉、月桂基硫酸單乙醇胺、月桂基硫酸三乙醇胺、月桂基硫酸銨、硬脂酸單乙醇胺、硬脂酸鈉、月桂基硫酸鈉、苯乙烯-丙烯酸共聚物之單乙醇胺、聚氧乙烯烷基醚磷酸酯等。 To the leveling agent, an anionic, cationic, nonionic, or amphoteric surfactant may also be added auxiliaryly. The surfactant may be used by mixing two or more kinds. Examples of the anionic surfactant to be added to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, and alkyl group. Sodium naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, styrene -Monoethanolamine, polyoxyethylene alkyl ether phosphate, etc. of acrylic copolymers.
作為輔助性地添加至調平劑中之陽離子性界面活性劑,可列舉烷基四級銨鹽或其等之環氧乙烷加成物。作為輔助性地添加至調平劑中之非離子性界面活性劑,可列舉:聚氧乙烯油醚、聚氧乙烯月桂醚、聚氧乙烯壬基苯醚、聚氧乙烯烷基醚磷酸酯、聚氧乙烯山梨醇酐單硬脂酸酯、聚乙二醇單月桂酸酯等。另外,作為輔助性地添加至調平劑中之兩性界面活性劑,可列舉:烷基二甲基胺基乙酸甜菜鹼等烷基甜菜鹼、烷基咪唑啉等兩性界 面活性劑。 Examples of the cationic surfactant to be added to the leveling agent include alkyl quaternary ammonium salts or ethylene oxide adducts thereof. Examples of non-ionic surfactants added to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, Polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate, etc. Examples of the amphoteric surfactants which are added to the leveling agent include alkyl betaines such as alkyldimethylaminoacetic acid betaine, and amphoteric surfactants such as alkylimidazoline.
<紫外線吸收劑、聚合抑制劑> <Ultraviolet absorbent, polymerization inhibitor>
本發明之彩色濾光片用著色組成物中,可含有紫外線吸收劑或聚合抑制劑。藉由含有紫外線吸收劑或聚合抑制劑,可控制圖案的形狀及成像性。 The coloring composition for color filters of this invention may contain a ultraviolet absorber or a polymerization inhibitor. By including an ultraviolet absorber or a polymerization inhibitor, the shape and imageability of the pattern can be controlled.
作為紫外線吸收劑,例如可列舉: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(2,4-二甲基苯基)-1,3,5-三嗪、2-(2-羥基-4-[1-辛氧基羰基乙氧基]苯基)-4,6-雙(4-苯基苯基)-1,3,5-三嗪等羥基苯基三嗪系、2-(5-甲基-2-羥基苯基)苯并***、2-(2H-苯并***-2-基)-4,6-雙(1-甲基-1-苯基乙基)苯酚、2-(3-第三丁基-5-甲基-2-羥基苯基)-5-氯苯并***等苯并***系、2,4-二羥基二苯甲酮、2-羥基-4-辛氧基二苯甲酮、2,2',4,4'-四羥基二苯甲酮等二苯甲酮系、水楊酸苯酯、水楊酸對第三丁基苯酯等水楊酸酯系、2-氰基-3,3'-二苯基丙烯酸乙酯等氰基丙烯酸酯系、2,2,6,6-四甲基哌啶-1-氧自由基(三丙酮-胺-N-氧自由基)、癸二酸雙(2,2,6,6-四甲基-4-哌啶基)酯、聚[[6-[(1,1,3,3-四丁基)胺基]-1,3,5-三嗪-2,4-二基][(2,2,6,6-四甲基-4-哌啶基)亞胺基]等受阻胺系等。該等紫外線吸收劑可單獨使用1種或視需要以任意之比率混合2種以上而使用。 Examples of the ultraviolet absorber include 2- [4-[(2-hydroxy-3- (dodecyl and tridecyl) oxypropyl) oxy] -2-hydroxyphenyl] -4 , 6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4 2,6-bis (4-phenylphenyl) -1,3,5-triazine and other hydroxyphenyltriazines, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (3-thirdbutyl-5-methyl-2- (Hydroxyphenyl) benzotriazoles such as 5-chlorobenzotriazole, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2,2 ', 4 2,4'-tetrahydroxybenzophenones and other benzophenones, salicylic acid phenyl esters, salicylic acid p-tert-butylphenyl esters and other salicylates, 2-cyano-3,3'- Cyanoacrylates such as diphenylethyl acrylate, 2,2,6,6-tetramethylpiperidine-1-oxy radical (triacetone-amine-N-oxy radical), sebacic acid bis ( 2,2,6,6-tetramethyl-4-piperidinyl) ester, poly [[6-[(1,1,3,3-tetrabutyl) amino] -1,3,5-tri Hindered amines such as hydrazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidinyl) imino]. These ultraviolet absorbers can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.
作為聚合抑制劑,例如可列舉:甲基對苯二酚、第三丁基對苯二酚、2,5-二第三丁基對苯二酚、4-苯醌、4-甲氧基苯酚、4-甲氧基-1-萘酚、第三丁基鄰苯二酚等對苯二酚衍生物及苯酚化合物、啡噻嗪、雙-(1-二甲基苄基)啡噻嗪、3,7-二辛基啡噻嗪 等胺化合物、二丁基二硫代胺基甲酸銅、二乙基二硫代胺基甲酸銅、二乙基二硫代胺基甲酸錳、二苯基二硫代胺基甲酸錳等銅及錳鹽化合物、4-亞硝基苯酚、N-亞硝基二苯基胺、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鹽或鋁鹽等。該等聚合抑制劑可單獨使用1種或視需要以任意之比率混合2種以上而使用。 Examples of the polymerization inhibitor include methyl hydroquinone, tert-butyl hydroquinone, 2,5-di-tert-butyl hydroquinone, 4-benzoquinone, and 4-methoxyphenol. Hydroquinone derivatives such as 4-methoxy-1-naphthol, tert-butylcatechol, and phenol compounds, phenothiazine, bis- (1-dimethylbenzyl) phenothiazine, Amine compounds such as 3,7-dioctylphenothiazine, copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, diphenyl Copper and manganese salt compounds such as manganese dithioaminoformate, 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxyamine, N-nitrosophenylhydroxyamine And other nitroso compounds and their ammonium or aluminum salts. These polymerization inhibitors can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.
紫外線吸收劑及聚合抑制劑可以相對於著色組成物中的著色劑100質量份,為0.01質量份至20質量份、較佳為0.05質量份至10質量份之量使用。 The ultraviolet absorber and the polymerization inhibitor may be used in an amount of 0.01 to 20 parts by mass, and preferably 0.05 to 10 parts by mass based on 100 parts by mass of the coloring agent in the coloring composition.
藉由使用0.01質量份以上之紫外線吸收劑或聚合抑制劑,可獲得更良好的成像度。 By using an ultraviolet absorber or a polymerization inhibitor in an amount of 0.01 parts by mass or more, a better imaging degree can be obtained.
<抗氧化劑> <Antioxidant>
本發明之彩色濾光片用著色組成物可含有抗氧化劑,以提高塗膜的透過率。抗氧化劑防止彩色濾光片用著色組成物中所含之光聚合起始劑因熱硬化或ITO(Indium Tin Oxide,氧化銦錫)退火時的熱步驟被氧化而黃變,因此可提高塗膜的透過率。因此,藉由含有抗氧化劑,可防止加熱步驟時因氧化所致之黃變,而獲得塗膜的高透過率。 The coloring composition for a color filter of the present invention may contain an antioxidant to increase the transmittance of the coating film. Antioxidants prevent the photopolymerization initiator contained in the coloring composition for color filters from yellowing due to oxidation by thermal steps during thermal hardening or ITO (Indium Tin Oxide) annealing, which can improve the coating film. Transmittance. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high transmittance of the coating film can be obtained.
作為較佳的抗氧化劑,可列舉:受阻酚系抗氧化劑、受阻胺系抗氧化劑、磷系抗氧化劑或硫醚系抗氧化劑等。另外,更佳為受阻酚系抗氧化劑、受阻胺系抗氧化劑、或磷系抗氧化劑。該等抗氧化劑可單獨使用1種或視需要以任意之比率混合2種以上而使用。 Examples of preferred antioxidants include hindered phenol antioxidants, hindered amine antioxidants, phosphorus antioxidants, and thioether antioxidants. Furthermore, a hindered phenol-based antioxidant, a hindered amine-based antioxidant, or a phosphorus-based antioxidant is more preferable. These antioxidants can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.
作為受阻酚系抗氧化劑,可列舉:2,4-雙[(月桂硫基)甲基]鄰甲酚、1,3,5-三(3,5-二第三丁基-4-羥基苄基)、1,3,5-三(4-第三丁基-3-羥基-2,6-二甲基苄基)、及2,4-雙-(正辛硫基)-6-(4-羥基-3,5-二第三丁基苯胺基)-1,3,5-三嗪、季戊四醇四[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯等。 Examples of the hindered phenol-based antioxidant include 2,4-bis [(laurylthio) methyl] o-cresol, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) ), 1,3,5-tris (4-third butyl-3-hydroxy-2,6-dimethylbenzyl), and 2,4-bis- (n-octylthio) -6- ( 4-hydroxy-3,5-di-tert-butylaniline) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid Esters, etc.
受阻胺系抗氧化劑可列舉:癸二酸雙(2,2,6,6-四甲基-4-哌啶基)酯、癸二酸雙(N-甲基-2,2,6,6-四甲基-4-哌啶基)酯、N,N'-雙(2,2,6,6-四甲基-4-哌啶基)-1,6-六亞甲基二胺、2-甲基-2-(2,2,6,6-四甲基-4-哌啶基)胺基-N-(2,2,6,6-四甲基-4-哌啶基)丙醯胺、1,2,3,4-丁烷四羧酸四(2,2,6,6-四甲基-4-哌啶基)酯、聚[{6-(1,1,3,3-四甲基丁基)亞胺基-1,3,5-三嗪-2,4-二基}{(2,2,6,6-四甲基-4-哌啶基)亞胺基}六甲基{(2,2,6,6-四甲基-4-哌啶基)亞胺基}]、聚[(6-嗎啉基-1,3,5-三嗪-2,4-二基){(2,2,6,6-四甲基-4-哌啶基)亞胺基}六次甲基{(2,2,6,6-四甲基-4-哌啶基)亞胺基}]、琥珀酸二甲酯與1-(2-羥基乙基)-4-羥基-2,2,6,6-四甲基哌啶之縮聚物、N,N'-4,7-四[4,6-雙{N-丁基-N-(1,2,2,6,6-五甲基-4-哌啶基)胺基}-1,3,5-三嗪-2-基]-4,7-二氮雜癸烷-1,10-二胺等。 Examples of hindered amine antioxidants include bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, and bis (N-methyl-2,2,6,6 sebacate -Tetramethyl-4-piperidinyl) ester, N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4-piperidinyl) amino-N- (2,2,6,6-tetramethyl-4-piperidinyl) Propylamine, tetrakis (2,2,6,6-tetramethyl-4-piperidinyl) 1,2,3,4-butanetetracarboxylic acid, poly [{6- (1,1,3 , 3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidinyl) Amine} hexamethyl {(2,2,6,6-tetramethyl-4-piperidinyl) imino}], poly [(6-morpholinyl-1,3,5-triazine- 2,4-diyl) {(2,2,6,6-tetramethyl-4-piperidinyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4 -Piperidinyl) imino}], polycondensate of dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine, N, N'-4,7-tetra [4,6-bis {N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidinyl) amino} -1,3 , 5-triazin-2-yl] -4,7-diazadecane-1,10-diamine and the like.
作為磷系抗氧化劑,可列舉:三[2-[[2,4,8,10-四(1,1-二甲基乙基)二苯并[d,f][1,3,2]二氧雜磷雜環庚烯-6-基]氧基]乙基]胺、三[2-[(4,6,9,11-四第三丁基二苯并[d,f][1,3,2]二氧雜磷雜環庚烯-2-基)氧基]乙基]胺、亞磷酸乙基雙(2,4-二第三丁基-6-甲基苯基)酯。 Examples of the phosphorus-based antioxidant include tris [2-[[2,4,8,10-tetra (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] Dioxaphosphoheptene-6-yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetratert-butyldibenzo [d, f] [1 , 3,2] Dioxaphosphohepten-2-yl) oxy] ethyl] amine, ethylbis (2,4-di-tert-butyl-6-methylphenyl) phosphite .
作為硫醚系抗氧化劑,可列舉:2,2-硫代-二伸乙基雙[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯]、2,4-雙[(辛硫基)甲基]鄰甲酚、2,4-雙[(月桂硫基)甲基]鄰甲酚等。 Examples of the thioether-based antioxidant include 2,2-thio-diethylidenebis [3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate], 2,4 -Bis [(octylthio) methyl] o-cresol, 2,4-bis [(laurylthio) methyl] o-cresol and the like.
抗氧化劑的含量較佳為以於彩色濾光片用著色組成物之固形物成分之合計100質量份中為0.1質量份至5質量份之量使用。於抗氧化劑少於0.1質量份之情形時,透過率提高的效果少,於多於5質量份之情形時,硬度大幅降低,且彩色濾光片用著色組成物的感度大幅降低。 The content of the antioxidant is preferably used in an amount of 0.1 to 5 parts by mass out of 100 parts by mass of the total solid components of the coloring composition for color filters. When the antioxidant is less than 0.1 parts by mass, the effect of improving the transmittance is small, and when it is more than 5 parts by mass, the hardness is greatly reduced, and the sensitivity of the coloring composition for a color filter is significantly reduced.
<其他成分> <Other ingredients>
本發明之彩色濾光片用著色組成物中,可含有矽烷偶合劑等密接提高劑以提高與透明基板之密接性,或具有將溶存氧還原之作用之胺系化合物等。 The coloring composition for a color filter of the present invention may contain an adhesion-improving agent such as a silane coupling agent to improve adhesion to a transparent substrate, or an amine compound having a function of reducing dissolved oxygen.
作為矽烷偶合劑,例如可列舉:乙烯基三(β-甲氧基乙氧基)矽烷、乙烯基乙氧基矽烷、乙烯基三甲氧基矽烷等乙烯基矽烷類、γ-甲基丙烯醯氧基丙基三甲氧基矽烷等(甲基)丙烯酸矽烷類、β-(3,4-環氧環己基)乙基三甲氧基矽烷、β-(3,4-環氧環己基)甲基三甲氧基矽烷、β-(3,4-環氧環己基)乙基三乙氧基矽烷、β-(3,4-環氧環己基)甲基三乙氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷、γ-縮水甘油氧基丙基三乙氧基矽烷等環氧矽烷類、N-β(胺基乙基)γ-胺基丙基三甲氧基矽烷、N-β(胺基乙基)γ-胺基丙基三乙氧基矽烷、N-β(胺基乙基)γ-胺基丙基甲基二乙氧基矽烷、γ-胺基丙基三乙氧基矽烷、γ-胺基丙基三甲氧基矽烷、N-苯基-γ-胺基丙基三甲氧基矽烷、N-苯基-γ-胺基丙基三乙氧基矽 烷等胺基矽烷類、γ-巰基丙基三甲氧基矽烷、γ-巰基丙基三乙氧基矽烷等硫代矽烷類等。 Examples of the silane coupling agent include vinyl silanes such as vinyltri (β-methoxyethoxy) silane, vinylethoxysilane, and vinyltrimethoxysilane, and γ-methacryloxy (Meth) acrylic silanes such as propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethyl Oxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) methyltriethoxysilane, γ-glycidyloxy Epoxysilanes such as propyltrimethoxysilane, γ-glycidyloxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β ( Aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxy Silanes, amines such as γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, etc. Thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane .
矽烷偶合劑可以相對於著色組成物中的著色劑100質量份,為0.01質量份至10質量份、較佳為0.05質量份至5質量份之量使用。 The silane coupling agent may be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, with respect to 100 parts by mass of the coloring agent in the coloring composition.
作為胺系化合物,可列舉:三乙醇胺、甲基二乙醇胺、三異丙醇胺、4-二甲基胺基苯甲酸甲酯、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸異戊酯、苯甲酸2-二甲基胺基乙酯、4-二甲基胺基苯甲酸2-乙基己酯、N,N-二甲基對甲苯胺等。 Examples of the amine-based compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylamine. Isoamylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethyl-p-toluidine and the like.
<彩色濾光片用著色組成物的製造方法> <Manufacturing method of coloring composition for color filters>
本發明之彩色濾光片用著色組成物可將著色劑於樹脂等著色劑載體及/或溶劑中,視需要與分散助劑一起使用捏合機、雙輥研磨機、三輥研磨機、球磨機、橫置式砂磨機、直立式砂磨機、環形珠磨機、或磨碎機等各種分散手段,微細地分散而製造(著色劑分散體)。此時,可將2種以上之著色劑等同時分散於著色劑載體,亦可將分別分散於著色材載體之著色劑混合。環氧化合物可於製備著色劑分散體之階段添加,但隨後添加至所製備之著色劑分散體中,亦可獲得同樣的效果。於染料等著色劑的溶解性高之情形時,具體而言,若對所使用之溶劑之溶解性高,藉由攪拌而溶解,為確認不到異物之狀態,則無需分散至如上述之微細狀態而進行製造。 In the coloring composition for color filters of the present invention, a colorant can be used in a colorant carrier such as a resin and / or a solvent, and a kneader, a two-roll mill, a three-roll mill, a ball mill, Various dispersing means such as a horizontal sand mill, a vertical sand mill, a ring bead mill, or an attritor are finely dispersed and produced (colorant dispersion). In this case, two or more kinds of coloring agents may be dispersed in the colorant carrier at the same time, or the coloring agents each dispersed in the coloring material carrier may be mixed. The epoxy compound can be added at the stage of preparing the colorant dispersion, but the same effect can also be obtained by subsequently adding it to the prepared colorant dispersion. When the solubility of a colorant such as a dye is high, specifically, if the solubility of the solvent used is high, and the solvent is dissolved by stirring, it is not necessary to disperse it to the fineness as described above, so that foreign matter is not recognized. Manufacturing.
另外,於將彩色濾光片用感光性著色組成物用作阻劑材料 之情形時,可製備成溶劑顯影型或鹼顯影型著色組成物。溶劑顯影型或鹼顯影型著色組成物可將前述著色劑分散體、光聚合性單體及/或光聚合起始劑、及視需要之溶劑、其他顏料分散劑、及添加劑等混合而製備。光聚合起始劑可於製備著色組成物之階段添加,亦可隨後添加至所製備之著色組成物中。 When a photosensitive coloring composition for a color filter is used as a resist material, a solvent-developing type or an alkali-developing coloring composition can be prepared. The solvent-developing or alkali-developing coloring composition can be prepared by mixing the aforementioned colorant dispersion, photopolymerizable monomer and / or photopolymerization initiator, and optionally a solvent, other pigment dispersant, and additives. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be subsequently added to the prepared coloring composition.
<分散助劑> <Dispersion aid>
將著色劑分散於著色劑載體中時,較佳為不僅含有樹脂型分散劑,而且亦適宜含有色素衍生物、界面活性劑等分散助劑。分散助劑防止分散後的著色劑之再凝聚之效果大,因此使用分散助劑將著色劑分散於著色劑載體中而成之著色組成物的亮度及保存穩定性良好。 When dispersing a colorant in a colorant carrier, it is preferred to contain not only a resin-based dispersant but also a dispersing aid such as a pigment derivative and a surfactant. The dispersing aid has a large effect of preventing the re-aggregation of the dispersing colorant. Therefore, the coloring composition obtained by dispersing the colorant in the colorant carrier using the dispersing aid has good brightness and storage stability.
<樹脂型分散劑> <Resin-based dispersant>
本發明之彩色濾光片用著色組成物較佳為進而含有具有酸性取代基之樹脂型分散劑。 The coloring composition for color filters of the present invention preferably further contains a resin-based dispersant having an acidic substituent.
樹脂型分散劑具備具有著色劑親和性部位(具有吸附於著色劑之性質)、及與著色劑載體具有相溶性之部位,發揮吸附於著色劑而使著色劑於著色劑載體中的分散穩定化之作用。作為樹脂型分散劑,具體而言,可使用聚胺基甲酸酯、聚丙烯酸酯等聚羧酸酯、不飽和聚醯胺、聚羧酸、聚羧酸(部分)胺鹽、聚羧酸銨鹽、聚羧酸烷基胺鹽、聚矽氧烷、長鏈聚胺基醯胺磷酸鹽、含羥基之聚羧酸酯、或該等之改質物、藉由聚(低級烯亞胺)與具有游離羧基之聚酯之反應所形成之醯胺或其鹽等油性分散劑、(甲基)丙烯酸-苯乙烯共聚物、(甲基)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、聚乙烯基吡咯啶 酮等水溶性樹脂或水溶性高分子化合物、聚酯系、改質聚丙烯酸酯系、環氧乙烷/環氧丙烷加成化合物、磷酸酯系等,該等可單獨使用或混合2種以上而使用,但未必限定於該等。 The resin-based dispersant includes a colorant affinity site (having the property of being adsorbed on a colorant) and a site compatible with the colorant carrier, and exerts adsorption on the colorant to stabilize the dispersion of the colorant in the colorant carrier. The role. As the resin-based dispersant, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamines, polycarboxylic acids, polycarboxylic acid (partial) amine salts, and polycarboxylic acids can be used. Ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminophosphonium phosphates, hydroxyl-containing polycarboxylic acid esters, or modifications thereof, by poly (lower eneimine) Oily dispersants such as amidine or its salt formed by reaction with a polyester having a free carboxyl group, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylate copolymer, styrene -Water-soluble resins such as maleic acid copolymers, polyvinyl alcohol, polyvinyl pyrrolidone or water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide / propylene oxide These compounds can be used alone or in combination of two or more, but they are not necessarily limited to these.
作為市售之樹脂型分散劑,可列舉:BYK-Chemie日本公司製造之Disperbyk-101、103、107、108、110、111、116、130、140、154、161、162、163、164、165、166、170、171、174、180、181、182、183、184、185、190、2000、2001、2020、2025、2050、2070、2095、2150、2155、或Anti-Terra-U、203、204、或BYK-P104、P104S、220S、6919、或Lactimon、Lactimon-WS或Bykumen等、日本Lubrizol公司製造之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、76500等、BASF公司製造之EFKA-46、47、48、452、4008、4009、4010、4015、4020、4047、4050、4055、4060、4080、4400、4401、4402、4403、4406、4408、4300、4310、4320、4330、4340、450、451、453、4540、4550、4560、4800、5010、5065、5066、5070、7500、7554、1101、120、150、1501、1502、1503等、味之素精細技術(Ajinomoto Fine-Techno)公司製造之Ajisper PA111、PB711、PB821、PB822、PB824等。 Examples of commercially available resin-based dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165 manufactured by BYK-Chemie Japan. , 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS, Bykumen, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, manufactured by Japan's Lubrizol Corporation, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., EFKA-46, 47 manufactured by BASF , 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451 , 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501 1502, 1503, etc., Ajisper manufactured by Ajinomoto Fine-Techno of (Ajinomoto Fine-Techno) Company PA111, PB711, PB821, PB822, PB824 and the like.
另外,作為本發明中所使用之樹脂型分散劑,較佳為具有酸性取代基之樹脂型分散劑,其中,較佳為具有芳香族羧基之樹脂型分散劑,原因在於,防止分散後的著色劑之再凝聚之效果特別大。作為具有芳香族羧基之樹脂型分散劑,較佳為包含下述(S1)或(S2)之樹脂型分散劑。 In addition, as the resin-based dispersant used in the present invention, a resin-based dispersant having an acidic substituent is preferable, and among them, a resin-based dispersant having an aromatic carboxyl group is preferable because it prevents coloring after dispersion. The effect of re-aggregation of the agent is particularly great. The resin-based dispersant having an aromatic carboxyl group is preferably a resin-based dispersant containing the following (S1) or (S2).
(S1)樹脂型分散劑,為具有羥基之聚合物的羥基與三羧酸酐及/或四羧酸二酐的酸酐基之反應產物。 (S1) A resin-based dispersant is a reaction product of a hydroxyl group of a polymer having a hydroxyl group and an acid anhydride group of a tricarboxylic anhydride and / or a tetracarboxylic dianhydride.
(S2)樹脂型分散劑,為於具有羥基之化合物的羥基與三羧酸酐及/或四羧酸二酐的酸酐基之反應產物之存在下,使乙烯性不飽和單體進行聚合而成之聚合物。 (S2) Resin-based dispersant is obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product of a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of a tricarboxylic anhydride and / or a tetracarboxylic dianhydride. polymer.
[樹脂型分散劑(S1)] [Resin-based dispersant (S1)]
樹脂型分散劑(S1)可利用WO2008/007776號公報、日本專利特開2008-029901號公報、日本專利特開2009-155406號公報等之公知的方法進行製造。具有羥基之聚合物(p)較佳為末端具有羥基之聚合物,例如可以如下聚合物之形式獲得,該聚合物係於具有羥基之化合物(q)之存在下,使乙烯性不飽和單體(r)進行聚合而成。作為具有羥基之化合物(q),較佳為分子內具有羥基及硫醇基之化合物。由於末端的羥基較佳為多個,故而其中可較佳地使用分子內具有2個羥基及1個硫醇基之化合物(q1)。 The resin-based dispersant (S1) can be produced by a known method such as WO2008 / 007776, Japanese Patent Laid-Open No. 2008-029901, and Japanese Patent Laid-Open No. 2009-155406. The polymer (p) having a hydroxyl group is preferably a polymer having a hydroxyl group at the terminal, and can be obtained, for example, in the form of a polymer which makes an ethylenically unsaturated monomer in the presence of the compound (q) having a hydroxyl group. (r) Polymerization. The compound (q) having a hydroxyl group is preferably a compound having a hydroxyl group and a thiol group in the molecule. Since there are preferably a plurality of terminal hydroxyl groups, a compound (q1) having two hydroxyl groups and one thiol group in the molecule can be preferably used among them.
亦即,作為更佳的一例之於一末端具有2個羥基之聚合物可以聚合物(p1)之形式獲得,該聚合物(p1)係於分子內具有2個羥基及1個硫醇基之化合物(q1)之存在下,使包含單體(r1)之乙烯性不飽和單體(r)進行聚合而成。具有羥基之聚合物(p)的羥基與三羧酸酐及/或四羧酸二酐的酸酐基反應而形成酯鍵,另一方 面,酸酐環開環而產生羧酸。 That is, as a better example, a polymer having two hydroxyl groups at one end can be obtained as a polymer (p1), which is a polymer having two hydroxyl groups and one thiol group in the molecule. The ethylenically unsaturated monomer (r) containing the monomer (r1) is polymerized in the presence of the compound (q1). The hydroxyl group of the polymer (p) having a hydroxyl group reacts with an acid anhydride group of a tricarboxylic anhydride and / or a tetracarboxylic dianhydride to form an ester bond. On the other hand, the acid anhydride ring is ring-opened to generate a carboxylic acid.
[樹脂型分散劑(S2)] [Resin-based dispersant (S2)]
樹脂型分散劑(S2)可利用日本專利特開2009-155406號公報、日本專利特開2010-185934號公報、日本專利特開2011-157416號公報等之公知的方法進行製造,例如可藉由下述方式而獲得,亦即,於具有羥基之化合物(q)的羥基與三羧酸酐及/或四羧酸二酐的酸酐基之反應產物之存在下,使乙烯性不飽和單體(r)進行聚合。其中,較佳為藉由下述方式而成之聚合物,亦即,於分子內具有2個羥基及1個硫醇基之化合物(q1)的羥基與三羧酸酐及/或四羧酸二酐的酸酐基之反應產物之存在下,使包含單體(r1)之乙烯性不飽和單體(r)進行聚合。 The resin-based dispersant (S2) can be produced by a known method such as Japanese Patent Laid-Open No. 2009-155406, Japanese Patent Laid-Open No. 2010-185934, and Japanese Patent Laid-Open No. 2011-157416. It is obtained by making an ethylenically unsaturated monomer (r) in the presence of a reaction product of a hydroxyl group of a compound (q) having a hydroxyl group with an acid anhydride group of a tricarboxylic anhydride and / or a tetracarboxylic dianhydride. ) Polymerize. Among them, a polymer formed by the following manner, that is, the hydroxyl group of the compound (q1) having two hydroxyl groups and one thiol group in the molecule, and tricarboxylic anhydride and / or tetracarboxylic acid di The ethylenically unsaturated monomer (r) containing the monomer (r1) is polymerized in the presence of the reaction product of the anhydride group of the anhydride.
(S1)與(S2)之差異在於,先進行還是後進行乙烯性不飽和單體(r)聚合之聚合物部位之導入。雖分子量等會因各種條件而有略微不同之情況,但只要原料及反應條件相同,則理論上相同。 The difference between (S1) and (S2) is in the introduction of the polymer site for polymerizing the ethylenically unsaturated monomer (r) first or later. Although molecular weight and the like may be slightly different depending on various conditions, as long as the raw materials and reaction conditions are the same, they are theoretically the same.
樹脂型分散劑相對於著色劑總量,較佳為使用5質量份至200質量份左右,就成膜性之觀點而言,更佳為使用5質量份至100質量份左右。 The resin-based dispersant is preferably used in an amount of about 5 parts by mass to about 200 parts by mass with respect to the total amount of the colorant, and more preferably used in a range of about 5 parts by mass to about 100 parts by mass from the viewpoint of film forming properties.
<色素衍生物> <Pigment derivative>
本發明之彩色濾光片用著色組成物較佳為進而含有色素衍生物。色素衍生物亦可包含於偶氮顏料中。 The coloring composition for a color filter of the present invention preferably further contains a pigment derivative. Pigment derivatives may also be included in azo pigments.
作為本發明中所使用之色素衍生物,可使用有機色素殘基具有酸性基、鹼性基、中性基等之公知的色素衍生物。例如可 列舉:具有磺基、羧基、磷酸基等酸性官能基之化合物及該等之胺鹽、或者具有磺醯胺基或末端具有三級胺基等鹼性官能基之化合物、具有苯基或鄰苯二甲醯亞胺烷基等中性官能基之化合物。作為有機色素,例如可列舉:二酮基吡咯并吡咯系顏料、酞菁銅、酞菁鋅、酞菁鋁、鹵化酞菁銅、鹵化酞菁鋅、鹵化酞菁鋁、無金屬酞菁等酞菁系顏料、胺基蒽醌、二胺基二蒽醌、蒽嘧啶、黃士酮、花蒽酮、陰丹士林、皮蒽酮、紫蒽酮等蒽醌系顏料、喹吖啶酮系顏料、二噁嗪系顏料、紫環酮(perinone)系顏料、苝系顏料、噻嗪靛藍系顏料、三嗪系顏料、苯并咪唑酮系顏料、苯并異吲哚等吲哚系顏料、異吲哚啉系顏料、異吲哚啉酮系顏料、喹酞酮系顏料、萘酚系顏料、士林(threne)系顏料、金屬錯合物系顏料、偶氮、雙偶氮、多偶氮等偶氮系顏料等。 As the pigment derivative used in the present invention, a known pigment derivative in which an organic pigment residue has an acidic group, a basic group, a neutral group, or the like can be used. Examples include compounds having acidic functional groups such as sulfo, carboxyl, and phosphate groups, and amine salts thereof, compounds having a sulfoamido group or basic functional groups such as tertiary amine groups at the ends, phenyl groups, or Compounds with neutral functional groups such as phthalimide alkyl groups. Examples of the organic pigment include phthalates such as diketopyrrolopyrrole-based pigments, copper phthalocyanine, zinc phthalocyanine, aluminum phthalocyanine, copper halogenated phthalocyanine, zinc halogenated phthalocyanine, aluminum halogenated phthalocyanine, and metal-free phthalocyanine. Cyan pigments, amino anthraquinone, diamino dianthraquinone, anthracene, anthraquinone, flavone, anthracene, indanthrene, dermatanthone, purple anthrone, and other anthraquinone pigments, quinacridone Pigments, dioxazine-based pigments, perinone-based pigments, fluorene-based pigments, thiazine indigo-based pigments, triazine-based pigments, benzimidazolone-based pigments, indole-based pigments such as benzoisoindole, Isoindoline-based pigments, isoindolinone-based pigments, quinophthalone-based pigments, naphthol-based pigments, threne-based pigments, metal-complex-based pigments, azo, disazo, polyazo Azo-based pigments such as nitrogen.
更具體而言,可列舉:日本專利特開昭61-246261號公報、日本專利特開昭63-264674號公報、日本專利特開平09-272812號公報、日本專利特開平10-245501號公報、日本專利特開平10-265697號公報、日本專利特開平11-199796號公報、日本專利特開2001-172520號公報、日本專利特開2001-220520號公報、日本專利特開2002-201377號公報、日本專利特開2003-165922號公報、日本專利特開2003-168208號公報、日本專利特開2003-171594號公報、日本專利特開2004-217842號公報、日本專利特開2005-213404號公報、日本專利特開2006-291194號公報、日本專利特開2007-079094號公報、日本專利特開2007-226161號公報、日本專利特開2007-314681號公報、日本專利特開2007-314785號公報、日本專利特開2008-31281號公報、日本專利特開2009-57478號公報、WO2009/025325號小冊子、WO2009/081930號小冊子、日本專 利特開2011-162662號公報、WO2011/052617號小冊子、日本專利特開2012-172092號公報、日本專利特開2012-208329號公報、日本專利特開2012-226110號公報、WO2012/102399號小冊子、日本專利特開2014-5439號公報、WO2016/163351號小冊子、日本專利特開2017-156397號公報、日本專利第5753266號公報等中所記載之公知的色素衍生物,該等可單獨使用或混合2種以上而使用。再者,該等文獻中,有時將色素衍生物記載為衍生物、顏料衍生物、顏料分散劑或簡單地記載為化合物等,前述之有機色素殘基具有酸性基、鹼性基、中性基等官能基之化合物與色素衍生物的含義相同。 More specific examples include: Japanese Patent Laid-Open No. 61-246261, Japanese Patent Laid-Open No. 63-264674, Japanese Patent Laid-Open No. 09-272812, Japanese Patent Laid-Open No. 10-245501, Japanese Patent Laid-Open No. 10-265697, Japanese Patent Laid-Open No. 11-199796, Japanese Patent Laid-Open No. 2001-172520, Japanese Patent Laid-Open No. 2001-220520, Japanese Patent Laid-Open No. 2002-201377, Japanese Patent Laid-Open No. 2003-165922, Japanese Patent Laid-Open No. 2003-168208, Japanese Patent Laid-Open No. 2003-171594, Japanese Patent Laid-Open No. 2004-217842, Japanese Patent Laid-Open No. 2005-213404, Japanese Patent Laid-Open No. 2006-291194, Japanese Patent Laid-Open No. 2007-079094, Japanese Patent Laid-Open No. 2007-226161, Japanese Patent Laid-Open No. 2007-314681, Japanese Patent Laid-Open No. 2007-314785, Japanese Patent Laid-Open No. 2008-31281, Japanese Patent Laid-Open No. 2009-57478, WO2009 / 025325 Booklet, WO2009 / 081930 Booklet, Japanese Patent Laid-Open No. 2011-162662, WO2011 / Booklet 052617, Japanese Patent Laid-Open Publication No. 2012-172092, Japanese Patent Laid-Open Publication No. 2012-208329, Japanese Patent Laid-Open Publication No. 2012-226110, WO2012 / 102399 Brochure, Japanese Patent Laid-Open Publication No. 2014-5439, The well-known pigment derivatives described in WO2016 / 163351 pamphlet, Japanese Patent Laid-Open No. 2017-156397, Japanese Patent No. 5753266, etc. can be used alone or in combination of two or more. Moreover, in these documents, a pigment derivative may be described as a derivative, a pigment derivative, a pigment dispersant, or simply as a compound. The organic pigment residue has an acidic group, a basic group, and a neutral group. A functional compound such as a radical has the same meaning as a pigment derivative.
本發明中所使用之色素衍生物中,就抑制顏料彼此之凝聚之效果顯著而言,較佳為具有鹼性取代基之色素衍生物。進而,作為有機色素殘基,就色相或對比度之觀點而言,較佳為源自二酮基吡咯并吡咯系顏料、蒽醌系顏料、喹酞酮系顏料或偶氮系顏料之殘基。 Among the pigment derivatives used in the present invention, a pigment derivative having a basic substituent is preferred because the effect of suppressing the aggregation of the pigments is significant. Further, as the organic pigment residue, from the viewpoint of hue or contrast, a residue derived from a diketopyrrolopyrrole-based pigment, an anthraquinone-based pigment, a quinophthalone-based pigment, or an azo-based pigment is preferred.
<界面活性劑> <Surfactant>
作為界面活性劑,可列舉:月桂基硫酸鈉、聚氧乙烯烷基醚硫酸鹽、十二烷基苯磺酸鈉、苯乙烯-丙烯酸共聚物之鹼鹽、硬脂酸鈉、烷基萘磺酸鈉、烷基二苯醚二磺酸鈉、月桂基硫酸單乙醇胺、月桂基硫酸三乙醇胺、月桂基硫酸銨、硬脂酸單乙醇胺、苯乙烯-丙烯酸共聚物之單乙醇胺、聚氧乙烯烷基醚磷酸酯等陰離子性界面活性劑;聚氧乙烯油醚、聚氧乙烯月桂醚、聚氧乙烯壬基苯醚、聚氧乙烯烷基醚磷酸酯、聚氧乙烯山梨醇酐單硬脂酸酯、聚乙二醇單月桂酸酯等非離子性界面活性劑; 烷基四級銨鹽或其等之環氧乙烷加成物等陽離子性界面活性劑;烷基二甲基胺基乙酸甜菜鹼等烷基甜菜鹼、烷基咪唑啉等兩性界面活性劑;該等可單獨使用或混合2種以上而使用,但未必限定於該等。 Examples of the surfactant include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, and alkylnaphthalenesulfonic acid. Sodium, alkyl diphenyl ether disulfonate, lauryl sulfate monoethanolamine, lauryl triethanolamine, lauryl ammonium sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkane Anionic surfactants such as polyether phosphate; polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearic acid Non-ionic surfactants such as esters, polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts or their ethylene oxide adducts; alkyldimethylaminoacetic acid Ampholytic surfactants such as alkyl betaines such as betaine and alkyl imidazolines; these may be used alone or in combination of two or more, but are not necessarily limited to these.
於添加界面活性劑之情形時,相對於著色劑100質量份,較佳為0.1質量份至55質量份,進而較佳為0.1質量份至45質量份。於界面活性劑的含量未達0.1質量份之情形時,難以獲得添加之效果,若含量多於55質量份,則有時會因過量的分散劑而對分散造成影響。 When a surfactant is added, it is preferably from 0.1 to 55 parts by mass, and more preferably from 0.1 to 45 parts by mass, with respect to 100 parts by mass of the colorant. When the content of the surfactant is less than 0.1 parts by mass, it is difficult to obtain the effect of addition. If the content is more than 55 parts by mass, the dispersion may be affected by an excessive amount of the dispersant.
<粗大粒子之去除> <Removal of Coarse Particles>
本發明之著色組成物較佳為藉由離心分離、利用燒結過濾器或薄膜過濾器之過濾等手段,將5μm以上之粗大粒子、較佳為1μm以上之粗大粒子、進而較佳為0.5μm以上之粗大粒子及混入之塵埃去除。如此,著色組成物較佳為實質上不含0.5μm以上之粒子。更佳為0.3μm以下。 The coloring composition of the present invention is preferably a centrifugal separation, a filtration using a sintering filter or a membrane filter, etc., to coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, and more preferably 0.5 μm or more Remove coarse particles and mixed dust. As described above, the coloring composition preferably does not substantially contain particles of 0.5 μm or more. It is more preferably 0.3 μm or less.
<彩色濾光片> <Color filter>
其次,對本發明之彩色濾光片進行說明。本發明之彩色濾光片係於基材上具備紅色濾光片段、綠色濾光片段、及藍色濾光片段之彩色濾光片,亦可為進而具備洋紅色濾光片段、青色濾光片段、或黃色濾光片段之彩色濾光片,且前述至少1個濾光片段由本發明之著色組成物所形成。 Next, the color filter of the present invention will be described. The color filter of the present invention is a color filter provided with a red filter segment, a green filter segment, and a blue filter segment on a substrate, and may further include a magenta filter segment, The color filter of the cyan filter segment or the yellow filter segment, and the at least one filter segment is formed by the coloring composition of the present invention.
<彩色濾光片的製造方法> <Manufacturing Method of Color Filter>
本發明之彩色濾光片可藉由印刷法或光微影法而進行製造。利用印刷法形成濾光片段時,僅藉由將製備成印刷油墨之著色組成物反覆印刷及乾燥便可實現圖案化,因此作為彩色濾光片的製造法,成本低且量產性優異。進而,隨著印刷技術之發展,可進行具有高尺寸精度及平滑度之微細圖案之印刷。為了進行印刷,較佳為設為如於印刷之版上或於印刷布(blanket)上油墨不乾燥、固化之組成。另外,控制印刷機上的油墨的流動性亦重要,亦可利用分散劑或體質顏料調整油墨黏度。 The color filter of the present invention can be manufactured by a printing method or a photolithography method. When the filter segment is formed by the printing method, patterning can be achieved only by repeatedly printing and drying the coloring composition prepared as a printing ink. Therefore, as a method for manufacturing a color filter, the cost is low and the mass productivity is excellent. Furthermore, with the development of printing technology, printing of fine patterns with high dimensional accuracy and smoothness can be performed. In order to print, it is preferable to set it as the composition which does not dry and solidify ink, such as on a printing plate or a printing blanket. In addition, it is also important to control the fluidity of the ink on the printing press. It is also possible to adjust the viscosity of the ink using dispersants or extender pigments.
於藉由光微影法形成濾光片段之情形時,將製備成上述溶劑顯影型或鹼顯影型著色阻劑材料之著色組成物,藉由噴霧塗佈或旋轉塗佈、狹縫式塗佈、輥式塗佈等塗佈方法,以乾燥膜厚成為0.2μm至5μm之方式,塗佈於透明基板上。對於視需要經乾燥之膜,經由以與該膜接觸或不接觸之狀態所設置且具有預定的圖案之遮罩而進行紫外線曝光。然後,浸漬於溶劑或鹼顯影液或者藉由噴射等來噴霧顯影液,將未硬化部去除而形成所期望的圖案,然後對他色反覆進行同樣的操作而可製造彩色濾光片。進而,為了促進著色阻劑材料之聚合,亦可視需要實施加熱。根據光微影法,可製造精度較上述印刷法高之彩色濾光片。 In the case of forming a filter segment by a photolithography method, the coloring composition prepared as the above-mentioned solvent-developed or alkali-developed coloring resist material is spray-coated or spin-coated, and slit-coated. Coating methods such as cloth and roll coating are applied on a transparent substrate so that the dry film thickness becomes 0.2 μm to 5 μm. The film which has been dried as necessary is subjected to ultraviolet exposure through a mask provided in a state of being in contact with or not in contact with the film and having a predetermined pattern. Then, the developer is immersed in a solvent or an alkali developing solution, or the developing solution is sprayed by spraying, etc., the uncured portion is removed to form a desired pattern, and then the same operation is repeated for other colors to produce a color filter. Furthermore, in order to accelerate the polymerization of the colored resist material, heating may be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.
顯影時,使用碳酸鈉、氫氧化鈉等之水溶液作為鹼顯影液,且亦可使用二甲基苄基胺、三乙醇胺等有機鹼。另外,顯影液中,亦可添加消泡劑或界面活性劑。 During the development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as the alkali developing solution, and an organic base such as dimethylbenzylamine or triethanolamine may also be used. A defoaming agent or a surfactant may be added to the developer.
再者,為了提高紫外線曝光感度,亦可在將上述著色阻劑材料塗佈乾燥後,將水溶性或鹼水溶性樹脂、例如聚乙烯醇或 水溶性丙烯酸樹脂等塗佈乾燥而形成防止因氧所致之聚合阻礙之膜後,進行紫外線曝光。 In addition, in order to increase the sensitivity of ultraviolet exposure, the color resist material may be coated and dried, and then a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin may be coated and dried to prevent the formation of oxygen. After the resulting polymerization-inhibited film, ultraviolet exposure was performed.
本發明之彩色濾光片除上述方法以外,亦可藉由電沈積法、轉印法、噴墨法等進行製造,本發明之著色組成物可用於任一種方法。再者,電沈積法係藉由下述方式而製造彩色濾光片之方法,亦即,利用形成於基板上之透明導電膜,藉由膠體粒子之電泳而於透明導電膜上電沈積形成各色濾光片段,藉此製造彩色濾光片。另外,轉印法係如下方法,亦即,於剝離性之轉印基片的表面預先形成濾光片段,將該濾光片段轉印至所期望的基板。 In addition to the above method, the color filter of the present invention can also be manufactured by an electrodeposition method, a transfer method, an inkjet method, or the like. The coloring composition of the present invention can be used in any method. In addition, the electrodeposition method is a method of manufacturing a color filter by the following methods, that is, using a transparent conductive film formed on a substrate and electrophoresis of colloidal particles on the transparent conductive film to form each color The segments are filtered, thereby making a color filter. The transfer method is a method in which a filter segment is formed in advance on the surface of a releasable transfer substrate, and the filter segment is transferred to a desired substrate.
於透明基板或反射基板等基材上形成各色濾光片段之前,可預先形成黑矩陣。作為黑矩陣,使用鉻或鉻/氧化鉻之多層膜、氮化鈦等無機膜、或分散有遮光劑之樹脂膜,但並不限定於該等。另外,亦可於上述之透明基板或反射基板上預先形成薄膜電晶體(TFT;Thin Film Transistor),然後形成各色濾光片段。另外,於本發明之彩色濾光片上,視需要形成外覆膜或透明導電膜等。 Before forming each color filter segment on a substrate such as a transparent substrate or a reflective substrate, a black matrix may be formed in advance. 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 is not limited. In addition, a thin film transistor (TFT; Thin Film Transistor) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment is formed. In addition, on the color filter of the present invention, an overcoat film, a transparent conductive film, or the like is formed as necessary.
濾光片段及黑矩陣的乾燥膜厚較佳為0.2μm至10μm,更佳為0.2μm至5μm。在使塗佈膜乾燥時,亦可使用減壓乾燥機、對流烘箱、IR(Infrared Radiation;紅外線)烘箱、加熱板等。 The dry film thickness of the filter segment and the black matrix is preferably 0.2 μm to 10 μm, and more preferably 0.2 μm to 5 μm. When drying the coating film, a reduced-pressure dryer, a convection oven, an IR (Infrared Radiation) oven, a heating plate, or the like may be used.
使用密封劑,將彩色濾光片與對向基板貼合,自設置於密封部之注入口注入液晶後,將注入口密封,視需要將偏光膜或 相位差膜貼合於基板的外側,藉此製造液晶顯示面板。 Use a sealant to attach the color filter to the opposite substrate. After injecting liquid crystal from the injection port provided in the sealing section, seal the injection port. If necessary, attach a polarizing film or retardation film to the outside of the substrate. This manufactures a liquid crystal display panel.
該液晶顯示面板可用於使用扭轉向列(TN)、超扭轉向列(STN;Super Twisted Nematic)、面內切換(IPS)、垂直配向(VA)、光學補償彎曲(OCB)等彩色濾光片進行彩色化之液晶顯示模式。 The LCD panel can be used for color filters such as twisted nematic (TN), super twisted nematic (STN; Super Twisted Nematic), in-plane switching (IPS), vertical alignment (VA), and optically compensated bending (OCB). LCD display mode for colorization.
作為透明基板,可使用鈉鈣玻璃、低鹼硼矽酸玻璃、無鹼鋁硼矽酸玻璃等玻璃板、或聚碳酸酯、聚甲基丙烯酸甲酯、聚對苯二甲酸乙二酯等樹脂板。另外,於玻璃板或樹脂板的表面,為了在製成面板後驅動液晶,亦可形成由氧化銦、氧化錫等構成之透明電極。 As the transparent substrate, glass plates such as soda-lime glass, low-alkali borosilicate glass, and alkali-free aluminum borosilicate glass, or resins such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate can be used. board. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of a glass plate or a resin plate in order to drive a liquid crystal after forming a panel.
[實施例] [Example]
以下,基於實施例對本發明進行說明,但本發明並不限定於此。再者,實施例中,「份」及「%」分別表示「質量份」及「質量%」。另外,「PGMAc」意指丙二醇單甲醚乙酸酯。 Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. Furthermore, in the examples, "part" and "%" represent "mass part" and "mass%", respectively. In addition, "PGMAc" means propylene glycol monomethyl ether acetate.
<樹脂的重量平均分子量(Mw)> <Weight average molecular weight (Mw) of the resin>
樹脂的重量平均分子量(Mw)係使用TSKgel管柱(東曹公司製造),利用裝備有RI(Refractive Index;折射率)檢測器之GPC(Gel Permeation Chromatography;凝膠滲透層析儀)(東曹公司製造、HLC-8120GPC),展開溶媒使用THF(Tetrahydrofuran;四氫呋喃)而測定之聚苯乙烯換算的重量平均分子量(Mw)。 The weight-average molecular weight (Mw) of the resin is a GPC (Gel Permeation Chromatography; GPC) equipped with a TSKgel column (manufactured by Tosoh Corporation) using a RI (Refractive Index; refractive index) detector (Tosoh (Manufactured by the company, HLC-8120GPC), and a weight average molecular weight (Mw) in terms of polystyrene measured by using THF (Tetrahydrofuran; tetrahydrofuran) as a developing solvent.
<偶氮顏料的鑑識方法> <Identification method of azo pigment>
鑑識本發明之偶氮顏料時,使用Bruker Daltonics公司製造之MALDI(Matrix Assisted Laser Desorptioh Ionization;基質輔 助雷射脫附游離)質譜分析裝置autoflex III(以下,稱為TOF-MS(Time of Flight-Mass Spectrometry;飛行時間質譜)),以所獲得之質譜圖的分子離子峰值與藉由計算所獲得之質量數一致進行鑑識,進而,使用PerkinElmer公司製造之2400 CHN Element Analyser,以所獲得之各元素之比率與理論值一致進行鑑識。 To identify the azo pigments of the present invention, a MALDI (Matrix Assisted Laser Desorptioh Ionization; matrix-assisted laser desorption free) mass spectrometry device manufactured by Bruker Daltonics was used. Spectrometry; time-of-flight mass spectrometry)), the molecular ion peak of the obtained mass spectrum is identified with the mass obtained by calculation, and further, 2400 CHN Element Analyser manufactured by PerkinElmer is used to obtain each element The ratio is consistent with the theoretical value for identification.
<塗膜的對比率> <Contrast ratio of coating film>
自液晶顯示器用背光單元發出之光通過偏光板而偏振,通過塗佈於玻璃基板上之著色組成物的乾燥塗膜,到達至偏光板。若偏光板與偏光板之偏光面平行,則光透過偏光板,但於偏光面正交之情形時,光由偏光板遮斷。但是,若藉由偏光板而偏振之光通過著色組成物的乾燥塗膜時,會引起顏料粒子所致之散射等,於偏光面的一部分產生偏差,則偏光板平行時,透過偏光板之光量減少,偏光板正交時,一部分光透過偏光板。測定該透過光作為偏光板上的亮度,算出偏光板平行時的亮度、與正交時的亮度之比(對比率)。 The light emitted from the backlight unit for a liquid crystal display is polarized by a polarizing plate, and reaches a polarizing plate through a dry coating film of a colored composition coated on a glass substrate. If the polarizing plate is parallel to the polarizing surface of the polarizing plate, the light passes through the polarizing plate, but when the polarizing surface is orthogonal, the light is blocked by the polarizing plate. However, if the polarized light passes through the dry coating film of the coloring composition when it passes through the dry coating film of the coloring composition, it will cause scattering due to pigment particles, etc., and cause a deviation in a part of the polarizing surface. When the polarizing plates are parallel, the amount of light transmitted through the polarizing plate When the polarizing plate is reduced, a part of the light passes through the polarizing plate. This transmitted light was measured as the brightness on the polarizing plate, and the ratio (contrast ratio) of the brightness when the polarizing plates were parallel to the brightness when the polarizing plates were orthogonal was calculated.
(對比率)=(平行時的亮度)/(正交時的亮度) (Contrast ratio) = (Brightness when parallel) / (Brightness when orthogonal)
再者,作為亮度計,使用色彩亮度計(Topcon公司製造之「BM-5A」),作為偏光板,使用偏光板(日東電工公司製造之「NPF-G1220DUN」)。再者,測定時,為了遮斷不需要的光,於測定部分放置開有1cm見方之孔之黑色遮罩。 As a luminance meter, a color luminance meter ("BM-5A" manufactured by Topcon Corporation) was used, and as a polarizing plate, a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used. During the measurement, in order to block unnecessary light, a black mask with a 1 cm square hole was placed on the measurement portion.
首先,對實施例、製造例及比較例中所使用之丙烯酸樹脂溶液、樹脂型分散劑溶液、著色劑、著色組成物、及感光性著色組成物的製造方法進行說明。 First, a method for producing an acrylic resin solution, a resin-based dispersant solution, a colorant, a coloring composition, and a photosensitive coloring composition used in Examples, Manufacturing Examples, and Comparative Examples will be described.
<丙烯酸樹脂溶液的製造方法> <Manufacturing method of acrylic resin solution>
(丙烯酸樹脂溶液1之製備) (Preparation of acrylic resin solution 1)
於可分離式四口燒瓶上安裝有溫度計、冷卻管、氮氣導入管、滴液管及攪拌裝置之反應容器中添加環己酮196份,升溫至80℃,對反應容器內進行氮氣置換後,自滴液管歷時2小時滴加甲基丙烯酸正丁酯37.2份、甲基丙烯酸2-羥基乙酯12.9份、甲基丙烯酸12.0份、對異丙苯基苯酚環氧乙烷改質丙烯酸酯(東亞合成股份有限公司製造之「Aronix M110」)20.7份、2,2'-偶氮雙異丁腈1.1份之混合物。滴加結束後,進而繼續反應3小時,獲得丙烯酸樹脂之溶液。冷卻至室溫後,取樣樹脂溶液約2份,以180℃、20分鐘進行加熱乾燥,測定不揮發成分,於先行合成之樹脂溶液中,以不揮發成分成為20%之方式添加乙酸甲氧基丙酯,製備丙烯酸樹脂溶液1。重量平均分子量(Mw)為26000。 In a separable four-necked flask, 196 parts of cyclohexanone was added to a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen introduction tube, a dropping tube and a stirring device, and the temperature was raised to 80 ° C. After the nitrogen in the reaction container was replaced, From the dropping tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, and p-cumylphenol ethylene oxide modified acrylate were added dropwise over 2 hours. A mixture of 20.7 parts of "Aronix M110" manufactured by Toa Synthesis Co., Ltd. and 1.1 parts of 2,2'-azobisisobutyronitrile. After 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, sample about 2 parts of the resin solution, heat dry at 180 ° C for 20 minutes, measure the non-volatile content, and add methoxyacetate to the previously synthesized resin solution so that the non-volatile content becomes 20%. Propyl ester to prepare an acrylic resin solution 1. The weight average molecular weight (Mw) was 26,000.
(丙烯酸樹脂溶液2之製備) (Preparation of acrylic resin solution 2)
於可分離式四口燒瓶上安裝有溫度計、冷卻管、氮氣導入管、滴液管及攪拌裝置之反應容器中添加環己酮207份,升溫至80℃,對反應容器內進行氮氣置換後,自滴液管歷時2小時滴加甲基丙烯酸20份、對異丙苯基苯酚環氧乙烷改質丙烯酸酯(東亞合成公司製造之Aronix M110)20份、甲基丙烯酸甲酯45份、甲基丙烯酸2-羥基乙酯8.5份、及2,2'-偶氮雙異丁腈1.33份之混合物。滴加結束後,進而繼續反應3小時,獲得共聚物樹脂溶液。其次,針對所獲得之共聚物溶液全部量,停止氮氣並一面注入乾燥空氣1小時一面進行攪拌,然後冷卻至室溫後, 於70℃歷時3小時滴加異氰酸2-甲基丙烯醯氧基乙酯(昭和電工公司製造之Karenz MOI)6.5份、月桂酸二丁基錫0.08份、環己酮26份之混合物。滴加結束後,進而繼續反應1小時,獲得丙烯酸樹脂之溶液。冷卻至室溫後,取樣樹脂溶液約2份,以180℃、20分鐘進行加熱乾燥,測定不揮發成分,於先行合成之樹脂溶液中,以不揮發成分成為20%之方式添加環己酮,製備丙烯酸樹脂溶液2。重量平均分子量(Mw)為18000。 207 parts of cyclohexanone was added to a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen introduction tube, a dropping tube and a stirring device, and the temperature was raised to 80 ° C. After the nitrogen in the reaction container was replaced, From the dropping tube, 20 parts of methacrylic acid, 20 parts of p-cumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Synthesis Corporation), 45 parts of methyl methacrylate, and A mixture of 8.5 parts of 2-hydroxyethyl methacrylate and 1.33 parts of 2,2'-azobisisobutyronitrile. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin solution. Next, with respect to the entire amount of the obtained copolymer solution, nitrogen was stopped, stirring was performed while injecting dry air for 1 hour, and then the mixture was cooled to room temperature, and then 2-methacrylic acid was added dropwise at 70 ° C for 3 hours. A mixture of 6.5 parts of ethyl methyl ester (Karenz MOI manufactured by Showa Denko Corporation), 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone. After 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, sample about 2 parts of the resin solution, heat dry at 180 ° C for 20 minutes, measure the non-volatile content, and add cyclohexanone to the previously synthesized resin solution so that the non-volatile content becomes 20%. Prepare an acrylic resin solution 2. The weight average molecular weight (Mw) was 18,000.
<樹脂型分散劑溶液的製造方法> <Manufacturing method of resin type dispersant solution>
(樹脂型分散劑溶液1之製備) (Preparation of resin-based dispersant solution 1)
於具備氣體導入管、溫度計、冷凝器、攪拌機之反應容器中,添加甲基丙烯酸10份、甲基丙烯酸甲酯100份、甲基丙烯酸異丁酯70份、甲基丙烯酸苄酯20份,利用氮氣進行置換。將反應容器內加熱至80℃,添加於3-巰基-1,2-丙二醇10份中溶解有2,2'-偶氮雙異丁腈0.1份之溶液,反應10小時。藉由固形物成分測定,確認95%反應。追加均苯四甲酸酐20份、乙酸甲氧基丙酯200.0份、作為觸媒之1,8-二氮雜雙環-[5.4.0]-7-十一烯0.40份,於120℃反應7小時。利用酸值之測定,確認98%以上之酸酐發生半酯化而結束反應,獲得酸值77mgKOH/g、數量平均分子量8500之聚酯分散劑。向該聚酯分散劑中以固形物成分測定中固形物成分成為40%之方式添加乙酸甲氧基丙酯而獲得具有芳香族羧基之樹脂型分散劑溶液1。 To a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of isobutyl methacrylate, and 20 parts of benzyl methacrylate were added and used. Replace with nitrogen. The reaction vessel was heated to 80 ° C., and a solution in which 0.1 parts of 2,2′-azobisisobutyronitrile was dissolved in 10 parts of 3-mercapto-1,2-propanediol was added and reacted for 10 hours. By measuring the solid content, a 95% reaction was confirmed. Add 20 parts of pyromellitic anhydride, 200.0 parts of methoxypropyl acetate, and 0.40 parts of 1,8-diazabicyclo- [5.4.0] -7-undecene as catalyst, and react at 120 ° C for 7 hour. According to the measurement of the acid value, it was confirmed that 98% or more of the acid anhydride was semi-esterified and the reaction was terminated, and a polyester dispersant having an acid value of 77 mgKOH / g and a number average molecular weight of 8,500 was obtained. To this polyester dispersant, methoxypropyl acetate was added so that the solid content in the solid content measurement was 40%, to obtain a resin-based dispersant solution 1 having an aromatic carboxyl group.
(樹脂型分散劑溶液2之製備) (Preparation of resin-based dispersant solution 2)
於具備氣體導入管、溫度計、冷凝器、攪拌機之反應容器中,添加甲基丙烯酸10份、甲基丙烯酸甲酯100份、甲基丙烯 酸異丁酯70份、甲基丙烯酸苄酯20份,利用氮氣進行置換。將反應容器內加熱至80℃,添加於3-巰基-1,2-丙二醇10份中溶解有2,2'-偶氮雙異丁腈0.1份之溶液,反應10小時。藉由固形物成分測定,確認95%反應。追加偏苯三甲酸酐36份、乙酸甲氧基丙酯200.0份、作為觸媒之1,8-二氮雜雙環-[5.4.0]-7-十一烯0.40份,於120℃反應7小時。利用酸值之測定,確認98%以上之酸酐發生半酯化而結束反應,獲得酸值109mgKOH/g、數量平均分子量8500之聚酯分散劑。向該聚酯分散劑中以固形物成分測定中固形物成分成為40%之方式添加乙酸甲氧基丙酯而獲得具有芳香族羧基之樹脂型分散劑溶液2。 To a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of isobutyl methacrylate, and 20 parts of benzyl methacrylate were added and used. Replace with nitrogen. The reaction vessel was heated to 80 ° C., and a solution in which 0.1 parts of 2,2′-azobisisobutyronitrile was dissolved in 10 parts of 3-mercapto-1,2-propanediol was added and reacted for 10 hours. By measuring the solid content, a 95% reaction was confirmed. Added 36 parts of trimellitic anhydride, 200.0 parts of methoxypropyl acetate, and 0.40 parts of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst, and reacted at 120 ° C for 7 hours . According to the measurement of the acid value, it was confirmed that 98% or more of the acid anhydride was semi-esterified and the reaction was terminated, and a polyester dispersant having an acid value of 109 mgKOH / g and a number average molecular weight of 8,500 was obtained. To this polyester dispersant, methoxypropyl acetate was added so that the solid content in the solid content measurement was 40%, to obtain a resin-based dispersant solution 2 having an aromatic carboxyl group.
(樹脂型分散劑溶液3之製備) (Preparation of resin-based dispersant solution 3)
於具備氣體導入管、溫度計、冷凝器、攪拌機之反應容器中,添加3-巰基-1,2-丙二醇6.5份、均苯四甲酸酐4.0份、二甲基苄基胺0.01份、乙酸甲氧基丙酯41.8份,利用氮氣進行置換。將反應容器內加熱至100℃,反應7小時。利用酸值之測定,確認98%以上之酸酐發生半酯化後,將系統內之溫度冷卻至70℃,添加甲基丙烯酸甲酯67份、甲基丙烯酸5.0份、丙烯酸第三丁酯16.0份、甲基丙烯酸羥基甲酯10.0份、丙烯酸乙酯2.0份,並添加2,2'-偶氮雙異丁腈0.10份及乙酸甲氧基丙酯60.0份,反應10小時。藉由固形物成分測定,確認聚合進行95%而結束反應,獲得酸值43mgKOH/g、數量平均分子量15000之聚酯分散劑。向該聚酯分散劑中以固形物成分測定中固形物成分成為40%之方式添加乙酸甲氧基丙酯而獲得具有芳香族羧基之樹脂型分散劑溶液3。 In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 6.5 parts of 3-mercapto-1,2-propanediol, 4.0 parts of pyromellitic anhydride, 0.01 parts of dimethylbenzylamine, and methoxyacetate were added. 41.8 parts of propyl propyl were replaced with nitrogen. The reaction vessel was heated to 100 ° C and reacted for 7 hours. After the acid value was measured, it was confirmed that more than 98% of the anhydride was semi-esterified, and then the temperature in the system was cooled to 70 ° C, and 67 parts of methyl methacrylate, 5.0 parts of methacrylic acid, and 16.0 parts of third butyl acrylate were added. , 10.0 parts of hydroxymethyl methacrylate, 2.0 parts of ethyl acrylate, and added 0.10 parts of 2,2'-azobisisobutyronitrile and 60.0 parts of methoxypropyl acetate, and reacted for 10 hours. According to the measurement of the solid content, it was confirmed that the polymerization proceeded at 95% and the reaction was completed. A polyester dispersant having an acid value of 43 mgKOH / g and a number average molecular weight of 15,000 was obtained. To this polyester dispersant, methoxypropyl acetate was added so that the solid content in the solid content measurement was 40%, to obtain a resin-based dispersant solution 3 having an aromatic carboxyl group.
(樹脂型分散劑溶液4之製備) (Preparation of resin-based dispersant solution 4)
於具備氣體導入管、溫度計、冷凝器、攪拌機之反應容器中,添加3-巰基-1,2-丙二醇6.5份、均苯四甲酸酐4.0份、二甲基苄基胺0.01份、乙酸甲氧基丙酯41.8份,利用氮氣進行置換。將反應容器內加熱至100℃,反應7小時。利用酸值之測定,確認98%以上之酸酐發生半酯化後,將系統內之溫度冷卻至70℃,添加甲基丙烯酸甲酯67份、甲基丙烯酸5.0份、丙烯酸第三丁酯16.0份、甲基丙烯酸(3-乙基氧雜環丁烷-3-基)甲酯10.0份、丙烯酸乙酯2.0份,並添加2,2'-偶氮雙異丁腈0.10份及乙酸甲氧基丙酯60.0份,反應10小時。藉由固形物成分測定,確認聚合進行95%而結束反應,獲得酸值47mgKOH/g、數量平均分子量15000之聚酯分散劑。向該聚酯分散劑中以固形物成分測定中固形物成分成為40%之方式添加乙酸甲氧基丙酯而獲得具有芳香族羧基之樹脂型分散劑溶液4。 In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 6.5 parts of 3-mercapto-1,2-propanediol, 4.0 parts of pyromellitic anhydride, 0.01 parts of dimethylbenzylamine, and methoxyacetate were added. 41.8 parts of propyl propyl were replaced with nitrogen. The reaction vessel was heated to 100 ° C and reacted for 7 hours. After the acid value was measured, it was confirmed that more than 98% of the anhydride was semi-esterified, and then the temperature in the system was cooled to 70 ° C, and 67 parts of methyl methacrylate, 5.0 parts of methacrylic acid, and 16.0 parts of third butyl acrylate were added. , 10.0 parts of (3-ethyloxetane-3-yl) methyl methacrylate, 2.0 parts of ethyl acrylate, and added 0.10 parts of 2,2'-azobisisobutyronitrile and methoxyacetate 60.0 parts of propyl ester, reacted for 10 hours. By measuring the solid content, it was confirmed that the polymerization proceeded at 95% and the reaction was terminated. A polyester dispersant having an acid value of 47 mgKOH / g and a number average molecular weight of 15,000 was obtained. To this polyester dispersant, methoxypropyl acetate was added so that the solid content in the solid content measurement was 40%, to obtain a resin-based dispersant solution 4 having an aromatic carboxyl group.
<色素衍生物的製造方法> <Method for producing pigment derivative>
以下顯示本發明中所使用之色素衍生物的製造方法及結構。再者,本發明並不限定於此。 The manufacturing method and structure of the pigment derivative used by this invention are shown below. The present invention is not limited to this.
(色素衍生物1之製造) (Manufacture of pigment derivative 1)
以日本專利第5748665號之合成例3為參考,製造式5所表示之色素衍生物1。 With reference to Synthesis Example 3 of Japanese Patent No. 5786665, the pigment derivative 1 represented by Formula 5 was produced.
式5
(色素衍生物2之製造) (Manufacture of pigment derivative 2)
以日本專利第4396778號之製造例21為參考,製造式6所表示之色素衍生物2。 With reference to Production Example 21 of Japanese Patent No. 4396778, the pigment derivative 2 represented by Formula 6 was produced.
(色素衍生物3之製造) (Manufacture of pigment derivative 3)
以日本專利第4983061號之製造例6為參考,製造式7所表示之色素衍生物3。 With reference to Production Example 6 of Japanese Patent No. 4,986,061, the pigment derivative 3 represented by Formula 7 was produced.
式7
(色素衍生物4之製造) (Manufacture of Pigment Derivative 4)
以日本專利第5316690號之實施例1為參考,製造式8所表示之色素衍生物4。 With reference to Example 1 of Japanese Patent No. 5316690, a pigment derivative 4 represented by Formula 8 was produced.
(色素衍生物5之製造) (Manufacture of Pigment Derivative 5)
使5-硝基間苯二甲酸16份及N,N-二甲基甲醯胺(DMF;N,N-Dimethylformamide)1.0份溶解於甲苯110份。向該溶液中歷時25分鐘滴加亞硫醯氯22.6份,於110℃回流1小時,合成5-硝基間苯二甲酸二氯化物。使4-胺基-N-(3-(二乙基胺基)丙基)苯甲醯胺38.0份分散於甲苯90份,向該溶液中於室溫下歷時1小時滴加上述5-硝基間苯二甲酸二氯化物後,進行4小時回流,結束反應。一面利用10%碳酸鈉水溶液進行中和,一面將甲苯蒸餾去除後,經過利用3%NaOH水溶液之再漿料化(reslurry)、 過濾、乾燥而獲得下述式9所表示之化合物28.0份。 16 parts of 5-nitroisophthalic acid and 1.0 part of N, N-dimethylformamide (DMF; N, N-Dimethylformamide) were dissolved in 110 parts of toluene. To this solution, 22.6 parts of thionyl chloride was added dropwise over 25 minutes, and refluxed at 110 ° C for 1 hour to synthesize 5-nitroisophthalic acid dichloride. 38.0 parts of 4-amino-N- (3- (diethylamino) propyl) benzamide was dispersed in 90 parts of toluene, and the above-mentioned 5-nitrate was added dropwise to the solution at room temperature for 1 hour. After diisophthalic acid dichloride, reflux was performed for 4 hours to complete the reaction. While neutralizing with a 10% sodium carbonate aqueous solution, distilling away toluene, reslurry using a 3% NaOH aqueous solution, filtering, and drying to obtain 28.0 parts of a compound represented by Formula 9 below.
繼而,使上述式9所表示之化合物25.0份溶解於100份之N-甲基吡咯啶酮,向該溶液中添加將硫氫化鈉水合物(含有硫氫化鈉65%)32份溶解於55份之水而成之水溶液後,回流6小時,獲得下述式10所表示之基礎化合物20.0份。 Next, 25.0 parts of the compound represented by the above formula 9 was dissolved in 100 parts of N-methylpyrrolidone, and 32 parts of sodium sulfide hydrate (containing 65% of sodium sulfide) was dissolved in 55 parts to this solution. The resulting solution was refluxed for 6 hours to obtain 20.0 parts of a basic compound represented by the following formula 10.
使上述式10所表示之基礎化合物20.0份分散於水200份,加冰而將溫度調整為5℃,添加35%鹽酸水溶液20.0份,攪拌 1小時後,添加將亞硝酸鈉3.60份添加至水11.0份而調製之水溶液,攪拌2小時。繼而,添加由80%乙酸水溶液59.0份、25%氫氧化鈉水溶液65.0份、及水64.0份構成之水溶液,製成重氮鎓鹽水溶液。另一方面,使N-[2-甲氧基-5-氯苯基]-3-羥基-2-萘甲醯胺18.7份、25%氫氧化鈉水溶液53.5份溶解於甲醇340份,製成成色劑(coupler)溶液。 Disperse 20.0 parts of the base compound represented by the above formula 10 in 200 parts of water, add ice to adjust the temperature to 5 ° C, add 20.0 parts of a 35% hydrochloric acid aqueous solution, and stir for 1 hour, then add 3.60 parts of sodium nitrite to water 11.0 parts of the prepared aqueous solution was stirred for 2 hours. Next, an aqueous solution consisting of 59.0 parts of an 80% acetic acid aqueous solution, 65.0 parts of a 25% sodium hydroxide aqueous solution, and 64.0 parts of water was added to prepare a diazonium salt aqueous solution. On the other hand, 18.7 parts of N- [2-methoxy-5-chlorophenyl] -3-hydroxy-2-naphthymidine and 53.5 parts of a 25% aqueous sodium hydroxide solution were dissolved in 340 parts of methanol to prepare Coupler solution.
將該成色劑溶液於5℃歷時30分鐘注入至上述重氮鎓鹽水溶液,進行偶合反應。此時之pH為4.4。攪拌1小時,確認重氮鎓鹽消失後,加熱至70℃,進行過濾、水洗,於90℃乾燥24小時,獲得35.8份之式11所表示之色素衍生物5。 This coupler solution was poured into the above diazonium salt aqueous solution at 5 ° C for 30 minutes, and a coupling reaction was performed. The pH at this time was 4.4. After stirring for 1 hour to confirm the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water, and dried at 90 ° C. for 24 hours to obtain 35.8 parts of the pigment derivative 5 represented by Formula 11.
(色素衍生物6之製造) (Manufacture of pigment derivative 6)
以日本專利第1863188號之製造例3為參考,製造式12所表示之色素衍生物6。 With reference to Production Example 3 of Japanese Patent No. 1863188, a pigment derivative 6 represented by Formula 12 was produced.
式12
<著色劑的製造方法> <Method for Manufacturing Colorant>
(基礎化合物) (Base compound)
此次使用之基礎化合物([B-1]至[B-18])記載於表1。表中的Ph表示苯基。 The basic compounds ([B-1] to [B-18]) used this time are shown in Table 1. Ph in the table represents a phenyl group.
(成色劑化合物[C-1]之製造) (Manufacture of Coupler Compound [C-1])
將3-羥基-2-萘甲酸167份、四氫呋喃1500份、N,N-二甲基甲醯胺1份混合後,添加亞硫醯氯221份,於室溫下攪拌1小時,藉此獲得羧醯氯溶液。此外,預先製備將N-甲基吡咯啶酮1000份、1,3-苯二胺48份混合而成之溶液,針對該溶液,歷時30分鐘滴加羧醯氯溶液。此時,一面將反應溶液的溫度保持為10℃以下,一面進行滴加。滴加結束後,於室溫下攪拌2小時後,濾取所析出之反應物,獲得目標物。進而,利用甲醇1000 份進行洗淨,於減壓下進行乾燥,藉此獲得成色劑化合物[C-1]196份(產率98.5%)。 After mixing 167 parts of 3-hydroxy-2-naphthoic acid, 1500 parts of tetrahydrofuran, and 1 part of N, N-dimethylformamide, 221 parts of thionyl chloride was added and stirred at room temperature for 1 hour to obtain Carboxamidine chloride solution. In addition, a solution prepared by mixing 1000 parts of N-methylpyrrolidone and 48 parts of 1,3-phenylenediamine was prepared in advance, and a carboxyphosphonium chloride solution was added dropwise to the solution over 30 minutes. At this time, the temperature of the reaction solution was kept at 10 ° C. or lower, and dropwise addition was performed. After completion of the dropwise addition, after stirring at room temperature for 2 hours, the precipitated reaction product was collected by filtration to obtain the target product. Furthermore, 196 parts (yield: 98.5%) of the coupler compound [C-1] was obtained by washing with 1000 parts of methanol and drying under reduced pressure.
(成色劑化合物[C-2]至成色劑化合物[C-70]之製造) (Manufacture of Coupler Compound [C-2] to Coupler Compound [C-70])
代替成色劑化合物[C-1]之製造中所使用之1,3-苯二胺48份,變更為表2中所記載之二胺類、質量份,除此以外,進行與成色劑化合物[C-1]之製造同樣之操作,製造成色劑化合物[C-2]至成色劑化合物[C-70]。 In place of 48 parts of 1,3-phenylenediamine used in the production of the coupler compound [C-1], the diamines and parts by mass described in Table 2 were changed, and in addition to the coupler compound [ C-1] Production The same operation was performed to produce a coupler compound [C-2] to a coupler compound [C-70].
<偶氮顏料之製造> <Manufacture of azo pigment>
[實施例1] [Example 1]
(偶氮顏料1之製造) (Manufacture of Azo Pigment 1)
於N-甲基吡咯啶酮1500份中添加基礎化合物[B-1]185份後,添加35%鹽酸294份,以成為-2℃至0℃之方式進行冷卻。於該溶液中添加25%亞硝酸鈉水溶液208份後,一面保持為0℃至5℃,一面攪拌30分鐘,製備重氮鎓溶液。此外,製備由成色劑化合物[C-1]167份、及25%氫氧化鈉溶液316份、甲醇1500份構成之成色劑溶液。將所製備之重氮鎓溶液及成色劑溶液同時以10分鐘滴加至pH5.4之乙酸緩衝溶液1000份。滴加結束後,於室溫下攪拌30分鐘後,進而,一面保持為80℃一面進行攪拌,濾取所析出之反應物,利用熱水進行洗淨後,進行乾燥而獲得343份之偶氮顏料1(產率:95.8%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料1。 After 185 parts of the basic compound [B-1] was added to 1500 parts of N-methylpyrrolidone, 294 parts of 35% hydrochloric acid was added, and the mixture was cooled to a temperature of -2 ° C to 0 ° C. After adding 208 parts of a 25% sodium nitrite aqueous solution to this solution, the solution was kept at 0 ° C. to 5 ° C. and stirred for 30 minutes to prepare a diazonium solution. In addition, a coupler solution composed of 167 parts of a coupler compound [C-1], 316 parts of a 25% sodium hydroxide solution, and 1500 parts of methanol was prepared. The prepared diazonium solution and the coupler solution were simultaneously added dropwise to 1000 parts of an acetic acid buffer solution at pH 5.4 over 10 minutes. After the dropwise addition was completed, the mixture was stirred at room temperature for 30 minutes, and further stirred while maintaining the temperature at 80 ° C. The precipitated reaction product was filtered, washed with hot water, and dried to obtain 343 parts of azo. Pigment 1 (yield: 95.8%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, it was identified as azo pigment 1.
[實施例2] [Example 2]
(偶氮顏料2之製造) (Manufacture of Azo Pigment 2)
代替偶氮顏料1之製造中所使用之基礎化合物[B-1]185份,使用基礎化合物[B-2]169份,除此以外,進行與偶氮顏料1之製造同樣之操作,獲得337份之偶氮顏料2(產率:98.1%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料2。 Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 1, and using 169 parts of the basic compound [B-2], the same operation as in the production of the azo pigment 1 was performed to obtain 337. Parts of azo pigment 2 (yield: 98.1%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, it was identified as azo pigment 2.
[實施例3] [Example 3]
(偶氮顏料3之製造) (Manufacture of Azo Pigment 3)
代替偶氮顏料1之製造中所使用之基礎化合物[B-1]185份,使用基礎化合物[B-3]210份,除此以外,進行與偶氮顏料1之製造同樣之操作,獲得371份之偶氮顏料3(產率:96.7%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料3。 Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 1, and using 210 parts of the basic compound [B-3], the same operation as in the production of the azo pigment 1 was performed to obtain 371 Parts of azo pigment 3 (yield: 96.7%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, it was identified as azo pigment 3.
[實施例4] [Example 4]
(偶氮顏料4之製造) (Manufacture of Azo Pigment 4)
代替偶氮顏料1之製造中所使用之基礎化合物[B-1]185份,使用基礎化合物[B-4]181份,除此以外,進行與偶氮顏料1之製造同樣之操作,獲得340份之偶氮顏料4(產率:95.6%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料4。 Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 1, and using 181 parts of the basic compound [B-4], the same operation as in the production of the azo pigment 1 was performed to obtain 340. Parts of azo pigment 4 (yield: 95.6%). Based on the mass spectrum analysis and elemental analysis of TOF-MS, it was identified as azo pigment 4.
[實施例5] [Example 5]
(偶氮顏料5之製造) (Manufacture of Azo Pigment 5)
代替偶氮顏料1之製造中所使用之基礎化合物[B-1]185份,使用基礎化合物[B-5]222份,除此以外,進行與偶氮顏料1之製造同樣之操作,獲得384份之偶氮顏料5(產率:97.1%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料5。 Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 1, and using 222 parts of the basic compound [B-5], the same operation as in the production of the azo pigment 1 was performed to obtain 384. Parts of azo pigment 5 (yield: 97.1%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, it was identified as azo pigment 5.
[實施例6] [Example 6]
(偶氮顏料6之製造) (Manufacture of Azo Pigment 6)
代替偶氮顏料1之製造中所使用之基礎化合物[B-1]185份,使用基礎化合物[B-6]228份,除此以外,進行與偶氮顏料1之製造同樣之操作,獲得393份之偶氮顏料6(產率:97.8%)。利用 TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料6。 Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 1 and using 228 parts of the basic compound [B-6], the same operation as in the production of the azo pigment 1 was performed to obtain 393 Parts of azo pigment 6 (yield: 97.8%). Based on the mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 6.
[實施例7] [Example 7]
(偶氮顏料7之製造) (Manufacture of Azo Pigment 7)
代替偶氮顏料1之製造中所使用之基礎化合物[B-1]185份,使用基礎化合物[B-7]124份,除此以外,進行與偶氮顏料1之製造同樣之操作,獲得287份之偶氮顏料7(產率:96.2%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料7。 Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 1 and using 124 parts of the basic compound [B-7], the same operation as in the production of the azo pigment 1 was performed to obtain 287 Parts of azo pigment 7 (yield: 96.2%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 7.
[實施例8] [Example 8]
(偶氮顏料8之製造) (Manufacture of Azo Pigment 8)
代替偶氮顏料1之製造中所使用之基礎化合物[B-1]185份,使用基礎化合物[B-8]128份,除此以外,進行與偶氮顏料1之製造同樣之操作,獲得296份之偶氮顏料8(產率:97.9%)。利用 TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料8。 Instead of 185 parts of the base compound [B-1] used in the production of the azo pigment 1, and 128 parts of the base compound [B-8], the same operation as in the production of the azo pigment 1 was performed to obtain 296 Parts of azo pigment 8 (yield: 97.9%). Based on the mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 8.
[實施例9] [Example 9]
(偶氮顏料9之製造) (Manufacture of Azo Pigment 9)
代替偶氮顏料1之製造中所使用之基礎化合物[B-1]185份,使用基礎化合物[B-9]156份,除此以外,進行與偶氮顏料1之製造同樣之操作,獲得322份之偶氮顏料9(產率:97.7%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料9。 Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 1, and using 156 parts of the basic compound [B-9], the same operation as in the production of the azo pigment 1 was performed to obtain 322 Parts of azo pigment 9 (yield: 97.7%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 9.
[實施例10] [Example 10]
(偶氮顏料10之製造) (Manufacture of Azo Pigment 10)
代替偶氮顏料1之製造中所使用之基礎化合物[B-1]185份,使用基礎化合物[B-10]187份,除此以外,進行與偶氮顏料1之製造同樣之操作,獲得357份之偶氮顏料10(產率:98.9%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料10。 Instead of 185 parts of the base compound [B-1] used in the production of the azo pigment 1, and 187 parts of the base compound [B-10], the same operation as in the production of the azo pigment 1 was performed to obtain 357 Parts of azo pigment 10 (yield: 98.9%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 10 was identified.
[實施例11] [Example 11]
(偶氮顏料11之製造) (Manufacture of Azo Pigment 11)
代替偶氮顏料1之製造中所使用之基礎化合物[B-1]185份,使用基礎化合物[B-11]190份,除此以外,進行與偶氮顏料1之製造同樣之操作,獲得352份之偶氮顏料11(產率:96.6%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料11。 Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 1, and using 190 parts of the basic compound [B-11], the same operation as in the production of the azo pigment 1 was performed to obtain 352 Parts of azo pigment 11 (yield: 96.6%). The result of mass spectrometry and elemental analysis of TOF-MS identified the azo pigment 11.
[實施例12] [Example 12]
(偶氮顏料12之製造) (Manufacture of Azo Pigment 12)
代替偶氮顏料1之製造中所使用之基礎化合物[B-1]185份,使用基礎化合物[B-12]240份,除此以外,進行與偶氮顏料1之製造同樣之操作,獲得399份之偶氮顏料12(產率:96.4%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料12。 Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 1 and using 240 parts of the basic compound [B-12], the same operation as in the production of the azo pigment 1 was performed to obtain 399 Parts of azo pigment 12 (yield: 96.4%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 12 was identified.
[實施例13] [Example 13]
(偶氮顏料13之製造) (Manufacture of Azo Pigment 13)
代替偶氮顏料1之製造中所使用之基礎化合物[B-1]185份,使用基礎化合物[B-13]207份,除此以外,進行與偶氮顏料1之製造同樣之操作,獲得373份之偶氮顏料13(產率:97.9%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料13。 Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 1 and using 207 parts of the basic compound [B-13], the same operation as in the production of the azo pigment 1 was performed to obtain 373 Parts of azo pigment 13 (yield: 97.9%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 13 was identified.
[實施例14] [Example 14]
(偶氮顏料14之製造) (Manufacture of Azo Pigment 14)
代替偶氮顏料1之製造中所使用之基礎化合物[B-1]185份,使用基礎化合物[B-14]241份,除此以外,進行與偶氮顏料1之製造同樣之操作,獲得394份之偶氮顏料14(產率:95.0%)。利用 TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料14。 Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 1 and using 241 parts of the basic compound [B-14], the same operation as in the production of the azo pigment 1 was performed to obtain 394 Parts of azo pigment 14 (yield: 95.0%). The TOF-MS mass spectrum analysis and elemental analysis identified the azo pigment 14.
[實施例15] [Example 15]
(偶氮顏料15之製造) (Manufacture of Azo Pigment 15)
代替偶氮顏料1之製造中所使用之基礎化合物[B-1]185份,使用基礎化合物[B-15]215份,除此以外,進行與偶氮顏料1之製造同樣之操作,獲得372份之偶氮顏料15(產率:95.8%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料15。 Instead of 185 parts of the base compound [B-1] used in the production of the azo pigment 1, and 215 parts of the base compound [B-15], the same operation as in the production of the azo pigment 1 was performed to obtain 372 Parts of azo pigment 15 (yield: 95.8%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 15 was identified.
[實施例16] [Example 16]
(偶氮顏料16之製造) (Manufacture of Azo Pigment 16)
代替偶氮顏料1之製造中所使用之基礎化合物[B-1]185份, 使用基礎化合物[B-16]233份,除此以外,進行與偶氮顏料1之製造同樣之操作,獲得390份之偶氮顏料16(產率:96.0%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料16。 Instead of 185 parts of the base compound [B-1] used in the production of the azo pigment 1, and 233 parts of the base compound [B-16], the same operation as in the production of the azo pigment 1 was performed to obtain 390 Parts of azo pigment 16 (yield: 96.0%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 16 was identified.
[實施例17] [Example 17]
(偶氮顏料17之製造) (Manufacture of Azo Pigment 17)
代替偶氮顏料1之製造中所使用之基礎化合物[B-1]185份,使用基礎化合物[B-17]298份,除此以外,進行與偶氮顏料1之製造同樣之操作,獲得455份之偶氮顏料17(產率:96.5%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料17。 Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 1, and using 298 parts of the basic compound [B-17], the same operation as in the production of the azo pigment 1 was performed to obtain 455 Parts of azo pigment 17 (yield: 96.5%). The result of mass spectrometry and elemental analysis of TOF-MS identified the azo pigment 17.
[實施例18] [Example 18]
(偶氮顏料18之製造) (Manufacture of Azo Pigment 18)
代替偶氮顏料1之製造中所使用之基礎化合物[B-1]185份,使用基礎化合物[B-18]415份,除此以外,進行與偶氮顏料1之製造同樣之操作,獲得567份之偶氮顏料18(產率:96.5%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料18。 Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 1 and using 415 parts of the basic compound [B-18], the same operation as in the production of the azo pigment 1 was performed to obtain 567 Parts of azo pigment 18 (yield: 96.5%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 18 was identified.
[實施例19] [Example 19]
(偶氮顏料19之製造) (Manufacture of Azo Pigment 19)
代替偶氮顏料1之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-57]219份,除此以外,進行與偶氮顏料1之製造同樣之操作,獲得396份之偶氮顏料19(產率:96.4%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料19。 Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 1, and using 219 parts of the coupler compound [C-57], the same operation as in the production of the azo pigment 1 396 parts of the azo pigment 19 was obtained (yield: 96.4%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 19 was identified.
偶氮顏料19
[實施例20] [Example 20]
(偶氮顏料20之製造) (Manufacture of Azo Pigment 20)
代替偶氮顏料19之製造中所使用之基礎化合物[B-1]185份,使用基礎化合物[B-2]169份,除此以外,進行與偶氮顏料19之製造同樣之操作,獲得390份之偶氮顏料20(產率:98.7%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料20。 Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 19 and using 169 parts of the basic compound [B-2], the same operation as in the production of the azo pigment 19 was performed to obtain 390 Parts of azo pigment 20 (yield: 98.7%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 20 was identified.
[實施例21] [Example 21]
(偶氮顏料21之製造) (Manufacture of Azo Pigment 21)
代替偶氮顏料19之製造中所使用之基礎化合物[B-1]185份,使用基礎化合物[B-3]210份,除此以外,進行與偶氮顏料19之製造同樣之操作,獲得430份之偶氮顏料21(產率:98.7%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料21。 Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 19 and using 210 parts of the basic compound [B-3], the same operation as in the production of the azo pigment 19 was performed to obtain 430 Parts of azo pigment 21 (yield: 98.7%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 21 was identified.
[實施例22] [Example 22]
(偶氮顏料22之製造) (Manufacture of Azo Pigment 22)
代替偶氮顏料19之製造中所使用之基礎化合物[B-1]185份,使用基礎化合物[B-4]181份,除此以外,進行與偶氮顏料19之製造同樣之操作,獲得397份之偶氮顏料22(產率:97.4%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料22。 Instead of using 185 parts of the base compound [B-1] used in the production of the azo pigment 19 and using 181 parts of the base compound [B-4], the same operation as in the production of the azo pigment 19 was performed to obtain 397 Parts of azo pigment 22 (yield: 97.4%). The result of mass spectrometry and elemental analysis of TOF-MS identified the azo pigment 22.
[實施例23] [Example 23]
(偶氮顏料23之製造) (Manufacture of Azo Pigment 23)
代替偶氮顏料19之製造中所使用之基礎化合物[B-1]185份,使用基礎化合物[B-5]222份,除此以外,進行與偶氮顏料19之製造同樣之操作,獲得433份之偶氮顏料23(產率:96.7%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料23。 Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 19 and using 222 parts of the basic compound [B-5], the same operation as in the production of the azo pigment 19 was performed to obtain 433 Parts of azo pigment 23 (yield: 96.7%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 23 was identified.
[實施例24] [Example 24]
(偶氮顏料24之製造) (Manufacture of Azo Pigment 24)
代替偶氮顏料19之製造中所使用之基礎化合物[B-1]185份,使用基礎化合物[B-6]228份,除此以外,進行與偶氮顏料19之製造同樣之操作,獲得435份之偶氮顏料24(產率:95.8%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料24。 Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 19 and using 228 parts of the basic compound [B-6], the same operation as in the production of the azo pigment 19 was performed to obtain 435 Parts of azo pigment 24 (yield: 95.8%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 24 was identified.
[實施例25] [Example 25]
(偶氮顏料25之製造) (Manufacture of Azo Pigment 25)
代替偶氮顏料19之製造中所使用之基礎化合物[B-1]185份,使用基礎化合物[B-7]124份,除此以外,進行與偶氮顏料19之製造同樣之操作,獲得344份之偶氮顏料25(產率:98.0%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料25。 Instead of 185 parts of the base compound [B-1] used in the production of the azo pigment 19 and 124 parts of the base compound [B-7], the same operation as in the production of the azo pigment 19 was performed, and 344 was obtained Parts of azo pigment 25 (yield: 98.0%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 25 was identified.
[實施例26] [Example 26]
(偶氮顏料26之製造) (Manufacture of Azo Pigment 26)
代替偶氮顏料19之製造中所使用之基礎化合物[B-1]185份,使用基礎化合物[B-8]128份,除此以外,進行與偶氮顏料19之製造同樣之操作,獲得337份之偶氮顏料26(產率:95.2%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料26。 Instead of 185 parts of the base compound [B-1] used in the production of the azo pigment 19 and 128 parts of the base compound [B-8], the same operation as in the production of the azo pigment 19 was performed to obtain 337 Parts of azo pigment 26 (yield: 95.2%). The TOF-MS mass spectrum analysis and elemental analysis identified the azo pigment 26.
[實施例27] [Example 27]
(偶氮顏料27之製造) (Manufacture of Azo Pigment 27)
代替偶氮顏料19之製造中所使用之基礎化合物[B-1]185份,使用基礎化合物[B-9]156份,除此以外,進行與偶氮顏料19之製造同樣之操作,獲得373份之偶氮顏料27(產率:97.6%)。利 用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料27。 Instead of using 185 parts of the base compound [B-1] used in the production of the azo pigment 19 and using 156 parts of the base compound [B-9], the same operation as in the production of the azo pigment 19 was performed to obtain 373 Parts of azo pigment 27 (yield: 97.6%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 27 was identified.
[實施例28] [Example 28]
(偶氮顏料28之製造) (Manufacture of Azo Pigment 28)
代替偶氮顏料19之製造中所使用之基礎化合物[B-1]185份,使用基礎化合物[B-10]187份,除此以外,進行與偶氮顏料19之製造同樣之操作,獲得393份之偶氮顏料28(產率:95.1%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料28。 Instead of using 185 parts of the base compound [B-1] used in the production of the azo pigment 19 and using 187 parts of the base compound [B-10], the same operation as in the production of the azo pigment 19 was performed to obtain 393 Parts of azo pigment 28 (yield: 95.1%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 28 was identified.
[實施例29] [Example 29]
(偶氮顏料29之製造) (Manufacture of Azo Pigment 29)
代替偶氮顏料19之製造中所使用之基礎化合物[B-1]185 份,使用基礎化合物[B-11]190份,除此以外,進行與偶氮顏料19之製造同樣之操作,獲得405份之偶氮顏料29(產率:97.4%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料29。 Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 19 and using 190 parts of the basic compound [B-11], the same operation as in the production of the azo pigment 19 was performed to obtain 405 Parts of azo pigment 29 (yield: 97.4%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 29 was identified.
[實施例30] [Example 30]
(偶氮顏料30之製造) (Manufacture of Azo Pigment 30)
代替偶氮顏料19之製造中所使用之基礎化合物[B-1]185份,使用基礎化合物[B-12]240份,除此以外,進行與偶氮顏料19之製造同樣之操作,獲得456份之偶氮顏料30(產率:97.8%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料30。 Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 19 and using 240 parts of the basic compound [B-12], the same operation as in the production of the azo pigment 19 was performed to obtain 456 Parts of azo pigment 30 (yield: 97.8%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 30 was identified.
[實施例31] [Example 31]
(偶氮顏料31之製造) (Manufacture of Azo Pigment 31)
代替偶氮顏料19之製造中所使用之基礎化合物[B-1]185份,使用基礎化合物[B-13]207份,除此以外,進行與偶氮顏料19之製造同樣之操作,獲得424份之偶氮顏料31(產率:97.8%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料31。 Instead of 185 parts of the base compound [B-1] used in the production of the azo pigment 19 and 207 parts of the base compound [B-13], the same operation as in the production of the azo pigment 19 was performed to obtain 424 Parts of azo pigment 31 (yield: 97.8%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 31 was identified.
[實施例32] [Example 32]
(偶氮顏料32之製造) (Manufacture of Azo Pigment 32)
代替偶氮顏料19之製造中所使用之基礎化合物[B-1]185份,使用基礎化合物[B-14]241份,除此以外,進行與偶氮顏料19之製造同樣之操作,獲得457份之偶氮顏料32(產率:97.8%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料32。 Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 19 and using 241 parts of the basic compound [B-14], the same operation as in the production of the azo pigment 19 was performed to obtain 457 Parts of azo pigment 32 (yield: 97.8%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 32 was identified.
偶氮顏料32
[實施例33] [Example 33]
(偶氮顏料33之製造) (Manufacture of Azo Pigment 33)
代替偶氮顏料19之製造中所使用之基礎化合物[B-1]185份,使用基礎化合物[B-15]215份,除此以外,進行與偶氮顏料19之製造同樣之操作,獲得428份之偶氮顏料33(產率:97.0%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料33。 Instead of using 185 parts of the base compound [B-1] used in the production of the azo pigment 19 and using 215 parts of the base compound [B-15], the same operation as in the production of the azo pigment 19 was performed to obtain 428 Parts of azo pigment 33 (yield: 97.0%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 33 was identified.
[實施例34] [Example 34]
(偶氮顏料34之製造) (Manufacture of Azo Pigment 34)
代替偶氮顏料19之製造中所使用之基礎化合物[B-1]185份,使用基礎化合物[B-16]233份,除此以外,進行與偶氮顏料19之製造同樣之操作,獲得445份之偶氮顏料34(產率:97.0%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料34。 Instead of 185 parts of the base compound [B-1] used in the production of the azo pigment 19 and 233 parts of the base compound [B-16], the same operation as in the production of the azo pigment 19 was performed to obtain 445 Parts of azo pigment 34 (yield: 97.0%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 34 was identified.
[實施例35] [Example 35]
(偶氮顏料35之製造) (Manufacture of Azo Pigment 35)
代替偶氮顏料19之製造中所使用之基礎化合物[B-1]185份,使用基礎化合物[B-17]298份,除此以外,進行與偶氮顏料19之製造同樣之操作,獲得500份之偶氮顏料35(產率:95.7%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料35。 Instead of 185 parts of the base compound [B-1] used in the production of the azo pigment 19 and 298 parts of the base compound [B-17], the same operation as in the production of the azo pigment 19 was performed to obtain 500 Parts of azo pigment 35 (yield: 95.7%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 35.
[實施例36] [Example 36]
(偶氮顏料36之製造) (Manufacture of Azo Pigment 36)
代替偶氮顏料19之製造中所使用之基礎化合物[B-1]185份,使用基礎化合物[B-18]415份,除此以外,進行與偶氮顏料 19之製造同樣之操作,獲得629份之偶氮顏料36(產率:98.4%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料36。 Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 19 and using 415 parts of the basic compound [B-18], the same operation as in the production of the azo pigment 19 was performed to obtain 629 Parts of azo pigment 36 (yield: 98.4%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 36 was identified.
[實施例37] [Example 37]
(偶氮顏料37之製造) (Manufacture of Azo Pigment 37)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-2]172份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得352份之偶氮顏料37(產率:97.6%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料37。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 172 parts of the coupler compound [C-2], the same operation as in the production of the azo pigment 4 was performed. 352 parts of the azo pigment 37 was obtained (yield: 97.6%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 37.
[實施例38] [Example 38]
(偶氮顏料38之製造) (Manufacture of Azo Pigment 38)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-3]172份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得357份之偶氮顏料38(產率:98.9%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料38。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 172 parts of the coupler compound [C-3], the same operation as in the production of the azo pigment 4 was performed. 357 parts of the azo pigment 38 was obtained (yield: 98.9%). Based on the mass spectrum analysis and elemental analysis of TOF-MS, the azo pigment 38 was identified.
[實施例39] [Example 39]
(偶氮顏料39之製造) (Manufacture of Azo Pigment 39)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-4]177份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得354份之偶氮顏料39(產率:96.7%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料39。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 177 parts of the coupler compound [C-4], the same operation as in the production of the azo pigment 4 was performed. 354 parts of the azo pigment 39 was obtained (yield: 96.7%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 39 was identified.
偶氮顏料39
[實施例40] [Example 40]
(偶氮顏料40之製造) (Manufacture of Azo Pigment 40)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-5]177份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得357份之偶氮顏料40(產率:97.6%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料40。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 177 parts of the coupler compound [C-5], the same operation as in the production of the azo pigment 4 was performed. 357 parts of the azo pigment 40 was obtained (yield: 97.6%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 40.
[實施例41] [Example 41]
(偶氮顏料41之製造) (Manufacture of azo pigment 41)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-6]182份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得355份之偶氮顏料41(產率:95.8%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料 41。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 182 parts of the coupler compound [C-6], the same operation as in the production of the azo pigment 4 was performed. 355 parts of the azo pigment 41 was obtained (yield: 95.8%). Based on the mass spectrum analysis and elemental analysis of TOF-MS, the azo pigment 41 was identified.
[實施例42] [Example 42]
(偶氮顏料42之製造) (Manufacture of Azo Pigment 42)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-7]193份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得366份之偶氮顏料42(產率:95.9%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料42。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 193 parts of the coupler compound [C-7], the same operation as in the production of the azo pigment 4 was performed. 366 parts of the azo pigment 42 was obtained (yield: 95.9%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 42 was identified.
[實施例43] [Example 43]
(偶氮顏料43之製造) (Manufacture of Azo Pigment 43)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167 份,使用成色劑化合物[C-8]192份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得369份之偶氮顏料43(產率:96.8%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料43。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4 and using 192 parts of the coupler compound [C-8], the same operation as in the production of the azo pigment 4 was performed, 369 parts of the azo pigment 43 was obtained (yield: 96.8%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 43 was identified.
[實施例44] [Example 44]
(偶氮顏料44之製造) (Manufacture of Azo Pigment 44)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-9]197份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得381份之偶氮顏料44(產率:98.7%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料44。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 197 parts of the coupler compound [C-9], the same operation as in the production of the azo pigment 4 was performed. 381 parts of the azo pigment 44 was obtained (yield: 98.7%). Based on the mass spectrum analysis and elemental analysis of TOF-MS, the azo pigment 44 was identified.
[實施例45] [Example 45]
(偶氮顏料45之製造) (Manufacture of Azo Pigment 45)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-10]178份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得356份之偶氮顏料45(產率:97.0%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料45。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 178 parts of the coupler compound [C-10], the same operation as in the production of the azo pigment 4 was performed. 356 parts of the azo pigment 45 was obtained (yield: 97.0%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 45 was identified.
[實施例46] [Example 46]
(偶氮顏料46之製造) (Manufacture of Azo Pigment 46)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-11]178份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得355份之偶氮顏料46(產率:97.0%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料46。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 178 parts of the coupler compound [C-11], the same operation as in the production of the azo pigment 4 was performed. 355 parts of the azo pigment 46 was obtained (yield: 97.0%). The result of mass spectrometry and elemental analysis of TOF-MS identified the azo pigment 46.
偶氮顏料46
[實施例47] [Example 47]
(偶氮顏料47之製造) (Manufacture of Azo Pigment 47)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-12]183份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得362份之偶氮顏料47(產率:97.3%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料47。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 183 parts of the coupler compound [C-12], the same operation as in the production of the azo pigment 4 was performed. 362 parts of the azo pigment 47 was obtained (yield: 97.3%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 47.
[實施例48] [Example 48]
(偶氮顏料48之製造) (Manufacture of Azo Pigment 48)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-13]198份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得382份之偶氮顏料48(產率:98.9%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料 48。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 198 parts of the coupler compound [C-13], the same operation as in the production of the azo pigment 4 was performed. 382 parts of the azo pigment 48 was obtained (yield: 98.9%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 48 was identified.
[實施例49] [Example 49]
(偶氮顏料49之製造) (Manufacture of azo pigment 49)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-14]173份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得355份之偶氮顏料49(產率:98.4%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料49。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 173 parts of the coupler compound [C-14], the same operation as in the production of the azo pigment 4 was performed. 355 parts of the azo pigment 49 was obtained (yield: 98.4%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 49 was identified.
[實施例50] [Example 50]
(偶氮顏料50之製造) (Manufacture of Azo Pigment 50)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167 份,使用成色劑化合物[C-15]179份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得358份之偶氮顏料50(產率:97.6%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料50。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 179 parts of the coupler compound [C-15], the same operation as in the production of the azo pigment 4 was performed. 358 parts of the azo pigment 50 was obtained (yield: 97.6%). Based on the mass spectrum analysis and elemental analysis of TOF-MS, the azo pigment 50 was identified.
[實施例51] [Example 51]
(偶氮顏料51之製造) (Manufacture of Azo Pigment 51)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-16]179份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得350份之偶氮顏料51(產率:95.3%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料51。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 179 parts of the coupler compound [C-16], the same operation as in the production of the azo pigment 4 was performed. 350 parts of the azo pigment 51 was obtained (yield: 95.3%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 51 was identified.
[實施例52] [Example 52]
(偶氮顏料52之製造) (Manufacture of Azo Pigment 52)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-17]176份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得360份之偶氮顏料52(產率:98.7%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料52。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 176 parts of the coupler compound [C-17], the same operation as in the production of the azo pigment 4 was performed. 360 parts of the azo pigment 52 was obtained (yield: 98.7%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 52 was identified.
[實施例53] [Example 53]
(偶氮顏料53之製造) (Manufacture of Azo Pigment 53)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-18]184份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得367份之偶氮顏料53(產率:98.6%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料53。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 184 parts of the coupler compound [C-18], the same operation as in the production of the azo pigment 4 was performed. 367 parts of the azo pigment 53 was obtained (yield: 98.6%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 53.
偶氮顏料53
[實施例54] [Example 54]
(偶氮顏料54之製造) (Manufacture of Azo Pigment 54)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-19]183份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得365份之偶氮顏料54(產率:98.2%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料54。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 183 parts of the coupler compound [C-19], the same operation as in the production of the azo pigment 4 was performed. 365 parts of the azo pigment 54 was obtained (yield: 98.2%). Based on the mass spectrum analysis and elemental analysis of TOF-MS, the azo pigment 54 was identified.
[實施例55] [Example 55]
(偶氮顏料55之製造) (Manufacture of Azo Pigment 55)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-20]183份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得353份之偶氮顏料55(產率:95.0%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料 55。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 183 parts of the coupler compound [C-20], the same operation as in the production of the azo pigment 4 was performed. 353 parts of the azo pigment 55 was obtained (yield: 95.0%). Using the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 55 was identified.
[實施例56] [Example 56]
(偶氮顏料56之製造) (Manufacture of Azo Pigment 56)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-21]183份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得365份之偶氮顏料56(產率:98.3%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料56。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 183 parts of the coupler compound [C-21], the same operation as in the production of the azo pigment 4 was performed. 365 parts of the azo pigment 56 was obtained (yield: 98.3%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 56.
[實施例57] [Example 57]
(偶氮顏料57之製造) (Manufacture of Azo Pigment 57)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-22]197份,除此以外,進行與偶氮顏 料4之製造同樣之操作,獲得379份之偶氮顏料57(產率:98.4%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料57。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4 and using 197 parts of the coupler compound [C-22], the same operation as in the production of the azo pigment 4 was performed 379 parts of azo pigment 57 was obtained (yield: 98.4%). The result of mass spectrometry analysis and elemental analysis of TOF-MS identified the azo pigment 57.
[實施例58] [Example 58]
(偶氮顏料58之製造) (Manufacture of Azo Pigment 58)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-23]180份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得352份之偶氮顏料58(產率:95.6%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料58。 Instead of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and 180 parts of the coupler compound [C-23], the same operations as those for the production of the azo pigment 4 were performed. 352 parts of azo pigment 58 was obtained (yield: 95.6%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, it was identified as azo pigment 58.
[實施例59] [Example 59]
(偶氮顏料59之製造) (Manufacture of Azo Pigment 59)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-24]196份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得369份之偶氮顏料59(產率:95.9%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料59。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 196 parts of the coupler compound [C-24], the same operation as in the production of the azo pigment 4 was performed. 369 parts of the azo pigment 59 was obtained (yield: 95.9%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 59.
[實施例60] [Example 60]
(偶氮顏料60之製造) (Manufacture of Azo Pigment 60)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-25]174份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得353份之偶氮顏料60(產率:97.6%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料60。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 174 parts of the coupler compound [C-25], the same operation as in the production of the azo pigment 4 was performed. 353 parts of the azo pigment 60 was obtained (yield: 97.6%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 60.
偶氮顏料60
[實施例61] [Example 61]
(偶氮顏料61之製造) (Manufacture of azo pigment 61)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-26]214份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得392份之偶氮顏料61(產率:96.0%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料61。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 214 parts of the coupler compound [C-26], the same operation as in the production of the azo pigment 4 was performed. 392 parts of the azo pigment 61 was obtained (yield: 96.0%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 61 was identified.
[實施例62] [Example 62]
(偶氮顏料62之製造) (Manufacture of Azo Pigment 62)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-27]192份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得362份之偶氮顏料62(產率:95.1%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料 62。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 192 parts of the coupler compound [C-27], the same operation as in the production of the azo pigment 4 was performed. 362 parts of the azo pigment 62 was obtained (yield: 95.1%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 62 was identified.
[實施例63] [Example 63]
(偶氮顏料63之製造) (Manufacture of Azo Pigment 63)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-28]180份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得364份之偶氮顏料63(產率:98.8%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料63。 Instead of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and 180 parts of the coupler compound [C-28], the same operations as those for the production of the azo pigment 4 were performed. 364 parts of the azo pigment 63 was obtained (yield: 98.8%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 63 was identified.
[實施例64] [Example 64]
(偶氮顏料64之製造) (Manufacture of Azo Pigment 64)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167 份,使用成色劑化合物[C-29]187份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得366份之偶氮顏料64(產率:97.5%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料64。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4 and using 187 parts of the coupler compound [C-29], the same operation as in the production of the azo pigment 4 was performed. 366 parts of azo pigment 64 was obtained (yield: 97.5%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 64.
[實施例65] [Example 65]
(偶氮顏料65之製造) (Manufacture of Azo Pigment 65)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-30]194份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得366份之偶氮顏料65(產率:95.8%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料65。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 194 parts of the coupler compound [C-30], the same operation as in the production of the azo pigment 4 was performed. 366 parts of the azo pigment 65 was obtained (yield: 95.8%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 65.
[實施例66] [Example 66]
(偶氮顏料66之製造) (Manufacture of Azo Pigment 66)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-31]196份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得374份之偶氮顏料66(產率:97.3%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料66。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 196 parts of the coupler compound [C-31], the same operation as in the production of the azo pigment 4 was performed. 374 parts of the azo pigment 66 was obtained (yield: 97.3%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 66.
[實施例67] [Example 67]
(偶氮顏料67之製造) (Manufacture of Azo Pigment 67)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-32]190份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得368份之偶氮顏料67(產率:97.3%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料67。 Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 190 parts of the coupler compound [C-32], the same operations as those for the production of the azo pigment 4 were performed. 368 parts of the azo pigment 67 was obtained (yield: 97.3%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 67.
偶氮顏料67
[實施例68] [Example 68]
(偶氮顏料68之製造) (Manufacture of Azo Pigment 68)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-33]186份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得360份之偶氮顏料68(產率:96.4%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料68。 Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4 and using 186 parts of the coupler compound [C-33], the same operation as in the production of the azo pigment 4 was performed. 360 parts of the azo pigment 68 was obtained (yield: 96.4%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 68.
[實施例69] [Example 69]
(偶氮顏料69之製造) (Manufacture of Azo Pigment 69)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-34]186份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得359份之偶氮顏料69(產率:95.9%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料 69。 Instead of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and 186 parts of the coupler compound [C-34], the same operations as those for the production of the azo pigment 4 were performed, 359 parts of the azo pigment 69 was obtained (yield: 95.9%). Based on the mass spectrometry and elemental analysis of TOF-MS, the azo pigment 69 was identified.
[實施例70] [Example 70]
(偶氮顏料70之製造) (Manufacture of Azo Pigment 70)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-35]212份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得393份之偶氮顏料70(產率:98.2%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料70。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 212 parts of the coupler compound [C-35], the same operation as in the production of the azo pigment 4 was performed. 393 parts of the azo pigment 70 was obtained (yield: 98.2%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 70.
[實施例71] [Example 71]
(偶氮顏料71之製造) (Manufacture of Azo Pigment 71)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167 份,使用成色劑化合物[C-36]178份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得352份之偶氮顏料71(產率:95.9%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料71。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 178 parts of the coupler compound [C-36], the same operation as in the production of the azo pigment 4 was performed. 352 parts of the azo pigment 71 was obtained (yield: 95.9%). Based on the mass spectrum analysis and elemental analysis of TOF-MS, the azo pigment 71 was identified.
[實施例72] [Example 72]
(偶氮顏料72之製造) (Manufacture of Azo Pigment 72)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-37]189份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得373份之偶氮顏料72(產率:98.8%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料72。 Instead of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and 189 parts of the coupler compound [C-37], the same operations as those in the production of the azo pigment 4 were performed, 373 parts of the azo pigment 72 was obtained (yield: 98.8%). Based on the mass spectrum analysis and elemental analysis of TOF-MS, the azo pigment 72 was identified.
[實施例73] [Example 73]
(偶氮顏料73之製造) (Manufacture of Azo Pigment 73)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-38]205份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得376份之偶氮顏料73(產率:95.6%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料73。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 205 parts of the coupler compound [C-38], the same operation as in the production of the azo pigment 4 was performed. 376 parts of azo pigment 73 was obtained (yield: 95.6%). The result of mass spectrometry and elemental analysis of TOF-MS identified the azo pigment 73.
[實施例74] [Example 74]
(偶氮顏料74之製造) (Manufacture of Azo Pigment 74)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-39]178份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得358份之偶氮顏料74(產率:97.8%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料74。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 178 parts of the coupler compound [C-39], the same operation as in the production of the azo pigment 4 was performed. 358 parts of the azo pigment 74 was obtained (yield: 97.8%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 74.
偶氮顏料74
[實施例75] [Example 75]
(偶氮顏料75之製造) (Manufacture of Azo Pigment 75)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-40]218份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得401份之偶氮顏料75(產率:98.8%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料75。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 218 parts of the coupler compound [C-40], the same operation as in the production of the azo pigment 4 was performed. 401 parts of the azo pigment 75 was obtained (yield: 98.8%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 75.
[實施例76] [Example 76]
(偶氮顏料76之製造) (Manufacture of Azo Pigment 76)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-41]183份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得367份之偶氮顏料76(產率:98.7%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料 76。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 183 parts of the coupler compound [C-41], the same operation as in the production of the azo pigment 4 was performed. 367 parts of azo pigment 76 was obtained (yield: 98.7%). The TOF-MS mass spectrum analysis and elemental analysis identified the azo pigment 76.
[實施例77] [Example 77]
(偶氮顏料77之製造) (Manufacture of Azo Pigment 77)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-42]185份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得356份之偶氮顏料77(產率:95.3%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料77。 Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4 and using 185 parts of the coupler compound [C-42], the same operation as in the production of the azo pigment 4 was performed. 356 parts of azo pigment 77 was obtained (yield: 95.3%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 77.
[實施例78] [Example 78]
(偶氮顏料78之製造) (Manufacture of Azo Pigment 78)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167 份,使用成色劑化合物[C-43]191份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得372份之偶氮顏料78(產率:98.0%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料78。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4 and using 191 parts of the coupler compound [C-43], the same operation as in the production of the azo pigment 4 was performed. 372 parts of azo pigment 78 was obtained (yield: 98.0%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 78.
[實施例79] [Example 79]
(偶氮顏料79之製造) (Manufacture of Azo Pigment 79)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-44]211份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得388份之偶氮顏料79(產率:97.2%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料79。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4 and using 211 parts of the coupler compound [C-44], the same operation as in the production of the azo pigment 4 was performed, 388 parts of the azo pigment 79 was obtained (yield: 97.2%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 79.
[實施例80] [Example 80]
(偶氮顏料80之製造) (Manufacture of Azo Pigment 80)
代替偶氮顏料7之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-2]172份,除此以外,進行與偶氮顏料7之製造同樣之操作,獲得301份之偶氮顏料80(產率:98.9%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料80。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 7, and using 172 parts of the coupler compound [C-2], the same operation as in the production of the azo pigment 7 was performed. 301 parts of azo pigment 80 was obtained (yield: 98.9%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 80.
[實施例81] [Example 81]
(偶氮顏料81之製造) (Manufacture of Azo Pigment 81)
代替偶氮顏料7之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-3]172份,除此以外,進行與偶氮顏料7之製造同樣之操作,獲得298份之偶氮顏料81(產率:98.0%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料81。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 7, and using 172 parts of the coupler compound [C-3], the same operation as in the production of the azo pigment 7 was performed. 298 parts of the azo pigment 81 was obtained (yield: 98.0%). Based on the mass spectrum analysis and elemental analysis of TOF-MS, the azo pigment 81 was identified.
[實施例82] [Example 82]
(偶氮顏料82之製造) (Manufacture of Azo Pigment 82)
代替偶氮顏料7之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-8]192份,除此以外,進行與偶氮顏料7之製造同樣之操作,獲得317份之偶氮顏料82(產率:98.0%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料82。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 7, and using 192 parts of the coupler compound [C-8], the same operation as in the production of the azo pigment 7 was performed. 317 parts of azo pigment 82 was obtained (yield: 98.0%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 82 was identified.
[實施例83] [Example 83]
(偶氮顏料83之製造) (Manufacture of Azo Pigment 83)
代替偶氮顏料7之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-11]178份,除此以外,進行與偶氮顏料7之製造同樣之操作,獲得300份之偶氮顏料83(產率:96.8%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料83。 Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 7 and using 178 parts of the coupler compound [C-11], the same operation as in the production of the azo pigment 7 was performed. 300 parts of azo pigment 83 was obtained (yield: 96.8%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 83 was identified.
[實施例84] [Example 84]
(偶氮顏料84之製造) (Manufacture of Azo Pigment 84)
代替偶氮顏料7之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-23]180份,除此以外,進行與偶氮顏料7之製造同樣之操作,獲得307份之偶氮顏料84(產率:98.6%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料84。 Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 7, and using 180 parts of the coupler compound [C-23], the same operation as in the manufacture of the azo pigment 7 was performed. 307 parts of the azo pigment 84 was obtained (yield: 98.6%). As a result of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 84 was identified.
[實施例85] [Example 85]
(偶氮顏料85之製造) (Manufacture of Azo Pigment 85)
代替偶氮顏料7之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-42]185份,除此以外,進行與偶氮顏料7之製造同樣之操作,獲得309份之偶氮顏料85(產率:98.6%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料85。 Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 7 and using 185 parts of the coupler compound [C-42], the same operation as in the production of the azo pigment 7 was performed. 309 parts of azo pigment 85 was obtained (yield: 98.6%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 85.
偶氮顏料85
[實施例86] [Example 86]
(偶氮顏料86之製造) (Manufacture of Azo Pigment 86)
代替偶氮顏料7之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-43]191份,除此以外,進行與偶氮顏料7之製造同樣之操作,獲得317份之偶氮顏料86(產率:98.4%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料86。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 7, and using 191 parts of the coupler compound [C-43], the same operation as in the production of the azo pigment 7 was performed. 317 parts of the azo pigment 86 was obtained (yield: 98.4%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 86.
[實施例87] [Example 87]
(偶氮顏料87之製造) (Manufacture of Azo Pigment 87)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-45]195份,除此以外,進行與偶氮顏料7之製造同樣之操作,獲得375份之偶氮顏料87(產率:97.7%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料87。 Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4 and using 195 parts of the coupler compound [C-45], the same operation as in the production of the azo pigment 7 was performed. 375 parts of azo pigment 87 was obtained (yield: 97.7%). Based on the mass spectrum analysis and elemental analysis of TOF-MS, the azo pigment 87 was identified.
偶氮顏料87
[實施例88] [Example 88]
(偶氮顏料88之製造) (Manufacture of Azo Pigment 88)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-46]200份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得373份之偶氮顏料88(產率:96.0%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料88。 Instead of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and 200 parts of the coupler compound [C-46], the same operations as those for the production of the azo pigment 4 were performed. 373 parts of azo pigment 88 was obtained (yield: 96.0%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 88.
[實施例89] [Example 89]
(偶氮顏料89之製造) (Manufacture of Azo Pigment 89)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-47]211份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得388份之偶氮顏料89(產率:97.3%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料89。 Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4 and using 211 parts of the coupler compound [C-47], the same operation as in the production of the azo pigment 4 was performed. 388 parts of azo pigment 89 was obtained (yield: 97.3%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 89.
[實施例90] [Example 90]
(偶氮顏料90之製造) (Manufacture of Azo Pigment 90)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-48]251份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得422份之偶氮顏料90(產率:96.1%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料90。 Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4 and using 251 parts of the coupler compound [C-48], the same operation as in the production of the azo pigment 4 was performed. 422 parts of the azo pigment 90 was obtained (yield: 96.1%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 90.
[實施例91] [Example 91]
(偶氮顏料91之製造) (Manufacture of azo pigment 91)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-49]261份,除此以外,進行與偶氮顏 料4之製造同樣之操作,獲得445份之偶氮顏料91(產率:98.9%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料91。 Instead of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and 261 parts of the coupler compound [C-49], the same operations as those in the production of the azo pigment 4 were performed, 445 parts of the azo pigment 91 was obtained (yield: 98.9%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 91.
[實施例92] [Example 92]
(偶氮顏料92之製造) (Manufacture of Azo Pigment 92)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-50]263份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得437份之偶氮顏料92(產率:96.9%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料92。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 263 parts of the coupler compound [C-50], the same operation as in the production of the azo pigment 4 was performed. 437 parts of the azo pigment 92 was obtained (yield: 96.9%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 92.
[實施例93] [Example 93]
(偶氮顏料93之製造) (Manufacture of Azo Pigment 93)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-51]223份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得396份之偶氮顏料93(產率:96.2%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料93。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 223 parts of the coupler compound [C-51], the same operation as in the production of the azo pigment 4 was performed. 396 parts of azo pigment 93 was obtained (yield: 96.2%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 93.
[實施例94] [Example 94]
(偶氮顏料94之製造) (Manufacture of Azo Pigment 94)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-52]229份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得409份之偶氮顏料94(產率:97.9%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料94。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 229 parts of the coupler compound [C-52], the same operation as in the production of the azo pigment 4 was performed. 409 parts of the azo pigment 94 was obtained (yield: 97.9%). As a result of mass spectrometry and elemental analysis by TOF-MS, the azo pigment 94 was identified.
[實施例95] [Example 95]
(偶氮顏料95之製造) (Manufacture of Azo Pigment 95)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-53]244份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得417份之偶氮顏料95(產率:96.3%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料95。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 244 parts of the coupler compound [C-53], the same operation as in the production of the azo pigment 4 was performed. 417 parts of the azo pigment 95 was obtained (yield: 96.3%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 95.
[實施例96] [Example 96]
(偶氮顏料96之製造) (Manufacture of Azo Pigment 96)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-54]201份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得382份之偶氮顏料96(產率:98.1%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料96。 Instead of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and 201 parts of the coupler compound [C-54], the same operation as in the production of the azo pigment 4 was performed, 382 parts of the azo pigment 96 was obtained (yield: 98.1%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 96.
偶氮顏料96
[實施例97] [Example 97]
(偶氮顏料97之製造) (Manufacture of Azo Pigment 97)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-55]207份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得383份之偶氮顏料97(產率:96.9%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料97。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4 and using 207 parts of the coupler compound [C-55], the same operation as in the production of the azo pigment 4 was performed 383 parts of the azo pigment 97 was obtained (yield: 96.9%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 97.
[實施例98] [Example 98]
(偶氮顏料98之製造) (Manufacture of Azo Pigment 98)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-56]206份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得383份之偶氮顏料98(產率:97.3%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料98。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 206 parts of the coupler compound [C-56], the same operation as in the production of the azo pigment 4 was performed. 383 parts of the azo pigment 98 were obtained (yield: 97.3%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 98.
[實施例99] [Example 99]
(偶氮顏料99之製造) (Manufacture of Azo Pigment 99)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-58]229份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得411份之偶氮顏料99(產率:98.4%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料99。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 229 parts of the coupler compound [C-58], the same operation as in the production of the azo pigment 4 was performed. 411 parts of the azo pigment 99 was obtained (yield: 98.4%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 99.
[實施例100] [Example 100]
(偶氮顏料100之製造) (Manufacture of Azo Pigment 100)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-59]229份,除此以外,進行與偶氮顏 料4之製造同樣之操作,獲得400份之偶氮顏料100(產率:95.8%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料100。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4 and using 229 parts of the coupler compound [C-59], the same operation as in the production of the azo pigment 4 was performed, 400 parts of the azo pigment 100 was obtained (yield: 95.8%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 100.
[實施例101] [Example 101]
(偶氮顏料101之製造) (Manufacture of Azo Pigment 101)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-60]270份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得441份之偶氮顏料101(產率:96.4%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料101。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 270 parts of the coupler compound [C-60], the same operation as in the production of the azo pigment 4 was performed. 441 parts of the azo pigment 101 was obtained (yield: 96.4%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 101.
[實施例102] [Example 102]
(偶氮顏料102之製造) (Manufacture of Azo Pigment 102)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-61]245份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得421份之偶氮顏料102(產率:97.3%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料102。 Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 245 parts of the coupler compound [C-61], the same operation as in the manufacture of the azo pigment 4 was performed. 421 parts of the azo pigment 102 was obtained (yield: 97.3%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 102 was identified.
[實施例103] [Example 103]
(偶氮顏料103之製造) (Manufacture of Azo Pigment 103)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-62]232份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得405份之偶氮顏料103(產率:96.3%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料103。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4 and using 232 parts of the coupler compound [C-62], the same operation as in the production of the azo pigment 4 was performed, 405 parts of the azo pigment 103 was obtained (yield: 96.3%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 103 was identified.
偶氮顏料103
[實施例104] [Example 104]
(偶氮顏料104之製造) (Manufacture of Azo Pigment 104)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-63]231份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得399份之偶氮顏料104(產率:96.3%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料104。 Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 231 parts of the coupler compound [C-63], the same operation as in the production of the azo pigment 4 was performed. 399 parts of the azo pigment 104 was obtained (yield: 96.3%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 104 was identified.
[實施例105] [Example 105]
(偶氮顏料105之製造) (Manufacture of Azo Pigment 105)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-64]241份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得423份之偶氮顏料105(產率:98.4%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶 氮顏料105。 Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4 and using 241 parts of the coupler compound [C-64], the same operation as in the production of the azo pigment 4 was performed. 423 parts of the azo pigment 105 was obtained (yield: 98.4%). Based on the results of mass spectrometry and elemental analysis by TOF-MS, the azo pigment 105 was identified.
[實施例106] [Example 106]
(偶氮顏料106之製造) (Manufacture of Azo Pigment 106)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-65]281份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得456份之偶氮顏料106(產率:97.1%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料106。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 281 parts of the coupler compound [C-65], the same operation as in the production of the azo pigment 4 was performed. 456 parts of the azo pigment 106 was obtained (yield: 97.1%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 106.
[實施例107] [Example 107]
(偶氮顏料107之製造) (Manufacture of azo pigment 107)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167 份,使用成色劑化合物[C-66]212份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得395份之偶氮顏料107(產率:98.7%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料107。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4 and using 212 parts of the coupler compound [C-66], the same operation as in the production of the azo pigment 4 was performed. 395 parts of the azo pigment 107 was obtained (yield: 98.7%). Based on the mass spectrum analysis and elemental analysis of TOF-MS, the azo pigment 107 was identified.
[實施例108] [Example 108]
(偶氮顏料108之製造) (Manufacture of Azo Pigment 108)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-67]211份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得390份之偶氮顏料108(產率:97.7%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料108。 Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4 and using 211 parts of the coupler compound [C-67], the same operation as in the production of the azo pigment 4 was performed. 390 parts of azo pigment 108 was obtained (yield: 97.7%). Using the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 108 was identified.
偶氮顏料108
[實施例109] [Example 109]
(偶氮顏料109之製造) (Manufacture of Azo Pigment 109)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-68]225份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得400份之偶氮顏料109(產率:96.9%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料109。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 225 parts of the coupler compound [C-68], the same operation as in the production of the azo pigment 4 was performed. 400 parts of the azo pigment 109 was obtained (yield: 96.9%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 109.
[實施例110] [Example 110]
(偶氮顏料110之製造) (Manufacture of Azo Pigment 110)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-69]230份,除此以外,進行與偶氮顏 料4之製造同樣之操作,獲得407份之偶氮顏料110(產率:97.4%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料110。 Instead of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and 230 parts of the coupler compound [C-69], the same operation as in the production of the azo pigment 4 was performed, 407 parts of the azo pigment 110 was obtained (yield: 97.4%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 110 was identified.
[實施例111] [Example 111]
(偶氮顏料111之製造) (Manufacture of Azo Pigment 111)
代替偶氮顏料4之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-70]237份,除此以外,進行與偶氮顏料4之製造同樣之操作,獲得409份之偶氮顏料111(產率:96.0%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料111。 Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 237 parts of the coupler compound [C-70], the same operation as in the production of the azo pigment 4 was performed. 409 parts of the azo pigment 111 was obtained (yield: 96.0%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 111.
偶氮顏料111
[實施例112] [Example 112]
(偶氮顏料112之製造) (Manufacture of Azo Pigment 112)
代替偶氮顏料7之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-46]200份,除此以外,進行與偶氮顏料7之製造同樣之操作,獲得320份之偶氮顏料112(產率:96.4%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料112。 Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 7 and using 200 parts of the coupler compound [C-46], the same operation as in the production of the azo pigment 7 was performed. 320 parts of the azo pigment 112 was obtained (yield: 96.4%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 112 was identified.
[實施例113] [Example 113]
(偶氮顏料113之製造) (Manufacture of Azo Pigment 113)
代替偶氮顏料7之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-47]211份,除此以外,進行與偶氮顏料7之製造同樣之操作,獲得329份之偶氮顏料113(產率:96.0%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶 氮顏料113。 Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 7 and using 211 parts of the coupler compound [C-47], the same operation as in the production of the azo pigment 7 was performed. 329 parts of the azo pigment 113 was obtained (yield: 96.0%). Based on the mass spectrum analysis and elemental analysis of TOF-MS, the azo pigment 113 was identified.
[實施例114] [Example 114]
(偶氮顏料114之製造) (Manufacture of Azo Pigment 114)
代替偶氮顏料7之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-48]251份,除此以外,進行與偶氮顏料7之製造同樣之操作,獲得374份之偶氮顏料114(產率:97.6%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料114。 Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 7, and using 251 parts of the coupler compound [C-48], the same operation as in the production of the azo pigment 7 was performed. 374 parts of the azo pigment 114 was obtained (yield: 97.6%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 114 was identified.
[實施例115] [Example 115]
(偶氮顏料115之製造) (Manufacture of Azo Pigment 115)
代替偶氮顏料7之製造中所使用之成色劑化合物[C-1]167 份,使用成色劑化合物[C-54]201份,除此以外,進行與偶氮顏料7之製造同樣之操作,獲得319份之偶氮顏料115(產率:95.7%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料115。 Instead of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 7, and 201 parts of the coupler compound [C-54], the same operation as in the production of the azo pigment 7 was performed. 319 parts of the azo pigment 115 was obtained (yield: 95.7%). According to the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 115 was identified.
[實施例116] [Example 116]
(偶氮顏料116之製造) (Manufacture of Azo Pigment 116)
代替偶氮顏料7之製造中所使用之成色劑化合物[C-1]167份,使用成色劑化合物[C-56]206份,除此以外,進行與偶氮顏料7之製造同樣之操作,獲得330份之偶氮顏料116(產率:97.7%)。利用TOF-MS之質譜分析及元素分析之結果,鑑識為偶氮顏料116。 Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 7, and using 206 parts of the coupler compound [C-56], the same operation as in the production of the azo pigment 7 was performed. 330 parts of azo pigment 116 was obtained (yield: 97.7%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 116.
[實施例117] [Example 117]
(偶氮顏料117之製造)偶氮顏料4之微細化步驟 (Production of azo pigment 117) Refinement step of azo pigment 4
將80份之偶氮顏料4、氯化鈉800份、及二乙二醇90份添加至不銹鋼製1加侖捏合機(井上製作所公司製造),於60℃混練6小時,進行鹽磨處理。將所獲得之混練物投入至3升之溫水,一面加熱至70℃一面攪拌1小時而製成漿料狀,反覆進行過濾、水洗而去除氯化鈉及二乙二醇後,於80℃乾燥一晝夜,獲得78份之偶氮顏料117。 80 parts of azo pigment 4, 800 parts of sodium chloride, and 90 parts of diethylene glycol were added to a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60 ° C. for 6 hours to perform a salt milling treatment. The obtained kneaded product was poured into 3 liters of warm water and stirred for 1 hour while heating to 70 ° C to prepare a slurry. After repeated filtration, washing with water to remove sodium chloride and diethylene glycol, the mixture was heated at 80 ° C. Drying all day and night, 78 parts of azo pigment 117 was obtained.
[實施例118] [Example 118]
(偶氮顏料118之製造)偶氮顏料22之微細化步驟 (Production of azo pigment 118) Refinement step of azo pigment 22
將80份之偶氮顏料22、氯化鈉800份、及二乙二醇90份添加至不銹鋼製1加侖捏合機(井上製作所公司製造),於60℃混練6小時,進行鹽磨處理。將所獲得之混練物投入至3升之溫水,一面加熱至70℃一面攪拌1小時而製成漿料狀,反覆進行過濾、水洗而去除氯化鈉及二乙二醇後,於80℃乾燥一晝夜,獲得78份之偶氮顏料118。 80 parts of azo pigment 22, 800 parts of sodium chloride, and 90 parts of diethylene glycol were added to a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60 ° C. for 6 hours to perform a salt milling treatment. The obtained kneaded product was poured into 3 liters of warm water and stirred for 1 hour while heating to 70 ° C to prepare a slurry. After repeated filtration, washing with water to remove sodium chloride and diethylene glycol, the mixture was heated at 80 ° C. Drying all day and night, 78 parts of azo pigment 118 was obtained.
[實施例119至實施例124] [Examples 119 to 124]
(偶氮顏料120至偶氮顏料125之製造) (Manufacture of azo pigment 120 to azo pigment 125)
於偶氮顏料117之製造中,代替偶氮顏料4,將偶氮顏料4及色素衍生物變更為表4-2所示之種類及比率,除此以外,以與偶氮顏料117同樣之方式,獲得偶氮顏料120至偶氮顏料125。 In the production of the azo pigment 117, the azo pigment 4 and the pigment derivative were changed to the types and ratios shown in Table 4-2 in place of the azo pigment 4, and otherwise, the same method as the azo pigment 117 was used. Azo pigments 120 to 125 were obtained.
[實施例125至實施例130] [Examples 125 to 130]
(偶氮顏料126至偶氮顏料131之製造) (Manufacture of azo pigments 126 to 131)
於偶氮顏料118之製造中,代替偶氮顏料22,將偶氮顏料22及色素衍生物變更為表4-2所示之種類及比率,除此以外,以與偶氮顏料118同樣之方式,獲得偶氮顏料126至偶氮顏料131。 In the production of the azo pigment 118, the azo pigment 22 and the pigment derivative were changed to the types and ratios shown in Table 4-2 in place of the azo pigment 22, and the method was the same as that of the azo pigment 118. Azo pigments 126 to 131 were obtained.
[製造例1] [Manufacturing example 1]
(偶氮顏料119之製造) (Manufacture of Azo Pigment 119)
以日本專利特開2014-160160號公報為參考,合成下述之偶氮顏料119。 With reference to Japanese Patent Laid-Open No. 2014-160160, the following azo pigment 119 was synthesized.
[製造例2至製造例13] [Production Example 2 to Production Example 13]
<其他顏料之製造> <Manufacture of other pigments>
(紅色著色劑1(RCP-1)之製造:PR254) (Manufacture of Red Colorant 1 (RCP-1): PR254)
將市售之C.I.顏料紅254(PR254)(BASF公司製造之「Irgazin Red D3656 HD」)100份、氯化鈉1200份、及二乙二醇120份添加至不銹鋼製1加侖捏合機(井上製作所公司製造),於60℃混練6小時,進行鹽磨處理。將所獲得之混練物投入至3升之溫水,一面加熱至70℃一面攪拌1小時而製成漿料狀,反覆進 行過濾、水洗而去除氯化鈉及二乙二醇後,於80℃乾燥一晝夜,獲得98份之紅色著色劑1(RCP-1)。平均一次粒徑為33nm。 100 parts of commercially available CI Pigment Red 254 (PR254) ("Irgazin Red D3656 HD" manufactured by BASF), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were added to a stainless steel 1-gallon kneader (Inoue Manufacturing Co., Ltd. (Manufactured by the company), kneaded at 60 ° C for 6 hours, and subjected to salt milling. The obtained kneaded product was poured into 3 liters of warm water and stirred for 1 hour while heating to 70 ° C to prepare a slurry. After repeated filtration, washing with water to remove sodium chloride and diethylene glycol, the mixture was heated at 80 ° C. Drying all day and night, 98 parts of red colorant 1 (RCP-1) was obtained. The average primary particle diameter was 33 nm.
(紅色著色劑2(RCP-2)之製造:PR177) (Manufacture of Red Colorant 2 (RCP-2): PR177)
將C.I.顏料紅254(BASF公司製造之「Irgazin Red D3656 HD」),變更為C.I.顏料紅177(PR177)(CINIC公司製造之「Cinilex Red SR3C」),除此以外,與紅色著色劑1之製造同樣地進行,獲得97份之紅色著色劑2(RCP-2)。平均一次粒徑為37nm。 CI Pigment Red 254 ("Irgazin Red D3656 HD" manufactured by BASF) was changed to CI Pigment Red 177 (PR177) ("Cinilex Red SR3C" manufactured by CINIC), in addition to the manufacture of red colorant 1 Similarly, 97 parts of red colorant 2 (RCP-2) was obtained. The average primary particle diameter was 37 nm.
(紅色著色劑3(RCP-3)之製造:PR242) (Manufacture of Red Colorant 3 (RCP-3): PR242)
將C.I.顏料紅254(BASF公司製造之「Irgazin Red D3656 HD」),變更為C.I.顏料紅242(PR242)(Clariant公司製造之「Sandorin Scarlet 4RF」),除此以外,與紅色著色劑1之製造同樣地進行,獲得98份之紅色著色劑3(RCP-3)。平均一次粒徑為39nm。 CI Pigment Red 254 ("Irgazin Red D3656 HD" manufactured by BASF) was changed to CI Pigment Red 242 (PR242) ("Sandorin Scarlet 4RF" manufactured by Clariant), in addition to the manufacture of red colorant 1 Similarly, 98 parts of red colorant 3 (RCP-3) was obtained. The average primary particle diameter was 39 nm.
(紅色著色劑4(RCP-4)之製造:PR269) (Manufacture of Red Colorant 4 (RCP-4): PR269)
將C.I.顏料紅254(BASF公司製造之「Irgazin Red D3656 HD」),變更為C.I.顏料紅269(PR269)(山陽色素股份有限公司製造之「Permanent Carmine 3810」),除此以外,與紅色著色劑1之製造同樣地進行,獲得98份之紅色著色劑4(RCP-4)。平均一次粒徑為35nm。 CI Pigment Red 254 ("Irgazin Red D3656 HD" manufactured by BASF) was changed to CI Pigment Red 269 (PR269) ("Permanent Carmine 3810" manufactured by Sanyo Pigment Co., Ltd.). Production of 1 was performed in the same manner, and 98 parts of red colorant 4 (RCP-4) was obtained. The average primary particle diameter was 35 nm.
(紅色著色劑5(RCP-5)之製造:溴化二酮基吡咯并吡咯顏料式(4)) (Production of red colorant 5 (RCP-5): brominated diketopyrrolopyrrole pigment formula (4))
於附回流管之不銹鋼製反應容器中,在氮氣氛圍下,添加 經分子篩脫水之第三戊醇200份、及第三戊基烷醇鈉140份,一面攪拌一面加熱至100℃,製備醇化物溶液。另一方面,於玻璃製燒瓶中,添加琥珀酸二異丙酯88份、4-溴苯甲腈153.6份,一面攪拌一面加熱至90℃而使之溶解,製備該等混合物之溶液。將該混合物之加熱溶液一面劇烈地攪拌,一面歷時2小時以固定的速度緩慢地滴加至加熱為100℃之上述醇化物溶液中。滴加結束後,於90℃繼續加熱攪拌2小時,獲得二酮基吡咯并吡咯系化合物之鹼金屬鹽。進而,於附玻璃製外套之反應容器中,添加甲醇600份、水600份、及乙酸304份,冷卻至-10℃。將該冷卻之混合物,一面使用高速攪拌分散機,使直徑8cm之剪切盤以4000rpm旋轉,一面向該混合物中逐次少量添加冷卻至75℃之上述獲得之二酮基吡咯并吡咯系化合物之鹼金屬鹽溶液。此時,一面以由甲醇、乙酸、及水構成之混合物的溫度始終保持-5℃以下之溫度之方式進行冷卻,且調整75℃之二酮基吡咯并吡咯系化合物之鹼金屬鹽的添加速度,一面歷時約120分鐘而逐次少量添加。添加鹼金屬鹽後,紅色的結晶析出,生成紅色的懸濁液。繼而,將所獲得之紅色的懸濁液於5℃利用超濾裝置洗淨後,進行過濾分離而獲得紅色糊劑。將該糊劑於冷卻至0℃之甲醇3500份中再分散,製成甲醇濃度約90%之懸濁液,於5℃攪拌3小時,進行伴隨結晶轉移之粒子造粒及洗淨。繼而,利用超濾機進行過濾分離,將所獲得之二酮基吡咯并吡咯系化合物之水糊劑於80℃乾燥24小時,並進行粉碎,藉此獲得式(4)所表示之溴化二酮基吡咯并吡咯顏料150.8份。 In a stainless steel reaction vessel with a reflux tube, under a nitrogen atmosphere, 200 parts of third pentanol dehydrated by molecular sieve and 140 parts of sodium third pentyl alkoxide were added, and heated to 100 ° C while stirring, to prepare an alcoholate. Solution. On the other hand, 88 parts of diisopropyl succinate and 153.6 parts of 4-bromobenzonitrile were added to a glass flask, and the mixture was heated to 90 ° C. while being stirred to dissolve it to prepare a solution of the mixture. The heated solution of this mixture was vigorously stirred and slowly added dropwise to the above-mentioned alcoholate solution heated at 100 ° C at a fixed rate for 2 hours. After the dropwise addition was completed, heating and stirring were continued at 90 ° C for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole-based compound. Furthermore, 600 parts of methanol, 600 parts of water, and 304 parts of acetic acid were added to the reaction container with a glass outer cover, and it cooled to -10 degreeC. The cooled mixture was rotated at a speed of 4000 rpm using a high-speed agitating disperser, while a small amount of the diketopyrrolopyrrole-based compound obtained by cooling to 75 ° C was added to the mixture one by one. Metal salt solution. At this time, while cooling the mixture of methanol, acetic acid, and water at a temperature of -5 ° C or lower, the addition rate of the alkali metal salt of the diketopyrrolopyrrole-based compound at 75 ° C was adjusted. On the one hand, it is added in small amounts one by one for about 120 minutes. When an alkali metal salt is added, red crystals are precipitated to form a red suspension. Then, the obtained red suspension was washed with an ultrafiltration device at 5 ° C, and then filtered and separated to obtain a red paste. This paste was re-dispersed in 3500 parts of methanol cooled to 0 ° C to prepare a suspension having a methanol concentration of about 90%. The suspension was stirred at 5 ° C for 3 hours, and granulation and washing with crystal transfer were performed. Then, it was separated by filtration using an ultrafiltration machine, and the obtained water paste of diketopyrrolopyrrole-based compound was dried at 80 ° C. for 24 hours and pulverized to obtain a brominated dibromide represented by formula (4). 150.8 parts of ketopyrrolopyrrole pigment.
將上述獲得之式(4)所表示之溴化二酮基吡咯并吡咯顏料100份、氯化鈉1200份、及二乙二醇120份添加至不銹鋼製1 加侖捏合機(井上製作所公司製造),於60℃混練6小時,進行鹽磨處理。將所獲得之混練物投入至3升之溫水,一面加熱至70℃一面攪拌1小時而製成漿料狀,反覆進行過濾、水洗而去除氯化鈉及二乙二醇後,於80℃乾燥一晝夜,獲得98份之紅色著色劑5(RCP-5)。平均一次粒徑為45nm。 100 parts of the diketopyrrolopyrrole pigment represented by the formula (4) obtained above, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were added to a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) , And kneaded at 60 ° C for 6 hours, and then carried out salt milling treatment. The obtained kneaded product was poured into 3 liters of warm water and stirred for 1 hour while heating to 70 ° C to prepare a slurry. After repeated filtration, washing with water to remove sodium chloride and diethylene glycol, the temperature was 80 ° C. Drying all day and night, 98 parts of red colorant 5 (RCP-5) was obtained. The average primary particle diameter was 45 nm.
(黃色著色劑1(YCP-1)之製造:PY138) (Production of Yellow Colorant 1 (YCP-1): PY138)
將喹酞酮系黃色顏料C.I.顏料黃138(BASF公司製造之「Paliotol Yellow L0962-HD」)500份、氯化鈉500份、及二乙二醇250份添加至不銹鋼製1加侖捏合機(井上製作所公司製造),於120℃混練8小時。其次,將該混練物投入至5升之溫水,一面加熱至70℃一面攪拌1小時而製成漿料狀,反覆進行過濾、水洗而去除氯化鈉及二乙二醇後,於80℃乾燥一晝夜,獲得490份之黃色著色劑1(YCP-1)。平均一次粒徑為63nm。 500 parts of quinophthalone-based yellow pigment CI Pigment Yellow 138 ("Paliotol Yellow L0962-HD" manufactured by BASF), 500 parts of sodium chloride, and 250 parts of diethylene glycol were added to a stainless steel 1-gallon kneader (Inoue Manufactured by Seisakusho Co., Ltd.), and kneaded at 120 ° C for 8 hours. Next, the kneaded product was poured into 5 liters of warm water, stirred for 1 hour while being heated to 70 ° C. to prepare a slurry, and filtered and washed repeatedly to remove sodium chloride and diethylene glycol at 80 ° C. Drying all day and night, 490 parts of yellow colorant 1 (YCP-1) was obtained. The average primary particle diameter was 63 nm.
(黃色著色劑2(YCP-2)之製造:PY139) (Production of Yellow Colorant 2 (YCP-2): PY139)
將異吲哚啉系黃色顏料C.I.顏料黃139(BASF公司製造之「Paliotol Yellow L1820」)500份、氯化鈉500份、及二乙二醇250份添加至不銹鋼製1加侖捏合機(井上製作所公司製造),於 120℃混練8小時。其次,將該混練物投入至5升之溫水,一面加熱至70℃一面攪拌1小時而製成漿料狀,反覆進行過濾、水洗而去除氯化鈉及二乙二醇後,於80℃乾燥一晝夜,獲得510份之黃色著色劑2(YCP-2)。平均一次粒徑為68nm。 500 parts of isoindoline yellow pigment CI Pigment Yellow 139 ("Paliotol Yellow L1820" manufactured by BASF Corporation), 500 parts of sodium chloride, and 250 parts of diethylene glycol were added to a stainless steel 1 gallon kneader (Inoue Seisakusho Manufactured by the company), and kneaded at 120 ° C for 8 hours. Next, the kneaded product was poured into 5 liters of warm water, stirred for 1 hour while being heated to 70 ° C. to prepare a slurry, and filtered and washed repeatedly to remove sodium chloride and diethylene glycol at 80 ° C. Drying all day and night, 510 parts of yellow colorant 2 (YCP-2) was obtained. The average primary particle diameter was 68 nm.
(黃色著色劑3(YCP-3)之製造:PY150) (Production of Yellow Colorant 3 (YCP-3): PY150)
將偶氮系黃色顏料C.I.顏料黃150(Clariant公司製造之「Hostaperm Yellow HN4G」)500份、氯化鈉500份、及二乙二醇250份添加至不銹鋼製1加侖捏合機(井上製作所公司製造),於120℃混練8小時。其次,將該混練物投入至5升之溫水,一面加熱至70℃一面攪拌1小時而製成漿料狀,反覆進行過濾、水洗而去除氯化鈉及二乙二醇後,於80℃乾燥一晝夜,獲得500份之黃色著色劑3(YCP-3)。平均一次粒徑為60nm。 500 parts of azo yellow pigment CI Pigment Yellow 150 ("Hostaperm Yellow HN4G" manufactured by Clariant), 500 parts of sodium chloride, and 250 parts of diethylene glycol were added to a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd. ) And knead at 120 ° C for 8 hours. Next, the kneaded product was poured into 5 liters of warm water, stirred for 1 hour while being heated to 70 ° C. to prepare a slurry, and filtered and washed repeatedly to remove sodium chloride and diethylene glycol at 80 ° C. Drying all day and night, 500 parts of yellow colorant 3 (YCP-3) was obtained. The average primary particle diameter was 60 nm.
(黃色著色劑4(YCP-4)之製造:喹酞酮化合物(b)) (Production of yellow colorant 4 (YCP-4): quinophthalone compound (b))
於苯甲酸甲酯200份中,添加8-胺基喹哪啶40份、2,3-萘二羧酸酐150份、苯甲酸154份,加熱至180℃,進行4小時攪拌。進而,冷卻至室溫後,將反應混合物投入至丙酮5440份,於室溫下攪拌1小時。將產物進行過濾分離,進行甲醇洗淨及乾燥,獲得116份之喹酞酮化合物(c)。利用TOF-MS之質譜分析之結果,鑑識為喹酞酮化合物(c)。 To 200 parts of methyl benzoate, 40 parts of 8-aminoquinalidine, 150 parts of 2,3-naphthalenedicarboxylic acid anhydride, and 154 parts of benzoic acid were added, and the mixture was heated to 180 ° C. and stirred for 4 hours. After cooling to room temperature, the reaction mixture was poured into 5440 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol, and dried to obtain 116 parts of a quinophthalone compound (c). As a result of mass spectrometry of TOF-MS, it was identified as a quinophthalone compound (c).
喹酞酮化合物(c)
進而,以喹酞酮化合物(c)作為原料,依據日本專利特開2008-81566號公報中所記載之合成方法,獲得化合物(c-2)。 Furthermore, using the quinophthalone compound (c) as a raw material, the compound (c-2) was obtained according to the synthesis method described in Japanese Patent Laid-Open No. 2008-81566.
於苯甲酸甲酯300份中,添加化合物(c-2)100份、四氯鄰苯二甲酸酐108份、及苯甲酸143份,加熱至180℃,反應4小時。藉由TOF-MS,確認喹酞酮化合物(b)之生成、及原料之化合物(c-2)之消失。進而,冷卻至室溫後,將反應混合物投入至丙酮3510份,於室溫下攪拌1小時。將產物進行過濾分離,進行甲醇洗淨及乾燥,獲得120份之喹酞酮化合物(b)。利用TOF-MS之質譜分析之結果,鑑識為喹酞酮化合物(b)。 To 300 parts of methyl benzoate, 100 parts of compound (c-2), 108 parts of tetrachlorophthalic anhydride, and 143 parts of benzoic acid were added, heated to 180 ° C, and reacted for 4 hours. By TOF-MS, the production of the quinophthalone compound (b) and the disappearance of the raw material compound (c-2) were confirmed. After cooling to room temperature, the reaction mixture was poured into 3510 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol, and dried to obtain 120 parts of a quinophthalone compound (b). As a result of mass spectrometry of TOF-MS, it was identified as a quinophthalone compound (b).
喹酞酮化合物(b)
將上述獲得之喹酞酮化合物(b)500份、氯化鈉500份、及二乙二醇250份添加至不銹鋼製1加侖捏合機(井上製作所公司製造),於120℃混練8小時。其次,將該混練物投入至5升之溫水,一面加熱至70℃一面攪拌1小時而製成漿料狀,反覆進行過濾、水洗而去除氯化鈉及二乙二醇後,於80℃乾燥一晝夜,獲得480份之黃色著色劑4(YCP-4)。平均一次粒徑為62nm。 500 parts of the quinophthalone compound (b) obtained above, 500 parts of sodium chloride, and 250 parts of diethylene glycol were added to a 1-gallon kneader (manufactured by Inoue Seisakusho) made of stainless steel, and kneaded at 120 ° C for 8 hours. Next, the kneaded product was poured into 5 liters of warm water, stirred for 1 hour while being heated to 70 ° C. to prepare a slurry, and filtered and washed repeatedly to remove sodium chloride and diethylene glycol at 80 ° C. Drying all day and night, 480 parts of yellow colorant 4 (YCP-4) was obtained. The average primary particle diameter was 62 nm.
(綠色著色劑1之製造:PG58) (Production of Green Colorant 1: PG58)
將酞菁系綠色顏料C.I.顏料綠58(DIC股份有限公司製造之「FASTOGEN GREEN A110)200份、氯化鈉1400份、及二乙二醇360份添加至不銹鋼製1加侖捏合機(井上製作所公司製造),於80℃混練6小時。其次,將該混練物投入至8000份之溫水,一面加熱至80℃一面攪拌2小時而製成漿料狀,反覆進行過濾、水洗而去除氯化鈉及二乙二醇後,於85℃乾燥一晝夜,獲得190份之綠色著色劑1。平均一次粒徑為69nm。 200 parts of phthalocyanine green pigment CI Pigment Green 58 ("FASTOGEN GREEN A110" manufactured by DIC Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were added to a stainless steel 1 gallon kneader (Inoue Manufacturing Co., Ltd. (Manufactured), kneaded for 6 hours at 80 ° C. Next, the kneaded product was poured into 8000 parts of warm water, and stirred while heating to 80 ° C. for 2 hours to prepare a slurry. The mixture was filtered and washed repeatedly to remove sodium chloride. After diethylene glycol and diethylene glycol were dried at 85 ° C for one day and night, 190 parts of green colorant 1 was obtained. The average primary particle diameter was 69 nm.
(藍色著色劑1之製作:PB15:6) (Production of blue colorant 1: PB15: 6)
將酞菁系藍色顏料C.I.顏料藍15:6(Toyocolor股份有限公司製造之「LIONOL BLUE ES」)200份、氯化鈉1400份、及二乙二醇360份添加至不銹鋼製1加侖捏合機(井上製作所公司製 造),於80℃混練6小時。其次,將該混練物投入至8000份之溫水,一面加熱至80℃一面攪拌2小時而製成漿料狀,反覆進行過濾、水洗而去除氯化鈉及二乙二醇後,於85℃乾燥一晝夜,獲得190份之藍色著色劑1。平均一次粒徑為74nm。 200 parts of phthalocyanine blue pigment CI Pigment Blue 15: 6 ("LIONOL BLUE ES" manufactured by Toyocolor Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were added to a stainless steel 1 gallon kneader (Manufactured by Inoue Seisakusho), and kneaded at 80 ° C for 6 hours. Next, the kneaded product was poured into 8000 parts of warm water, and heated to 80 ° C while stirring for 2 hours to make a slurry. After repeated filtration, washing with water to remove sodium chloride and diethylene glycol, the temperature was at 85 ° C. Drying all day and night, 190 parts of blue colorant 1 was obtained. The average primary particle diameter was 74 nm.
(紫色著色劑1之製作:PV23) (Production of purple colorant 1: PV23)
將二噁嗪系紫色顏料C.I.顏料紫23(Toyocolor股份有限公司製造之「LIONOGEN VIOLET RL」)200份、氯化鈉1400份、及二乙二醇360份添加至不銹鋼製1加侖捏合機(井上製作所公司製造),於80℃混練6小時。其次,將該混練物投入至8000份之溫水,一面加熱至80℃一面攪拌2小時而製成漿料狀,反覆進行過濾、水洗而去除氯化鈉及二乙二醇後,於85℃乾燥一晝夜,獲得190份之紫色著色劑1。平均一次粒徑為69nm。 200 parts of dioxazine purple pigment CI Pigment Violet 23 ("LIONOGEN VIOLET RL" manufactured by Toyocolor Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were added to a stainless steel 1 gallon kneader (Inoue Manufactured by Seisakusho Co., Ltd.) and kneaded at 80 ° C for 6 hours. Next, the kneaded product was poured into 8000 parts of warm water, and heated to 80 ° C while stirring for 2 hours to make a slurry. After repeated filtration, washing with water to remove sodium chloride and diethylene glycol, the temperature was 85 ° C Drying all day and night, 190 parts of purple colorant 1 was obtained. The average primary particle diameter was 69 nm.
以上實施例1至實施例116中所製造之偶氮顏料中質譜分析、元素分析之結果示於表3、表4。另外,所製造之全部之顏料中平均一次粒徑的評價結果示於表4。 Tables 3 and 4 show the results of mass spectrometry analysis and elemental analysis in the azo pigments produced in the above Examples 1 to 116. Table 4 shows the evaluation results of the average primary particle diameter of all the pigments produced.
<著色組成物的製造方法> <Manufacturing method of coloring composition>
[實施例201] [Example 201]
(著色組成物(RM-1)之製作) (Production of coloring composition (RM-1))
將下述之混合物以成為均勻之方式攪拌混合後,使用直徑0.5mm之氧化鋯珠,利用顏料分散研磨機(Eiger mill)(Eiger日本公司製造之「Minimodel M-250 MKII」)分散3小時後,利用孔徑5.0μm之過濾器進行過濾,製作不揮發成分為20質量%之著色組成物(RM-1)。 The following mixture was stirred and mixed in a uniform manner, and then dispersed using a zirconia bead with a diameter of 0.5 mm using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 3 hours. It was filtered with a filter having a pore size of 5.0 μm to produce a colored composition (RM-1) with a non-volatile content of 20% by mass.
紅色著色劑(RP-1):12.0份 Red colorant (RP-1): 12.0 parts
丙烯酸樹脂溶液1:19.2份 Acrylic resin solution 1: 19.2 parts
丙二醇單甲醚乙酸酯(PGMAc):60.8份 Propylene glycol monomethyl ether acetate (PGMAc): 60.8 parts
酸性樹脂型分散劑溶液(BYK-Chemie公司製造之「Disperbyk-110」(固形物成分52%)):8.0份 Acid resin type dispersant solution ("Disperbyk-110" (by solid content 52%) manufactured by BYK-Chemie): 8.0 parts
[實施例202至實施例330、比較例1] [Example 202 to Example 330, Comparative Example 1]
(著色組成物(RM-2至131) (Coloring composition (RM-2 to 131)
以下,變更為表5及表5-2所示之組成,除此以外,以與著色組成物(RM-1)同樣之方式,製備著色組成物(RM-2至131)。 Hereinafter, the coloring compositions (RM-2 to 131) were prepared in the same manner as the coloring composition (RM-1) except that the compositions shown in Tables 5 and 5-2 were changed.
[實施例331] [Example 331]
(著色組成物(RM-132)之製作) (Production of colored composition (RM-132))
將下述之混合物以成為均勻之方式攪拌混合後,使用直徑0.5mm之氧化鋯珠,利用顏料分散研磨機(Eiger日本公司製造之「Minimodel M-250 MKII」)分散3小時後,利用孔徑5.0μm之過濾器進行過濾,製作不揮發成分為20質量%之著色組成物(RM-132)。 The following mixture was stirred and mixed uniformly, and then dispersed using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then using a pore size of 5.0 A μm filter was used to produce a colored composition (RM-132) with a non-volatile content of 20% by mass.
紅色著色劑(RP-4):12.0份 Red colorant (RP-4): 12.0 parts
丙烯酸樹脂溶液1:19.2份 Acrylic resin solution 1: 19.2 parts
丙二醇單甲醚乙酸酯(PGMAc):60.5份 Propylene glycol monomethyl ether acetate (PGMAc): 60.5 parts
酸性樹脂型分散劑溶液(Lubrizol公司製造之「SOLSPERSE-55000」(固形物成分50%)):8.3份 Acid resin type dispersant solution ("SOLSPERSE-55000" (solid content 50%) manufactured by Lubrizol): 8.3 parts
[實施例332] [Example 332]
(著色組成物(RM-133)之製作) (Production of colored composition (RM-133))
將下述之混合物以成為均勻之方式攪拌混合後,使用直徑0.5mm之氧化鋯珠,利用顏料分散研磨機(Eiger日本公司製造 之「Minimodel M-250 MKII」)分散3小時後,利用孔徑5.0μm之過濾器進行過濾,製作不揮發成分為20質量%之著色組成物(RM-133)。 The following mixture was stirred and mixed uniformly, and then dispersed using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then using a pore size of 5.0 Filtered by a μm filter to produce a colored composition (RM-133) with a non-volatile content of 20% by mass.
紅色著色劑(RP-4):12.0份 Red colorant (RP-4): 12.0 parts
丙烯酸樹脂溶液1:19.2份 Acrylic resin solution 1: 19.2 parts
丙二醇單甲醚乙酸酯(PGMAc):58.4份 Propylene glycol monomethyl ether acetate (PGMAc): 58.4 parts
鹼性樹脂型分散劑溶液(BYK-Chemie公司製造之「Disperbyk-2000」(固形物成分40%)):10.4份 Alkaline resin-based dispersant solution ("Disperbyk-2000" (by solid content 40%) manufactured by BYK-Chemie): 10.4 parts
[實施例333] [Example 333]
(著色組成物(RM-134)之製作) (Production of colored composition (RM-134))
將下述之混合物以成為均勻之方式攪拌混合後,使用直徑0.5mm之氧化鋯珠,利用顏料分散研磨機(Eiger日本公司製造之「Minimodel M-250 MKII」)分散3小時後,利用孔徑5.0μm之過濾器進行過濾,製作不揮發成分為20質量%之著色組成物(RM-134)。 The following mixture was stirred and mixed uniformly, and then dispersed using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then using a pore size of 5.0 Filtered by a μm filter to produce a colored composition (RM-134) with a non-volatile content of 20% by mass.
紅色著色劑(RP-4):12.0份 Red colorant (RP-4): 12.0 parts
丙烯酸樹脂溶液1:40.0份 Acrylic resin solution 1: 40.0 parts
丙二醇單甲醚乙酸酯(PGMAc):48.0份 Propylene glycol monomethyl ether acetate (PGMAc): 48.0 parts
[實施例334] [Example 334]
(著色組成物(RM-135)之製作) (Production of colored composition (RM-135))
將下述之混合物以成為均勻之方式攪拌混合後,使用直徑0.5mm之氧化鋯珠,利用顏料分散研磨機(Eiger日本公司製造之「Minimodel M-250 MKII」)分散3小時後,利用孔徑5.0μm之過濾器進行過濾,製作不揮發成分為20質量%之著色組成物 (RM-135)。 The following mixture was stirred and mixed uniformly, and then dispersed using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then using a pore size of 5.0 A μm filter was used to produce a colored composition (RM-135) with a non-volatile content of 20% by mass.
紅色著色劑(RP-4):12.0份 Red colorant (RP-4): 12.0 parts
丙烯酸樹脂溶液1:19.2份 Acrylic resin solution 1: 19.2 parts
丙二醇單甲醚乙酸酯(PGMAc):58.4份 Propylene glycol monomethyl ether acetate (PGMAc): 58.4 parts
酸性樹脂型分散劑溶液(樹脂型分散劑溶液1):10.4份 Acid resin type dispersant solution (resin type dispersant solution 1): 10.4 parts
[實施例335至實施例337] [Examples 335 to 337]
(著色組成物(RM-136至138)) (Coloring composition (RM-136 to 138))
以下,變更為表5-3所示之組成,除此以外,以與著色組成物(RM-135)同樣之方式,製備著色組成物(RM-136至138)。 Hereinafter, except that the composition shown in Table 5-3 was changed, a colored composition (RM-136 to 138) was prepared in the same manner as the colored composition (RM-135).
[實施例338] [Example 338]
(著色組成物(RM-139) (Coloring composition (RM-139)
將紅色著色劑(RP-4)變更為紅色著色劑(RP-22),除此以外,以與著色組成物(RM-132)同樣之方式,製備著色組成物(RM-139)。 A colored composition (RM-139) was prepared in the same manner as the colored composition (RM-132), except that the red colorant (RP-4) was changed to a red colorant (RP-22).
[實施例339] [Example 339]
(著色組成物(RM-140)) (Coloring composition (RM-140))
將紅色著色劑(RP-4)變更為紅色著色劑(RP-22),除此以外,以與著色組成物(RM-133)同樣之方式,製備著色組成物(RM-140)。 A colored composition (RM-140) was prepared in the same manner as the colored composition (RM-133), except that the red colorant (RP-4) was changed to a red colorant (RP-22).
[實施例340] [Example 340]
(著色組成物(RM-141)) (Coloring composition (RM-141))
將紅色著色劑(RP-4)變更為紅色著色劑(RP-22),除此以 外,以與著色組成物(RM-134)同樣之方式,製備著色組成物(RM-141)。 A colored composition (RM-141) was prepared in the same manner as the colored composition (RM-134), except that the red colorant (RP-4) was changed to a red colorant (RP-22).
[實施例341] [Example 341]
(著色組成物(RM-142)) (Coloring composition (RM-142))
將紅色著色劑(RP-4)變更為紅色著色劑(RP-22),除此以外,以與著色組成物(RM-135)同樣之方式,製備著色組成物(RM-142)。 A colored composition (RM-142) was prepared in the same manner as the colored composition (RM-135), except that the red colorant (RP-4) was changed to a red colorant (RP-22).
[實施例342至實施例344] [Example 342 to Example 344]
(著色組成物(RM-143至145)) (Coloring composition (RM-143 to 145))
以下,變更為表5-3所示之組成,除此以外,以與著色組成物(RM-142)同樣之方式,製備著色組成物(RM-143至145)。 Hereinafter, except that the composition shown in Table 5-3 was changed, a coloring composition (RM-143 to 145) was prepared in the same manner as the coloring composition (RM-142).
[實施例345] [Example 345]
(著色組成物(RM-146)之製作) (Production of colored composition (RM-146))
將下述之混合物以成為均勻之方式攪拌混合後,使用直徑0.5mm之氧化鋯珠,利用顏料分散研磨機(Eiger日本公司製造之「Minimodel M-250 MKII」)分散3小時後,利用孔徑5.0μm之過濾器進行過濾,製作不揮發成分為20質量%之著色組成物(RM-146)。 The following mixture was stirred and mixed uniformly, and then dispersed using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then using a pore size of 5.0 Filtered by a μm filter to produce a colored composition (RM-146) with a non-volatile content of 20% by mass.
紅色著色劑(RP-4):10.8份 Red colorant (RP-4): 10.8 parts
色素衍生物1:1.2份 Pigment derivative 1: 1.2 parts
丙烯酸樹脂溶液1:19.2份 Acrylic resin solution 1: 19.2 parts
丙二醇單甲醚乙酸酯(PGMAc):60.8份 Propylene glycol monomethyl ether acetate (PGMAc): 60.8 parts
酸性樹脂型分散劑溶液(BYK-Chemie公司製造之 「Disperbyk-110」):8.0份 Acid resin type dispersant solution ("Disperbyk-110" manufactured by BYK-Chemie): 8.0 parts
[實施例346至實施例350、實施例353至實施例358] [Examples 346 to 350, Examples 353 to 358]
(著色組成物(RM-147至151、154至159)) (Coloring composition (RM-147 to 151, 154 to 159))
以下,變更為表5-4所示之組成,除此以外,以與著色組成物(RM-146)同樣之方式,製備著色組成物(RM-147至151、154至159)。 Hereinafter, except that the composition shown in Table 5-4 was changed, a colored composition (RM-147 to 151, 154 to 159) was prepared in the same manner as the colored composition (RM-146).
[實施例351] [Example 351]
(著色組成物(RM-152)之製作) (Production of colored composition (RM-152))
將下述之混合物以成為均勻之方式攪拌混合後,使用直徑0.5mm之氧化鋯珠,利用顏料分散研磨機(Eiger日本公司製造之「Minimodel M-250 MKII」)分散3小時後,利用孔徑5.0μm之過濾器進行過濾,製作不揮發成分為20質量%之著色組成物(RM-152)。 The following mixture was stirred and mixed uniformly, and then dispersed using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then using a pore size of 5.0 Filtered by a μm filter to produce a colored composition (RM-152) with a non-volatile content of 20% by mass.
紅色著色劑(RP-4):10.8份 Red colorant (RP-4): 10.8 parts
色素衍生物1:1.2份 Pigment derivative 1: 1.2 parts
丙烯酸樹脂溶液1:19.2份 Acrylic resin solution 1: 19.2 parts
丙二醇單甲醚乙酸酯(PGMAc):58.4份 Propylene glycol monomethyl ether acetate (PGMAc): 58.4 parts
酸性樹脂型分散劑溶液(樹脂型分散劑溶液1):10.4份 Acid resin type dispersant solution (resin type dispersant solution 1): 10.4 parts
[實施例352、實施例359、實施例360] [Example 352, Example 359, Example 360]
(著色組成物(RM-153、160、161)) (Coloring composition (RM-153, 160, 161))
以下,變更為表5-4所示之組成,除此以外,以與著色組成物(RM-152)同樣之方式,製備著色組成物(RM-153、160、161)。 Hereinafter, a coloring composition (RM-153, 160, 161) was prepared in the same manner as the coloring composition (RM-152) except that the composition shown in Table 5-4 was changed.
[比較例2] [Comparative Example 2]
(著色組成物(RCM-2):PR177) (Coloring composition (RCM-2): PR177)
將下述之混合物以成為均勻之方式攪拌混合後,使用直徑0.5mm之氧化鋯珠,利用顏料分散研磨機(Eiger日本公司製造之「Minimodel M-250 MKII」)分散3小時後,利用孔徑5.0μm之過濾器進行過濾,製作不揮發成分為20質量%之著色組成物(RCM-2)。 The following mixture was stirred and mixed uniformly, and then dispersed using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then using a pore size of 5.0 The filter was filtered by a μm filter to produce a colored composition (RCM-2) having a nonvolatile content of 20% by mass.
紅色著色劑2(RCP-2)(PR177):12.0份 Red colorant 2 (RCP-2) (PR177): 12.0 parts
丙烯酸樹脂溶液1:36.4份 Acrylic resin solution 1: 36.4 parts
丙二醇單甲醚乙酸酯(PGMAc):50.2份 Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts
酸性樹脂型分散劑溶液(BYK-Chemie公司製造之「Disperbyk-110」):1.4份 Acid resin type dispersant solution ("Disperbyk-110" manufactured by BYK-Chemie): 1.4 parts
[比較例3] [Comparative Example 3]
(著色組成物(RCM-4):PR269) (Coloring composition (RCM-4): PR269)
將下述之混合物以成為均勻之方式攪拌混合後,使用直徑0.5mm之氧化鋯珠,利用顏料分散研磨機(Eiger日本公司製造之「Minimodel M-250 MKII」)分散3小時後,利用孔徑5.0μm之過濾器進行過濾,製作不揮發成分為20質量%之著色組成物(RCM-4)。 The following mixture was stirred and mixed uniformly, and then dispersed using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then using a pore size of 5.0 The filter was filtered by a μm filter to produce a colored composition (RCM-4) having a nonvolatile content of 20% by mass.
紅色著色劑4(RCP-4)(PR269):12.0份 Red colorant 4 (RCP-4) (PR269): 12.0 parts
丙烯酸樹脂溶液1:36.4份 Acrylic resin solution 1: 36.4 parts
丙二醇單甲醚乙酸酯(PGMAc):50.2份 Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts
酸性樹脂型分散劑溶液(BYK-Chemie公司製造之「Disperbyk-110」):1.4份 Acid resin type dispersant solution ("Disperbyk-110" manufactured by BYK-Chemie): 1.4 parts
(著色組成物(RCM-1):PR254) (Coloring composition (RCM-1): PR254)
將下述之混合物以成為均勻之方式攪拌混合後,使用直徑0.5mm之氧化鋯珠,利用顏料分散研磨機(Eiger日本公司製造之「Minimodel M-250 MKII」)分散3小時後,利用孔徑5.0μm之過濾器進行過濾,製作不揮發成分為20質量%之著色組成物(RCM-1)。 The following mixture was stirred and mixed uniformly, and then dispersed using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then using a pore size of 5.0 The filter was filtered by a μm filter to produce a colored composition (RCM-1) having a non-volatile content of 20% by mass.
紅色著色劑1(RCP-1)(PR254):12.0份 Red colorant 1 (RCP-1) (PR254): 12.0 parts
丙烯酸樹脂溶液1:36.4份 Acrylic resin solution 1: 36.4 parts
丙二醇單甲醚乙酸酯(PGMAc):50.2份 Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts
酸性樹脂型分散劑溶液(BYK-Chemie公司製造之「Disperbyk-110」):1.4份 Acid resin type dispersant solution ("Disperbyk-110" manufactured by BYK-Chemie): 1.4 parts
(著色組成物(RCM-3):PR242) (Coloring composition (RCM-3): PR242)
將下述之混合物以成為均勻之方式攪拌混合後,使用直徑0.5mm之氧化鋯珠,利用顏料分散研磨機(Eiger日本公司製造之「Minimodel M-250 MKII」)分散3小時後,利用孔徑5.0μm之過濾器進行過濾,製作不揮發成分為20質量%之著色組成物(RCM-3)。 The following mixture was stirred and mixed uniformly, and then dispersed using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then using a pore size of 5.0 The filter was filtered by a μm filter to produce a colored composition (RCM-3) having a nonvolatile content of 20% by mass.
紅色著色劑3(RCP-3)(PR242):12.0份 Red colorant 3 (RCP-3) (PR242): 12.0 parts
丙烯酸樹脂溶液1:36.4份 Acrylic resin solution 1: 36.4 parts
丙二醇單甲醚乙酸酯(PGMAc):50.2份 Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts
酸性樹脂型分散劑溶液(BYK-Chemie公司製造之「Disperbyk-110」):1.4份 Acid resin type dispersant solution ("Disperbyk-110" manufactured by BYK-Chemie): 1.4 parts
(著色組成物(RCM-5):式(4)) (Coloring composition (RCM-5): Formula (4))
將下述之混合物以成為均勻之方式攪拌混合後,使用直徑0.5mm之氧化鋯珠,利用顏料分散研磨機(Eiger日本公司製造之「Minimodel M-250 MKII」)分散3小時後,利用孔徑5.0μm之過濾器進行過濾,製作不揮發成分為20質量%之著色組成物(RCM-5)。 The following mixture was stirred and mixed uniformly, and then dispersed using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then using a pore size of 5.0 The filter was filtered by a μm filter to produce a colored composition (RCM-5) having a nonvolatile content of 20% by mass.
紅色著色劑5(RCP-5)(式(4)):12.0份 Red colorant 5 (RCP-5) (formula (4)): 12.0 parts
丙烯酸樹脂溶液1:36.4份 Acrylic resin solution 1: 36.4 parts
丙二醇單甲醚乙酸酯(PGMAc):50.2份 Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts
酸性樹脂型分散劑溶液(BYK-Chemie公司製造之「 Disperbyk-110」):1.4份 Acid resin type dispersant solution ("Disperbyk-110" manufactured by BYK-Chemie): 1.4 parts
(著色組成物(YCM-1):PY138) (Coloring composition (YCM-1): PY138)
將下述之混合物以成為均勻之方式攪拌混合後,使用直徑0.5mm之氧化鋯珠,利用顏料分散研磨機(Eiger日本公司製造之「Minimodel M-250 MKII」)分散3小時後,利用孔徑5.0μm之過濾器進行過濾,製作不揮發成分為20質量%之著色組成物(YCM-1)。 The following mixture was stirred and mixed uniformly, and then dispersed using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then using a pore size of 5.0 A μm filter was used to produce a colored composition (YCM-1) having a non-volatile content of 20% by mass.
黃色著色劑1(YCP-1)(PY138):12.0份 Yellow colorant 1 (YCP-1) (PY138): 12.0 parts
丙烯酸樹脂溶液1:36.4份 Acrylic resin solution 1: 36.4 parts
丙二醇單甲醚乙酸酯(PGMAc):50.2份 Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts
酸性樹脂型分散劑溶液(BYK-Chemie公司製造之「Disperbyk-110」):1.4份 Acid resin type dispersant solution ("Disperbyk-110" manufactured by BYK-Chemie): 1.4 parts
(著色組成物(YCM-2):PY139) (Coloring composition (YCM-2): PY139)
將下述之混合物以成為均勻之方式攪拌混合後,使用直徑0.5mm之氧化鋯珠,利用顏料分散研磨機(Eiger日本公司製造 之「Minimodel M-250 MKII」)分散3小時後,利用孔徑5.0μm之過濾器進行過濾,製作不揮發成分為20質量%之著色組成物(YCM-2)。 The following mixture was stirred and mixed uniformly, and then dispersed using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then using a pore size of 5.0 The filter was filtered by a μm filter to produce a colored composition (YCM-2) having a nonvolatile content of 20% by mass.
黃色著色劑2(YCP-2)(PY139):12.0份 Yellow colorant 2 (YCP-2) (PY139): 12.0 parts
丙烯酸樹脂溶液1:36.4份 Acrylic resin solution 1: 36.4 parts
丙二醇單甲醚乙酸酯(PGMAc):50.2份 Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts
酸性樹脂型分散劑溶液(BYK-Chemie公司製造之「Disperbyk-110」):1.4份 Acid resin type dispersant solution ("Disperbyk-110" manufactured by BYK-Chemie): 1.4 parts
(著色組成物(YCM-3):PY150) (Coloring composition (YCM-3): PY150)
將下述之混合物以成為均勻之方式攪拌混合後,使用直徑0.5mm之氧化鋯珠,利用顏料分散研磨機(Eiger日本公司製造之「Minimodel M-250 MKII」)分散3小時後,利用孔徑5.0μm之過濾器進行過濾,製作不揮發成分為20質量%之著色組成物(YCM-3)。 The following mixture was stirred and mixed uniformly, and then dispersed using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then using a pore size of 5.0 A μm filter was used to produce a colored composition (YCM-3) having a nonvolatile content of 20% by mass.
黃色著色劑3(YCP-3)(PY150):12.0份 Yellow colorant 3 (YCP-3) (PY150): 12.0 parts
丙烯酸樹脂溶液1:36.4份 Acrylic resin solution 1: 36.4 parts
丙二醇單甲醚乙酸酯(PGMAc):50.2份 Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts
酸性樹脂型分散劑溶液(BYK-Chemie公司製造之「Disperbyk-110」):1.4份 Acid resin type dispersant solution ("Disperbyk-110" manufactured by BYK-Chemie): 1.4 parts
(著色組成物(YCM-4):喹酞酮化合物(b)) (Coloring composition (YCM-4): quinophthalone compound (b))
將下述之混合物以成為均勻之方式攪拌混合後,使用直徑0.5mm之氧化鋯珠,利用顏料分散研磨機(Eiger日本公司製造之「Minimodel M-250 MKII」)分散3小時後,利用孔徑5.0μm之過濾器進行過濾,製作不揮發成分為20質量%之著色組成物 (YCM-4)。 The following mixture was stirred and mixed uniformly, and then dispersed using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then using a pore size of 5.0 A μm filter was used to produce a colored composition (YCM-4) with a non-volatile content of 20% by mass.
黃色著色劑4(YCP-4)喹酞酮化合物(b)):12.0份 Yellow colorant 4 (YCP-4) quinophthalone compound (b)): 12.0 parts
丙烯酸樹脂溶液1:36.4份 Acrylic resin solution 1: 36.4 parts
丙二醇單甲醚乙酸酯(PGMAc):50.2份 Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts
酸性樹脂型分散劑溶液(BYK-Chemie公司製造之「Disperbyk-110」):1.4份 Acid resin type dispersant solution ("Disperbyk-110" manufactured by BYK-Chemie): 1.4 parts
(著色組成物之評價) (Evaluation of colored composition)
利用下述方法進行所獲得之著色組成物及使用該著色組成物所製作之塗膜的耐熱性、耐光性、塗膜異物及保存穩定性之評價。評價結果示於表5。 The evaluation of the heat resistance, light resistance, coating film foreign matter, and storage stability of the obtained colored composition and the coating film produced using the colored composition was performed by the following method. The evaluation results are shown in Table 5.
(耐熱性評價) (Evaluation of heat resistance)
使用旋轉塗佈機,將著色組成物以乾燥膜厚成為2.0μm之方式塗佈於100mm×100mm、1.1mm厚之玻璃基板上,接著於70℃乾燥20分鐘,繼而於230℃加熱60分鐘,並放置冷卻,藉此製作塗膜基板(彩色濾光片的一態樣)。使用顯微分光光度計(Olympus光學公司製造之「OSP-SP100」),測定所獲得之塗膜在C光源下的色度([L*(1)、a*(1)、b*(1)])。進而,作為耐熱性試驗於250℃加熱1小時,測定C光源下的色度([L*(2)、a*(2)、b*(2)]),藉由下述計算式,求出色差△Eab*,按照下述之4個等級進行評價。 Using a spin coater, apply the colored composition to a 100 mm × 100 mm, 1.1 mm thick glass substrate so that the dry film thickness becomes 2.0 μm, and then dry at 70 ° C. for 20 minutes, and then heat at 230 ° C. for 60 minutes. The substrate was left to cool, thereby preparing a coating film substrate (a state of a color filter). Using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.), the chromaticity of the obtained coating film under a C light source ((L * (1), a * (1), b * (1 )]). Furthermore, as a heat resistance test, it was heated at 250 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) under a C light source was measured. The excellent difference ΔEab * was evaluated according to the following four levels.
△Eab*=√((L*(2)-L*(1))2+(a*(2)-a*(1))2+(b*(2)-b*(1))2) △ Eab * = √ ((L * (2) -L * (1)) 2 + (a * (2) -a * (1)) 2 + (b * (2) -b * (1)) 2 )
◎:△Eab*未達1.0(極其良好) ◎: △ Eab * less than 1.0 (very good)
○:△Eab*為1.0以上且未達2.5(良好) ○: △ Eab * is 1.0 or more and less than 2.5 (good)
△:△Eab*為2.5以上且未達5.0(不良) △: △ Eab * is 2.5 or more and less than 5.0 (defective)
×:△Eab*為5.0以上(極其不良) ×: △ Eab * 5.0 or more (very bad)
(耐光性評價) (Evaluation of light resistance)
利用與耐熱性評價時同樣之方法,製作塗膜基板,使用顯微分光光度計(Olympus光學公司製造之「OSP-SP100」),測定C光源下的色度([L*(1)、a*(1)、b*(1)])。繼而,於該基板上貼合紫外線截止濾光片(HOYA公司製造之「COLORED OPTICAL GLASS L38」),使用470W/m2之氙氣燈,照射紫外線100小時後,測定C光源下的色度([L*(2)、a*(2)、b*(2)]),藉由上述計算式,求出色差△Eab*,按照與耐熱性相同的基準進行評價。 A coating film substrate was prepared by the same method as in the evaluation of heat resistance, and the chromaticity under the C light source ([L * (1), a) was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). * (1), b * (1)]). Next, an ultraviolet cut filter ("COLORED OPTICAL GLASS L38" manufactured by HOYA) was attached to the substrate, and a 470 W / m 2 xenon lamp was used to irradiate ultraviolet rays for 100 hours, and then the chromaticity under the C light source was measured ([ L * (2), a * (2), b * (2)]), the difference ΔEab * was obtained from the above calculation formula, and evaluation was performed on the same basis as heat resistance.
(塗膜異物評價) (Evaluation of coating foreign matter)
使用旋轉塗佈機,將著色組成物以乾燥膜厚成為2.0μm之方式塗佈於100mm×100mm、1.1mm厚之玻璃基板上,接著於70℃乾燥20分鐘,繼而於230℃加熱60分鐘,並放置冷卻,藉此製作塗膜基板。評價係使用Olympus System公司製造之金屬顯微鏡「BX60」進行表面觀察。倍率係設為500倍,利用透過計數任意之5個視野中可觀測到之粒子的數量。按照下述之4個等級進行評價。 Using a spin coater, apply the colored composition to a 100 mm × 100 mm, 1.1 mm thick glass substrate so that the dry film thickness becomes 2.0 μm, and then dry at 70 ° C. for 20 minutes, and then heat at 230 ° C. for 60 minutes. Then, it was left to cool to prepare a coating film substrate. The evaluation was performed using a metal microscope "BX60" manufactured by Olympus System. The magnification is set to 500 times, and the number of particles that can be observed in any of the 5 fields of view through transmission counting is used. Evaluation was performed according to the following four levels.
◎:異物的數量未達5個(極其良好) ◎: The number of foreign objects is less than 5 (very good)
○:異物的數量為5個以上且未達10個(良好) ○: The number of foreign objects is 5 or more and less than 10 (good)
△:異物的數量為10個以上且未達60個(不良) △: The number of foreign objects is 10 or more and less than 60 (defective)
×:異物的數量為60個以上(極其不良) ×: The number of foreign objects is 60 or more (very bad)
(保存穩定性試驗方法) (Storage stability test method)
使用E型黏度計(東機產業公司製造之TUE-20L型),以轉速20rpm測定著色組成物在25℃的黏度。根據著色組成物之製作當天的起始黏度、及在40℃之恆溫室中保存7天後測定之黏度,算出黏度變化率(%)(=(在40℃保存7天後的黏度-起始黏度)/起始黏度×100),按照下述之基準評價保存穩定性。 The viscosity of the colored composition at 25 ° C. was measured using an E-type viscometer (TUE-20L type manufactured by Toki Sangyo Co., Ltd.) at a rotation speed of 20 rpm. Calculate the viscosity change rate (%) based on the initial viscosity on the day of production of the coloring composition and the viscosity measured after 7 days of storage in a constant temperature room at 40 ° C (= (viscosity after 7 days of storage at 40 ° C-onset) Viscosity) / initial viscosity × 100), and storage stability was evaluated according to the following criteria.
◎:黏度變化率未達10%(極其良好) ◎: Viscosity change rate is less than 10% (very good)
○:黏度變化率為10%以上且未達20%(良好) ○: The viscosity change rate is 10% or more and less than 20% (good)
△:黏度變化率為20%以上且未達50%(不良) △: The viscosity change rate is 20% or more and less than 50% (bad)
×:黏度變化率為50%以上(極其不良) ×: Viscosity change rate is 50% or more (very bad)
如表5所示,使用本發明之著色劑之著色組成物在塗膜的耐熱性、耐光性、塗膜異物、及保存穩定性方面為良好的結果。尤其是,於與使用偶氮顏料119之著色組成物(比較例1)比較之情形時,藉由顏料之高次立體位阻而分散更穩定,因此可見到品質提升。另外,尤其是藉由併用具有芳香族羧酸之樹脂型分散劑或色素衍生物,可獲得耐熱性或耐光性優異,塗膜異物及保存穩定性良好之結果。 As shown in Table 5, the coloring composition using the coloring agent of the present invention has good results in terms of heat resistance, light resistance, foreign matter of the coating film, and storage stability of the coating film. In particular, when compared with a coloring composition (Comparative Example 1) using an azo pigment 119, the dispersion is more stable due to the high-order steric hindrance of the pigment, and thus quality improvement can be seen. In addition, by using a resin-based dispersant or a pigment derivative having an aromatic carboxylic acid in combination, excellent heat resistance or light resistance can be obtained, and results of coating film foreign matter and storage stability can be obtained.
<彩色濾光片用感光性著色組成物的製造方法> <Manufacturing method of the photosensitive coloring composition for color filters>
[實施例401] [Example 401]
(感光性著色組成物(RR-1)) (Photosensitive coloring composition (RR-1))
將下述之混合物(合計100份)以成為均勻之方式攪拌混合後,利用孔徑1.0μm之過濾器進行過濾,獲得感光性著色組成物(RR-1)。 The following mixture (100 parts in total) was stirred and mixed to become uniform, and then filtered through a filter having a pore size of 1.0 μm to obtain a photosensitive coloring composition (RR-1).
著色組成物(RM-1):23.0份 Coloring composition (RM-1): 23.0 parts
著色組成物(RCM-1):27.0份 Coloring composition (RCM-1): 27.0 parts
丙烯酸樹脂溶液2:7.5份 Acrylic resin solution 2: 7.5 parts
光聚合性單體(東亞合成公司製造之「Aronix M-402」):2.0份 Photopolymerizable monomer ("Aronix M-402" manufactured by Toa Synthesis Corporation): 2.0 parts
二季戊四醇六丙烯酸酯 Dipentaerythritol hexaacrylate
光聚合起始劑(BASF公司製造之「OXE-02」):1.5份 Photopolymerization initiator ("OXE-02" manufactured by BASF): 1.5 parts
乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O- 乙醯基肟) Ethyl ketone, 1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl]-, 1- (O-acetamidooxime)
環己酮:39.0份 Cyclohexanone: 39.0 parts
[實施例402至實施例567、比較例4至比較例13] [Examples 402 to 567, Comparative Examples 4 to 13]
(感光性著色組成物(RR-2至177)) (Photosensitive coloring composition (RR-2 to 177))
如表6所示,調整著色組成物的種類及比率,除此以外,以與感光性著色組成物(RR-1)相同之方式,獲得感光性著色組成物(RR-2至177)。 As shown in Table 6, the photosensitive coloring composition (RR-2 to 177) was obtained in the same manner as the photosensitive coloring composition (RR-1) except that the type and ratio of the coloring composition were adjusted.
<彩色濾光片用感光性著色組成物之評價> <Evaluation of the photosensitive coloring composition for color filters>
利用下述方法進行所獲得之感光性著色組成物的亮度、對比率、膜厚之評價。評價結果示於表6。另外,移染性之評價示於表7。 The brightness, contrast ratio, and film thickness of the obtained photosensitive coloring composition were evaluated by the following methods. The evaluation results are shown in Table 6. The evaluation of the transferability is shown in Table 7.
(亮度之評價) (Evaluation of brightness)
於玻璃基板上,塗佈所獲得之感光性著色組成物,於70℃乾燥20分鐘後,進而於230℃加熱60分鐘,獲得基板的色度在C光源下成為x=0.683、y=0.313之塗佈基板。利用顯微分光光度計(Olympus光學公司製造之「OSP-SP200」)測定所獲得之基板的亮度(Y)。 The obtained photosensitive coloring composition was coated on a glass substrate, dried at 70 ° C for 20 minutes, and then heated at 230 ° C for 60 minutes. The chromaticity of the obtained substrate became x = 0.683, y = 0.313 under the C light source. Coated substrate. The brightness (Y) of the obtained substrate was measured using a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.).
(對比率(CR)之評價) (Evaluation of Contrast Ratio (CR))
使用經測定亮度之基板,測定對比率。 The contrast ratio was measured using a substrate on which the brightness was measured.
(膜厚之評價) (Evaluation of film thickness)
使用經測定亮度之基板,測定膜厚。膜厚之測定係使用表面形狀測定器DEKTAK150(ULVAC ES公司製造)。 The film thickness was measured using a substrate on which the brightness was measured. The film thickness was measured using a surface shape measuring instrument DEKTAK150 (manufactured by ULVAC ES).
(移染性之評價) (Evaluation of transferability)
使用狹縫模嘴塗佈機,將彩色濾光片用感光性著色組成物塗佈於玻璃基板上後,利用90℃之加熱板進行2分鐘預烘烤,形成膜厚2.4μm之塗膜。繼而,將形成有塗膜之基板冷卻至室溫後,使用高壓水銀燈,經由條紋狀光罩,利用包含365nm、405nm及436nm之各波長之放射線,以1,000J/m2之曝光量對塗膜進行曝光。進行鹼顯影後,利用超純水進行洗淨,進而於230℃進行20分鐘後烘烤,藉此於基板上形成紅色之條紋狀像素。繼而,測定與紅色之條紋狀像素相距僅8μm之玻璃基板上的520nm的透過率(T1)。進而,使用狹縫模嘴塗佈機,將丙烯酸樹脂溶液2塗佈於該基板上後,利用90℃之加熱板進行2分鐘預烘烤,形成膜厚2.5μm之塗膜。進而,於230℃進行20分鐘後烘烤。繼而,測定與紅色之條紋狀像素相距僅8μm之玻璃基板上的520nm的透過率(T2)。將T1與T2之差量設為△T(%),按照下述之4個等級進行評價。可謂△T值愈小,向鄰接之他色濾光片段之顏色轉移所致之亮度降低愈少,移染性愈得到抑制。 Using a slit die coater, a photosensitive coloring composition for a color filter was coated on a glass substrate, and then prebaked for 2 minutes using a 90 ° C. hot plate to form a coating film having a thickness of 2.4 μm. Then, after cooling the substrate on which the coating film was formed to room temperature, the coating film was exposed to 1,000 J / m 2 by using a high-pressure mercury lamp, through a stripe-shaped mask, and using radiation having wavelengths of 365 nm, 405 nm, and 436 nm. Make an exposure. After alkaline development, washing with ultrapure water, and post-baking at 230 ° C. for 20 minutes, thereby forming red striped pixels on the substrate. Then, the transmittance (T1) of 520 nm on a glass substrate only 8 μm from the red stripe-shaped pixel was measured. Furthermore, after applying the acrylic resin solution 2 on the substrate using a slit die coater, pre-baking was performed on a hot plate at 90 ° C. for 2 minutes to form a coating film having a film thickness of 2.5 μm. Furthermore, it baked at 230 degreeC for 20 minutes. Then, a transmittance (T2) of 520 nm on a glass substrate which is only 8 μm away from the red striped pixels was measured. The difference between T1 and T2 was set as ΔT (%), and evaluation was performed on the following four levels. It can be said that the smaller the value of △ T, the less the brightness reduction caused by the color transfer to the adjacent other color filter segments, and the more inhibited the migration.
◎:△T未達0.5%(極其良好) ◎: △ T is less than 0.5% (very good)
○:△T為0.5%以上且未達1.0%(良好) ○: △ T is 0.5% or more and less than 1.0% (good)
△:△T為1.0%以上且未達3.0%(不良) △: △ T is 1.0% or more and less than 3.0% (defective)
×:△T為3.0%以上(極其不良) ×: △ T is 3.0% or more (very bad)
根據表6之結果,顯然使用本發明之著色劑之實施例之亮度優異而成為薄膜。尤其是藉由代替先前用作帶藍色之顏料之C.I.顏料紅177、C.I.顏料紅269或偶氮顏料119來使用,確認到顯著的效果。 From the results in Table 6, it is clear that the examples using the coloring agent of the present invention are excellent in brightness and become thin films. In particular, a significant effect was confirmed by using C.I. Pigment Red 177, C.I. Pigment Red 269, or Azo Pigment 119, which was previously used as a blue-colored pigment.
進而,如表7所示,可確認到使用本發明之著色劑之著色組成物的移染性良好。 Furthermore, as shown in Table 7, it was confirmed that the coloring composition using the coloring agent of the present invention had good migration properties.
<彩色濾光片用綠色及藍色感光性著色組成物的製造方法> <Manufacturing method of green and blue photosensitive coloring composition for color filters>
(綠色感光性著色組成物1:PG58/PY138) (Green photosensitive coloring composition 1: PG58 / PY138)
將下述之混合物以成為均勻之方式攪拌混合後,使用直徑0.5mm之氧化鋯珠,利用顏料分散研磨機(Eiger日本公司製造之「Minimodel M-250 MKII」)分散5小時後,利用孔徑5.0μm之過濾器進行過濾,製作不揮發成分為20質量%之綠色顏料分散體。 The following mixture was stirred and mixed uniformly, and then dispersed using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm, and then using a pore size of 5.0 The filter was filtered with a μm to produce a green pigment dispersion having a non-volatile content of 20% by mass.
綠色著色劑1(C.I.顏料綠58):12.0份 Green colorant 1 (C.I. Pigment Green 58): 12.0 parts
丙烯酸樹脂溶液1:36.4份 Acrylic resin solution 1: 36.4 parts
丙二醇單甲醚乙酸酯(PGMAc):50.2份 Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts
酸性樹脂型分散劑溶液(BYK-Chemie公司製造之「Disperbyk-110」):1.4份 Acid resin type dispersant solution ("Disperbyk-110" manufactured by BYK-Chemie): 1.4 parts
將下述之混合物以成為均勻之方式攪拌混合後,使用直徑0.5mm之氧化鋯珠,利用顏料分散研磨機(Eiger日本公司製造之「Minimodel M-250 MKII」)分散5小時後,利用孔徑5.0μm之過濾器進行過濾,製作不揮發成分為20質量%之黃色顏料分散體。 The following mixture was stirred and mixed uniformly, and then dispersed using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm, and then using a pore size of 5.0 The filter was filtered by a μm filter to prepare a yellow pigment dispersion having a non-volatile content of 20% by mass.
黃色著色劑1(C.I.顏料黃138):12.0份 Yellow colorant 1 (C.I. Pigment Yellow 138): 12.0 parts
丙烯酸樹脂溶液1:36.4份 Acrylic resin solution 1: 36.4 parts
丙二醇單甲醚乙酸酯(PGMAc):50.2份 Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts
酸性樹脂型分散劑溶液(BYK-Chemie公司製造之「Disperbyk-110」):1.4份 Acid resin type dispersant solution ("Disperbyk-110" manufactured by BYK-Chemie): 1.4 parts
繼而,將下述組成之混合物以成為均勻之方式攪拌混合後,利用孔徑1μm之過濾器進行過濾,製作綠色感光性著色組成物1。 Next, the mixture of the following composition was stirred and mixed to make it uniform, and then filtered through a filter having a pore size of 1 μm to produce a green photosensitive coloring composition 1.
綠色顏料分散體:32.0份 Green pigment dispersion: 32.0 parts
黃色顏料分散體:18.0份 Yellow pigment dispersion: 18.0 parts
丙烯酸樹脂溶液2:7.5份 Acrylic resin solution 2: 7.5 parts
光聚合性單體(東亞合成公司製造之「Aronix M-402」):2.0份 Photopolymerizable monomer ("Aronix M-402" manufactured by Toa Synthesis Corporation): 2.0 parts
二季戊四醇六丙烯酸酯 Dipentaerythritol hexaacrylate
光聚合起始劑(BASF公司製造之「OXE-02」):1.5份 Photopolymerization initiator ("OXE-02" manufactured by BASF): 1.5 parts
乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(0-乙醯基肟) Ethyl ketone, 1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl]-, 1- (0-acetamidooxime)
環己酮:39.0份 Cyclohexanone: 39.0 parts
(藍色感光性著色組成物1:PB15:6/PV23) (Blue photosensitive coloring composition 1: PB15: 6 / PV23)
將綠色著色劑1(C.I.顏料綠58)變更為藍色著色劑1(C.I.顏料藍15:6),除此以外,以與綠色顏料分散體同樣之方式,獲得不揮發成分為20質量%之藍色顏料分散體。 Except changing the green colorant 1 (CI Pigment Green 58) to the blue colorant 1 (CI Pigment Blue 15: 6), in the same manner as the green pigment dispersion, a nonvolatile content of 20% by mass was obtained. Blue pigment dispersion.
將綠色著色劑1(C.I.顏料綠58)變更為紫色著色劑1(C.I.顏料紫23),除此以外,以與綠色顏料分散體同樣之方式,獲得不揮發成分為20質量%之紫色顏料分散體。 Except changing green colorant 1 (CI Pigment Green 58) to purple colorant 1 (CI Pigment Violet 23), a purple pigment dispersion having a non-volatile content of 20% by mass was obtained in the same manner as the green pigment dispersion. body.
繼而,將綠色顏料分散體32.0份、黃色顏料分散體18.0份之合計50.0份,置換為藍色分散體46.0份、紫色分散體4.0份之合計50.0份,除此以外,以與綠色感光性著色組成物1同樣之方式,獲得藍色感光性著色組成物1。 Next, 30.0 parts of a green pigment dispersion and 50.0 parts of a total of 18.0 parts of a yellow pigment dispersion were replaced with 46.0 parts of a blue dispersion and 50.0 parts of a total of 4.0 parts of a purple dispersion. In the same manner as in Composition 1, a blue photosensitive colored composition 1 was obtained.
<彩色濾光片之製作及評價> <Production and Evaluation of Color Filters>
使用狹縫模嘴塗佈機,將紅色感光性著色組成物(RR-1)塗佈於形成有黑矩陣之玻璃基板上,然後利用90℃之加熱板進行2分鐘預烘烤,形成塗膜。繼而,將形成有塗膜之基板冷卻至室溫後,使用高壓水銀燈,經由條紋狀光罩,利用包含365nm、405nm及436nm之各波長之放射線,以1,000J/m2之曝光量對塗膜進行曝光。進行鹼顯影後,利用超純水進行洗淨,進而於230℃進行20分鐘後烘烤,藉此於基板上形成紅色之條紋狀像素。 Using a slit die coater, a red photosensitive coloring composition (RR-1) was coated on a glass substrate formed with a black matrix, and then pre-baked for 2 minutes using a 90 ° C hot plate to form a coating film. . Next, after cooling the substrate on which the coating film was formed to room temperature, the coating film was exposed to 1,000 J / m 2 by using a high-pressure mercury lamp through a stripe-shaped mask, using radiation including wavelengths of 365 nm, 405 nm, and 436 nm. Make an exposure. After alkaline development, washing with ultrapure water, and post-baking at 230 ° C. for 20 minutes, thereby forming red striped pixels on the substrate.
繼而,藉由同樣之方法,使用綠色感光性著色組成物1,於紅色之條紋狀像素之近旁形成綠色之條紋狀像素。進而,使用藍色感光性著色組成物1,同樣地形成與紅色、綠色像素鄰接之藍色之條紋狀像素。 Then, by using the same method, a green photosensitive coloring composition 1 is used to form a green striped pixel near a red striped pixel. Furthermore, the blue photosensitive coloring composition 1 was used to similarly form blue striped pixels adjacent to the red and green pixels.
繼而,於由紅色、綠色、藍色之3色構成之像素上,使用光硬化性樹脂組成物形成保護膜。以此種方式,可製成亮度高且各種耐性優異之RGB3色彩色濾光片。 Then, a protective film is formed on a pixel composed of three colors of red, green, and blue using a photocurable resin composition. In this way, an RGB 3-color color filter with high brightness and excellent resistance can be produced.
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