TWI443458B - Red-coloring composition for color filter and color filter - Google Patents

Red-coloring composition for color filter and color filter Download PDF

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TWI443458B
TWI443458B TW100113570A TW100113570A TWI443458B TW I443458 B TWI443458 B TW I443458B TW 100113570 A TW100113570 A TW 100113570A TW 100113570 A TW100113570 A TW 100113570A TW I443458 B TWI443458 B TW I443458B
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red
pigment
resin
acid
group
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TW100113570A
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TW201214030A (en
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Yuki Saito
Yishitake Oryu
Toshiharu Yoshizawa
Rihito Ito
Tomomi Yamazaki
Kenichi Kitamura
natsuko Kokubo
Masayuki Yamamoto
Kanae Sasaki
Toshiyuki Sato
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Toyo Ink Sc Holdings Co Ltd
Toyocolor Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials

Description

彩色濾光片用紅色著色組成物及彩色濾光片 Color filter with red coloring composition and color filter

本發明係關於一種製造用於彩色液晶顯示裝置、彩色攝像管元件等之彩色濾光片時所使用的彩色濾光片用紅色著色組成物，以及具備利用其所形成的濾光片區段之彩色濾光片。在此，紅色著色組成物可適用於紅色用、洋紅色用之彩色濾光片。 The present invention relates to a red coloring composition for a color filter used for manufacturing a color filter for a color liquid crystal display device, a color image pickup device element, or the like, and a filter segment formed therewith Color filter. Here, the red coloring composition can be applied to a color filter for red or magenta.

液晶顯示裝置係藉由2片偏光板所夾住的液晶層，來控制通過第1片偏光板的光之偏光程度，並控制通過第2片偏光板之光量來進行顯示之顯示裝置，其主流係利用扭轉向列(TN)型液晶的類型。液晶顯示裝置可藉由在2片偏光板之間設置彩色濾光片來進行彩色顯示。因此，液晶顯示裝置對於電視或個人電腦監視器用途的應用日益進展。 The liquid crystal display device is a display device that controls the degree of polarization of light passing through the first polarizing plate and controls the amount of light passing through the second polarizing plate to display the liquid crystal layer sandwiched between the two polarizing plates. The type of twisted nematic (TN) type liquid crystal is utilized. The liquid crystal display device can perform color display by providing a color filter between two polarizing plates. Therefore, the application of liquid crystal display devices to television or personal computer monitor applications is progressing.

其他代表性的液晶顯示裝置之顯示方式包括：於一側基板上設置一對電極，對基板往平行方向施加電解之平面切換(IPS)方式；令具有負介電各向異性之向列液晶呈垂直配向之垂直對準(VA)方式；或令單軸性之相位差膜之光軸相互正交而進行光學補償之光學補償彎曲(OCB)方式等；各方式已被實用化。 Other representative liquid crystal display devices are provided by: providing a pair of electrodes on one substrate, applying an electrolytic plane switching (IPS) method to the parallel direction of the substrate; and making the nematic liquid crystal having negative dielectric anisotropy The vertical alignment (VA) method for vertical alignment or the optical compensation bending (OCB) method for optically compensating the optical axes of the uniaxial retardation film are orthogonal to each other; each method has been put into practical use.

一般而言，彩色濾光片係形成於玻璃等透明基板表面，平行或交叉配置有由紅色濾光片層(R)、綠色濾光片層(G)及藍色濾光片層(B)所組 成的微細帶(條紋)狀之濾光片區段(像素)，或者以縱橫一定的排列配置有微細的濾光片區段而組成。濾光片區段為數微米至數百微米，甚微細，而且依每色相，以特定排列整齊地配置。 Generally, a color filter is formed on a surface of a transparent substrate such as glass, and a red filter layer (R), a green filter layer (G), and a blue filter layer (B) are arranged in parallel or in a crosswise manner. Group A fine strip (striped) filter segment (pixel) is formed, or a fine filter segment is arranged in a vertical and horizontal arrangement. The filter segments are from a few micrometers to hundreds of micrometers, are very fine, and are arranged neatly in a particular arrangement for each hue.

於用在彩色液晶顯示裝置之彩色濾光片上，一般藉由蒸鍍或濺鍍來形成用以驅動液晶之透明電極，進而於其上，形成用以令液晶往一定方向配向之配向膜。為了充分獲得該等透明電極及配向膜之性能，一般須以200℃，更宜以230℃以上的高溫進行該形成步驟。 For use in a color filter of a color liquid crystal display device, a transparent electrode for driving a liquid crystal is generally formed by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is formed thereon. In order to sufficiently obtain the properties of the transparent electrode and the alignment film, the formation step is generally carried out at a high temperature of 200 ° C, more preferably 230 ° C or higher.

對彩色濾光片所要求的品質項目可舉出對比率及亮度。若利用對比率低的彩色濾光片，則使得液晶所控制的偏光度程度紊亂，於須阻隔光時(關閉狀態)漏出光，亦或於須透光時(開啟狀態)，穿透光衰減，因此畫面變得模糊。因此，為了實現高品質的液晶顯示裝置，高對比率係不可或缺。 For the quality items required for color filters, the contrast ratio and brightness can be cited. If a color filter with a low contrast ratio is used, the degree of polarization controlled by the liquid crystal is disordered, and when light is blocked (closed state), light is leaked, or when light is required to be transmitted (on state), the transmitted light is attenuated. , so the picture becomes blurred. Therefore, in order to realize a high quality liquid crystal display device, a high contrast ratio is indispensable.

又，若使用亮度低的彩色濾光片，則由於光的穿透率低，因此畫面昏暗，為了使得畫面明亮，須增加作為光源之背光數。因此，從抑制消耗電力的觀點來看，彩色濾光片之高亮度化已為趨勢。 Further, when a color filter having a low luminance is used, since the transmittance of light is low, the screen is dim, and in order to make the screen bright, the number of backlights as a light source must be increased. Therefore, from the viewpoint of suppressing power consumption, the high luminance of the color filter has been trending.

進而言之，如前述，由於彩色液晶裝置利用於電視或個人電腦監視器等，因此對於彩色濾光片，除了要求高對比率、高亮度化以外，並且對於寬廣的色彩重現區域或高可靠性的要求亦升高。 Further, as described above, since the color liquid crystal device is used for a television or a personal computer monitor or the like, the color filter is required to have a high contrast ratio and high brightness, and a wide color reproduction area or high reliability. Sexual requirements are also rising.

又，由C-MOS(Complementary Metal Oxide Semiconductor：互補型金屬氧化膜半導體)、CCD(Charge Coupled Device：電荷耦合元件)等所代表的彩色攝像管元件，一般係於其受光元件上，分別配設具備紅色濾光片層(R)、綠色濾光片層(G)及藍色濾光片層(B)之加法混合之原色濾光片區段 之彩色濾光片，並進行色彩分解。又，為了獲得比原色之彩色濾光片高之感度，亦經常利用具備相當於紅色、綠色、藍色之補色，即青色、洋紅、黃色(CMY)之濾光片區段之彩色濾光片。補色之彩色濾光片多半採用在難以利用閃光燈等輔助光源之攝影機等。 In addition, a color image sensor element represented by a C-MOS (Complementary Metal Oxide Semiconductor) or a CCD (Charge Coupled Device) is generally disposed on the light receiving element. A primary color filter section having an additive mixture of a red filter layer (R), a green filter layer (G), and a blue filter layer (B) Color filters and color decomposition. Moreover, in order to obtain a higher sensitivity than the color filter of the primary color, a color filter having a filter segment corresponding to a complementary color of red, green, and blue, that is, cyan, magenta, and yellow (CMY) is often used. . Color filters of complementary colors are mostly used in cameras that are difficult to use auxiliary light sources such as flash lamps.

近年來，針對用於彩色攝像管元件之彩色濾光片，高穿透率、亦即亮度及可靠性等類的要求亦升高。 In recent years, for color filters used for color image sensor elements, requirements for high transmittance, that is, brightness and reliability have also increased.

彩色濾光片之製造方法包括使用染料、鹵化染料作為著色劑之染色法、染料分散法、或使用顏料作為著色劑之顏料分散法、印刷法、電鍍法、噴墨法等。其中，染色法或染色分散法之著色劑為染料，因此具有耐熱性或耐光性稍差的缺點。故，彩色濾光片之著色劑多半利用耐熱性或耐光性良好的顏料，從形成方法之精度或安定性考量，製造方法多半利用顏料分散法。 The method for producing a color filter includes a dyeing method using a dye, a halogenated dye as a colorant, a dye dispersion method, a pigment dispersion method using a pigment as a colorant, a printing method, a plating method, an inkjet method, and the like. Among them, the coloring agent of the dyeing method or the dyeing and dispersing method is a dye, and therefore has a disadvantage that heat resistance or light resistance is slightly inferior. Therefore, most of the color filter coloring agents use pigments having good heat resistance or light resistance, and the manufacturing method mostly uses the pigment dispersion method in consideration of the accuracy or stability of the formation method.

顏料分散法係於樹脂中分散有作為著色劑之顏料粒子分散之物，混合‧調配感光劑或添加劑等，藉此使其成為彩色抗蝕劑，於基板上，藉由旋轉塗布機等塗布裝置，將該彩色抗蝕劑形成塗膜，並藉由對準機或步進機，中介光罩選擇性地進行曝光，並進行鹼顯影、熱硬化處理而予以圖案化，藉由重複該操作而製作彩色濾光片之方法。 In the pigment dispersion method, a pigment particle dispersed as a colorant is dispersed in a resin, and a sensitizer or an additive is mixed and mixed to form a color resist, and a coating device such as a spin coater is applied to the substrate. Forming the color resist into a coating film, and selectively exposing the mask by an alignment machine or a stepper, performing alkali development and heat hardening treatment to pattern, by repeating the operation A method of making a color filter.

一般於顏料粒子進行微細化處理，製造使該經微細化之顏料已達極限地逼近一次粒子之顏料分散體，藉此抑制由顏料所造成的光散射，可達成高對比率。又，由於分散體之透明度亦提升，因此分散體之分光光譜具有高穿透率，可實現高亮度化。藉由於彩色抗蝕劑使用該分散體，可獲得具高對比、高亮度之彩色濾光片。 Generally, the pigment particles are subjected to a refining treatment to produce a pigment dispersion in which the finely pigmented pigment has reached the limit of the primary particles, thereby suppressing light scattering by the pigment, and a high contrast ratio can be achieved. Further, since the transparency of the dispersion is also improved, the spectral spectrum of the dispersion has a high transmittance and high luminance can be achieved. By using the dispersion as a color resist, a color filter having high contrast and high brightness can be obtained.

以往，作為用於形成紅色濾光片區段(像素)或洋紅色濾光片區段(像素)之著色劑，一般多半利用耐受性及色調良好的二酮吡咯并吡咯系顏料、蒽醌系顏料、喹吖酮系顏料、萘酚系顏料、偶氮系顏料等。 Conventionally, as a coloring agent for forming a red filter segment (pixel) or a magenta filter segment (pixel), a diketopyrrolopyrrole pigment and a ruthenium which are excellent in tolerance and color tone are generally used. A pigment, a quinophthalone pigment, a naphthol pigment, an azo pigment, or the like.

就以往利用冷陰極管類型背光之液晶顯示裝置等顯示裝置而言，藉由於紅色濾光片區段，組合二酮吡咯并吡咯系顏料或蒽醌系顏料與喹吖酮系顏料等，可達成高亮度及寬度的色彩顯示區域。 In the conventional display device such as a liquid crystal display device using a cold cathode tube type backlight, a combination of a diketopyrrolopyrrole pigment, an anthraquinone pigment, and a quinophthalone pigment can be achieved by a red filter segment. High brightness and wide color display area.

又，洋紅色濾光片區段的情況係利用喹吖酮系顏料、玫瑰紅色澱顏料等。 Further, in the case of the magenta filter segment, a quinophthalone pigment, a rose red lake pigment or the like is used.

然而，如前述，對於彩色濾光片係要求進一步之高亮度化及寬度的色彩重現區域。 However, as described above, for the color filter system, a color reproduction region of further high luminance and width is required.

為了符合該要求，已提案一種作為著色劑非令顏料而令染料溶解於樹脂等之技術(參考例如日本特開平6-75375號公報)。 In order to meet the requirements, a technique in which a dye is dissolved in a resin or the like as a coloring agent is proposed (refer to Japanese Laid-Open Patent Publication No. Hei 6-75375, for example).

又，亦已檢討一種洋紅色用之彩色濾光片用墨水，其係含有紅色顏料、紅色酸性染料、及具有松香構造之1級胺鹽化合物。然而，顯色性雖良好，但耐熱性、耐光性不佳，並非可使用之物(參考例如日本特開平11-189733號公報)。 Further, a color filter ink for magenta having a red pigment, a red acid dye, and a first-grade amine salt compound having a rosin structure has been reviewed. However, although the color rendering property is good, heat resistance and light resistance are not good, and it is not usable (refer to Japanese Laid-Open Patent Publication No. Hei 11-189733, for example).

本發明之目的係在於提供一種色彩特性、耐熱性、耐光性、耐溶劑性良好，對塗膜亦不發生異物之安定的彩色濾光片用紅色著色組成物，以及利用其之色彩特性、耐熱性、耐光性、耐溶劑性良好之彩色濾光片。 An object of the present invention is to provide a red coloring composition for a color filter which is excellent in color characteristics, heat resistance, light resistance, and solvent resistance, and which does not cause a foreign matter to be stabilized on a coating film, and which utilizes its color characteristics and heat resistance. Color filter with good light resistance, light resistance and solvent resistance.

本發明者等係為了解決前述諸問題而銳意地累積研究，結果發現藉由使用包含呫噸系酸性染料與具有陽離子性基之化合物形成有鹽類之鹵化生成物(A)、及紅色顏料之著色劑，來作為彩色濾光片用紅色著色組成物之著色劑，可實現高亮度及寬廣的色彩重現區域，而且對塗膜亦不發生異物，耐受性方面亦良好，根據該酌見而完成本發明。 The present inventors have earnestly accumulated research in order to solve the above problems, and as a result, found that a halogenated product (A) having a salt and a red pigment are formed by using a compound containing a xanthene-based acid dye and a compound having a cationic group. A coloring agent is used as a coloring agent for coloring a red coloring composition to achieve high brightness and a wide color reproduction area, and foreign matter does not occur on the coating film, and the resistance is also good, according to the discretion. The present invention has been completed.

亦即，若依據本發明之1個面向係提供一種彩色濾光片用紅色著色組成物，其特徵為包含著色劑及樹脂黏結劑；前述著色劑包含：呫噸系酸性染料與具有陽離子性基之化合物之鹵化生成物(A)、及紅色顏料。 That is, according to one aspect of the present invention, a red coloring composition for a color filter is provided, which is characterized by comprising a coloring agent and a resin binder; the coloring agent comprises: a xanthene-based acid dye and a cationic group The halogenated product (A) of the compound and the red pigment.

於本發明中，於前述具有陽離子性基之化合物包含：四級銨鹽化合物、及於側鏈具有陽離子性基之樹脂。 In the present invention, the compound having a cationic group includes a quaternary ammonium salt compound and a resin having a cationic group in a side chain.

於本發明之1個或其以上之態樣中，四級銨鹽化合物之陽離子部位(反陰離子除外的部分)之分子量係在190~900的範圍內。 In one or more aspects of the present invention, the molecular weight of the cation moiety (the portion excluding the counter anion) of the quaternary ammonium salt compound is in the range of from 190 to 900.

於本發明之1個或其以上之態樣中，四級銨鹽化合物係由下述一般式(1-1)所表示； In one or more aspects of the present invention, the quaternary ammonium salt compound is represented by the following general formula (1-1);

(於一般式(1-1)中，R1~R4分別獨立表示碳數1~20之烷基或 苄基，R1、R2、R3、R4中之至少2個具有5~20個碳原子。Y-表示無機或有機之陰離子)。 (In the general formula (1-1), R 1 to R 4 each independently represent an alkyl group or a benzyl group having 1 to 20 carbon atoms, and at least two of R 1 , R 2 , R 3 and R 4 have 5 to 5; 20 carbon atoms. Y- represents an inorganic or organic anion).

於本發明之1個或其以上之態樣中，於側鏈具有陽離子性基之樹脂係由一般式(1-2)所表示； In one or more aspects of the present invention, the resin having a cationic group in the side chain is represented by the general formula (1-2);

(於一般式(1-2)中，R5表示氫原子、或置換或者無置換之烷基。R6~R8分別獨立表示氫原子、置換或者無置換之烷基、置換或者無置換之烯基、或置換或者無置換之芳基，R6~R8中之2個相互結合而形成環亦可。Q表示亞烷基、亞芳基、-CONH-R9-或-COO-R9-，R9表示亞烷基。Y-表示無機或有機之陰離子)。 (In the general formula (1-2), R 5 represents a hydrogen atom, or a substituted or unsubstituted alkyl group. R 6 to R 8 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substitution or no substitution. Alkenyl, or substituted or unsubstituted aryl, two of R 6 to R 8 are bonded to each other to form a ring. Q represents an alkylene group, an arylene group, -CONH-R 9 - or -COO-R 9 -, R 9 represents an alkylene group, and Y- represents an inorganic or organic anion).

又，於本發明之1個或其以上之態樣中，呫噸系酸性染料被分類為C.I.酸性紅。 Further, in one or more aspects of the present invention, the xanthene-based acid dye is classified into C.I. acid red.

又，於本發明之1個或其以上之態樣中，前述呫噸系酸性染料係從C.I.酸性紅(C.I.Acid Red)52、C.I.酸性紅87、C.I.酸性紅92、C.I.酸性紅289及C.I.酸性紅388所組成的群組選擇之至少一種。 Further, in one or more aspects of the present invention, the xanthene acid dye is from CI Acid Red 52, CI Acid Red 87, CI Acid Red 92, CI Acid Red 289, and CI. At least one of the group consisting of acid red 388 is selected.

又，於本發明之1個或其以上之態樣中，紅色顏料為二酮吡咯并吡咯系顏料及/或蒽醌系顏料及/或單偶氮系或二偶氮系顏料。 Further, in one or more aspects of the present invention, the red pigment is a diketopyrrolopyrrole pigment and/or an anthraquinone pigment and/or a monoazo or diazo pigment.

又，於本發明之1個或其以上之態樣中，紅色顏料係從C.I.顏料紅(C.I.Pigment Red)254、C.I.顏料紅177、C.I.顏料紅48：1、166、C.I.顏料紅220、C.I.顏料紅242及C.I.顏料橘38所組成的群組選擇之至少一種。 Further, in one or more aspects of the present invention, the red pigment is from CI Pigment Red 254, CI Pigment Red 177, CI Pigment Red 48: 1, 166, CI Pigment Red 220, CI. At least one of the group consisting of Pigment Red 242 and CI Pigment Orange 38 is selected.

又，於本發明之1個或其以上之態樣中，前述著色劑進一步含有黃色顏料。 Further, in one or more aspects of the invention, the colorant further contains a yellow pigment.

又，於本發明之1個或其以上之態樣中，進一步含有光聚合性單體及/或光聚合起始劑。 Further, in one or more aspects of the present invention, a photopolymerizable monomer and/or a photopolymerization initiator are further contained.

又，若依據本發明之其他面向係提供一種彩色濾光片，其特徵為具備至少1個紅色濾光片區段、至少1個綠色濾光片區段及至少1個藍色濾光片區段；前述至少1個紅色濾光片區段係由本發明之彩色濾光片用紅色著色組成物所形成。 In addition, a color filter according to another aspect of the present invention is characterized in that it has at least one red filter segment, at least one green filter segment, and at least one blue filter region. The at least one red filter segment is formed of the red coloring composition of the color filter of the present invention.

於本發明中，藉由利用由一彩色濾光片用紅色著色組成物所形成的彩色濾光片，可獲得具有高亮度及寬廣的色彩重現區域，並藉由製成鹵化生成物，其耐受性亦良好之彩色濾光片；而前述一彩色濾光片用紅色著色組成物係利用：著色劑，其係包含呫噸系酸性染料與具有陽離子性基之化合物之鹵化生成物(A)、及紅色顏料；及樹脂。 In the present invention, by using a color filter formed by a coloring composition of a color filter with red color, a color reproduction region having high luminance and a wide color can be obtained, and by forming a halogenated product, a color filter having good tolerance; and the color filter of the above-mentioned color filter is a coloring agent comprising a halogenated product of a xanthene-based acid dye and a compound having a cationic group (A) ), and red pigment; and resin.

又，本發明之彩色濾光片用紅色著色組成物係藉由含有呫噸系酸性染料與具有陽離子性基之化合物之鹵化生成物(A)，來作為著色劑，可比以往組合二酮吡咯并吡咯系顏料與蒽醌系顏料之彩色濾光片用著色組成物，在波長590~630nm附近維持分光光譜高之穿透率。因此，對於位在冷陰極管等許多背光所具有的波長600~650nm附近之峰值，會有效地發揮 作用，可獲得高亮度。 Further, the red coloring composition for a color filter of the present invention is a coloring agent by using a halogenated product (A) containing a xanthene-based acid dye and a compound having a cationic group, and can be combined with a diketopyrrole in comparison with the prior art. A coloring composition for a color filter of a pyrrole pigment and an anthraquinone pigment maintains a high transmittance of a spectroscopic spectrum at a wavelength of from 590 to 630 nm. Therefore, it is effective for the peaks near the wavelength of 600 to 650 nm which are located in many backlights such as cold cathode tubes. Function, high brightness can be obtained.

以下，詳細說明本發明。 Hereinafter, the present invention will be described in detail.

以下所記載的「C.I.」係意味色彩索引號碼(C.I.)。 The "C.I." described below means a color index number (C.I.).

本發明之彩色濾光片用紅色著色組成物包含：樹脂黏結劑；著色劑，其包含：紅色顏料；及呫噸系酸性染料與具有陽離子性基之化合物之鹵化生成物(A)。 The red coloring composition for a color filter of the present invention comprises: a resin binder; a coloring agent comprising: a red pigment; and a halogenated product (A) of a xanthene-based acid dye and a compound having a cationic group.

<著色劑> <colorant>

本發明之彩色濾光片用紅色著色組成物之著色劑包含：呫噸系酸性染料與具有陽離子性基之化合物之鹵化生成物(A)；及紅色顏料。 The coloring agent for the red coloring composition of the color filter of the present invention comprises: a halogenated product (A) of a xanthene-based acid dye and a compound having a cationic group; and a red pigment.

藉由同時使用鹵化生成物(A)及紅色顏料，如前述於許多背光所具有的特徵性峰值之波長600~650nm附近，可具有分光光譜高之穿透率，可比以往組合二酮吡咯并吡咯系顏料與蒽醌系顏料之彩色濾光片，獲得更高亮度及寬廣的色彩重現性。進而言之，藉由將呫噸系酸性染料予以鹵化，可同時具有高耐熱性、耐光性、耐溶劑性。 By using the halogenated product (A) and the red pigment at the same time, as described above in the vicinity of the characteristic peak wavelength of many backlights of 600 to 650 nm, the transmittance of the spectroscopic spectrum can be high, and the diketopyrrolopyrrole can be combined with the prior art. Color filters for pigments and lanthanide pigments for higher brightness and wide color reproducibility. Further, by halogenating a xanthene-based acid dye, it is possible to simultaneously have high heat resistance, light resistance, and solvent resistance.

由呫噸系酸性染料及四級銨鹽化合物所組成的鹵化生成物(A) Halogenated product composed of xanthene acid dye and quaternary ammonium salt compound (A)

呫噸系酸性染料呈現紅色、紫色，並具有染料形態。 The xanthene acid dyes are red, purple, and have a dye form.

呈現紅色、紫色之染料係屬於C.I.酸性紅、C.I.酸性紫等酸性染料、C.I.直接紅、CI.酸性紫等直接染料。在此，直接染料具有磺酸基，因 此於本發明中視為與酸性染料同義。 The dyes exhibiting red and purple are direct dyes such as C.I. acid red, C.I. acid violet and the like, C.I. direct red, CI. acid violet. Here, the direct dye has a sulfonic acid group, because This is considered synonymous with acid dyes in the present invention.

進而言之，鹵化生成物(A)係由該等呫噸系酸性染料(亦包含酸性染料)、與作為反離子起作用之四級銨鹽化合物經鹵化、改質後之鹵化染料。 Further, the halogenated product (A) is a halogenated dye which is halogenated and modified by the above-mentioned xanthene-based acid dye (including an acid dye) and a quaternary ammonium salt compound which acts as a counter ion.

呫噸系酸性染料 Xanthene acid dye

說明關於呫噸系染料之酸性染料。作為呫噸系染料之酸性染料可使用C.I.酸性紅51(赤蘚紅(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、虎紅B(食用紅色5號)、酸性玫瑰紅G、C.I.酸性紫9、C.I.酸性紫9、C.I.酸性紫30。 Describe the acid dyes for xanthene dyes. As the acid dye of the xanthene dye, CI Acid Red 51 (erythro red (food red No. 3)), CI acid red 52 (acid rose red), CI acid red 87 (blush G (edible red No. 103) can be used. ), CI Acid Red 92 (Acid oleander red PB (edible red 104)), CI Acid Red 289, CI Acid Red 388, Tiger Red B (Edible Red No. 5), Acid Rose Red G, CI Acid Violet 9, CI Acid Violet 9, CI Acid Violet 30.

其中特別適宜使用C.I.酸性紅52、C.I.酸性紅87、C.I.酸性紅92、C.I.酸性紅289、C.I.酸性紅388。 Among them, C.I. Acid Red 52, C.I. Acid Red 87, C.I. Acid Red 92, C.I. Acid Red 289, C.I. Acid Red 388 are particularly suitable.

本發明所用之呫噸系酸性染料係就穿透光譜而言，於650nm區域，穿透率宜為90%以上，於600nm區域，穿透率宜為75%以上，於550nm區域，穿透率宜為5%以下，於400nm區域，穿透率宜為70%以上。於650nm區域，穿透率更宜為95%以上，於600nm區域，穿透率更宜為80%以上，550nm之穿透率更宜為10%以下，400nm之穿透率更宜為75%以上。 The xanthene acid dye used in the present invention has a transmittance of preferably 90% or more in the 650 nm region and a transmittance of 75% or more in the region of 650 nm in the transmittance spectrum in the region of 650 nm. It is preferably 5% or less, and in the 400 nm region, the transmittance is preferably 70% or more. In the 650 nm region, the transmittance is more preferably 95% or more. In the 600 nm region, the transmittance is more preferably 80% or more, the transmittance at 550 nm is preferably 10% or less, and the transmittance at 400 nm is more preferably 75%. the above.

又，作為呫噸系酸性染料，就顯色性良好的觀點考量，宜使用玫瑰紅系酸性染料。 Further, as a xanthene-based acid dye, a rose-red acid dye is preferably used from the viewpoint of good color rendering properties.

具有陽離子之化合物 Compound with cation

於本發明中，與前述呫噸系酸性染料生成鹵化生成物之具有陽離子性基之化合物包含：四級銨鹽化合物、及於側鏈具有陽離子性基之 樹脂。 In the present invention, the compound having a cationic group which forms a halogenated product with the xanthene-based acid dye includes a quaternary ammonium salt compound and a cationic group in the side chain. Resin.

首先，說明關於四級銨鹽化合物。 First, the description will be given regarding the quaternary ammonium salt compound.

鹵化生成物(A)之陽離子成分之四級銨鹽化合物之較佳形態係無色或呈白色。 The preferred form of the quaternary ammonium salt compound of the cationic component of the halogenated product (A) is colorless or white.

在此，無色或白色係意味透明狀態，其定義為：於可見光區域之400~700nm之全波長區域，穿透率為95%以上，更宜為98%以上之狀態。亦即，須不妨礙染色成分顯色，不引起色彩變化。 Here, the colorless or white color means a transparent state, which is defined as a state in which the transmittance is 95% or more, and more preferably 98% or more in the entire wavelength range of 400 to 700 nm in the visible light region. That is, it is necessary not to hinder the coloration of the dyeing component, and does not cause color change.

四級銨鹽化合物之陽離子部分之分子量宜在190~900之範圍內。在此，陽離子部分係指四級銨鹽化合物之反陰離子除外的部分，例如相當於下述一般式(1-1)所示之四級銨鹽化合物之(NR1R2R3R4)+的部分。陽離子部分之分子量小於190時，耐光性、耐熱性會降低，進而對溶劑之溶解性降低。又，陽離子部分之分子量大於900時，分子中之顯色成分之比率降低，顯色性降低，亮度亦降低。更適宜之陽離子部分之分子量為240~850之範圍內，陽離子部分之分子量尤宜在350~800之範圍內。陽離子部分之分子量為350~800時，溶劑溶解性良好，在與紅色顏料同時使用時，耐熱性、耐光性、耐溶劑性良好。 The molecular weight of the cationic portion of the quaternary ammonium salt compound is preferably in the range of from 190 to 900. Here, the cation moiety means a moiety other than the counter anion of the quaternary ammonium salt compound, and is, for example, a moiety corresponding to (NR1R2R3R4)+ of the quaternary ammonium salt compound represented by the following general formula (1-1). When the molecular weight of the cationic moiety is less than 190, the light resistance and heat resistance are lowered, and the solubility in a solvent is lowered. Further, when the molecular weight of the cationic portion is more than 900, the ratio of the coloring component in the molecule is lowered, the color rendering property is lowered, and the brightness is also lowered. The molecular weight of the more suitable cationic moiety is in the range of 240 to 850, and the molecular weight of the cationic moiety is particularly preferably in the range of 350 to 800. When the molecular weight of the cationic moiety is from 350 to 800, the solvent solubility is good, and when used together with the red pigment, heat resistance, light resistance, and solvent resistance are good.

在此，陽離子部分之分子量係根據構造式而進行計算，C之原子量設為12，H之原子量設為1，N之原子量設為14而計算分子量。 Here, the molecular weight of the cation moiety is calculated according to the structural formula, and the atomic weight of C is 12, the atomic weight of H is 1, and the atomic weight of N is 14 to calculate the molecular weight.

於本發明之1個或其以上之態樣中，四級銨鹽化合物係利用下述一般式(1-1)所示之物。 In one or more aspects of the present invention, the quaternary ammonium salt compound is represented by the following general formula (1-1).

(於一般式(1-1)中，R1~R4分別獨立表示碳數1~20之烷基或苄基，R1、R2、R3、R4中之至少2個具有5~20個碳原子。Y-表示無機或有機之陰離子)。 (In the general formula (1-1), R 1 to R 4 each independently represent an alkyl group or a benzyl group having 1 to 20 carbon atoms, and at least two of R 1 , R 2 , R 3 and R 4 have 5 to 5; 20 carbon atoms. Y- represents an inorganic or organic anion).

R1~R4之至少2個具有5~20個碳原子，藉此對於溶劑之溶解性變得良好。若碳原子之數目小於5之烷基為3個以上，則對於溶劑之溶解性變差，容易發生塗膜異物。又，若存在有C之數目超過20之烷基，則有損鹵化生成物(A)之顯色性。 At least two of R 1 to R 4 have 5 to 20 carbon atoms, whereby solubility in a solvent becomes good. When the number of the alkyl groups having a carbon number of less than 5 is three or more, the solubility in a solvent is deteriorated, and a coating film foreign matter is likely to occur. Further, if an alkyl group having a C number exceeding 20 is present, the color rendering property of the halogenated product (A) is impaired.

具體而言，作為四級銨鹽化合物宜使用四甲基氯化銨(陽離子部分之分子量為74)、四乙基氯化銨(陽離子部分之分子量為122)、單硬脂醯甲基氯化銨(陽離子部分之分子量為312)、二硬脂醯甲基氯化銨(陽離子部分之分子量為550)、三硬脂醯單甲基氯化銨(陽離子部分之分子量為788)、十六三甲基氯化銨(陽離子部分之分子量為284)、三辛基甲基氯化銨(陽離子部分之分子量為368)、二辛基甲基氯化銨(陽離子部分之分子量為270)、單月桂基甲基氯化銨(陽離子部分之分子量為382)、三月桂基甲基氯化銨(陽離子部分之分子量為536)、三胺基苄基氯化銨(陽離子部分之分子量為318)、三己基苄基氯化銨(陽離子部分之分子量為360)、三辛基苄基氯化銨(陽離子部分之 分子量為444)、三月桂基苄基氯化銨(陽離子部分之分子量為612)、苄基二甲基硬脂醯氯化銨(陽離子部分之分子量為388)、及苄基二甲基辛基氯化銨(陽離子部分之分子量為248)、二烷基(烷基為C14~C18)二甲基氯化銨(硬化牛脂)(陽離子部分之分子量為438~550)等。 Specifically, as the quaternary ammonium salt compound, tetramethylammonium chloride (having a molecular weight of 74 in the cationic portion), tetraethylammonium chloride (having a molecular weight of 122 in the cationic portion), and monostearic acid methyl chloride are preferably used. Ammonium (the molecular weight of the cationic moiety is 312), distearyl hydrazine methyl ammonium chloride (the molecular weight of the cationic moiety is 550), tristearic acid monomethyl ammonium chloride (the molecular weight of the cationic moiety is 788), sixteen Methyl ammonium chloride (molecular weight of the cationic moiety is 284), trioctylmethyl ammonium chloride (molecular weight of the cationic moiety is 368), dioctylmethyl ammonium chloride (the molecular weight of the cationic moiety is 270), single laurel Methyl ammonium chloride (the molecular weight of the cationic moiety is 382), trilauryl methyl ammonium chloride (the molecular weight of the cationic moiety is 536), triaminobenzyl ammonium chloride (the molecular weight of the cationic moiety is 318), three Hexylbenzylammonium chloride (molecular weight of the cationic moiety is 360), trioctylbenzylammonium chloride (cationic moiety) Molecular weight: 444), trilaurylbenzylammonium chloride (molecular weight of the cationic moiety is 612), benzyldimethylstilbene ammonium chloride (the molecular weight of the cationic moiety is 388), and benzyldimethyloctyl Ammonium chloride (molecular weight of the cationic moiety is 248), dialkyl (alkyl is C14-C18) dimethylammonium chloride (hardened tallow) (the molecular weight of the cationic moiety is 438 to 550), and the like.

構成陰離子之Y-若為無機或有機之陰離子即可，宜為鹵素，一般為氯。 The Y-constituting the anion may be an inorganic or organic anion, and is preferably a halogen, and is generally chlorine.

具體的四級銨鹽化合物製品可舉出花王公司製之QUARTAMIN 24P、QUARTAMIN 86P CONC、QUARTAMIN 60W、QUARTAMIN 86W、QUARTAMIN D86P、SANISOL C、SANISOL B-50等、LION公司製之ARQUAD 210-80E、2C-75、2HT-75、2HT FLAKE、2O-75I、2HP-75、2HP FLAKE等，其中尤以QUARTAMIN D86P(二硬脂醯二甲基氯化銨)、ARQUAD 2HT-75(二烷基(烷基為C14~C18)二甲基氯化銨)為宜。 Specific quaternary ammonium salt compound products include QUARTAMIN 24P, QUARTAMIN 86P CONC, QUARTAMIN 60W, QUARTAMIN 86W, QUARTAMIN D86P, SANISOL C, SANISOL B-50, manufactured by Kao Corporation, and ARQUAD 210-80E, 2C manufactured by LION Corporation. -75, 2HT-75, 2HT FLAKE, 2O-75I, 2HP-75, 2HP FLAKE, etc., among them QUARTAMIN D86P (distearyl dimethyl ammonium chloride), ARQUAD 2HT-75 (dialkyl (alkane) The base is preferably C 14 ~ C 18 ) dimethyl ammonium chloride).

接著，說明關於在側鏈具有陽離子性基之樹脂。 Next, a resin having a cationic group in a side chain will be described.

於鹵化生成物(A)之陽離子成分之側鏈具有陽離子性基之樹脂之較佳形態，係呈無色或白色。 A preferred form of the resin having a cationic group in the side chain of the cationic component of the halogenated product (A) is colorless or white.

在此，無色或白色係意味透明狀態，其定義為：於可見光區域之400~700nm之全波長區域，穿透率為95%以上，更宜為98%以上之狀態。亦即，須不妨礙染色成分顯色，不引起色彩變化。 Here, the colorless or white color means a transparent state, which is defined as a state in which the transmittance is 95% or more, and more preferably 98% or more in the entire wavelength range of 400 to 700 nm in the visible light region. That is, it is necessary not to hinder the coloration of the dyeing component, and does not cause color change.

作為用以獲得鹵化生成物(A)之側鏈具有陽離子性基之樹脂，若於側鏈至少具有1個鎓鹽基之物均可，並未特別限制，作為適宜的鎓鹽構造，若從取得難易的觀點考量，宜為銨鹽、碘鹽、硫鹽、重氮鹽及鏻鹽，若考慮保存安定性(熱安定性)，則較宜為銨鹽、碘鹽及鏻鹽。進而以銨 鹽更適宜。 The resin having a cationic group in the side chain for obtaining the halogenated product (A) is not particularly limited as long as it has at least one onium salt group in the side chain, and is a suitable onium salt structure. The viewpoint of obtaining difficulty is preferably ammonium salt, iodized salt, sulfur salt, diazonium salt and barium salt. If storage stability (thermal stability) is considered, it is preferably ammonium salt, iodized salt and barium salt. Ammonium Salt is more suitable.

如此側鏈具有陽離子性基之樹脂，可使用包含由下述一般式(1-2)所示之構造單位之乙烯基系樹脂； As the resin having a cationic group in the side chain, a vinyl-based resin containing a structural unit represented by the following general formula (1-2) can be used;

於一般式(1-2)中，R5表示氫原子、或置換或者無置換之烷基。R5所示之烷基可舉出例如甲基、乙基、丙基、n-丁基、i-丁基、t-丁基、n-己基、環己基。該烷基宜為碳數1~12之烷基，更宜為碳數1~8之烷基，碳數1~4之烷基尤其適宜。 In the general formula (1-2), R 5 represents a hydrogen atom, or an alkyl group which is substituted or unsubstituted. The alkyl group represented by R 5 may, for example, be a methyl group, an ethyl group, a propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-hexyl group or a cyclohexyl group. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 4 carbon atoms is particularly suitable.

該等烷基具有置換基時，該置換基可舉出例如羥基、烷氧基等。 When the alkyl group has a substituent group, the substituent group may, for example, be a hydroxyl group or an alkoxy group.

R5最宜為氫原子或甲基。 R 5 is most preferably a hydrogen atom or a methyl group.

於一般式(1-2)中，R6~R8分別獨立表示氫原子、置換或者無置換之烷基、置換或者無置換之烯基、或置換或者無置換之芳基。 In the general formula (1-2), R 6 to R 8 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group.

在此，R6~R8所示之烷基可舉出例如直鏈烷基(甲基、乙基、正丙基、正丁基、正戊基、正辛基、正十二基、正十四基、正十六基及正十八基等)、分支烷基(異丙基、異丁基、二級丁基、三級丁基、異戊基、新戊基、三級戊基、異己基、2-乙基己基及1,1,3,3-四甲基丁基等)、環烷基(環 丙基、環丁基、環戊基及環己基等)、及架橋環式烷基(降冰片基、金剛烷基及蒎基)。烷基宜為碳數1~18之烷基，進而宜為碳數1~8之烷基。 Here, the alkyl group represented by R 6 to R 8 may, for example, be a linear alkyl group (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-dodeyl, ortho. Tetradecyl, n-hexadecanyl and n-octadecyl, etc., branched alkyl (isopropyl, isobutyl, secondary butyl, tert-butyl, isopentyl, neopentyl, tertiary pentyl) , isohexyl, 2-ethylhexyl and 1,1,3,3-tetramethylbutyl, etc.), cycloalkyl (cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, etc.), and bridging rings Alkyl (norbornyl, adamantyl and fluorenyl). The alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms.

R6~R8所示之烯基可舉出例如直鏈或分枝之烯基(乙烯基、烯丙基、1-丙烯基、2-丙烯基、1-丁烯基、2-丁烯基、3-丁烯基、1-甲基-1-丙烯基、1-甲基-2-丙烯基、2-甲基-1-丙烯基及2-甲基-2-丙烯基等)、環烯基(2-環己烯基及3-環己烯基等)。烯基宜為碳數2~18之烷基，進而宜為碳數2~8之烷基。 The alkenyl group represented by R 6 to R 8 may, for example, be a linear or branched alkenyl group (vinyl group, allyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butene group). a group, a 3-butenyl group, a 1-methyl-1-propenyl group, a 1-methyl-2-propenyl group, a 2-methyl-1-propenyl group, a 2-methyl-2-propenyl group, etc., Cycloalkenyl (2-cyclohexenyl and 3-cyclohexenyl, etc.). The alkenyl group is preferably an alkyl group having 2 to 18 carbon atoms, and more preferably an alkyl group having 2 to 8 carbon atoms.

R6~R8所示之芳基可舉出例如單環式芳基(苯基等)、縮合多環式芳基(萘基、蒽基、菲基、蒽喹啉基、芴基、萘喹啉基等)、及芳香族雜環碳化氫基(噻吩基(從噻吩衍生的基))、呋喃基(從呋喃衍生的基)、哌喃基(從哌喃衍生的基)、吡啶基(從吡啶衍生的基)、9-羰呫噸基(從呫噸衍生的基)及9-羰噻吨基(從噻吨衍生的基等)。 Examples of the aryl group represented by R 6 to R 8 include a monocyclic aryl group (phenyl group or the like), a condensed polycyclic aryl group (naphthyl group, anthryl group, phenanthryl group, anthracene quinolyl group, anthracenyl group, and naphthalene group). a quinolyl group, and an aromatic heterocyclic hydrocarbon group (thienyl group (a group derived from thiophene)), a furyl group (a group derived from furan), a pipenyl group (a group derived from a piper group), a pyridyl group (Base derived from pyridine), 9-carbonylxanthene (a group derived from xanthene), and 9-carbonylthioxanyl group (a group derived from thioxanthene, etc.).

關於R6~R8所，當上述烷基、烯基、芳基具有置換基時，該置換基可舉出從例如鹵素原子、羥基、烷氧基、芳氧基、烯基、醯基、烷氧羰基、羰基及苯基等所選擇的置換基。置換基尤其以鹵素原子、羥基、烷氧基、苯基為宜。 In the case of R 6 to R 8 , when the above alkyl group, alkenyl group or aryl group has a substituent group, the substituent group may, for example, be a halogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, an alkenyl group or a fluorenyl group. A selected substituent such as an alkoxycarbonyl group, a carbonyl group or a phenyl group. The substituent group is preferably a halogen atom, a hydroxyl group, an alkoxy group or a phenyl group.

從安定性的觀點考量，R6~R8宜為置換或無置換之烷基，更宜為無置換之烷基。 From the standpoint of stability, R 6 to R 8 are preferably a substituted or unsubstituted alkyl group, more preferably an unsubstituted alkyl group.

又，R6~R8中之2個相互結合而形成環亦可。 Further, two of R 6 to R 8 may be bonded to each other to form a ring.

於一般式(1-2)中，連結乙烯基與銨鹽基之Q係表示亞烷基、亞芳基、-CONH-R9-或-COO-R9-，R9表示亞烷基。其中，從生成包含一般式(1-2)所示之構造單位之乙烯基系樹脂之單體的聚合性、取得難易之理由 考量，Q宜為-CONH-R9-或-COO-R9-。又，R9更宜為甲烷基、乙烷基、丙烷基或丁烷基，尤其宜為乙烷基。 In the general formula (1-2), the Q group linking the vinyl group and the ammonium salt group means an alkylene group, an arylene group, -CONH-R 9 - or -COO-R 9 -, and R 9 represents an alkylene group. Among them, Q is preferably -CONH-R 9 - or -COO-R 9 from the viewpoint of obtaining polymerizability of a monomer containing a vinyl-based resin having a structural unit represented by the general formula (1-2) and obtaining difficulty. -. Further, R 9 is more preferably a methyl group, an ethane group, a propane group or a butylene group, and particularly preferably an ethane group.

一般式(1-2)中之Y-(反陰離子)若為無機或有機之陰離子即可。反陰離子可採用任何習知之物，具體而言可舉出：氫氧化物離子、氯化物離子、溴化物離子、碘化物離子等鹵化物離子；甲酸離子、醋酸離子等羰酸離子；碳酸離子、碳酸氫離子、硝酸離子、硫酸離子、亞硫酸離子、鉻酸離子、重鉻酸鉀離子、磷酸離子、過錳酸離子等無機酸離子；氰化物離子；進而可舉出諸如己氰鐵(III)酸離子等錯合物離子等。從合成適性或安定性方面來看，宜為鹵化物離子及羧酸離子，最宜為鹵化物離子。反陰離子為羧酸離子等有機酸離子時，有機酸離子有機結合於樹脂骨架，該有機酸離子形成側鏈之陽離子性基及分子內鹽亦可。 In the general formula (1-2) Y - (counter-anion) if it is an inorganic or organic anion can. The counter anion may be any conventional one, and specifically, a halide ion such as a hydroxide ion, a chloride ion, a bromide ion or an iodide ion; a carboxylate ion such as a formate ion or an acetate ion; a carbonate ion; a mineral acid ion such as a hydrogencarbonate ion, a nitrate ion, a sulfate ion, a sulfite ion, a chromate ion, a potassium dichromate ion, a phosphate ion or a permanganate ion; a cyanide ion; and further, such as iron hexacyanoferrate (III) ) Complex ions such as acid ions. From the viewpoint of synthetic suitability or stability, it is preferably a halide ion and a carboxylate ion, and is most preferably a halide ion. When the counter anion is an organic acid ion such as a carboxylic acid ion, the organic acid ion is organically bonded to the resin skeleton, and the organic acid ion may form a cationic group or an intramolecular salt of the side chain.

包含一般式(1-2)所示之構造單位之乙烯基樹脂一般為共聚樹脂。為了獲得該類共聚樹脂，不僅可藉由將具有胺基之乙烯性不飽和單體與寡聚物共聚之方法，亦可藉由將具有胺基之乙烯性不飽和單體與寡聚物共聚，令所獲得具有胺基之共聚樹脂與鎓氯化劑反應而銨氯化之方法來獲得。 The vinyl resin containing the structural unit represented by the general formula (1-2) is generally a copolymer resin. In order to obtain such a copolymer resin, not only a method of copolymerizing an ethylenically unsaturated monomer having an amine group with an oligomer but also copolymerizing an ethylenically unsaturated monomer having an amine group with an oligomer can be obtained. It is obtained by a method in which a copolymer resin having an amine group is obtained by reacting with a hydrazine chlorinating agent and ammonium chlorination.

以下表示用以獲得包含由一般式(1-2)所示之構造單位之乙烯基樹脂可使用之乙烯性不飽和單體。再者，於本說明書中，表示「丙烯基、甲基丙烯基」之某一者或雙方時，有時記載為「(甲基)丙烯基」。同樣地，表示「丙烯醯及/或甲基丙烯醯」之某一者或雙方時，有時記載為「(甲基)丙烯醯胺」。 The following shows an ethylenically unsaturated monomer which can be used to obtain a vinyl resin containing a structural unit represented by the general formula (1-2). In addition, in the present specification, when one or both of "acryloyl group and methacryl group" are shown, it may be described as "(meth)acrylyl group". Similarly, when one or both of "acrylonitrile and/or methacryl" are indicated, "(meth)acrylamide" may be described.

具有4級銨鹽基之乙烯性不飽和單體可舉出例如：(甲基)丙 烯醯氧乙基三甲基氯化銨、(甲基)丙烯醯氧乙基三乙基氯化銨、(甲基)丙烯醯氧乙基二甲基氯化銨、(甲基)丙烯醯氧乙基嗎啉氯化銨等烷基(甲基)丙烯酸酯系第4級銨鹽；(甲基)丙烯醯胺丙基三甲基氯化銨、(甲基)丙烯醯胺乙基三乙基氯化銨、(甲基)丙烯醯胺乙基二甲基苄基氯化銨等烷基(甲基)丙烯醯胺系第4級銨鹽；二甲基二烯丙基銨甲基硫酸鹽；及三甲基乙烯基苯基氯化銨等。 The ethylenically unsaturated monomer having a quaternary ammonium salt group may, for example, be (meth) propyl Ethylenyloxyethyltrimethylammonium chloride, (meth)acryloyloxyethyltriethylammonium chloride, (meth)acryloyloxyethyldimethylammonium chloride, (meth)acrylic acid An alkyl (meth) acrylate such as oxyethylmorpholine ammonium chloride is a fourth-order ammonium salt; (meth) acrylamidopropyltrimethylammonium chloride, (meth) acrylamide-ethylamine Alkyl (meth) acrylamide amine grade 4 ammonium salt such as ethyl ammonium chloride or (meth) acrylamide amine dimethyl benzyl ammonium chloride; dimethyl diallyl ammonium methyl Sulfate; and trimethylvinylphenyl ammonium chloride and the like.

具有胺基之乙烯性不飽和單體可舉出例如二甲基胺乙基(甲基)丙烯酸酯、二乙基胺乙基(甲基)丙烯酸酯、二丙基胺乙基(甲基)丙烯酸酯、二異丙基胺乙基(甲基)丙烯酸酯、二丁基胺乙基(甲基)丙烯酸酯、二異丁基胺乙基(甲基)丙烯酸酯、二三級-丁基胺乙基(甲基)丙烯酸酯、二甲基胺丙基(甲基)丙烯酸酯、二乙基胺乙基(甲基)丙烯酸酯、二乙基胺丙基(甲基)丙烯醯胺、二丙基胺丙基(甲基)丙烯醯胺、二異丙基胺丙基(甲基)丙烯醯胺、二丁基胺丙基(甲基)丙烯醯胺、二異丁基胺丙基(甲基)丙烯醯胺、二三級-丁基胺丙基(甲基)丙烯醯胺等具有二烷基胺基之(甲基)丙烯酸酯或(甲基)丙烯醯胺；並可舉出：二甲基胺苯乙烯、二甲基胺甲基苯乙烯等具有二烷基胺基之苯乙烯類；二烯甲基胺、二烯胺等二烯胺化合物；N-乙烯基吡咯烷、N-乙烯基吡咯烷酮、N-乙烯基咔唑等含有胺基之芳香族乙烯基系單體。 Examples of the ethylenically unsaturated monomer having an amine group include dimethylamine ethyl (meth) acrylate, diethyl amine ethyl (meth) acrylate, and dipropyl amine ethyl (methyl). Acrylate, diisopropylamine ethyl (meth) acrylate, dibutylamine ethyl (meth) acrylate, diisobutylamine ethyl (meth) acrylate, di-tertiary-butyl Amine ethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethyl amine ethyl (meth) acrylate, diethyl propyl propyl (meth) acrylamide, Dipropylaminopropyl (meth) acrylamide, diisopropylamine propyl (meth) acrylamide, dibutylamine propyl (meth) acrylamide, diisobutylamine propyl a (meth) acrylate or (meth) acrylamide having a dialkylamino group such as (meth) acrylamide or di-tert-butylaminopropyl (meth) acrylamide; : styrenes having a dialkylamine group such as dimethylamine styrene and dimethylamine methyl styrene; dienamine compounds such as dienylmethylamine and dienamine; N-vinylpyrrolidine , N-vinylpyrrolidone, N-vinylcarbazole, etc. Group of aromatic vinyl monomers.

鎓氯化劑可舉出例如：二甲基硫酸、二乙基硫酸或二丙基硫酸等烷基硫酸；對甲苯磺酸甲基或苯磺酸甲基等磺酸酯；溴化甲烷、溴化乙烷、溴化丙烷或溴化辛烷等烷基溴化物；或者苄基氯或苄基溴等。 The hydrazine chlorinating agent may, for example, be an alkylsulfate such as dimethylsulfuric acid, diethylsulfonic acid or dipropylsulfuric acid; a sulfonic acid ester such as p-toluenesulfonic acid methyl or benzenesulfonic acid methyl; methane bromide or bromine; An alkyl bromide such as ethane, propane bromide or octyl bromide; or benzyl chloride or benzyl bromide.

具有胺基之乙烯性不飽和單體與鎓氯化劑之反應，一般可藉由於具有胺基之乙烯性不飽和單體溶液，滴下相對於胺基為等莫耳以下之 鎓氯化劑而進行。銨氯化反應時之溫度為90℃程度以下，尤其在將乙烯基單體予以銨氯化時，宜為30℃程度以下，反應時間為1~4小時程度。 The reaction of the ethylenically unsaturated monomer having an amine group with the hydrazine chlorinating agent can generally be carried out by a solution of an ethylenically unsaturated monomer having an amine group, and the dropping is lower than the amine group. It is carried out with a chlorinating agent. The temperature at the time of the ammonium chlorination reaction is about 90 ° C or less, and particularly when the vinyl monomer is ammonium chlorinated, it is preferably about 30 ° C or less, and the reaction time is about 1 to 4 hours.

此外，亦可使用烷氧羰基烷基鹵化物來作為鎓氯化劑。烷氧羰基烷基鹵化物可由下述一般式(2)表示。 Further, an alkoxycarbonylalkyl halide can also be used as the hydrazine chlorinating agent. The alkoxycarbonylalkyl halide can be represented by the following general formula (2).

Z-R10-COOR11 一般式(2) ZR 10 -COOR 11 general formula (2)

(於一般式(2)中，Z為氯、溴等鹵素，宜為溴；R10係碳數為1~6、宜為1~5、更宜為1~3之亞烷基；R11係碳數為1~6、宜為1~3之低級烷基)。 (In the general formula (2), Z is a halogen such as chlorine or bromine, and is preferably bromine; R 10 is an alkylene group having 1 to 6, preferably 1 to 5, more preferably 1 to 3 carbon atoms; R 11 It is a lower alkyl group having a carbon number of 1 to 6, preferably 1 to 3.

具有胺基之乙烯性不飽和單體與烷氧羰基烷基鹵化物之反應，可藉由令相對於胺基為等莫耳以下之烷氧羰基烷基鹵化物，與上述鎓氯化劑同樣反應後，將COOR11予以水解轉換為羰酸離子(-COO-)而獲得。藉此，可獲得具有羰基甜菜鹼構造、具有銨鹽基之乙烯性不飽和單體。 The reaction of an amine group-containing ethylenically unsaturated monomer with an alkoxycarbonylalkyl halide can be carried out by the same alkoxycarbonylalkyl halide as the above-mentioned oxime chlorinating agent with respect to the amine group. After the reaction, COOR 11 is hydrolyzed to a carboxylate ion (-COO-) to obtain. Thereby, an ethylenically unsaturated monomer having a carbonyl betaine structure and having an ammonium salt group can be obtained.

又，如先前所述，令具有胺基之乙烯性不飽和單體與其他乙烯性不飽和單體共聚而獲得之共聚樹脂，採與上述同樣的方法而與鎓鹽氯化劑反應，可獲得具有4級銨鹽基之共聚樹脂。 Further, as described above, a copolymer resin obtained by copolymerizing an ethylenically unsaturated monomer having an amine group and another ethylenically unsaturated monomer can be obtained by reacting with a cerium salt chlorinating agent in the same manner as described above. A copolymer resin having a 4-stage ammonium salt group.

上述共聚單體可利用乙烯性不飽和單體。該乙烯性不飽和單體宜為例如(甲基)丙烯酸酯類、巴豆酸酯類、乙烯酯類、順丁烯二酸二酯類、反丁烯二酸二酯類、衣康酸二酯類、(甲基)丙烯醯胺類、乙烯醚類、乙烯醇之酯類、苯乙烯類、(甲基)丙烯腈等。 The above comonomer can utilize an ethylenically unsaturated monomer. The ethylenically unsaturated monomer is preferably, for example, a (meth) acrylate, a crotonate, a vinyl ester, a maleic acid diester, a fumaric acid diester, an itaconate diester. And (meth) acrylamide, vinyl ether, vinyl alcohol ester, styrene, (meth) acrylonitrile, and the like.

該類乙烯基單體(共聚單體)之具體例可舉出例如以下之化合物。 Specific examples of such a vinyl monomer (comonomer) include, for example, the following compounds.

(甲基)丙烯酸酯類之例子可舉出(甲基)丙烯酸甲基、(甲基) 丙烯酸乙基、(甲基)丙烯酸正丙基、(甲基)丙烯酸異丙基、(甲基)丙烯酸正丁基、(甲基)丙烯酸異丁基、(甲基)丙烯酸三級丁基、(甲基)丙烯酸正己基、(甲基)丙烯酸環己基、(甲基)丙烯酸三級丁基環己基、(甲基)丙烯酸2-乙基己基、(甲基)丙烯酸三級辛基、(甲基)丙烯酸十二基、(甲基)丙烯酸十八基、(甲基)丙烯酸乙醯氧基乙基、(甲基)丙烯酸苯基、(甲基)丙烯酸2-羥基乙基、(甲基)丙烯酸2-甲氧基乙基、(甲基)丙烯酸2-乙氧基乙基、(甲基)丙烯酸2-(2-甲氧基乙氧基)乙基、(甲基)丙烯酸3-苯氧基-2-羥基丙基、(甲基)丙烯酸苄基、(甲基)丙烯酸二乙二醇單甲基醚、(甲基)丙烯酸二乙二醇單乙基醚、(甲基)丙烯酸三乙二醇單甲基醚、(甲基)丙烯酸三乙二醇單乙基醚、(甲基)丙烯酸聚乙二醇單甲基醚、(甲基)丙烯酸聚乙二醇單乙基醚、(甲基)丙烯酸β-苯氧基乙氧基乙基、(甲基)丙烯酸壬基苯氧基聚乙二醇、(甲基)丙烯酸二環戊烯氧乙基、(甲基)丙烯酸三氟乙基、(甲基)丙烯酸辛氟戊基、(甲基)丙烯酸全氟辛基乙基、(甲基)丙烯酸二環戊基、(甲基)丙烯酸三溴苯基、(甲基)丙烯酸三溴苯氧乙基等。 Examples of the (meth) acrylates include methyl (meth) acrylate and (methyl) Ethyl acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, (meth)acrylic acid n-hexyl, (meth)acrylic acid cyclohexyl, (meth)acrylic acid tert-butylcyclohexyl, (meth)acrylic acid 2-ethylhexyl, (meth)acrylic acid tri-octyl, ( Dodecyl group of methyl)acrylate, octadecyl (meth)acrylate, ethoxylated ethyl (meth)acrylate, phenyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (A) 2-methoxyethyl acrylate, 2-ethoxyethyl (meth) acrylate, 2-(2-methoxyethoxy)ethyl (meth) acrylate, (meth) acrylate 3 -phenoxy-2-hydroxypropyl, benzyl (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, (methyl ) Triethylene glycol monomethyl ether acrylate, triethylene glycol monoethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol (meth) acrylate Ether, β-phenoxyethoxyethyl (meth)acrylate, (A ) decyl phenoxy ethoxypolyethylene glycol, dicyclopentene oxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octyl fluoride (meth) acrylate, (meth) acrylate Perfluorooctylethyl, dicyclopentyl (meth)acrylate, tribromophenyl (meth)acrylate, tribromophenoxyethyl (meth)acrylate, and the like.

巴豆酸酯類之例子可舉出巴豆酸丁基及巴豆酸酯己基等。 Examples of the crotonate include crotonate butyl and crotonate hexyl groups.

乙烯酯類之例子可舉出乙烯乙酯、乙烯丙酯、乙烯丁酯、乙烯甲氧乙酯及安息香酸乙烯等。順丁烯二酸二酯類之例子可舉出順丁烯二酸二甲基、順丁烯二酸二乙基及順丁烯二酸二丁基等。 Examples of the vinyl esters include vinyl ethyl ester, ethylene propyl ester, vinyl butyl carbonate, vinyl methoxyethyl ester, and benzoic acid ethylene. Examples of the maleic acid diesters include dimethyl maleic acid, diethyl maleate, and dibutyl maleate.

反丁烯二酸二酯類之例子可舉出反丁烯二酸二甲基、反丁烯二酸二乙基及反丁烯二酸二丁基等。 Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

衣康酸二酯類之例子可舉出衣康酸二甲基、衣康酸二乙基及衣康酸二丁基等。 Examples of the itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

(甲基)丙烯醯胺類之例子可舉出(甲基)丙烯醯胺、N-甲基(甲基)丙烯醯胺、N-乙基(甲基)丙烯醯胺、N-丙基(甲基)丙烯醯胺、N-異丙基(甲基)丙烯醯胺、N-正丁基(甲基)丙烯醯胺、N-三級丁基(甲基)丙烯醯胺、N-環己基(甲基)丙烯醯胺、N-(2-甲氧乙基)(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺、N-苯基(甲基)丙烯醯胺、N-苄基(甲基)丙烯醯胺、(甲基)丙烯醯基嗎啉、二丙酮丙烯醯胺等。 Examples of the (meth)acrylamides include (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, and N-propyl ( Methyl) acrylamide, N-isopropyl (meth) acrylamide, N-n-butyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-ring Hexyl (meth) acrylamide, N-(2-methoxyethyl)(meth) acrylamide, N,N-dimethyl(meth) acrylamide, N,N-diethyl ( Methyl) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) propylene morpholine, diacetone acrylamide, and the like.

乙烯醚類之例子可舉出甲基乙烯醚、丁基乙烯醚、己基乙烯醚及甲氧乙基乙烯醚等。苯乙烯類之例子可舉出苯乙烯、甲基苯乙烯、二甲基苯乙烯、三甲基苯乙烯、乙基苯乙烯、異丙基苯乙烯、丁基苯乙烯、羥基苯乙烯、甲氧苯乙烯、丁氧苯乙烯、乙醯氧基苯乙烯、氟苯乙烯、二氟苯乙烯、溴苯乙烯、氟甲基苯乙烯、由可藉由酸性物質脫除保護之基(例如三級Boc等)所保護的羥基苯乙烯、乙烯安息香酸甲基、及α-甲基苯乙烯等。 Examples of the vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether. Examples of the styrenes include styrene, methyl styrene, dimethyl styrene, trimethylstyrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxystyrene, and methoxy. Styrene, butoxystyrene, ethoxylated styrene, fluorostyrene, difluorostyrene, bromostyrene, fluoromethylstyrene, protected by an acid-removable group (eg tertiary Boc) Etc.) Protected hydroxystyrene, ethylene benzoic acid methyl, and α-methylstyrene.

又，作為共聚單體之乙烯性不飽和單體亦可具有酸基。具有酸基之乙烯性不飽和單體可舉出：丙烯酸、甲基丙烯酸、巴豆酸、α-氯丙烯酸、肉桂酸等不飽和單羧酸類；順丁烯二酸、順丁烯二酸酐、反丁烯二酸、衣康酸、衣康酸酐、檸康酸、檸康酸酐、中康酸等不飽和二羧酸或其酐類；3價以上之不飽和多價羧酸或其酐類；琥珀酸單(2-丙烯醯氧乙基)、琥珀酸單(2-甲基丙烯醯氧乙基)、鄰苯二甲酸單(2-丙烯醯氧乙基)、鄰苯二甲酸單(2-甲基丙烯醯氧乙基)等2價以上之多價羧酸之單[(甲基)丙烯醯氧烷基]酯類；ω-羧基-聚己內酯單丙烯酸酯、ω-羧基-聚己內酯單甲基丙烯酸酯等兩末端羧基聚合物之單(甲基)丙烯酸酯類等。 Further, the ethylenically unsaturated monomer as a comonomer may have an acid group. Examples of the ethylenically unsaturated monomer having an acid group include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; maleic acid, maleic anhydride, and anti- An unsaturated dicarboxylic acid or anhydride thereof such as butenedioic acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride or mesaconic acid; an unsaturated polyvalent carboxylic acid having three or more valences or an anhydride thereof; Succinic acid mono(2-propenyloxyethyl), succinic acid mono(2-methylpropenyloxyethyl), phthalic acid mono(2-propenyloxyethyl), phthalic acid mono(2) Mono[(methyl)acryloxyalkylene] ester of a polyvalent carboxylic acid of two or more valences such as -methacryloyloxyethyl); ω-carboxy-polycaprolactone monoacrylate, ω-carboxyl- A mono(meth)acrylate such as a polycaprolactone monomethacrylate or the like having a terminal carboxyl group polymer.

獲得包含一般式(1-2)所示之構造單位之乙烯系樹脂之方法，可採用陰離子聚合、活性陰離子聚合、陽離子聚合、活性陽離子聚合、自由基聚合及活性自由基聚合等習知的方法。其中以自由基聚合或活性自由基聚合為宜。 A method of obtaining an ethylene-based resin containing a structural unit represented by the general formula (1-2) can be carried out by a conventional method such as anionic polymerization, living anionic polymerization, cationic polymerization, living cationic polymerization, radical polymerization, and living radical polymerization. . Among them, radical polymerization or living radical polymerization is preferred.

活性自由基聚合的情況宜使用聚合起始劑。聚合起始劑可利用偶氮系化合物及有機過氧化物。偶氮系化合物之例子可舉出2,2’-偶氮雙異丁腈、2,2’-偶氮雙(2-甲基丁腈)、1,1’-偶氮雙(環己烷1-羧腈)、2,2’-偶氮雙(2,4-二甲基戊腈)、2,2’-偶氮雙(2,4-二甲基-4-甲氧戊腈)、二甲基2,2’-偶氮雙(2-甲基丙酸酯)、4,4’-偶氮雙(4-氰基戊酸)、2,2’-偶氮雙(2-羥基甲基戊腈)及2,2’-偶氮雙[2-(2-咪唑啉-2-基)丙烷]等。有機過氧化物之例子可舉出過氧化苯甲醯、三級氫過氧化丁醯、二異丙基過氧化碳酸酯、二正丙基過氧化碳酸酯、二(2-乙氧基乙基)過氧化碳酸酯、三級丁基過氧化新葵酸酯、(3,5,5-三甲基己醯)過氧化物、二丙醯基過氧化物及二乙醯基過氧化物等。該等聚合起始劑可單獨或組合兩種以上來使用。聚合反應溫度宜為40~150℃，更宜為50~110℃，聚合反應時間宜為3~30小時，更宜為5~20小時。 In the case of living radical polymerization, a polymerization initiator is preferably used. As the polymerization initiator, an azo compound and an organic peroxide can be used. Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), and 1,1'-azobis(cyclohexane). 1-carboxonitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile) , dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2- Hydroxymethylvaleronitrile) and 2,2'-azobis[2-(2-imidazolin-2-yl)propane]. Examples of the organic peroxides include benzammonium peroxide, tertiary hydrogen peroxide butadiene, diisopropyl peroxycarbonate, di-n-propyl peroxycarbonate, and di(2-ethoxyethyl). Peroxycarbonate, tertiary butyl peroxy neoacetate, (3,5,5-trimethylhexyl) peroxide, dipropyl hydrazine peroxide and diethyl hydrazine peroxide . These polymerization initiators may be used singly or in combination of two or more. The polymerization temperature is preferably 40 to 150 ° C, more preferably 50 to 110 ° C, and the polymerization time is preferably 3 to 30 hours, more preferably 5 to 20 hours.

活性自由基聚合法會抑制一般自由基聚合所發生的副反應，進而由於會平均引發聚合的成長，因此可容易合成嵌段聚合物或分子量一致的樹脂。 The living radical polymerization method suppresses side reactions which occur in general radical polymerization, and further increases the polymerization growth, so that a block polymer or a resin having a uniform molecular weight can be easily synthesized.

其中尤其以有機鹵化物或鹵化碸基化合物作為起始劑、以過渡金屬錯合物作為觸媒之原子移動自由基聚合法，係就可適應廣泛的單體方面來看、可採用能適應既有設備之聚合溫度方面來看，較為適宜。原子 移動自由基聚合法可採下述參考文獻1~8等所記載的方法來進行。 Among them, an atomic mobile radical polymerization method using an organic halide or a halogenated fluorenyl compound as a starting agent and a transition metal complex as a catalyst can be adapted to a wide range of monomers. It is more suitable in terms of the polymerization temperature of the equipment. atom The mobile radical polymerization method can be carried out by the methods described in the following References 1 to 8.

(參考文獻1)Fukuda等人，Prog.Polym.Sci.2004,29,329 (Reference 1) Fukuda et al., Prog. Polym. Sci. 2004, 29, 329

(參考文獻2)Matyjaszewski等人，Chem.Rev.2001，101，2921 (Reference 2) Matyjaszewski et al., Chem. Rev. 2001, 101, 2921

(參考文獻3)Matyjaszewski等人，.Am.Chem.Soc.1995，117，5614 (Reference 3) Matyjaszewski et al., Am. Chem. Soc. 1995, 117, 5614

(參考文獻4)Macromolecules 1995，28，7901，Science，1996，272，866 (Reference 4) Macromolecules 1995, 28, 7901, Science, 1996, 272, 866

(參考文獻5)WO96/030421 (Reference 5) WO96/030421

(參考文獻6)WO97/018247 (Reference 6) WO97/018247

(參考文獻7)日本特開平9-208616號公報 (Reference 7) Japanese Patent Laid-Open No. 9-208616

(參考文獻8)日本特開平8-41117號公報 (Reference 8) Japanese Patent Laid-Open No. 8-41117

於上述聚合宜使用有機溶劑。有機溶劑並未特別限定，但可使用例如醋酸乙基、醋酸正丁基、醋酸異丁基、甲苯、二甲苯、丙酮、己酮、甲基乙酮、環己酮、丙二醇單甲基醚乙酯、二丙二醇單甲基醚乙酯、乙二醇單乙基醚乙酯、乙二醇單丁基醚乙酯、二乙二醇單乙基醚乙酯或乙二醇單丁基醚乙酯等。該等聚合溶媒可混合2種以上來使用。 It is preferred to use an organic solvent for the above polymerization. The organic solvent is not particularly limited, but for example, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexanone, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether B can be used. Ester, dipropylene glycol monomethyl ether ethyl ester, ethylene glycol monoethyl ether ethyl ester, ethylene glycol monobutyl ether ethyl ester, diethylene glycol monoethyl ether ethyl ester or ethylene glycol monobutyl ether Ester and the like. These polymerization solvents can be used by mixing two or more types.

於側鏈具有陽離子性基之樹脂中所存在的陽離子性基量並未特別限定，但該樹脂之陽離子鹽價宜為10~200mgKOH/g，更宜為20~130mgKOH/g。陽離子鹽價係表示作鎓鹽價、四級銨鹽價、胺鹽價。包含由一般式(1-2)所示之構造單位之乙烯基系樹脂中所存在的銨鹽基、胺鹽基之量，係該樹脂之銨鹽價、胺鹽價亦宜為10~200mgKOH/g，更宜為20~130mgKOH/g。於本發明中，銨鹽價係例如以與包含一般式(1-2)所示之構造單位之乙烯基系樹脂1公克中之全部銨鹽基之中和所需之硝酸銀等量之氫 化鉀(KOH)之毫克數來表示。又，胺鹽價係例如以與包含一般式(1-2)所示之構造單位之乙烯基系樹脂1公克中之全部胺鹽基之中和所需之鹽酸等量之氫化鉀(KOH)之毫克數來表示。 The amount of the cationic group present in the resin having a cationic group in the side chain is not particularly limited, but the cationic salt of the resin is preferably 10 to 200 mgKOH/g, more preferably 20 to 130 mgKOH/g. The cation salt value is expressed as a ruthenium salt price, a quaternary ammonium salt value, and an amine salt price. The amount of the ammonium salt group or the amine salt group present in the vinyl resin containing the structural unit represented by the general formula (1-2) is preferably an ammonium salt value or an amine salt value of the resin of 10 to 200 mgKOH. /g, more preferably 20~130mgKOH/g. In the present invention, the ammonium salt is, for example, neutralized with the required silver nitrate equivalent amount of all ammonium salts in 1 gram of the vinyl resin containing the structural unit represented by the general formula (1-2). The number of milligrams of potassium (KOH) is expressed. Further, the amine salt value is, for example, an equivalent amount of potassium hydride (KOH) which is neutralized with the entire amine salt group in 1 gram of the vinyl resin containing the structural unit represented by the general formula (1-2). The number of milligrams is expressed.

當陽離子鹽價小於10mgKOH/g時，來自呫噸系酸性染料之色素之濃度低，樹脂成分變多，未能作為著色劑成分發揮作用。又，當大於200mgKOH/g時，染料成分變多，溶劑溶解性降低。 When the cation salt value is less than 10 mgKOH/g, the concentration of the dye derived from the xanthene-based acid dye is low, and the resin component is increased, and it does not function as a colorant component. Further, when it is more than 200 mgKOH/g, the dye component is increased and the solvent solubility is lowered.

本發明所使用包含一般式(1-2)所示之構造單位之乙烯基系樹脂之分子量並未特別限定，但由凝膠滲透層析儀(GPC)所測定之換算重量平均分子量宜為1,000~500,000，更宜為3,000~150,000。 The molecular weight of the vinyl-based resin containing the structural unit represented by the general formula (1-2) used in the present invention is not particularly limited, but the converted weight average molecular weight measured by a gel permeation chromatography (GPC) is preferably 1,000. ~500,000, more preferably 3,000~150,000.

又，包含一般式(1-2)所示之構造單位之乙烯基系樹脂，宜具有溶解於廣泛使用於彩色濾光片用著色組成物之溶劑之特性。藉此可獲得不產生異物之塗膜。尤其更宜溶解於丙二醇單甲基醚乙酯。 Further, the vinyl-based resin containing the structural unit represented by the general formula (1-2) preferably has a property of being dissolved in a solvent widely used for a coloring composition for a color filter. Thereby, a coating film which does not generate foreign matter can be obtained. It is especially preferred to dissolve in propylene glycol monomethyl ether ethyl ester.

於側鏈具有陽離子性基之樹脂中，由上述一般式(1-2)所示之構造單位之總含有量並未特別限制，但於側鏈具有陽離子性基之樹脂所含有的總構造單位設為100質量%時，從鹵化生成物之溶劑溶解性及著色力方面來看，由上述一般式(1-2)所示之構造單位之總含有量宜為5質量%以上，更宜為10~50質量%。 In the resin having a cationic group in the side chain, the total content of the structural unit represented by the above general formula (1-2) is not particularly limited, but the total structural unit contained in the resin having a cationic group in the side chain. When it is 100% by mass, the total content of the structural unit represented by the above general formula (1-2) is preferably 5% by mass or more, more preferably from the viewpoint of solvent solubility and coloring power of the halogenated product. 10~50% by mass.

鹵化 Halogenation

本發明所使用的鹵化生成物可藉由令呫噸系酸性染料與具有陽離子性基之化合物反應，生成鹽類而獲得。 The halogenated product used in the present invention can be obtained by reacting a xanthene-based acid dye with a compound having a cationic group to form a salt.

呫噸系酸性染料與四級銨鹽化合物之鹵化生成物可藉由以往已知之方法來合成。具體手法係揭示於日本特開平11-72969號公報等。 The halogenated product of the xanthene acid dye and the quaternary ammonium salt compound can be synthesized by a conventionally known method. The specific method is disclosed in Japanese Laid-Open Patent Publication No. Hei 11-72969.

若舉出一例來說，於水中溶解呫噸系酸性染料後，添加四級銨鹽化合物，一面攪拌一面進行反應即可。在此，呫噸系酸性染料中之磺酸基(-SO3H、-SO3Na)部分與四級銨鹽化合物之銨基(NH4+)部分結合後之鹽類(鹵化生成物)。又，亦可使用甲醇、乙醇來取代水作為溶媒。 As an example, after dissolving a xanthene-based acid dye in water, a quaternary ammonium salt compound may be added and the reaction may be carried out while stirring. Here, a salt (halogenated product) in which a sulfonic acid group (-SO3H, -SO3Na) moiety of a xanthene-based acid dye is bonded to an ammonium group (NH4+) moiety of a quaternary ammonium salt compound. Further, methanol or ethanol may be used instead of water as a solvent.

接著，呫噸系酸性染料與側鏈具有陽離子性基之樹脂之鹵化生成物，可容易藉由攪拌或振動令側鏈具有陽離子性基之樹脂、與陰離子性染料溶解後之水溶液，或於攪拌或振動下，令側鏈具有陽離子性基之樹脂與陰離子性染料混合而獲得。於水溶液中，樹脂之陽離子性基與染料之陰離子性基被離子化，該等進行離子結合而形成鹽類，該鹽類為不溶水性，因此會析出。相反地，由於樹脂之反陰離子與陰離子性染料之反陽離子所組成的鹽類為水溶性，因此可藉由水洗等而去除。所使用的側鏈具有陽離子性基之樹脂、及陰離子性染料係各個僅使用單一種類，或使用構造不同之複數種類均可。 Next, a halogenated product of a xanthene-based acid dye and a resin having a cationic group in a side chain can be easily stirred or vibrated to cause a resin having a cationic group in a side chain, an aqueous solution dissolved in an anionic dye, or stirred. It is obtained by mixing a resin having a cationic group in a side chain and an anionic dye under vibration. In the aqueous solution, the cationic group of the resin and the anionic group of the dye are ionized, and these ions are ionically bonded to form a salt, and the salt is insoluble in water and precipitates. On the contrary, since the salt composed of the reverse anion of the resin and the counter cation of the anionic dye is water-soluble, it can be removed by washing with water or the like. The resin having a cationic group in the side chain to be used and the anionic dye system may be used in a single type or in a plurality of types having different structures.

形成鹽類時所使用的溶劑係令側鏈具有陽離子性基之樹脂、與陰離子性染料溶解，因此亦可使用水與水溶性有機溶劑之混合溶液。水溶性有機溶劑可舉出甲醇、乙醇、正丙醇、異丙醇、1-甲氧-2-丙醇、1-乙氧-2-丙醇、正丁醇、異丁醇、2-(甲氧甲氧基)乙醇、2-丁氧基乙醇、2-(異丙氧基)乙醇、2-(己氧基)乙醇、2-(己氧基)乙醇、二乙二醇、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單丁基醚、三乙二醇、三乙二醇單甲基醚、聚乙二醇、甘油、四乙二醇、二丙二醇、丙酮、二丙酮醇、苯胺、吡啶、醋酸乙基、醋酸丙基、甲基乙基酮、N,N-二甲基甲醯胺、二甲基亞碸、四氫呋喃(THF)、二噁烷、2-砒喀烷酮、2-甲基砒喀烷酮、N-甲基-2- 砒喀烷酮、1,2-己二醇、2,4,6-己三醇、四呋喃甲醇、4-甲氧基-4戊酮等。該等水溶性有機溶劑係以水溶液之總重量作為基準，宜以5~50重量%之比率使用，最宜以5~20重量%之比率使用。 The solvent used in the formation of the salt is a resin having a cationic group in the side chain and is dissolved in the anionic dye. Therefore, a mixed solution of water and a water-soluble organic solvent can also be used. The water-soluble organic solvent may, for example, be methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, n-butanol, isobutanol or 2-( Methoxymethoxy)ethanol, 2-butoxyethanol, 2-(isopropoxy)ethanol, 2-(hexyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethyl Glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, polyethylene glycol, glycerin, tetraethylene glycol , dipropylene glycol, acetone, diacetone alcohol, aniline, pyridine, ethyl acetate, propyl acetate, methyl ethyl ketone, N, N-dimethylformamide, dimethyl hydrazine, tetrahydrofuran (THF), Dioxane, 2-oxanone, 2-methylxanthone, N-methyl-2- 砒 Caridone, 1,2-hexanediol, 2,4,6-hexanetriol, tetrafuranmethanol, 4-methoxy-4pentanone, and the like. These water-soluble organic solvents are preferably used in a ratio of 5 to 50% by weight, based on the total weight of the aqueous solution, and are most preferably used in a ratio of 5 to 20% by weight.

紅色顏料與鹵化生成物(A)之使用比率係相對於紅色顏料100重量部，鹵化生成物(A)宜為1~80重量部，更宜為5~60重量部。當鹵化生成物(A)之添加量少於1重量部時，可重現之色度區域變窄，而當超過80重量部時，色相會變化，因此不適宜。 The ratio of use of the red pigment to the halogenated product (A) is preferably from 1 to 80 parts by weight, more preferably from 5 to 60 parts by weight, based on 100 parts by weight of the red pigment. When the amount of the halogenated product (A) added is less than 1 part by weight, the reproducible chromaticity region becomes narrow, and when it exceeds 80 parts by weight, the hue changes, which is not preferable.

鹵化生成物(A)係藉由與紅色顏料同時使用而顯示出良好特性，此係由於鹵化生成物(A)一面溶解、分散於溶劑中，一面吸附於紅色顏料。 The halogenated product (A) exhibits good characteristics by being used together with the red pigment. The halogenated product (A) is adsorbed to the red pigment while being dissolved and dispersed in a solvent.

<紅色顏料> <red pigment>

用於本發明之紅色著色組成物之紅色顏料可使用以往所用之下述色彩索引號碼之紅色顏料。 The red pigment used in the red coloring composition of the present invention can use a red pigment of the following color index number used in the past.

包括C.I.顏料紅(Pigment Red)7、14、41、48：1、48：2、48：3、48：4、57：1、81、81：1、81：2、81：3、81：4、97、122、123、146、149、166、168、169、176、177、178、180、184、185、187、192、200、202、208、209、210、215、216、217、220、223、224、226、227、228、240、242、246、254、255、264、270、272、273、276、277、278、279、280、281、282、283、284、285、286及287等。 Including 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, 97, 122, 123, 146, 149, 166, 168, 169, 176, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 209, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 246, 254, 255, 264, 270, 272, 273, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286 and 287, etc.

又，橘色系之紅色顏料可使用例如C.I.顏料橘13、34、36、38、43、51、55、59、61、71及73等。 Further, as the orange red pigment, for example, C.I. Pigment Orange 13, 34, 36, 38, 43, 51, 55, 59, 61, 71, and 73 can be used.

該等紅色顏料可單獨使用或使用兩種以上。 These red pigments may be used singly or in combination of two or more.

該等之中，用於本發明之紅色著色組成物之紅色顏料宜使用二酮吡咯并吡咯系顏料及/或蒽醌系顏料及/或單偶氮系或二偶氮系顏料。尤其若含有二酮吡咯并吡咯系顏料，可達成高亮度，就該點而言非常適宜作為紅色顏料。 Among these, the red pigment used in the red coloring composition of the present invention is preferably a diketopyrrolopyrrole pigment and/or an anthraquinone pigment and/or a monoazo or diazo pigment. In particular, if a diketopyrrolopyrrole pigment is contained, high brightness can be achieved, and as such, it is very suitable as a red pigment.

具體而言，二酮吡咯并吡咯系顏料宜為C.I.顏料紅254、255等，蒽醌系顏料宜為C.I.顏料紅177。單偶氮系或二偶氮系顏料宜為C.I.顏料紅166、220、242及C.I.顏料橘(Pigment Orange)38。 Specifically, the diketopyrrolopyrrole pigment is preferably C.I. Pigment Red 254, 255, etc., and the fluorene pigment is preferably C.I. Pigment Red 177. The monoazo or diazo pigment is preferably C.I. Pigment Red 166, 220, 242 and C.I. Pigment Orange 38.

於鹵化生成物(A)與紅色顏料之組合中，就甚少產生塗膜異物，耐熱性、耐光性、耐溶劑性良好，進而可達成高亮度方面而言，含C.I.酸性紅52之鹵化生成物(A)與C.I.顏料紅254之組合、或含C.I.酸性紅52之鹵化生成物(A)與C.I.顏料紅242之組合係非常適宜。 In the combination of the halogenated product (A) and the red pigment, coating film foreign matter is less likely to occur, and heat resistance, light resistance, and solvent resistance are good, and further, halogenation formation of CI acid red 52 can be achieved in terms of high brightness. The combination of the substance (A) and the CI Pigment Red 254 or the combination of the halogenated product (A) containing CI Acid Red 52 and CI Pigment Red 242 is very suitable.

用於本發明之紅色著色組成物之著色劑係除了含目前為止所述之鹵化生成物(A)及紅色顏料以外，亦可含黃色顏料。 The coloring agent used in the red coloring composition of the present invention may contain a yellow pigment in addition to the halogenated product (A) and the red pigment described so far.

黃色顏料可使用例如C.I.顏料黃(Pigment Yellow)1、2、3、4、5、6、10、12、13、14、15、16、17、18、20、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、86、93、94、95、97、98、100、101、104、106、108、109、110、113、114、115、116、117、118、119、120、123、125、126、127、128、129、137、138、139、147、148、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及199等。 For the yellow pigment, for example, Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 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, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 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, and 199, and the like.

其中尤以C.I.顏料黃138、139、150及185為宜。 Among them, C.I. Pigment Yellow 138, 139, 150 and 185 are preferred.

除了由鹵化生成物(A)及紅色顏料所組成的著色劑以外，藉由同時使用黃色顏料作為補色，可調整色相。 In addition to the coloring agent composed of the halogenated product (A) and the red pigment, the hue can be adjusted by using a yellow pigment as a complementary color.

顏料微細化 Pigment refinement

使用於本發明之紅色著色組成物之紅色顏料及視情況所使用的顏料，係宜進行鹽磨處理予以微細化。從對著色劑載體(樹脂黏結劑)中之良好分散來考量，顏料之一次粒徑宜為20nm以上。又，從可形成對比率高的濾光片區段來考量，顏料之一次粒徑宜為100nm以下。尤其適宜之顏料之一次粒徑的範圍為25~85nm。再者，顏料之一次粒徑係採用從藉由顏料之TEM(穿透型電子顯微鏡)所取得的電子顯微鏡照片，直接計測一次粒子大小之方法來進行。具體而言，計測各個顏料之一次粒子之短軸徑及長軸徑，取平均作為該顏料粒子之粒徑。接著，針對100個以上之顏料粒子，與已求出粒徑之立方體逼近而求出各粒子之體積，將體積平均粒徑設為平均一次粒子徑。 The red pigment used in the red coloring composition of the present invention and the pigment used as the case may be subjected to a salt milling treatment to be fine. From the viewpoint of good dispersion in the colorant carrier (resin binder), the primary particle diameter of the pigment is preferably 20 nm or more. Further, from the viewpoint of forming a filter segment having a high contrast ratio, the primary particle diameter of the pigment is preferably 100 nm or less. Particularly suitable pigments have a primary particle size ranging from 25 to 85 nm. Further, the primary particle diameter of the pigment is carried out by directly measuring the particle size from an electron microscope photograph obtained by a TEM (transmission electron microscope) of a pigment. Specifically, the short axis diameter and the major axis diameter of the primary particles of each pigment are measured and averaged as the particle diameter of the pigment particles. Next, for the 100 or more pigment particles, the volume of each particle is obtained by approximating the cube of the obtained particle diameter, and the volume average particle diameter is defined as the average primary particle diameter.

鹽磨處理係指使用捏合機、2輥研磨機、3輥研磨機、球研磨機、磨碎機及砂磨機等混合攪拌機，一面將顏料、水溶性無機鹽與水溶性有機溶劑之混合物加熱，一面機械性地混合攪拌後，藉由水洗去除水溶性無機鹽及水溶性有機溶劑之處理。水溶性無機鹽係作為粉碎助劑而發揮功能。於鹽磨時，利用無機鹽之高硬度來粉碎顏料。藉由將顏料予以鹽磨處理時之條件最佳化，可獲得一次粒徑非常微細或分布範圍窄、具有清晰之粒度分布之顏料。 The salt milling treatment refers to heating a mixture of a pigment, a water-soluble inorganic salt and a water-soluble organic solvent using a kneader, a 2-roll mill, a 3-roll mill, a ball mill, an attritor, and a sand mill. After mechanically mixing and stirring, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt functions as a pulverization aid. In salt milling, the high hardness of the inorganic salt is used to pulverize the pigment. By optimizing the conditions in which the pigment is subjected to a salt milling treatment, a pigment having a very fine primary particle diameter or a narrow distribution range and a clear particle size distribution can be obtained.

水溶性無機鹽可使用例如氯化鈉、氯化鋇、氯化鉀或硫酸鈉。從價格面來看，宜使用氯化鈉(食鹽)。從處理效率及生產效率兩方面來 看，水溶性無機鹽係於以顏料之總重量作為基準(100重量%)時，宜使用50~2000重量%，最宜使用300~1000重量%。 As the water-soluble inorganic salt, for example, sodium chloride, cesium chloride, potassium chloride or sodium sulfate can be used. From the price point of view, sodium chloride (salt) should be used. From the aspects of processing efficiency and production efficiency When the water-soluble inorganic salt is based on the total weight of the pigment (100% by weight), it is preferably used in an amount of 50 to 2000% by weight, and most preferably 300 to 1000% by weight.

水溶性有機溶劑係發揮濕潤顏料及水溶性無機鹽的作用，若是溶解(混合)於水且實質上不溶解於所用無機鹽之物均可，並未特別限定。但於鹽磨時，溫度上升，溶劑成為易蒸發的狀態，因此從安全性的觀點考量，宜為沸點120℃以上之高沸點溶劑。可使用例如2-(甲氧甲氧基)乙烷、2-丁氧基乙烷、2-(異丙氧基)乙烷、2-(己氧基)乙烷、2-(己氧基)乙烷、二乙二醇、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單丁基醚、三乙二醇、三乙二醇單甲基醚、液狀的聚乙二醇、1-甲氧基-2-丙烷、1-乙氧基-2-丙烷、二丙二醇、二丙二醇單甲基醚、二丙二醇單乙基醚或液狀的聚丙二醇等。水溶性有機溶劑係於以顏料之總重量作為基準(100重量%)時，宜使用5~1000重量%，最宜使用50~500重量%。 The water-soluble organic solvent functions as a wet pigment and a water-soluble inorganic salt, and is not particularly limited as long as it is dissolved (mixed) in water and substantially not dissolved in the inorganic salt to be used. However, in the case of salt milling, the temperature rises and the solvent becomes in a state of easy evaporation. Therefore, from the viewpoint of safety, it is preferably a high boiling point solvent having a boiling point of 120 ° C or higher. For example, 2-(methoxymethoxy)ethane, 2-butoxyethane, 2-(isopropoxy)ethane, 2-(hexyloxy)ethane, 2-(hexyloxy) can be used. Ethylene, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propane, 1-ethoxy-2-propane, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether or liquid polypropylene glycol Wait. The water-soluble organic solvent is preferably used in an amount of 5 to 1000% by weight, and most preferably 50 to 500% by weight, based on the total weight of the pigment (100% by weight).

在將顏料予以鹽磨處理時，亦可因應需要添加樹脂。所用樹脂之種類並未特別限定，可使用例如天然樹脂、改質天然樹脂、合成樹脂或由天然樹脂改質之合成樹脂等。所用樹脂宜在室溫下呈固體、為不溶水性，且一部分可溶於上述有機溶劑更適宜。樹脂之使用量係於以顏料之總重量作為基準(100重量%)時，宜使用5~200重量%。 When the pigment is subjected to salt milling, the resin may be added as needed. The kind of the resin to be used is not particularly limited, and for example, a natural resin, a modified natural resin, a synthetic resin, or a synthetic resin modified from a natural resin can be used. The resin to be used is preferably solid at room temperature, is insoluble in water, and is partially soluble in the above organic solvent. The amount of the resin used is preferably from 5 to 200% by weight based on the total weight of the pigment (100% by weight).

<樹脂黏結劑> <Resin Adhesive>

樹脂黏結劑係令著色劑，尤其令鹵化生成物分散之物，或令鹵化生成物染色、滲透之物，可舉出熱塑性樹脂、熱硬化性樹脂。 The resin binder is a thermoplastic resin or a thermosetting resin, which is a material which disperses a halogenated product, or which dyes and permeates a halogenated product.

樹脂黏結劑係宜於可見光區之400~700nm之全波長區內，分光穿透率為80%以上，更宜為95%以上之樹脂。又，以鹼顯影型著色抗蝕劑 之形態時，宜使用將含有酸性基之乙烯性不飽和單體共聚後之鹼可溶性乙烯基系樹脂。又，為了更加提升光感度，亦可使用具有乙烯性不飽和雙重結合之活性能量線硬化性樹脂。 The resin binder is preferably in a wavelength range of 400 to 700 nm in the visible light region, and has a spectral transmittance of 80% or more, more preferably 95% or more. Further, an alkali developing type coloring resist In the case of the form, an alkali-soluble vinyl-based resin obtained by copolymerizing an ethylenically unsaturated monomer having an acidic group is preferably used. Further, in order to further enhance the light sensitivity, an active energy ray-curable resin having a double bond of ethylenic unsaturated can also be used.

尤其藉由將側鏈具有乙烯性不飽和雙重結合之活性能量線硬化性樹脂，用於彩色濾光片用鹼顯影型抗蝕劑，塗布鹵化生成物(A)後之塗膜不產生異物，抗蝕劑材料中之鹵化生成物(A)之安定性受到改善，故較為適宜。使用側鏈不具有乙烯性不飽和雙重結合之直鏈狀樹脂黏結劑時，於混有樹脂黏結劑與染料之液中，染料不易被樹脂黏結劑捕捉，具有自由度，從而染料成分容易凝集‧析出，但藉由使用側鏈具有乙烯性不飽和雙重結合之活性能量線硬化性樹脂來作為樹脂黏結劑，於混有樹脂黏結劑與染料之液中，染料易被樹脂黏結劑捕捉，從而染料成分不易凝集‧析出，而於進一步以活性能量線進行曝光而形成膜時，樹脂黏結劑受到3次元架橋而固定染料分子，推測即便於其後之顯影步驟去除溶劑，染料成分仍不易凝集‧析出。 In particular, an active energy ray-curable resin in which a side chain has an ethylenic unsaturated double bond is used for an alkali-developing resist for a color filter, and a coating film obtained by applying a halogenated product (A) does not generate foreign matter. The stability of the halogenated product (A) in the resist material is improved, which is preferable. When a linear resin binder having no side chain and no ethylenic unsaturated double bond is used, the dye is less likely to be trapped by the resin binder in the liquid mixed with the resin binder and the dye, and has a degree of freedom, so that the dye component is easily aggregated. Precipitation, but by using an active energy ray-curable resin having an ethylenic unsaturated double bond in a side chain as a resin binder, in a liquid mixed with a resin binder and a dye, the dye is easily caught by the resin binder, thereby dyeing The component is not easily agglomerated and precipitated, and when the film is further exposed by the active energy ray, the resin binder is fixed by the 3 dimensional bridge to fix the dye molecules, and it is presumed that the dye component is not easily aggregated even after the subsequent development step removes the solvent. .

樹脂黏結劑之重量平均分子量(Mw)係為了令著色劑適宜地分散，宜為10,000~100,000之範圍，更宜為10,000~80,000之範圍。又，數量平均分子量(Mn)宜為5,000~50,000之範圍，Mw/Mn之值宜為10以下。 The weight average molecular weight (Mw) of the resin binder is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000, in order to suitably disperse the colorant. Further, 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.

使用樹脂作為彩色濾光片用感光性著色組成物時，從顏料及鹵化生成物之分散性、滲透性、顯影性及耐熱性的觀點考量，吸附著色劑的基及顯影時作為鹼可溶性基發揮作用之羧基、著色劑載體、及作為對於溶劑之親和性基發揮作用之脂肪族基及芳香族基之均衡，係對於顏料及鹵化生成物之分散性、滲透性、顯影性，進而對於耐久性甚為重要，宜使用 酸價為20~300mgKOH/g之樹脂黏結劑。酸價若小於20mgKOH/g，則對於顯影液之溶解性不佳，難以形成微細圖案。樹脂黏結劑之酸價若超過300mgKOH/g，則未能留下微細圖案。 When a resin is used as a photosensitive coloring composition for a color filter, it is considered as an alkali-soluble group from the viewpoint of dispersibility, permeability, developability, and heat resistance of the pigment and the halogenated product. The balance between the carboxyl group, the colorant carrier, and the aliphatic group and the aromatic group which act as an affinity group for the solvent, and the dispersibility, permeability, developability, and durability of the pigment and the halogenated product. Very important, should be used A resin binder having an acid value of 20 to 300 mgKOH/g. When the acid value is less than 20 mgKOH/g, the solubility in the developer is not good, and it is difficult to form a fine pattern. If the acid value of the resin binder exceeds 300 mgKOH/g, a fine pattern cannot be left.

從成膜性及各種耐受性良好的觀點考量，樹脂黏結劑係於以著色劑之總重量作為基準(100重量%)時，宜使用30重量%以上，由於著色劑濃度高，可顯現良好的色彩特性，因此宜以500重量%以下的量來使用。 The resin binder is preferably used in an amount of 30% by weight or more based on the total weight of the colorant from the viewpoint of good film formability and various resistances, and is excellent in colorant concentration. The color characteristics are therefore preferably used in an amount of 500% by weight or less.

熱塑性樹脂 Thermoplastic resin

作為樹脂黏結劑使用之熱塑性樹脂可舉出例如丙烯酸樹脂、丁縮醛樹脂、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-醋酸乙烯共聚物、聚醋酸乙烯、聚氨酯樹脂、聚酯樹脂、乙烯基系樹脂、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(高密度聚乙烯)、LDPE(低密度聚乙烯))、聚丁二烯及聚醯亞胺樹脂等。 The thermoplastic resin used as the resin binder may, for example, be an acrylic resin, a butyral resin, a styrene-maleic acid copolymer, a chlorinated polyethylene, a chlorinated polypropylene, a polyvinyl chloride, a vinyl chloride-vinyl acetate. Copolymer, polyvinyl acetate, polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, cellulose, polyethylene ( HDPE (high density polyethylene), LDPE (low density polyethylene), polybutadiene, and polyimide resin.

作為將上述含有酸性基之乙烯性不飽和單體予以共聚後之乙烯基系鹼可溶性樹脂，可舉出例如具有羧基、磺基等酸性基之樹脂。具體而言，鹼可溶性樹脂可舉出具有酸性基之丙烯酸樹脂、α-烯烴-(酐)順丁烯二酸共聚物、苯乙烯-苯乙烯磺酸共聚物、苯乙烯-(甲基)丙烯酸共聚物或異丁烯-(酐)順丁烯二酸共聚物等。其中尤其選自具有酸性基之丙烯酸樹脂、及苯乙烯/苯乙烯磺酸共聚物之至少1種樹脂，特別是具有酸性基之丙烯酸樹脂係耐熱性、透明性高，因此適宜使用。 The vinyl alkali-soluble resin obtained by copolymerizing the above-mentioned acidic group-containing ethylenically unsaturated monomer may, for example, be a resin having an acidic group such as a carboxyl group or a sulfo group. Specifically, the alkali-soluble resin may, for example, be an acrylic resin having an acidic group, an α-olefin-(anhydride) maleic acid copolymer, a styrene-styrenesulfonic acid copolymer, or a styrene-(meth)acrylic acid. Copolymer or isobutylene-(anhydride) maleic acid copolymer or the like. Among them, at least one type of resin selected from the group consisting of an acrylic resin having an acidic group and a styrene/styrenesulfonic acid copolymer is used, and in particular, an acrylic resin having an acidic group is preferably used because it has high heat resistance and transparency.

作為上述具有乙烯性不飽和雙重結合之活性能量線硬化性樹脂，可舉出例如藉由以下所示方法(a)或(b)而導入有不飽和乙烯性雙重結 合之樹脂。 The active energy ray-curable resin having the ethylenic unsaturated double bond may be, for example, an unsaturated ethylenic double knot introduced by the method (a) or (b) shown below. Combined resin.

[方法(a)] [method (a)]

作為方法(a)，包括例如藉由將具有環氧基之不飽和乙烯性單體與其他1種以上之單體予以共聚，於所獲得之共聚物之側鏈環氧基，令具有不飽和乙烯性雙重結合之不飽和一價酸之羧基進行附加反應，進而於已生成的羥基，令多價酸酐反應，以導入不飽和乙烯性雙重結合及羧基之方法。 As the method (a), for example, by copolymerizing an ethylenically unsaturated ethylenic monomer having another epoxy group with one or more other monomers, the side chain epoxy group of the obtained copolymer is rendered unsaturated. The ethylenic double-bonded unsaturated carboxyl group of the monovalent acid is subjected to an additional reaction, and the polyhydroxy acid anhydride is reacted with the generated hydroxyl group 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，可舉出例如環氧丙基(甲基)丙烯酸酯、甲基環氧丙基(甲基)丙烯酸酯、2-環氧丙氧基(甲基)丙烯酸酯、3,4環氧丁基(甲基)丙烯酸酯及3,4環氧環己基(甲基)丙烯酸酯。該等單獨使用或同時使用兩種以上均無妨。從下一步驟中與不飽和一價酸之反應性的觀點考量，宜為環氧丙基(甲基)丙烯酸酯。 Examples of the unsaturated ethylenic monomer having an epoxy group include a glycidyl (meth) acrylate, a methyl epoxypropyl (meth) acrylate, and a 2-epoxypropoxy group (A). Acrylate, 3,4 epoxybutyl (meth) acrylate and 3,4 epoxy cyclohexyl (meth) acrylate. These may be used alone or in combination of two or more. From the standpoint of reactivity with an unsaturated monovalent acid in the next step, it is preferably a propylenepropyl (meth) acrylate.

作為不飽和一價酸，可舉出例如(甲基)丙烯酸、巴豆酸、o-、m-或p-乙烯基安息香酸及(甲基)丙烯酸之α位鹵烷、烷氧、鹵素、硝、氰置換體等單羧酸等。該等單獨使用或同時使用兩種以上均無妨。 Examples of the unsaturated monovalent acid include (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, and α-halogenane, alkoxy, halogen, and nitrate of (meth)acrylic acid. And a monocarboxylic acid such as a cyanide substituent. These may be used alone or in combination of two or more.

作為多價酸酐可舉出四氫苯二酸酐、苯二酸酐、六氫苯二酸酐、琥珀酸酐、順丁烯二酸酐等。該等單獨使用或同時使用兩種以上均無妨。因應需要而增加羧基數等，使用偏苯三酸酐等三羧酸酐，亦或使用均苯四甲酸二酐等四羧酸二酐，亦可將殘留的酐基予以加水分解等。又，作為多價酸酐若使用具有不飽和乙烯性雙重結合之四氫苯二酸酐或順丁烯二酸酐，可進一步增加不飽和乙烯性雙重結合。 Examples of the polyvalent acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. These may be used alone or in combination of two or more. If necessary, the number of carboxyl groups and the like may be increased, and a tricarboxylic acid anhydride such as trimellitic anhydride may be used, or a tetracarboxylic dianhydride such as pyromellitic dianhydride may be used, or the residual anhydride group may be hydrolyzed or the like. Further, as the polyvalent acid anhydride, if tetrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used, the unsaturated ethylenic double bond can be further increased.

作為與方法(a)類似之方法，包括例如於藉由將具有羧基之 不飽和乙烯性單體、與其他1種以上之單體共聚所獲得的共聚物之側鏈羧基之一部分，令具有環氧基之不飽和乙烯性單體進行附加反應，以導入不飽和乙烯性雙重結合及羧基之方法。 As a method similar to the method (a), including, for example, by having a carboxyl group One part of the side chain carboxyl group of the copolymer obtained by copolymerizing an unsaturated ethylenic monomer with one or more other monomers, and an ethylenically unsaturated ethylenic monomer is additionally reacted to introduce an unsaturated ethyl group. A method of dual bonding and carboxyl groups.

[方法(b)] [method (b)]

作為方法(b)，包括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價基酸或其他單體予以共聚，於所獲得的共聚物之側鏈羥基，令具有異氰酸酯基之不飽和乙烯性單體之異氰酸酯基進行反應之方法。 As the method (b), comprising using an unsaturated ethylenic monomer having a hydroxyl group, copolymerizing with another unsaturated monovalent acid having a carboxyl group or another monomer, and having a side chain hydroxyl group of the obtained copolymer, having an isocyanate A method of reacting an isocyanate group of a ethylenically unsaturated ethylenic monomer.

作為具有羥基之不飽和乙烯性單體可舉出2-羥基乙基(甲基)丙烯酸酯、2-或3-羥基丙基(甲基)丙烯酸酯、2-或3-或4-羥基丁基(甲基)丙烯酸酯、丙三醇(甲基)丙烯酸酯及環己烷二甲醇單(甲基)丙烯酸酯等羥基烷基(甲基)丙烯酸酯類。該等單獨使用或同時使用兩種以上均無妨。又，亦可使用於上述羥基烷基(甲基)丙烯酸酯，令乙烯過氧化物、丙烯過氧化物及/或丁基過氧化物等進行附加聚合而成之聚醚單(甲基)丙烯酸酯，或附加有(聚)γ-戊內酯、(聚)ε-己內酯及/或(聚)12-羥基硬酯酸等之(聚)酯單(甲基)丙烯酸酯。從抑制塗膜異物的觀點考量，宜為2-羥基乙基(甲基)丙烯酸酯或丙三醇(甲基)丙烯酸酯。 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 4-hydroxy butyl A hydroxyalkyl (meth) acrylate such as a (meth) acrylate, a glycerol (meth) acrylate or a cyclohexane dimethanol mono (meth) acrylate. These may be used alone or in combination of two or more. Further, it can also be used in the above-mentioned hydroxyalkyl (meth) acrylate, and polyether mono(meth)acrylic acid obtained by additionally polymerizing an ethylene peroxide, a propylene peroxide, and/or a butyl peroxide. An ester or a (poly)ester mono(meth)acrylate to which (poly)γ-valerolactone, (poly)ε-caprolactone, and/or (poly)12-hydroxystearic acid are added. From the viewpoint of suppressing the coating film foreign matter, it is preferably 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate.

具有異氰酸酯基之不飽和乙烯性單體可舉出2-(甲基)丙烯醯氧乙基異氰酸酯或1,1-雙[(甲基)丙烯醯氧]乙基異氰酸酯等，但不限定於該等，亦可同時使用兩種以上。 Examples of the unsaturated ethylenic monomer having an isocyanate group include 2-(meth)acryloyloxyethyl isocyanate or 1,1-bis[(meth)acryloxime]ethyl isocyanate, but are not limited thereto. Alternatively, you can use two or more types at the same time.

熱硬化性樹脂 Thermosetting resin

作為樹脂黏結劑使用之熱硬化性樹脂可舉出例如環氧樹 脂、苯并胺樹脂、松香改質順丁烯二酸樹脂、松香改質富馬酸樹脂、三聚氰胺樹脂、尿素樹脂及酚樹脂等。 The thermosetting resin used as the resin binder may, for example, be an epoxy tree. Fat, benzoamine resin, rosin modified maleic acid resin, rosin modified fumaric acid resin, melamine resin, urea resin and phenol resin.

<溶劑> <solvent>

於本發明之紅色著色組成物可含有溶劑，以使得著色劑充分分散、滲透於著色劑載體中，於玻璃基板等基板上，塗布為乾燥膜厚成為0.2~5μ而容易形成濾光片區段。 The red coloring composition of the present invention may contain a solvent so that the coloring agent is sufficiently dispersed and infiltrated into the coloring agent carrier, and coated on a substrate such as a glass substrate to have a dry film thickness of 0.2 to 5 μ to easily form a filter segment. .

作為溶劑可舉出例如乳酸乙基、苄基醇、1,2,3-三氯丙烷、1,3-丁二醇、1,3-丁二醇、1,3-丁二醇二乙酸鹽、1,4-二噁烷、2-庚酮、2-甲基-1,3-丙二醇、3,3,5-三甲基-2-環己烯-1-酮、3,5,5三甲基環己酮、3-乙氧基丙酸乙基、3-甲氧基-3-甲基乙酸丁酯、3-甲氧基丁醇、3-甲氧基乙酸丁酯、4-庚酮、間二甲苯、間二乙苯、間二氯苯、N,N-二甲基乙醯胺、正丁苯、正乙酸丙酯、N-吡咯酮、鄰二甲苯、鄰氯甲苯、鄰二乙苯、鄰二氯苯、對氯甲苯、對二乙苯、二級丁苯、三級丁苯、異佛酮、乙二醇二***、乙二醇二丁醚、乙二醇單***乙酸鹽、乙二醇單第三丁醚、乙二醇單丁醚乙酸鹽、乙二醇單丙醚、二異丁酮、環己醇乙酸鹽、二丙二醇二甲醚、二丙二醇甲醚乙酸鹽、二丙二醇單丁醚、二丙酮醇、丙二醇二乙酸鹽、丙二醇苯基醚、丙二醇單***、丙二醇單丙醚、丙二醇單甲醚、丙二醇單甲醚乙酸鹽、丙二醇單甲醚丙酸鹽、苯基醇、甲基異丁酮、甲基環己醇、醋酸正胺基、醋酸正丁基、醋酸異胺基、醋酸異丁基、醋酸丙基、二價酸酯等。 The solvent may, for example, be ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butanediol or 1,3-butanediol diacetate. , 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,3,5-trimethyl-2-cyclohexen-1-one, 3,5,5 Trimethylcyclohexanone, ethyl 3-ethoxypropionate, butyl 3-methoxy-3-methylacetate, 3-methoxybutanol, 3-methoxyacetate, 4- Heptone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, n-butylbenzene, propyl orthoacetate, N-pyrrolidone, o-xylene, o-chlorotoluene, o-Diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, secondary butylbenzene, tertiary butylbenzene, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol Ethyl acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, diisobutyl ketone, cyclohexanol acetate, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether Acetate, dipropylene glycol monobutyl ether, diacetone alcohol, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, phenyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-aminoacetate, n-butyl acetate, isoamyl acetate, isobutyl acetate , propyl acetate, divalent acid ester, and the like.

其中從本發明之顏料、鹵化生成物(A))之分散、溶解良好的觀點來看，宜使用乳酸乙基、丙二醇單甲基醚醋酸酯、丙二醇單乙基醚醋 酸酯、乙二醇單甲基醚醋酸酯及乙二醇單乙基醚醋酸酯等醇醋酸酯類、芐基醇等芳香族醇類、或環己酮等酮類。 Among them, from the viewpoint of dispersing and dissolving the pigment and the halogenated product (A) of the present invention, it is preferred to use ethyl lactate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether vinegar. Alcohol acetates such as acid esters, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate; aromatic alcohols such as benzyl alcohol; and ketones such as cyclohexanone.

溶劑可單獨使用1種或混合2種以上使用。又，溶劑由於可將著色組成物調節為適當黏度，形成作為目標之膜厚均勻的著色層，因此於以著色劑之總重量作為基準(100重量%)時，宜以800~4000重量%的量來使用。 The solvent may be used alone or in combination of two or more. Further, since the solvent can adjust the coloring composition to an appropriate viscosity to form a target coloring layer having a uniform film thickness, it is preferably 800 to 4000% by weight based on the total weight of the coloring agent (100% by weight). The amount to use.

<著色組成物之製造方法> <Method for Producing Colored Composition>

本發明之紅色著色組成物係可藉由將包含紅色顏料及鹵化生成物(A)之著色劑，溶解或分散於前述樹脂黏結劑、及因應需要之溶劑所組成的著色劑載體中來製造。分散製造時，宜與色素衍生物等分散助劑一同利用3輥研磨機、2輥研磨機、砂磨機、捏合機及磨碎機等各種分散機構予以微細地分散製造。又，本發明之紅色著色組成物亦可將鹵化生成物(A)、紅色顏料等其他著色劑等個別溶解或分散於著色劑載體，予以混合而製造。 The red colored composition of the present invention can be produced by dissolving or dispersing a coloring agent containing a red pigment and a halogenated product (A) in a colorant carrier composed of the above-mentioned resin binder and a solvent which is required. In the case of dispersion production, it is preferably dispersed and produced together with a dispersing aid such as a pigment derivative by a dispersing mechanism such as a three-roll mill, a two-roll mill, a sand mill, a kneader or an attritor. Further, the red coloring composition of the present invention may be obtained by separately dissolving or dispersing other coloring agents such as a halogenated product (A) and a red pigment in a colorant carrier and mixing them.

分散助劑 Dispersing aid

將著色劑分散於著色劑載體中時，可適當地使用色素衍生物、樹脂型顏料分散劑及界面活性劑等分散助劑。分散助劑係分散著色劑之能力良好，防止分散後之著色劑再凝結的效果甚大，因此使用利用分散助劑以令著色劑分散於著色劑載體中而成之著色組成物時，可獲得分光穿透率高之彩色濾光片。於本發明中，鹵化生成物(A)亦可發揮作為紅色顏料分散助劑之作用，故為適宜的組合。 When the colorant is dispersed in the colorant carrier, a dispersion aid such as a dye derivative, a resin type pigment dispersant, or a surfactant can be suitably used. The dispersing aid has a good ability to disperse the coloring agent, and the effect of preventing re-coagulation of the dispersing coloring agent is very large. Therefore, when a dispersing aid is used to disperse the coloring agent in the coloring agent carrier, the coloring composition can be obtained. A color filter with high penetration. In the present invention, the halogenated product (A) can also function as a red pigment dispersing aid, and thus is a suitable combination.

色素衍生物可舉出於有機顏料、蒽醌、吖啶酮或三嗪中，導入有鹼性置換基、酸性置換基或亦可具有置換基之鄰苯二甲醯亞胺甲基之 化合物。 The pigment derivative may be exemplified by an organic pigment, anthracene, acridone or a triazine, and a basic substituent, an acidic substituent or a phthalimidomethyl group which may have a substituent may be introduced. Compound.

於本發明中，色素衍生物宜為顏料衍生物，其構造係由下述一般式(2)所示之化合物。 In the present invention, the dye derivative is preferably a pigment derivative, and its structure is a compound represented by the following general formula (2).

P-(L)n 式(2) P-(L)n (2)

(於一般式(2)，P係表示有機顏料殘基、蒽醌骨架、吖啶酮骨架或三嗪骨架等，L係表示鹼性置換基、酸性置換基或亦可具有置換基之鄰苯二甲醯亞胺甲基，n為1~4的整數)。 (In general formula (2), P represents an organic pigment residue, an anthracene skeleton, an acridone skeleton or a triazine skeleton, and the L system represents a basic substituent, an acidic substituent or an orthobenzene which may have a substituent. Methyl quinone imine methyl, n is an integer from 1 to 4).

作為構成P之有機顏料殘基之有機顏料可舉出例如：吡咯并吡咯二酮系顏料；偶氮、雙偶氮、聚偶氮等偶氮系顏料；銅酞菁、鹵化銅酞菁、無金屬酞菁等酞菁系顏料；胺蔥醌、二胺二蔥醌、蒽嘧啶、黃蒽酮、嵌二蒽酮、標準還原藍、呋喃酮、蒽酮紫染料等蔥醌系顏料；喹吖酮系顏料；二噻嗪系顏料；苝系顏料；芘系顏料；噻嗪靛藍系顏料；異吲哚滿系顏料；異吲哚滿酮系顏料；喹吖酮系顏料；杜烯系顏料；及金屬錯合體顏料等。 Examples of the organic pigment constituting the organic pigment residue of P include pyrrolopyrroledione pigments; azo pigments such as azo, disazo, and polyazo; copper phthalocyanine, copper halide phthalocyanine, and Phthalocyanine pigments such as metal phthalocyanine; onion quinone pigments such as amine lysine, diamine lysine, pyrimidine, flavonoid, indolinone, standard reduction blue, furanone, anthrone violet dye; Ketone pigment; dithiazine pigment; anthraquinone pigment; anthraquinone pigment; thiazin indigo pigment; isoindane pigment; isoindolinone pigment; quinophthalone pigment; durene pigment; And metal-missing pigments and the like.

色素衍生物可使用例如日本特開昭63-305173號、日本特公昭57-15620號、日本特公昭59-40172號、日本特公昭63-17102號、日本特公平5-9469號等所記載之物，該等可單獨使用或混合兩種以上使用。 The pigment derivative can be described, for example, in JP-A-63-305173, JP-A-57-15620, JP-A-59-40172, JP-A-63-17102, JP-A-5-9469, and the like. These may be used singly or in combination of two or more.

從分散性提升的觀點考量，色素衍生物之調配量係於以著色劑總量為基準(100重量%)時，宜為1重量%以上，最宜為3重量%以上。又，從耐熱性、耐光性的觀點考量，以著色劑之總量為基準(100重量%)時，宜為40重量%以下，最宜為35重量%以下。 From the viewpoint of the improvement of the dispersibility, the blending amount of the dye derivative is preferably 1% by weight or more, and most preferably 3% by weight or more based on the total amount of the coloring agent (100% by weight). Moreover, from the viewpoint of heat resistance and light resistance, it is preferably 40% by weight or less, and most preferably 35% by weight or less based on the total amount of the coloring agent (100% by weight).

樹脂型分散劑係具有具吸附於顏料之性質之顏料親和性部 位、及與顏料載體具相溶性之部位，具有吸附於著色劑以使著色劑對於顏料載體之分散安定化之作用。具體之樹脂型分散劑可使用聚氨酯、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、聚羧酸烷胺鹽、聚矽氧烷、長鏈聚胺基醯胺磷酸鹽、含烴基之聚羧酸酯或此等之改質物、藉由與具有聚合(低級烷亞胺)及游離之羧基之聚酯反應所形成之醯胺或其鹽等之油性分散劑、(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、聚乙烯吡咯醇等水溶性樹脂或水溶性高分子化合物、聚酯系分散劑、改質聚丙烯酸酯系分散劑、乙烯氧化物/丙烯氧化物附加化合物、燐酸酯系分散劑等，該等可單獨使用或混合兩種以上來使用，但未必要限定在該等。 The resin type dispersant has a pigment affinity portion having a property of adsorbing to a pigment The position and the portion compatible with the pigment carrier have an effect of being adsorbed to the colorant to stabilize the dispersion of the colorant with respect to the pigment carrier. The specific resin type dispersant may be a polycarboxylate such as polyurethane or polyacrylate, an unsaturated polyamine, a polycarboxylic acid, a polycarboxylic acid (partial) amine salt, a polycarboxylic acid ammonium salt, or a polycarboxylic acid alkylamine salt. , polyoxyalkylene oxide, long-chain polyamine decylamine phosphate, hydrocarbon-containing polycarboxylate or the like, by reacting with a polyester having a polymerized (lower alkylenimine) and a free carboxyl group An oily dispersant such as a guanamine or a salt thereof, a (meth)acrylic acid-(meth)acrylate copolymer, a styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone a resin, a water-soluble polymer compound, a polyester-based dispersant, a modified polyacrylate-based dispersant, an ethylene oxide/propylene oxide-addition compound, a phthalate-based dispersant, etc., which may be used alone or in combination. It is used above, but it is not necessarily limited to these.

市售的樹脂型分散劑可舉出BYK-Chemie公司製之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、2090、2091、2164或2163、Anti-Terra-U、203及204、BYK-P104、P104S、220S及6919、Lactimon、Lactimom-WS以及Bykumen、日本Lubrizol公司製之SOLSPERSE-3000、9000、13240、13650、13940、17000、18000、20000、21000、24000、26000、27000、28000、31845、32000、32500、32600、34750、36600、38500、41000、41090、53095、55000及76500、日本千葉公司製之EFKA-46、47、48、452、LP4008、4009、LP4010、LP4050、LP4055、400、401、402、403、450、451、453、4540、4550、4560、4800、5010、5065、5066、5070、7500、7554、1101、120、150、1501、1502及1503、Ajinomoto Fine-Techno公司製之AJISPER-PA111、PB711、PB821、PB822、PB824 等。 Commercially available resin type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166 manufactured by BYK-Chemie. 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2090, 2091, 2164 or 2163, Anti-Terra-U, 203 and 204, BYK-P104, P104S, 220S and 6919, Lactimon, Lactimom-WS, and Bykumen, SOLSPERSE 3000, 9000, 13240, 13650, 13940, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, manufactured by Lubrizol, Japan. 32600, 34750, 36600, 38500, 41000, 41090, 53095, 55000, and 76500, EFKA-46, 47, 48, 452, LP4008, 4009, LP4010, LP4050, LP4055, 400, 401, 402, manufactured by Chiba Corporation, Japan. 403, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, and 1503, AJISPER-PA111 manufactured by Ajinomoto Fine-Techno Co., Ltd. , PB711, PB821, PB822, PB824 Wait.

作為界面活性劑可舉出聚環氧乙烷醚硫酸鹽、十二烷基苯磺酸鈉、苯乙烯-丙烯酸共聚物之丙烯酸鹽、烷基萘磺酸鈉、烷基二苯醚二磺酸鈉、月桂基硫酸乙醇胺、月桂基硫酸三乙醇胺、月桂基硫酸銨、硬脂酸乙醇胺、硬脂酸銨、月桂基硫酸鈉、苯乙烯-丙烯酸共聚物之乙醇胺、聚環氧乙烷醚磷酸醚等陰離子性界面活性劑；聚環氧乙烯油醚、聚環氧乙烯月桂醚、聚環氧乙烯壬基苯醚、聚環氧乙烷醚磷酸酯、聚環氧乙烯山梨糖醇酐甘油硬脂酸等陽離子性界面活性劑；烷基4級銨鹽或其等之環氧乙烷附加物等生膠乾餾性界面活性劑；烷基二甲胺醋酸季銨羧酸內鹽等烷基季銨羧酸內鹽；或烷基咪唑啉等雙性界面活性劑，該等可單獨或混合2種以上來使用，但未必要限定在該等。 Examples of the surfactant include polyethylene oxide ether sulfate, sodium dodecylbenzenesulfonate, styrene-acrylic acid copolymer acrylate, alkylnaphthalenesulfonate sodium, and alkyl diphenyl ether disulfonic acid. Sodium, lauryl ethanolamine, lauryl triethanolamine, ammonium lauryl sulfate, stearic acid ethanolamine, ammonium stearate, sodium lauryl sulfate, styrene-acrylic acid copolymer ethanolamine, polyoxyethylene ether phosphate ether And other anionic surfactants; polyethylene oxide oleyl ether, polyethylene oxide lauryl ether, polyethylene oxide nonylphenyl ether, polyethylene oxide ether phosphate, polyethylene oxide sorbitan glycerol hard fat a cationic surfactant such as an acid; an alkyl quaternary ammonium salt; an alkyl quaternary ammonium carboxylic acid such as a quaternary ammonium salt; An amphoteric surfactant such as a carboxylic acid inner salt or an alkyl imidazoline may be used singly or in combination of two or more kinds, but it is not necessarily limited thereto.

添加樹脂型分散劑、界面活性劑時，其量係於以著色劑之總量作為基準(100重量%)時，宜為0.1~55重量%，進而更宜為0.1~45重量%。樹脂型分散劑、界面活性劑之調配量小於0.1重量%時，難以獲得添加效果，調配量多於55重量%時，由於過多的分散劑，可能會對分散造成影響。 When the resin-type dispersant or the surfactant is added, the amount is preferably from 0.1 to 55% by weight, and more preferably from 0.1 to 45% by weight, based on the total amount of the coloring agent (100% by weight). When the amount of the resin-type dispersant or the surfactant is less than 0.1% by weight, it is difficult to obtain an effect of addition, and when the amount is more than 55% by weight, excessive dispersion may affect the dispersion.

本發明之紅色著色組成物可進一步添加光聚合性單體及/或光聚合起始劑，以作為彩色濾光片用感光性著色組成物來使用。 Further, a photopolymerizable monomer and/or a photopolymerization initiator may be further added to the red coloring composition of the present invention to be used as a photosensitive coloring composition for a color filter.

光聚合性單體 Photopolymerizable monomer

光聚合性單體包含藉由紫外線或熱等硬化而生成透明樹脂之單體或寡聚物，該等可單獨或混合2種以上來使用。單體之調配量係於以著色劑之總重量作為基準(100重量%)時，宜為5~400重量%，從光硬化性及顯影性的觀點考量，更宜為10~300重量%。 The photopolymerizable monomer contains a monomer or an oligomer which is formed by curing by ultraviolet rays or heat, and may be used alone or in combination of two or more. The amount of the monomer is preferably from 5 to 400% by weight based on the total weight of the colorant (100% by weight), and is preferably from 10 to 300% by weight from the viewpoint of photocurability and developability.

藉由紫外線或熱等硬化而生成透明樹脂之單體、寡聚物可舉出例如：甲基(甲基)丙烯酸酯、乙基(甲基)丙烯酸酯、2-羥基乙基(甲基)丙烯酸酯、2-羥基丙基(甲基)丙烯酸酯、環己基(甲基)丙烯酸酯、β-羧基(甲基)丙烯酸酯、聚乙二醇單(甲基)丙烯酸酯、1,6-己二醯二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯及、三丙二醇二(甲基)丙烯酸酯、三羥甲基丙烷(甲基)丙烯酸酯、新戊四醇(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、1,6-丁二醇二縮水甘油基醚、雙酚A二縮水甘油基醚、新戊二醇甘油基醚、羥甲基化三聚氰胺等各種丙烯酸酯及甲基丙烯酸酸酯、(甲基)丙烯酸、苯乙烯、醋酸乙烯、羥基乙基乙烯醚、乙二醇二乙烯醚、新戊四醇三乙烯醚、(甲基)丙烯醯胺、N-羥基甲基(甲基)丙烯醯胺、N-乙烯甲醯胺、丙烯醯腈等，但未必限定於該等。 Examples of the monomer or oligomer which forms a transparent resin by curing by ultraviolet rays or heat include methyl (meth) acrylate, ethyl (meth) acrylate, and 2-hydroxyethyl (methyl). Acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxy (meth) acrylate, polyethylene glycol mono (meth) acrylate, 1, 6- Hexane di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane (meth)acrylate, neopentyl alcohol (Meth) acrylate, neopentyl alcohol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-butyl Various acrylates such as diol diglycidyl ether, bisphenol A diglycidyl ether, neopentyl glycol glyceryl ether, methylolated melamine, methacrylate, (meth)acrylic acid, styrene, Vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, neopentyl alcohol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinyl methyl Amine, nitrile Bing Xixi, but not necessarily limited to such.

光聚合起始劑 Photopolymerization initiator

於本發明之彩色濾光片用著色組成物，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區段時，可加入光聚合起始劑等，以溶劑顯影型或鹼顯影型著色抗蝕劑材料的形態來調整。使用光聚合起始劑時之調配量係於以著色劑之總量作為基準時，宜為5~200重量%，從光硬化性及顯影性的觀點考量，更宜為10~150重量% In the colored composition for a color filter of the present invention, the composition is cured by ultraviolet irradiation, and when a filter segment is formed by photolithography, a photopolymerization initiator or the like may be added to form a solvent development type. Or the form of the alkali-developing type coloring resist material is adjusted. The amount of the photopolymerization initiator to be used is preferably from 5 to 200% by weight based on the total amount of the colorant, and is preferably from 10 to 150% by weight from the viewpoint of photocurability and developability.

光聚合起始劑可使用例如：4-苯氧基二氯代苯乙酮、4-t-丁基二氯代苯乙酮、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-羥基環己基苯酮、2-苄基二甲基胺-1-(4-嗎啉苯基)-丁烷-1-酮等乙醯苯系化合物；苯并、苯并甲醚、苯并***、苯并異 丙醚、苄基二甲基縮酮等苯并系化合物；二苯甲酮、苯醯安息香酸、苯醯安息香酸甲基、4-苯基二苯甲酮、羥基二苯甲酮、丙烯醯化二苯甲酮、4-苯醯-4’-甲基二苯基硫化物、3,3’,4,4’-四(t-丁基過氧羧基)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、2,4-二乙基噻噸酮等噻噸酮系化合物；2,4,6-三氯-鄰三嗪、2-苯基-4,6-雙(三氯甲基)-鄰三嗪、2-(對甲氧基苯基)-4,6-雙(三氯甲基)-鄰三嗪、2-(對甲苯基)-4,6-雙(三氯甲基)-鄰三嗪、2-胡椒基-4,6-雙(三氯甲基)-鄰三嗪、2,4-雙(三氯甲基)-6-苯乙烯基-鄰三嗪、2-(萘并-1-基)-4,6-雙(三氯甲基)-鄰三嗪、2-(4-甲氧基萘并-1-基)-4,6-雙(三氯甲基)-鄰三嗪、2,4-三氯甲基-(胡椒基)-6-三嗪、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-苯并肟)]、O-(乙醯)-N-(1-苯基-2-羰-2-(4’-甲氧基-萘基)亞乙基)羥胺等肟酯系化合物；雙(2,4,6-三甲基苯并)環氧苯膦、2,4,6-三甲基苯并環氧苯膦等膦系化合物；9,10-菲醌、樟腦醌、乙基蒽醌等醌系化合物；硼酸酯系化合物；咔唑系化合物；或者咪唑系化合物等。 As the photopolymerization initiator, for example, 4-phenoxydichloroacetophenone, 4-t-butyldichloroacetophenone, diethoxyacetophenone, 1-(4-isopropyl group can be used. Phenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl benzophenone, 2-benzyldimethylamine-1-(4-morpholinylphenyl)-butane-1 - an acetophenone compound such as a ketone; benzo, benzoxyl ether, benzoethyl ether, benzopyrene a benzo compound such as propyl ether or benzyl dimethyl ketal; benzophenone, benzoquinone benzoic acid, benzoquinone benzoic acid methyl, 4-phenylbenzophenone, hydroxybenzophenone, propylene oxime Dibenzophenone, 4-phenylindole-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis (t-butylperoxycarboxy)benzophenone Ketone compounds; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthiophene a thioxanthone compound such as ketone; 2,4,6-trichloro-o-triazine, 2-phenyl-4,6-bis(trichloromethyl)-o-triazine, 2-(p-methoxy) Phenyl)-4,6-bis(trichloromethyl)-o-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-o-triazine, 2-piperidin-4 ,6-bis(trichloromethyl)-o-triazine, 2,4-bis(trichloromethyl)-6-styryl-o-triazine, 2-(naphtho-1-yl)-4, 6-bis(trichloromethyl)-o-triazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-o-triazine, 2,4- a triazine-based compound such as trichloromethyl-(piperidyl)-6-triazine or 2,4-trichloromethyl (4'-methoxystyryl)-6-triazine; 1,2-octyl Diketone, 1-[4-(phenylthio)-, 2(O- And oxime ester compound such as O-(acetyl)-N-(1-phenyl-2-carbonyl-2-(4'-methoxy-naphthyl)ethylidene)hydroxylamine; Phosphine compounds such as 2,4,6-trimethylbenzo)epoxyphenylphosphine, 2,4,6-trimethylbenzoepoxyphenylphosphine; 9,10-phenanthrenequinone, camphorquinone, ethylhydrazine An anthraquinone compound; a borate ester compound; an oxazole compound; or an imidazole compound.

該等光聚合起始劑可使用1種，或因應需要而以任意比率混合2種以上來使用。該等光聚合起始劑係於以彩色濾光片用紅色著色組成物中之著色劑之總重作為基準(100重量%)時，宜為5~200重量%，從光硬化性及顯影性的觀點考量，更宜為10~150重量%。 These photopolymerization initiators may be used alone or in combination of two or more kinds in any ratio as needed. The photopolymerization initiator is preferably from 5 to 200% by weight, based on the total weight of the coloring agent in the red coloring composition of the color filter, from photocurability and developability. The viewpoint of the viewpoint is more preferably 10 to 150% by weight.

增感劑 Sensitizer

進而言之，於本發明之彩色濾光片用紅色著色組成物中，可 進一步含有增感劑。 Further, in the coloring composition of the color filter of the present invention, Further containing a sensitizer.

增感劑可舉出由黃酮衍生物或二亞芐基丙酮等所代表之不飽和酮類、由芐或樟腦醌等所代表之1,2-二酮衍生物、苯并衍生物、芴衍生物、萘醌衍生物、蒽醌衍生物、呫噸衍生物、硫代呫噸衍生物、呫噸酮衍生物、硫代呫噸酮衍生物、香豆素衍生物、香豆素酮衍生物、花菁衍生物、部花菁衍生物、類菁衍生物等聚甲炔色素、吖啶衍生物、氮雜苯衍生物、二烯陸圜衍生物、噁嗪衍生物、吲哚啉衍生物、薁衍生物、薁鎓鹽衍生物、方酸內鎓鹽衍生物、卟啉衍生物、四苯卟啉衍生物、三芳甲烷衍生物、四苯并卟啉衍生物、四吡嗪卟啉衍生物、酞菁衍生物、四偶氮卟啉衍生物、四喹喔啉卟啉衍生物、萘酞菁衍生物、次酞菁衍生物、吡啶鎓鹽衍生物、硫代吡啶鎓鹽衍生物、四卟啉衍生物、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、米氏酮衍生物、α-醯氧基醚、醯基磷化氫氧化物、甲苯基乙醛酸、苄基-9,10-菲并杜烯醌、樟腦醌、乙基蒽醌、4,4’-二乙基酞酚酮、3,3’或4,4’-四(三級丁基過氧羧基)二苯甲酮、4,4’-二甲基胺二苯甲酮等。 The sensitizer may, for example, be an unsaturated ketone represented by a flavonoid derivative or dibenzylideneacetone, a 1,2-diketone derivative represented by benzyl or camphorquinone, a benzo derivative or a hydrazine derivative. , naphthoquinone derivatives, anthracene derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, coumarin derivatives a polymethine pigment such as a cyanine derivative, a merocyanine derivative, or a cyanine derivative, an acridine derivative, an azabenzene derivative, a diene terpene derivative, an oxazine derivative, or a porphyrin derivative. , anthracene derivative, sulfonium salt derivative, squaraine ylide derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazine porphyrin derivative , phthalocyanine derivative, tetrazoporphyrin derivative, tetraquinoxaline porphyrin derivative, naphthalocyanine derivative, phthalocyanine derivative, pyridinium salt derivative, thiopyridinium salt derivative, Tetraporphyrin derivative, olefin derivative, spiropyran derivative, spirooxazine derivative, thiospirol derivative, metal aromatic hydrocarbon Complex, organic hydrazine complex, methyl ketone derivative, α-decyloxy ether, decyl phosphide hydroxide, tolyl glyoxylic acid, benzyl-9,10-phenanthrene Camphor, ethyl hydrazine, 4,4'-diethyl phenol ketone, 3,3' or 4,4'-tetrakis (tertiary butylperoxycarboxy) benzophenone, 4,4'- Dimethylamine benzophenone and the like.

進而具體而言，可舉出大河原信等人所編「色素手冊」(1986年、講談社)、大河原信等人所編「功能性色素的化學」(1981年、CMC)及池森忠三朗等人所編「特殊功能材料」(1986年、CMC)所記載之增感劑，但不限定於該等。又，此外，亦可含有對於從紫外至近紅外區的光顯示出吸收之增感劑。 Specifically, the "Pigment Handbook" (1986, Kodansha), and the "Chemistry of Functional Pigments" (1981, CMC) and Chisen-Sang Sanlang, etc., edited by Ohara Shinto et al. The sensitizers described in "Special Functional Materials" (1986, CMC) are not limited to these. Further, it may contain a sensitizer which exhibits absorption of light from the ultraviolet to the near-infrared region.

因應需要而以任意比率使用兩種以上之增感劑亦無妨。使用增感劑時，其調配量係於以著色組成物中所含之光聚合起始劑之總重量作 為基準(100重量%)時，宜為3~60重量%，從光硬化性及顯影性的觀點考量，更宜為5~50重量%。 It is also possible to use two or more sensitizers at any ratio as needed. When a sensitizer is used, the blending amount is based on the total weight of the photopolymerization initiator contained in the coloring composition. The content (100% by weight) is preferably from 3 to 60% by weight, and is preferably from 5 to 50% by weight from the viewpoint of photocurability and developability.

胺系化合物 Amine compound

又，於本發明之彩色濾光片用紅色著色組成物中，可含有具有還原溶存氧的作用之胺系化合物。 Further, in the red colored composition for a color filter of the present invention, an amine-based compound having a function of reducing dissolved oxygen may be contained.

該類胺系化合物可舉出三乙醇胺、甲基二乙醇胺、三異丙醇胺、4-二甲基胺安息香酸甲基、4-二甲基胺安息香酸乙基、4-二甲基胺安息香酸2-乙基己基及N,N-二甲基對甲苯胺等。 Examples of such amine-based compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylaminebenzoic acid methyl, 4-dimethylamine benzoic acid ethyl, 4-dimethylamine. Benzoic acid 2-ethylhexyl and N,N-dimethyl-p-toluidine and the like.

均染劑 Leveling agent

於本發明之紅色著色組成物中，為了改善組成物在透明基板上之均染性，宜添加均染劑。均染劑宜於主鏈具有聚醚構造或聚酯構造之二甲基矽氧烷。作為於主鏈具有聚醚構造之二甲基矽氧烷之具體例，可舉出例如TORAY‧Dow Corning公司製之FZ-2122及BYK公司製之BYK-333。作為於主鏈具有聚酯構造之二甲基矽氧烷之具體例，可舉出例如BYK公司製之BYK-310及BYK-370等。亦可同時使用於主鏈具有聚醚構造之二甲基矽氧烷與於主鏈具有聚酯構造之二甲基矽氧烷。均染劑之含有量一般係於以紅色著色組成物之總重量作為基準(100重量%)時，宜使用0.003~0.5重量%。 In the red colored composition of the present invention, in order to improve the leveling property of the composition on the transparent substrate, it is preferred to add a leveling agent. The leveling agent is preferably a dimethyl siloxane having a polyether structure or a polyester structure in the main chain. Specific examples of the dimethyl siloxane having a polyether structure in the main chain include FZ-2122 manufactured by TORAY‧Dow Corning Co., Ltd. and BYK-333 manufactured by BYK Corporation. Specific examples of the dimethyl siloxane having a polyester structure in the main chain include, for example, BYK-310 and BYK-370 manufactured by BYK Corporation. It is also possible to use dimethyl methoxyoxane having a polyether structure in the main chain and dimethyl methoxy oxane having a polyester structure in the main chain. The content of the leveling agent is generally 0.003 to 0.5% by weight based on the total weight of the red colored composition (100% by weight).

尤其適宜的均染劑係於分子內具有疏水基及親水基之化合物，其為所謂界面活性劑之一種，具有親水性而同時對於水的溶解性低，添加於紅色著色組成物時，具有其表面張力降低能力低的特徵，進而即便表面張力降低能力低，但對玻璃板之潤澤性良好之物甚為有用，宜使用在 不出現起泡所造成的塗膜缺陷之添加量內，可充分抑制帶電性之物。具有該類適宜特性之均染劑宜使用具有聚環氧烷單位之二甲基矽氧烷。聚環氧烷單位包括聚環氧乙烯單位及聚環氧丙烯單位；二甲基矽氧烷亦可具有聚環氧乙烯單位及聚環氧丙烯單位雙方。 A particularly suitable leveling agent is a compound having a hydrophobic group and a hydrophilic group in the molecule, which is a kind of a so-called surfactant, which has hydrophilicity and low solubility in water, and is added to a red colored composition. The feature that the surface tension reducing ability is low, and even if the surface tension reducing ability is low, it is useful for a material having good lubricity of a glass plate, and it is preferably used. The chargeable substance can be sufficiently suppressed without increasing the amount of coating film defects caused by foaming. It is preferred to use a dimethyl siloxane having a polyalkylene oxide unit as a leveling agent having such suitable characteristics. The polyalkylene oxide unit includes a polyethylene oxide unit and a polyoxypropylene unit; the dimethyloxane may also have both a polyethylene oxide unit and a polypropylene oxide unit.

又，聚環氧烷單位與二甲基矽氧烷之結合形態為以下任一型均可：聚環氧烷單位在二甲基矽氧烷之重複單位中結合之垂飾型；聚環氧烷單位結合於二甲基矽氧烷末端之末端改質型；及聚環氧烷單位與二甲基矽氧烷交互重複結合之直鏈狀嵌段共聚物型。具有聚環氧烷單位之二甲基矽氧烷係由TORAY‧Dow Corning公司市售，可舉出例如FZ-2110、FZ-2122、FZ-2130、FZ-2166、FZ-2191、FZ-2203、FZ-2207，但不限定於該等。 Further, the combination of the polyalkylene oxide unit and the dimethyloxane may be any of the following types: a pendant type in which a polyalkylene oxide unit is combined in a repeating unit of dimethyloxane; a polyepoxy a terminal unit modified with an alkane unit bonded to a terminal end of dimethyloxane; and a linear block copolymer type in which a polyalkylene oxide unit is repeatedly and repeatedly bonded to dimethyloxane. A dimethyl methoxy olefin having a polyalkylene oxide unit is commercially available from TORAY‧Dow Corning Co., Ltd., and examples thereof include FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, and FZ-2203. FZ-2207, but is not limited to these.

於均染劑亦可輔助性地加入陰離子性、陽離子性、非離子性或雙性的界面活性劑。界面活性劑係混合2種以上使用亦無妨。 Anionic, cationic, nonionic or amphoteric surfactants may also be added to the leveling agent. It is also possible to use two or more kinds of surfactants in combination.

輔助性地加入於均染劑之陰離子性界面活性劑可舉出聚環氧乙烷醚硫酸鹽、十二烷基苯磺酸鈉、苯乙烯-丙烯酸共聚物之丙烯酸鹽、烷基萘磺酸鈉、烷基二苯醚二磺酸鈉、月桂基硫酸乙醇胺、月桂基硫酸三乙醇胺、月桂基硫酸銨、硬脂酸乙醇胺、硬脂酸銨、月桂基硫酸鈉、苯乙烯-丙烯酸共聚物之單乙醇胺及聚環氧乙烷醚磷酸醚等。 Examples of the anionic surfactant which is auxiliaryly added to the leveling agent include polyethylene oxide ether sulfate, sodium dodecylbenzenesulfonate, styrene-acrylic acid copolymer acrylate, and alkylnaphthalenesulfonic acid. Sodium, sodium alkyl diphenyl ether disulfonate, ethanolyl lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, ethanolamine stearate, ammonium stearate, sodium lauryl sulfate, styrene-acrylic acid copolymer Monoethanolamine and polyethylene oxide ether phosphate ether.

輔助均染劑之陽離子性界面活性劑可舉出烷基4級銨鹽及其等之環氧乙烷附加物。 The cationic surfactant of the auxiliary leveling agent may, for example, be an alkyl 4-grade ammonium salt or the like.

輔助性地加入於均染劑之非離子性界面活性劑可舉出聚環氧乙烯油醚、聚環氧乙烯月桂醚、聚環氧乙烯壬基苯醚、聚環氧乙烷醚磷酸酯、聚環氧乙烯山梨糖醇酐甘油硬脂酸、聚乙二醇單月桂酯、烷基二甲 胺醋酸季銨羧酸內鹽等烷基季銨羧酸內鹽及烷基咪唑啉等雙性界面活性劑、及氟系或矽基系界面活性劑。 Examples of the nonionic surfactant that is auxiliaryly added to the leveling agent include polyethylene oxide oleyl ether, polyethylene oxide lauryl ether, polyepoxy decyl phenyl ether, and polyethylene oxide ether phosphate. Polyethylene oxide sorbitan glyceryl stearate, polyethylene glycol monolauryl ester, alkyl dimethyl An amphoteric surfactant such as an alkyl quaternary ammonium carboxylate inner salt such as an amine quaternary ammonium carboxylate inner salt or an alkyl imidazoline; and a fluorine-based or sulfhydryl-based surfactant.

硬化劑、硬化促進劑 Hardener, hardening accelerator

又，為了輔助熱硬化性樹脂之硬化，於本發明之紅色著色組成物中，亦可因應需要來含有硬化劑、硬化促進劑等。有用之硬化劑為苯酚系樹脂、胺系化合物、酸酐、活性酯、羧酸系化合物、磺酸系化合物等，但並未特別限定於該等，若可與熱硬化性樹脂反應之物，使用任何硬化劑均可。又，該等之中，尤宜舉出1分子內具有2個以上之苯酚性羥基之化合物、胺系硬化劑。前述硬化促進劑可舉出例如：胺化合物(例如雙氰胺、苄基二甲基胺、4-(二甲基胺)-N,N-二甲基苄基胺、4-甲氧基-N,N-二甲基苄基胺及4-甲基-N,N-二甲基苄基胺等)；4級銨氯化合物(例如三乙基苄基氯化銨等)；嵌段異氰酸酯化合物(例如二甲基胺等)；咪唑基衍生物二環式脒化合物及其鹽(例如咪唑基、2-甲基咪唑基、2-乙基咪唑基、2-乙基-4-甲基咪唑基、2-苯基咪唑基、4-苯基咪唑基、1-氰基乙基-2-苯基咪唑基及1-(2-氰基乙基)-2-乙基-4-甲基咪唑基等)；磷化合物(例如三苯膦等)；胍胺化合物(例如三聚氰胺、胍胺、乙醯胍胺及苯并胍胺等)；以及S-三嗪衍生物(例如2,4-二胺-6-甲基丙烯醯氧乙基-S-三嗪、2-乙烯基-2,4-二胺-6-三嗪、2-乙烯基-4,6-二胺-S-三嗪‧異氰酸酯酸附加物及2,4-二胺-6-甲基丙烯醯氧乙基-S-三嗪‧異氰酸酯酸附加物等)。該等可單獨使用1種或同時使用兩種以上均可。前述硬化促進劑之含有量係對於熱硬化性樹脂總量，宜為0.01~15重量%。 Moreover, in order to assist the hardening of the thermosetting resin, the red coloring composition of the present invention may contain a curing agent, a curing accelerator, and the like as needed. The hardening agent to be used is a phenol resin, an amine compound, an acid anhydride, an active ester, a carboxylic acid compound, a sulfonic acid compound, etc., but is not particularly limited thereto, and may be used in a reaction with a thermosetting resin. Any hardener can be used. In addition, among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine-based curing agent are particularly preferable. The hardening accelerator may, for example, be an amine compound (for example, dicyandiamide, benzyldimethylamine, 4-(dimethylamine)-N,N-dimethylbenzylamine, 4-methoxy- N,N-dimethylbenzylamine and 4-methyl-N,N-dimethylbenzylamine, etc.); 4-stage ammonium chloride compound (for example, triethylbenzylammonium chloride, etc.); blocked isocyanate a compound (for example, dimethylamine or the like); an imidazolyl derivative bicyclic hydrazine compound and a salt thereof (for example, imidazolyl, 2-methylimidazolyl, 2-ethylimidazolyl, 2-ethyl-4-methyl Imidazolyl, 2-phenylimidazolyl, 4-phenylimidazolyl, 1-cyanoethyl-2-phenylimidazolyl and 1-(2-cyanoethyl)-2-ethyl-4-methyl a pyridyl group or the like; a phosphorus compound (for example, triphenylphosphine, etc.); a guanamine compound (for example, melamine, guanamine, acetamide, benzoguanamine, etc.); and an S-triazine derivative (for example, 2, 4) -diamine-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamine-6-triazine, 2-vinyl-4,6-diamine-S- Triazine ‧ isocyanate acid addenda and 2,4-diamine-6-methyl propylene oxyethyl-S-triazine ‧ isocyanate acid addenda, etc.). These may be used alone or in combination of two or more. The content of the hardening accelerator is preferably from 0.01 to 15% by weight based on the total amount of the thermosetting resin.

<其他添加劑成分> <Other additive ingredients>

於本發明之著色組成物中，為了令組成物之經時黏度安定化，可含有儲藏安定劑。又，為了提高與透明基板之密貼性，亦可含有矽烷耦合劑等密貼提升劑。 In the colored composition of the present invention, a storage stabilizer may be contained in order to stabilize the viscosity of the composition over time. Further, in order to improve the adhesion to the transparent substrate, a adhesion promoter such as a decane coupling agent may be contained.

儲藏安定劑可舉出例如：芐基三甲基氯化物及二甲基羥胺等4級銨氯化物；乳酸及草酸等有機酸及其乙基醚；三級丁基焦兒茶酚；四乙基膦及四苯基膦等有機膦類；以及亞磷酸鹽等。儲藏安定劑係於以著色劑之總量作為基準(100重量%)時，宜以0.1~10重量%的量來使用。 Examples of the storage stabilizer include 4-grade ammonium chlorides such as benzyltrimethyl chloride and dimethylhydroxylamine; organic acids such as lactic acid and oxalic acid, and ethyl ether; tertiary butyl pyrocatechol; Organic phosphines such as phosphines and tetraphenylphosphines; and phosphites. The storage stabilizer is preferably used in an amount of 0.1 to 10% by weight based on the total amount of the colorant (100% by weight).

密貼提升劑可舉出以下矽烷耦合劑：乙烯三(β-甲氧基以氧基)矽烷、乙烯乙氧基矽烷及乙烯三甲氧基矽烷等乙烯矽烷類；γ-甲基丙烯氧基丙烯三甲氧基矽烷等(甲基)丙烯酸矽烷類；β-(3,4-環氧環烷基)乙基三甲氧基矽烷、β-(3,4-環氧環烷基)甲基三甲氧基矽烷、β-(3,4-環氧環烷基)乙基三乙氧基矽烷、β-(3,4-環氧環烷基)甲基三乙氧基矽烷、γ-環氧丙氧基丙基三甲氧基矽烷、γ-環氧丙氧基丙基三乙氧基矽烷等環氧矽烷類；N-β(胺乙基)γ-胺丙基三甲氧基矽烷、N-β(胺乙基)γ-胺丙基三乙氧基矽烷、N-β(胺乙基)γ-胺丙基甲基二乙氧基矽烷、γ-胺丙基三乙氧基矽烷、γ-胺丙基三甲氧基矽烷、N-苯基-γ-胺丙基三甲氧基矽烷、N-苯基-γ-胺丙基三乙氧基矽烷等胺矽烷類；以及γ-巰基丙基三甲氧基矽烷、γ-巰基丙基三甲乙基矽烷等硫代矽烷類等。密貼提升劑係於以紅色著色組成物中之著色劑總量為基準(100重量%)時，能夠以0.01~10重量%，宜以0.05~5重量%的量來使用。 Examples of the adhesion promoter include the following decane coupling agents: ethylene decane such as ethylene tris(β-methoxy oxy) decane, ethylene ethoxy decane, and ethylene trimethoxy decane; γ-methyl propylene oxy propylene; (meth)acrylic acid decane such as trimethoxydecane; β-(3,4-epoxycycloalkyl)ethyltrimethoxydecane, β-(3,4-epoxycycloalkyl)methyltrimethoxy Pyrantane, β-(3,4-epoxycycloalkyl)ethyltriethoxydecane, β-(3,4-epoxycycloalkyl)methyltriethoxydecane, γ-glycidyl Epoxy decanes such as oxypropyltrimethoxydecane and γ-glycidoxypropyltriethoxydecane; N-β(aminoethyl)γ-aminopropyltrimethoxydecane, N-β (Amineethyl) γ-aminopropyltriethoxydecane, N-β(aminoethyl)γ-aminopropylmethyldiethoxydecane, γ-aminopropyltriethoxydecane, γ- Amino decane such as aminopropyltrimethoxydecane, N-phenyl-γ-aminopropyltrimethoxydecane, N-phenyl-γ-aminopropyltriethoxydecane; and γ-mercaptopropyltrimethyl A thiononane such as oxydecane or γ-mercaptopropyltrimethylethyl decane. The adhesion enhancer can be used in an amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the total amount of the coloring agent in the red colored composition (100% by weight).

<去除粗粒子> <Remove coarse particles>

利用離心分離、燒結過濾器、薄膜過濾器等機構，從本發明 之紅色著色組成物，進行5μm以上之粗粒子，更宜為1μm以上之粗粒子，進而為0.5μm以上之粗粒子及混入微塵之去除。如此，紅色著色組成物實質上宜不含0.5μm以上之粒子。更宜為0.3μm以下。 Using a mechanism such as centrifugal separation, sintering filter, membrane filter, etc., from the present invention The red colored composition is a coarse particle of 5 μm or more, more preferably a coarse particle of 1 μm or more, and further a coarse particle of 0.5 μm or more and a fine dust mixed therein. Thus, the red coloring composition is preferably substantially free of particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<彩色濾光片> <Color Filter>

接著，說明關於本發明之彩色濾光片。本發明之彩色濾光片具備至少1個紅色濾光片區段、至少1個綠色濾光片區段及至少1個藍色濾光片區段，前述至少1個紅色濾光片區段係使用本發明之彩色濾光片用紅色著色組成物所形成。 Next, a color filter relating to the present invention will be described. The color filter of the present invention comprises at least one red filter segment, at least one green filter segment and at least one blue filter segment, and the at least one red filter segment is The color filter of the present invention is formed using a red colored composition.

綠色濾光片區段可使用包含綠色顏料及顏料載體之一般綠色著色組成物來形成。綠色顏料可使用例如C.I.顏料綠(Pigment Green)7、10、36、37、58等。 The green filter segments can be formed using a generally green colored composition comprising a green pigment and a pigment carrier. As the green pigment, for example, C.I. Pigment Green 7, 10, 36, 37, 58, and the like can be used.

又，綠色著色組成物可與黃色顏料同時使用。可同時使用的黃色顏料可舉出例如C.I.顏料黃(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、95、97、98、100、101、104、106、108、109、110、113、114、115、116、117、118、119、120、123、126、127、128、129、138、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或221等黃色顏料。又，亦可同時使用呈現黃色之鹼性染料、酸性染料之鹵化生成物。 Further, the green coloring composition can be used simultaneously with the yellow pigment. The yellow pigment which can be used at the same time may, for example, be Pig 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, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138 , 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 Yellow pigment such as 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220 or 221. Further, a halogenated product of a yellow basic dye or an acid dye may be used at the same time.

藍色濾光片區段可使用含藍色顏料與著色劑載體之一般藍 色著色組成物來形成。藍色顏料係使用酞菁系顏料及/或三芳基甲烷系色澱顏料等。酞菁系顏料宜為使用銅酞菁藍顏料之物。 The blue filter section can use a blue color containing a blue pigment and a colorant carrier. The coloring composition is formed. As the blue pigment, a phthalocyanine-based pigment and/or a triarylmethane-based lake pigment or the like is used. The phthalocyanine-based pigment is preferably a copper phthalocyanine blue pigment.

銅酞菁藍顏料可舉出C.I.顏料藍15、C.I.顏料藍15：1、C.I.顏料藍15：2、C.I.顏料藍15：3、C.I.顏料藍15：4、C.I.顏料藍15：6等顏料。其中尤以具有ε型、α型構造之銅酞菁藍顏料。具體而言，該類適宜顏料為C.I.顏料藍15：6及C.I.顏料藍15：1。 The copper phthalocyanine blue pigment may, for example, be a pigment such as C.I. Pigment Blue 15, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:2, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 15:6. Among them, a copper phthalocyanine blue pigment having an ε-type or an α-type structure is particularly preferable. Specifically, such suitable pigments are C.I. Pigment Blue 15:6 and C.I. Pigment Blue 15:1.

三芳基甲烷系色澱顏料可舉出C.I.顏料藍1、同1：2、同1：3、C.I.顏料藍2、同2：1、同2：2、C.I.顏料藍3、C.I.顏料藍8、C.I.顏料藍9、C.I.顏料藍10、同10：1、C.I.顏料藍11、C.I.顏料藍12、C.I.顏料藍18、C.I.顏料藍19、C.I.顏料藍24、同24：1、C.I.顏料藍53、C.I.顏料藍56、.同56：1、C.I.顏料藍57、C.I.顏料藍58、C.I.顏料藍59、C.I.顏料藍61、C.I.顏料藍62等。 The triarylmethane-based lake pigments include CI Pigment Blue 1, Same as 1:2, Same 1:3, CI Pigment Blue 2, Same as 2:1, Same as 2:2, CI Pigment Blue 3, CI Pigment Blue 8, CI Pigment Blue 9, CI Pigment Blue 10, Same as 10:1, CI Pigment Blue 11, CI Pigment Blue 12, CI Pigment Blue 18, CI Pigment Blue 19, CI Pigment Blue 24, Same 24:1, CI Pigment Blue 53, CI Pigment Blue 56,. Same as 56:1, CI Pigment Blue 57, CI Pigment Blue 58, CI Pigment Blue 59, CI Pigment Blue 61, CI Pigment Blue 62, and the like.

該等之中，藍色顏料宜使用C.I.顏料藍15：6。 Among these, the blue pigment is preferably C.I. Pigment Blue 15:6.

又，除了前述藍色顏料以外，宜同時使用呈紫色、紅色之二噁嗪系顏料、蒽醌系顏料、偶氮系顏料、喹吖酮系顏料。其中尤宜同時使用二噁嗪系顏料。二噁嗪系顏料宜使用C.I.顏料紫23。藉由於本發明之藍色著色組成物同時使用二噁嗪系顏料，可製成耐熱性、耐光性、耐溶劑性更加良好、安定的高品質藍色著色組成物。 Further, in addition to the blue pigment described above, it is preferred to use a purple or red dioxazine-based pigment, an anthraquinone-based pigment, an azo-based pigment, or a quinophthalone-based pigment. Among them, it is particularly preferable to use a dioxazine-based pigment at the same time. The dioxazine-based pigment is preferably C.I. Pigment Violet 23. By using the dioxazine-based pigment together with the blue coloring composition of the present invention, it is possible to obtain a high-quality blue coloring composition which is more excellent in heat resistance, light resistance, and solvent resistance.

<彩色濾光片之製造方法> <Method of Manufacturing Color Filter>

本發明之彩色濾光片可藉由印刷法或光微影來製造。 The color filter of the present invention can be produced by a printing method or photolithography.

藉由印刷法形成濾光片區段時，僅重複作為印刷墨水所調製的著色組成物之印刷與乾燥，即可完成圖案化，因此作為彩色濾光片之製造法，係成本低且量產性良好。進而藉由印刷技術的發展，可進行具有高 尺寸精度及平滑度之微細圖案之印刷。進行印刷時，宜為墨水在印刷板上或於毛氈布上不會乾燥及固化之組成。又，印刷機上之墨水流動性之控制亦甚重要，可藉由分散劑或體質顏料來進行墨水黏度的調整。 When the filter segment is formed by the printing method, only the printing and drying of the coloring composition prepared by the printing ink are repeated, and the patterning can be completed. Therefore, the color filter is manufactured at a low cost and mass production. Good sex. And by the development of printing technology, it can be carried out with high Printing of fine patterns of dimensional accuracy and smoothness. When printing, it is preferable that the ink does not dry and solidify on the printing plate or on the felt cloth. Moreover, the control of the fluidity of the ink on the printing press is also very important, and the viscosity of the ink can be adjusted by a dispersing agent or an extender pigment.

藉由光微影法形成濾光片區段時，於透明基板上，藉由噴霧塗布或旋轉塗布、狹縫塗布、輥塗布等塗布方法，來將作為上述溶劑顯影型或鹼顯影型著色抗蝕劑材料所調製的著色組成物，塗布為乾燥膜厚成為0.2~5μm。於依需要受到乾燥之膜，經由與該膜呈接觸或非接觸狀態而設置、具特定圖案之光罩，進行紫外線曝光。其後，浸漬於溶劑或鹼顯影劑中，或藉由噴霧器等，將顯影液予以噴霧，去除未硬化部，形成所需圖案後，針對其他色彩重複同樣操作，可製造彩色濾光片。進而為了促進著色抗蝕劑材料之聚合，亦可因應需要施以加熱。若藉由光微影法，可製造精度高於上述印刷法之彩色濾光片。 When the filter segment is formed by photolithography, the solvent development type or alkali development type coloring resistance is applied to the transparent substrate by a coating method such as spray coating or spin coating, slit coating or roll coating. The colored composition prepared by the etchant material is applied to have a dry film thickness of 0.2 to 5 μm. The film which is dried as needed is subjected to ultraviolet light exposure through a mask having a specific pattern which is provided in contact with or non-contact with the film. Thereafter, the solution is immersed in a solvent or an alkali developer, or the developer is sprayed by a sprayer or the like to remove the uncured portion, and a desired pattern is formed, and then the same operation is repeated for other colors to produce a color filter. Further, in order to promote polymerization of the colored resist material, heating may be applied as needed. If the photolithography method is used, a color filter having a higher precision than the above printing method can be manufactured.

顯影時，作為鹼顯影液係使用例如碳酸鈉及氫氧化鈉等之水溶液，亦可使用二甲基芐基胺及三乙醇胺等有機鹼。又，於顯影液中亦可添加消泡劑或界面活性劑。 At the time of 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 can also be used. Further, an antifoaming agent or a surfactant may be added to the developer.

再者，為了提高紫外線曝光感度，亦可於塗布乾燥上述著色抗蝕劑後，塗布乾燥水溶性或鹼水溶性樹脂之例如聚乙烯醇或水溶性丙烯酸樹脂等，形成防止氧阻礙聚合之膜後，進行紫外線曝光。 Further, in order to increase the ultraviolet exposure sensitivity, after drying and drying the coloring resist, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin may be applied to form a film which prevents oxygen from inhibiting polymerization. , UV exposure.

除了上述方法以外，本發明之彩色濾光片亦可藉由電沈積法、轉印法、噴墨法等來製造，本發明之著色組成物可利用於任一方法。再者，電沈積法係利用形成於基板上之透明導電膜，藉由膠體粒子之電泳，於透明導電膜上，將各色濾光片區段予以電沈積而形成，藉此製造彩色濾 光片之方法。又，轉印法係於剝離性之轉印基片表面，預先形成濾光片區段，令該濾光片區段轉印到所需基板之方法。噴墨法係藉由噴墨方式，將濾光片區段予以印字、製作之方法。 In addition to the above methods, the color filter of the present invention can also be produced by an electrodeposition method, a transfer method, an inkjet method, or the like, and the colored composition of the present invention can be used in any method. Furthermore, the electrodeposition method uses a transparent conductive film formed on a substrate to form a color filter by electrodepositing the color filter segments on the transparent conductive film by electrophoresis of colloidal particles. The method of light film. Further, the transfer method is a method in which a filter segment is formed in advance on the surface of the transferable transfer substrate, and the filter segment is transferred to a desired substrate. The inkjet method is a method in which a filter segment is printed and produced by an inkjet method.

於透明基板或反射基板上形成各色濾光片區段前，可預先形成黑矩陣。黑矩陣係利用鉻或鉻/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，但不限定於該等。又，亦可於前述透明基板或反射基板上，預先形成薄膜電晶體(TFT)，其後形成各色濾光片區段。又，於本發明之彩色濾光片上，亦可因應需要形成覆膜及透明導電膜等。 A black matrix may be formed in advance before forming the color filter segments on the transparent substrate or the reflective substrate. The black matrix is 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, but is not limited thereto. Further, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. Further, in the color filter of the present invention, a film, a transparent conductive film, or the like may be formed as needed.

【實施例】 [Examples]

以下根據實施例來說明本發明，但本發明不受限於此。再者，只要未特別註明，「部」係意味「重量部」。 Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In addition, unless otherwise specified, "part" means "weight".

又，丙烯酸樹脂之重量平均分子量(Mw)係換算為聚苯乙烯之重量平均分子量，其係利用TSKgel管柱(TOSOH公司製)，以裝備有RI檢測器之GPC(TOSOH公司製、HLC-8120GPC)，使用THF作為展開溶劑而測定。 In addition, the weight average molecular weight (Mw) of the acrylic resin is converted into a weight average molecular weight of polystyrene, and a TSKgel column (manufactured by TOSOH Co., Ltd.) is used as a GPC equipped with an RI detector (manufactured by TOSOH Co., Ltd., HLC-8120GPC). ), using THF as a developing solvent.

首先，從實施例及比較例所用之丙烯酸樹脂(樹脂黏結劑)溶液、側鏈具有陽離子性基之樹脂、微細化顏料、鹵化生成物(A)、呫噸系化合物、顏料分散體、含有鹵化生成物之樹脂溶液、藍色抗蝕劑材料、綠色抗蝕劑材料之製造方法說明。 First, the acrylic resin (resin binder) solution used in the examples and the comparative examples, the resin having a cationic group in the side chain, the fine pigment, the halogenated product (A), the xanthene compound, the pigment dispersion, and the halogenated product. Description of a method for producing a resin solution, a blue resist material, and a green resist material.

<丙烯酸樹脂溶液1~4之調製> <Modulation of Acrylic Resin Solution 1~4>

丙烯酸樹脂溶液1 Acrylic resin solution 1

於具備溫度計、冷卻管、氮氣導入管、滴下管及攪拌裝置之分離式的4支燒瓶，放入環己酮207部，升溫至80℃，以氮氣置換反應容器內 之後，藉由滴下管歷經2小時滴下正丁基甲基丙烯酸酯13.3部、2-羥乙基甲基丙烯酸酯4.6部、甲基丙烯酸4.3部、對枯基酚環氧乙烷改質丙烯酸酯(東亞合成股份有限公司製「ARONIX M110」)7.4部、2,2’-偶氮雙異丁腈0.4部之混合物。滴下結束後，進一步繼續反應3小時，獲得重量平均分子量(Mw)26000之丙烯酸樹脂之溶液。將該溶液冷卻至室溫後，將樹脂溶液取樣約2g，以180℃加熱20分鐘以使其乾燥，測定未揮發成分，根據其測定結果，於先前合成之樹脂溶液添加甲氧丙基醋酸酯，使得未揮發成分成為20重量%而調製成丙烯酸樹脂溶液1。 In a separate four-piece flask equipped with a thermometer, a cooling tube, a nitrogen inlet tube, a dropping tube, and a stirring device, 207 parts of cyclohexanone were placed, and the temperature was raised to 80 ° C, and the reaction vessel was replaced with nitrogen. Thereafter, 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, and modified acrylate of p-cumyl oxirane were added by dropping the tube over 2 hours (East Asia "ARONIX M110" manufactured by Synthetic Co., Ltd.) A mixture of 7.4 parts and 0.4 parts of 2,2'-azobisisobutyronitrile. After the completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a solution of an acrylic resin having a weight average molecular weight (Mw) of 26,000. After the solution was cooled to room temperature, the resin solution was sampled to about 2 g, heated at 180 ° C for 20 minutes to dry, and the non-volatile components were measured. According to the measurement results, methoxypropyl acetate was added to the previously synthesized resin solution. The non-volatile component was made 20% by weight to prepare an acrylic resin solution 1.

丙烯酸樹脂溶液2 Acrylic resin solution 2

於具備溫度計、冷卻管、氮氣導入管、滴下管及攪拌裝置之分離式的4支燒瓶，放入環己酮70.0部，升溫至80℃，以氮氣置換反應容器內之後，藉由滴下管歷經2小時滴下甲基丙烯酸20部、對枯基酚環氧乙烷改質丙烯酸酯(東亞合成股份有限公司製「ARONIX M110」)20部、甲基丙烯酸甲基45部、2-羥乙基甲基丙烯酸酯8.5部及2,2’-偶氮雙異丁腈1.33部之混合物。滴下結束後，進一步繼續反應3小時，獲得樹脂溶液。 In a separate four-piece flask equipped with a thermometer, a cooling tube, a nitrogen inlet tube, a dropping tube, and a stirring device, 70.0 parts of cyclohexanone was placed, and the temperature was raised to 80 ° C. After replacing the inside of the reaction vessel with nitrogen, the tube was passed through the dropping tube. 20 parts of methacrylic acid, 20 parts of p-cumyl phenol ethylene oxide modified acrylate ("ARONIX M110" manufactured by Toagosei Co., Ltd.), 45 methyl methacrylate, and 2-hydroxyethyl group were dropped in 2 hours. A mixture of 8.5 parts of acrylate and 1.33 part of 2,2'-azobisisobutyronitrile. After the completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a resin solution.

接著，停止供給氮氣，對於上面所獲得的樹脂溶液總量，一面注入乾燥空氣1小時一面攪拌，隨後冷卻至室溫。於該冷卻之樹脂溶液，以70℃歷經3小時滴下2-甲基丙烯醯氧乙基異氰酸酯(昭和電工公司製Karenz MOI)6.5部、月桂酸二丁基錫0.08部及環己酮26部之混合物。 Next, the supply of nitrogen gas was stopped, and the total amount of the resin solution obtained above was stirred while injecting dry air for 1 hour, followed by cooling to room temperature. To the cooled resin solution, a mixture of 6.5 parts of 2-methylpropenyloxyethyl isocyanate (Karenz MOI, manufactured by Showa Denko Co., Ltd.), 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone was dropped at 70 ° C for 3 hours.

將所獲得的樹脂溶液取樣約2g，以180℃加熱20分鐘以使其乾燥，測定未揮發成分，根據其測定結果，於先前合成之樹脂溶液添加環己酮，使得未揮發成分成為20重量%而調製成丙烯酸樹脂溶液2。丙烯酸樹 脂之重量平均分子量(Mw)為18000。 The obtained resin solution was sampled by about 2 g, heated at 180 ° C for 20 minutes to be dried, and the nonvolatile component was measured. According to the measurement result, cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile component became 20% by weight. The acrylic resin solution 2 was prepared. Acrylic tree The weight average molecular weight (Mw) of the fat was 18,000.

丙烯酸樹脂溶液3 Acrylic resin solution 3

於具備溫度計、冷卻管、氮氣導入管、滴下管及攪拌裝置之分離式的4支燒瓶，放入環己酮207部，升溫至80℃，以氮氣置換反應容器內之後，藉由滴下管歷經2小時滴下甲基丙烯酸20部、對枯基酚環氧乙烷改質丙烯酸酯(東亞合成股份有限公司製「ARONIX M110」)20部、甲基丙烯酸甲基45部、丙三醇單甲基丙烯酸酯8.5部及2,2’-偶氮雙異丁腈1.33部之混合物。滴下結束後，進一步繼續反應3小時，獲得樹脂溶液。 In a separate four-stage flask equipped with a thermometer, a cooling tube, a nitrogen inlet tube, a dropping tube, and a stirring device, 207 parts of cyclohexanone were placed, and the temperature was raised to 80 ° C. After the reaction vessel was replaced with nitrogen, the tube was passed through the dropping tube. 20 parts of methacrylic acid, 20 parts of p-cumylphenol ethylene oxide modified acrylate ("ARONIX M110" manufactured by Toagosei Co., Ltd.), 45 methyl methacrylate, and glycerol monomethyl group were dropped in 2 hours. A mixture of 8.5 parts of acrylate and 1.33 parts of 2,2'-azobisisobutyronitrile. After the completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a resin solution.

接著，停止供給氮氣，對於上面所獲得的樹脂溶液總量，一面注入乾燥空氣1小時一面攪拌，隨後冷卻至室溫。於該冷卻之樹脂溶液，以70℃歷經3小時滴下2-甲基丙烯醯氧乙基異氰酸酯6.5部、月桂酸二丁基錫0.08部及環己酮26部之混合物。 Next, the supply of nitrogen gas was stopped, and the total amount of the resin solution obtained above was stirred while injecting dry air for 1 hour, followed by cooling to room temperature. To the cooled resin solution, a mixture of 6.5 parts of 2-methylpropenyloxyethyl isocyanate, 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone was dropped at 70 ° C for 3 hours.

將所獲得的樹脂溶液取樣約2g，以180℃加熱20分鐘以使其乾燥，測定未揮發成分，根據其測定值，於先前合成之樹脂溶液添加環己酮，使得未揮發成分成為20重量%而調製成丙烯酸樹脂溶液3。丙烯酸樹脂之重量平均分子量(Mw)為19000。 The obtained resin solution was sampled by about 2 g, heated at 180 ° C for 20 minutes to be dried, and the nonvolatile component was measured. According to the measured value, cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile component became 20% by weight. It was prepared into an acrylic resin solution 3. The weight average molecular weight (Mw) of the acrylic resin was 19,000.

丙烯酸樹脂溶液4 Acrylic resin solution 4

於具備溫度計、冷卻管、氮氣導入管、滴下管及攪拌裝置之分離式的4支燒瓶，放入環己酮370部，升溫至80℃，以氮氣置換反應容器內之後，藉由滴下管歷經2小時滴下對枯基酚環氧乙烷改質丙烯酸酯(東亞合成股份有限公司製「ARONIX M110」)18部、苄基甲基丙烯酸酯10部、縮水甘油基甲基丙烯酸酯18.2部、甲基丙烯酸甲基25部及2,2’-偶氮雙異丁腈2.0 部之混合物。滴下後，以100℃進一步使其反應3小時後，添加令偶氮雙異丁腈1.0部溶解於環己酮50部而成之物，以100℃進一步使其反應1小時。接著，以空氣置換容器內，對上述容器內放入丙烯酸9.3部(丙三醇基之100%)、三二甲基胺苯酚0.5部及對苯二酚0.1部，以120℃繼續反應6小時，於固體成分之酸值成為0.5時結束反應，獲得丙烯酸樹脂之溶液。進而接著加入四氫苯二酸酐19.5部(生成之羥基之100%)、三乙基胺0.5部，以120℃歷經3.5小時使其反應，獲得丙烯酸樹脂之溶液。 In a separate four-piece flask equipped with a thermometer, a cooling tube, a nitrogen inlet tube, a dropping tube, and a stirring device, 370 parts of cyclohexanone were placed, and the temperature was raised to 80 ° C. After replacing the inside of the reaction vessel with nitrogen, the tube was passed through the dropping tube. 18 parts of p-cumyl epoxide modified acrylate ("ARONIX M110" manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, and 18.2 parts of glycidyl methacrylate were added dropwise for 2 hours. Methyl methacrylate 25 and 2,2'-azobisisobutyronitrile 2.0 a mixture of parts. After the dropwise addition, the mixture was further reacted at 100 ° C for 3 hours, and then 1.0 portion of azobisisobutyronitrile was dissolved in 50 parts of cyclohexanone, and further reacted at 100 ° C for 1 hour. Next, the inside of the container was replaced with air, and 9.3 parts (100% of glycerol group), 0.5 part of trimethylaminophenol, and 0.1 part of hydroquinone were placed in the container, and the reaction was continued at 120 ° C for 6 hours. When the acid value of the solid component became 0.5, the reaction was terminated to obtain a solution of an acrylic resin. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl group) and 0.5 part of triethylamine were added, and the mixture was reacted at 120 ° C for 3.5 hours to obtain a solution of an acrylic resin.

將所獲得的丙烯酸樹脂溶液冷卻至室溫後，將其取樣約2g，以180℃加熱20分鐘以使其乾燥，測定未揮發成分，根據其測定值，於上述丙烯酸樹脂溶液添加環己酮，使得未揮發成分成為20重量%而調製成丙烯酸樹脂溶液4。丙烯酸樹脂之重量平均分子量(Mw)為19000。 After cooling the obtained acrylic resin solution to room temperature, it was sampled by about 2 g, heated at 180 ° C for 20 minutes to be dried, and the nonvolatile component was measured, and cyclohexanone was added to the above acrylic resin solution based on the measured value. The non-volatile component was made 20% by weight to prepare an acrylic resin solution 4. The weight average molecular weight (Mw) of the acrylic resin was 19,000.

<於側鏈具有陽離子性基之樹脂之調製> <Preparation of a resin having a cationic group in a side chain>

於側鏈具有陽離子性基之樹脂1 Resin 1 having a cationic group in the side chain

於具備溫度計、攪拌機、蒸餾管、冷卻器之4支分離式的燒瓶，放入甲基乙酮67.3部，於氮氣流下升溫至75℃。另外均勻混合甲基丙烯酸甲酯34.0部、正丁基丙烯酸甲酯28.0部、2-乙基己基丙烯酸甲酯28.0部、二甲基胺乙基丙烯酸甲酯10.0部、2,2’-偶氮雙(2,4-二甲基戊腈)6.5部、及甲基乙酮25.1部後，將所獲得的混合物放入滴下漏斗，將該滴下漏斗安裝於上述4支分離式的燒瓶，歷經2小時滴下該混合物。滴下結束2小時後，從固體成分確認聚合產率為98%，重量平均分子量(Mw)為6830，並冷卻至50℃。於該冷卻後之反應混合物，追加氯化甲基3.2部、乙醇22.0部，以50℃反應2小時後，歷經1小時加溫至80℃，進一步反應2小時。如此獲得樹脂成分47 重量%、於側鏈具有陽離子性基之樹脂1。所獲得的樹脂之銨鹽價為34mgKOH/g。 In a separate flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, 67.3 parts of methyl ethyl ketone was placed, and the temperature was raised to 75 ° C under a nitrogen stream. In addition, 34.0 parts of methyl methacrylate, 28.0 parts of methyl n-butyl acrylate, 28.0 parts of methyl 2-ethylhexyl acrylate, 10.0 parts of methyl dimethylamine ethacrylate, and 2,2'-azo were uniformly mixed. After 6.5 parts of bis(2,4-dimethylvaleronitrile) and 25.1 parts of methyl ethyl ketone, the obtained mixture was placed in a dropping funnel, and the dropping funnel was attached to the above four separate flasks, and it was passed through 2 The mixture was dropped in an hour. Two hours after the end of the dropwise addition, the polymerization yield was confirmed to be 98% from the solid content, the weight average molecular weight (Mw) was 6,830, and it was cooled to 50 °C. To the cooled reaction mixture, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added, and after reacting at 50 ° C for 2 hours, the mixture was heated to 80 ° C over 1 hour, and further reacted for 2 hours. The resin component 47 thus obtained Resin 1 having a weight percentage of a cationic group in a side chain. The ammonium salt value of the obtained resin was 34 mgKOH/g.

在此，於側鏈具有陽離子性基之樹脂之重量平均分子量(Mw)，係藉由以聚苯乙烯作為標準物質之凝膠滲透層析儀(GPC)來測定。又，於側鏈具有陽離子性基之樹脂之銨鹽價係以5%鉻酸鉀水液作為指示藥劑，以0.1N之硝酸銀水溶液進行滴定，求出中和銨鹽基所需之硝酸銀量後，換算為氫氧化鉀之當量值，其表示固體成分之銨鹽價。 Here, the weight average molecular weight (Mw) of the resin having a cationic group in the side chain is measured by a gel permeation chromatography (GPC) using polystyrene as a standard substance. Further, the ammonium salt value of the resin having a cationic group in the side chain is titrated with a 0.1 N aqueous solution of silver nitrate using a 5% potassium chromate aqueous solution as an indicator agent, and the amount of silver nitrate required for neutralizing the ammonium salt group is determined. It is converted into the equivalent value of potassium hydroxide, which represents the ammonium salt value of a solid component.

於側鏈具有陽離子性基之樹脂2 Resin 2 having a cationic group in the side chain

於具備溫度計、攪拌機、蒸餾管、冷卻器之4支分離式的燒瓶，放入異丙醇62.4部，於氮氣流下升溫至75℃。另外均勻混合乙基丙烯酸甲酯32.1部、正丙基丙烯酸甲酯25.1部、月桂基丙烯酸甲酯25.1部、甲基丙烯醯胺丙基三甲基氯化銨17.7部、2,2’-偶氮雙(2,4-二甲基戊腈)5.7部、及乙基乙酮15.6部後，將所獲得的混合物放入滴下漏斗，將該滴下漏斗安裝於上述4支分離式的燒瓶，歷經2小時滴下該混合物。滴下結束2小時後，從固體成分確認聚合產率為98%，重量平均分子量(Mw)為7420，並冷卻至50℃。於該冷卻後之反應混合物，追加異丙醇72部，獲得樹脂成分40重量%、於側鏈具有陽離子性基之樹脂2。所獲得的樹脂之銨鹽價為45mgKOH/g。 In a separate flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, 62.4 parts of isopropyl alcohol was placed, and the temperature was raised to 75 ° C under a nitrogen stream. In addition, 32.1 parts of methyl acrylate, 25.1 parts of methyl propyl acrylate, 25.1 parts of methyl lauryl methacrylate, 17.7 parts of methacrylamidamine propyl trimethyl ammonium chloride, and 2, 2'-even were uniformly mixed. After 5.7 parts of nitrogen bis(2,4-dimethylvaleronitrile) and 15.6 parts of ethyl ethyl ketone, the obtained mixture was placed in a dropping funnel, and the dropping funnel was attached to the above-mentioned four separate flasks. The mixture was dropped over 2 hours. Two hours after the end of the dropwise addition, the polymerization yield was confirmed to be 98% from the solid content, the weight average molecular weight (Mw) was 7,420, and it was cooled to 50 °C. To the cooled reaction mixture, 72 parts of isopropyl alcohol were added to obtain a resin 2 having a resin component of 40% by weight of a resin component and a cationic group in a side chain. The ammonium salt value of the obtained resin was 45 mgKOH/g.

於側鏈具有陽離子性基之樹脂3 Resin 3 having a cationic group in the side chain

於具備溫度計、攪拌機、蒸餾管、冷卻器之4支分離式的燒瓶，放入甲基乙酮67.3部，於氮氣流下升溫至75℃。另外均勻混合異丙基丙烯酸甲酯27.5部、苄基丙烯酸甲酯25.0部、2-乙基己基丙烯酸甲酯27.5部、N,N-二甲基胺甲基苯乙烯20.0部、2,2’-偶氮雙(2,4-二甲基戊腈)6.7部、及 甲基乙酮25.1部後放入滴下漏斗，安裝於4支分離式的燒瓶，歷經2小時滴下。滴下結束2小時後，從固體成分確認聚合產率為98%，重量平均分子量(Mw)為6770，並冷卻至50℃。於該冷卻後之反應混合物，追加氯化苄基15.7部、乙醇22.0部，以50℃反應2小時後，歷經1小時加溫至80℃，進一步反應2小時。如此獲得樹脂成分50重量%、於側鏈具有陽離子性基之樹脂3。所獲得的樹脂之銨鹽價為60mgKOH/g。 In a separate flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, 67.3 parts of methyl ethyl ketone was placed, and the temperature was raised to 75 ° C under a nitrogen stream. In addition, 27.5 parts of methyl isopropyl acrylate, 25.0 parts of methyl benzyl acrylate, 27.5 parts of methyl 2-ethylhexyl acrylate, 20.0 parts of N, N-dimethylaminomethyl styrene, 2, 2' were uniformly mixed. - azobis(2,4-dimethylvaleronitrile) 6.7, and After 25.1 portions of methyl ethyl ketone, they were placed in a dropping funnel, and placed in four separate flasks, and dropped over 2 hours. Two hours after the end of the dropwise addition, the polymerization yield was confirmed to be 98% from the solid content, the weight average molecular weight (Mw) was 6,770, and it was cooled to 50 °C. To the cooled reaction mixture, 15.7 parts of benzyl chloride and 22.0 parts of ethanol were added, and the mixture was reacted at 50 ° C for 2 hours, and then heated to 80 ° C over 1 hour, and further reacted for 2 hours. Thus, the resin 3 having 50% by weight of the resin component and having a cationic group in the side chain was obtained. The obtained ammonium salt value of the resin was 60 mgKOH/g.

於側鏈具有陽離子性基之樹脂4 Resin 4 having a cationic group in the side chain

於具備溫度計、攪拌機、蒸餾管、冷卻器之4支分離式的燒瓶，放入異丙醇62.4部，於氮氣流下升溫至75℃。另外均勻混合甲基丙烯酸甲酯25.0部、硬脂醯丙烯酸甲酯20.0部、環己基丙烯酸甲酯20.0部、BLEMMER PE90(日油公司製、二乙二醇單丙烯酸甲酯)15.0部、N-乙烯基砒喀烷酮20.0部、2,2’-偶氮雙(2,4-二甲基戊腈)4.7部、及異丙醇15.6部後，將所獲得的混合物放入滴下漏斗，將該滴下漏斗安裝於上述4支分離式的燒瓶，歷經2小時滴下該混合物。滴下結束2小時後，從固體成分確認聚合產率為98%，重量平均分子量(Mw)為7550，並冷卻至50℃。於該冷卻後之反應混合物，追加氯化甲基9.0部、異丙醇22.0部，以50℃反應2小時後，歷經1小時加溫至80℃，進一步反應2小時。其後，加入異丙醇50部，獲得樹脂成分44重量%、於側鏈具有陽離子性基之樹脂4。所獲得的樹脂之銨鹽價為92mgKOH/g。 In a separate flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, 62.4 parts of isopropyl alcohol was placed, and the temperature was raised to 75 ° C under a nitrogen stream. In addition, 25.0 parts of methyl methacrylate, 20.0 parts of stearyl acrylate, 20.0 parts of methyl cyclohexyl acrylate, 15.0 parts of BLEMMER PE90 (made by Nippon Oil Co., Ltd., diethylene glycol monomethyl acrylate), N- 20.0 parts of vinyl carbaryl ketone, 4.7 parts of 2,2'-azobis(2,4-dimethylvaleronitrile), and 15.6 parts of isopropyl alcohol, the obtained mixture was placed in a dropping funnel, The dropping funnel was attached to the above four separate flasks, and the mixture was dropped over 2 hours. Two hours after the end of the dropwise addition, the polymerization yield was confirmed to be 98% from the solid content, the weight average molecular weight (Mw) was 7,550, and it was cooled to 50 °C. To the reaction mixture after the cooling, 9.0 parts of methyl chloride and 22.0 parts of isopropyl alcohol were added, and after reacting at 50 ° C for 2 hours, the mixture was heated to 80 ° C over 1 hour, and further reacted for 2 hours. Thereafter, 50 parts of isopropyl alcohol was added to obtain a resin 4 having a resin component of 44% by weight and a cationic group in the side chain. The obtained ammonium salt value of the resin was 92 mgKOH/g.

於側鏈具有陽離子性基之樹脂5 Resin 5 having a cationic group in the side chain

於具備溫度計、攪拌機、蒸餾管、冷卻器之4支分離式的燒瓶，放入甲基乙酮82.0部，於氮氣流下升溫至75℃。另外均勻混合乙基丙烯酸甲酯23.5部、三級丁基丙烯酸甲酯26.0部、月桂基丙烯酸甲酯25.0部、 KAYAMAR PM-21(日本化藥公司製、ε-己內酯1莫耳附加2-羥基乙基丙烯酸甲酯之磷酸酯)10.0部、二乙基胺丙基丙烯酸甲酯17.5部、2,2’-偶氮雙(2,4-二甲基戊腈)6.0部、及甲基乙酮25.6部後，將所獲得的混合物放入滴下漏斗，將該滴下漏斗安裝於上述4支分離式的燒瓶，歷經2小時滴下該混合物。滴下結束2小時後，從固體成分確認聚合產率為98%，重量平均分子量(Mw)為7010，並冷卻至50℃。如此獲得樹脂成分48重量%、於側鏈具有陽離子性基之樹脂5。所獲得的樹脂之銨鹽價為49mgKOH/g。在此，於側鏈具有陽離子性基之樹脂之胺價係利用0.1N之鹽酸水溶液，藉由電位差滴定法求出中和所需之鹽酸量後，換算為氫氧化鉀之當量。 In a separate flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, 82.0 parts of methyl ethyl ketone was placed, and the temperature was raised to 75 ° C under a nitrogen stream. In addition, 23.5 parts of ethyl methacrylate, 26.0 parts of methyl butyl acrylate and 25.0 parts of methyl lauryl acrylate were uniformly mixed. KAYAMAR PM-21 (manufactured by Nippon Kagaku Co., Ltd., ε-caprolactone 1 molar plus 2-hydroxyethyl methacrylate phosphate) 10.0 parts, diethylaminopropyl acrylate 17.5 parts, 2, 2 After -6.0 parts of azobis(2,4-dimethylvaleronitrile) and 25.6 parts of methyl ethyl ketone, the obtained mixture was placed in a dropping funnel, and the dropping funnel was attached to the above-mentioned four-part separation type. The flask was dropped over 2 hours. Two hours after the end of the dropwise addition, the polymerization yield was confirmed to be 98% from the solid content, the weight average molecular weight (Mw) was 7010, and it was cooled to 50 °C. Thus, the resin 5 having a resin component of 48% by weight and having a cationic group in the side chain was obtained. The obtained ammonium salt value of the resin was 49 mgKOH/g. Here, the amine valence of the resin having a cationic group in the side chain is determined by the potentiometric titration method to determine the amount of hydrochloric acid required for neutralization using a 0.1 N aqueous hydrochloric acid solution, and then converted to the equivalent of potassium hydroxide.

<微細化顏料之製作> <Production of Micronized Pigments>

紅色微細化顏料1 Red micronized pigment 1

將二酮吡咯並吡咯系紅色顏料C.I.顏料紅254(日本千葉公司製「IRGAZIN RED 2030」)200部、氯化鈉1400部及二乙二醇360部放入不銹鋼製1加侖捏合機(井上製作所製)，以80℃混合攪拌6小時。接著，將該混合攪拌物放入8公升的溫水中，一面加熱至80℃，一面攪拌2小時而製成漿狀，重複過濾、水洗以去除氯化鈉及二乙二醇後，以85℃乾燥一晝夜，獲得190部的紅色微細化顏料1。紅色微細化顏料1之相對表面積為70m2/g。 200 parts of diketopyrrolopyrrole-based red pigment CI Pigment Red 254 ("IRGAZIN RED 2030" manufactured by Chiba Corporation, Japan), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a 1-gallon kneading machine made of stainless steel (Inoue Manufacturing Co., Ltd.) The mixture was stirred and mixed at 80 ° C for 6 hours. Next, the kneaded material was placed in 8 liters of warm water, heated to 80 ° C, and stirred for 2 hours to form a slurry. The mixture was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then 85 ° C. After drying for a day and night, 190 red fine pigments 1 were obtained. The red micronized pigment 1 has a relative surface area of 70 m 2 /g.

紅色微細化顏料2 Red micronized pigment 2

將蔥醌系紅色顏料C.I.顏料紅177(千葉特殊化學股份有限公司製「CHROMOPHTAL RED A2B」)、氯化鈉1400部及二乙二醇360部放入不銹鋼製1加侖捏合機(井上製作所製)，以80℃混合攪拌6小時。接著，將該混合攪拌物放入8公升的溫水中，一面加熱至80℃，一面攪拌2小時而製成漿 狀，重複過濾、水洗以去除氯化鈉及二乙二醇後，以85℃乾燥一晝夜，獲得190部的紅色微細化顏料2。紅色微細化顏料2之相對表面積為80m2/g。 In the 加 醌 red pigment CI Pigment Red 177 ("CHROMOPHTAL RED A2B" by Chiba Special Chemical Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a stainless steel one-gallon kneader (manufactured by Inoue Co., Ltd.) The mixture was stirred and mixed at 80 ° C for 6 hours. Next, the kneaded material was placed in 8 liters of warm water, heated to 80 ° C, and stirred for 2 hours to form a slurry. The mixture was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then 85 ° C. After drying for a day and night, 190 red fine pigments 2 were obtained. The red micronized pigment 2 has a relative surface area of 80 m 2 /g.

紅色微細化顏料3 Red micronized pigment 3

將紅色顏料C.I.顏料紅242(Clariant公司製「NOVOPERM SCARLET 4RF」)200部、氯化鈉1400部及二乙二醇360部放入不銹鋼製1加侖捏合機(井上製作所製)，以80℃混合攪拌6小時。接著，將該混合攪拌物放入8公升的溫水中，一面加熱至80℃，一面攪拌2小時而製成漿狀，重複過濾、水洗以去除氯化鈉及二乙二醇後，以85℃乾燥一晝夜，獲得190部的紅色微細化顏料3。 200 parts of red pigment CI Pigment Red 242 ("NOVOPERM SCARLET 4RF" by Clariant Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Co., Ltd.) and mixed at 80 ° C. Stir for 6 hours. Next, the kneaded material was placed in 8 liters of warm water, heated to 80 ° C, and stirred for 2 hours to form a slurry. The mixture was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then 85 ° C. After drying for a whole day and night, 190 red fine pigments 3 were obtained.

紅色微細化顏料4 Red micronized pigment 4

將紅色顏料C.I.顏料橘38(Clariant公司製「NOVOPERM RED HFG」)200部、氯化鈉1400部及二乙二醇360部放入不銹鋼製1加侖捏合機(井上製作所製)，以80℃混合攪拌6小時。接著，將該混合攪拌物放入8公升的溫水中，一面加熱至80℃，一面攪拌2小時而製成漿狀，重複過濾、水洗以去除氯化鈉及二乙二醇後，以85℃乾燥一晝夜，獲得190部的紅色微細化顏料4。 200 pieces of red pigment CI Pigment Orange 38 ("NOVOPERM RED HFG" by Clariant Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and mixed at 80 ° C. Stir for 6 hours. Next, the kneaded material was placed in 8 liters of warm water, heated to 80 ° C, and stirred for 2 hours to form a slurry. The mixture was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then 85 ° C. After drying for a day and night, 190 red fine pigments 4 were obtained.

紅色微細化顏料5 Red micronized pigment 5

將紅色顏料C.I.顏料紅166(BASF公司製「Cromophtal Scarlet RN」)200部、氯化鈉1400部及二乙二醇360部放入不銹鋼製1加侖捏合機(井上製作所製)，以80℃混合攪拌6小時。接著，將該混合攪拌物放入8公升的溫水中，一面加熱至80℃，一面攪拌2小時而製成漿狀，重複過濾、水洗以去除氯化鈉及二乙二醇後，以85℃乾燥一晝夜，獲得190部的紅色微細化顏 料5。 200 pieces of red pigment CI Pigment Red 166 ("Cromophtal Scarlet RN" manufactured by BASF Corporation), 1400 parts of sodium chloride and 360 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and mixed at 80 ° C. Stir for 6 hours. Next, the kneaded material was placed in 8 liters of warm water, heated to 80 ° C, and stirred for 2 hours to form a slurry. The mixture was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then 85 ° C. Dry for a long night, get 190 red fines Material 5.

紅色微細化顏料6 Red micronized pigment 6

將紅色顏料C.I.顏料紅220(BASF公司製「Cromophtal Red G」)200部、氯化鈉1400部及二乙二醇360部放入不銹鋼製1加侖捏合機(井上製作所製)，以80℃混合攪拌6小時。接著，將該混合攪拌物放入8公升的溫水中，一面加熱至80℃，一面攪拌2小時而製成漿狀，重複過濾、水洗以去除氯化鈉及二乙二醇後，以85℃乾燥一晝夜，獲得190部的紅色微細化顏料6。 200 pieces of red pigment CI Pigment Red 220 ("Cromophtal Red G" manufactured by BASF Corporation), 1400 parts of sodium chloride and 360 parts of diethylene glycol were placed in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and mixed at 80 ° C. Stir for 6 hours. Next, the kneaded material was placed in 8 liters of warm water, heated to 80 ° C, and stirred for 2 hours to form a slurry. The mixture was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then 85 ° C. After drying for a day and night, 190 red fine pigments 6 were obtained.

紅色微細化顏料7 Red micronized pigment 7

將紅色顏料C.I.顏料紅48：1(東洋墨水製造股份有限公司製「LIONOL RED TT-4801G」)200部、氯化鈉1400部及二乙二醇360部放入不銹鋼製1加侖捏合機(井上製作所製)，以80℃混合攪拌6小時。接著，將該混合攪拌物放入8公升的溫水中，一面加熱至80℃，一面攪拌2小時而製成漿狀，重複過濾、水洗以去除氯化鈉及二乙二醇後，以85℃乾燥一晝夜，獲得190部的紅色微細化顏料7。 200 pieces of red pigment CI Pigment Red 48:1 ("LIONOL RED TT-4801G" manufactured by Toyo Ink Co., Ltd.), 1400 parts of sodium chloride and 360 parts of diethylene glycol were placed in a stainless steel 1 gallon kneader (Inoue The product was mixed and stirred at 80 ° C for 6 hours. Next, the kneaded material was placed in 8 liters of warm water, heated to 80 ° C, and stirred for 2 hours to form a slurry. The mixture was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then 85 ° C. After drying for a day and night, 190 red fine pigments 7 were obtained.

黃色微細化顏料1 Yellow micronized pigment 1

將鎳錯合物系黃色顏料C.I.顏料黃150(LANXESS公司製「E-4GN」)200部、氯化鈉1400部及二乙二醇360部放入不銹鋼製1加侖捏合機(井上製作所製)，以80℃混合攪拌6小時。接著，將該混合攪拌物放入8公升的溫水中，一面加熱至80℃，一面攪拌2小時而製成漿狀，重複過濾、水洗以去除氯化鈉及二乙二醇後，以85℃乾燥一晝夜，獲得190部的黃色微細化顏料1。黃色微細化顏料1之相對表面積為65m2/g。 200 parts of nickel complex compound yellow pigment CI Pigment Yellow 150 ("E-4GN" manufactured by LANXESS Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) The mixture was stirred and mixed at 80 ° C for 6 hours. Next, the kneaded material was placed in 8 liters of warm water, heated to 80 ° C, and stirred for 2 hours to form a slurry. The mixture was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then 85 ° C. After drying for a day and night, 190 yellow fine pigments 1 were obtained. The yellow fine pigment 1 has a relative surface area of 65 m 2 /g.

黃色微細化顏料2 Yellow micronized pigment 2

將鎳錯合物系黃色顏料C.I.顏料黃150(東洋墨水製造股份有限公司製「LIONOGEN YELLOW DT1200」)200部、氯化鈉1400部及二乙二醇360部放入不銹鋼製1加侖捏合機(井上製作所製)，以80℃混合攪拌6小時。接著，將該混合攪拌物放入8公升的溫水中，一面加熱至80℃，一面攪拌2小時而製成漿狀，重複過濾、水洗以去除氯化鈉及二乙二醇後，以85℃乾燥一晝夜，獲得190部的黃色微細化顏料2。 200 parts of nickel complex compound yellow pigment CI Pigment Yellow 150 ("LIONOGEN YELLOW DT1200" manufactured by Toyo Ink Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a 1-gallon kneader made of stainless steel ( It was mixed and stirred at 80 ° C for 6 hours. Next, the kneaded material was placed in 8 liters of warm water, heated to 80 ° C, and stirred for 2 hours to form a slurry. The mixture was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then 85 ° C. After drying for a day and night, 190 yellow fine pigments 2 were obtained.

藍色微細化顏料1 Blue micronized pigment 1

將酞菁系藍色顏料之C.I.顏料藍15：6(東洋墨水製造股份有限公司製「Lionol Blue ES」)200部、氯化鈉1400部及二乙二醇360部放入不銹鋼製1加侖捏合機(井上製作所製)，以80℃混合攪拌6小時。接著，將該混合攪拌物放入8公升的溫水中，一面加熱至80℃，一面攪拌2小時而製成漿狀，重複過濾、水洗以去除氯化鈉及二乙二醇後，以85℃乾燥一晝夜，獲得190部的藍色微細化顏料1。藍色微細化顏料1之相對表面積為80m2/g。 200 pieces of CI Pigment Blue 15:6 ("Lionol Blue ES" manufactured by Toyo Ink Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a stainless steel one-gallon kneading. The machine (manufactured by Inoue Seisakusho Co., Ltd.) was mixed and stirred at 80 ° C for 6 hours. Next, the kneaded material was placed in 8 liters of warm water, heated to 80 ° C, and stirred for 2 hours to form a slurry. The mixture was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then 85 ° C. After drying for a whole day and night, 190 blue fine pigments 1 were obtained. The relative surface area of the blue fine pigment 1 was 80 m 2 /g.

紫色微細化顏料1 Purple micronized pigment 1

將二噁嗪系紫色色顏料之C.I.顏料紫23(東洋墨水製造公司製「LIONOGEN VIOLET RL」)200部、氯化鈉1400部及二乙二醇360部放入不銹鋼製1加侖捏合機(井上製作所製)，以80℃混合攪拌6小時。接著，將該混合攪拌物放入8公升的溫水中，一面加熱至80℃，一面攪拌2小時而製成漿狀，重複過濾、水洗以去除氯化鈉及二乙二醇後，以85℃乾燥一晝夜，獲得190部的紫色微細化顏料1。紫色微細化顏料1之相對表面積為95m2/g。 200 pieces of CI Pigment Violet 23 ("LIONOGEN VIOLET RL" made by Toyo Ink Co., Ltd.), 1400 parts of sodium chloride and 360 parts of diethylene glycol were placed in a stainless steel 1 gallon kneader (Inoue) The product was mixed and stirred at 80 ° C for 6 hours. Next, the kneaded material was placed in 8 liters of warm water, heated to 80 ° C, and stirred for 2 hours to form a slurry. The mixture was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then 85 ° C. After drying for a day and night, 190 purple fine pigments 1 were obtained. The purple fine refining pigment 1 has a relative surface area of 95 m 2 /g.

綠色微細化顏料1 Green micronized pigment 1

將酞菁系綠色顏料之C.I.顏料綠36(東洋墨水製造股份有限 公司製「Lionol Green 6YK」)200部、氯化鈉1400部及二乙二醇360部放入不銹鋼製1加侖捏合機(井上製作所製)，以80℃混合攪拌6小時。接著，將該混合攪拌物放入8公升的溫水中，一面加熱至80℃，一面攪拌2小時而製成漿狀，重複過濾、水洗以去除氯化鈉及二乙二醇後，以85℃乾燥一晝夜，獲得190部的綠色微細化顏料1。綠色微細化顏料1之相對表面積為75m2/g。 200 pieces of CI Pigment Green 36 ("Lionol Green 6YK" manufactured by Toyo Ink Co., Ltd.), 1400 parts of sodium chloride and 360 parts of diethylene glycol were placed in a stainless steel 1 gallon kneader (Inoue) The product was mixed and stirred at 80 ° C for 6 hours. Next, the kneaded material was placed in 8 liters of warm water, heated to 80 ° C, and stirred for 2 hours to form a slurry. The mixture was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then 85 ° C. After drying for a day and night, 190 green fine pigments 1 were obtained. The green fine refining pigment 1 has a relative surface area of 75 m 2 /g.

<鹵化生成物(A)之製造> <Manufacture of halogenated product (A)>

鹵化生成物(A-1) Halogenated product (A-1)

採下述程序，製作由C.I.酸性紅52及二硬脂醯二甲基氯化銨(QUARTAMIN D86P)(陽離子部分之分子量550)所組成的鹵化生成物(A-1)。 The halogenated product (A-1) consisting of C.I. Acid Red 52 and distearyl dimethylammonium chloride (QUARTAMIN D86P) (molecular weight of the cationic moiety 550) was prepared by the following procedure.

於7~15莫耳%之氫氧化鈉溶液中，令C.I.酸性紅52溶解，充分進行混合‧攪拌，加熱至70~90℃後，逐次些許滴下QUARTAMIN D86P(再者，QUARTAMIN D86P溶解於水而作為水溶液使用亦可)。滴下QUARTAMIN D86P後，以70~90℃攪拌60分鐘，充分進行反應。反應終點之確認係於濾紙滴下反應液，不會滲開時即為終點，可判斷獲得鹵化生成物。其後，一面攪拌所獲得的反應混合物，一面放冷到室溫後，進行吸引過濾，水洗後，以乾燥機將殘留於濾紙上之鹵化生成物去除水分予以乾燥，獲得C.I.酸性紅52與二硬脂醯二甲基氯化銨之鹵化生成物(鹵化生成物(A-1))。 In 7~15 mol% sodium hydroxide solution, dissolve CI Acid Red 52, mix thoroughly, stir, heat to 70-90 °C, and then drop QUARTAMIN D86P several times (again, QUARTAMIN D86P is dissolved in water) It can also be used as an aqueous solution). After dropping QUARTAMIN D86P, the mixture was stirred at 70 to 90 ° C for 60 minutes to sufficiently carry out the reaction. The end point of the reaction was confirmed by dropping the reaction liquid on the filter paper, and the end point was not bleed, and it was judged that the halogenated product was obtained. Thereafter, the obtained reaction mixture was stirred while being allowed to cool to room temperature, and then suction-filtered, and after washing with water, the halogenated product remaining on the filter paper was removed by a dryer and dried to obtain CI Acid Red 52 and II. A halogenated product of stearyl dimethylammonium chloride (halogenated product (A-1)).

鹵化生成物(A-2) Halogenated product (A-2)

採下述程序，製作由C.I.酸性紅52及二硬脂醯二甲基氯化銨(陽離子部分之分子量382)所組成的鹵化生成物(A-2)。 The halogenated product (A-2) consisting of C.I. Acid Red 52 and distearyl dimethylammonium chloride (molecular weight 382 of the cationic moiety) was produced by the following procedure.

於7~15莫耳%之氫氧化鈉溶液中，令C.I.酸性紅52溶解，充分進行混合‧攪拌，加熱至70~90℃後，逐次些許滴下二硬脂醯二甲基氯化 銨(再者，二硬脂醯二甲基氯化銨溶解於水而作為水溶液使用亦可)。滴下二硬脂醯二甲基氯化銨後，以70~90℃攪拌60分鐘，充分進行反應。反應終點之確認係於濾紙滴下反應液，不會滲開時即為終點，可判斷獲得鹵化生成物。其後，一面攪拌所獲得的反應混合物，一面放冷到室溫後，進行吸引過濾，水洗後，以乾燥機將殘留於濾紙上之鹵化生成物去除水分予以乾燥，獲得C.I.酸性紅52與二硬脂醯二甲基氯化銨之鹵化生成物(鹵化生成物(A-2))。 In 7~15 mol% sodium hydroxide solution, dissolve C.I. acid red 52, mix thoroughly, stir, heat to 70-90 ° C, and then drip the distearyl dimethyl chloride Ammonium (in addition, distearyl dimethyl ammonium chloride is dissolved in water and used as an aqueous solution). After dropping distearyl dimethyl ammonium chloride, the mixture was stirred at 70 to 90 ° C for 60 minutes to sufficiently carry out the reaction. The end point of the reaction was confirmed by dropping the reaction liquid on the filter paper, and the end point was not bleed, and it was judged that the halogenated product was obtained. Thereafter, the obtained reaction mixture was stirred while being allowed to cool to room temperature, and then suction-filtered, and after washing with water, the halogenated product remaining on the filter paper was removed by a dryer and dried to obtain CI Acid Red 52 and II. A halogenated product of stearyl dimethylammonium chloride (halogenated product (A-2)).

鹵化生成物(A-3) Halogenated product (A-3)

採下述程序，製作由C.I.酸性紅52及三硬脂醯單甲基氯化銨(陽離子部分之分子量788)所組成的鹵化生成物(A-3)。 The halogenated product (A-3) consisting of C.I. Acid Red 52 and tristearate monomethylammonium chloride (molecular weight 788 of the cationic moiety) was produced by the following procedure.

於7~15莫耳%之氫氧化鈉溶液中，令C.I.酸性紅52溶解，充分進行混合‧攪拌，加熱至70~90℃後，逐次些許滴下三硬脂醯二甲基氯化銨(再者，三硬脂醯單甲基氯化銨溶解於水而作為水溶液使用亦可)。滴下三硬脂醯單甲基氯化銨後，以70~90℃攪拌60分鐘，充分進行反應。反應終點之確認係於濾紙滴下反應液，不會滲開時即為終點，可判斷獲得鹵化生成物。其後，一面攪拌所獲得的反應混合物，一面放冷到室溫後，進行吸引過濾，水洗後，以乾燥機將殘留於濾紙上之鹵化生成物去除水分予以乾燥，獲得C.I.酸性紅52與三硬脂醯單甲基氯化銨之鹵化生成物(鹵化生成物(A-3))。 In 7~15 mol% sodium hydroxide solution, dissolve CI Acid Red 52, mix thoroughly, stir, heat to 70-90 °C, and then drop tristearate dimethylammonium chloride a little later (again The tristearic acid monomethylammonium chloride is dissolved in water and used as an aqueous solution). After dropping tristearyl monomethylammonium chloride, the mixture was stirred at 70 to 90 ° C for 60 minutes to sufficiently carry out the reaction. The end point of the reaction was confirmed by dropping the reaction liquid on the filter paper, and the end point was not bleed, and it was judged that the halogenated product was obtained. Thereafter, the obtained reaction mixture was stirred while being allowed to cool to room temperature, and then subjected to suction filtration. After washing with water, the halogenated product remaining on the filter paper was removed by a dryer and dried to obtain CI Acid Red 52 and III. A halogenated product of a stearin monomethylammonium chloride (halogenated product (A-3)).

鹵化生成物(A-4) Halogenated product (A-4)

採下述程序，製作由C.I.酸性紅289及二硬脂醯二甲基氯化銨(QUARTAMIN D86P)(陽離子部分之分子量550)所組成的鹵化生成物(A-4)。 A halogenated product (A-4) composed of C.I. Acid Red 289 and distearyl dimethylammonium chloride (QUARTAMIN D86P) (having a molecular weight of 550 in the cationic portion) was produced by the following procedure.

於7~15莫耳%之氫氧化鈉溶液中，令C.I.酸性紅289溶解，充分進行混合‧攪拌，加熱至70~90℃後，逐次些許滴下QUARTAMIN D86P(再者，QUARTAMIN D86P溶解於水而作為水溶液使用亦可)。滴下QUARTAMIN D86P後，以70~90℃攪拌60分鐘，充分進行反應。反應終點之確認係於濾紙滴下反應液，不會滲開時即為終點，可判斷獲得鹵化生成物。其後，一面攪拌所獲得的反應混合物，一面放冷到室溫後，進行吸引過濾，水洗後，以乾燥機將殘留於濾紙上之鹵化生成物去除水分予以乾燥，獲得C.I.酸性紅289與二硬脂醯二甲基氯化銨之鹵化生成物(鹵化生成物(A-4))。 In 7~15 mol% sodium hydroxide solution, dissolve CI Acid Red 289, mix thoroughly, stir, heat to 70~90 °C, then drop QUARTAMIN D86P one by one (again, QUARTAMIN D86P is dissolved in water) It can also be used as an aqueous solution). After dropping QUARTAMIN D86P, the mixture was stirred at 70 to 90 ° C for 60 minutes to sufficiently carry out the reaction. The end point of the reaction was confirmed by dropping the reaction liquid on the filter paper, and the end point was not bleed, and it was judged that the halogenated product was obtained. Thereafter, the obtained reaction mixture was stirred while being allowed to cool to room temperature, and then suction-filtered, and after washing with water, the halogenated product remaining on the filter paper was removed by a dryer and dried to obtain CI Acid Red 289 and II. A halogenated product of a stearin dimethyl ammonium chloride (halogenated product (A-4)).

鹵化生成物(A-5) Halogenated product (A-5)

採下述程序，製作由C.I.酸性紅87及二硬脂醯二甲基氯化銨(QUARTAMIN D86P)(陽離子部分之分子量550)所組成的鹵化生成物(A-5)。 The halogenated product (A-5) consisting of C.I. Acid Red 87 and distearyl dimethylammonium chloride (QUARTAMIN D86P) (molecular weight of the cationic moiety 550) was prepared by the following procedure.

於7~15莫耳%之氫氧化鈉溶液中，令C.I.酸性紅87溶解，充分進行混合‧攪拌，加熱至70~90℃後，逐次些許滴下QUARTAMIN D86P(再者，QUARTAMIN D86P溶解於水而作為水溶液使用亦可)。滴下QUARTAMIN D86P後，以70~90℃攪拌60分鐘，充分進行反應。反應終點之確認係於濾紙滴下反應液，不會滲開時即為終點，可判斷獲得鹵化生成物。其後，一面攪拌所獲得的反應混合物，一面放冷到室溫後，進行吸引過濾，水洗後，以乾燥機將殘留於濾紙上之鹵化生成物去除水分予以乾燥，獲得C.I.酸性紅87與二硬脂醯二甲基氯化銨之鹵化生成物(鹵化生成物(A-5))。 In 7~15 mol% sodium hydroxide solution, dissolve CI Acid Red 87, mix thoroughly, stir, heat to 70-90 °C, and then drop QUARTAMIN D86P one by one (again, QUARTAMIN D86P is dissolved in water) It can also be used as an aqueous solution). After dropping QUARTAMIN D86P, the mixture was stirred at 70 to 90 ° C for 60 minutes to sufficiently carry out the reaction. The end point of the reaction was confirmed by dropping the reaction liquid on the filter paper, and the end point was not bleed, and it was judged that the halogenated product was obtained. Thereafter, the obtained reaction mixture was stirred while being allowed to cool to room temperature, and then suction-filtered, and after washing with water, the halogenated product remaining on the filter paper was removed by a dryer and dried to obtain CI Acid Red 87 and II. A halogenated product of stearyl dimethylammonium chloride (halogenated product (A-5)).

鹵化生成物(A-6) Halogenated product (A-6)

採下述程序，製作由C.I.酸性紅92及三硬脂醯單甲基氯化銨 (陽離子部分之分子量612)所組成的鹵化生成物(A-6)。 The following procedure was used to prepare C.I. Acid Red 92 and tristearate monomethylammonium chloride. A halogenated product (A-6) composed of (molecular weight 612 of a cationic moiety).

於7~15莫耳%之氫氧化鈉溶液中，令C.I.酸性紅92溶解，充分進行混合‧攪拌，加熱至70~90℃後，逐次些許滴下三硬脂醯二甲基氯化銨(再者，三硬脂醯單甲基氯化銨溶解於水而作為水溶液使用亦可)。滴下三硬脂醯單甲基氯化銨後，以70~90℃攪拌60分鐘，充分進行反應。反應終點之確認係於濾紙滴下反應液，不會滲開時即為終點，可判斷獲得鹵化生成物。其後，一面攪拌所獲得的反應混合物，一面放冷到室溫後，進行吸引過濾，水洗後，以乾燥機將殘留於濾紙上之鹵化生成物去除水分予以乾燥，獲得C.I.酸性紅92與三硬脂醯單甲基氯化銨之鹵化生成物(鹵化生成物(A-6))。 In 7~15 mol% sodium hydroxide solution, dissolve CI Acid Red 92, mix thoroughly, stir, heat to 70-90 °C, and then drop tristearate dimethylammonium chloride a little later (again The tristearic acid monomethylammonium chloride is dissolved in water and used as an aqueous solution). After dropping tristearyl monomethylammonium chloride, the mixture was stirred at 70 to 90 ° C for 60 minutes to sufficiently carry out the reaction. The end point of the reaction was confirmed by dropping the reaction liquid on the filter paper, and the end point was not bleed, and it was judged that the halogenated product was obtained. Thereafter, the obtained reaction mixture was stirred while being allowed to cool to room temperature, and then suction-filtered, and after washing with water, the halogenated product remaining on the filter paper was removed by a dryer and dried to obtain CI Acid Red 92 and III. A halogenated product of a stearin monomethylammonium chloride (halogenated product (A-6)).

鹵化生成物(A-7) Halogenated product (A-7)

採下述程序，製作由C.I.酸性紅388及二硬脂醯二甲基氯化銨(QUARTAMIN D86P)(陽離子部分之分子量550)所組成的鹵化生成物(A-7)。 A halogenated product (A-7) composed of C.I. Acid Red 388 and distearyl dimethylammonium chloride (QUARTAMIN D86P) (having a molecular weight of 550 in the cationic portion) was produced by the following procedure.

於7~15莫耳%之氫氧化鈉溶液中，令C.I.酸性紅388溶解，充分進行混合‧攪拌，加熱至70~90℃後，逐次些許滴下QUARTAMIN D86P(再者，QUARTAMIN D86P溶解於水而作為水溶液使用亦可)。滴下QUARTAMIN D86P後，以70~90℃攪拌60分鐘，充分進行反應。反應終點之確認係於濾紙滴下反應液，不會滲開時即為終點，可判斷獲得鹵化生成物。其後，一面攪拌所獲得的反應混合物，一面放冷到室溫後，進行吸引過濾，水洗後，以乾燥機將殘留於濾紙上之鹵化生成物去除水分予以乾燥，獲得C.I.酸性紅388與二硬脂醯二甲基氯化銨之鹵化生成物(鹵化生成物(A-7))。 In 7~15 mol% sodium hydroxide solution, dissolve CI Acid Red 388, mix thoroughly, stir, heat to 70~90 °C, then drop QUARTAMIN D86P one by one (again, QUARTAMIN D86P is dissolved in water) It can also be used as an aqueous solution). After dropping QUARTAMIN D86P, the mixture was stirred at 70 to 90 ° C for 60 minutes to sufficiently carry out the reaction. The end point of the reaction was confirmed by dropping the reaction liquid on the filter paper, and the end point was not bleed, and it was judged that the halogenated product was obtained. Thereafter, the obtained reaction mixture was stirred while being allowed to cool to room temperature, and then suction-filtered, and after washing with water, the halogenated product remaining on the filter paper was removed by a dryer and dried to obtain CI Acid Red 388 and II. A halogenated product of a stearin dimethyl ammonium chloride (halogenated product (A-7)).

鹵化生成物(A-8) Halogenated product (A-8)

採下述程序，製作由C.I.酸性紅52及二烷基(烷基為C14~C18)二甲基氯化銨(Arquad 2HT-75)(陽離子部分之分子量438~550)所組成的鹵化生成物(A-8)。 The following procedure was used to prepare a halogenated product consisting of CI Acid Red 52 and a dialkyl (alkyl group C14 to C18) dimethyl ammonium chloride (Arquad 2HT-75) (having a molecular weight of 438 to 550 in the cationic portion). (A-8).

於7~15莫耳%之氫氧化鈉溶液中，令C.I.酸性紅52溶解，充分進行混合‧攪拌，加熱至70~90℃後，逐次些許滴下Arquad 2HT-75。又，Arquad 2HT-75溶解於水而作為水溶液使用亦可。滴下Arquad 2HT-75後，以70~90℃攪拌60分鐘，充分進行反應。反應終點之確認係於濾紙滴下反應液，不會滲開時即為終點，可判斷獲得鹵化生成物。其後，一面攪拌所獲得的反應混合物，一面放冷到室溫後，進行吸引過濾，水洗後，以乾燥機將殘留於濾紙上之鹵化生成物去除水分予以乾燥，獲得C.I.酸性紅52與二烷基(烷基為C14~C18)二甲基氯化銨(Arquad 2HT-75)之鹵化生成物(鹵化生成物(A-8))。 In 7~15 mol% sodium hydroxide solution, C.I. Acid Red 52 was dissolved, mixed thoroughly, stirred, heated to 70-90 ° C, and then Arquad 2HT-75 was added dropwise. Further, Arquad 2HT-75 may be dissolved in water and used as an aqueous solution. After dropping Arquad 2HT-75, the mixture was stirred at 70 to 90 ° C for 60 minutes to sufficiently carry out the reaction. The end point of the reaction was confirmed by dropping the reaction liquid on the filter paper, and the end point was not bleed, and it was judged that the halogenated product was obtained. Thereafter, the obtained reaction mixture was stirred while being allowed to cool to room temperature, and then suction-filtered, and after washing with water, the halogenated product remaining on the filter paper was removed by a dryer and dried to obtain CI Acid Red 52 and II. A halogenated product (halogenated product (A-8)) of an alkyl group (alkyl group is C14 to C18) dimethylammonium chloride (Arquad 2HT-75).

鹵化生成物(A-9) Halogenated product (A-9)

採下述程序，製作由C.I.酸性紅289及二烷基(烷基為C14~C18)二甲基氯化銨(Arquad 2HT-75)(陽離子部分之分子量438~550)所組成的鹵化生成物(A-9)。 The halogenated product consisting of CI Acid Red 289 and dialkyl (alkyl C14-C18) dimethylammonium chloride (Arquad 2HT-75) (molecular weight of the cationic moiety 438-550) was prepared by the following procedure. (A-9).

於7~15莫耳%之氫氧化鈉溶液中，令C.I.酸性紅289溶解，充分進行混合‧攪拌，加熱至70~90℃後，逐次些許滴下Arquad 2HT-75(再者，Arquad 2HT-75溶解於水而作為水溶液使用亦可)。滴下Arquad 2HT-75後，以70~90℃攪拌60分鐘，充分進行反應。反應終點之確認係於濾紙滴下反應液，不會滲開時即為終點，可判斷獲得鹵化生成物。其後，一面攪拌 所獲得的反應混合物，一面放冷到室溫後，進行吸引過濾，水洗後，以乾燥機將殘留於濾紙上之鹵化生成物去除水分予以乾燥，獲得C.I.酸性紅289與二烷基(烷基為C14~C18)二甲基氯化銨(Arquad 2HT-75)之鹵化生成物(鹵化生成物(A-9))。 In 7~15 mol% sodium hydroxide solution, dissolve CI Acid Red 289, mix thoroughly, stir, heat to 70-90 °C, and then drop Arquad 2HT-75 (again, Arquad 2HT-75) It can be dissolved in water and used as an aqueous solution). After dropping Arquad 2HT-75, the mixture was stirred at 70 to 90 ° C for 60 minutes to sufficiently carry out the reaction. The end point of the reaction was confirmed by dropping the reaction liquid on the filter paper, and the end point was not bleed, and it was judged that the halogenated product was obtained. Then, stirring on one side The obtained reaction mixture is allowed to be suction-filtered while being allowed to cool to room temperature, and after washing with water, the halogenated product remaining on the filter paper is removed by a dryer and dried to obtain CI Acid Red 289 and a dialkyl group (alkyl group). It is a halogenated product (halogenated product (A-9)) of C14 to C18) dimethylammonium chloride (Arquad 2HT-75).

鹵化生成物(A-10) Halogenated product (A-10)

採下述程序，製作由C.I.酸性紅52及單月桂基三甲基氯化銨(陽離子部分之分子量228)所組成的鹵化生成物(A-10)。 The halogenated product (A-10) consisting of C.I. Acid Red 52 and monolauryl trimethylammonium chloride (molecular weight 228 of the cationic moiety) was produced by the following procedure.

於7~15莫耳%之氫氧化鈉溶液中，令C.I.酸性紅52溶解，充分進行混合‧攪拌，加熱至70~90℃後，逐次些許滴下單月桂基三甲基氯化銨(再者，單月桂基三甲基氯化銨溶解於水而作為水溶液使用亦可)。滴下單月桂基三甲基氯化銨後，以70~90℃攪拌60分鐘，充分進行反應。反應終點之確認係於濾紙滴下反應液，不會滲開時即為終點，可判斷獲得鹵化生成物。其後，一面攪拌所獲得的反應混合物，一面放冷到室溫後，進行吸引過濾，水洗後，以乾燥機將殘留於濾紙上之鹵化生成物去除水分予以乾燥，獲得C.I.酸性紅52與單月桂基三甲基氯化銨之鹵化生成物(鹵化生成物(A-10))。 In 7~15 mol% sodium hydroxide solution, dissolve CI acid red 52, mix thoroughly, stir, heat to 70~90 °C, and then drop monolauryl trimethylammonium chloride (again , monolauryl trimethyl ammonium chloride is dissolved in water and used as an aqueous solution). After the monolauryl trimethylammonium chloride was dropped, the mixture was stirred at 70 to 90 ° C for 60 minutes to sufficiently carry out the reaction. The end point of the reaction was confirmed by dropping the reaction liquid on the filter paper, and the end point was not bleed, and it was judged that the halogenated product was obtained. Thereafter, the obtained reaction mixture was stirred while being allowed to cool to room temperature, and then suction-filtered, and after washing with water, the halogenated product remaining on the filter paper was removed by a dryer and dried to obtain CI Acid Red 52 and a single Halogenated product of lauryl trimethylammonium chloride (halogenated product (A-10)).

鹵化生成物(A-11) Halogenated product (A-11)

採下述程序，製作由C.I.酸性紅52及四乙基氯化銨(陽離子部分之分子量122)所組成的鹵化生成物(A-11)。 The halogenated product (A-11) consisting of C.I. Acid Red 52 and tetraethylammonium chloride (molecular weight 122 of the cationic moiety) was produced by the following procedure.

於7~15莫耳%之氫氧化鈉溶液中，令C.I.酸性紅52溶解，充分進行混合‧攪拌，加熱至70~90℃後，逐次些許滴下四乙基氯化銨(再者，四乙基氯化銨溶解於水而作為水溶液使用亦可)。滴下四乙基氯化銨後，以 70~90℃攪拌60分鐘，充分進行反應。反應終點之確認係於濾紙滴下反應液，不會滲開時即為終點，可判斷獲得鹵化生成物。其後，一面攪拌所獲得的反應混合物，一面放冷到室溫後，進行吸引過濾，水洗後，以乾燥機將殘留於濾紙上之鹵化生成物去除水分予以乾燥，獲得C.I.酸性紅52與四乙基氯化銨之鹵化生成物(鹵化生成物(A-11))。 In 7~15 mol% sodium hydroxide solution, dissolve CI acid red 52, mix thoroughly, stir, heat to 70~90 °C, and then drop tetraethylammonium chloride a little bit (again, four The ammonium chloride is dissolved in water and used as an aqueous solution). After dropping tetraethylammonium chloride, Stir at 70 to 90 ° C for 60 minutes to fully carry out the reaction. The end point of the reaction was confirmed by dropping the reaction liquid on the filter paper, and the end point was not bleed, and it was judged that the halogenated product was obtained. Thereafter, the obtained reaction mixture was stirred while being allowed to cool to room temperature, and then suction-filtered, and after washing with water, the halogenated product remaining on the filter paper was removed by a dryer and dried to obtain CI Acid Red 52 and 4. Halogenated product of ethyl ammonium chloride (halogenated product (A-11)).

鹵化生成物(A-12) Halogenated product (A-12)

除了將鹵化生成物(A-8)之C.I.酸性紅52改變為C.I.酸性紅87以外，均與鹵化生成物(A-8)同樣地獲得鹵化生成物(A-12)。 The halogenated product (A-12) was obtained in the same manner as the halogenated product (A-8) except that the C.I. acid red 52 of the halogenated product (A-8) was changed to C.I. acid red 87.

鹵化生成物(A-13) Halogenated product (A-13)

除了將鹵化生成物(A-8)之C.I.酸性紅52改變為C.I.酸性紅92以外，均與鹵化生成物(A-8)同樣地獲得鹵化生成物(A-13)。 The halogenated product (A-13) was obtained in the same manner as the halogenated product (A-8) except that the C.I. acid red 52 of the halogenated product (A-8) was changed to C.I. acid red 92.

鹵化生成物(A-14) Halogenated product (A-14)

除了將鹵化生成物(A-8)之C.I.酸性紅52改變為C.I.酸性紅388以外，均與鹵化生成物(A-8)同樣地獲得鹵化生成物(A-14)。 The halogenated product (A-14) was obtained in the same manner as the halogenated product (A-8) except that the C.I. acid red 52 of the halogenated product (A-8) was changed to C.I. acid red 388.

鹵化生成物(A2-1) Halogenated product (A2-1)

採下述程序，製作由C.I.酸性紅52及側鏈具有陽離子性基之樹脂1所組成的鹵化生成物(A2-1)。 The halogenated product (A2-1) composed of C.I. Acid Red 52 and a resin 1 having a cationic group in a side chain was produced by the following procedure.

於水2000部添加側鏈具有陽離子性基之樹脂1，充分攪拌混合後，加熱至60℃。另，調製於90部之水中，令10部之C.I.酸性紅52溶解而成之水溶液，於先前之樹脂溶液逐次些許滴下。滴下後，以60℃攪拌120分鐘，充分進行反應。反應終點之確認係於濾紙滴下反應液，不會滲開時即為終點，可判斷獲得鹵化生成物。其後，一面攪拌所獲得的反應混合物， 一面放冷到室溫後，進行吸引過濾，水洗後，以乾燥機將殘留於濾紙上之鹵化生成物去除水分予以乾燥，獲得32部之C.I.酸性紅52與側鏈具有陽離子性基之樹脂1之鹵化生成物(鹵化生成物(A2-1))。 The resin 1 having a cationic group in its side chain was added to the water 2000, and after sufficiently stirring and mixing, it was heated to 60 °C. Further, an aqueous solution prepared by dissolving 10 parts of C.I. Acid Red 52 in water of 90 parts was successively dropped in the previous resin solution. After dropping, the mixture was stirred at 60 ° C for 120 minutes to sufficiently carry out the reaction. The end point of the reaction was confirmed by dropping the reaction liquid on the filter paper, and the end point was not bleed, and it was judged that the halogenated product was obtained. Thereafter, the obtained reaction mixture is stirred while stirring. After being allowed to cool to room temperature, it is subjected to suction filtration, and after washing with water, the halogenated product remaining on the filter paper is removed by a dryer and dried to obtain 32 parts of CI acid red 52 and a resin having a cationic group in the side chain. The halogenated product (halogenated product (A2-1)).

鹵化生成物(A2-2) Halogenated product (A2-2)

採下述程序，製作由C.I.酸性紅52及側鏈具有陽離子性基之樹脂2所組成的鹵化生成物(A2-2)。 A halogenated product (A2-2) composed of C.I. Acid Red 52 and a resin 2 having a cationic group in a side chain was produced by the following procedure.

於10%之甲醇水溶液2000部添加88部之側鏈具有陽離子性基之樹脂2，充分攪拌混合後，加熱至60℃。另，調製於90部之水中，令10部之C.I.酸性紅52溶解而成之水溶液，於先前之樹脂溶液逐次些許滴下。滴下後，以60℃攪拌120分鐘，充分進行反應。反應終點之確認係於濾紙滴下反應液，不會滲開時即為終點，可判斷獲得鹵化生成物。其後，一面攪拌所獲得的反應混合物，一面放冷到室溫後，進行吸引過濾，水洗後，以乾燥機將殘留於濾紙上之鹵化生成物去除水分予以乾燥，獲得43部之C.I.酸性紅52與側鏈具有陽離子性基之樹脂2之鹵化生成物(鹵化生成物(A2-2))。 To the 2000 part of a 10% methanol aqueous solution, 88 parts of a resin 2 having a cationic group in a side chain were added, and after sufficiently stirring and mixing, the mixture was heated to 60 °C. Further, an aqueous solution prepared by dissolving 10 parts of C.I. Acid Red 52 in water of 90 parts was successively dropped in the previous resin solution. After dropping, the mixture was stirred at 60 ° C for 120 minutes to sufficiently carry out the reaction. The end point of the reaction was confirmed by dropping the reaction liquid on the filter paper, and the end point was not bleed, and it was judged that the halogenated product was obtained. Thereafter, the obtained reaction mixture was stirred while being allowed to cool to room temperature, and then subjected to suction filtration. After washing with water, the halogenated product remaining on the filter paper was removed by a dryer and dried to obtain 43 CI reds. And a halogenated product (halogenated product (A2-2)) of the resin 2 having a cationic group in the side chain.

鹵化生成物(A2-3) Halogenated product (A2-3)

採下述程序，製作由C.I.酸性紅52及側鏈具有陽離子性基之樹脂3所組成的鹵化生成物(A2-3)。 A halogenated product (A2-3) composed of C.I. Acid Red 52 and a resin 3 having a cationic group in a side chain was produced by the following procedure.

於10%之N,N-二甲基甲醯胺水溶液2000部添加46.7部之側鏈具有陽離子性基之樹脂3，充分攪拌混合後，加熱至70℃。另，調製於90部之水中，令10部之C.I.酸性紅52溶解而成之水溶液，於先前之樹脂溶液逐次些許滴下。滴下後，以70℃攪拌120分鐘，充分進行反應。反應終點之確認係於濾紙滴下反應液，不會滲開時即為終點，可判斷獲得鹵化生成物。 其後，一面攪拌所獲得的反應混合物，一面放冷到室溫後，進行吸引過濾，水洗後，以乾燥機將殘留於濾紙上之鹵化生成物去除水分予以乾燥，獲得29部之C.I.酸性紅52與側鏈具有陽離子性基之樹脂3之鹵化生成物(鹵化生成物(A2-3))。 To 4 parts of a 10% N,N-dimethylformamide aqueous solution, 46.7 parts of a resin 3 having a cationic group having a side chain was added thereto, and the mixture was stirred and mixed, and then heated to 70 °C. Further, an aqueous solution prepared by dissolving 10 parts of C.I. Acid Red 52 in water of 90 parts was successively dropped in the previous resin solution. After dropping, the mixture was stirred at 70 ° C for 120 minutes to sufficiently carry out the reaction. The end point of the reaction was confirmed by dropping the reaction liquid on the filter paper, and the end point was not bleed, and it was judged that the halogenated product was obtained. Thereafter, the obtained reaction mixture was stirred while being allowed to cool to room temperature, and then suction-filtered, and after washing with water, the halogenated product remaining on the filter paper was removed by a dryer and dried to obtain 29 CI reds. And a halogenated product (halogenated product (A2-3)) of the resin 3 having a cationic group in the side chain.

鹵化生成物(A2-4) Halogenated product (A2-4)

採下述程序，製作由C.I.酸性紅52及側鏈具有陽離子性基之樹脂4所組成的鹵化生成物(A2-4)。 A halogenated product (A2-4) composed of C.I. Acid Red 52 and a resin 4 having a cationic group in a side chain was produced by the following procedure.

調製於1000部之水中溶解側鏈具有陽離子性基之樹脂4而成之溶液，充分攪拌混合後，加熱至70℃。另，調製於90部之水中，令10部之C.I.酸性紅52溶解而成之水溶液，於先前之樹脂溶液逐次些許滴下。滴下後，以60℃攪拌120分鐘，充分進行反應。反應終點之確認係於濾紙滴下反應液，不會滲開時即為終點，可判斷獲得鹵化生成物。其後，一面攪拌所獲得的反應混合物，一面放冷到室溫後，進行吸引過濾，水洗後，以乾燥機將殘留於濾紙上之鹵化生成物去除水分予以乾燥，獲得19部之C.I.酸性紅52與側鏈具有陽離子性基之樹脂4之鹵化生成物(鹵化生成物(A2-4))。 A solution prepared by dissolving a resin 4 having a cationic group in a side chain in water of 1000 parts was stirred and mixed, and then heated to 70 °C. Further, an aqueous solution prepared by dissolving 10 parts of C.I. Acid Red 52 in water of 90 parts was successively dropped in the previous resin solution. After dropping, the mixture was stirred at 60 ° C for 120 minutes to sufficiently carry out the reaction. The end point of the reaction was confirmed by dropping the reaction liquid on the filter paper, and the end point was not bleed, and it was judged that the halogenated product was obtained. Thereafter, the obtained reaction mixture was stirred while being allowed to cool to room temperature, and then suction-filtered, and after washing with water, the halogenated product remaining on the filter paper was removed by a dryer and dried to obtain 19 CI red acid. And a halogenated product (halogenated product (A2-4)) of the resin 4 having a cationic group in the side chain.

鹵化生成物(A2-5) Halogenated product (A2-5)

採下述程序，製作由C.I.酸性紅52及側鏈具有陽離子性基之樹脂5所組成的鹵化生成物(A2-5)。 A halogenated product (A2-5) composed of C.I. Acid Red 52 and a resin having a cationic group in a side chain was produced by the following procedure.

於20%醋酸2000部添加63.2部之側鏈具有陽離子性基之樹脂5，充分攪拌混合後，加熱至60℃，進行側鏈之3級胺基之銨氯化。另，調製於90部之水中，令10部之C.I.酸性紅52溶解而成之水溶液，於先前之樹脂溶液逐次些許滴下。滴下後，以60℃攪拌120分鐘，充分進行反應。反應終點 之確認係於濾紙滴下反應液，不會滲開時即為終點，可判斷獲得鹵化生成物。其後，一面攪拌所獲得的反應混合物，一面放冷到室溫後，進行吸引過濾，水洗後，以乾燥機將殘留於濾紙上之鹵化生成物去除水分予以乾燥，獲得38部之C.I.酸性紅52與側鏈具有陽離子性基之樹脂5之鹵化生成物(鹵化生成物(A2-5))。 To the 2000 part of 20% acetic acid, 63.2 parts of a resin having a cationic group having a side chain was added, and after sufficiently stirring and mixing, the mixture was heated to 60 ° C to carry out ammonium chlorination of the tertiary amine group of the side chain. Further, an aqueous solution prepared by dissolving 10 parts of C.I. Acid Red 52 in water of 90 parts was successively dropped in the previous resin solution. After dropping, the mixture was stirred at 60 ° C for 120 minutes to sufficiently carry out the reaction. Reaction end point It was confirmed that the reaction liquid was dropped on the filter paper, and the end point was not bleed, and it was judged that the halogenated product was obtained. Thereafter, the obtained reaction mixture was stirred while being allowed to cool to room temperature, and then suction-filtered, and after washing with water, the halogenated product remaining on the filter paper was removed by a dryer to remove moisture, and 38 parts of CI acid red were obtained. And a halogenated product (halogenated product (A2-5)) of the resin 5 having a cationic group in the side chain.

鹵化生成物(A2-6) Halogenated product (A2-6)

採下述程序，製作由C.I.酸性紅52及Disperbyk-2000(BYK Chemie Japan公司製、改質丙烯酸系嵌段共聚物、銨鹽價61mgKOH/g)所組成的鹵化生成物(A2-6)。 The halogenated product (A2-6) composed of C.I. Acid Red 52 and Disperbyk-2000 (modified acrylic block copolymer, ammonium salt price: 61 mgKOH/g) was produced by the following procedure.

於水2000部添加50.9部之Disperbyk-2000，充分攪拌混合後，加熱至60℃。另，調製於90部之水中，令10部之C.I.酸性紅52溶解而成之水溶液，於先前之樹脂溶液逐次些許滴下。滴下後，以60℃攪拌120分鐘，充分進行反應。反應終點之確認係於濾紙滴下反應液，不會滲開時即為終點，可判斷獲得鹵化生成物。其後，一面攪拌所獲得的反應混合物，一面放冷到室溫後，進行吸引過濾，水洗後，以乾燥機將殘留於濾紙上之鹵化生成物去除水分予以乾燥，獲得31部之C.I.酸性紅52與Disperbyk-2000之鹵化生成物(鹵化生成物(A2-6))。 Add 50.9 parts of Disperbyk-2000 to 2000, mix well, and heat to 60 °C. Further, an aqueous solution prepared by dissolving 10 parts of C.I. Acid Red 52 in water of 90 parts was successively dropped in the previous resin solution. After dropping, the mixture was stirred at 60 ° C for 120 minutes to sufficiently carry out the reaction. The end point of the reaction was confirmed by dropping the reaction liquid on the filter paper, and the end point was not bleed, and it was judged that the halogenated product was obtained. Thereafter, the obtained reaction mixture was stirred while being allowed to cool to room temperature, and then suction-filtered, and after washing with water, the halogenated product remaining on the filter paper was removed by a dryer to remove water, and 31 parts of CI acid red were obtained. The halogenated product (halogenated product (A2-6)) of 52 and Disperbyk-2000.

鹵化生成物(A2-7) Halogenated product (A2-7)

採下述程序，製作由C.I.酸性紅289及側鏈具有陽離子性基之樹脂1所組成的鹵化生成物(A2-7)。 A halogenated product (A2-7) composed of C.I. Acid Red 289 and a resin 1 having a cationic group in a side chain was produced by the following procedure.

於水2000部添加51部之側鏈具有陽離子性基之樹脂1，充分攪拌混合後，加熱至60℃。另，調製於90部之水中，令10部之C.I.酸性紅289 溶解而成之水溶液，於先前之樹脂溶液逐次些許滴下。滴下後，以60℃攪拌120分鐘，充分進行反應。反應終點之確認係於濾紙滴下反應液，不會滲開時即為終點，可判斷獲得鹵化生成物。其後，一面攪拌所獲得的反應混合物，一面放冷到室溫後，進行吸引過濾，水洗後，以乾燥機將殘留於濾紙上之鹵化生成物去除水分予以乾燥，獲得32部之C.I.酸性紅289與側鏈具有陽離子性基之樹脂1之鹵化生成物(鹵化生成物(A2-7))。 A resin having a cationic group of 51 side chains was added to the water 2000, and the mixture was stirred and mixed, and then heated to 60 °C. In addition, it is prepared in 90 parts of water, making 10 parts of C.I. Acid Red 289 The dissolved aqueous solution was successively dropped in the previous resin solution. After dropping, the mixture was stirred at 60 ° C for 120 minutes to sufficiently carry out the reaction. The end point of the reaction was confirmed by dropping the reaction liquid on the filter paper, and the end point was not bleed, and it was judged that the halogenated product was obtained. Thereafter, the obtained reaction mixture was stirred while being allowed to cool to room temperature, and then suction-filtered, and after washing with water, the halogenated product remaining on the filter paper was removed by a dryer and dried to obtain 32 parts of CI acid red. A halogenated product (halogenated product (A2-7)) of 209 and a resin having a cationic group in a side chain.

鹵化生成物(A2-8) Halogenated product (A2-8)

採下述程序，製作由C.I.酸性紅388及側鏈具有陽離子性基之樹脂1所組成的鹵化生成物(A2-8)。 A halogenated product (A2-8) composed of C.I. Acid Red 388 and a resin having a cationic group in a side chain was produced by the following procedure.

於水2000部添加51部之側鏈具有陽離子性基之樹脂1，充分攪拌混合後，加熱至60℃。另，調製於90部之水中，令10部之C.I.酸性紅388溶解而成之水溶液，於先前之樹脂溶液逐次些許滴下。滴下後，以60℃攪拌120分鐘，充分進行反應。反應終點之確認係於濾紙滴下反應液，不會滲開時即為終點，可判斷獲得鹵化生成物。其後，一面攪拌所獲得的反應混合物，一面放冷到室溫後，進行吸引過濾，水洗後，以乾燥機將殘留於濾紙上之鹵化生成物去除水分予以乾燥，獲得32部之C.I.酸性紅388與側鏈具有陽離子性基之樹脂1之鹵化生成物(鹵化生成物(A2-8))。 A resin having a cationic group of 51 side chains was added to the water 2000, and the mixture was stirred and mixed, and then heated to 60 °C. Further, an aqueous solution prepared by dissolving 10 parts of C.I. Acid Red 388 in water of 90 parts was successively dropped in the previous resin solution. After dropping, the mixture was stirred at 60 ° C for 120 minutes to sufficiently carry out the reaction. The end point of the reaction was confirmed by dropping the reaction liquid on the filter paper, and the end point was not bleed, and it was judged that the halogenated product was obtained. Thereafter, the obtained reaction mixture was stirred while being allowed to cool to room temperature, and then suction-filtered, and after washing with water, the halogenated product remaining on the filter paper was removed by a dryer and dried to obtain 32 parts of CI acid red. A halogenated product (halogenated product (A2-8)) of 388 and a resin having a cationic group in a side chain.

鹵化生成物(A2-9) Halogenated product (A2-9)

採下述程序，製作由C.I.酸性紅87及側鏈具有陽離子性基之樹脂1所組成的鹵化生成物(A2-9)。 The halogenated product (A2-9) composed of C.I. Acid Red 87 and a resin 1 having a cationic group in a side chain was produced by the following procedure.

於水2000部添加51部之側鏈具有陽離子性基之樹脂1，充分攪拌混合後，加熱至60℃。另，調製於90部之水中，令10部之C.I.酸性紅87 溶解而成之水溶液，於先前之樹脂溶液逐次些許滴下。滴下後，以60℃攪拌120分鐘，充分進行反應。反應終點之確認係於濾紙滴下反應液，不會滲開時即為終點，可判斷獲得鹵化生成物。其後，一面攪拌所獲得的反應混合物，一面放冷到室溫後，進行吸引過濾，水洗後，以乾燥機將殘留於濾紙上之鹵化生成物去除水分予以乾燥，獲得32部之C.I.酸性紅87與側鏈具有陽離子性基之樹脂1之鹵化生成物(鹵化生成物(A2-9))。 A resin having a cationic group of 51 side chains was added to the water 2000, and the mixture was stirred and mixed, and then heated to 60 °C. In addition, it is prepared in 90 parts of water, making 10 parts of C.I. Acid Red 87 The dissolved aqueous solution was successively dropped in the previous resin solution. After dropping, the mixture was stirred at 60 ° C for 120 minutes to sufficiently carry out the reaction. The end point of the reaction was confirmed by dropping the reaction liquid on the filter paper, and the end point was not bleed, and it was judged that the halogenated product was obtained. Thereafter, the obtained reaction mixture was stirred while being allowed to cool to room temperature, and then suction-filtered, and after washing with water, the halogenated product remaining on the filter paper was removed by a dryer and dried to obtain 32 parts of CI acid red. A halogenated product (halogenated product (A2-9)) of a resin 1 having a cationic group with a side chain.

鹵化生成物(A2-10) Halogenated product (A2-10)

採下述程序，製作由C.I.酸性紅92及側鏈具有陽離子性基之樹脂1所組成的鹵化生成物(A2-10)。 A halogenated product (A2-10) composed of C.I. Acid Red 92 and a resin having a cationic group in a side chain was produced by the following procedure.

於水2000部添加51部之側鏈具有陽離子性基之樹脂1，充分攪拌混合後，加熱至60℃。另，調製於90部之水中，令10部之C.I.酸性紅92溶解而成之水溶液，於先前之樹脂溶液逐次些許滴下。滴下後，以60℃攪拌120分鐘，充分進行反應。反應終點之確認係於濾紙滴下反應液，不會滲開時即為終點，可判斷獲得鹵化生成物。其後，一面攪拌所獲得的反應混合物，一面放冷到室溫後，進行吸引過濾，水洗後，以乾燥機將殘留於濾紙上之鹵化生成物去除水分予以乾燥，獲得32部之C.I.酸性紅92與側鏈具有陽離子性基之樹脂1之鹵化生成物(鹵化生成物(A2-10))。 A resin having a cationic group of 51 side chains was added to the water 2000, and the mixture was stirred and mixed, and then heated to 60 °C. Further, an aqueous solution prepared by dissolving 10 parts of C.I. Acid Red 92 in water of 90 parts was successively dropped in the previous resin solution. After dropping, the mixture was stirred at 60 ° C for 120 minutes to sufficiently carry out the reaction. The end point of the reaction was confirmed by dropping the reaction liquid on the filter paper, and the end point was not bleed, and it was judged that the halogenated product was obtained. Thereafter, the obtained reaction mixture was stirred while being allowed to cool to room temperature, and then suction-filtered, and after washing with water, the halogenated product remaining on the filter paper was removed by a dryer and dried to obtain 32 parts of CI acid red. And a halogenated product (halogenated product (A2-10)) of the resin 1 having a cationic group in the side chain.

鹵化生成物(A2-11) Halogenated product (A2-11)

採下述程序，製作由C.I.酸性紅289及側鏈具有陽離子性基之樹脂5所組成的鹵化生成物(A2-11)。 A halogenated product (A2-11) composed of C.I. Acid Red 289 and a resin having a cationic group in a side chain was produced by the following procedure.

於20%醋酸2000部添加63.2部之側鏈具有陽離子性基之樹脂5，充分攪拌混合後，加熱至60℃，進行側鏈之3級胺基之銨氯化。另，調製 於90部之水中，令10部之C.I.酸性紅289溶解而成之水溶液，於先前被進行銨氯化之樹脂溶液逐次些許滴下。滴下後，以60℃攪拌120分鐘，充分進行反應。反應終點之確認係於濾紙滴下反應液，不會滲開時即為終點，可判斷獲得鹵化生成物。其後，一面攪拌所獲得的反應混合物，一面放冷到室溫後，進行吸引過濾，水洗後，以乾燥機將殘留於濾紙上之鹵化生成物去除水分予以乾燥，獲得38部之C.I.酸性紅289與側鏈具有陽離子性基之樹脂5之鹵化生成物(鹵化生成物(A2-11))。 To the 2000 part of 20% acetic acid, 63.2 parts of a resin having a cationic group having a side chain was added, and after sufficiently stirring and mixing, the mixture was heated to 60 ° C to carry out ammonium chlorination of the tertiary amine group of the side chain. Another, modulation In 90 parts of water, an aqueous solution obtained by dissolving 10 parts of C.I. Acid Red 289 was successively dropped in a resin solution previously subjected to ammonium chlorination. After dropping, the mixture was stirred at 60 ° C for 120 minutes to sufficiently carry out the reaction. The end point of the reaction was confirmed by dropping the reaction liquid on the filter paper, and the end point was not bleed, and it was judged that the halogenated product was obtained. Thereafter, the obtained reaction mixture was stirred while being allowed to cool to room temperature, and then suction-filtered, and after washing with water, the halogenated product remaining on the filter paper was removed by a dryer to remove moisture, and 38 parts of CI acid red were obtained. A halogenated product (halogenated product (A2-11)) of 289 and a resin having a cationic group in a side chain.

<呫噸系化合物之製造方法> <Method for producing xanthene compound>

呫噸系化合物(C-1) Xanthene compound (C-1)

藉由常法，將C.I.酸性紅52予以磺醯氯化後，於二噁烷中，與理論當量之十二胺反應，獲得C.I.酸性紅52之磺醯化合物(呫噸系化合物(C-1))(根據日本特開平6-194828號公報之記載)。 The CI acid red 52 is sulfonated and chlorinated by a conventional method, and reacted with a theoretical equivalent of dodecylamine in dioxane to obtain a sulfonate compound of CI acid red 52 (a ton ton compound (C-1) )) (According to the Japanese Patent Publication No. 6-194928).

呫噸系化合物(C-2) Xanthene compound (C-2)

藉由常法，將C.I.酸性紅289予以磺醯氯化後，於二噁烷中，與理論當量之十二胺反應，獲得C.I.酸性紅289之磺醯化合物(呫噸系化合物(C-2))(根據日本特開平6-194828號公報之記載)。 The CI acid red 289 is sulfonated and chlorinated by a conventional method, and reacted with a theoretical equivalent of dodecylamine in dioxane to obtain a sulfonate compound of CI Acid Red 289 (a ton ton compound (C-2) )) (According to the Japanese Patent Publication No. 6-194928).

<顏料分散體之製造方法> <Method for Producing Pigment Dispersion>

顏料分散體(DP-1) Pigment dispersion (DP-1)

將下述混合物攪拌混合均勻後，使用直徑0.5mm之氧化鋯珠，藉由IGER研磨機(IGER Japan公司製「Mini Model M-250 MKII」)予以分散5小時後，以5.0μm的過濾器過濾而製作顏料分散體(DP-1)。 After the mixture was stirred and mixed uniformly, the zirconia beads having a diameter of 0.5 mm were dispersed by an IGER mill ("Mini Model M-250 MKII" manufactured by IGER Japan Co., Ltd.) for 5 hours, and then filtered through a 5.0 μm filter. A pigment dispersion (DP-1) was produced.

紅色微細化顏料1(C.I.顏料紅254)：11.0部 Red micronized pigment 1 (C.I. Pigment Red 254): 11.0

丙烯酸樹脂溶液1：40.0部 Acrylic resin solution 1: 40.0

丙二醇單乙基醚乙酯(PGMAC)：48.0部 Propylene glycol monoethyl ether ethyl ester (PGMAC): 48.0

樹脂型分散劑(日本千葉公司製「EFKA4300」)：1.0部 Resin type dispersant ("EFKA4300" manufactured by Chiba Corporation, Japan): 1.0

除了將紅色微細化顏料1及丙烯酸樹脂溶液1變更為表1所示之微細化顏料及丙烯酸樹脂溶液以外，其他均與上述顏料分散體(DP-1)同樣地製作顏料分散體(DP-2~11、14~17)。 A pigment dispersion (DP-2) was produced in the same manner as in the above pigment dispersion (DP-1) except that the red fine pigment 1 and the acrylic resin solution 1 were changed to the fine pigment and the acrylic resin solution shown in Table 1. ~11, 14~17).

<含有鹵化生成物之樹脂溶液及含有呫噸系化合物之樹脂溶液之製造> <Manufacture of resin solution containing halogenated product and resin solution containing xanthene-based compound>

含有鹵化生成物之樹脂溶液(DA-1) Resin solution containing halogenated product (DA-1)

將下述混合物攪拌混合均勻後，以5.0μm的過濾器過濾而製造含有鹵化生成物之樹脂溶液(DA-1)。 The mixture was stirred and mixed uniformly, and then filtered through a 5.0 μm filter to prepare a resin solution (DA-1) containing a halogenated product.

鹵化生成物(A-1)：11.0部 Halogenated product (A-1): 11.0

丙烯酸樹脂溶液1：40.0部 Acrylic resin solution 1: 40.0

丙二醇單乙基醚乙酯(PGMAC)：49.0部 Propylene glycol monoethyl ether ethyl ester (PGMAC): 49.0

含有鹵化生成物之樹脂溶液(DA-2~17)、含有呫噸系化合物之樹脂溶液(DC-1、2) Resin solution containing halogenated product (DA-2~17), resin solution containing xanthene compound (DC-1, 2)

除了將鹵化生成物(A-1)變更為下述表2-1所示之鹵化生成物或呫噸系化合物，將丙烯酸樹脂溶液1變更為同表2-1所示之丙烯酸樹脂溶液以外，其他均與含有鹵化生成物之樹脂溶液(DA-1)同樣地製作含有鹵化生成物之樹脂溶液(DA-2~DA-17)、及含有呫噸系化合物之樹脂溶液(DC-1、DC-2)。 The acrylic resin solution 1 was changed to the acrylic resin solution shown in Table 2-1 except that the halogenated product (A-1) was changed to the halogenated product or the xanthene compound shown in the following Table 2-1. In the same manner as the resin solution (DA-1) containing a halogenated product, a resin solution (DA-2 to DA-17) containing a halogenated product and a resin solution containing a xanthene-based compound (DC-1, DC) were produced. -2).

含有鹵化生成物之樹脂溶液(DA2-1~DA2-11)之製作 Production of resin solution (DA2-1~DA2-11) containing halogenated product

含有鹵化生成物之樹脂溶液(DA2-1) Resin solution containing halogenated product (DA2-1)

將下述混合物攪拌混合均勻後，以5.0μm的過濾器過濾而製 造含有鹵化生成物之樹脂溶液(DA2-1)。 The following mixture was stirred and mixed uniformly, and then filtered through a 5.0 μm filter. A resin solution (DA2-1) containing a halogenated product was produced.

鹵化生成物(A2-1)：11.0部 Halogenated product (A2-1): 11.0

丙烯酸樹脂溶液1：40.0部 Acrylic resin solution 1: 40.0

丙二醇單乙基醚乙酯(PGMAC)：49.0部 Propylene glycol monoethyl ether ethyl ester (PGMAC): 49.0

含有鹵化生成物之樹脂溶液(DA2-2~11) Resin solution containing halogenated product (DA2-2~11)

除了將鹵化生成物(A2-1)變更為下述表2-2所示之鹵化生成物以外，其他均與含有鹵化生成物之樹脂溶液(DA-1)同樣地製作含有鹵化生成物之樹脂溶液(DA2-2~DA2-11)。 A resin containing a halogenated product was produced in the same manner as the resin solution (DA-1) containing a halogenated product, except that the halogenated product (A2-1) was changed to the halogenated product shown in the following Table 2-2. Solution (DA2-2~DA2-11).

<藍色、綠色抗蝕劑材料之製造方法> <Method for Producing Blue and Green Resist Material>

藍色抗蝕劑材料 Blue resist material

將下述混合物攪拌混合均勻後，以1.0μm的過濾器過濾而獲得藍色抗蝕劑材料。 The mixture was stirred and mixed uniformly, and then filtered through a 1.0 μm filter to obtain a blue resist material.

顏料分散體(DP-4)：50.0部 Pigment dispersion (DP-4): 50.0 parts

顏料分散體(DP-5)：10.0部 Pigment Dispersion (DP-5): 10.0

丙烯酸樹脂溶液1：11.0部 Acrylic resin solution 1:11.0

三烴甲基丙烷三丙烯酸酯：4.2部 Trihydrocarbylmethylpropane triacrylate: 4.2

(新中村化學公司製「NK酯ATMPT」) ("Nippon Nakamura Chemical Co., Ltd." "NK ester ATMPT")

光聚合起始劑：1.2部 Photopolymerization initiator: 1.2

(日本千葉公司製「IRGACURE 907」 (IRGACURE 907, manufactured by Chiba Corporation, Japan)

增感劑(保土谷化學公司製「EAB-F」)：0.4部 Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4

乙二醇單甲基醚乙酯：23.2部 Ethylene glycol monomethyl ether ethyl ester: 23.2

綠色抗蝕劑材料 Green resist material

將下述混合物攪拌混合均勻後，以1.0μm的過濾器過濾而獲得綠色抗蝕劑材料。 The mixture was stirred and mixed uniformly, and then filtered through a 1.0 μm filter to obtain a green resist material.

顏料分散體(DP-6)：45.0部 Pigment Dispersion (DP-6): 45.0

顏料分散體(DP-3)：15.0部 Pigment Dispersion (DP-3): 15.0

丙烯酸樹脂溶液1：11.0部 Acrylic resin solution 1:11.0

三烴甲基丙烷三丙烯酸酯：4.2部 Trihydrocarbylmethylpropane triacrylate: 4.2

(新中村化學公司製「NK酯ATMPT」) ("Nippon Nakamura Chemical Co., Ltd." "NK ester ATMPT")

光聚合起始劑：1.2部 Photopolymerization initiator: 1.2

(日本千葉公司製「IRGACURE 907」 (IRGACURE 907, manufactured by Chiba Corporation, Japan)

增感劑(保土谷化學公司製「EAB-F」)：0.4部 Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4

乙二醇單甲基醚乙酯：23.2部 Ethylene glycol monomethyl ether ethyl ester: 23.2

<實施例1~22、比較例1、2> <Examples 1 to 22, Comparative Examples 1, 2>

實施例1：著色組成物(DB-1) Example 1: Coloring composition (DB-1)

將下述混合物攪拌混合均勻後，以5.0μm的過濾器過濾而製造混合著色組成物。 The mixture was stirred and mixed uniformly, and then filtered through a 5.0 μm filter to prepare a mixed coloring composition.

含有鹵化生成物之樹脂溶液(DA-1)：3.8部 Resin solution containing halogenated product (DA-1): 3.8

顏料分散體(DP-1)：7.2部 Pigment Dispersion (DP-1): Section 7.2

丙烯酸樹脂溶液1：40.0部 Acrylic resin solution 1: 40.0

丙二醇單乙基醚乙酯(PGMAC)：49.0部 Propylene glycol monoethyl ether ethyl ester (PGMAC): 49.0

實施例2~22、比較例1、2：著色組成物(DB-2~13及DB2-1~DB2-11) Examples 2 to 22, Comparative Examples 1 and 2: Colored compositions (DB-2 to 13 and DB2-1 to DB2-11)

除了將含有鹵化生成物之樹脂溶液(DA-1)變更為下述表3所示之含有鹵化生成物之樹脂溶液以外，其他均與著色組成物(DB-1)同樣地製作著色組成物(DB-2~13及DB2-1~2-11)。其中，顏料分散體(DP-1)係於實施例2~22、比較例1、2中，亦與實施例1同樣地固定使用。 A coloring composition was produced in the same manner as the coloring composition (DB-1) except that the resin solution (DA-1) containing the halogenated product was changed to the resin solution containing the halogenated product shown in Table 3 below. DB-2~13 and DB2-1~2-11). Among them, the pigment dispersion (DP-1) was used in the same manner as in Example 1 except that it was used in Examples 2 to 22 and Comparative Examples 1 and 2.

<塗膜異物試驗> <Coating film foreign matter test>

於透明基板上，以乾燥塗膜成為約2.0μm之方式塗布著色組成物，於烤箱中，以230℃加熱20分鐘而獲得試驗基板。利用Olympus系統公司製金屬顯微鏡(「BX60」)進行乾燥塗膜之表面觀察。倍率設為500倍，採穿透而於任意五視野，計算可觀測之粒子數。 The colored composition was applied onto the transparent substrate so that the dried coating film was about 2.0 μm, and heated in an oven at 230 ° C for 20 minutes to obtain a test substrate. The surface of the dried coating film was observed using a metal microscope ("BX60") manufactured by Olympus Systems. The magnification is set to 500 times, and the number of particles that can be observed is calculated by penetrating into any five fields of view.

於下述評估結果中，◎、○為良好，△為異物多但使用上不構成問題之層級，×係因異物而發生塗工不均(斑痕)。 Among the following evaluation results, ◎ and ○ are good, and Δ is a foreign matter having a large number of foreign materials, but the use is not a problem, and X is uneven due to foreign matter (spots).

◎：粒子數小於5個 ◎: The number of particles is less than 5

○：粒子數5個以上、小於20個 ○: The number of particles is 5 or more and less than 20

△：粒子數20個以上、小於100個 △: The number of particles is 20 or more and less than 100

×：粒子數100個以上 ×: The number of particles is 100 or more

於表3一併記載結果。 The results are shown together in Table 3.

使用鹵化生成物(A)時，於基板評估中為異物(未溶解異物)少的結果，使用呫噸系化合物(C-1、C-2)時為異物非常多的結果。由此可知，比起有機合成地轉換呫噸系化合物之置換基，鹵化生成物帶來較良好的結果。 When the halogenated product (A) was used, the amount of foreign matter (undissolved foreign matter) was small in the evaluation of the substrate, and when the xanthene-based compound (C-1, C-2) was used, the foreign matter was extremely large. From this, it was found that the halogenated product brought about a good result as compared with the substitution of the xanthene compound by organic synthesis.

再者，鹵化生成物為包含式(1-1)之四級銨鹽化合物之鹵化生成物時，該陽離子部分之四級銨鹽部分之烷基鏈係與實施例1~9相比較，實施例10係C數(碳數)5以上之烷基鏈僅有1個，實施例11係4個均烷基鏈之C數小於5，因此實施例10、11雖可容許，但與實施例1~9比較時，則結果稍差。結果，四級銨鹽部分係C數5~20之鏈宜在2條以上。 Further, when the halogenated product is a halogenated product containing the quaternary ammonium salt compound of the formula (1-1), the alkyl chain system of the quaternary ammonium salt portion of the cationic portion is compared with Examples 1 to 9 In Example 10, there are only one alkyl chain having 5 or more C numbers (carbon number), and the C number of the four homoalkyl chains in Example 11 is less than 5, so Examples 10 and 11 are acceptable, but examples and examples When comparing 1~9, the result is slightly worse. As a result, the chain of the quaternary ammonium salt is preferably two or more chains having a C number of 5-20.

<實施例23~35、比較例3~5> <Examples 23 to 35, Comparative Examples 3 to 5>

實施例23：抗蝕劑材料(R-1) Example 23: Resist material (R-1)

將下述混合物攪拌混合均勻後，以1.0μm的過濾器過濾而獲得鹼顯影型抗蝕劑材料(R-1)。 The mixture was stirred and mixed uniformly, and then filtered through a 1.0 μm filter to obtain an alkali-developable resist material (R-1).

著色劑分散體　　　(合計60.0部) Colorant dispersion (total 60.0 parts)

含有鹵化生成物之樹脂溶液(DA-1)：21.0部 Resin solution containing halogenated product (DA-1): 21.0 parts

顏料分散體(DP-1)：39.0部 Pigment Dispersion (DP-1): 39.0

丙烯酸樹脂溶液1：11.0部 Acrylic resin solution 1:11.0

三烴甲基丙烷三丙烯酸酯：4.2部 Trihydrocarbylmethylpropane triacrylate: 4.2

(新中村化學公司製「NK酯ATMPT」) ("Nippon Nakamura Chemical Co., Ltd." "NK ester ATMPT")

光聚合起始劑：1.2部 Photopolymerization initiator: 1.2

(日本千葉公司製「IRGACURE 907」 (IRGACURE 907, manufactured by Chiba Corporation, Japan)

增感劑(保土谷化學公司製「EAB-F」)：0.4部 Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4

乙二醇單甲基醚乙酯：23.2部 Ethylene glycol monomethyl ether ethyl ester: 23.2

實施例24~35、比較例3~5：抗蝕劑材料(R-2~R-16) Examples 24 to 35, Comparative Examples 3 to 5: Resist materials (R-2 to R-16)

除了將著色劑分散體改變為表4-1所示之著色劑分散體(顏料分散體、含有鹵化生成物之樹脂溶液或含有呫噸系化合物之樹脂溶液)之種類及調配量以外，其他均與抗蝕劑材料(R-1)同樣地獲得鹼顯影型抗蝕劑材料(R-2~R-16)。於抗蝕劑材料係同時使用兩種或其以上之著色劑分散體(顏料分散體、含有鹵化生成物之樹脂溶液或含有呫噸系化合物之樹脂溶液)，但著色劑分散體之總量係於所有抗蝕劑材料為60部。 Except that the colorant dispersion was changed to the type and amount of the colorant dispersion (pigment dispersion, resin solution containing halogenated product or resin solution containing xanthene compound) shown in Table 4-1, An alkali developing resist material (R-2 to R-16) was obtained in the same manner as the resist material (R-1). In the resist material, two or more colorant dispersions (pigment dispersion, resin solution containing a halogenated product or a resin solution containing a xanthene compound) are simultaneously used, but the total amount of the colorant dispersion is There are 60 parts for all resist materials.

表4-1： Table 4-1:

<實施例36~41：抗蝕劑材料(R-17~R-22) <Examples 36 to 41: Resist material (R-17 to R-22)

除了將實施例32之丙烯酸樹脂溶液1改變為丙烯酸樹脂溶液2、3、4以外，其他均與抗蝕劑材料(R-10)同樣地分別獲得鹼顯影型抗蝕劑材料R-17、R-18、R-19。進而將實施例33之丙烯酸樹脂溶液1改變為丙烯酸樹脂溶液2、3、4以外，與抗蝕劑材料(R-11)同樣地分別獲得鹼顯影型抗蝕劑材料R-20、R-21、R-22。 An alkali-developing resist material R-17, R was obtained in the same manner as the resist material (R-10) except that the acrylic resin solution 1 of Example 32 was changed to the acrylic resin solutions 2, 3, and 4. -18, R-19. Further, in the same manner as the resist material (R-11), the alkali-developing resist materials R-20 and R-21 were obtained, respectively, except that the acrylic resin solution 1 of Example 33 was changed to the acrylic resin solutions 2, 3, and 4. , R-22.

<實施例42~54、比較例6、7(R2-1~R2-15)> <Examples 42 to 54 and Comparative Examples 6 and 7 (R2-1 to R2-15)>

實施例42：抗蝕劑材料(R2-1) Example 42: Resist material (R2-1)

將下述混合物攪拌混合均勻後，以1.0μm的過濾器過濾而獲得鹼顯影型抗蝕劑材料(R2-1)。 The mixture was stirred and mixed uniformly, and then filtered through a 1.0 μm filter to obtain an alkali-developable resist material (R2-1).

含有鹵化生成物之樹脂溶液(DA2-1)：21.0部 Resin solution containing halogenated product (DA2-1): 21.0 parts

顏料分散體(DP-1)：39.0部 Pigment Dispersion (DP-1): 39.0

丙烯酸樹脂溶液1：11.0部 Acrylic resin solution 1:11.0

三烴甲基丙烷三丙烯酸酯：4.2部 Trihydrocarbylmethylpropane triacrylate: 4.2

(新中村化學公司製「NK酯ATMPT」) ("Nippon Nakamura Chemical Co., Ltd." "NK ester ATMPT")

光聚合起始劑：1.2部 Photopolymerization initiator: 1.2

(日本千葉公司製「IRGACURE 907」 (IRGACURE 907, manufactured by Chiba Corporation, Japan)

增感劑(保土谷化學公司製「EAB-F」)：0.4部 Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4

乙二醇單甲基醚乙酯：23.2部 Ethylene glycol monomethyl ether ethyl ester: 23.2

實施例43~54 Examples 43 to 54

除了將著色劑分散體改變為表4-2所示之著色劑分散體(顏料分散體、含有鹵化生成物之樹脂溶液或含有呫噸系化合物之樹脂溶液)之種類及調配量以外，其他均與抗蝕劑材料(R2-1)同樣地獲得鹼顯影型抗蝕劑材料(R2-2~R2-15)。於抗蝕劑材料係同時使用兩種或其以上之著色劑分散體(顏料分散體、含有鹵化生成物之樹脂溶液或含有呫噸系化合物之樹脂溶液)，但著色劑分散體之總量係於所有抗蝕劑材料為60部。 In addition to changing the colorant dispersion to the type and amount of the colorant dispersion (pigment dispersion, resin solution containing halogenated product or resin solution containing xanthene compound) shown in Table 4-2, An alkali developing resist material (R2-2 to R2-15) was obtained in the same manner as the resist material (R2-1). In the resist material, two or more colorant dispersions (pigment dispersion, resin solution containing a halogenated product or a resin solution containing a xanthene compound) are simultaneously used, but the total amount of the colorant dispersion is There are 60 parts for all resist materials.

實施例55~60：抗蝕劑材料(R2-16~R2-21) Examples 55-60: Resist material (R2-16~R2-21)

除了將實施例51之丙烯酸樹脂溶液1改變為丙烯酸樹脂溶液2、3、4以外，其他均與抗蝕劑材料(R2-10)同樣地分別獲得鹼顯影型抗蝕劑材料R2-16、R2-17、R2-18。進而將實施例52之丙烯酸樹脂溶液1改變為丙烯酸樹脂溶液2、3、4以外，與抗蝕劑材料(R2-11)同樣地分別獲得鹼顯影型抗蝕劑材料R2-19、R2-20、R2-21。 An alkali-developing resist material R2-16, R2 was obtained in the same manner as the resist material (R2-10) except that the acrylic resin solution 1 of Example 51 was changed to the acrylic resin solutions 2, 3, and 4. -17, R2-18. Further, the acrylic resin solution 1 of Example 52 was changed to the acrylic resin solutions 2, 3, and 4, and alkali-developing resist materials R2-19 and R2-20 were obtained in the same manner as the resist material (R2-11). , R2-21.

<抗蝕劑材料之評估> <Evaluation of resist material>

採下述方法進行抗蝕劑材料(R-1~22及R2-1~R2-21)之塗膜之色度、異物、耐熱性、耐光性及耐溶劑性之各試驗。於表5-1及5-2表示試驗結果。 Each of the tests for the chromaticity, foreign matter, heat resistance, light resistance, and solvent resistance of the coating materials of the resist materials (R-1 to 22 and R2-1 to R2-21) was carried out by the following method. The test results are shown in Tables 5-1 and 5-2.

塗膜異物試驗 Film foreign body test

於透明基板上，以乾燥塗膜成為約2.5μm之方式塗布著色組成物，於烤箱中，以230℃加熱20分鐘而獲得評估基板。利用Olympus系統公司製金屬顯微鏡(「BX60」)進行乾燥塗膜之表面觀察。倍率設為500倍，採穿透而於任意五視野，計算可觀測之粒子數。於下述評估結果中，◎、○為良好，△為異物多但使用上不構成問題之層級，×係因異物而發生塗工不均。 The colored composition was applied to the transparent substrate so that the dried coating film became about 2.5 μm, and heated in an oven at 230 ° C for 20 minutes to obtain an evaluation substrate. The surface of the dried coating film was observed using a metal microscope ("BX60") manufactured by Olympus Systems. The magnification is set to 500 times, and the number of particles that can be observed is calculated by penetrating into any five fields of view. Among the following evaluation results, ◎ and ○ are good, and Δ is a foreign matter, but the level of use does not constitute a problem, and x is uneven due to foreign matter.

◎：粒子數小於5個 ◎: The number of particles is less than 5

○：粒子數5個以上、小於20個 ○: The number of particles is 5 or more and less than 20

△：粒子數20個以上、小於100個 △: The number of particles is 20 or more and less than 100

×：粒子數100個以上 ×: The number of particles is 100 or more

於表5-1及表5-2表示結果。 The results are shown in Table 5-1 and Table 5-2.

色彩特性評估 Color characterization

於玻璃基板上，將抗蝕劑材料塗布成在C光源下成為x=0.640、y=0.315之膜厚。將該基板以230℃歷經20分鐘加熱。其後，以顯微分光光度計(Olympus光學公司製「OSP-SP200」)測定所獲得基板之亮度(Y)。 On the glass substrate, the resist material was applied to have a film thickness of x=0.640 and y=0.315 under a C light source. The substrate was heated at 230 ° C for 20 minutes. Thereafter, the brightness (Y) of the obtained substrate was measured by a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optics Co., Ltd.).

於表5-1及表5-2表示結果。 The results are shown in Table 5-1 and Table 5-2.

塗膜耐熱性試驗 Film heat resistance test

於透明基板上，將抗蝕劑材料塗布為乾燥塗膜成為2.5μm，中介具有特定圖案之光罩進行紫外線曝光後，藉由噴霧其來噴霧鹼顯影液，去除未硬化部分，形成所需圖案。其後，於烤箱內，以230℃加熱20分鐘，放冷後，利用顯微分光光度計(Olympus光學公司製「OSP-SP200」)，測定所獲得塗膜在C光源下之色差1(L*(1)、a*(1)、b*(1))。進而於其後，作為耐熱試驗而於烤箱內，以250℃加熱1小時，測定C光源下之色度2(L*(2)、a*(2)、b*(2))。 On the transparent substrate, the resist material is applied as a dry coating film to be 2.5 μm, and a mask having a specific pattern is interposed to perform ultraviolet exposure, and then the alkali developer is sprayed by spraying to remove the uncured portion to form a desired pattern. . Thereafter, the mixture was heated at 230 ° C for 20 minutes in an oven, and after cooling, the color difference 1 (L) of the obtained coating film under a C light source was measured by a microscopic spectrophotometer ("OSP-SP200" manufactured by Olympus Optics Co., Ltd.). *(1), a*(1), b*(1)). Further, after that, it was heated in an oven at 250 ° C for 1 hour as a heat resistance test, and the chromaticity 2 (L*(2), a*(2), b*(2)) under the C light source was measured.

利用測定之色差值，藉由下述計算式算出色差△Eab*，採下述4階段評估塗膜之耐熱性。 Using the measured color difference value, the color difference ΔEab* was calculated by the following calculation formula, and the heat resistance of the coating film was evaluated in the following four stages.

△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*小於1.5 ◎: △Eab* is less than 1.5

○：△Eab*為1.5以上、小於3.0 ○: △Eab* is 1.5 or more and less than 3.0

△：△Eab*為3.0以上、小於5.0 △: ΔEab* is 3.0 or more and less than 5.0

×：△Eab*為5.0以上 ×: △Eab* is 5.0 or more

於表5-1及表5-2表示結果。 The results are shown in Table 5-1 and Table 5-2.

塗膜耐光性試驗 Film coating light resistance test

採用與塗膜耐熱性試驗相同的程序製作試驗用基板，利用顯微分光光度計(Olympus光學公司製「OSP-SP200」)測定C光源下之色度1(L*(1)、a*(1)、b*(1))。其後，將基板放入耐光性試驗機(TOYOSEIKI公司製「SUNTEST CPS+」)，放置500小時。取出基板後，測定C光源下之色度2(L*(2)、a*(2)、b*(2))，與塗膜耐熱性試驗同樣地算出色差△Eab*，依據與耐熱性相同的基準評估塗膜之耐光性。 The test substrate was prepared by the same procedure as the film heat resistance test, and the chromaticity 1 under the C light source was measured by a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optics Co., Ltd.) (L*(1), a*( 1), b*(1)). Thereafter, the substrate was placed in a light resistance tester ("SUNTEST CPS+" manufactured by TOYOSEIKI Co., Ltd.), and left for 500 hours. After the substrate was taken out, the chromaticity 2 (L*(2), a*(2), b*(2)) under the C light source was measured, and the color difference ΔEab* was calculated in the same manner as the coating film heat resistance test, and the heat resistance was determined. The same benchmark was used to evaluate the lightfastness of the film.

於表5-1及表5-2表示結果。 The results are shown in Table 5-1 and Table 5-2.

塗膜耐溶劑性試驗 Film resistance test

採用與耐熱性試驗相同的程序製作試驗用基板，利用顯微分光光度計(Olympus光學公司製「OSP-SP200」)測定C光源下之色度1(L*(1)、a*(1)、b*(1))。其後，將基板浸泡於N-甲基砒喀烷酮。取出基板後，測定C光源下之色度2(L*(2)、a*(2)、b*(2))，與塗膜耐熱性試驗同樣地算出色差△Eab*，依據與耐熱性相同的基準評估塗膜之耐溶劑性。 The test substrate was prepared by the same procedure as the heat resistance test, and the chromaticity 1 under the C light source was measured by a microscopic spectrophotometer ("OSP-SP200" manufactured by Olympus Optics Co., Ltd.) (L*(1), a*(1) , b*(1)). Thereafter, the substrate was immersed in N-methylxanthone. After the substrate was taken out, the chromaticity 2 (L*(2), a*(2), b*(2)) under the C light source was measured, and the color difference ΔEab* was calculated in the same manner as the coating film heat resistance test, and the heat resistance was determined. The same benchmark was used to evaluate the solvent resistance of the film.

於表5-1及表5-2表示結果。 The results are shown in Table 5-1 and Table 5-2.

實施例23~34、36~41之抗蝕劑材料(R-1~12、14~19)之耐光性良好。又，實施例35之抗蝕劑材料(R-13)之色彩特性良好，結果耐熱性、 耐光性、耐溶劑性稍差，但用於彩色濾光片在品質上不構成問題。又，實施例42~60之抗蝕劑材料(R2-1~R2-13、R2-16~R2-21)之耐光性亦良好。 The resist materials (R-1 to 12, 14 to 19) of Examples 23 to 34 and 36 to 41 were excellent in light resistance. Further, the resist material (R-13) of Example 35 had good color characteristics, and as a result, heat resistance, Light resistance and solvent resistance are slightly inferior, but the color filter does not pose a problem in quality. Further, the resist materials (R2-1 to R2-13, R2-16 to R2-21) of Examples 42 to 60 were also excellent in light resistance.

相對於此，比較例3、4、6、7之抗蝕劑材料(R-14、R-15、R2-14、R2-15)之異物多，難以使用。與實施例23~41及實施例42~60相比較，比較例5之抗蝕劑材料(R-16)之亮度(Y)較低。 On the other hand, the resist materials (R-14, R-15, R2-14, and R2-15) of Comparative Examples 3, 4, 6, and 7 have many foreign matters and are difficult to use. The luminance (Y) of the resist material (R-16) of Comparative Example 5 was lower than that of Examples 23 to 41 and Examples 42 to 60.

又，從實施例36~41之抗蝕劑材料(R-17~R-22)及實施例55-60(R2-16~R2-21)之結果可知，藉由使用具有乙烯性不飽和雙重結合之活性能量線硬化樹脂，可更減低塗膜異物。 Further, from the results of the resist materials (R-17 to R-22) of Examples 36 to 41 and Examples 55 to 60 (R2-16 to R2-21), it is understood that the use of the ethylenic unsaturated double Combined with the active energy ray hardening resin, the foreign matter of the coating film can be further reduced.

<實施例61~98、比較例8~12> <Examples 61 to 98, Comparative Examples 8 to 12>

實施例61：彩色濾光片(CF-1)及液晶顯示裝置之製作 Example 61: Production of color filter (CF-1) and liquid crystal display device

彩色濾光片 Color filter

於彩色基板上，將黑矩陣予以圖案加工，於該基板上，以旋轉塗布機塗布紅色抗蝕劑材料(R-1)，塗布為會成為x=0.640、y=0.315之膜厚，形成著色被膜。於該塗膜，中介光罩而利用超高壓水銀燈照射300mJ/cm2之紫外線。接著，藉由0.2重量%碳酸鈉水溶液所組成的鹼顯影液進行噴霧顯影，去除未曝光部分後，以離子交換水洗淨，以230℃將該基板加熱20分鐘，形成紅色濾光片區段。藉由同樣方法，分別塗布綠色抗蝕劑材料，塗布為會成為x=0.300、y=0.600之膜厚，利用藍色抗蝕劑材料，塗布為會成為x=0.150、y=0.060之膜厚，形成綠色濾光片區段、藍色濾光片區段，獲得彩色濾光片(CF-1)。 The black matrix was patterned on the color substrate, and the red resist material (R-1) was applied onto the substrate by a spin coater to form a film thickness of x=0.640 and y=0.315 to form a color. Membrane. In the coating film, an ultraviolet ray of 300 mJ/cm 2 was irradiated with an ultrahigh pressure mercury lamp by interposing a photomask. Next, spray development was carried out by an alkali developing solution composed of a 0.2% by weight aqueous sodium carbonate solution, and the unexposed portion was removed, and then washed with ion-exchanged water, and the substrate was heated at 230 ° C for 20 minutes to form a red filter segment. . By applying the green resist material in the same manner, the coating is applied to have a film thickness of x=0.300 and y=0.600, and is coated with a blue resist material to have a film thickness of x=0.150 and y=0.060. A green filter segment and a blue filter segment were formed to obtain a color filter (CF-1).

液晶顯示裝置 Liquid crystal display device

於所獲得的RGB之彩色濾光片上，形成ITO透明電極板，於 其上形成聚醯亞胺配向層。於該玻璃基板之另一表面形成偏光板。另，於別的(第2)玻璃基板之一表面形成TFT陣列及像素電極，於另一表面形成偏光板。如此，令準備好之2個玻璃基板對向配置為電極層彼此面對面，利用間隔珠，一面將兩基板之間隔保持在一定，一面進行位置對齊，留下液晶組成物注入用開口部而利用密封劑密封周圍。從開口部注入液晶組成物後，密封開口部。將如此製作之液晶顯示裝置與背光單元之3波長CCFL光源組合，製作成彩色顯示裝置。 Forming an ITO transparent electrode plate on the obtained RGB color filter, A polyimine alignment layer is formed thereon. A polarizing plate is formed on the other surface of the glass substrate. Further, a TFT array and a pixel electrode were formed on one surface of the other (second) glass substrate, and a polarizing plate was formed on the other surface. In this way, the two glass substrates which are prepared are disposed so that the electrode layers face each other, and the spacers are used to position the two substrates while maintaining a constant spacing therebetween, leaving the liquid crystal composition injection opening and sealing. The agent seals around. After the liquid crystal composition is injected from the opening, the opening is sealed. The liquid crystal display device thus produced was combined with a three-wavelength CCFL light source of a backlight unit to fabricate a color display device.

實施例62~79、比較例8~10 Examples 62 to 79 and Comparative Examples 8 to 10

除了將紅色抗蝕劑材料取代為表6-1所示之紅色抗蝕劑材料以外，其他均藉由與實施例61同樣的方法，製作實施例62~79、比較例8~10之彩色濾光片(CF-2~CF-22)及彩色顯示裝置。 The color filters of Examples 62 to 79 and Comparative Examples 8 to 10 were produced in the same manner as in Example 61 except that the red resist material was replaced with the red resist material shown in Table 6-1. Light film (CF-2~CF-22) and color display device.

實施例80~98、比較例11~12 Examples 80 to 98 and Comparative Examples 11 to 12

除了將紅色抗蝕劑材料取代為表6-2所示之紅色抗蝕劑材料以外，其他均藉由與實施例61同樣的方法，製作實施例80~98、比較例11~12之彩色濾光片(CF2-1~CF2-21)及彩色顯示裝置。 The color filters of Examples 80 to 98 and Comparative Examples 11 to 12 were produced in the same manner as in Example 61 except that the red resist material was replaced with the red resist material shown in Table 6-2. Light film (CF2-1~CF2-21) and color display device.

於實施例61~98、比較例8~12所獲得的彩色顯示裝置，令光源發光，顯示彩色圖像，以顯微分光光度計(Olympus光學公司製「OSP-SP200」)測定各色濾光片區段部分之亮度。於表6-1及6-2表示結果。 In the color display devices obtained in Examples 61 to 98 and Comparative Examples 8 to 12, the light source was caused to emit light, and a color image was displayed, and each color filter was measured by a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.). The brightness of the segment portion. The results are shown in Tables 6-1 and 6-2.

若比較實施例61~98與比較例10(彩色濾光片(CF-16))，於白顯示，比起由以往所用含有二酮吡咯并吡咯系顏料及蒽醌系顏料之抗蝕劑材料所形成的彩色濾光片(彩色濾光片(CF-16))，於由含有紅色顏料及鹵化生成物(A)之本發明之抗蝕劑材料所形成的彩色濾光片(彩色濾光片(CF-1~13、CF-17~22、CF2-1~CF2-19))，可獲得較高亮度。比較例6、7、11、12(彩色濾光片(CF-14、CF-15、CF2-20、CF2-21))之亮度雖高，但如前述產生許多異物，因此在實用上難以使用。 Comparing Examples 61 to 98 with Comparative Example 10 (color filter (CF-16)), it was shown in white as compared with the resist material containing a diketopyrrolopyrrole pigment and an anthraquinone pigment which have been conventionally used. The formed color filter (color filter (CF-16)) is a color filter formed by the resist material of the present invention containing a red pigment and a halogenated product (A) (color filter) The film (CF-1~13, CF-17~22, CF2-1~CF2-19)) can obtain higher brightness. Comparative Examples 6, 7, 11, and 12 (color filters (CF-14, CF-15, CF2-20, CF2-21)) have high brightness, but many foreign substances are generated as described above, so that it is practically difficult to use. .

<實施例99~113、比較例13~18> <Examples 99 to 113, Comparative Examples 13 to 18>

實施例99 Example 99

將下述混合物攪拌混合均勻後，以5.0μm的過濾器過濾而製作紅色著色樹脂組成物。 The mixture was stirred and mixed uniformly, and then filtered through a 5.0 μm filter to prepare a red colored resin composition.

顏料分散體(DP-7)：7.2部 Pigment dispersion (DP-7): 7.2

含有鹵化生成物之樹脂溶液(DA-8)：3.8部 Resin solution containing halogenated product (DA-8): 3.8

丙烯酸樹脂溶液1：40.0部 Acrylic resin solution 1: 40.0

丙二醇單乙基醚乙酯(PGMAC)：49.0部 Propylene glycol monoethyl ether ethyl ester (PGMAC): 49.0

實施例100 Example 100

除了將顏料分散體(DP-7)改變為顏料分散體(DP-8)，調整顏料分散體與含有鹵化生成物之樹脂溶液之比率，使其成為與實施例99相同色度以外，其他均與實施例99同樣地獲得紅色著色樹脂組成物。 In addition to changing the pigment dispersion (DP-7) to the pigment dispersion (DP-8), the ratio of the pigment dispersion to the resin solution containing the halogenated product was adjusted so that it became the same color as in Example 99, and the others were A red colored resin composition was obtained in the same manner as in Example 99.

實施例101 Example 101

除了將顏料分散體(DP-7)改變為顏料分散體(DP-9)，調整顏 料分散體與含有鹵化生成物之樹脂溶液之比率，使其成為與實施例99相同色度以外，其他均與實施例99同樣地獲得紅色著色樹脂組成物。 In addition to changing the pigment dispersion (DP-7) to a pigment dispersion (DP-9), adjust the color A red colored resin composition was obtained in the same manner as in Example 99 except that the ratio of the material dispersion to the resin solution containing the halogenated product was the same as that of Example 99.

實施例102 Example 102

除了將顏料分散體(DP-7)改變為顏料分散體(DP-10)，調整顏料分散體與含有鹵化生成物之樹脂溶液之比率，使其成為與實施例99相同色度以外，其他均與實施例99同樣地獲得紅色著色樹脂組成物。 In addition to changing the pigment dispersion (DP-7) to the pigment dispersion (DP-10), the ratio of the pigment dispersion to the resin solution containing the halogenated product was adjusted to be the same as that of Example 99, and the others were A red colored resin composition was obtained in the same manner as in Example 99.

實施例103 Example 103

除了將顏料分散體(DP-7)改變為顏料分散體(DP-11)，調整顏料分散體與含有鹵化生成物之樹脂溶液之比率，使其成為與實施例99相同色度以外，其他均與實施例99同樣地獲得紅色著色樹脂組成物。 In addition to changing the pigment dispersion (DP-7) to the pigment dispersion (DP-11), the ratio of the pigment dispersion to the resin solution containing the halogenated product was adjusted so that it became the same color as in Example 99, and the others were A red colored resin composition was obtained in the same manner as in Example 99.

實施例104 Example 104

除了將顏料分散體(DP-8)改變為顏料分散體(DP-12)，調整顏料分散體與含有鹵化生成物之樹脂溶液之比率，使其成為與實施例99相同色度以外，其他均與實施例99同樣地獲得紅色著色樹脂組成物。 In addition to changing the pigment dispersion (DP-8) to the pigment dispersion (DP-12), the ratio of the pigment dispersion to the resin solution containing the halogenated product was adjusted so that it became the same color as in Example 99, and the others were A red colored resin composition was obtained in the same manner as in Example 99.

實施例105 Example 105

除了將顏料分散體(DP-8)改變為顏料分散體(DP-13)，調整顏料分散體與含有鹵化生成物之樹脂溶液之比率，使其成為與實施例99相同色度以外，其他均與實施例99同樣地獲得紅色著色樹脂組成物。 In addition to changing the pigment dispersion (DP-8) to the pigment dispersion (DP-13), the ratio of the pigment dispersion to the resin solution containing the halogenated product was adjusted to be the same as that of Example 99, and the others were A red colored resin composition was obtained in the same manner as in Example 99.

實施例106 Example 106

除了將顏料分散體(DP-8)改變為顏料分散體(DP-9)，調整顏料分散體與含有鹵化生成物之樹脂溶液之比率，使其成為與實施例99相同色度以外，其他均與實施例99同樣地獲得紅色著色樹脂組成物。 In addition to changing the pigment dispersion (DP-8) to the pigment dispersion (DP-9), the ratio of the pigment dispersion to the resin solution containing the halogenated product was adjusted so that it became the same color as in Example 99, and the others were A red colored resin composition was obtained in the same manner as in Example 99.

實施例107 Example 107

除了將顏料分散體(DP-8)改變為顏料分散體(DP-14)，調整顏料分散體與含有鹵化生成物之樹脂溶液之比率，使其成為與實施例99相同色度以外，其他均與實施例99同樣地獲得紅色著色樹脂組成物。 In addition to changing the pigment dispersion (DP-8) to the pigment dispersion (DP-14), the ratio of the pigment dispersion to the resin solution containing the halogenated product was adjusted so that it became the same color as in Example 99, and the others were A red colored resin composition was obtained in the same manner as in Example 99.

實施例108 Example 108

除了將顏料分散體(DP-7)改變為顏料分散體(DP-8)，將含有鹵化生成物之樹脂溶液(DA-8)改變為含有鹵化生成物之樹脂溶液(DA-13)，調整顏料分散體與含有鹵化生成物之樹脂溶液之比率，使其成為與實施例99相同色度以外，其他均與實施例99同樣地獲得紅色著色樹脂組成物。 In addition to changing the pigment dispersion (DP-7) to a pigment dispersion (DP-8), the resin solution (DA-8) containing the halogenated product was changed to a resin solution (DA-13) containing a halogenated product, and adjusted. A red colored resin composition was obtained in the same manner as in Example 99 except that the ratio of the pigment dispersion to the resin solution containing the halogenated product was the same as that of Example 99.

實施例109 Example 109

除了將顏料分散體(DP-7)改變為顏料分散體(DP-8)，將含有鹵化生成物之樹脂溶液(DA-8)改變為含有鹵化生成物之樹脂溶液(DA-14)，調整顏料分散體與含有鹵化生成物之樹脂溶液之比率，使其成為與實施例99相同色度以外，其他均與實施例99同樣地獲得紅色著色樹脂組成物。 In addition to changing the pigment dispersion (DP-7) to a pigment dispersion (DP-8), the resin solution (DA-8) containing the halogenated product was changed to a resin solution (DA-14) containing a halogenated product, and adjusted. A red colored resin composition was obtained in the same manner as in Example 99 except that the ratio of the pigment dispersion to the resin solution containing the halogenated product was the same as that of Example 99.

實施例110 Example 110

除了將顏料分散體(DP-7)改變為顏料分散體(DP-10)，進一步加入顏料分散體(DP-14)，調整顏料分散體與含有鹵化生成物之樹脂溶液之比率，使其成為與實施例99相同色度以外，其他均與實施例99同樣地獲得紅色著色樹脂組成物。 In addition to changing the pigment dispersion (DP-7) to a pigment dispersion (DP-10), a pigment dispersion (DP-14) is further added, and the ratio of the pigment dispersion to the resin solution containing the halogenated product is adjusted to become A red colored resin composition was obtained in the same manner as in Example 99 except for the same chromaticity as in Example 99.

實施例111 Example 111

除了將顏料分散體(DP-7)改變為顏料分散體(DP-15)，將含有鹵化生成物之樹脂溶液(DA-8)改變為含有鹵化生成物之樹脂溶液(DA-15)，將丙烯酸樹脂溶液1改變為丙烯酸樹脂溶液2，調整顏料分散體與含有鹵化生成物之樹脂溶液之比率，使其成為與實施例99相同色度以外，其他均與實施例99同樣地獲得紅色著色樹脂組成物。 In addition to changing the pigment dispersion (DP-7) to a pigment dispersion (DP-15), changing the resin solution (DA-8) containing the halogenated product to a resin solution (DA-15) containing a halogenated product, The acrylic resin solution 1 was changed to the acrylic resin solution 2, and the ratio of the pigment dispersion to the resin solution containing the halogenated product was adjusted to have the same chromaticity as in Example 99, and the red colored resin was obtained in the same manner as in Example 99. Composition.

實施例112 Example 112

除了將顏料分散體(DP-7)改變為顏料分散體(DP-16)，將含有鹵化生成物之樹脂溶液(DA-8)改變為含有鹵化生成物之樹脂溶液(DA-16)，將丙烯酸樹脂溶液1改變為丙烯酸樹脂溶液3，調整顏料分散體與含有鹵化生成物之樹脂溶液之比率，使其成為與實施例99相同色度以外，其他均與實施例99同樣地獲得紅色著色樹脂組成物。 In addition to changing the pigment dispersion (DP-7) to a pigment dispersion (DP-16), changing the resin solution (DA-8) containing the halogenated product to a resin solution (DA-16) containing a halogenated product, The acrylic resin solution 1 was changed to the acrylic resin solution 3, and the ratio of the pigment dispersion to the resin solution containing the halogenated product was adjusted to have the same chromaticity as in Example 99, and the red colored resin was obtained in the same manner as in Example 99. Composition.

實施例113 Example 113

除了將顏料分散體(DP-7)改變為顏料分散體(DP-17)，將含有鹵化生成物之樹脂溶液(DA-8)改變為含有鹵化生成物之樹脂溶液(DA-17)，將丙烯酸樹脂溶液1改變為丙烯酸樹脂溶液4，調整顏料分散體與含有鹵化生成物之樹脂溶液之比率，使其成為與實施例99相同色度以外，其他均與實施例99同樣地獲得紅色著色樹脂組成物。 In addition to changing the pigment dispersion (DP-7) to a pigment dispersion (DP-17), changing the resin solution (DA-8) containing the halogenated product to a resin solution (DA-17) containing a halogenated product, The acrylic resin solution 1 was changed to the acrylic resin solution 4, and the ratio of the pigment dispersion to the resin solution containing the halogenated product was adjusted to have the same chromaticity as in Example 99, and the red colored resin was obtained in the same manner as in Example 99. Composition.

比較例13 Comparative Example 13

除了將顏料分散體(DP-7)改變為顏料分散體(DP-1)，將含有鹵化生成物之樹脂溶液(DA-8)改變為顏料分散體(DP-2)，調整顏料分散體之比率，使其成為與實施例99相同色度以外，其他均與實施例99同樣地獲得紅色著色樹脂組成物。 In addition to changing the pigment dispersion (DP-7) to a pigment dispersion (DP-1), the resin solution (DA-8) containing the halogenated product was changed to a pigment dispersion (DP-2), and the pigment dispersion was adjusted. A red colored resin composition was obtained in the same manner as in Example 99 except that the ratio was the same as that of Example 99.

比較例14 Comparative Example 14

除了將顏料分散體(DP-8)改變為顏料分散體(DP-2)，調整顏料分散體之比率，使其成為與實施例99相同色度以外，其他均與實施例99同樣地獲得紅色著色樹脂組成物。 Red was obtained in the same manner as in Example 99 except that the pigment dispersion (DP-8) was changed to the pigment dispersion (DP-2), and the ratio of the pigment dispersion was adjusted to have the same chromaticity as in Example 99. A colored resin composition.

比較例15 Comparative Example 15

除了將顏料分散體(DP-7)改變為顏料分散體(DP-9)，將含有鹵化生成物之樹脂溶液(DA-8)改變為顏料分散體(DP-2)，調整顏料分散體之比率，使其成為與實施例99相同色度以外，其他均與實施例99同樣地獲得紅色著色樹脂組成物。 In addition to changing the pigment dispersion (DP-7) to a pigment dispersion (DP-9), the resin solution (DA-8) containing the halogenated product was changed to a pigment dispersion (DP-2), and the pigment dispersion was adjusted. A red colored resin composition was obtained in the same manner as in Example 99 except that the ratio was the same as that of Example 99.

比較例16 Comparative Example 16

除了將顏料分散體(DP-7)改變為顏料分散體(DP-10)，將含有鹵化生成物之樹脂溶液(DA-8)改變為顏料分散體(DP-2)，調整顏料分散體之比率，使其成為與實施例99相同色度以外，其他均與實施例99同樣地獲得紅色著色樹脂組成物。 In addition to changing the pigment dispersion (DP-7) to a pigment dispersion (DP-10), the resin solution (DA-8) containing the halogenated product was changed to a pigment dispersion (DP-2), and the pigment dispersion was adjusted. A red colored resin composition was obtained in the same manner as in Example 99 except that the ratio was the same as that of Example 99.

比較例17 Comparative Example 17

除了將顏料分散體(DP-7)改變為顏料分散體(DP-11)，將含有鹵化生成物之樹脂溶液(DA-8)改變為顏料分散體(DP-2)，調整顏料分散體之比率，使其成為與實施例99相同色度以外，其他均與實施例99同樣地獲得紅色著色樹脂組成物。 In addition to changing the pigment dispersion (DP-7) to a pigment dispersion (DP-11), the resin solution (DA-8) containing the halogenated product was changed to a pigment dispersion (DP-2), and the pigment dispersion was adjusted. A red colored resin composition was obtained in the same manner as in Example 99 except that the ratio was the same as that of Example 99.

比較例18 Comparative Example 18

除了將顏料分散體(DP-7)改變為顏料分散體(DP-8)，將含有鹵化生成物之樹脂溶液(DA-8)改變為顏料分散體(DP-2)，調整顏料分散體之 比率，使其成為與實施例99相同色度以外，其他均與實施例99同樣地獲得紅色著色樹脂組成物。 In addition to changing the pigment dispersion (DP-7) to a pigment dispersion (DP-8), the resin solution (DA-8) containing the halogenated product was changed to a pigment dispersion (DP-2), and the pigment dispersion was adjusted. A red colored resin composition was obtained in the same manner as in Example 99 except that the ratio was the same as that of Example 99.

<實施例114~118、比較例19~24> <Examples 114 to 118, Comparative Examples 19 to 24>

實施例114 Example 114

將下述混合物攪拌混合均勻後，以5.0μm的過濾器過濾而製作紅色著色樹脂組成物。 The mixture was stirred and mixed uniformly, and then filtered through a 5.0 μm filter to prepare a red colored resin composition.

顏料分散體(DP-7)：7.2部 Pigment dispersion (DP-7): 7.2

含有鹵化生成物之樹脂溶液(DA2-1)：3.8部 Resin solution containing halogenated product (DA2-1): 3.8

丙烯酸樹脂溶液1：40.0部 Acrylic resin solution 1: 40.0

丙二醇單乙基醚乙酯(PGMAC)：49.0部 Propylene glycol monoethyl ether ethyl ester (PGMAC): 49.0

實施例115 Example 115

除了將含有鹵化生成物之樹脂溶液(DA2-1)改變為含有鹵化生成物之樹脂溶液(DA2-9)，調整顏料分散體與含有鹵化生成物之樹脂溶液之比率，使其成為與實施例114相同色度以外，其他均與實施例114同樣地獲得紅色著色樹脂組成物。 The ratio of the pigment dispersion to the resin solution containing the halogenated product was adjusted to be the same as the example except that the resin solution (DA2-1) containing the halogenated product was changed to the resin solution (DA2-9) containing the halogenated product. A red colored resin composition was obtained in the same manner as in Example 114 except for the same chromaticity.

實施例116 Example 116

除了將含有鹵化生成物之樹脂溶液(DA2-1)改變為含有鹵化生成物之樹脂溶液(DA2-10)，調整顏料分散體與含有鹵化生成物之樹脂溶液之比率，使其成為與實施例114相同色度以外，其他均與實施例114同樣地獲得紅色著色樹脂組成物。 The ratio of the pigment dispersion to the resin solution containing the halogenated product was adjusted to be the same as the example except that the resin solution (DA2-1) containing the halogenated product was changed to the resin solution (DA2-10) containing the halogenated product. A red colored resin composition was obtained in the same manner as in Example 114 except for the same chromaticity.

實施例117 Example 117

除了將含有鹵化生成物之樹脂溶液(DA2-1)改變為含有鹵化 生成物之樹脂溶液(DA2-7)，調整顏料分散體與含有鹵化生成物之樹脂溶液之比率，使其成為與實施例114相同色度以外，其他均與實施例114同樣地獲得紅色著色樹脂組成物。 In addition to changing the resin solution (DA2-1) containing a halogenated product to contain halogenation A red colored resin was obtained in the same manner as in Example 114 except that the ratio of the pigment dispersion to the resin solution containing the halogenated product was adjusted to be the same as that of Example 114. Composition.

實施例118 Example 118

除了將含有鹵化生成物之樹脂溶液(DA2-1)改變為含有鹵化生成物之樹脂溶液(DA2-8)，調整顏料分散體與含有鹵化生成物之樹脂溶液之比率，使其成為與實施例114相同色度以外，其他均與實施例114同樣地獲得紅色著色樹脂組成物。 The ratio of the pigment dispersion to the resin solution containing the halogenated product was adjusted to be the same as the example except that the resin solution (DA2-1) containing the halogenated product was changed to the resin solution (DA2-8) containing the halogenated product. A red colored resin composition was obtained in the same manner as in Example 114 except for the same chromaticity.

比較例19 Comparative Example 19

除了將顏料分散體(DP-7)改變為顏料分散體(DP-1)，將含有鹵化生成物之樹脂溶液(DA2-1)改變為顏料分散體(DP-2)，調整顏料分散體之比率，使其成為與實施例114相同色度以外，其他均與實施例114同樣地獲得紅色著色樹脂組成物。 In addition to changing the pigment dispersion (DP-7) to a pigment dispersion (DP-1), the resin solution (DA2-1) containing the halogenated product was changed to a pigment dispersion (DP-2), and the pigment dispersion was adjusted. A red colored resin composition was obtained in the same manner as in Example 114 except that the ratio was the same as that of Example 114.

比較例20 Comparative Example 20

除了將將含有鹵化生成物之樹脂溶液(DA2-1)改變為顏料分散體(DP-2)，調整顏料分散體之比率，使其成為與實施例114相同色度以外，其他均與實施例114同樣地獲得紅色著色樹脂組成物。 The ratio of the pigment dispersion was adjusted to be the same as that of Example 114 except that the resin solution (DA2-1) containing the halogenated product was changed to the pigment dispersion (DP-2), and the examples were the same as the examples. 114 A red colored resin composition was obtained in the same manner.

比較例21 Comparative Example 21

除了將顏料分散體(DP-7)改變為顏料分散體(DP-8)，將含有鹵化生成物之樹脂溶液(DA2-1)改變為顏料分散體(DP-2)，調整顏料分散體之比率，使其成為與實施例114相同色度以外，其他均與實施例114同樣地獲得紅色著色樹脂組成物。 In addition to changing the pigment dispersion (DP-7) to a pigment dispersion (DP-8), the resin solution (DA2-1) containing the halogenated product was changed to a pigment dispersion (DP-2), and the pigment dispersion was adjusted. A red colored resin composition was obtained in the same manner as in Example 114 except that the ratio was the same as that of Example 114.

比較例22 Comparative Example 22

除了將顏料分散體(DP-7)改變為顏料分散體(DP-9)，將含有鹵化生成物之樹脂溶液(DA2-1)改變為顏料分散體(DP-2)，調整顏料分散體之比率，使其成為與實施例114相同色度以外，其他均與實施例114同樣地獲得紅色著色樹脂組成物。 In addition to changing the pigment dispersion (DP-7) to a pigment dispersion (DP-9), the resin solution (DA2-1) containing the halogenated product was changed to a pigment dispersion (DP-2), and the pigment dispersion was adjusted. A red colored resin composition was obtained in the same manner as in Example 114 except that the ratio was the same as that of Example 114.

比較例23 Comparative Example 23

除了將顏料分散體(DP-7)改變為顏料分散體(DP-10)，將含有鹵化生成物之樹脂溶液(DA2-1)改變為顏料分散體(DP-2)，調整顏料分散體之比率，使其成為與實施例114相同色度以外，其他均與實施例114同樣地獲得紅色著色樹脂組成物。 In addition to changing the pigment dispersion (DP-7) to a pigment dispersion (DP-10), the resin solution (DA2-1) containing the halogenated product was changed to a pigment dispersion (DP-2), and the pigment dispersion was adjusted. A red colored resin composition was obtained in the same manner as in Example 114 except that the ratio was the same as that of Example 114.

比較例24 Comparative Example 24

除了將顏料分散體(DP-7)改變為顏料分散體(DP-11)，將含有鹵化生成物之樹脂溶液(DA2-1)改變為顏料分散體(DP-2)，調整顏料分散體之比率，使其成為與實施例114相同色度以外，其他均與實施例114同樣地獲得紅色著色樹脂組成物。 In addition to changing the pigment dispersion (DP-7) to a pigment dispersion (DP-11), the resin solution (DA2-1) containing the halogenated product was changed to a pigment dispersion (DP-2), and the pigment dispersion was adjusted. A red colored resin composition was obtained in the same manner as in Example 114 except that the ratio was the same as that of Example 114.

將實施例99~118、比較例13~24所獲得的紅色著色樹脂組成物，於透明基板上旋轉塗布成膜厚2.0μ，以60℃乾燥(預烤)5分鐘後，以230℃加熱20分鐘(曝後烤)而製作成塗膜基板。 The red colored resin compositions obtained in Examples 99 to 118 and Comparative Examples 13 to 24 were spin-coated on a transparent substrate to a film thickness of 2.0 μ, dried at 60° C. (pre-baked) for 5 minutes, and then heated at 230° C. 20 A coated substrate was prepared in minutes (baked after exposure).

以顯微分光光度計(Olympus光學公司製「OSP-SP200」)測定所製作的塗膜基板之亮度(Y)。 The brightness (Y) of the produced coating film substrate was measured by a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optics Co., Ltd.).

如表7-1、7-2所示，於實施例99~118之紅色著色樹脂組成物，與比較例13~24之紅色著色樹脂組成物相比較可獲得亮度較高之紅色塗膜。此時，於表8顯示出未出現預烤/曝後烤之亮度差降低，可維持耐受性。 As shown in Tables 7-1 and 7-2, in the red colored resin compositions of Examples 99 to 118, red paint films having higher brightness were obtained as compared with the red colored resin compositions of Comparative Examples 13 to 24. At this time, in Table 8, it was shown that the difference in luminance difference between the pre-bake/exposure roasting did not occur, and the tolerance was maintained.

實施例119 Example 119

將下述混合物攪拌混合均勻後，以1.0μm的過濾器過濾而獲得鹼顯影型紅色抗蝕劑材料。 The mixture was stirred and mixed uniformly, and then filtered through a 1.0 μm filter to obtain an alkali-developable red resist material.

含有鹵化生成物之樹脂溶液(DA-8)：21.0部 Resin solution containing halogenated product (DA-8): 21.0 parts

顏料分散體(DP-7)：39.0部 Pigment Dispersion (DP-7): 39.0

丙烯酸樹脂溶液1：11.0部 Acrylic resin solution 1:11.0

三烴甲基丙烷三丙烯酸酯：4.2部 Trihydrocarbylmethylpropane triacrylate: 4.2

(新中村化學公司製「NK酯ATMPT」) ("Nippon Nakamura Chemical Co., Ltd." "NK ester ATMPT")

光聚合起始劑：1.2部 Photopolymerization initiator: 1.2

(日本千葉公司製「IRGACURE 907」 (IRGACURE 907, manufactured by Chiba Corporation, Japan)

增感劑(保土谷化學公司製「EAB-F」)：0.4部 Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4

乙二醇單甲基醚乙酯：23.2部 Ethylene glycol monomethyl ether ethyl ester: 23.2

實施例120 Example 120

將下述混合物攪拌混合均勻後，以1.0μm的過濾器過濾而獲得鹼顯影型紅色抗蝕劑材料。 The mixture was stirred and mixed uniformly, and then filtered through a 1.0 μm filter to obtain an alkali-developable red resist material.

含有鹵化生成物之樹脂溶液(DA2-1)：21.0部 Resin solution containing halogenated product (DA2-1): 21.0 parts

顏料分散體(DP-7)：39.0部 Pigment Dispersion (DP-7): 39.0

丙烯酸樹脂溶液1：11.0部 Acrylic resin solution 1:11.0

三烴甲基丙烷三丙烯酸酯：4.2部 Trihydrocarbylmethylpropane triacrylate: 4.2

(新中村化學公司製「NK酯ATMPT」) ("Nippon Nakamura Chemical Co., Ltd." "NK ester ATMPT")

光聚合起始劑：1.2部 Photopolymerization initiator: 1.2

(日本千葉公司製「IRGACURE 907」 (IRGACURE 907, manufactured by Chiba Corporation, Japan)

增感劑(保土谷化學公司製「EAB-F」)：0.4部 Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4

乙二醇單甲基醚乙酯：23.2部 Ethylene glycol monomethyl ether ethyl ester: 23.2

比較例25 Comparative Example 25

除了分別將顏料分散體(DP-7)及含有鹵化生成物之樹脂溶液(DA-8)，改變為顏料分散體(DP-1)及顏料分散體(DP-2)，調整顏料分散體之比率，使其成為與實施例119相同色度以外，其他均與實施例119同樣地獲得鹼顯影型紅色抗蝕劑材料。 In addition to the pigment dispersion (DP-7) and the resin solution (DA-8) containing the halogenated product, respectively, the pigment dispersion (DP-1) and the pigment dispersion (DP-2) were adjusted to adjust the pigment dispersion. The alkali-developing type red resist material was obtained in the same manner as in Example 119 except that the ratio was the same as that of Example 119.

將實施例119~120、比較例25所獲得的鹼顯影型紅色抗蝕劑材料，於透明基板上旋轉塗布成膜厚2.5μ，以60℃乾燥(預烤)5分鐘後，以230℃加熱20分鐘(曝後烤)而製作成塗膜基板，如先前記載來測定所製作的塗膜基板之亮度(Y)。 The alkali-developing type red resist materials obtained in Examples 119 to 120 and Comparative Example 25 were spin-coated on a transparent substrate to a film thickness of 2.5 μ, dried at 60° C. (pre-baked) for 5 minutes, and then heated at 230° C. The coating film substrate was produced for 20 minutes (baked after exposure), and the brightness (Y) of the produced coating film substrate was measured as described above.

於表9表示結果。 The results are shown in Table 9.

如表9所示，於實施例119~120之鹼顯影型紅色抗蝕劑材料，與比較例25之鹼顯影型紅色抗蝕劑材料相比較可獲得亮度較高之紅色塗膜。 As shown in Table 9, in the alkali-developable red resist materials of Examples 119 to 120, a red paint film having a higher luminance was obtained as compared with the alkali-developable red resist material of Comparative Example 25.

Claims (9)

一種彩色濾光片用紅色著色組成物，其特徵為包含著色劑及樹脂黏結劑；前述著色劑包含：呫噸系酸性染料與具有陽離子性基之化合物之鹵化生成物(A)、及紅色顏料，前述具有陽離子性基之化合物係於側鏈具有陽離子性基之樹脂。 A coloring composition for a color filter comprising a coloring agent and a resin binder; the coloring agent comprising: a halogenated product (A) of a xanthene-based acid dye and a compound having a cationic group, and a red pigment The compound having a cationic group is a resin having a cationic group in a side chain. 如申請專利範圍第1項之彩色濾光片用紅色著色組成物，其中前述於側鏈具有陽離子性基之樹脂係乙烯基系樹脂，其係包含由下述一般式(1-2)所表示的構造單位； (於一般式(1-2)中，R5表示氫原子、或置換或者無置換之烷基。R6~R8分別獨立表示氫原子、置換或者無置換之烷基、置換或者無置換之烯基、或置換或者無置換之芳基，R6~R8中之2個相互結合而形成環亦可。Q表示亞烷基、亞芳基、-CONH-R9-或-COO-R9-，R9表示亞烷基。Y-表示無機或有機之陰離子)。 The red coloring composition for a color filter according to the first aspect of the invention, wherein the resin-based vinyl resin having a cationic group in a side chain is represented by the following general formula (1-2); Construction unit (In the general formula (1-2), R 5 represents a hydrogen atom, or a substituted or unsubstituted alkyl group. R 6 to R 8 each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substitution or no substitution. Alkenyl, or substituted or unsubstituted aryl, two of R 6 to R 8 are bonded to each other to form a ring. Q represents an alkylene group, an arylene group, -CONH-R 9 - or -COO-R 9 -, R 9 represents an alkylene group, and Y - represents an inorganic or organic anion). 如申請專利範圍第1項之彩色濾光片用紅色著色組成物，其中前述呫噸系酸性染料被分類為C.I.酸性紅。 The color filter of claim 1 is a red coloring composition, wherein the aforementioned xanthene acid dye is classified into C.I. acid red. 如申請專利範圍第1項之彩色濾光片用紅色著色組成物，其中前述呫噸系酸性染料係從C.I.酸性紅(C.I.Acid Red)52、C.I.酸性紅87、C.I.酸性紅92、C.I.酸性紅289及C.I.酸性紅388所組成的群組選擇之至少一種。 For example, the color filter of claim 1 is a red coloring composition, wherein the xanthene acid dye is from CI Acid Red 52, CI Acid Red 87, CI Acid Red 92, CI Acid Red. At least one of the group selection consisting of 289 and CI Acid Red 388. 如申請專利範圍第1項之彩色濾光片用紅色著色組成物，其中前述紅色顏料為二酮吡咯并吡咯系顏料及/或蒽醌系顏料及/或單偶氮系或二偶氮系顏料。 The red coloring composition for a color filter according to claim 1, wherein the red pigment is a diketopyrrolopyrrole pigment and/or an anthraquinone pigment and/or a monoazo or diazo pigment. . 如申請專利範圍第1項之彩色濾光片用紅色著色組成物，其中前述紅色顏料係從C.I.顏料紅(C.I.Pigment Red)254、C.I.顏料紅177、C.I.顏料紅48：1、166、C.I.顏料紅220、C.I.顏料紅242及C.I.顏料橘38所組成的群組選擇之至少一種。 The color filter of claim 1 is a red coloring composition, wherein the red pigment is from CI Pigment Red 254, CI Pigment Red 177, CI Pigment Red 48:1, 166, CI Pigment. At least one of the group consisting of Red 220, CI Pigment Red 242, and CI Pigment Orange 38 is selected. 如申請專利範圍第1項之彩色濾光片用紅色著色組成物，其中前述著色劑進一步含有黃色顏料。 The color filter of claim 1 is a red coloring composition, wherein the coloring agent further contains a yellow pigment. 如申請專利範圍第1項之彩色濾光片用紅色著色組成物，其中進一步含有光聚合性單體及/或光聚合起始劑。 The color filter of claim 1 is a red coloring composition further comprising a photopolymerizable monomer and/or a photopolymerization initiator. 一種彩色濾光片，其係具備至少1個紅色濾光片區段、至少1個綠色濾光片區段及至少1個藍色濾光片區段；前述至少1個紅色濾光片區段係由申請專利範圍第1至7項中任一項之彩色濾光片用紅色著色組成物所形成。 A color filter comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment; the at least one red filter segment The color filter of any one of claims 1 to 7 is formed of a red colored composition.
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