TWI444441B - Coloring composition and color filter - Google Patents

Description

著色組成物及彩色濾光片 Coloring composition and color filter

本發明係關於一種著色組成物，其係使用於製造彩色液晶顯示裝置及彩色攝像裝置等之彩色濾光片。又，本發明係關於一種彩色濾光片，其係具備利用該著色組成物而形成之濾光片區段。 The present invention relates to a coloring composition for use in manufacturing a color filter such as a color liquid crystal display device or a color image pickup device. Moreover, the present invention relates to a color filter comprising a filter segment formed using the colored composition.

液晶顯示裝置具有例如於1對偏光板之間夾著液晶層之構造。該類液晶顯示裝置係利用液晶分子之配向，而令穿透一偏光板之偏光狀態變化，藉此控制穿透另一偏光板之光量。 The liquid crystal display device has a structure in which, for example, a liquid crystal layer is sandwiched between a pair of polarizing plates. This type of liquid crystal display device utilizes the alignment of liquid crystal molecules to change the polarization state of a polarizing plate, thereby controlling the amount of light penetrating through the other polarizing plate.

液晶顯示裝置之顯示模式包括：VA(垂直對準)模式、IPS(平面切換)模式及TN(扭轉向列)模式。其中尤以TN模式為主流。該等液晶顯示裝置可藉由於偏光板之間設置彩色濾光片以顯示彩色圖像。彩色液晶顯示裝置近年來利用在電視受像機及個人電腦監視器等各種機器。因此，對彩色濾光片要求高對比及高亮度化，對於寬廣的色彩重現區域及高可靠性之要求亦升高。 The display modes of the liquid crystal display device include a VA (Vertical Alignment) mode, an IPS (Plane Switching) mode, and a TN (Twisted Nematic) mode. Among them, the TN mode is the mainstream. The liquid crystal display devices can display color images by providing color filters between the polarizing plates. In recent years, color liquid crystal display devices have been used in various devices such as television receivers and personal computer monitors. Therefore, high contrast and high brightness are required for color filters, and the requirements for a wide color reproduction area and high reliability are also increased.

再者，彩色濾光片具有於玻璃等透明基板上，配置2種以上色相不同之濾光片區段之構造。各濾光片區段甚微細，其寬度為數微米至數百微米。於濾光片區段可實現條紋排列及三角排列等各種形狀及配置。無論如何，該等濾光片區段均依每色相，以特定排列整齊地配置。 又，於利用C-MOS(互補金屬氧化物半導體)或CCD(電荷耦合元件)之彩色攝像裝置，一般於攝像元件之受光面上，配設加法混色之三原色，亦即藍(B)、綠(B)及紅(R)色，或其等之補色之黃(Y)、洋紅(M)及青(C)色之濾光片區段而成之彩色濾光片。近年來，對於彩色攝像裝置所用之彩色濾光片，關於高穿透率，亦即關於高亮度及寬廣的色彩重現區域等色彩特性之要求升高。彩色濾光片之製造方法包括例如：如利用鹵化呈色之染色法及染料分散法般使用染料作為著色劑之方法；使用著色劑作為顏料之顏料分散法；印刷法；及電鍍法。 Further, the color filter has a structure in which two or more kinds of filter segments having different hue are disposed on a transparent substrate such as glass. Each filter segment is very fine and has a width of a few microns to hundreds of microns. Various shapes and configurations such as stripe arrangement and triangular arrangement can be realized in the filter section. In any event, the filter segments are arranged neatly in a particular arrangement for each hue. Further, in a color imaging device using a C-MOS (Complementary Metal Oxide Semiconductor) or a CCD (Charge Coupled Device), generally, three primary colors of additive color mixing, that is, blue (B), green, are disposed on the light receiving surface of the image sensor. Color filters made of (B) and red (R) colors, or their complementary yellow (Y), magenta (M), and cyan (C) color filter segments. In recent years, for color filters used in color image pickup devices, demands for high transmittance, that is, color characteristics such as high brightness and wide color reproduction regions have increased. The method for producing a color filter includes, for example, a method of using a dye as a colorant by a dyeing method using halogenation coloring and a dye dispersion method, a pigment dispersion method using a colorant as a pigment, a printing method, and an electroplating method.

顏料分散法係使用彩色抗蝕劑，其係藉由令著色劑之顏料粒子分散於透明樹脂中，於此混合感光劑及添加劑等而獲得。然後，於基板上，藉由旋轉塗布機等塗布裝置塗布該彩色抗蝕劑，中介光罩對於該塗膜選擇性地進行曝光。將該曝光後之塗膜依序供作鹼顯影及熱硬化處理，藉此獲得濾光片區段。就每一色彩重複以上操作而完成彩色濾光片。自以往，藍色濾光片區段及青色濾光片區段在許多情況下均利用耐受性及色調良好的酞菁顏料。酞菁顏料具有a型、b型、d型及e型等不同結晶型，由於任一型均具有彩度及著色力高的良好性質，因此適合作為彩色濾光片用著色劑。 In the pigment dispersion method, a color resist is used, which is obtained by dispersing pigment particles of a colorant in a transparent resin, mixing a sensitizer, an additive, and the like. Then, the color resist is applied onto the substrate by a coating device such as a spin coater, and the intermediate mask selectively exposes the coating film. The exposed coating film is sequentially subjected to alkali development and heat hardening treatment, whereby a filter segment is obtained. The color filter is completed by repeating the above operations for each color. In the past, blue filter segments and cyan filter segments have utilized phthalocyanine pigments which are well tolerated and have good tones in many cases. The phthalocyanine pigment has different crystal forms such as a-type, b-type, d-type, and e-type, and is suitable as a coloring agent coloring agent because it has good coloring property and high coloring power.

酞菁顏料據知有具有銅、鋅、鎳、鈷及鋁等各種中心金屬之物。其中尤其以銅酞菁顏料之彩度最高，因此廣受利用。此外，無金屬銅酞菁顏料、鋅酞菁顏料、氧化鋁酞菁顏料及鈷酞菁顏料等異種金屬酞菁顏料亦已實用化。 The phthalocyanine pigment is known to have various central metals such as copper, zinc, nickel, cobalt, and aluminum. Among them, copper phthalocyanine pigments are widely used because they have the highest chroma. Further, dissimilar metal phthalocyanine pigments such as metal-free copper phthalocyanine pigments, zinc phthalocyanine pigments, alumina phthalocyanine pigments, and cobalt phthalocyanine pigments have also been put into practical use.

紅色濾光片區段及洋紅色濾光片區段在許多情況下均利用 耐受性及色調良好之二酮吡咯并吡咯顏料、喹吖酮顏料及蒽醌顏料等。該等之任一者均具有彩度及著色力高的良好性質，因此適合作為彩色濾光片用著色劑。 Red filter segments and magenta filter segments are utilized in many cases A diketopyrrolopyrrole pigment, a quinophthalone pigment, and an anthraquinone pigment which are well tolerated and have a good hue. Any of these has good properties of high chroma and coloring power, and is therefore suitable as a coloring agent for color filters.

形成綠色濾光片區段時，在許多情況下均利用耐受性及色調良好之鹵化酞菁顏料等。該等之任一者均具有彩度及著色力高的良好性質，因此適合作為彩色濾光片用著色劑。又，與藍色顏料相同，據知有具有銅、鋅、鎳、鈷及鋁等各種中心金屬之物。其中尤其以鋅酞菁顏料及鋁酞菁顏料之彩度最高，因此廣受利用。 When a green filter segment is formed, a halogenated phthalocyanine pigment having good tolerance and color tone is used in many cases. Any of these has good properties of high chroma and coloring power, and is therefore suitable as a coloring agent for color filters. Further, similarly to the blue pigment, it is known that there are various central metals such as copper, zinc, nickel, cobalt, and aluminum. Among them, zinc phthalocyanine pigments and aluminum phthalocyanine pigments have the highest chroma, and are therefore widely used.

就利用冷陰極管類型背光之以往的液晶顯示裝置而言，例如藍色濾光片區段或青色濾光片區段係使用銅酞菁顏料與二酮吡咯并吡咯系顏料之組合，藍色濾光片區段或洋紅濾光片區段係使用蒽醌顏料與二酮吡咯并吡咯顏料之組合，綠色濾光片區段係利用鹵化酞菁顏料，藉此可達成高亮度及寬度的色彩顯示區域。然而，如前述，對彩色濾光片要求進一步之高亮度化及寬度的色彩顯示區域。 In the case of a conventional liquid crystal display device using a cold cathode tube type backlight, for example, a blue filter segment or a cyan filter segment is a combination of a copper phthalocyanine pigment and a diketopyrrolopyrrole pigment, blue. The filter segment or the magenta filter segment is a combination of an anthraquinone pigment and a diketopyrrolopyrrole pigment, and the green filter segment utilizes a halogenated phthalocyanine pigment, thereby achieving high brightness and width. Display area. However, as described above, a color display area which is further high in brightness and width is required for the color filter.

於日本特開平6-75375號中，記載一種為了解決上述課題，作為著色劑非令顏料而令染料溶解於樹脂等之技術。又，於日本特開2001-81348號中，記載將三芳基甲烷系染料、玫瑰紅系染料及偶氮染料予以色澱化，使用該等沈澱色料作為彩色濾光片用著色劑。然而，染料具有與顏料相比較，其耐熱性、耐光性及耐溶濟性較差的問題。 In order to solve the above-mentioned problems, a technique in which a dye is dissolved in a resin or the like as a coloring agent without a pigment is described in the Japanese Patent Publication No. 6-75375. Further, Japanese Laid-Open Patent Publication No. 2001-81348 discloses that a triarylmethane dye, a rosin dye, and an azo dye are subjected to lake formation, and these precipitated colorants are used as colorants for color filters. However, the dye has a problem of poor heat resistance, light resistance, and solvent resistance as compared with the pigment.

於日本特開2008-304766號中，記載為了令耐熱性、耐光性及耐溶濟性提升，而將三芳基甲烷系染料及芳香族單磺酸之鹵化生成物或三芳基甲烷系鹼性染料，作為彩色率光片用著色劑使用。然而，三芳基甲 烷系鹼性染料及芳香族單磺酸之鹵化生成物之分子量小，因此具有耐久性不佳的缺點。又，即便直接使用鹼性染料，當然其耐久性仍舊不佳。 In order to improve heat resistance, light resistance, and solvent resistance, a halogenated product of a triarylmethane dye and an aromatic monosulfonic acid or a triarylmethane-based basic dye is described in JP-A-2008-304766. It is used as a coloring agent for a color rate light sheet. However, triaryl Since the halogenated product of the alkali-based basic dye and the aromatic monosulfonic acid has a small molecular weight, it has a disadvantage of poor durability. Moreover, even if a basic dye is directly used, the durability is of course not good.

本發明提供一種色彩特性、耐熱性、耐光性及耐溶劑性良好之彩色濾光片，及使用於其製造之著色組成物。 The present invention provides a color filter excellent in color characteristics, heat resistance, light resistance, and solvent resistance, and a colored composition used in the production thereof.

為了解決前述問題，本發明者等銳意累積研究，結果發現作為著色組成物之著色劑，藉由使用鹼性染料及分子量在特定範圍內之相對化合物成鹽而成之生成物，可實現高亮度及寬廣的色彩重現區域，又發現關於耐熱性、耐光性及耐溶劑性亦可達成良好性能。然後，根據該酌見而完成以下第1及第2態樣之發明。 In order to solve the above problems, the inventors of the present invention have intensively accumulated research, and as a result, it has been found that a coloring agent as a coloring composition can achieve high brightness by using a basic dye and a product obtained by salting a relative compound having a molecular weight within a specific range. And a wide color reproduction area, and found that heat resistance, light resistance and solvent resistance can also achieve good performance. Then, according to this discretion, the inventions of the first and second aspects below are completed.

亦即，本發明之第1態樣係關於一種彩色濾光片用著色組成物，其係含有透明樹脂及著色劑；前述著色劑包含由鹼性染料及陰離子成分之相對化合物所組成的成鹽生成物；前述相對化合物之分子量係在200至3500之範圍內。 That is, the first aspect of the present invention relates to a coloring composition for a color filter comprising a transparent resin and a coloring agent; the coloring agent comprising a salt composed of a basic dye and an anionic component. The product; the molecular weight of the aforementioned relative compound is in the range of 200 to 3,500.

前述相對化合物之分子量亦可在250至3500之範圍內。前述相對化合物亦可從由雜多酸、有機磺酸、有機羧酸及酸性染料所組成的群組選擇之至少一者。 The molecular weight of the aforementioned relative compound may also be in the range of 250 to 3,500. The aforementioned relative compound may also be selected from at least one selected from the group consisting of heteropolyacids, organic sulfonic acids, organic carboxylic acids, and acid dyes.

前述著色劑亦可進一步包含具有酸基之樹脂。前述具有酸基之樹脂之重量平均分子量亦可在400至12000之範圍內。前述具有酸基之樹脂亦可為松香改質順丁烯二酸樹脂。前述具有酸價之樹脂之酸價亦可在100至300mgKOH/g之範圍內。 The colorant may further contain a resin having an acid group. The weight average molecular weight of the aforementioned acid group-containing resin may also be in the range of 400 to 12,000. The resin having an acid group may also be a rosin-modified maleic acid resin. The acid value of the aforementioned acid having a acid value may also be in the range of 100 to 300 mgKOH/g.

前述鹼性染料亦可從由三芳基甲烷系染料、玫瑰紅系染 料、亞甲藍系染料及黃素系染料所組成的群組選擇之至少一者。 The aforementioned basic dye may also be dyed from a triarylmethane dye or rose red. At least one of a group consisting of a material, a methylene blue dye, and a flavin dye.

該彩色濾光片用著色組成物亦可進一步含有光聚合性組成物及/或光聚合起始劑。 The coloring composition for a color filter may further contain a photopolymerizable composition and/or a photopolymerization initiator.

又，本發明之第2態樣係關於一種彩色濾光片，其係具備由上述彩色濾光片用著色組成物所形成的濾光片區段。 Further, a second aspect of the invention relates to a color filter comprising a filter segment formed of the coloring composition for a color filter.

又，為了解決前述問題，本發明者等銳意累積研究，結果發現使用三芳基甲烷系染料及呫噸系染料所組成的成鹽生成物，可實現高亮度及寬廣的色彩重現區域，又發現關於耐受性亦可達成良好性能。然後，根據該酌見而完成以下第3及第4態樣之發明。 Further, in order to solve the above problems, the inventors of the present invention have intensively accumulated research, and as a result, it has been found that a salt-forming product composed of a triarylmethane-based dye and a xanthene-based dye can realize a high-brightness and a wide color reproduction region, and it is found that Good performance can also be achieved with regard to tolerance. Then, according to this discretion, the inventions of the following third and fourth aspects are completed.

亦即，本發明之第3態樣係關於一種彩色濾光片用藍色著色組成物，其係含有透明樹脂及著色劑；前述著色劑包含由三芳基甲烷系染料及呫噸系染料所組成的成鹽生成物。 That is, the third aspect of the present invention relates to a blue colored composition for a color filter comprising a transparent resin and a color former; and the colorant comprises a triarylmethane dye and a xanthene dye. Salt-forming product.

前述三芳基甲烷系染料係三芳基甲烷系鹼性染料，前述呫噸系染料係呫噸系酸性染料亦可。或者，前述三芳基甲烷系染料係三芳基甲烷系酸性染料，前述呫噸系染料係呫噸系鹼性染料亦可。 The triarylmethane-based dye is a triarylmethane-based basic dye, and the xanthene-based dye may be a xanthene-based acid dye. Alternatively, the triarylmethane-based dye is a triarylmethane-based acid dye, and the xanthene-based dye may be a xanthene-based basic dye.

前述呫噸系染料亦可為玫瑰紅系染料。 The aforementioned xanthene dye may also be a rose red dye.

前述著色劑亦可進一步包含酞菁系顏料。又，前述著色劑亦可進一步包含二噁嗪系顏料。 The colorant may further contain a phthalocyanine-based pigment. Further, the colorant may further contain a dioxazine-based pigment.

該彩色濾光片用藍色著色組成物亦可含有光聚合性單體及/或光聚合起始劑。 The blue coloring composition for the color filter may further contain a photopolymerizable monomer and/or a photopolymerization initiator.

又，本發明之第4態樣係關於一種彩色濾光片，其係具備由上述彩色濾光片用藍色著色組成物所形成的藍色濾光片區段。 Further, a fourth aspect of the invention relates to a color filter comprising a blue filter segment formed of the blue coloring composition for the color filter.

進而言之，為了解決前述問題，本發明者等銳意累積研究，結果發現使用呫噸系鹼性染料及呫噸系酸性染料所組成的成鹽生成物，可實現高亮度及寬廣的色彩重現區域，又發現關於耐受性亦可達成良好性能。然後，根據該酌見而完成以下第5及第6態樣之發明。 Further, in order to solve the above problems, the inventors of the present invention have intensively accumulated research and found that a salt-forming product composed of a xanthene-based basic dye and a xanthene-based acid dye can realize high brightness and wide color reproduction. The region has also found that good performance can also be achieved with regard to tolerance. Then, according to this discretion, the inventions of the following fifth and sixth aspects are completed.

亦即，亦即，本發明之第5態樣係關於一種彩色濾光片用著色組成物，其係含有透明樹脂及著色劑；前述著色劑包含由呫噸系鹼性染料及呫噸系酸性染料所組成的成鹽生成物。 That is, the fifth aspect of the present invention relates to a coloring composition for a color filter comprising a transparent resin and a coloring agent; the coloring agent comprising a xanthene-based basic dye and a xanthene-based acid A salt-forming product composed of a dye.

前述呫噸系鹼性染料亦可為玫瑰紅系染料。 The above-mentioned xanthene-based basic dye may also be a rose-red dye.

前述著色劑亦可進一步含有酞菁系顏料。又，前述著色劑進一步包含二噁嗪系顏料。 The colorant may further contain a phthalocyanine-based pigment. Further, the colorant further contains a dioxazine-based pigment.

該彩色濾光片用著色組成物亦可含有光聚合性單體及/或光聚合起始劑。 The coloring composition for a color filter may further contain a photopolymerizable monomer and/or a photopolymerization initiator.

又，本發明之第6態樣係關於一種彩色濾光片，其係具備由上述彩色濾光片用著色組成物所形成的濾光片區段。 Further, a sixth aspect of the invention relates to a color filter comprising a filter segment formed of the coloring composition for a color filter.

第1圖係表示實施例及比較例所使用之背光之發光光譜之圖。 Fig. 1 is a view showing the luminescence spectrum of the backlight used in the examples and the comparative examples.

以下詳細說明本發明之態樣。 The aspects of the invention are described in detail below.

再者，在此只要未特別說明，「(甲基)丙烯醯」、「(甲基)丙烯基」、「(甲基)丙烯酸」、「(甲基)丙烯酸酯」及「(甲基)丙烯醯胺」係分別表示「丙烯醯及/或甲基丙烯醯」、「丙烯基及/或甲基丙烯基」、「丙烯酸及/或丙 烯酸」、「丙烯酸酯及甲基丙烯酸酯」及「丙烯醯胺及甲基丙烯醯胺」。又，「C.I.」係意味色彩索引號碼(C.I.)。 In addition, unless otherwise specified, "(meth) propylene oxime", "(meth) propylene group, "(meth)acrylic acid", "(meth) acrylate", and ((meth)) "Acrylamide" means "acrylonitrile and / or methacryl", "acrylic and / or methacryl", "acrylic and / or C" Ethyl acid, "acrylate and methacrylate" and "acrylamide and methacrylamide". Also, "C.I." means a color index number (C.I.).

￮第1態樣 ○The first aspect

首先，說明關於本發明之第1態樣。 First, a first aspect of the present invention will be described.

<<彩色濾光片用著色組成物>> <<Coloring composition for color filter>>

本發明之第1態樣之彩色濾光片用著色組成物含有透明樹脂及著色劑。該著色劑包含鹼性染料與陰離子來源之相對化合物之成鹽生成物。然後，該相對化合物之分子量在特定範圍內。亦即，該著色劑包含以具有特定分子量之陰離子，置換色素離子為陰離子之染料之相對離子而成之鹽。因此，若使用該著色組成物，可製造一種彩色濾光片，其係具有高亮度及寬廣之色彩重現區域，且耐熱性、耐光性及耐溶劑性良好。 A coloring composition for a color filter according to a first aspect of the present invention contains a transparent resin and a coloring agent. The colorant comprises a salt-forming product of a relative dye of a basic dye and an anion source. Then, the molecular weight of the relative compound is within a specific range. That is, the colorant contains a salt having a specific molecular weight anion and a relative ion of a dye in which the dye ion is an anion. Therefore, when the colored composition is used, a color filter having a high luminance and a wide color reproduction region and having good heat resistance, light resistance, and solvent resistance can be produced.

<著色劑> <colorant>

於該著色組成物中可適宜使用之成鹽生成物係呈現藍色、紫色、綠色、紅色、洋紅色、青色或黃色之物。亦即，於該著色組成物中可適宜使用之成鹽生成物係藉由分類為C.I.基本藍、C.I.基本紫、C.I.基本綠、C.I.基本紅及C.I.基本黃等之鹼性染料，與分子量在特定範圍內之相對化合物之成鹽反應所獲得的成鹽生成物。 The salt-forming product which can be suitably used in the coloring composition is blue, purple, green, red, magenta, cyan or yellow. That is, the salt-forming product which can be suitably used in the coloring composition is a basic dye classified by CI basic blue, CI basic violet, CI basic green, CI basic red, and CI basic yellow, and the molecular weight is A salt-forming product obtained by a salt formation reaction of a relative compound in a specific range.

鹼性染料與相對化合物可藉由例如令兩者溶解於水溶液或醇溶液中，以生成成鹽生成物。或者，一面加熱兩者，一面予以溶融混合攪拌，藉此亦可獲得成鹽生成物。 The basic dye and the relative compound can be formed into a salt-forming product by, for example, dissolving both in an aqueous solution or an alcohol solution. Alternatively, the salt-forming product can also be obtained by heating and stirring both of them while being melted and mixed.

鹼性染料雖然具有良好的分光特性，但卻與一般染料同樣極為缺乏耐光性及耐熱性。亦即，鹼性染料用在要求高可靠性之彩色顯示 裝置或彩色攝像裝置之彩色濾光片時，其特性尚不足夠。 Although basic dyes have good spectral characteristics, they are extremely lacking in light resistance and heat resistance as in general dyes. That is, basic dyes are used in color displays that require high reliability. When the color filter of a device or a color camera device is used, its characteristics are not sufficient.

因此，在此為了解除鹼性染料之缺點，以分子量更大之陰離子置換鹼性染料之陰離子。具體而言，使用鹼性染料與分子量在特定範圍內之相對化合物之成鹽生成物。然後，宜藉由具有酸基之樹脂來將該成鹽生成物改質。 Therefore, in order to eliminate the disadvantage of the basic dye, the anion of the basic dye is replaced with an anion having a larger molecular weight. Specifically, a salt-forming product of a basic dye and a relative compound having a molecular weight within a specific range is used. Then, the salt-forming product is preferably modified by a resin having an acid group.

相對化合物之分子量係在200至3500之範圍內。相對化合物之分子量宜在250至3500之範圍內，較宜在300至3500之範圍內。或者，相對化合物之分子量宜在200至750之範圍內。使用分子量小之相對化合物時，難以達成充分的耐熱性及耐光性。使用分子量大之相對化合物時，不易於單位體積中，使得成鹽生成物以大莫耳數存在，難以充分呈色。 The molecular weight of the relative compound is in the range of from 200 to 3,500. The molecular weight of the relative compound is preferably in the range of from 250 to 3,500, more preferably in the range of from 300 to 3,500. Alternatively, the molecular weight of the relative compound is preferably in the range of from 200 to 750. When a relative compound having a small molecular weight is used, it is difficult to achieve sufficient heat resistance and light resistance. When a relative compound having a large molecular weight is used, it is not easy to be in a unit volume, so that the salt-forming product exists in a large molar number, and it is difficult to sufficiently develop a color.

[鹼性染料] [basic dye]

鹼性染料可舉出包含三芳基甲烷系鹼性染料、玫瑰紅系鹼性染料之呫噸系染料、黃素系鹼性染料、奧黃系鹼性染料、番紅系鹼性染料、夾竹桃紅系鹼性染料及亞甲藍系鹼性染料等。 Examples of the basic dye include a triarylmethane-based basic dye, a rosin-based basic dye, a xanthene-based dye, a flavin-based basic dye, an alkaloid basic dye, a fragrant basic dye, and an oleander red. It is a basic dye and a methylene blue basic dye.

具體的三芳基甲烷系鹼性染料可舉出例如：C.I.基本紫1(甲基紫)、C.I.基本紫3(水晶紫)及C.I.基本紫14(Magenta)；C.I.基本藍1(基本菁6G)、C.I.基本藍5(基本菁EX)、C.I.基本藍7(維多利亞純藍BO)及C.I.基本藍26(維多利亞藍B conc.)；以及C.I.基本綠1(亮綠GX)及C.I.基本綠4(孔雀石綠)。其中尤宜使用C.I.基本藍7、C.I.基本綠4、C.I.基本紫1或C.I.基本紫3。又，玫瑰紅系鹼性染料可舉出例如：C.I.基本紅1(玫瑰紅6G、6GCP)及C.I.基本紅8(玫瑰紅G)；以及C.I.基本紫10(玫瑰紅B)。其中尤宜使用C.I.基本紅1或C.I.基本紫10。 Specific triarylmethane-based basic dyes include, for example, CI basic violet 1 (methyl violet), CI basic violet 3 (crystal violet), and CI basic violet 14 (Magenta); CI basic blue 1 (basic cyanine 6G) , CI Basic Blue 5 (Basic Crystal EX), CI Basic Blue 7 (Victoria Pure Blue BO) and CI Basic Blue 26 (Victoria Blue B conc.); and CI Basic Green 1 (Bright Green GX) and CI Basic Green 4 ( Malachite green). Among them, it is preferable to use C.I. Basic Blue 7, C.I. Basic Green 4, C.I. Basic Violet 1 or C.I. Basic Violet 3. Further, examples of the rose-red basic dye include C.I. Basic Red 1 (Rose Red 6G, 6GCP) and C.I. Basic Red 8 (Rose Red G); and C.I. Basic Violet 10 (Rose Red B). Among them, it is preferable to use C.I. Basic Red 1 or C.I. Basic Violet 10.

又，黃素系鹼性染料可舉出例如C.I.基本黃1。奧黃系鹼性染料可舉出例如C.I.基本黃2及C.I.基本黃3。番紅系鹼性染料可具出例如C.I.基本紅2。夾竹桃紅系鹼性染料可舉出例如C.I.基本紅12。亞甲藍系鹼性染料可舉出例如C.I.基本藍9(亞甲藍FZ、亞甲藍B)、C.I.基本藍25(基本藍GO)及C.I.基本藍24(新亞甲藍NX)。 Further, the flavin-based basic dye may, for example, be C.I. Basic Yellow 1. The rhodamine alkaline dye may, for example, be C.I. Basic Yellow 2 and C.I. Basic Yellow 3. The safranin basic dye may have, for example, C.I. Basic Red 2. The oleander red basic dye may, for example, be C.I. Basic Red 12. The methylene blue basic dye may, for example, be C.I. Basic Blue 9 (methylene blue FZ, methylene blue B), C.I. Basic Blue 25 (Basic Blue GO), and C.I. Basic Blue 24 (New Methylene Blue NX).

其中尤宜使用C.I.基本黃1、C.I.基本藍9、C.I.基本藍24或C.I.基本藍25。 Among them, it is preferable to use C.I. Basic Yellow 1, C.I. Basic Blue 9, C.I. Basic Blue 24 or C.I. Basic Blue 25.

在呈色性良好方面，其中尤宜使用三芳基甲烷系鹼性染料、玫瑰紅系鹼性染料或亞甲藍系鹼性染料。又，在形成紅色像素上，作為補色之黃素系鹼性染料為有效的材料。 Among the good color rendering properties, among them, a triarylmethane-based basic dye, a rose-red basic dye, or a methylene blue-based basic dye is particularly preferably used. Further, a yellow pigment-based basic dye is an effective material for forming a red pixel.

亞甲藍鹼性染料呈現鮮明的藍色，製成上述成鹽生成物時，在耐熱性良好方面為適宜的材料。又，黃素系鹼性染料呈現鮮明的黃色，製成上述成鹽生成物時，在耐熱性良好方面為適宜的材料。 The methylene blue basic dye exhibits a vivid blue color, and when it is used as the salt-forming product, it is a suitable material for good heat resistance. Further, the flavin-based basic dye exhibits a vivid yellow color, and when the salt-forming product is produced, it is a suitable material for good heat resistance.

關於三芳基甲烷系鹼性染料及玫瑰紅系鹼性染料，於以下詳細敘述。 The triarylmethane-based basic dye and the rose-red basic dye are described in detail below.

(三芳基甲烷系鹼性染料) (triarylmethane basic dye)

三芳基甲烷系鹼性染料係對於中心碳處於對位之NH₂或OH基氧化，藉此取得醌構造而發色之物。三芳基甲烷系鹼性染料係依NH₂或OH基之數目而分成以下3種類型。從良好地呈現藍色、紅色及綠色的觀點來看，其中以三胺三苯甲烷系之鹼性染料尤其適宜。 The triarylmethane-based basic dye is obtained by oxidizing the NH ₂ or OH group in which the center carbon is in the para position, thereby obtaining a ruthenium structure and coloring. The triarylmethane-based basic dyes are classified into the following three types depending on the number of NH ₂ or OH groups. Among them, a triamine triphenylmethane-based basic dye is particularly preferable from the viewpoint of exhibiting blue, red, and green in a good manner.

a)二胺三苯甲烷系鹼性染料 a) diamine triphenylmethane basic dye

b)三胺三苯甲烷系鹼性染料 b) triamine triphenylmethane basic dye

c)具有OH基之薔薇酸酸系鹼性染料 c) Rose acid-based basic dye with OH group

三胺三苯甲烷系鹼性染料及二胺三苯甲烷系鹼性染料係就色調良好、日光堅固性較他物良好方面而言較為適宜。又，二苯萘甲烷鹼性染料及/或三苯甲烷鹼性燃料亦適宜。 The triamine triphenylmethane-based basic dye and the diamine triphenylmethane-based basic dye are preferable in terms of good color tone and strong sunlight. Further, a benzophenone basic dye and/or a triphenylmethane alkaline fuel are also suitable.

藍色系之三芳基甲烷系鹼性染料係於400至440nm之波長範圍內，具有穿透率高之分光特性。 The blue triarylmethane-based basic dye has a spectral transmittance of 400 to 440 nm and has a high transmittance.

(玫瑰紅系鹼性染料) (Rose red alkaline dye)

接著，說明關於玫瑰紅系鹼性染料。 Next, the rosin-based basic dye will be described.

於該著色組成物中可適宜使用之玫瑰紅系鹼性染料係呈現紅色或紫色之物。 The rose-red basic dye which can be suitably used in the coloring composition is red or purple.

呈現紅色或紫色之鹼性染料係屬於例如C.I.基本紅及C.I.基本紫等鹼性染料。 Basic dyes exhibiting red or purple are basic dyes such as C.I. basic red and C.I. basic violet.

玫瑰紅系鹼性染料係於400至430nm之波長範圍內，具有穿透率高之分光特性。 The rose-red basic dye is in the wavelength range of 400 to 430 nm and has a high transmittance.

玫瑰紅系鹼性染料係宜對於波長650nm以上之光之穿透率在90%以上，對於波長600nm之光之穿透率在75%以上，穿透率在波長500至550nm之範圍內為5%以下，對於波長400nm之光之穿透率在70%以上。更宜對於波長650nm以上之光之穿透率在95%以上，對於波長600nm之光之穿透率在80%以上，穿透率在波長500至550nm之範圍內為10%以下，對於波長400nm之光之穿透率在75%以上。 The rose-red basic dye is preferably more than 90% for light having a wavelength of 650 nm or more, 75% or more for light having a wavelength of 600 nm, and 5 for a transmittance of 500 to 550 nm. Below %, the transmittance for light having a wavelength of 400 nm is 70% or more. More preferably, the transmittance of light having a wavelength of 650 nm or more is 95% or more, the transmittance of light having a wavelength of 600 nm is 80% or more, and the transmittance is 10% or less in the range of 500 to 550 nm, for a wavelength of 400 nm. The penetration rate of light is above 75%.

就每色總歸而言，上述鹼性染料可用於藍色像素之物為例 如三芳基甲烷系鹼性染料或亞甲藍系鹼性染料，具體而言，可舉出例如C.I.基本藍1(基本菁6G)、C.I.基本藍5(基本菁EX)、C.I.基本藍7(維多利亞純藍BO)、C.I.基本藍9(亞甲藍FZ、亞甲藍B)、C.I.基本藍24(新亞甲藍NX)、C.I.基本藍25(基本藍GO)及C.I.基本藍26(維多利亞藍B conc.)。又，作為藍色像素之補色，玫瑰紅系鹼性染料、以及後述呈現紅色之番紅系鹼性染料及夾竹桃紅系鹼性染料亦有效。 For each color total, the above basic dye can be used for blue pixels as an example. For example, a triarylmethane-based basic dye or a methylene blue-based basic dye may, for example, be CI basic blue 1 (basic cyanine 6G), CI basic blue 5 (basic cyanine EX), or CI basic blue 7 ( Victoria Pure Blue BO), CI Basic Blue 9 (Methylene Blue FZ, Methylene Blue B), CI Basic Blue 24 (New Methylene Blue NX), CI Basic Blue 25 (Basic Blue GO) and CI Basic Blue 26 (Victoria Blue B conc.). Further, as a complementary color of the blue pixel, a rose-red basic dye, and a red-based basic dye and an oleander red-based basic dye which are described later are also effective.

例如藉由並用銅酞菁顏料(C.I.Pigment Blue 15：6)與呈現紅色之來自鹼性染料之成鹽生成物，可獲得高亮度之藍色像素。尤其銅酞菁顏料(C.I.Pigment Blue 15：6)與玫瑰紅系鹼性染料之成鹽生成物之組合可獲得高亮度，較為適宜。 For example, by using a copper phthalocyanine pigment (C.I. Pigment Blue 15:6) in combination with a salt-forming product derived from a basic dye in red, a blue pixel of high brightness can be obtained. In particular, a combination of a copper phthalocyanine pigment (C.I. Pigment Blue 15:6) and a salt forming product of a rose-red basic dye can obtain high brightness and is suitable.

可用於紅色像素之鹼性染料為例如玫瑰紅系鹼性染料、番紅系鹼性染料或竹夾桃紅系鹼性染料，可舉出例如C.I.基本紅1(玫瑰紅6G及6GCP)、C.I.基本紅2(番紅系鹼性染料)、C.I.基本紅8(玫瑰紅G)、C.I.基本紅12(夾竹桃紅系鹼性染料)及C.I.基本紫10(玫瑰紅B)。又，作為紅色像素之補色宜為呈現黃色之黃素系鹼性染料。 The basic dye which can be used for the red pixel is, for example, rose-red basic dye, fragrant basic dye or bamboo-pink-based basic dye, and examples thereof include CI basic red 1 (Rose red 6G and 6GCP), CI basic. Red 2 (saffron-based basic dye), CI basic red 8 (Rose red G), CI basic red 12 (Oleander red-based basic dye) and CI basic purple 10 (Rose red B). Further, the complementary color of the red pixel is preferably a yellow flavin-based basic dye.

可用於綠色像素之鹼性染料為例如三芳基甲烷系鹼性染料，具體而言可舉出例如C.I.基本綠1(亮綠GX)及C.I.基本綠4(孔雀石綠)。 The basic dye which can be used for a green pixel is, for example, a triarylmethane-based basic dye, and specific examples thereof include C.I. Basic Green 1 (Bright Green GX) and C.I. Basic Green 4 (Manet Green).

[相對化合物] [relative compound]

於該著色組成物所使用之相對化合物係分子量在200至3500之範圍內之陰離子性之化合物。相對化合物之分子量宜在250至3500之範圍內，更宜在300至3500之範圍內。或者，相對化合物之分子量宜在200至750之範圍內。又，該相對化合物之陰離子之分子量宜在199至3499之範 圍內，較宜在249至3499之範圍內或199至749之範圍內。具體之相對化合物為例如雜多酸、芳香族磺酸等有機磺酸、芳香族羧酸及脂肪酸等有機羧酸或酸性染料。 The relative compound used in the coloring composition is an anionic compound having a molecular weight in the range of 200 to 3,500. The molecular weight of the relative compound is preferably in the range of from 250 to 3,500, more preferably in the range of from 300 to 3,500. Alternatively, the molecular weight of the relative compound is preferably in the range of from 200 to 750. Moreover, the molecular weight of the anion of the relative compound is preferably in the range of 199 to 3499. Within the circumference, it is preferably in the range of 249 to 3499 or in the range of 199 to 749. Specific specific compounds are, for example, organic sulfonic acids such as heteropolyacids and aromatic sulfonic acids, organic carboxylic acids such as aromatic carboxylic acids and fatty acids, or acid dyes.

相對化合物宜為有機磺酸或酸性染料。該情況下，相對化合物之分子量宜在200至750之範圍內。 The relative compound is preferably an organic sulfonic acid or an acid dye. In this case, the molecular weight of the relative compound is preferably in the range of 200 to 750.

再者，於此所規定之分子量及平均分子量係藉由四捨五入根據分子構造及原子量所算出的理論值之小數第1位而獲得之值。又，相對化合物為鈉鹽時，於此所規定之分子量及平均分子量係意味以氫置換鈉而成之分子之值。 Further, the molecular weight and the average molecular weight defined herein are values obtained by rounding off the first decimal place of the theoretical value calculated from the molecular structure and the atomic weight. Further, when the relative compound is a sodium salt, the molecular weight and the average molecular weight defined herein mean the value of the molecule obtained by replacing sodium with hydrogen.

(雜多酸) (Heteropolyacids)

雜多酸可舉出例如磷鎢酸H₃(PW₁₂O₄₀)‧nH₂O(n≒30；≒表示幾乎等於)(分子量3421)、矽鎢酸H₄(SiW₁₂O₄₀)‧nH₂O(n≒30)(分子量3418)、磷錳酸H₃(PMo₁₂O₄₀)‧nH₂O(n≒30)(分子量2205)、矽錳酸H₃(SiMo₁₂O₄₀)‧nH₂O(n≒30)(分子量2202)、磷鎢錳酸H₃(PW_12-XMo_XO₄₀)‧nH₂O(6<X<12)及磷釩錳酸H_15-X(PV_12-XMo_XO₄₀)‧nH₂O(n≒30)。 The heteropoly acid may, for example, be phosphotungstic acid H ₃ (PW ₁₂ O ₄₀ ) ‧nH ₂ O (n≒30; ≒ indicates almost equal) (molecular weight 3421), tungstic acid H ₄ (SiW ₁₂ O ₄₀ ) ‧nH ₂ O(n≒30) (molecular weight 3418), manganese acid H ₃ (PMo ₁₂ O ₄₀ ) ‧nH ₂ O(n≒30) (molecular weight 2205), manganic acid H ₃ (SiMo ₁₂ O ₄₀ )‧nH ₂ O(n≒30) (molecular weight 2202), phosphotungstic acid H ₃ (PW _12-X Mo _X O ₄₀ ) ‧nH ₂ O (6<X<12) and phosphovanadomanganic acid H _15-X (PV _12-X Mo _X O ₄₀ )‧nH ₂ O(n≒30).

磷鎢錳酸、磷釩錳酸及矽鎢錳酸係藉由改變磷鎢酸、磷錳酸、矽鎢酸及矽錳酸等構成成分之含有量，而可於2202至3421之範圍內調整分子量。 Phospho-tungstic acid, phosphovanadomanganic acid and lanthanum-manganese acid can be adjusted in the range of 2202 to 3421 by changing the content of constituents such as phosphotungstic acid, manganic acid, lanthanum tungstic acid and lanthanum manganic acid. Molecular weight.

使用雜多酸作為相對化合物時，其平均分子量宜在2820至3421之範圍內。此係由於當相對化合物包含錳及鎢時，鎢的比率宜超過50%。磷鎢錳酸的情況下，藉由減少Mo含有量而含較多W，可獲得穿透性良好之色材。 When a heteropolyacid is used as the relative compound, the average molecular weight thereof is preferably in the range of from 2820 to 3421. This is because the ratio of tungsten is preferably more than 50% when the relative compound contains manganese and tungsten. In the case of phosphotungstic acid, a large amount of W is contained by reducing the Mo content, and a color material having good penetrability can be obtained.

(有機酸：有機磺酸及有機羧酸) (Organic acids: organic sulfonic acids and organic carboxylic acids)

有機磺酸可使用例如芳香族磺酸。作為芳香族磺酸，適宜之化合物可舉出例如1-萘胺-4,8-二磺酸(分子量303)、1-萘胺-3,8-二磺酸(分子量303)、1-萘胺-5,7-二磺酸(分子量303)、1-萘胺-3,6-二磺酸(分子量303)、1-萘胺-3,6,8-二磺酸(分子量383)、2-萘胺-6,8-二磺酸(分子量303)、2-萘胺-1,6-二磺酸(分子量303)、2-萘胺-4,8-二磺酸(分子量303)、2-萘胺-3,6-二磺酸(胺基-R酸)(分子量303)、2-萘胺-5,7-二磺酸(胺基J酸)(分子量303)、1-萘酚-4,8-二磺酸(分子量304)、1-萘酚-3,8-二磺酸(e酸)(分子量304)、1-萘酚-3,6-二磺酸(分子量304)、1-萘酚-3,6,8-三磺酸(分子量384)、2-萘酚-6,8-二磺酸(分子量304)、2-萘酚-3,6,8-三磺酸(分子量384)、N-苯基-1-萘胺-8-磺酸(分子量299)、N-對甲苯基-1-萘胺-8-磺酸(分子量313)、N-苯基-1-萘胺-5-磺酸(分子量299)、N-苯基-2-萘胺-6-磺酸(分子量299)、N-乙醯-7-胺基-1-萘酚-3-磺酸(分子量281)、N-苯基-7-胺基-1-萘酚-3-磺酸(分子量315)、N-乙醯-6-胺基-1-萘酚-3-磺酸(分子量281)、N-苯基-6-胺基-1-萘酚-3-磺酸(分子量315)、1,8-二氫-3,6-二磺酸(色變酸)(分子量320)、8-胺基-1-萘酚-5,7-二磺酸(分子量319)、1,6-二胺基-2-萘酚-4-二磺酸(分子量254)、1-胺基-2-萘酚-6,8-二磺酸(分子量319)、1-胺基-2-萘酚-3,6-二磺酸(分子量319)、2,8-二胺基-1-萘酚-5,7-二磺酸(分子量334)、2,7-二胺基-1-萘酚-3-磺酸(分子量254)、2,6-二胺基-1-萘酚-3-磺酸(分子量254)、2,8-二胺基-1-萘酚-3,6-二磺酸(分子量334)及2-胺基-7-苯胺-1-萘酚-3-磺酸(分子量330)。 For example, an aromatic sulfonic acid can be used as the organic sulfonic acid As the aromatic sulfonic acid, a suitable compound is, for example, 1-naphthylamine-4,8-disulfonic acid (molecular weight: 303), 1-naphthylamine-3,8-disulfonic acid (molecular weight: 303), 1-naphthalene Amine-5,7-disulfonic acid (molecular weight 303), 1-naphthylamine-3,6-disulfonic acid (molecular weight 303), 1-naphthylamine-3,6,8-disulfonic acid (molecular weight 383), 2-naphthylamine-6,8-disulfonic acid (molecular weight 303), 2-naphthylamine-1,6-disulfonic acid (molecular weight 303), 2-naphthylamine-4,8-disulfonic acid (molecular weight 303) , 2-naphthylamine-3,6-disulfonic acid (amino-R acid) (molecular weight 303), 2-naphthylamine-5,7-disulfonic acid (amino J acid) (molecular weight 303), 1- Naphthol-4,8-disulfonic acid (molecular weight 304), 1-naphthol-3,8-disulfonic acid (e acid) (molecular weight 304), 1-naphthol-3,6-disulfonic acid (molecular weight 304), 1-naphthol-3,6,8-trisulphonic acid (molecular weight 384), 2-naphthol-6,8-disulfonic acid (molecular weight 304), 2-naphthol-3,6,8- Trisulfonic acid (molecular weight 384), N-phenyl-1-naphthylamine-8-sulfonic acid (molecular weight 299), N-p-tolyl-1-naphthylamine-8-sulfonic acid (molecular weight 313), N-benzene 1-naphthylamine-5-sulfonic acid (molecular weight 299), N-phenyl-2-naphthylamine-6-sulfonic acid (molecular weight 299), N-acetam-7-amino-1-naphthol- 3-sulfonic acid (molecular weight 281), N-phenyl-7-amino-1-naphthol-3-sulfonic acid (molecular weight 315), N-acetam-6-amino-1-naphthol-3-sulfonic acid (molecular weight 281), N-phenyl-6-amino-1-naphthol-3-sulfonic acid (molecular weight 315), 1, 8-Dihydro-3,6-disulfonic acid (chromogenic acid) (molecular weight 320), 8-amino-1-naphthol-5,7-disulfonic acid (molecular weight 319), 1,6-diamine 2-naphthol-4-disulfonic acid (molecular weight 254), 1-amino-2-naphthol-6,8-disulfonic acid (molecular weight 319), 1-amino-2-naphthol-3 ,6-disulfonic acid (molecular weight 319), 2,8-diamino-1-naphthol-5,7-disulfonic acid (molecular weight 334), 2,7-diamino-1-naphthol-3 -sulfonic acid (molecular weight 254), 2,6-diamino-1-naphthol-3-sulfonic acid (molecular weight 254), 2,8-diamino-1-naphthol-3,6-disulfonic acid (Molecular weight 334) and 2-amino-7-aniline-1-naphthol-3-sulfonic acid (molecular weight 330).

又，亦適宜使用蒽磺酸(分子量258)、蒽醌-2-磺酸或蒽醌-1-磺酸(分子量288)。 Further, hydrazine sulfonic acid (molecular weight 258), hydrazine-2-sulfonic acid or hydrazine-1-sulfonic acid (molecular weight 288) is also suitably used.

若使用具有1個胺基及1個磺酸基之萘胺磺酸，可達成良好的耐熱性及耐光性。萘胺磺酸可舉出例如2-胺基-1-萘磺酸(吐氏酸、分子量223)、4-胺基-1-萘磺酸(萘磺酸、分子量223)、8-胺基-1-萘磺酸(周位酸、分子量223)、2-胺基-6-萘磺酸(Broenner acid、分子量223)、1-胺基-5-萘磺酸(羅倫茲酸、分子量223)、5-胺基-2-萘磺酸(分子量223)、1-胺基-6-萘磺酸(分子量223)、6-胺基-1-萘磺酸(分子量223)及3-胺基-1-萘磺酸(分子量223)。其中尤以2-胺基-1-萘磺酸(吐氏酸)特別適宜。 When naphthylaminesulfonic acid having one amine group and one sulfonic acid group is used, good heat resistance and light resistance can be achieved. Examples of the naphthylaminesulfonic acid include 2-amino-1-naphthalenesulfonic acid (Tour acid, molecular weight 223), 4-amino-1-naphthalenesulfonic acid (naphthalenesulfonic acid, molecular weight 223), and 8-amino group. 1-naphthalenesulfonic acid (peripheric acid, molecular weight 223), 2-amino-6-naphthalenesulfonic acid (Broenner acid, molecular weight 223), 1-amino-5-naphthalenesulfonic acid (Lorentz acid, molecular weight 223), 5-amino-2-naphthalenesulfonic acid (molecular weight 223), 1-amino-6-naphthalenesulfonic acid (molecular weight 223), 6-amino-1-naphthalenesulfonic acid (molecular weight 223) and 3- Amino-1-naphthalenesulfonic acid (molecular weight 223). Among them, 2-amino-1-naphthalenesulfonic acid (toluic acid) is particularly preferable.

亦宜使用具有1個羥基及1個磺酸基之羥萘磺酸。羥萘磺酸可舉出例如2-羥基-6-萘磺酸(西法酸、分子量224)、1-羥基-4-萘磺酸(尼文酸：NW酸、分子量224)、1-羥基-5-萘磺酸(L酸、分子量224)及2-羥基-8-萘磺酸(藏花精酸、分子量224)。 It is also preferred to use a hydroxynaphthalenesulfonic acid having one hydroxyl group and one sulfonic acid group. The hydroxynaphthalenesulfonic acid may, for example, be 2-hydroxy-6-naphthalenesulfonic acid (sialon, molecular weight 224), 1-hydroxy-4-naphthalenesulfonic acid (Nieic acid: NW acid, molecular weight 224), 1-hydroxy- 5-naphthalenesulfonic acid (L acid, molecular weight 224) and 2-hydroxy-8-naphthalenesulfonic acid (chamoic acid, molecular weight 224).

從呈色性良好、可達成高亮度的觀點來看，其中尤宜為具有2至3個磺酸基之有機磺酸。若是具有4個以上之磺酸，則環境安定性不佳，容易引起經時變化，若是1個磺酸，則由於鹼性染料與相對化合物會以1：1反應，因此在作為主色時，發色性可能變差。 From the viewpoint of good color rendering and high brightness, an organic sulfonic acid having 2 to 3 sulfonic acid groups is particularly preferable. If there are four or more sulfonic acids, the environmental stability is not good, and it is easy to cause a change with time. If it is one sulfonic acid, since the basic dye and the relative compound react 1:1, when it is a primary color, Color development may be worse.

但分子量在200至250之範圍內之有機磺酸的情況下，由於相對化合物之分子量小，因此即便每1分子之磺酸基為1個，仍不會損及呈色性。 However, in the case of an organic sulfonic acid having a molecular weight of from 200 to 250, since the molecular weight of the relative compound is small, even if the sulfonic acid group per molecule is one, the color rendering property is not impaired.

有機磺酸可使用例如芳香族磺酸或脂肪酸。具體的有機磺酸可舉出例如四氯苯二甲酸(分子量304)、棕櫚酸(分子量257)、硬酯酸(分子量285)、花生酸(分子量313)、山酸(分子量341)、二十四烷酸(分子量369)、油酸(分子量282)、反油酸(分子量282)、芥酸(分子量339)、神經酸(分子量 367)、亞麻油酸(分子量280)、gamolenic acid(分子量278)、花生四烯酸(分子量305)、a-亞麻油酸(分子量278)、次亞麻油酸(分子量276)、二十碳五烯酸(分子量302)及二十二碳六烯酸(分子量328)。 The organic sulfonic acid can use, for example, an aromatic sulfonic acid or a fatty acid Specific examples of the organic sulfonic acid include tetrachlorophthalic acid (molecular weight 304), palmitic acid (molecular weight 257), stearic acid (molecular weight 285), arachidic acid (molecular weight 313), sorbic acid (molecular weight 341), and twenty. Tetraic acid (molecular weight 369), oleic acid (molecular weight 282), oleic acid (molecular weight 282), erucic acid (molecular weight 339), nervonic acid (molecular weight 367), linoleic acid (molecular weight 280), gamolenic acid (molecular weight 278), arachidonic acid (molecular weight 305), a-linolenic acid (molecular weight 278), linoleic acid (molecular weight 276), twenty carbon five Oleic acid (molecular weight 302) and docosahexaenoic acid (molecular weight 328).

在有機酸的情況下，分子量宜為200至400，較宜為250至400。藉由將分子量設在該範圍，可製成耐受性及著色力取得良好平衡之著色劑。再者，在有機酸的情況下，分子量之範圍亦可為300至400。 In the case of an organic acid, the molecular weight is preferably from 200 to 400, more preferably from 250 to 400. By setting the molecular weight within this range, a coloring agent having a good balance between tolerance and coloring power can be obtained. Further, in the case of an organic acid, the molecular weight may range from 300 to 400.

(酸性染料) (Acid Dyestuff)

藉由使用酸性染料作為相對化合物，亦可控制色相。 The hue can also be controlled by using an acid dye as the relative compound.

如上述，紅色像素可使用例如來自玫瑰紅系鹼性染料、番紅系鹼性染料或竹夾桃紅系鹼性染料之成鹽生成物。該情況下，適宜作為相對化合物之酸性染料為例如C.I.酸性黃11(分子量380)、C.I.酸性黃23(分子量534)、C.I.酸性紅52(酸性玫瑰紅B)(分子量580)、C.I.酸性紅52(酸性玫瑰紅B)(分子量580)、C.I.酸性紅87(曙紅G)(分子量691.6)及C.I.酸性紅289(分子量676.7)。 As described above, for the red pixel, for example, a salt-forming product derived from a rose-red basic dye, a fragrant basic dye, or a bamboo-pink-based basic dye can be used. In this case, an acid dye suitable as a relative compound is, for example, CI Acid Yellow 11 (molecular weight 380), CI Acid Yellow 23 (molecular weight 534), CI Acid Red 52 (Acid Rose B) (molecular weight 580), CI Acid Red 52. (Acid Rose B) (molecular weight 580), CI Acid Red 87 (Eosin G) (molecular weight 691.6) and CI Acid Red 289 (molecular weight 676.7).

藍色像素可使用例如來自三芳基甲烷系鹼性染料或亞甲藍系鹼性染料之成鹽生成物。該情況下，適宜作為相對化合物之酸性染料為例如C.I.酸性紅52(酸性玫瑰紅B)(分子量580)、C.I.酸性紅87(曙紅G)(分子量691.6)及C.I.酸性紅289(分子量676.7)。 As the blue pixel, for example, a salt-forming product derived from a triarylmethane-based basic dye or a methylene blue-based basic dye can be used. In this case, an acid dye suitable as a relative compound is, for example, CI Acid Red 52 (Acid Rose B) (molecular weight 580), CI Acid Red 87 (Eosin G) (molecular weight 691.6), and CI Acid Red 289 (molecular weight 676.7). .

綠色像素可使用例如C.I.基本綠1(亮綠GX)及C.I.基本綠4(孔雀石綠)等來自三芳基甲烷系鹼性染料之成鹽生成物。該情況下，適宜作為相對化合物之酸性染料為例如C.I.酸性綠3(食用綠色1號)(分子量690)、C.I.酸性綠5(食用綠色2號)(分子量671)、C.I.酸性綠9(分子量724)、C.I.酸性 綠16(分子量560)、C.I.酸性綠19(分子量625)及C.I.酸性綠25(分子量622)。 As the green pixel, a salt-forming product derived from a triarylmethane-based basic dye such as C.I. Basic Green 1 (bright green GX) and C.I. Basic Green 4 (malachite green) can be used. In this case, an acid dye suitable as a relative compound is, for example, CI Acid Green 3 (Edible Green No. 1) (molecular weight 690), CI Acid Green 5 (Edible Green No. 2) (molecular weight 671), CI Acid Green 9 (molecular weight 724). ), CI acidity Green 16 (molecular weight 560), C.I. acid green 19 (molecular weight 625) and C.I. acid green 25 (molecular weight 622).

在酸性染料的情況下，分子量之範圍宜為300至750，較宜為350至700。若將分子量設在該範圍，可獲得耐受性及著色力取得良好平衡之著色劑。 In the case of an acid dye, the molecular weight is preferably in the range of from 300 to 750, more preferably from 350 to 700. When the molecular weight is set in this range, a coloring agent which has a good balance between tolerance and coloring power can be obtained.

尤其玫瑰紅系鹼性染料及黃色酸性染料係獲得紅色色素時之適宜材料。 In particular, rose red basic dyes and yellow acid dyes are suitable materials for obtaining red pigments.

鹼性染料與相對化合物之成鹽生成物可藉由以往習知之方法來合成。具體手法揭示於例如日本特開2003-215850號。 The salt-forming product of the basic dye and the relative compound can be synthesized by a conventional method. The specific method is disclosed, for example, in Japanese Patent Laid-Open No. 2003-215850.

舉例使用三芳基甲烷系鹼性染料之例子，於水中溶解三芳基甲烷系鹼性染料後，於該溶液添加有機磺酸溶液並攪拌，藉以發生成鹽反應即可。藉此，可獲得三芳基甲烷系鹼性染料之胺基(-NHC₂H₅)與有機磺酸之磺酸基(-SO₃H)結合之成鹽生成物。 For example, using an example of a triarylmethane-based basic dye, after dissolving a triarylmethane-based basic dye in water, an organic sulfonic acid solution is added to the solution and stirred to thereby form a salt-forming reaction. Thereby, a salt-forming product of the amine group of the triarylmethane-based basic dye (-NHC ₂ H ₅ ) and the sulfonic acid group of the organic sulfonic acid (-SO ₃ H) can be obtained.

有機磺酸亦可於成鹽反應前，溶解於氫氧化鈉等鹼溶液。例如有機磺酸亦可採磺酸鈉(-SO₃Na)之形態來使用。亦即，磺酸溶液包含磺酸基(-SO₃H)之氫原子未置換之化合物之溶液、及磺酸基之氫原子已置換之化合物之例如磺酸鈉溶液。 The organic sulfonic acid may also be dissolved in an alkali solution such as sodium hydroxide before the salt formation reaction. For example, the organic sulfonic acid can also be used in the form of sodium sulfonate (-SO ₃ Na). That is, the sulfonic acid solution contains a solution of a compound in which a hydrogen atom of a sulfonic acid group (-SO ₃ H) is not substituted, and a sodium sulfonate solution such as a compound in which a hydrogen atom of a sulfonic acid group has been replaced.

[具有酸基之樹脂] [Resin with acid group]

成鹽生成物若添加具有酸基之樹脂，例如添加松香改質順丁烯二酸樹脂及松香改質反丁烯二酸樹脂般具有酸基之樹脂、松香酯、聚酯樹脂或具有酸價之苯乙烯丙烯酸共聚物等，則對黏結樹脂中之相溶性及分散性、以及對溶劑之分散性會大幅提升。其結果，可實現更加良好之呈色性、耐熱性及耐光性。在此，酸基宜為羧基(-COOH)或磺酸基(例如-SO₃H 或-SO₃Na)。 If a salt-forming product is added with a resin having an acid group, for example, a resin having an acid group, a rosin ester, a polyester resin, or an acid value, which is added with a rosin-modified maleic acid resin and a rosin-modified fumaric acid resin. The styrene acrylic copolymer or the like greatly improves the compatibility and dispersibility in the binder resin and the dispersibility to the solvent. As a result, more excellent color rendering properties, heat resistance, and light resistance can be achieved. Here, the acid group is preferably a carboxyl group (-COOH) or a sulfonic acid group (for example, -SO ₃ H or -SO ₃ Na).

又，具有酸基之樹脂之重量平均分子量宜在400至12000之範圍內，較宜在400至6000之範圍內，更宜在400至2000之範圍內。該類樹脂係與成鹽生成物之相溶性良好，因此若使用其，成鹽生成物對黏結樹脂中之分散會變得良好。 Further, the weight average molecular weight of the resin having an acid group is preferably in the range of from 400 to 12,000, more preferably in the range of from 400 to 6,000, still more preferably in the range of from 400 to 2,000. Since such a resin is excellent in compatibility with a salt-forming product, when it is used, the salt-forming product is excellent in dispersion in the binder resin.

再者，如以下測定具有酸基之樹脂之重量平均分子量。於檢體加入四氫呋喃(THF)，放置12小時。其後，過濾檢體之THF溶液，測定溶解於濾液中之檢體之分子量。測定係利用凝膠滲透層析儀(GPC)法，從利用標準聚苯乙烯而製作之檢量線計算分子量。以下記載測定條件之一例。 Further, the weight average molecular weight of the resin having an acid group was measured as follows. The sample was added to tetrahydrofuran (THF) and allowed to stand for 12 hours. Thereafter, the THF solution of the sample was filtered, and the molecular weight of the sample dissolved in the filtrate was measured. The measurement was carried out by a gel permeation chromatography (GPC) method from a calibration curve prepared using standard polystyrene. An example of the measurement conditions is described below.

GPC裝置：TORAY股份有限公司製HLC-8120GPC GPC device: HLC-8120GPC manufactured by TORAY Co., Ltd.

管柱：TORAY股份有限公司製TSK Guardcolumn SuperH-HT/SK-GEL/SuperHM-M連結3座 Pipe column: TSK Guardcolumn SuperH-HT/SK-GEL/SuperHM-M link 3 from TORAY Co., Ltd.

流速：1.0ml/min(THF) Flow rate: 1.0 ml/min (THF)

具有酸基之樹脂宜使用松香改質順丁烯二酸樹脂。松香改質順丁烯二酸樹脂具有：具有酸之極性基、及無極性之松香骨架。該具有酸之極性基係來自未反應之松香酸之羧基及順丁烯二酸之羧基，與黏結樹脂之極性基反應及相溶。另，無極性之松香骨架係與黏結樹脂之非極性部相溶。進而言之，松香改質順丁烯二酸樹脂之具有酸之極性基係與鹼性染料(成鹽生成物中之未反應之鹼性染料)之胺基反應。 The resin having an acid group is preferably a rosin-modified maleic acid resin. The rosin-modified maleic acid resin has a polar group having an acid and a non-polar rosin skeleton. The acidic polar group is derived from the carboxyl group of the unreacted rosin acid and the carboxyl group of the maleic acid, and reacts and is compatible with the polar group of the binder resin. In addition, the non-polar rosin skeleton is compatible with the non-polar portion of the binder resin. Further, the acid-based polar group of the rosin-modified maleic acid resin reacts with the amine group of the basic dye (unreacted basic dye in the salt-forming product).

具有酸基之樹脂之酸價宜在100至300mgKOH/g之範圍內。若酸價小，則樹脂與成鹽生成物之相溶性不足。又，若酸價大，在將該著色組成物利用作為後述之鹼顯影型著色抗蝕劑時，容易發生顯影不良。再 者，於此所謂酸價係藉由JISK-0070中所規定的方法而測定之值。 The acid value of the acid group-containing resin is preferably in the range of 100 to 300 mgKOH/g. If the acid value is small, the compatibility of the resin with the salt-forming product is insufficient. In addition, when the coloring composition is used as an alkali-developing type coloring resist to be described later, development failure is likely to occur. again Here, the acid value is a value measured by the method specified in JIS K-0070.

成鹽生成物與具有酸基之樹脂之混合係採例如以下方法而進行。 The mixing of the salt-forming product and the resin having an acid group is carried out, for example, by the following method.

(1)混合溶解於溶劑之樹脂與成鹽生成物之方法 (1) A method of mixing a resin dissolved in a solvent with a salt-forming product

(2)混合已溶解之樹脂與成鹽生成物之方法 (2) Method of mixing dissolved resin and salt-forming product

再者，成鹽生成物與具有酸基之樹脂之混合亦可採其他方法進行。 Further, the mixing of the salt-forming product with the resin having an acid group can also be carried out by other methods.

以下記載上述混合法(1)及(2)之具體例。在此表示利用玫瑰紅系鹼性染料及松香改質順丁烯二酸樹脂之事例。 Specific examples of the above mixing methods (1) and (2) are described below. Here, an example in which a rosin-based basic dye and a rosin-modified maleic acid resin are used is shown.

(1)混合溶解於溶劑之樹脂與成鹽生成物之方法 (1) A method of mixing a resin dissolved in a solvent with a salt-forming product

(1-1) (1-1)

於水中溶解玫瑰紅系鹼性染料，一面攪拌該溶液，一面於其添加有機磺酸等相對化合物。如此一來，玫瑰紅系鹼性染料之胺基(-NHC₂H₅)與相對化合物之酸基結合，獲得成鹽生成物。再者，相對化合物亦可於成鹽反應前，先溶解於氫氧化鈉等鹼溶液，以例如磺酸鈉的形態(-SO₃Na)使用。 The rose-red basic dye is dissolved in water, and the solution is stirred while adding a relative compound such as an organic sulfonic acid. As a result, the amine group of the rose red basic dye (-NHC ₂ H ₅ ) is combined with the acid group of the opposite compound to obtain a salt-forming product. Further, the relative compound may be dissolved in an alkali solution such as sodium hydroxide before the salt formation reaction, and used in the form of, for example, sodium sulfonate (-SO ₃ Na).

(1-2) (1-2)

接著，於含成鹽生成物之先前的液體中，添加松香改質順丁烯二酸樹脂。具體而言，首先於含成鹽生成物之上述液體中，添加氫氧化鈉水溶液等鹼水溶液，將該液體調整為中性。接著，於該溶液中，添加已溶解於鹼水溶液之松香改質順丁烯二酸樹脂並予以攪拌。其後，於該溶液添加鹽酸及硫酸等礦物酸，將液體調整為酸性。藉此令松香改質順丁烯 二酸樹脂不溶化。進而進行過濾、洗淨及乾燥，獲得著色組成物。再者，必要時亦可於其後，將著色組成物粉碎成所需粒度。 Next, a rosin-modified maleic acid resin is added to the previous liquid containing the salt-forming product. Specifically, first, an alkali aqueous solution such as a sodium hydroxide aqueous solution is added to the liquid containing the salt-forming product, and the liquid is adjusted to be neutral. Next, in this solution, a rosin-modified maleic acid resin which has been dissolved in an aqueous alkali solution is added and stirred. Thereafter, a mineral acid such as hydrochloric acid or sulfuric acid is added to the solution to adjust the liquid to acidity. In this way, the rosin is modified to be butylene. The diacid resin is insoluble. Further, filtration, washing, and drying were carried out to obtain a colored composition. Further, if necessary, the colored composition may be pulverized to a desired particle size thereafter.

(2)混合已溶解之樹脂與成鹽生成物之方法 (2) Method of mixing dissolved resin and salt-forming product

於加熱捏合機、班布瑞密閉式混合機、3輥研磨機、2輥研磨機、震動研磨機、球研磨機、輥磨機、磨碎機及擠出機等混合攪拌機，放入成鹽生成物及具有酸基之樹脂，在此為松香改質順丁烯二酸樹脂，以具有酸基之樹脂之軟化點以上之溫度進行溶融混合攪拌。藉此，成鹽生成物會均勻地分散於具有酸基之樹脂中。再者，於此所獲得的著色組成物係處於具有酸基之樹脂被成鹽生成物包覆的形態。進而將該著色組成物予以粗碎及粉碎，調整為所需粒度。 Mixing mixer such as heating kneader, Bamburi closed mixer, 3-roll mill, 2-roll mill, vibrating mill, ball mill, roll mill, grinder and extruder, into salt The product and the resin having an acid group, here a rosin-modified maleic acid resin, are melt-mixed and stirred at a temperature higher than a softening point of the resin having an acid group. Thereby, the salt-forming product is uniformly dispersed in the resin having an acid group. Further, the coloring composition obtained here is in a form in which a resin having an acid group is coated with a salt-forming product. Further, the colored composition was coarsely crushed and pulverized, and adjusted to a desired particle size.

成鹽生成物與具有酸基之樹脂之質量比(成鹽生成物：具有酸基之樹脂)宜在70：30至95：5之範圍。具有酸基之樹脂在著色組成物所佔比率越大，呈色性越降低。具體而言，來自具有酸基之樹脂之色彩係因著色組成物之色相而造成甚大影響。又，具有酸基之樹脂在著色組成物所佔比率越小，成鹽生成物對黏結樹脂中之分散性提升效果越小。成鹽生成物與具有酸基之樹脂之質量比(成鹽生成物：具有酸基之樹脂)較宜在75：25至90：10之範圍內。 The mass ratio of the salt-forming product to the resin having an acid group (salt-forming product: resin having an acid group) is preferably in the range of 70:30 to 95:5. The greater the ratio of the resin having an acid group to the coloring composition, the lower the color rendering property. Specifically, the color from the resin having an acid group is greatly affected by the hue of the coloring composition. Further, the smaller the ratio of the resin having an acid group to the coloring composition, the smaller the effect of improving the dispersibility of the salt-forming product in the binder resin. The mass ratio of the salt-forming product to the resin having an acid group (salt-forming product: resin having an acid group) is preferably in the range of 75:25 to 90:10.

[其他著色劑] [other colorants]

於該著色組成物中，例如以進一步提升耐熱性為目的，亦可含有更多顏料。 In the colored composition, for example, in order to further improve heat resistance, more pigment may be contained.

就紅色著色組成物而言，可使用例如C.I.Pigment Red 168、177、179、242及254等紅色顏料。又，於紅色著色組成物，可並用C.I.Pigment Yellow 13、138、139、150、185及214等黃色顏料或黃色染料成鹽生成物，或C.I.Pigment Orange 38、43、71及73等橘色顏料或橘色染料成鹽生成物。就紅色著色組成物而言，可使用例如C.I.Pigment Green 7、36及58等綠色顏料。又，於綠色著色組成物中，可並用上述黃色顏料或黃色成鹽生成物。就藍色著色組成物而言，可使用例如C.I.Pigment Blue 15、15：1、15：2、15：3、15：4、15：6及80等藍色顏料。又，於藍色著色組成物中，可並用C.I.Pigment Violet 19及23等紫色顏料或紫色染料成鹽生成物。 As the red coloring composition, red pigments such as C.I. Pigment Red 168, 177, 179, 242, and 254 can be used. Also, in the red coloring composition, C.I.Pigment can be used in combination. A yellow pigment or a yellow dye salt-forming product such as Yellow 13, 138, 139, 150, 185, and 214, or an orange pigment or an orange dye salt-forming product such as C.I. Pigment Orange 38, 43, 71, and 73. As the red coloring composition, green pigments such as C.I. Pigment Green 7, 36 and 58 can be used. Further, in the green coloring composition, the above yellow pigment or yellow salt-forming product may be used in combination. As the blue coloring composition, for example, a blue pigment such as C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, and 80 can be used. Further, in the blue coloring composition, a purple pigment such as C.I. Pigment Violet 19 or 23 or a violet dye may be used in combination to form a salt product.

於黃色著色組成物中，可使用上述黃色顏料或黃色成鹽生成物。 In the yellow colored composition, the above yellow pigment or yellow salt-forming product can be used.

就洋紅色著色組成物而言，可使用例如C.I.Pigment Red 122、144、146、169、192、202、207及209等洋紅色顏料。又，於洋紅色著色組成物中，可並用上述黃色顏料或黃色成鹽生成物。 As the magenta coloring composition, magenta pigments such as C.I. Pigment Red 122, 144, 146, 169, 192, 202, 207, and 209 can be used. Further, in the magenta colored composition, the above yellow pigment or yellow salt-forming product may be used in combination.

就青色著色組成物而言，可使用例如C.I.Pigment Blue 15：1、15：2、15：4、15：3、15：6及80等藍色顏料。又，於青色著色組成物中，可並用C.I.Pigment Violet 19及23等紫色顏料或紫色染料成鹽生成物。為了保有充分亮度，對於上述成鹽生成物100質量部，顏料成分宜為500質量部以下。該情況下，即便著色劑相對於上述成鹽生成物含較多顏料，仍可達成高亮度。 As the cyan coloring composition, for example, blue pigments such as C.I. Pigment Blue 15:1, 15:2, 15:4, 15:3, 15:6, and 80 can be used. Further, in the cyan coloring composition, a purple pigment such as C.I. Pigment Violet 19 or 23 or a violet dye may be used in combination to form a salt product. In order to maintain sufficient brightness, the pigment component is preferably 500 parts by mass or less based on 100 parts by mass of the salt-forming product. In this case, even if the coloring agent contains a large amount of pigment with respect to the salt-forming product, high brightness can be achieved.

(顏料微細化) (pigment refinement)

上述顏料可藉由例如鹽磨處理予以微細化。從對著色劑載體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，該一次粒徑宜為100nm以下。一次粒徑尤其適 宜的範圍為25至85nm。 The above pigment can be refined by, for example, a salt milling treatment. From the viewpoint of good dispersion in the colorant carrier, the primary particle diameter of the pigment is preferably 20 nm or more. Further, it is considered from the viewpoint of forming a filter segment having a high contrast ratio, and the primary particle diameter is preferably 100 nm or less. Primary particle size is especially suitable A suitable range is 25 to 85 nm.

再者，顏料之一次粒徑係從藉由TEM(穿透型電子顯微鏡)所取得的顏料之電子顯微鏡照片而求出。具體而言，首先從TEM像中，選擇1個可觀看到全體之一次粒子之顏料粒子。接著，從連接該顏料粒子像輪廓上之兩點之線段中，選擇長度最大的線段。該線段設為第1線段。接著，從連接該顏料粒子像輪廓上之兩點之線段中，選擇與第1線段在其中間正交之線段。該線段設為第2線段。然後，求出第1線段之長度L₁與第2線段之長度L₂之平均，將其設為平均長度L_av，進而求出一邊長度與平均長度L_av相等之立方體之體積V。針對100個以上之顏料粒子進行以上測定及計算，求出體積V之平均，將其設為平均體積V_av。具有該平均體積V_av之立方體之一邊長度設為顏料粒子之平均一次粒徑。 Further, the primary particle diameter of the pigment was determined from an electron micrograph of the pigment obtained by TEM (transmission electron microscope). Specifically, first, from the TEM image, one pigment particle that can see the entire primary particle is selected. Next, the line segment having the largest length is selected from the line segments connecting the two points on the contour of the pigment particle image. This line segment is set to the first line segment. Next, from the line segments connecting the two points on the contour of the pigment particle image, a line segment orthogonal to the first line segment is selected. This line segment is set to the second line segment. Then, the average length L ₁ of the first line segment and the length L ₂ of the second line segment are obtained, and the average length L _{av is} obtained, and the volume V of the cube whose one side length is equal to the average length L _av is obtained. The above measurement and calculation were performed on 100 or more pigment particles, and the average of the volume V was determined, and this was made into the average volume V _av . The length of one side of the cube having the average volume V _av is set as the average primary particle diameter of the pigment particles.

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小、或其分布寬度窄，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, it is possible to obtain a pigment having a very small primary particle diameter or a narrow distribution width and having a clear particle size distribution.

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的觀點考量，水溶性無機鹽係於顏料之總質量設為100質量部時，宜以50至2000質量部之範圍內之量來使用，較宜以300至1000質量部之範圍內之量來使用。 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水溶性無機鹽之物均可，並未特別限定。但於鹽磨處理時，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。水溶性有機溶劑係於顏料之總質量設為100質量部時，宜以5至1000質量部之範圍內之量來使用，較宜以50至500質量部之範圍內之量來使用。 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 viewpoints of processing efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of from 50 to 2,000 parts by mass, preferably from 300 to 1,000 parts by mass, when the total mass of the pigment is set to 100 parts by mass. The amount within the range is used. 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 water-soluble inorganic salt. However, in the salt milling treatment, the temperature rises and the solvent is 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 . When the total mass of the pigment is 100 parts by mass, the water-soluble organic solvent is preferably used in an amount of from 5 to 1,000 parts by mass, and more preferably in an amount of from 50 to 500 parts by mass.

在將顏料予以鹽磨處理時，亦可添加樹脂。該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。該樹脂宜在室溫下呈固體且不溶於水，一部分可溶於上述有機溶劑更適宜。樹脂之使用量係於顏料之總質量設為100重量部時，宜在5至200重量部之範圍內。 When the pigment is subjected to salt milling treatment, a resin may also be added. The kind of the resin 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 is preferably solid at room temperature and insoluble in water, and a part is soluble in the above organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by weight when the total mass of the pigment is 100 parts by weight.

在將顏料予以鹽磨處理(微細化)時，宜與上述同時添加上述成鹽生成物。由於該成鹽生成物係不溶於水及醇，因此可獲得更良好的著色劑。 When the pigment is subjected to salt milling treatment (fine refinement), it is preferred to add the above salt-forming product at the same time as described above. Since the salt-forming product is insoluble in water and alcohol, a more excellent color former can be obtained.

<透明樹脂> <Transparent Resin>

透明樹脂係令著色劑，尤其令成鹽生成物分散及/或溶解之物。透明樹脂可舉出例如熱塑性樹脂及熱硬化性樹脂。再者，於此之著色 劑係例如成鹽生成物或成鹽生成物與顏料之混合物。 The transparent resin is a coloring agent, especially a substance which disperses and/or dissolves the salt-forming product. The transparent resin may, for example, be a thermoplastic resin or a thermosetting resin. Again, this color The agent is, for example, a salt-forming product or a mixture of a salt-forming product and a pigment.

透明樹脂宜於可見光區，亦即於400至700nm之全波長區內，分光穿透率為80%以上，更宜為95%以上。以鹼顯影型著色抗蝕劑之形態使用著色組成物時，宜使用令包含酸性基與乙烯結合之單體共聚而成之鹼可溶性乙烯基系樹脂。又，為了更加提升光感度，亦可使用具有乙烯結合之能量線硬化性樹脂。 The transparent resin is preferably in the visible light region, that is, in the entire wavelength region of 400 to 700 nm, the spectral transmittance is 80% or more, more preferably 95% or more. When a coloring composition is used in the form of an alkali-developing type colored resist, an alkali-soluble vinyl-based resin obtained by copolymerizing a monomer containing an acidic group and ethylene is preferably used. Further, in order to further enhance the light sensitivity, an energy ray-curable resin having ethylene bonding may also be used.

作為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、LDPE)、丁二烯樹脂及聚醯亞胺樹脂。 Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, and polyacetic acid. Ethylene, urethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, cellulose, polyethylene (HDPE, LDPE), Butadiene resin and polyimide resin.

作為令包含酸性基與乙烯結合之單體共聚而成之鹼可溶性乙烯基系樹脂，可舉出例如具有羧基及磺酸基等酸性基之樹脂。具體的鹼可溶性樹脂可舉出例如具有酸性基之丙烯酸樹脂、a-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)丙烯酸共聚物及異丁烯-(酐)順丁烯二酸共聚物。其中尤其選自具有酸性基之丙烯酸樹脂及具有酸性基之苯乙烯-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及透明性高，因此適宜使用。 The alkali-soluble vinyl-based resin obtained by copolymerizing a monomer containing an acidic group and ethylene is exemplified by a resin having an acidic group such as a carboxyl group or a sulfonic acid group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an a-olefin-(anhydride) maleic acid copolymer, a styrene-styrenesulfonic acid copolymer, and a styrene-(meth)acrylic acid copolymer. And isobutylene-(anhydride) maleic acid copolymer. Among them, at least one resin selected from the group consisting of an acrylic resin having an acidic group and a styrene-styrenesulfonic acid copolymer having an acidic group is preferable, and an acrylic resin having an acidic group is particularly preferably used because it has high heat resistance and transparency.

作為具有乙烯結合之活性能量線硬化性樹脂係使用例如使具有羥基、羧基及胺基等反應性置換基之高分子，與具有異氰酸酯基、醛基及環氧基等反應性置換基之(甲基)丙烯酸化合物或肉桂酸反應，於該高分子導入有(甲基)丙烯醯基及苯乙烯基等光架橋性基之樹脂。又，亦使用藉由 羥烷基(甲基)丙烯酸酯等具有羥基之(甲基)丙烯酸化合物，來將含有苯乙烯-順丁烯二酸酐共聚物或a-烯烴-順丁烯二酸酐共聚物等酸酐之高分子予以半酯化之物。 As the active energy ray-curable resin having ethylene bonding, for example, a polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amine group, and a reactive substituent having an isocyanate group, an aldehyde group, and an epoxy group are used. A resin which reacts with an acrylic acid compound or cinnamic acid to introduce a photo-branching group such as a (meth)acryl fluorenyl group or a styryl group. Also, use a (meth)acrylic compound having a hydroxyl group such as a hydroxyalkyl (meth) acrylate to polymerize an acid anhydride such as a styrene-maleic anhydride copolymer or an a-olefin-maleic anhydride copolymer Semi-esterified.

作為具有乙烯結合之活性能量線硬化性樹脂，可舉出例如藉由以下方法(a)或(b)而導入乙烯結合之樹脂。 The active energy ray-curable resin having an ethylene bond may, for example, be a resin obtained by introducing ethylene in combination by the following method (a) or (b).

於方法(a)，例如藉由將具有環氧基及乙烯結合之單體與其他1種以上之單體予以共聚，獲得於側鏈具有環氧基之共聚物。接著，於側鏈，令具有乙烯結合及羧基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，令酸酐反應。如此獲得導入有乙烯結合及羧基之樹脂。作為具有環氧基及乙烯結合之單體，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。該等單獨使用或並用兩種以上均無妨。以下一步驟中與不飽和一價酸之反應性之觀點考量，宜為環氧丙基(甲基)丙烯酸酯。 In the method (a), for example, a copolymer having an epoxy group and an ethylene-bonded monomer is copolymerized with one or more other monomers to obtain a copolymer having an epoxy group in a side chain. Next, in the side chain, an aromatic reaction is carried out by reacting a carboxyl group having an unsaturated monovalent acid having an ethylene bond and a carboxyl group, and further reacting the generated hydroxyl group with an acid anhydride. Thus, a resin into which an ethylene bond and a carboxyl group were introduced was obtained. Examples of the monomer having an epoxy group and an ethylene bond include a glycidyl (meth)acrylate, a methyl epoxypropyl (meth)acrylate, and a 2-glycidoxy group (methyl group). 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. The viewpoint of reactivity with an unsaturated monovalent acid in the next step is preferably a glycidyl (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a位鹵烷、烷氧、鹵素、硝、氰置換體等單羧酸等。該等單獨使用或並用兩種以上均無妨。 Examples of the unsaturated monovalent acid include (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, and a-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.

作為酸酐可舉出例如四氫苯二酸酐、苯二酸酐、六氫苯二酸酐、琥珀酸酐、順丁烯二酸酐等。該等單獨使用或並用兩種以上均無妨。 Examples of the 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.

用以取代具有2個羧基之酸酐，或除了具有2個羧基之酸酐以外，亦可使用具有3個以上羧基之酸酐，例如偏苯三酸酐等三羧酸酐或均苯四甲酸二酐等四羧酸二酐。該情況下，羥基與酸酐反應後所殘留的酐基 亦可予以加水分解。 An acid anhydride having two carboxyl groups or an acid anhydride having two carboxyl groups may be used. An acid anhydride having three or more carboxyl groups may be used. For example, a tetracarboxylic acid anhydride such as trimellitic anhydride or a tetracarboxylic acid dianhydride such as pyromellitic dianhydride may be used. . In this case, the anhydride group remaining after the reaction of the hydroxyl group with the acid anhydride It can also be hydrolyzed.

作為酸酐亦可使用四氫苯二酸酐及順丁烯二酸酐等具有乙烯結合之酸酐。如此可進一步增加乙烯結合。 As the acid anhydride, an acid anhydride having ethylene bonding such as tetrahydrophthalic anhydride or maleic anhydride can also be used. This can further increase the ethylene bond.

再者，作為與方法(a)類似之方法有例如以下方法。首先，令具有羧基及乙烯結合之單體與其他1種以上之單體共聚，獲得於側鏈具有羧基之共聚物。接著，於側鏈之羧基之一部分，令具有乙烯結合及環氧基之單體進行附加反應。如此獲得導入有乙烯結合及羧基之樹脂。 Further, as a method similar to the method (a), for example, the following method. First, a monomer having a carboxyl group and an ethylene bond is copolymerized with one or more other monomers to obtain a copolymer having a carboxyl group in a side chain. Next, an monomer having an ethylene bond and an epoxy group is subjected to an additional reaction in a part of the carboxyl group of the side chain. Thus, a resin into which an ethylene bond and a carboxyl group were introduced was obtained.

於方法(b)，令具有羥基及乙烯結合之單體，與具有羧基及乙烯結合之不飽和一價基酸或其他單體共聚，獲得於側鏈具有羥基之共聚物。接著，於側鏈之羥基，令具有異氰酸酯基及乙烯結合之單體之異氰酸酯基進行反應。如此獲得導入有乙烯結合及羧基之樹脂。 In the method (b), a monomer having a hydroxyl group and an ethylene bond is copolymerized with an unsaturated monovalent acid having a carboxyl group and ethylene or another monomer to obtain a copolymer having a hydroxyl group in a side chain. Next, the isocyanate group of the monomer having an isocyanate group and ethylene is reacted in the hydroxyl group of the side chain. Thus, a resin into which an ethylene bond and a carboxyl group were introduced was obtained.

作為具有羥基及乙烯結合之單體可舉出例如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。該等單獨使用或並用兩種以上均無妨。又，亦可使用於羥基烷基(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化合物，例如聚醚單(甲基)丙烯酸酯，或於羥基烷基(甲基)丙烯酸酯，附加有(聚)g-戊內酯、(聚)e-己內酯及(聚)12-羥基硬酯酸之至少一者而成之(聚)酯單(甲基)丙烯酸酯。從抑制異物混入塗膜的觀點考量，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 monomer having a hydroxyl group and an ethylene bond include 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyrate. 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 a hydroxyalkyl (meth) acrylate, a compound obtained by additionally polymerizing an ethylene peroxide, a propylene peroxide, and/or a butyl peroxide, for example, a polyether mono (methyl). An acrylate, or a hydroxyalkyl (meth) acrylate, with at least one of (poly) g-valerolactone, (poly)e-caprolactone, and (poly) 12-hydroxystearic acid A (poly)ester mono(meth)acrylate. From the viewpoint of suppressing the incorporation of foreign matter into the coating film, it is preferably 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate.

具有異氰酸酯基及乙烯結合之單體可舉出例如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。該等單獨使用或並用兩種以上均可。 The monomer having an isocyanate group and an ethylene bond may, for example, be 2-(methyl)propyl. An ene oxyethyl isocyanate or a 1,1-bis[(meth) propylene oxime] ethyl isocyanate or the like. These may be used alone or in combination of two or more.

再者，作為熱塑性樹脂，於彩色濾光片用著色組成物中，亦適宜使用同時具有鹼可溶性能及能量線硬化性能之物。 Further, as the thermoplastic resin, an object having both alkali solubility and energy ray hardening properties is preferably used in the coloring composition for a color filter.

作為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。 Examples of the thermosetting resin include an epoxy resin, a benzoamide resin, a rosin-modified maleic acid resin, a rosin-modified fumaric acid resin, a melamine resin, a urea resin, and a phenol resin.

以令著色劑分散或溶解的觀點考量，樹脂之重量平均分子量(Mw)宜在10,000至100,000之範圍內，較宜在10,000至80,000之範圍內。又，數量平均分子量(Mn)宜在5,000至50,000之範圍內。樹脂之重量平均分子量(Mw)與數量平均分子量(Mn)之比Mw/Mn宜在10以下。 The weight average molecular weight (Mw) of the resin is preferably in the range of from 10,000 to 100,000, more preferably in the range of from 10,000 to 80,000, from the viewpoint of dispersing or dissolving the colorant. Further, the number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000. The ratio Mw/Mn of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the resin is preferably 10 or less.

從成膜性及各種耐受性的觀點考量，透明樹脂係於著色劑之總質量設為100質量部時，宜以30質量部以上之量來使用。又，由於著色劑濃度高時，可顯現良好的色彩特性，因此透明樹脂係於著色劑之總質量設為100質量部時，宜以500質量部以下之量來使用。 When the total mass of the coloring agent is 100 parts by mass, it is preferable to use it in an amount of 30 parts by mass or more, from the viewpoint of film forming properties and various kinds of resistance. In addition, when the colorant concentration is high, good color characteristics can be exhibited. Therefore, when the total mass of the colorant is 100 parts by mass, the transparent resin is preferably used in an amount of 500 parts by mass or less.

<分散> <scatter>

該著色組成物係可藉由將包含鹼性染料及相對化合物之成鹽生成物之著色劑、由透明樹脂及因應需要而使用之溶劑所組成的著色劑載體，宜與色素衍生物等分散助劑一同供作利用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之處理來製造。又，該著色組成物亦可藉由令數種著色劑個別分散於著色劑載體，其後混合其等而製造。 The coloring composition can be dispersed by a coloring agent comprising a coloring agent containing a basic dye and a salt-forming product of a relative compound, a transparent resin, and a solvent used as needed. The agent is produced together by treatment with various dispersing mechanisms such as a 3-roll mill, a 2-roll mill, a sand mill, a kneader, and an attritor. Further, the colored composition may be produced by separately dispersing a plurality of coloring agents on a colorant carrier, and then mixing them.

(分散助劑) (dispersion 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，再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。 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 the re-coagulation of the dispersing coloring agent is great. Therefore, when a coloring composition obtained by dispersing a coloring agent in a coloring agent carrier by using a dispersing aid is used, a color filter having a high spectral transmittance can be obtained.

色素衍生物可舉出於有機顏料及有機染料等有機色素、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 an organic dye such as an organic pigment or an organic dye, an anthracene, an acridone or a triazine, and a basic substituent, an acidic substituent or a phthalic acid which may have a substituent may be introduced. A compound of an amine methyl group.

該等之中，顏料衍生物尤其適宜。於下述式(1)表示其構造。P-L_n 式(1)其中，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。 Among these, pigment derivatives are particularly suitable. The structure is represented by the following formula (1). PL _n Formula (1) wherein 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 also have a substituent. Methyl quinone imine methyl, n is an integer from 1 to 4.

作為構成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 include pyrrolopyrroledione pigments; azo-based pigments such as azo, disazo, and polyazo; copper phthalocyanine, copper halide phthalocyanine, and metal-free ruthenium; Phthalocyanine pigments such as phthalocyanine; amine onion, diamine, onion, pyrimidine, xanthone, indolinone, standard reduction blue, furanone, anthrone violet dye, etc.; quinophthalone Pigment; dithiazine pigment; anthraquinone pigment; anthraquinone pigment; thiazin indigo pigment; isoindane pigment; isoindolinone pigment; quinophthalone pigment; durene pigment; Mismatched pigments, etc.

色素衍生物可使用例如日本特開昭63-3005173號、日本特公昭57-15620號、日本特公昭59-40172號及日本特公平5-9469號所記載之物。 該等可單獨使用或混合兩種以上使用。 The pigment derivative can be, for example, those described in JP-A-63-3005173, JP-A-57-15620, JP-A-59-40172, and JP-A-5-9469. These may be used alone 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對於著色劑100質量部，宜為1質量部以上，更宜為3質量部以上，最宜為5質量部以上。又，從耐熱性及耐光性的觀點考量，色素衍生物之調配量係對於著色劑100質量部，宜為50質量部以下，更宜為30質量部以下，最宜為25質量部以下。 The amount of the pigment derivative to be added is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and most preferably 5 parts by mass or more, from the viewpoint of the improvement of the dispersibility. In addition, it is preferable that the amount of the pigment derivative is 50 parts by mass or less, more preferably 30 parts by mass or less, and most preferably 25 parts by mass or less, from the viewpoint of the heat resistance and the light resistance.

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例如聚氨酯、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。該等可單獨使用或混合兩種以上來使用。樹脂型分散劑未必要限定在該等。 The resin type dispersant has a pigment affinity site having a property of adsorbing on a pigment and a site compatible with a pigment carrier, and has a function of adsorbing to a colorant to stabilize the dispersion of the colorant with respect to the pigment carrier. As the specific resin type dispersant, for example, a polycarboxylate such as polyurethane or polyacrylate, an unsaturated polyamine, a polycarboxylic acid, a polycarboxylic acid (partial) amine salt, a polycarboxylate ammonium salt, a polycarboxylic acid alkylamine can be used. a salt, a polyoxyalkylene, a long-chain polyamine phthalamide phosphate, a hydrocarbon-containing polycarboxylate or a modification thereof, by reacting with a polyester having a polymerization (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 polyvinylpyrrolol A resin or a water-soluble polymer compound, a polyester-based dispersant, a modified polyacrylate-based dispersant, an ethylene oxide/propylene oxide-addition compound, and a phthalate-based dispersant. These may be used alone or in combination of two or more. The resin type dispersant is not necessarily limited to these.

界面活性劑可舉出例如月桂基硫酸鈉、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。該等可單獨使用或混合兩種以上來使用。界面活性劑未必要限定在該等。 The surfactant may, for example, be sodium lauryl sulfate, polyethylene oxide ether sulfate, sodium dodecylbenzenesulfonate, an acrylate of a styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate or an alkyl group. Sodium phenyl ether disulfonate, ethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, ethanolamine stearate, ammonium stearate, sodium lauryl sulfate, ethanolamine of styrene-acrylic acid copolymer, polyepoxy Anionic surfactant such as ethane ether phosphate; polyethylene oxide a cationic surfactant such as a olefin ether, a polyethylene oxide lauryl ether, a polyethylene oxide decyl phenyl ether, a polyethylene oxide ether phosphate, or a polyethylene oxide sorbitan glyceryl stearic acid; a raw rubber dry-distillation surfactant such as a 4-grade ammonium salt or an ethylene oxide add-on thereof; an alkyl quaternary ammonium carboxylate internal salt such as an alkyl dimethylamine acetic acid quaternary ammonium carboxylate; or an alkyl imidazoline And other amphoteric surfactants. These may be used alone or in combination of two or more. The surfactant is not necessarily limited to these.

<溶劑> <solvent>

於著色組成物中可含有溶劑，以便令著色劑充分分散於著色劑載體中，容易於玻璃基板等基板上，塗布為乾燥膜後成為例如0.2至5mm，形成濾光片區段。 A solvent may be contained in the coloring composition so that the coloring agent can be sufficiently dispersed in the coloring agent carrier, and it can be easily applied to a substrate such as a glass substrate, and after being applied as a dried film, for example, it is 0.2 to 5 mm to form a filter segment.

作為溶劑可舉出例如1,2,3-三氯丙烷、1,3-丁二醇(1,3-Butanediol)、1,3-丁二醇(1,3-Butylene glycol)、芐基醇、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、醋酸丙基及二價酸酯。 Examples of the solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, and benzyl alcohol. , 1,3-butanediol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,3,5-trimethyl-2-cyclohexane En-1-one, 3,5,5-trimethylcyclohexanone, 3-ethoxypropionic acid ethyl, 3-methoxy-3-methylacetate butyl ester, 3-methoxybutanol, 3-methoxyacetic acid butyl ester, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, n-butylbenzene, n-propyl acetate, N- Pyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, dibutylbenzene, tertiary butylbenzene, isophorone, ethylene glycol diethyl ether, Ethylene glycol dibutyl ether, ethylene glycol monoethyl ether 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-amine acetate, n-butyl acetate, acetic acid Isoamino group, isobutyl acetate, propyl acetate and dibasic acid ester.

其中從著色劑之分散性或溶解性良好的觀點來看，宜使用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、環己酮等酮類或芐基醇等芳香族醇類。 Among them, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl group are preferably used from the viewpoint of good dispersibility or solubility of the colorant. An alcohol such as an alcohol acetate such as an ether acetate or a ketone such as cyclohexanone or an aromatic alcohol such as a benzyl alcohol.

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，因此於著色劑之總質量設為100質量部時，宜以800至4000質量部之量來使用。 The solvent may be used alone or in combination of two or more. In addition, since the solvent can adjust the coloring composition to an appropriate viscosity to form a coloring layer having a uniform film thickness, it is preferable to use it in an amount of 800 to 4,000 parts by mass when the total mass of the coloring agent is 100 parts by mass. .

<光聚合性組成物> <Photopolymerizable composition>

於光聚合性組成物中使用之單體或寡聚物可舉出例如：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、b-羧基(甲基)丙烯酸酯及tricyclodecenylmethacrylate等單官能(甲基)丙烯酸酯類；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、等二官能(甲基)丙烯酸酯類；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)丙烯酸酯及二新戊四醇六(甲基)丙烯酸酯等三官能以上之多官能(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、新戊二醇甘油基醚及酚醛樹脂等環氧化合物與(甲基)丙烯酸之反應物，即環氧(甲基)丙烯酸酯；聚酯、聚氨酯、異氰酸酯及羥甲基化三聚氰胺等經改質之各種(甲基)丙烯酸酯類；以及(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(甲基)丙烯酸酯以外之單體。該等可單獨使用或混合兩種以上來使用。單體或寡聚物未必要限定在該等 Examples of the monomer or oligomer used in the photopolymerizable composition include methyl (meth) acrylate, ethyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. Monofunctional (meth) acrylates such as 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, b-carboxy (meth) acrylate, and tricyclodecenylmethacrylate; polyethylene glycol mono Acrylate, 1,6-hexanedioxane (meth) acrylate, triethylene glycol di(meth) acrylate, tripropylene glycol di(meth) acrylate, etc. difunctional (methyl) Acrylates; trimethylolpropane (meth) acrylate, neopentyl alcohol (meth) acrylate, neopentyl alcohol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate a trifunctional or higher polyfunctional (meth) acrylate such as an ester or dipentaerythritol hexa(meth) acrylate; 1,6-butanediol diglycidyl ether, bisphenol A diglycidyl ether, a reaction product of an epoxy compound such as neopentyl glycol glyceryl ether and a phenol resin with (meth)acrylic acid, that is, epoxy (meth) acrylate; polyester, polyurethane, isocyanate and Various modified (meth) acrylates such as methylolated melamine; and (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, and neopentyl alcohol Vinyl ether, (meth) acrylamide, N-hydroxyl A monomer other than a (meth) acrylate such as methyl (meth) acrylamide, N-ethylene methamine or acrylonitrile. These may be used alone or in combination of two or more. Monomers or oligomers are not necessarily limited to such

<光聚合起始劑> <Photopolymerization initiator>

藉由利用紫外線照射之光微影，從彩色濾光片用著色組成物形成濾光片區段時，於該著色組成物添加光聚合起始劑等。 When a filter segment is formed from a coloring composition for a color filter by photolithography of ultraviolet light irradiation, a photopolymerization initiator or the like is added to the coloring composition.

光聚合起始劑可舉出例如：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；及咪唑系化合物等。 The photopolymerization initiator may, for example, be 4-phenoxydichloroacetophenone, 4-t-butyldichloroacetophenone, diethoxyacetophenone, 1-(4-isopropyl Phenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl benzophenone, 2-benzyldimethylamine-1-(4-morpholinylphenyl)-butane- An acetophenone compound such as 1-ketone; a benzo compound such as benzo, benzoxyl ether, benzoethyl ether, benzoisopropyl ether or benzyldimethylketal; benzophenone, benzoquinone benzoic acid , benzoquinone benzoic acid methyl, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoquinone-4'-methyldiphenyl sulfide, 3,3 a benzophenone compound such as ',4,4'-tetrakis(t-butylperoxycarboxy)benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropyl Thiophenone compounds such as thioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone; 2,4,6-trichloro-o-triazine, 2-benzene 4-,6-bis(trichloromethyl)-o-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-o-triazine, 2-(p-toluene) -4,6-bis(trichloromethyl)-o-triazine, 2-piperidin-4,6-bis(trichloromethyl)-ortho Triazine, 2,4-bis(trichloromethyl)-6-styryl-o-triazine, 2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-ortho Pyrazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-o-triazine, 2,4-trichloromethyl-(piperidinyl)-6- a triazine compound such as triazine or 2,4-trichloromethyl (4'-methoxystyryl)-6-triazine; 1,2-octanedione, 1-[4-(phenylthio) )-,2(O-benzopyrene)], O- (Ethyl)-N-(1-phenyl-2-carbonyl-2-(4'-methoxy-naphthyl)ethylidene)hydroxylamine and other oxime ester compounds; bis(2,4,6-three a phosphine compound such as methylbenzo)epoxyphenylphosphine or 2,4,6-trimethylbenzoepoxyphenylphosphine; an anthraquinone compound such as 9,10-phenanthrenequinone, camphorquinone or ethylhydrazine; boron An acid ester compound; an oxazole compound; and an imidazole compound.

該等光聚合起始劑可單獨以1種或混合2種以上來使用。該等光聚合起始劑係對於彩色濾光片用著色組成物中之著色劑100重量部，宜以5至200重量部之量來使用，從光硬化性及顯影性的觀點來看，較宜以10至150重量部之量來使用。 These photopolymerization initiators may be used alone or in combination of two or more. The photopolymerization initiator is preferably used in an amount of from 5 to 200 parts by weight based on 100 parts by weight of the coloring agent in the coloring composition for a color filter, from the viewpoint of photocurability and developability. It should be used in an amount of 10 to 150 parts by weight.

<增感劑> <sensitizer>

於彩色濾光片用著色組成物中，可進一步含有增感劑。 The coloring composition for a color filter may further contain a sensitizer.

增感劑可舉出例如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、Tetraphyrin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、a-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’,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 an anthracene. Derivatives, naphthoquinone derivatives, anthracene derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, coumarin derivatives Polymethine pigment, acridine derivative, azabenzene derivative, diene terpene derivative, oxazine derivative, porphyrin derivative, etc., such as a cyanine derivative, a merocyanine derivative, and a cyanine derivative , anthracene derivative, sulfonium salt derivative, squaric acid 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 , Tetraphyrin derivatives, olefin derivatives, spiropyran derivatives, spirooxazine derivatives, thiospirol derivatives, gold Arene complexes, organic ruthenium compound, Michler's ketone derivatives, ether oxygen A- acyl, acyl phosphine oxide, methylphenyl glyoxylate, Benzyl-9,10-phenanthrene, camphorquinone, ethylhydrazine, 4,4'-diethylnonanol, 3,3',4,4'-tetra (tertiary butyl Oxycarbonyl group) 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「特殊功能材料」(1986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。增感劑不限定於該等。又，於著色組成物中，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 "Special Functional Materials" (1986, CMC) compiled by the "Pigment Handbook" compiled by Ohara Shinto and others, and the "Special Functional Materials" (1986, CMC) and Chisen-Sang Sanlang, etc. Sensitizers described in "Special Functional Materials" (1986, CMC). The sensitizer is not limited to these. Further, the coloring composition may further contain a sensitizer which exhibits absorption of light from the ultraviolet to the near-infrared region.

增感劑能夠以任意比率組合2種以上亦可。使用增感劑時，其調配量係於著色組成物中所含之光聚合起始劑設為100質量部時，宜在3至60質量部之範圍內，從光硬化性及顯影性的觀點來看，較宜在5至50質量部之範圍內。或者，增感劑亦可對於著色組成物中之光聚合起始劑100質量部，以例如0.1至60質量部之量來使用。 The sensitizer may be combined in two or more kinds at any ratio. When the sensitizer is used in an amount of 100 parts by mass in the photopolymerization initiator contained in the coloring composition, it is preferably in the range of 3 to 60 parts by mass, from the viewpoint of photocurability and developability. In view of it, it is better to be within the range of 5 to 50 mass parts. Alternatively, the sensitizer may be used in an amount of, for example, 0.1 to 60 parts by mass for 100 parts by mass of the photopolymerization initiator in the coloring composition.

<胺系化合物> <Amine compound>

於彩色濾光片用著色組成物中，可進一步含有具有還原溶存氧的作用之胺系化合物。 The coloring composition for a color filter may further contain an amine compound having a function of reducing dissolved oxygen.

該類胺系化合物可舉出例如三乙醇胺、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。 Examples of such an amine-based compound include triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylamine benzoic acid methyl, 4-dimethylamine benzoic acid ethyl, 4-dimethyl group. Amine benzoic acid 2-ethylhexyl and N,N-dimethyl-p-toluidine.

<均染劑> <leveling agent>

於該著色組成物中，為了改善組成物在透明基板上之均染性，宜進一步添加均染劑。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。亦可並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。均染劑之含有量通常在著色組成物之總質量設為100質量%時，宜在0.003至0.5重量%之範圍內。 In the colored composition, in order to improve the leveling property of the composition on the transparent substrate, it is preferred to further add a leveling agent. The leveling agent is preferably one of a polyether structure or a polyester structure in the main chain. Methyl decane. 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 methoxy olefin having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Corporation. It can also be used in combination with dimethyl methoxy alkane 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 usually in the range of 0.003 to 0.5% by weight, based on the total mass of the coloring composition being 100% by mass.

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；其添加於著色組成物時，特別有用之物為顯示出其降低表面張力的能力低之特徵，進而對玻璃板之潤澤性良好者。其中尤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。聚環氧烷單位包括例如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。 The 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 when it is added to a coloring composition, it is particularly useful. It shows that it has a low ability to lower the surface tension, and further has good lubricity to the glass plate. Among them, it is preferable to use a substance which can sufficiently suppress the chargeability in the amount of addition of the coating film defect 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, for example, a polyethylene oxide unit and a polyoxypropylene unit. Dimethyloxane may also have both polyethylene oxide units and polypropylene oxide units.

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。具有聚環氧烷單位之二甲基矽氧烷可舉出例如由TORAY‧Dow Corning公司市售之FZ-2110、FZ-2122、FZ-2130、FZ-2166、FZ-2191、FZ-2203及FZ-2207。具有聚環氧烷單位之二甲基矽氧烷不限定於該等。 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 polyalkylene oxide unit; a terminal modified type bonded to a terminal end of dimethyloxane; and a linear block copolymer in which a polyalkylene oxide unit is repeatedly and repeatedly bonded to dimethyloxane. Examples of the dimethyloxane having a polyalkylene oxide unit include FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, and FZ-2203 which are commercially available from TORAY‧Dow Corning Co., Ltd., and FZ-2207. The dimethyl siloxane having a polyalkylene oxide unit 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。界面活性劑可單獨使用1種，或混合2種以上使用。輔助性地加入於均染劑之陰離子性界面活性劑可舉出例如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。 Anionic, cationic, nonionic can also be added to the leveling agent. Sexual or amphoteric surfactant. The surfactant may be used singly or in combination of two or more. 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 alkyl naphthalenesulfonate. Sodium, sodium alkyl diphenyl ether disulfonate, ethanolamine 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例如烷基4級銨鹽及其等之環氧乙烷附加物。輔助性地加入於均染劑之非離子性界面活性劑，可舉出例如聚環氧乙烯油醚、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。 The cationic surfactant of the auxiliary leveling agent may, for example, be an alkyl 4-grade ammonium salt or the like. The nonionic surfactant which is auxiliaryly added to the leveling agent may, for example, be a polyethylene oxide oleyl ether, a polyethylene oxide lauryl ether, a polyethylene oxide decyl phenyl ether, or a polyethylene oxide ether phosphate. Alkyl quaternary ammonium carboxylate inner salt such as ester, polyethylene oxide sorbitan glyceryl stearic acid, polyethylene glycol monolauryl ester, alkyl dimethylamine acetic acid quaternary ammonium carboxylate, and alkyl imidazoline An amphoteric surfactant, and a fluorine- or sulfhydryl surfactant.

<硬化劑及硬化促進劑> <hardener and hardening accelerator>

為了輔助熱硬化性樹脂之硬化，於該著色組成物中，亦可因應需要來含有硬化劑及硬化促進劑。 In order to assist the hardening of the thermosetting resin, a curing agent and a curing accelerator may be contained in the colored composition as needed.

有用之硬化劑為例如苯酚系樹脂、胺系化合物、酸酐、活性酯、羧酸系化合物及磺酸系化合物。硬化劑並未特別限定於此。若可與熱硬化性樹脂反應之物，使用任何硬化劑均可。該等之中，尤以1分子內具有2個以上之苯酚性羥基之化合物及胺系硬化劑為宜。 Useful hardeners are, for example, phenol resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, and sulfonic acid compounds. The hardener is not particularly limited to this. Any hardener may be used if it can react with the thermosetting resin. Among these, a compound having two or more phenolic hydroxyl groups and an amine-based curing agent in one molecule are preferable.

硬化促進劑可舉出例如：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-二甲基苄基胺等胺化合物；三乙基苄基氯化銨等4級銨氯化合物；二甲基胺等嵌 段異氰酸酯化合物；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-甲基咪唑基等咪唑基衍生物二環式脒化合物及其鹽；三苯膦等磷化合物；三聚氰胺、胍胺、乙醯胍胺及苯并胍胺等胍胺化合物；以及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S-三嗪衍生物。效果促進劑可單獨使用1種或並用兩種以上來使用。硬化促進劑之含有量係以熱硬化性樹脂總量作為基準，宜在0.01至15質量%之範圍內。 Examples of the hardening accelerator include dicyandiamide, benzyldimethylamine, 4-(dimethylamine)-N,N-dimethylbenzylamine, 4-methoxy-N,N-di An amine compound such as methylbenzylamine or 4-methyl-N,N-dimethylbenzylamine; a 4-grade ammonium chloride compound such as triethylbenzylammonium chloride; Segment isocyanate compound; imidazolyl, 2-methylimidazolyl, 2-ethylimidazolyl, 2-ethyl-4-methylimidazolyl, 2-phenylimidazolyl, 4-phenylimidazolyl, 1-cyano Imidazolyl derivatives such as 2-ethyl-2-phenylimidazolyl and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazolyl and their salts; triphenylphosphine Phosphate compounds; guanamine compounds such as melamine, guanamine, acetamide and benzoguanamine; and 2,4-diamine-6-methylpropenyloxyethyl-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 oxime S-triazine derivatives such as s-S-triazine ‧ isocyanate acid addenda. The effect accelerator may be used singly or in combination of two or more. The content of the hardening accelerator is preferably in the range of 0.01 to 15% by mass based on the total amount of the thermosetting resin.

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

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

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。儲藏安定劑係對於著色組成物中之著色劑100質量部，能夠以例如0.1至10重量部的量來使用。 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 can be used in an amount of, for example, 0.1 to 10 parts by weight for 100 parts by mass of the coloring agent in the coloring composition.

密貼提升劑可舉出例如以下矽烷耦合劑：乙烯三(b-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；g-甲基丙烯氧基丙烯三甲氧基矽烷等(甲基)丙烯酸矽烷類；b-(3,4-環氧環烷基)乙基三甲氧基矽烷、b-(3,4-環氧環烷基)甲基三甲氧基矽烷、b-(3,4-環氧環烷基)乙基三乙氧基矽烷、b-(3,4-環氧環烷基)甲基三乙氧基矽烷、g- 環氧丙氧基丙基三甲氧基矽烷、g-環氧丙氧基丙基三乙氧基矽烷等環氧矽烷類；N-b(胺乙基)g-胺丙基三甲氧基矽烷、N-b(胺乙基)g-胺丙基三乙氧基矽烷、N-b(胺乙基)g-胺丙基甲基二乙氧基矽烷、g-胺丙基三乙氧基矽烷、g-胺丙基三甲氧基矽烷、N-苯基-g-胺丙基三甲氧基矽烷、N-苯基-g-胺丙基三乙氧基矽烷等胺矽烷類；以及g-巰基丙基三甲氧基矽烷、g-巰基丙基三甲乙基矽烷等硫代矽烷類。密貼提升劑係對於著色組成物中之著色劑100質量部，能夠以例如0.01至10質量部的量來使用，宜以0.05至5質量部的量來使用。 Examples of the adhesion promoter include the following decane coupling agents: ethylene decane such as ethylene tris(b-methoxy-oxy)decane, ethylene ethoxy decane, and ethylene trimethoxy decane; g-methacryloxy group (meth)acrylic acid decane such as propylene trimethoxydecane; b-(3,4-epoxycycloalkyl)ethyltrimethoxydecane, b-(3,4-epoxycycloalkyl)methyltrimethyl Oxydecane, b-(3,4-epoxycycloalkyl)ethyltriethoxydecane, b-(3,4-epoxycycloalkyl)methyltriethoxydecane, g- Epoxy decanes such as glycidoxypropyltrimethoxydecane, g-glycidoxypropyltriethoxydecane; Nb (amine ethyl) g-aminopropyltrimethoxydecane, Nb ( Aminoethyl)g-aminopropyltriethoxydecane, Nb(amineethyl)g-aminopropylmethyldiethoxydecane, g-aminopropyltriethoxydecane, g-aminopropyl Amino decanes such as trimethoxy decane, N-phenyl-g-aminopropyltrimethoxydecane, N-phenyl-g-aminopropyltriethoxydecane; and g-mercaptopropyltrimethoxydecane And thiononane such as g-mercaptopropyltrimethylethyl decane. The adhesion enhancer can be used in an amount of, for example, 0.01 to 10 parts by mass, and is preferably used in an amount of 0.05 to 5 parts by mass, based on 100 parts by mass of the coloring agent in the coloring composition.

<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，從該著色組成物，進行5mm以上之粗粒子，更宜為1mm以上之粗粒子，尤宜為0.5mm以上之粗粒子及混入微塵之去除。如此，著色組成物宜不含0.5mm以上之粒子。又，著色組成物更宜實質上不含0.3mm以上之粒子。 By using a mechanism such as a centrifugal separation, a sintered filter, or a membrane filter, coarse particles of 5 mm or more are preferably used, and coarse particles of 1 mm or more are more preferably used, and coarse particles of 0.5 mm or more and removal of fine dust are particularly preferably removed. . Thus, the coloring composition is preferably free of particles of 0.5 mm or more. Further, the colored composition is more preferably substantially free of particles of 0.3 mm or more.

<<彩色濾光片>> <<Color filter>>

接著說明關於本發明之第2態樣之彩色濾光片。 Next, a color filter according to a second aspect of the present invention will be described.

第2態樣之彩色濾光片包含吸收光譜不同、典型上規則地排列之複數個濾光片區段。一形態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。另一形態之彩色濾光片具備至少1個洋紅色濾光片區段、至少1個青色濾光片區段及至少1個黃色濾光片區段。於第2態樣之彩色濾光片，該等濾光片區段之至少1個係由上述彩色濾光片用著色組成物所形成。 The color filter of the second aspect comprises a plurality of filter segments having different absorption spectra, typically regularly arranged. A color filter of one form includes at least one red filter segment, at least one green filter segment, and at least one blue filter segment. Another aspect of the color filter includes at least one magenta filter segment, at least one cyan filter segment, and at least one yellow filter segment. In the color filter of the second aspect, at least one of the filter segments is formed of the coloring composition for the color filter.

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

該彩色濾光片可藉由例如印刷法或光微影製造。 The color filter can be manufactured by, for example, a printing method or photolithography.

若藉由印刷法，僅重複作為印刷油墨所調製的著色組成物之印刷與乾燥，即可形成已圖案化之濾光片區段。因此，印刷法係低成本且量產性良好。進而言之，藉由印刷技術的發展，可利用印刷形成具有高尺寸精度及平滑度之微細圖案。 The patterned filter segments can be formed by printing and drying only the coloring composition prepared as the printing ink by the printing method. Therefore, the printing method is low in cost and good in mass production. Further, by the development of printing technology, it is possible to form a fine pattern having high dimensional accuracy and smoothness by printing.

於印刷中使用油墨時，宜為油墨在印刷板上或於毛氈布不會乾燥及固化之組成。又，印刷機上之油墨流動性之控制亦重要。油墨流動性可藉由利用分散劑或體質顏料，進行墨水黏度調整來控制。 When the ink is used in printing, it is preferred 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 important. The ink fluidity can be controlled by adjusting the ink viscosity by using a dispersant or an extender pigment.

若藉由光微影法，相較於印刷法，能夠以較高精度製造彩色濾光片。 According to the photolithography method, the color filter can be manufactured with higher precision than the printing method.

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彩色抗蝕劑材料所調製之著色組成物，塗布為乾燥膜厚成為例如0.2至5mm之範圍內。依需要乾燥塗膜，經由與該塗膜呈接觸或非接觸狀態而設置之具特定圖案之光罩，以紫外線將該塗膜予以曝光。其後，將塗膜浸漬於溶劑或鹼顯影劑中，或於塗膜噴霧溶劑或鹼顯影劑，從塗膜去除未硬化部。藉此獲得對應於某色之濾光片區段之薄膜圖案。除了使用其他色之濾光片區段用之著色組成物以外，重複與上述同樣的操作，形成對應於剩餘濾光片區段之薄膜圖案。其後，藉由燒成該等薄膜圖案而獲得彩色濾光片。再者，燒成亦可於每當形成薄膜圖案時進行。 When the filter segment is formed by the photolithography method, the solvent development type or the alkali development type color 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 so that the dry film thickness is in the range of, for example, 0.2 to 5 mm. The coating film is dried as needed, and the coating film is exposed to ultraviolet rays through a mask having a specific pattern which is provided in contact or non-contact with the coating film. Thereafter, the coating film is immersed in a solvent or an alkali developer, or a solvent or an alkali developer is sprayed on the coating film to remove the uncured portion from the coating film. Thereby, a film pattern corresponding to a filter segment of a certain color is obtained. The same operation as described above was repeated except that the coloring composition for the color filter segments of other colors was used to form a film pattern corresponding to the remaining filter segments. Thereafter, a color filter is obtained by firing the film patterns. Further, the firing may be performed each time a film pattern is formed.

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. An organic base such as dimethylbenzylamine or triethanolamine can also be used. Also, in the developer An antifoaming agent or a surfactant may be added.

再者，為了提高紫外線曝光感度，亦可於塗布及乾燥上述著色抗蝕劑而成之著色抗蝕劑膜上，塗布水溶性或鹼可溶性樹脂之例如聚乙烯醇或水溶性丙烯酸樹脂，令該塗膜乾燥，其後進行紫外線曝光亦可。由水溶性或鹼可溶性樹脂所組成的塗膜係防止氧阻礙著色抗蝕劑膜之聚合。 Further, in order to increase the ultraviolet exposure sensitivity, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin may be applied onto the colored resist film obtained by applying and drying the colored resist. The coating film is dried, and then ultraviolet exposure is also possible. A coating film composed of a water-soluble or alkali-soluble resin prevents oxygen from inhibiting polymerization of the colored resist film.

彩色濾光片亦可採印刷法及光微影以外之方法製造。例如可藉由電沈積法或轉印法來製造。上述著色組成物可利用於任何方法。 The color filter can also be manufactured by a method other than printing or photolithography. For example, it can be produced by an electrodeposition method or a transfer method. The above colored composition can be utilized in any method.

再者，於利用電沈積法之彩色濾光片之製造中，準備於一主面設有透明導電膜之基板，將該透明導電膜利用作為電極，令膠體粒子往透明導電膜上進行電泳，藉此形成濾光片區段。又，於利用轉印法之彩色濾光片之製造中，於一主面具有離模性之轉印基片之先前的主面上，預先形成濾光片區段，將該濾光片區段從轉印基片轉印至基板。 Further, in the manufacture of a color filter using an electrodeposition method, a substrate having a transparent conductive film on one main surface is prepared, and the transparent conductive film is used as an electrode to cause colloidal particles to be electrophoresed on the transparent conductive film. Thereby a filter segment is formed. Further, in the manufacture of a color filter using a transfer method, a filter segment is formed in advance on a previous main surface of a transfer substrate having a release surface on a main surface, and the filter region is formed. The segment is transferred from the transfer substrate to the substrate.

於透明基板上，在形成濾光片區段前形成遮光圖案之黑矩陣亦可。黑矩陣係利用例如鉻膜等金屬膜、鉻/氧化鉻膜等多層膜、氮化鈦等無機化合物膜、或於樹脂中分散有遮光材料而成之樹脂膜。 On the transparent substrate, a black matrix in which a light-shielding pattern is formed before forming the filter segment may be used. The black matrix is made of, for example, a metal film such as a chromium film, a multilayer film such as a chromium/chromium oxide film, an inorganic compound film such as titanium nitride, or a resin film in which a light shielding material is dispersed in a resin.

於透明基板，在形成彩色濾光片前形成電路，例如形成包含薄膜電晶體(TFT)之主動矩陣電路。又，於彩色濾光片上，亦可因應需要進一步形成覆膜及透明導電膜等其他層。 On the transparent substrate, a circuit is formed before the color filter is formed, for example, an active matrix circuit including a thin film transistor (TFT) is formed. Further, on the color filter, other layers such as a film and a transparent conductive film may be further formed as needed.

形成彩色濾光片之基板並非透明亦可。例如彩色濾光片亦可形成於反射基板上。 The substrate on which the color filter is formed is not transparent. For example, a color filter may also be formed on the reflective substrate.

○第2態樣 ○Second aspect

接著說明關於本發明之第2態樣。 Next, a second aspect of the present invention will be described.

於日本特開平11-223720號中，就彩色濾光片之藍色像素，提案並用三苯基甲烷系染料與呫噸系染料。在此，混合三苯基甲烷系酸性染料與呫噸系酸性染料，為了提升耐性而使用金屬錯合物。然而，在現狀下，僅單純混合酸性染料，呈色性仍不足，無法獲得高亮度。又，該技術須利用在環境負擔的觀點下不宜使用之重金屬錯合物，仍留有改善的餘地。本發明者等人銳意累積研究，結果發現作為彩色濾光片用著色組成物之著色劑，藉由使用來自三芳基甲烷系染料及呫噸系染料之成鹽生成物，可實現高亮度及寬廣的色彩重現區域，又發現可達成良好的耐受性，根據該酌見而達成本態樣之發明。 In Japanese Patent Laid-Open No. Hei 11-223720, a triphenylmethane dye and a xanthene dye are proposed in combination with blue pixels of a color filter. Here, a triphenylmethane-based acid dye and a xanthene-based acid dye are mixed, and a metal complex is used in order to improve resistance. However, in the current situation, only the acid dye is simply mixed, and the color rendering property is still insufficient, and high brightness cannot be obtained. Moreover, this technology requires the use of heavy metal complexes that are unsuitable for use in the environmental burden, and there is still room for improvement. The inventors of the present invention have intensively studied and found that as a coloring agent for a coloring composition for a color filter, high-brightness and broadness can be achieved by using a salt-forming product derived from a triarylmethane-based dye and a xanthene-based dye. The color reproduction area has been found to achieve good tolerance, and according to this discretion, the invention of this aspect is achieved.

亦即，本發明之第2態樣係關於一種彩色濾光片用藍色著色組成物，其係含有透明樹脂及著色劑；前述著色劑包含由三芳基甲烷系染料及呫噸系染料所組成的成鹽生成物。 That is, the second aspect of the present invention relates to a blue colored composition for a color filter comprising a transparent resin and a color former; and the colorant comprises a triarylmethane dye and a xanthene dye. Salt-forming product.

再者，呫噸系染料係如日本特開2005-292305號所記載，作為例如洋紅色色素而為人所知。可使用於洋紅色濾光片區段之色素係選擇範圍極窄，但呫噸系色素具有良好的分光特性。具體而言，呫噸系色素係與洋紅色喹吖酮系色素比較，在短波長側(400至500nm)之穿透率較高。因此，呫噸系色素用在許多洋紅色濾光片區段。 Further, the xanthene dye is known as, for example, a magenta dye as described in JP-A-2005-292305. The pigment system used for the magenta filter segment can be selected to be extremely narrow, but the xanthene pigment has good spectral characteristics. Specifically, the xanthene-based pigment system has a higher transmittance on the short-wavelength side (400 to 500 nm) than the magenta quinophthalone-based dye. Therefore, xanthene pigments are used in many magenta filter segments.

關於第2態樣之彩色濾光片用藍色著色組成物，作為著色劑係包含由三芳基甲烷系染料及玫瑰紅系染料所組成的成鹽生成物。因此，藉由從該藍色著色組成物形成彩色濾光片之濾光片區段，除了可達成高亮度及寬廣的色彩重現區域以外，還可達成良好的耐受性。 The blue colored composition for the color filter of the second aspect includes a salt-forming product composed of a triarylmethane-based dye and a rose-red dye as a colorant. Therefore, by forming the filter segments of the color filter from the blue coloring composition, in addition to achieving high brightness and a wide color reproduction region, good resistance can be achieved.

又，以往組合銅酞菁藍顏料與二噁嗪系顏料等之彩色濾光片用藍色著色組成物之穿透率光譜，其峰值位置存在於450nm附近，於450nm以下之短波長側，穿透率急遽下降。 Further, in the past, a transmittance spectrum of a blue coloring composition for a color filter such as a copper phthalocyanine blue pigment or a dioxin-based pigment is used, and the peak position thereof is in the vicinity of 450 nm, and is worn on the short wavelength side of 450 nm or less. The penetration rate has dropped sharply.

相對於此，本態樣之彩色濾光片用藍色著色組成物係作為著色劑之至少一部分，利用三芳基甲烷系色素與呫噸系色素之成鹽生成物。因此，從本態樣之彩色濾光片用著色組成物所獲得的濾光片區段可達成高亮度。 On the other hand, in the color filter of the present aspect, the blue coloring composition is used as at least a part of the coloring agent, and a salt formation product of the triarylmethane-based dye and the xanthene-based dye is used. Therefore, the high-intensity can be achieved from the filter segment obtained by the coloring composition of the color filter of the present aspect.

<<彩色濾光片用著色組成物>> <<Coloring composition for color filter>>

如上述，本發明之第2態樣之彩色濾光片用著色組成物係含有透明樹脂及著色劑之彩色濾光片用藍色著色組成物。該著色劑為三芳基甲烷系染料與呫噸系染料之成鹽生成物。呫噸系染料係例如第1態樣之鹼性染料、相對化合物或其等之混合物。另，三芳基甲烷系染料係亦例如第1態樣之鹼性染料、相對化合物或其等之混合物。再者，於第2態樣中，相對化合物典型上具有第1態樣中，針對相對化合物已於上面敘述之範圍內之分子量，但具有該範圍外之分子量亦可。 As described above, the coloring composition for a color filter according to the second aspect of the present invention contains a blue coloring composition for a color filter of a transparent resin and a coloring agent. This coloring agent is a salt-forming product of a triarylmethane-based dye and a xanthene-based dye. The xanthene dye is, for example, a basic dye of the first aspect, a relative compound or a mixture thereof. Further, the triarylmethane dye is also a mixture of, for example, a basic dye of the first aspect, a relative compound, or the like. Further, in the second aspect, the relative compound typically has a molecular weight within the range described above for the relative compound in the first aspect, but may have a molecular weight outside the range.

<著色劑> <colorant>

第2態樣所使用之著色劑包含三芳基甲烷系染料及呫噸系染料。 The coloring agent used in the second aspect includes a triarylmethane dye and a xanthene dye.

藉由三芳基甲烷系染料與呫噸系染料之成鹽，如前述，可於420至440nm之波長範圍內或其附近達成高穿透率。因此，與組合銅酞菁藍顏料與二噁嗪系顏料之以往的濾光片區段相比較，可實現高亮度及寬廣的色彩重現性。進而言之，亦可實現耐熱性、耐光性及耐溶劑性。 By forming a salt of a triarylmethane dye and a xanthene dye, as described above, high transmittance can be achieved in the vicinity of the wavelength range of 420 to 440 nm. Therefore, high brightness and wide color reproducibility can be achieved as compared with the conventional filter section in which a copper phthalocyanine blue pigment and a dioxin-based pigment are combined. Further, heat resistance, light resistance, and solvent resistance can also be achieved.

[三芳基甲烷系染料] [Triarylmethane dye]

首先，說明關於三芳基甲烷系染料。 First, the description will be given regarding a triarylmethane dye.

在此可適宜使用之三芳基甲烷系染料係呈現藍色、紫色或綠色之物，具有酸性染料及/或鹼性染料之形態。 The triarylmethane-based dye which can be suitably used herein has a blue, violet or green color and has an acid dye and/or a basic dye.

呈現藍色、紫色或綠色之染料係屬於例如：C.I.基本藍、C.I.基本紫及C.I.基本綠等鹼性染料；C.I.酸性藍、C.I.酸性紫及C.I.酸性綠等酸性染料；及C.I.直接藍、C.I.直接紫及C.I.直接綠等直接染料之物。在此，直接染料係於構造中具有磺酸基之染料。於本態樣中，直接染料係視為酸性染料。 The dyes exhibiting blue, purple or green are, for example, basic dyes such as CI basic blue, CI basic violet and CI basic green; acid dyes such as CI acid blue, CI acid violet and CI acid green; and CI direct blue, CI Direct purple and direct direct dyes such as CI direct green. Here, the direct dye is a dye having a sulfonic acid group in the structure. In this aspect, the direct dye is considered an acid dye.

三芳基甲烷系鹼性染料係對於中心碳處於對位之NH₂或OH基氧化，藉此取得醌構造而發色之物。三芳基甲烷系染料主要為鹼性染料，藉由導入磺酸基而成為酸性染料。 The triarylmethane-based basic dye is obtained by oxidizing the NH ₂ or OH group in which the center carbon is in the para position, thereby obtaining a ruthenium structure and coloring. The triarylmethane dye is mainly a basic dye which becomes an acid dye by introducing a sulfonic acid group.

三芳基甲烷系鹼性染料係依NH₂或OH基之數目而分成以下3種類型。從良好地呈現藍色觀點來看，其中以三胺三芳甲烷系染料尤其適宜。 The triarylmethane-based basic dyes are classified into the following three types depending on the number of NH ₂ or OH groups. Among them, a triamine triarylmethane dye is particularly preferable from the viewpoint of a good blue color.

a)二胺三芳甲烷系染料 a) Diamine triarylmethane dye

b)三胺三芳甲烷系染料 b) triamine triarylmethane dye

c)具有OH基之薔薇酸酸系染料 c) Rose acid dyes having an OH group

三胺三芳甲烷系染料係就色調良好、日光堅固性較他物良好方面而言較為適宜。其中尤以鹼性染料之二苯萘甲烷染料為宜。 The triamine triarylmethane dye system is suitable for good color tone and solid sunlight. Among them, a benzene naphthalene dye which is particularly a basic dye is preferred.

三芳基甲烷系染料係於400至430nm之波長範圍內，具有穿透率高之分光特性。然而，三芳基甲烷系染料係與一般染料相同，極為缺 乏耐光性及耐熱性。亦即，三芳基甲烷系染料用在要求高可靠性之彩色顯示裝置或彩色攝像裝置之彩色濾光片時，其特性仍不足。在此，為了改善該缺點，將三芳基甲烷系染料作為與呫噸系染料之鹽來使用。 The triarylmethane dye is in the wavelength range of 400 to 430 nm and has a high transmittance. However, triarylmethane dyes are the same as general dyes and are extremely scarce. Lack of light resistance and heat resistance. That is, when the triarylmethane dye is used in a color filter which requires a high reliability color display device or a color image pickup device, its characteristics are still insufficient. Here, in order to improve this disadvantage, a triarylmethane dye is used as a salt with a xanthene dye.

三芳基甲烷系鹼性染料可舉出例如C.I.基本藍1(基本菁6G)、C.I.基本藍5(基本菁BX)、C.I.基本藍7(維多利亞純藍)、C.I.基本藍26、C.I.基本紫1(甲基紫)及C.I.基本紫3(水晶紫)。其中從呈色良好的觀點考量，尤宜使用C.I.基本藍7。 The triarylmethane-based basic dye may, for example, be CI basic blue 1 (basic cyanine 6G), CI basic blue 5 (basic cyanine BX), CI basic blue 7 (Victoria pure blue), CI basic blue 26, CI basic violet 1 (Methyl Violet) and CI Basic Violet 3 (Crystal Violet). Among them, from the viewpoint of good color rendering, it is preferable to use C.I. Basic Blue 7.

三芳基甲烷系酸性染料適宜使用例如C.I.酸性藍1(食用藍色101號)、C.I.酸性藍3(酸性純藍)、C.I.酸性藍7(湖藍II)、C.I.酸性藍9(食用藍色1號)、C.I.酸性藍22、C.I.酸性藍83、C.I.酸性藍90、C.I.酸性藍93、C.I.酸性藍100、C.I.酸性藍103、C.I.酸性藍104或C.I.酸性藍109。其中尤宜使用C.I.酸性藍1、C.I.酸性藍3或C.I.酸性藍93。 Triarylmethane-based acid dyes are suitably used, for example, CI Acid Blue 1 (Edible Blue No. 101), CI Acid Blue 3 (Acid Pure Blue), CI Acid Blue 7 (Lake Blue II), CI Acid Blue 9 (Edible Blue 1) No.), CI Acid Blue 22, CI Acid Blue 83, CI Acid Blue 90, CI Acid Blue 93, CI Acid Blue 100, CI Acid Blue 103, CI Acid Blue 104 or CI Acid Blue 109. Among them, it is preferable to use C.I. Acid Blue 1, C.I. Acid Blue 3 or C.I. Acid Blue 93.

[呫噸系染料] [呫吨系染料]

接著，說明關於呫噸系染料。 Next, the xanthene dye will be described.

在本態樣可適宜使用之呫噸系染料係呈現紅色或紫色之物，具有酸性染料及/或鹼性染料之形態。 The xanthene dyes which can be suitably used in this aspect are red or purple, and have the form of an acid dye and/or a basic dye.

呈現紅色或紫色之染料係屬於例如：C.I.基本紅及C.I.基本紫等鹼性染料；C.I.酸性紅及C.I.酸性紫等酸性染料；或C.I.直接紅及C.I.直接紫等直接染料之物。在此，直接染料係於構造中具有磺酸基之染料。於本態樣中，直接染料係視為酸性染料。 The dyes exhibiting red or purple are, for example, C.I. basic red and C.I. basic violet and other basic dyes; C.I. acid red and C.I. acid violet and other acid dyes; or C.I. direct red and C.I. direct violet and other direct dyes. Here, the direct dye is a dye having a sulfonic acid group in the structure. In this aspect, the direct dye is considered an acid dye.

呫噸系染料係於400至430nm之波長範圍內，具有穿透率高之分光特性。然而，呫噸系染料係與一般染料相同，極為缺乏耐光性及耐 熱性。亦即，呫噸系染料用在要求高可靠性之彩色顯示裝置或彩色攝像裝置之彩色濾光片時，其特性仍不足。在此，為了改善該缺點，將呫噸系染料作為與三芳基甲烷系染料之鹽來使用。 The xanthene dye is in the wavelength range of 400 to 430 nm and has a high spectral transmittance. However, the xanthene dye system is the same as the general dye, and it is extremely lacking in light resistance and resistance. Heat. That is, when the xanthene dye is used in a color filter which requires a high reliability color display device or a color image pickup device, its characteristics are still insufficient. Here, in order to improve this disadvantage, a xanthene-based dye is used as a salt with a triarylmethane-based dye.

呫噸系染料係宜對於波長650nm以上之光之穿透率在90%以上，對於波長600nm之光之穿透率在75%以上，穿透率在波長500至550nm之範圍內為5%以下，對於波長400nm之光之穿透率在70%以上。更宜對於波長650nm以上之光之穿透率在95%以上，對於波長600nm之光之穿透率在80%以上，穿透率在波長500至550nm之範圍內為10%以下，對於波長400nm之光之穿透率在75%以上。 The xanthene dye is preferably at least 90% for light having a wavelength of 650 nm or more, 75% or more for light having a wavelength of 600 nm, and 5% or less at a wavelength of 500 to 550 nm. The transmittance for light having a wavelength of 400 nm is 70% or more. More preferably, the transmittance of light having a wavelength of 650 nm or more is 95% or more, the transmittance of light having a wavelength of 600 nm is 80% or more, and the transmittance is 10% or less in the range of 500 to 550 nm, for a wavelength of 400 nm. The penetration rate of light is above 75%.

呫噸系酸性染料可舉出例如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104號)、C.I.酸性紅92(酸性夾竹桃紅PB：食用紅色104號)、虎紅B(食用紅色5號)、酸性玫瑰紅G、酸性紅289或C.I.酸性紫9。 Examples of the xanthene-based acid dyes include CI Acid Red 51 (erythropurine: Edible Red No. 3), CI Acid Red 52 (Acid Rose Red), CI Acid Red 87 (Crimson G: Edible Red No. 104), and CI. Acid red 92 (acid oleander red PB: edible red No. 104), tiger red B (edible red No. 5), acid rose red G, acid red 289 or CI acid purple 9.

其中特別適宜使用C.I.酸性紅51、C.I.酸性紅87或C.I.酸性紅289。 Among them, C.I. Acid Red 51, C.I. Acid Red 87 or C.I. Acid Red 289 is particularly suitable.

呫噸系鹼性染料可舉出例如C.I.基本紅1(玫瑰紅6GCP)、C.I.基本紅8(玫瑰紅G)及C.I.基本紫10(玫瑰紅B)。 The xanthene-based basic dye may, for example, be C.I. Basic Red 1 (Rose Red 6GCP), C.I. Basic Red 8 (Rose Red G), and C.I. Basic Violet 10 (Rose Red B).

其中尤宜使用C.I.基本紅1或C.I.基本紫10。 Among them, it is preferable to use C.I. Basic Red 1 or C.I. Basic Violet 10.

呫噸系染料中，玫瑰紅系染料由於呈色性及耐受性良好，因此尤其適宜。 Among the xanthene dyes, the rose red dye is particularly suitable because it has good coloring properties and resistance.

[三芳基甲烷系染料與呫噸系染料所組成的成鹽生成物] [Salt formation product of triarylmethane dye and xanthene dye]

三芳基甲烷系染料與呫噸系染料所組成的成鹽生成物宜為 以下兩種形態之任一者。 The salt formation product of the triarylmethane dye and the xanthene dye is preferably Any of the following two forms.

(A)三芳基甲烷系鹼性染料與呫噸系酸性染料所組成的成鹽生成物 (A) a salt-forming product composed of a triarylmethane-based basic dye and a xanthene-based acid dye

(B)三芳基甲烷系酸性染料與呫噸系鹼性染料所組成的成鹽生成物該等可從前述酸性染料與鹼性染料之組合獲得。 (B) a salt-forming product composed of a triarylmethane-based acid dye and a xanthene-based basic dye, which can be obtained from a combination of the aforementioned acid dye and a basic dye.

形態(A)的情況下，具體而言反應安定性及呈色性特別良好的組合如下：C.I.基本藍7與C.I.酸性紅289之組合、C.I.基本藍7與C.I.酸性紅52之組合、C.I.基本藍7與C.I.酸性紅87之組合、C.I.基本藍7與C.I.酸性紅92之組合、C.I.基本紫3與C.I.酸性紅87之組合及C.I.基本紫3與C.I.酸性紅52之組合。當然亦可使用從其他組合獲得之成鹽生成物。 In the case of the form (A), specifically, the combination of the reaction stability and the color rendering property is particularly good as follows: a combination of CI basic blue 7 and CI acid red 289, a combination of CI basic blue 7 and CI acid red 52, CI basic The combination of Blue 7 and CI Acid Red 87, the combination of CI Basic Blue 7 and CI Acid Red 92, the combination of CI Basic Violet 3 and CI Acid Red 87, and the combination of CI Basic Violet 3 and CI Acid Red 52. It is of course also possible to use salt-forming products obtained from other combinations.

形態(B)的情況下，具體而言反應安定性及呈色性特別良好的組合如下：C.I.基本紅1與C.I.酸性藍1之組合、C.I.基本紅1與C.I.酸性藍93之組合、C.I.基本紫10與C.I.酸性藍1之組合及C.I.基本紫1與C.I.酸性藍3之組合。當然亦可使用例如從前述染料之組合獲得之其他成鹽生成物。 In the case of the form (B), specifically, the combination of the reaction stability and the color rendering property is particularly good as follows: a combination of CI basic red 1 and CI acid blue 1, a combination of CI basic red 1 and CI acid blue 93, and CI basic Combination of Violet 10 with CI Acid Blue 1 and combination of CI Basic Violet 1 and CI Acid Blue 3. It is of course also possible to use, for example, other salt-forming products obtained from the combination of the aforementioned dyes.

其中，三芳基甲烷系酸性染料與玫瑰紅系鹼性染料所組成的成鹽生成物係耐受性良好，故特別適宜。三芳基甲烷系染料與呫噸系染料之成鹽生成物可藉由以往習知的方法來合成。 Among them, a salt forming product composed of a triarylmethane-based acid dye and a rose-red basic dye is particularly resistant, and thus is particularly suitable. The salt-forming product of the triarylmethane dye and the xanthene dye can be synthesized by a conventional method.

例如使用三芳基甲烷系酸性染料及呫噸系鹼性染料時，於水中溶解三芳基甲烷系酸性染料後，於此添加呫噸系鹼性染料或其水溶液並攪拌，藉以發生成鹽反應即可。藉此，可獲得三芳基甲烷系酸性染料之磺酸基(例如-SO₃H或-SO₃Na)與呫噸系鹼性染料之胺基結合之成鹽生成物。 For example, when a triarylmethane-based acid dye and a xanthene-based basic dye are used, after dissolving a triarylmethane-based acid dye in water, a xanthene-based basic dye or an aqueous solution thereof is added thereto and stirred to thereby form a salt-forming reaction. . Thereby, a salt-forming product in which a sulfonic acid group of a triarylmethane-based acid dye (for example, -SO ₃ H or -SO ₃ Na) is bonded to an amine group of a xanthene-based basic dye can be obtained.

又，使用呫噸系酸性染料及三芳基甲烷系鹼性染料時，於 水中溶解呫噸系酸性染料後，於此添加三芳基甲烷系鹼性染料或其水溶液並攪拌，藉以發生成鹽反應即可。藉此，可獲得呫噸系酸性染料之磺酸基(例如-SO₃H或-SO₃Na)與三芳基甲烷系鹼性染料之胺基結合之成鹽生成物。 In addition, when a xanthene-based acid dye and a triarylmethane-based basic dye are used, after dissolving a xanthene-based acid dye in water, a triarylmethane-based basic dye or an aqueous solution thereof is added thereto and stirred, whereby a salt-forming reaction occurs. can. Thereby, a salt-forming product in which a sulfonic acid group of a xanthene-based acid dye (for example, -SO ₃ H or -SO ₃ Na) is bonded to an amine group of a triarylmethane-based basic dye can be obtained.

[具有酸基之樹脂] [Resin with acid group]

與第1態樣之說明相同，上述成鹽生成物若藉由以具有酸基之樹脂來改質，則可製成較安定之色材。 As described in the first aspect, the salt-forming product can be made into a relatively stable color material by modifying it with a resin having an acid group.

該成鹽生成物若添加具有酸基之樹脂，例如具有羧基等酸基之樹脂、或松香酯、松香改質順丁烯二酸樹脂及松香改質反丁烯二酸樹脂，則對黏結樹脂中之相溶性及分散性、以及對溶劑之分散性會大幅提升。其結果，可實現更加良好之呈色性、耐熱性及耐光性。在此，酸基宜為羧基(-COOH)或磺酸基(例如-SO₃H或-SO₃Na)。 When the salt-forming product is added with a resin having an acid group, for example, a resin having an acid group such as a carboxyl group, or a rosin ester, a rosin-modified maleic acid resin, and a rosin-modified fumaric acid resin, the binder resin is added. The compatibility and dispersibility in the solvent and the dispersibility to the solvent are greatly improved. As a result, more excellent color rendering properties, heat resistance, and light resistance can be achieved. Here, the acid group is preferably a carboxyl group (-COOH) or a sulfonic acid group (for example, -SO ₃ H or -SO ₃ Na).

其中尤宜使用松香改質順丁烯二酸樹脂。松香改質順丁烯二酸樹脂具有：具有酸之極性基、及無極性之松香骨架。該具有酸之極性基係來自未反應之松香酸之羧基及順丁烯二酸之羧基，與黏結樹脂之極性基反應及相溶。另，無極性之松香骨架係與黏結樹脂之非極性部相溶。進而言之，松香改質順丁烯二酸樹脂之具有酸之極性基係與鹼性染料(成鹽生成物中之未反應之鹼性染料)之胺基反應。 Among them, rosin-modified maleic acid resin is particularly suitable. The rosin-modified maleic acid resin has a polar group having an acid and a non-polar rosin skeleton. The acidic polar group is derived from the carboxyl group of the unreacted rosin acid and the carboxyl group of the maleic acid, and reacts and is compatible with the polar group of the binder resin. In addition, the non-polar rosin skeleton is compatible with the non-polar portion of the binder resin. Further, the acid-based polar group of the rosin-modified maleic acid resin reacts with the amine group of the basic dye (unreacted basic dye in the salt-forming product).

又，具有酸基之樹脂之重量平均分子量典型上係在第1樣態所說明的範圍內。但在此，具有酸基之樹脂之重量平均分子量亦可在第1樣態所說明的範圍外。 Further, the weight average molecular weight of the resin having an acid group is typically within the range described in the first aspect. However, the weight average molecular weight of the acid group-containing resin may be outside the range described in the first aspect.

成鹽生成物與具有酸基之樹脂之混合係採例如以下方法而進行。在此作為一例，具有酸基之樹脂為松香改質順丁烯二酸樹脂。 The mixing of the salt-forming product and the resin having an acid group is carried out, for example, by the following method. Here, as an example, the resin having an acid group is a rosin-modified maleic acid resin.

(1)於溶劑中溶解松香改質順丁烯二酸樹脂，於該溶液添加成鹽生成物之方法 (1) A method of dissolving a rosin-modified maleic acid resin in a solvent and adding a salt-forming product to the solution

(2)利用混合攪拌機來混合已溶解之松香改質順丁烯二酸樹脂與成鹽生成物之方法 (2) A method of mixing a dissolved rosin-modified maleic acid resin and a salt-forming product by using a mixing mixer

再者，成鹽生成物與具有酸基之樹脂之混合亦可採其他方法進行。 Further, the mixing of the salt-forming product with the resin having an acid group can also be carried out by other methods.

成鹽生成物與具有酸基之樹脂之質量比(成鹽生成物：具有酸基之樹脂)宜在70：30至95：5之範圍。具有酸基之樹脂在著色組成物所佔比率越大，呈色性越降低。具體而言，來自具有酸基之樹脂之色彩係因著色組成物之色相而造成甚大影響。又，具有酸基之樹脂在著色組成物所佔比率越小，成鹽生成物對黏結樹脂中之分散性提升效果越小。成鹽生成物與具有酸基之樹脂之質量比(成鹽生成物：具有酸基之樹脂)較宜在75：25至90：10之範圍內。 The mass ratio of the salt-forming product to the resin having an acid group (salt-forming product: resin having an acid group) is preferably in the range of 70:30 to 95:5. The greater the ratio of the resin having an acid group to the coloring composition, the lower the color rendering property. Specifically, the color from the resin having an acid group is greatly affected by the hue of the coloring composition. Further, the smaller the ratio of the resin having an acid group to the coloring composition, the smaller the effect of improving the dispersibility of the salt-forming product in the binder resin. The mass ratio of the salt-forming product to the resin having an acid group (salt-forming product: resin having an acid group) is preferably in the range of 75:25 to 90:10.

具有酸基之樹脂，例如松香酯或松香改質順丁烯二酸樹脂之酸價宜在20至200mgKOH/g之範圍內。該著色組成物作為鹼顯影型著色抗蝕劑材料使用時，樹脂之羧基會發揮著色劑吸附劑及顯影時之鹼可溶基的作用，脂肪族基及芳香族基會發揮著色劑載體及對於溶劑之親和性基的作用。因此，樹脂的酸價會對顏料及成鹽生成物之分散性或溶解性、顯影性及耐久性發揮作用。具體而言，若酸價小，樹脂與成鹽生成物之相溶性不足。又，若酸價小，在將該著色組成物利用作為例如鹼顯影型著色抗蝕劑時，未硬化之著色組成物對於顯影液之溶解性不足。又，若酸價大，在將該著色組成物利用作為例如鹼顯影型著色抗蝕劑時，可能連曝光部都藉由 顯影而去除。再者，於此所謂酸價係藉由JISK-0070中所規定的方法而測定之值。 The acid value of the acid group-containing resin such as rosin ester or rosin-modified maleic acid resin is preferably in the range of 20 to 200 mgKOH/g. When the coloring composition is used as an alkali-developing type coloring resist material, the carboxyl group of the resin functions as a colorant adsorbent and an alkali-soluble group during development, and the aliphatic group and the aromatic group act as a colorant carrier and The role of the affinity group of the solvent. Therefore, the acid value of the resin acts on the dispersibility, solubility, developability, and durability of the pigment and the salt-forming product. Specifically, if the acid value is small, the compatibility of the resin with the salt-forming product is insufficient. Further, when the acid value is small, when the coloring composition is used as, for example, an alkali-developing type coloring resist, the solubility of the uncured coloring composition to the developing solution is insufficient. Further, when the acid value is large, when the coloring composition is used as, for example, an alkali-developing type coloring resist, it is possible that even the exposed portion is used. Removed by development. Here, the acid value is a value measured by the method specified in JIS K-0070.

[其他著色劑] [other colorants]

於該著色組成物中，可在不對效果帶來妨礙的範圍內，進一步添加其他著色劑。其中尤其當並用成鹽生成物與有機顏料時，可達成較良好的耐受性。 Further, in the colored composition, other coloring agents may be added to the extent that the effect is not hindered. Among them, particularly when a salt-forming product and an organic pigment are used in combination, a better tolerance can be achieved.

有機顏料宜使用酞菁系顏料、二噁嗪系顏料、蒽醌系顏料、偶氮系顏料或喹吖酮系顏料。 As the organic pigment, a phthalocyanine pigment, a dioxazine pigment, an anthraquinone pigment, an azo pigment or a quinophthalone pigment is preferably used.

其中特別適宜使用酞菁系顏料或二噁嗪系顏料。酞菁藍顏料可舉出例如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及C.I.Pigment Blue 15：6。其中尤以具有e型、b型或a型之銅酞菁藍顏料為宜。該等適宜顏料具體而言為例如C.I.Pigment Blue 15：6、C.I.Pigment Blue 15：3及C.I.Pigment Blue 15：1。 Among them, a phthalocyanine-based pigment or a dioxazine-based pigment is particularly preferably used. The phthalocyanine blue pigment may, for example, be 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, and C.I. Pigment Blue 15:6. Among them, a copper phthalocyanine blue pigment having an e-type, a b-type or an a-type is preferable. Such suitable pigments are, for example, C.I. Pigment Blue 15:6, C.I. Pigment Blue 15:3 and C.I. Pigment Blue 15:1.

又，二噁嗪系顏料宜使用C.I.Pigment Violet 23。該等顏料係於上述成鹽生成物之量設為100質量部時，宜以50質量部以下之量來使用。 Further, as the dioxazine-based pigment, C.I. Pigment Violet 23 is preferably used. When the amount of the salt-forming product is 100 parts by mass, the pigment is preferably used in an amount of 50 parts by mass or less.

尤其若並用上述成鹽生成物、與銅酞菁系顏料及/或二噁嗪系顏料時，除了可獲得良好的耐候性，還可獲得超越顏料單獨使用時之亮度。 In particular, when the salt-forming product, the copper phthalocyanine-based pigment, and/or the dioxazine-based pigment are used in combination, in addition to obtaining good weather resistance, it is possible to obtain brightness beyond the use of the pigment alone.

(顏料之微細化) (fineness of pigment)

上述顏料可藉由例如鹽磨處理來予以微細化。顏料之一次 粒徑宜設在第1態樣所說明的範圍內。鹽磨處理可藉由與例如第1態樣之說明方法相同的方法來進行。又，於鹽磨處理可使用與第1態樣之說明相同的水溶性有機無機鹽、水溶性有機溶劑及樹脂。各種材料之使用量宜設在第1態樣所說明的範圍內。 The above pigment can be refined by, for example, a salt milling treatment. Once the pigment The particle size is preferably set within the range described in the first aspect. The salt milling treatment can be carried out by the same method as the method of the first aspect, for example. Further, in the salt milling treatment, the same water-soluble organic inorganic salt, water-soluble organic solvent, and resin as those described in the first aspect can be used. The amount of each material used should be within the range described in the first aspect.

<透明樹脂> <Transparent Resin>

透明樹脂係令著色劑，尤其令成鹽生成物分散及/或溶解之物。透明樹脂可使用與例如第1態樣之說明相同之物。又，透明樹脂之使用量宜設在第1態樣所說明的範圍內。 The transparent resin is a coloring agent, especially a substance which disperses and/or dissolves the salt-forming product. As the transparent resin, the same as the description of the first aspect, for example, can be used. Further, the amount of the transparent resin to be used is preferably within the range described in the first aspect.

<溶劑> <solvent>

與第1態樣之著色組成物相同，於該著色組成物中可含有溶劑，以便令著色劑充分分散於著色劑載體中，容易於玻璃基板等基板上，塗布為乾燥膜後成為例如0.2至5mm，形成濾光片區段。溶劑可使用與例如第1態樣之說明相同之物。又，溶劑之使用量宜設在第1態樣所說明的範圍內。 In the same manner as the coloring composition of the first aspect, the coloring composition may contain a solvent so that the coloring agent is sufficiently dispersed in the coloring agent carrier, and is easily applied to a substrate such as a glass substrate, and is applied as a dried film to, for example, 0.2 to 5 mm, forming a filter section. As the solvent, the same as the description of the first aspect, for example, can be used. Further, the amount of the solvent to be used is preferably within the range described in the first aspect.

<分散> <scatter>

該著色組成物可藉由與例如第1態樣之說明方法相同的方法來製造。 This colored composition can be produced by the same method as the method of the first aspect, for example.

(分散助劑) (dispersion aid)

將著色劑分散於著色劑載體中時，與第1態樣相同，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。 When the colorant is dispersed in the colorant carrier, a dispersing aid such as a dye derivative, a resin type pigment dispersant, or a surfactant can be suitably used in the same manner as in the first embodiment.

色素衍生物可使用與例如第1態樣之說明相同之物。從分散性提升的觀點考量，色素衍生物之調配量係對於著色劑100質量部，宜為0.5 質量部以上，更宜為1質量部以上，最宜為3質量部以上。又，從耐熱性及耐光性的觀點考量，色素衍生物之調配量係對於著色劑100質量部，宜為40質量部以下，最宜為35質量部以下。 As the dye derivative, the same as the description of the first aspect, for example, can be used. From the viewpoint of improvement in dispersibility, the amount of the pigment derivative is preferably 0.5 for the mass portion of the colorant. Above the mass portion, it is more preferably 1 mass or more, and most preferably 3 mass or more. In addition, the blending amount of the dye derivative is preferably 40 parts by mass or less, and most preferably 35 parts by mass or less, based on 100 parts by mass of the coloring agent, from the viewpoint of heat resistance and light resistance.

樹脂型分散劑可使用與例如第1態樣之說明相同之物。作為市售的樹脂型顏料分散劑可使用例如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及PB824。 As the resin type dispersant, the same as the description of the first aspect, for example, can be used. As a commercially available resin type pigment dispersant, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165 manufactured by BYK-Chemie Co., Ltd. can be used. 166, 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 by Lubrizol, Japan 32500, 32600, 34750, 36600, 38500, 41000, 41090, 53095, 55000, and 76500, EFKA-46, 47, 48, 452, LP4008, 4009, LP4010, LP4050, LP4055, 400, 401, manufactured by Chiba Corporation, Japan. 402, 403, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, and 1503, AJISPER manufactured by Ajinomoto Fine-Techno -PA111, PB711, PB821, PB822 and PB824.

界面活性劑可使用與例如第1態樣之說明相同之物。 As the surfactant, the same as the description of the first aspect can be used.

添加樹脂型分散劑及/或界面活性劑時，其等之合計量係於著色劑之總量設為100質量部時，宜在0.1至55質量部之範圍內，較宜在0.1至45質量部之範圍內。樹脂型分散劑與界面活性劑之合計量少時，難以獲得添加其等的效果。又，該合計調配量多時，由於過多的分散劑，可能會 對分散造成影響。 When a resin type dispersant and/or a surfactant is added, the total amount thereof is preferably in the range of 0.1 to 55 parts by mass, preferably 0.1 to 45 mass, when the total amount of the colorant is 100 parts by mass. Within the scope of the Ministry. When the total amount of the resin-type dispersant and the surfactant is small, it is difficult to obtain an effect of adding the same. Moreover, when the total amount of the mixture is large, it may be due to excessive dispersing agent. Affects dispersion.

該著色組成物可進一步添加光聚合性組成物及/或光聚合起始劑，以作為彩色濾光片用感光性著色組成物(抗蝕劑)來使用。 Further, a photopolymerizable composition and/or a photopolymerization initiator may be added to the coloring composition to be used as a photosensitive coloring composition (resist) for a color filter.

<光聚合性組成物> <Photopolymerizable composition>

於光聚合性組成物中使用之單體或寡聚物可舉出例如：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、b-羧基(甲基)丙烯酸酯及tricyclodecenylmethacrylate等單官能(甲基)丙烯酸酯類；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、等二官能(甲基)丙烯酸酯類；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)丙烯酸酯及二新戊四醇六(甲基)丙烯酸酯等三官能以上之多官能(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、新戊二醇甘油基醚及酚醛樹脂等環氧化合物與(甲基)丙烯酸之反應物，即環氧(甲基)丙烯酸酯；聚酯、聚氨酯、異氰酸酯及羥甲基化三聚氰胺等經改質之各種(甲基)丙烯酸酯類；以及(甲基)丙烯酸、苯乙烯、醋酸乙烯、羥基乙基乙烯醚、乙二醇二乙烯醚及新戊四醇三乙烯醚等乙烯醚；(甲基)丙烯醯胺；N-羥基甲基(甲基)丙烯醯胺；N-乙烯甲醯胺；以及丙烯醯腈。該等可單獨使用或混合兩種以上來使用。單體或寡聚物未必要限定在該等。 Examples of the monomer or oligomer used in the photopolymerizable composition include methyl (meth) acrylate, ethyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. Monofunctional (meth) acrylates such as 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, b-carboxy (meth) acrylate, and tricyclodecenylmethacrylate; polyethylene glycol mono Acrylate, 1,6-hexanedioxane (meth) acrylate, triethylene glycol di(meth) acrylate, tripropylene glycol di(meth) acrylate, etc. difunctional (methyl) Acrylates; trimethylolpropane (meth) acrylate, neopentyl alcohol (meth) acrylate, neopentyl alcohol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate a trifunctional or higher polyfunctional (meth) acrylate such as an ester or dipentaerythritol hexa(meth) acrylate; 1,6-butanediol diglycidyl ether, bisphenol A diglycidyl ether, a reaction product of an epoxy compound such as neopentyl glycol glyceryl ether and a phenol resin with (meth)acrylic acid, that is, epoxy (meth) acrylate; polyester, polyurethane, isocyanate and Various modified (meth) acrylates such as methylolated melamine; and (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether and neopentyl alcohol a vinyl ether such as vinyl ether; (meth) acrylamide; N-hydroxymethyl (meth) acrylamide; N-ethylene carbamide; and acrylonitrile. These may be used alone or in combination of two or more. Monomers or oligomers are not necessarily limited to these.

該等單體及寡聚物之合計調配量係於著色劑之總質量設為100質量部時，宜在5至400質量部之範圍內，從光硬化性及顯影性的觀點考量，較宜在10至300質量部之範圍內。 When the total mass of the monomer and the oligomer is 100 parts by mass, it is preferably in the range of 5 to 400 parts by mass, and it is preferable from the viewpoint of photocurability and developability. Within the range of 10 to 300 mass parts.

<光聚合起始劑> <Photopolymerization initiator>

藉由利用紫外線照射之光微影，從彩色濾光片用藍色著色組成物形成濾光片區段時，於該著色組成物添加光聚合起始劑等。光聚合起始劑可使用與例如第1態樣之說明相同之物。使用光聚合起始劑時，其調配量宜與第1態樣之說明相同。 When a filter segment is formed from a color filter using a blue coloring composition by photolithography of ultraviolet light, a photopolymerization initiator or the like is added to the coloring composition. As the photopolymerization initiator, the same as the description of the first aspect, for example, can be used. When a photopolymerization initiator is used, the amount thereof is preferably the same as that described in the first aspect.

<增感劑> <sensitizer>

於彩色濾光片用著色組成物中，可進一步含有增感劑。 The coloring composition for a color filter may further contain a sensitizer.

增感劑可使用與例如第1態樣之說明相同之物。使用增感劑時，其調配量宜與第1態樣之說明相同。 As the sensitizer, the same as the description of the first aspect, for example, can be used. When a sensitizer is used, the amount thereof is preferably the same as that described in the first aspect.

<胺系化合物> <Amine compound>

於彩色濾光片用著色組成物中，可進一步含有具有還原溶存氧的作用之胺系化合物。胺系化合物可使用與例如第1態樣之說明相同之物。 The coloring composition for a color filter may further contain an amine compound having a function of reducing dissolved oxygen. As the amine compound, for example, the same as the description of the first aspect can be used.

<均染劑> <leveling agent>

於該藍色著色組成物中，為了改善組成物在透明基板上之均染性，宜進一步添加均染劑。 In the blue coloring composition, in order to improve the leveling property of the composition on the transparent substrate, it is preferred to further add a leveling agent.

均染劑可使用與例如第1態樣之說明相同之物。使用均染劑時，其調配量宜與第1態樣之說明相同。 As the leveling agent, the same as the description of the first aspect, for example, can be used. When a leveling agent is used, the amount thereof is preferably the same as that described in the first aspect.

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。界面活性劑可單獨使用1種，或混合2種以上使用。該等界面活性劑可使用與例如第1態樣之說明相同之物。 Anionic, cationic, nonionic or amphoteric surfactants may also be added to the leveling agent. The surfactant may be used singly or in combination of two or more. As the surfactant, for example, the same as the description of the first aspect can be used.

<硬化劑及硬化促進劑> <hardener and hardening accelerator>

為了輔助熱硬化性樹脂之硬化，於該著色組成物中，亦可因應需要來含有硬化劑及硬化促進劑。硬化劑及硬化促進劑可使用與例如第1態樣之說明相同之物。使用硬化促進劑時，其調配量宜與第1態樣之說明相同。 In order to assist the hardening of the thermosetting resin, a curing agent and a curing accelerator may be contained in the colored composition as needed. As the curing agent and the hardening accelerator, the same as the description of the first aspect, for example, can be used. When a hardening accelerator is used, the amount thereof is preferably the same as that described in the first aspect.

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

於該藍色著色組成物中，為了令組成物之經時黏度安定化，可含有儲藏安定劑。又，於該藍色著色組成物中，為了提高與透明基板之密貼性，亦可含有矽烷耦合劑。 In the blue coloring composition, a storage stabilizer may be contained in order to stabilize the viscosity of the composition over time. Further, in the blue colored composition, a decane coupling agent may be contained in order to improve the adhesion to the transparent substrate.

儲藏安定劑可使用與例如第1態樣之說明相同之物。使用儲藏安定劑及/或密貼提升劑時，其調配量宜與第1態樣之說明相同。 As the storage stabilizer, the same as the description of the first aspect, for example, can be used. When using a storage stabilizer and/or a sticking enhancer, the amount of the stabilizer should be the same as that described in the first aspect.

<著色組成物之製法> <Method of Producing Colored Composition>

該藍色著色組成物係於採溶劑顯影型或鹼顯影型著色抗蝕劑材料的形態使用時，可藉由例如以下方法來製造。首先，將著色劑與透明樹脂及任意地含有機溶劑之著色劑載體混合。接著，將此以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處理，令著色劑均勻分散於著色劑載體中。進一步於如此獲得之著色劑分散體中，混合光聚合性單體及/或寡聚物、光聚合起始劑、以及因應需要而使用之其他樹脂、溶劑、分散劑及添加劑等。如以上獲得藍色著色組成物。 When the blue coloring composition is used in the form of a solvent-developing type or an alkali-developing type coloring resist material, it can be produced, for example, by the following method. First, the colorant is mixed with a transparent resin and a colorant carrier optionally containing an organic solvent. Next, this is treated with various dispersing mechanisms such as a three-roll mill, a two-roll mill, a sand mill, a kneader, and an attritor to uniformly disperse the colorant in the colorant carrier. Further, in the colorant dispersion thus obtained, a photopolymerizable monomer and/or oligomer, a photopolymerization initiator, and other resins, solvents, dispersants, additives, and the like which are used as needed are mixed. A blue coloring composition was obtained as above.

<去除粗粒子> <Remove coarse particles>

宜從該著色組成物，與第1態樣相同地去除粗粒子及混入微塵。亦即，該著色組成物實質上宜不含0.5mm以上之粒子，更宜實質上不含0.3mm以上之粒子。 It is preferable to remove the coarse particles and mix the fine dust from the colored composition in the same manner as in the first aspect. That is, the coloring composition is preferably substantially free of particles of 0.5 mm or more, and more preferably contains substantially no particles of 0.3 mm or more.

<<彩色濾光片>> <<Color filter>>

接著，說明關於本發明之第2態樣之彩色濾光片。 Next, a color filter according to a second aspect of the present invention will be described.

第2態樣之彩色濾光片包含吸收光譜不同、典型上規則地排列之複數個濾光片區段。一形態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。於第2態樣之彩色濾光片，至少1個藍色濾光片區段係由上述彩色濾光片用藍色著色組成物所形成。 The color filter of the second aspect comprises a plurality of filter segments having different absorption spectra, typically regularly arranged. A color filter of one form includes at least one red filter segment, at least one green filter segment, and at least one blue filter segment. In the color filter of the second aspect, at least one of the blue filter segments is formed of the blue coloring composition of the color filter.

紅色著色組成物可使用例如包含紅色顏料及顏料載體之一般的紅色著色組成物來形成。紅色顏料可使用例如C.I.Pigment Red 7、14、41、48：1、48：2、48：3、48：4、81：1、81：2、81：3、81：4、122、146、168、177、178、184、185、187、200、202、208、210、242、246、254、255、264、270、272、273、274、276、277、278、279、280、281、282、283、284、285、286或287。取代紅色顏料或除了紅色顏料以外，亦可使用鹼性染料與酸性染料之呈現紅色之成鹽生成物。例如亦可使用第1態樣所說明的成鹽生成物。 The red coloring composition can be formed using, for example, a general red coloring composition comprising a red pigment and a pigment carrier. Red pigments can be used, for example, CIPigment Red 7, 14, 41, 48:1, 48:2, 48:3, 48:4, 81:1, 81:2, 81:3, 81:4, 122, 146, 168, 177, 178, 184, 185, 187, 200, 202, 208, 210, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286 or 287. Instead of or in addition to the red pigment, a salty product of a red dye and a basic dye of an acid dye may be used. For example, the salt-forming product described in the first aspect can also be used.

於紅色著色組成物，亦可並用C.I.Pigment Orange 43、71、73等橘色顏料、C.I.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及221等黃色顏料或其等之混合物。亦可使用鹼性染料與酸性染料之呈現橘色或黃色之成鹽生成物。例如亦可使用第1態樣所說明的成鹽生成物。 For red coloring composition, it is also possible to use CIPigment Orange 43, 71, 73 and other orange pigments, CIPigment 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, Yellow pigments such as 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, and 221 Or a mixture thereof. It is also possible to use a basic dye and an acid dye to form an orange or yellow salt-forming product. For example, the salt-forming product described in the first aspect can also be used.

綠色濾光片區段可使用例如包含綠色顏料及顏料載體之一般的綠色著色組成物來形成。綠色顏料可使用例如C.I.Pigment Green 7、10、36、37或58 The green filter segments can be formed using, for example, a typical green coloring composition comprising a green pigment and a pigment carrier. Green pigments can be used, for example, C.I. Pigment Green 7, 10, 36, 37 or 58

綠色著色組成物可與黃色顏料並用。可並用的黃色顏料可舉出例如C.I.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及221。取代黃色顏料或除了黃色顏料以外，亦可使用鹼性染料與酸性染料之呈現黃色之成鹽生成物。例如亦可使用第1態樣所說明的成鹽生成物。 The green coloring composition can be used in combination with a yellow pigment. The yellow pigment which can be used in combination may, for example, be CIPigment 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, and 221. Instead of or in addition to the yellow pigment, a yellow salt-forming product of a basic dye and an acid dye may be used. For example, the salt-forming product described in the first aspect can also be used.

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

該彩色濾光片可藉由與例如第1態樣之說明方法相同的方法來製造。 The color filter can be manufactured by the same method as the method of the first aspect, for example.

○第3態樣 ○3rd aspect

接著，說明關於本發明之第3態樣。 Next, a third aspect of the present invention will be described.

本發明者等人銳意累積研究，結果發現作為彩色濾光片用著色組成物之著色劑，藉由使用來自呫噸系鹼性染料及呫噸系酸性染料之成鹽生成物，可實現高亮度及寬廣的色彩重現區域，又發現可達成良好的耐受性，根據該酌見而達成本態樣之發明。 The inventors of the present invention have intensively conducted research, and as a result, it has been found that a coloring agent for a coloring composition for a color filter can achieve high brightness by using a salt-forming product derived from a xanthene-based basic dye and a xanthene-based acid dye. And a wide color reproduction area, and found that good tolerance can be achieved, according to this discretion to achieve the invention of this aspect.

亦即，本發明之第3態樣係關於一種彩色濾光片用著色組成物，其係含有透明樹脂及著色劑；前述著色劑包含由呫噸系鹼性染料及呫噸系酸性染料所組成的成鹽生成物。 That is, the third aspect of the present invention relates to a coloring composition for a color filter comprising a transparent resin and a coloring agent; and the coloring agent comprises a xanthene-based basic dye and a xanthene-based acid dye. Salt-forming product.

第3態樣之彩色濾光片用著色組成物係作為著色劑，包含由呫噸系鹼性染料及呫噸系酸性染料所組成的成鹽生成物。因此，藉由從該著色組成物形成彩色濾光片之濾光片區段，除了可達成高亮度及寬廣的色彩重現區域以外，還可達成良好的耐受性。該彩色濾光片用著色組成物特別適宜用在藍色或洋紅色之濾光片區段。 In the color filter of the third aspect, the coloring composition is used as a coloring agent, and a salt-forming product composed of a xanthene-based basic dye and a xanthene-based acid dye is contained. Therefore, by forming the filter segments of the color filter from the colored composition, in addition to achieving high brightness and a wide color reproduction region, good resistance can be achieved. The color filter composition for color filters is particularly suitable for use in a blue or magenta filter segment.

再者，以往的藍色濾光片區段係使用例如銅酞菁藍顏料與二噁嗪系顏料之組合。組合有銅酞菁藍顏料與二噁嗪系顏料等之彩色濾光片用藍色著色組成物之穿透率光譜，其峰值位置存在於450nm附近，於450nm以下之短波長側，穿透率急遽下降。 Further, in the conventional blue filter segment, for example, a combination of a copper phthalocyanine blue pigment and a dioxazine-based pigment is used. A transmittance spectrum of a blue coloring composition for a color filter in which a copper phthalocyanine blue pigment and a dioxin-based pigment are combined, the peak position of which is present at around 450 nm, on the short wavelength side below 450 nm, and the transmittance Rapid decline.

相對於此，本態樣之彩色濾光片用組成物係作為著色劑之至少一部分，利用由呫噸系鹼性染料及呫噸系酸性染料所組成的成鹽生成物，更宜與酞菁系顏料一同使用。因此，使用本態樣之彩色濾光片用組成物時，於450nm以下之短波長側，與利用銅酞菁藍顏料與二噁嗪系顏料之組合時相比較，會達成高亮度。然後，冷陰極管等許多背光之發光光譜係於 425至440nm之波長範圍內，或於其附近具有峰值波長。因此，從本態樣之彩色濾光片用著色組成物獲得之濾光片區段可達成高亮度。 On the other hand, the composition for a color filter of the present aspect is a salt-forming product composed of a xanthene-based basic dye and a xanthene-based acid dye as a coloring agent, and is preferably a phthalocyanine-based product. The pigment is used together. Therefore, when the composition for a color filter of the present aspect is used, high luminance is achieved on the short wavelength side of 450 nm or less compared with the case of using a combination of a copper phthalocyanine blue pigment and a dioxin-based pigment. Then, the luminescence spectrum of many backlights, such as cold cathode tubes, is It has a peak wavelength in the wavelength range of 425 to 440 nm or in the vicinity thereof. Therefore, a high brightness can be achieved from the filter section obtained by the coloring composition of the color filter of the present aspect.

又，用於補色之彩色濾光片之補色顏料係選擇範圍極窄，現狀下難以取得具有良好分光特性之補色顏料。該點係成為在採用補色之彩色濾光片之攝像元件，難以獲得良好的色彩重現性之理由之一。尤其關於洋紅色濾光片區段，難以獲得充分的分光特性。例如喹吖酮系之洋紅色顏料之C.I.Pigment Red 122係於短波長側(400至500nm)之穿透率低，因此難以將彩色濾光片之色彩平衡最佳化。 Further, the complementary color of the color filter used for the complementary color filter is extremely narrow, and it is difficult to obtain a complementary color pigment having good spectral characteristics under the current situation. This point is one of the reasons why it is difficult to obtain good color reproducibility in an image pickup element using a complementary color filter. Especially with respect to the magenta filter section, it is difficult to obtain sufficient spectral characteristics. For example, the C.I. Pigment Red 122 of the quinacone-based magenta pigment has a low transmittance on the short-wavelength side (400 to 500 nm), so that it is difficult to optimize the color balance of the color filter.

呫噸系染料係作為例如顯現洋紅色之染料而為人所知。呫噸系染料具有良好的分光特性。具體而言，呫噸系色素係與喹吖酮系色素相比較，在400至450nm波長範圍或其附近之穿透率高。因此，如日本特開2005-292305號所記載，呫噸系色素用在許多洋紅色濾光片區段。然而，如上述，與顏料相比較，染料之耐受性較差。 The xanthene dye is known as, for example, a dye which exhibits magenta. The xanthene dye has good spectroscopic properties. Specifically, the xanthene-based pigment system has a high transmittance in the vicinity of the wavelength range of 400 to 450 nm as compared with the quinophthalone-based dye. Therefore, as described in JP-A-2005-292305, a xanthene dye is used in many magenta filter segments. However, as described above, the dye is less tolerant than the pigment.

本態樣之著色組成物係與喹吖酮系色素相比較，於短波長側(400至500nm)之穿透率較高。然後，若使用本態樣之著色組成物，可獲得耐受性良好的濾光片區段。因此，若於洋紅色之濾光片區段使用本態樣之著色組成物，可獲得例如色彩平衡及耐受性良好的補色之彩色濾光片。 The coloring composition of this aspect has a higher transmittance on the short-wavelength side (400 to 500 nm) than the quinophthalone-based dye. Then, if the colored composition of this aspect is used, a filter segment having good tolerance can be obtained. Therefore, if the color composition of this aspect is used in the magenta filter section, a color filter such as a color balance and a complementary color complement can be obtained.

<<彩色濾光片用著色組成物>> <<Coloring composition for color filter>>

如上述，本發明之第3態樣之彩色濾光片用著色組成物係含有透明樹脂及著色劑之彩色濾光片用藍色著色組成物。該著色劑包含由呫噸系鹼性染料及呫噸系酸性染料所組成的成鹽生成物。例如呫噸系鹼性染料及呫噸系酸性染料分別為第1態樣之鹼性染料及相對化合物。再者，於第 3態樣中，相對化合物典型上具有第1態樣中，針對相對化合物已於上面敘述之範圍內之分子量，但具有該範圍外之分子量亦可。 As described above, the coloring composition for a color filter according to the third aspect of the present invention contains a blue coloring composition for a color filter of a transparent resin and a coloring agent. The coloring agent contains a salt-forming product composed of a xanthene-based basic dye and a xanthene-based acid dye. For example, a xanthene-based basic dye and a xanthene-based acid dye are each a basic dye and a relative compound of the first aspect. Furthermore, Yu Di In the third aspect, the relative compound typically has a molecular weight within the range described above for the relative compound in the first aspect, but may have a molecular weight outside the range.

<著色劑> <colorant>

第3態樣所使用之著色劑包含由呫噸系酸性染料及呫噸系鹼性染料所組成的成鹽生成物。 The coloring agent used in the third aspect contains a salt-forming product composed of a xanthene-based acid dye and a xanthene-based basic dye.

該著色劑係於與例如銅酞菁顏料並用時，可於420至440nm之波長範圍內或其附近達成高穿透率。因此，與組合銅酞菁藍顏料與二噁嗪系顏料之以往的藍色濾光片區段相比較，可實現高亮度及寬廣的色彩重現性。又，由於在4000至450nm之波長範圍之穿透率高，因此可獲得色彩平衡良好的補色之彩色濾光片。 The colorant is capable of achieving high transmittance in or near the wavelength range of 420 to 440 nm when used in combination with, for example, a copper phthalocyanine pigment. Therefore, high brightness and wide color reproducibility can be achieved as compared with the conventional blue filter section in which a copper phthalocyanine blue pigment and a dioxin-based pigment are combined. Further, since the transmittance in the wavelength range of 4000 to 450 nm is high, a color filter having a good color balance and a complementary color can be obtained.

[呫噸系酸性染料及呫噸系鹼性染料] [呫 系 acid dyes and xanthene basic dyes]

以下，說明關於呫噸系酸性染料及呫噸系鹼性染料。 Hereinafter, the xanthene-based acid dye and the xanthene-based basic dye will be described.

(呫噸系染料) (呫 tons of dyes)

在此可適宜使用之呫噸系染料係呈現紅色或紫色之物，具有酸性染料及/或鹼性染料之形態。 The xanthene dyes which can be suitably used herein are red or purple and have the form of an acid dye and/or a basic dye.

呈現紅色或紫色之染料係屬於例如：C.I.基本紅及C.I.基本紫等鹼性染料；C.I.酸性紅及C.I.酸性紫等酸性染料；或C.I.直接紅及C.I.直接紫等直接染料之物。在此，直接染料係於構造中具有磺酸基(-SO₃H或-SO₃Na)之染料。於本態樣中，直接染料係視為酸性染料。又，油溶性中，具有磺酸基而實質上如酸性染料般發揮功能之物，於本態樣亦視為酸性染料。 The dyes exhibiting red or purple are, for example, basic dyes such as CI basic red and CI basic violet; acid dyes such as CI acid red and CI acid violet; or direct dyes such as CI direct red and CI direct violet. Here, the direct dye is a dye having a sulfonic acid group (-SO ₃ H or -SO ₃ Na) in the structure. In this aspect, the direct dye is considered an acid dye. Further, in the oil solubility, a substance having a sulfonic acid group and functioning substantially as an acid dye is also considered as an acid dye in this aspect.

呫噸系酸性染料及呫噸系鹼性染料係於400至450nm之波長 範圍內，具有穿透率高之分光特性。然而，呫噸系酸性染料及呫噸系鹼性染料係與一般染料相同，極為缺乏耐光性及耐熱性。亦即，呫噸系酸性染料及呫噸系鹼性染料用在要求高可靠性之彩色濾光片時，其特性仍不足。在此，為了改善該缺點，使用呫噸系酸性染料與呫噸系鹼性染料之鹽。該鹽係具有呈色基之物彼此之成鹽生成物，呈色性良好。 Xanthene acid dyes and xanthene alkaline dyes are used at wavelengths from 400 to 450 nm Within the range, there is a spectral characteristic with high transmittance. However, xanthene-based acid dyes and xanthene-based basic dyes are the same as general dyes, and are extremely resistant to light and heat. That is, when the xanthene-based acid dye and the xanthene-based basic dye are used in a color filter requiring high reliability, the characteristics are still insufficient. Here, in order to improve this disadvantage, a salt of a xanthene-based acid dye and a xanthene-based basic dye is used. This salt is a salt-forming product of a substance having a color base, and has good coloritivity.

呫噸系酸性染料及呫噸系鹼性染料係宜對於波長650nm之光之穿透率在90%以上，對於波長600nm之光之穿透率在75%以上，穿透率在波長500至550nm之範圍內為5%以下，對於波長400nm之光之穿透率在70%以上。更宜對於波長650nm以上之光之穿透率在95%以上，對於波長600nm之光之穿透率在80%以上，穿透率在波長500至550nm之範圍內為10%以下，對於波長400nm之光之穿透率在75%以上。 The xanthene-based acid dye and the xanthene-based basic dye are preferably more than 90% for light having a wavelength of 650 nm, more than 75% for light having a wavelength of 600 nm, and a transmittance of 500 to 550 nm for a wavelength of 500 to 550 nm. The range is 5% or less, and the transmittance for light having a wavelength of 400 nm is 70% or more. More preferably, the transmittance of light having a wavelength of 650 nm or more is 95% or more, the transmittance of light having a wavelength of 600 nm is 80% or more, and the transmittance is 10% or less in the range of 500 to 550 nm, for a wavelength of 400 nm. The penetration rate of light is above 75%.

(呫噸系酸性染料) (呫 tons of acid dyes)

呫噸系酸性染料可舉出例如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104號)、C.I.酸性紅92(酸性夾竹桃紅PB：食用紅色104號)、虎紅B(食用紅色5號)、酸性玫瑰紅G、酸性紅289或C.I.酸性紫9。 Examples of the xanthene-based acid dyes include CI Acid Red 51 (erythropurine: Edible Red No. 3), CI Acid Red 52 (Acid Rose Red), CI Acid Red 87 (Crimson G: Edible Red No. 104), and CI. Acid red 92 (acid oleander red PB: edible red No. 104), tiger red B (edible red No. 5), acid rose red G, acid red 289 or CI acid purple 9.

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或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 or C.I. Acid Red 388 are particularly suitable.

(呫噸系鹼性染料) (呫 tons are basic dyes)

呫噸系鹼性染料可舉出例如C.I.基本紅1(玫瑰紅6GCP)、C.I.基本紅8(玫瑰紅G)及C.I.基本紫10(玫瑰紅B)。 The xanthene-based basic dye may, for example, be C.I. Basic Red 1 (Rose Red 6GCP), C.I. Basic Red 8 (Rose Red G), and C.I. Basic Violet 10 (Rose Red B).

其中尤宜使用C.I.基本紅1或C.I.基本紫10。 Among them, it is preferable to use C.I. Basic Red 1 or C.I. Basic Violet 10.

呫噸系鹼性染料中，玫瑰紅系鹼性染料由於呈色性及耐受性良好，因此尤其適宜。 Among the xanthene-based basic dyes, the rose-red basic dye is particularly suitable because it has good coloring properties and resistance.

[由呫噸系酸性染料及呫噸系鹼性染料所組成的成鹽生成物] [Salt-forming product composed of xanthene acid dye and xanthene-based basic dye]

呫噸系酸性染料與呫噸系鹼性染料之成鹽生成物具有高耐熱性、耐光性及耐溶劑性。該成鹽生成物宜為以下組合之至少一種。 The salt-forming product of the xanthene-based acid dye and the xanthene-based basic dye has high heat resistance, light resistance, and solvent resistance. The salt-forming product is preferably at least one of the following combinations.

具體而言，C.I.基本紅1與C.I.酸性紅52之組合、C.I.基本紅1與C.I.酸性紅87之組合、C.I.基本紅1與C.I.酸性紅92之組合、C.I.基本紅1與C.I.酸性紅289之組合、C.I.基本紅1與C.I.酸性紅388之組合、C.I.基本紫10與C.I.酸性紅52之組合、C.I.基本紫10與C.I.酸性紅87之組合、C.I.基本紫10與C.I.酸性紅92之組合、C.I.基本紫10與C.I.酸性紅289之組合、C.I.基本紫10與C.I.酸性紅388之組合、C.I.基本紅8與C.I.酸性紅52、C.I.基本紅8與C.I.酸性紅87、C.I.基本紅8與C.I.酸性紅92、C.I.基本紅8與C.I.酸性紅289及C.I.基本紅8與C.I.酸性紅388之組合係反應安定性及呈色性特別良好。。當然亦可使用從其他組合獲得之成鹽生成物。 Specifically, a combination of CI basic red 1 and CI acid red 52, a combination of CI basic red 1 and CI acid red 87, a combination of CI basic red 1 and CI acid red 92, CI basic red 1 and CI acid red 289 Combination, combination of CI basic red 1 and CI acid red 388, combination of CI basic purple 10 and CI acid red 52, combination of CI basic purple 10 and CI acid red 87, combination of CI basic purple 10 and CI acid red 92, Combination of CI Basic Violet 10 and CI Acid Red 289, CI Basic Violet 10 and CI Acid Red 388, CI Basic Red 8 and CI Acid Red 52, CI Basic Red 8 and CI Acid Red 87, CI Basic Red 8 and CI The combination of acid red 92, CI basic red 8 and CI acid red 289, and CI basic red 8 and CI acid red 388 is particularly good in reaction stability and color rendering. . It is of course also possible to use salt-forming products obtained from other combinations.

呫噸系鹼性染料與呫噸系酸性染料之成鹽生成物可藉由以往習知的方法來合成。 The salt-forming product of the xanthene-based basic dye and the xanthene-based acid dye can be synthesized by a conventional method.

例如於水中溶解呫噸系酸性染料後，於此添加呫噸系鹼性染料或其水溶液並攪拌，藉以發生成鹽反應即可。藉此，可獲得呫噸系酸性染料之磺酸基(例如-SO₃H或-SO₃Na)與呫噸系鹼性染料之胺基結合之成鹽生成物。 For example, after dissolving a xanthene-based acid dye in water, a xanthene-based basic dye or an aqueous solution thereof is added thereto and stirred to form a salt-forming reaction. Thereby, a salt-forming product in which a sulfonic acid group of a xanthene-based acid dye (for example, -SO ₃ H or -SO ₃ Na) is bonded to an amine group of a xanthene-based basic dye can be obtained.

[具有酸基之樹脂] [Resin with acid group]

上述成鹽生成物若藉由以具有酸基之樹脂來改質，則可製成較安定之色材。關於具有酸基之樹脂之事項係與第2態樣之說明相同。 When the salt-forming product is modified by a resin having an acid group, a relatively stable color material can be obtained. The matter of the resin having an acid group is the same as that of the second aspect.

[其他著色劑] [other colorants]

於該著色組成物中，可在不對效果帶來妨礙的範圍內，進一步添加其他著色劑。其中尤其當並用成鹽生成物與有機顏料時，可達成較良好的耐受性。 Further, in the colored composition, other coloring agents may be added to the extent that the effect is not hindered. Among them, particularly when a salt-forming product and an organic pigment are used in combination, a better tolerance can be achieved.

有機顏料宜使用酞菁系顏料、二噁嗪系顏料、蒽醌系顏料、偶氮系顏料或喹吖酮系顏料。其中特別適宜使用酞菁系顏料或二噁嗪系顏料。 As the organic pigment, a phthalocyanine pigment, a dioxazine pigment, an anthraquinone pigment, an azo pigment or a quinophthalone pigment is preferably used. Among them, a phthalocyanine-based pigment or a dioxazine-based pigment is particularly preferably used.

酞菁藍顏料可舉出例如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及C.I.Pigment Blue 15：6。其中尤以具有e型、b型或a型之銅酞菁藍顏料為宜。該等適宜顏料具體而言為例如C.I.Pigment Blue 15：6、C.I.Pigment Blue 15：3及C.I.Pigment Blue 15：1。 The phthalocyanine blue pigment may, for example, be 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, and C.I. Pigment Blue 15:6. Among them, a copper phthalocyanine blue pigment having an e-type, a b-type or an a-type is preferable. Such suitable pigments are, for example, C.I. Pigment Blue 15:6, C.I. Pigment Blue 15:3 and C.I. Pigment Blue 15:1.

又，二噁嗪系顏料宜使用C.I.Pigment Violet 23。 Further, as the dioxazine-based pigment, C.I. Pigment Violet 23 is preferably used.

該等顏料係於上述成鹽生成物之量設為100質量部時，宜在2至100質量部之範圍內來使用。 When the amount of the salt-forming product is 100 parts by mass, the pigment is preferably used in an amount of from 2 to 100 parts by mass.

尤其若並用上述成鹽生成物、與銅酞菁系顏料及/或二噁嗪系顏料時，除了可獲得良好的耐候性，還可獲得超越顏料單獨使用時之亮度。 In particular, when the salt-forming product, the copper phthalocyanine-based pigment, and/or the dioxazine-based pigment are used in combination, in addition to obtaining good weather resistance, it is possible to obtain brightness beyond the use of the pigment alone.

從上述著色組成物形成洋紅色濾光片區段時，以色彩調整為目的，可並用上述成鹽生成物與其他紅色或洋紅色顏料。可並用之其他 顏料可舉出例如C.I.Pigment122、C.I.Pigment 192、C.I.Pigment 202、C.I.Pigment 207及C.I.Pigment 209。其中從耐熱性、耐光性及耐溶劑性良好方面來看，宜使用喹吖酮顏料。 When the magenta filter segment is formed from the above colored composition, the above salt-forming product and other red or magenta pigments may be used in combination for the purpose of color adjustment. Others that can be used together The pigment may, for example, be C.I. Pigment 122, C.I. Pigment 192, C.I. Pigment 202, C.I. Pigment 207, and C.I. Pigment 209. Among them, a quinacridone pigment is preferably used from the viewpoint of good heat resistance, light resistance and solvent resistance.

該等顏料係從增廣色渡區域、獲得良好分光特性的觀點考量，於上述成鹽生成物之質量設為100質量部時，宜以40質量部以下之量來使用。 The pigment is preferably used in an amount of 40 parts by mass or less when the mass of the salt-forming product is 100 parts by mass, from the viewpoint of obtaining a good color separation property.

(顏料之微細化) (fineness of pigment)

上述顏料可藉由例如鹽磨處理來予以微細化。顏料之一次粒徑宜設在第1態樣所說明的範圍內。鹽磨處理可藉由與例如第1態樣之說明方法相同的方法來進行。又，於鹽磨處理可使用與第1態樣之說明相同的水溶性有機無機鹽、水溶性有機溶劑及樹脂。各種材料之使用量宜設在第1態樣所說明的範圍內。 The above pigment can be refined by, for example, a salt milling treatment. The primary particle diameter of the pigment should preferably be within the range described in the first aspect. The salt milling treatment can be carried out by the same method as the method of the first aspect, for example. Further, in the salt milling treatment, the same water-soluble organic inorganic salt, water-soluble organic solvent, and resin as those described in the first aspect can be used. The amount of each material used should be within the range described in the first aspect.

<透明樹脂> <Transparent Resin>

透明樹脂係令著色劑，尤其令成鹽生成物分散及/或溶解之物。透明樹脂可使用與例如第1態樣之說明相同之物。又，透明樹脂之使用量可與第1態樣之說明相同。 The transparent resin is a coloring agent, especially a substance which disperses and/or dissolves the salt-forming product. As the transparent resin, the same as the description of the first aspect, for example, can be used. Further, the amount of the transparent resin used can be the same as that of the first aspect.

<分散> <scatter>

該著色組成物可藉由與例如第1態樣之說明方法相同的方法來製造。 This colored composition can be produced by the same method as the method of the first aspect, for example.

(分散助劑) (dispersion aid)

將著色劑分散於著色劑載體中時，與第1態樣相同，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。 When the colorant is dispersed in the colorant carrier, a dispersing aid such as a dye derivative, a resin type pigment dispersant, or a surfactant can be suitably used in the same manner as in the first embodiment.

色素衍生物可使用與例如第1態樣之說明相同之物。從分散性提升的觀點考量，色素衍生物之調配量從提升分散性的觀點考量，宜與第2態樣之說明相同。 As the dye derivative, the same as the description of the first aspect, for example, can be used. From the viewpoint of improving the dispersibility, the amount of the pigment derivative to be added is considered to be the same as that of the second aspect, from the viewpoint of improving the dispersibility.

樹脂型分散劑可使用與例如第1態樣之說明相同之物。作為市售的樹脂型顏料分散劑可使用例如第2態樣所例示之物。 As the resin type dispersant, the same as the description of the first aspect, for example, can be used. As the commercially available resin type pigment dispersant, for example, those exemplified in the second aspect can be used.

界面活性劑可使用與例如第1態樣之說明相同之物。 As the surfactant, the same as the description of the first aspect can be used.

添加樹脂型分散劑及/或界面活性劑時，其等之合計量宜在第2態樣所說明的範圍內。 When a resin type dispersant and/or a surfactant is added, the total amount thereof is preferably within the range described in the second aspect.

該著色組成物可進一步添加光聚合性組成物及/或光聚合起始劑，以作為彩色濾光片用感光性著色組成物(抗蝕劑)來使用。 Further, a photopolymerizable composition and/or a photopolymerization initiator may be added to the coloring composition to be used as a photosensitive coloring composition (resist) for a color filter.

<光聚合性組成物> <Photopolymerizable composition>

光聚合性組成物可使用例如第2態樣所例示的單體或寡聚物。該等單體及寡聚物之合計調配量宜在第2態樣所說明的範圍內。 As the photopolymerizable composition, for example, a monomer or an oligomer exemplified in the second aspect can be used. The total amount of the monomers and oligomers is preferably within the range described in the second aspect.

<光聚合起始劑> <Photopolymerization initiator>

藉由利用紫外線照射之光微影，從彩色濾光片用藍色著色組成物形成濾光片區段時，於該著色組成物添加光聚合起始劑等。光聚合起始劑可使用與例如第1態樣之說明相同之物。使用光聚合起始劑時，其調配量宜與第1態樣之說明相同。 When a filter segment is formed from a color filter using a blue coloring composition by photolithography of ultraviolet light, a photopolymerization initiator or the like is added to the coloring composition. As the photopolymerization initiator, the same as the description of the first aspect, for example, can be used. When a photopolymerization initiator is used, the amount thereof is preferably the same as that described in the first aspect.

<增感劑> <sensitizer>

於彩色濾光片用著色組成物中，可進一步含有增感劑。 The coloring composition for a color filter may further contain a sensitizer.

增感劑可使用與例如第1態樣之說明相同之物。使用增感劑時，其調配量宜與第1態樣之說明相同。 As the sensitizer, the same as the description of the first aspect, for example, can be used. When a sensitizer is used, the amount thereof is preferably the same as that described in the first aspect.

<胺系化合物> <Amine compound>

於彩色濾光片用著色組成物中，可進一步含有具有還原溶存氧的作用之胺系化合物。胺系化合物可使用與例如第1態樣之說明相同之物。 The coloring composition for a color filter may further contain an amine compound having a function of reducing dissolved oxygen. As the amine compound, for example, the same as the description of the first aspect can be used.

<均染劑> <leveling agent>

於該著色組成物中，為了改善組成物在透明基板上之均染性，宜進一步添加均染劑。 In the colored composition, in order to improve the leveling property of the composition on the transparent substrate, it is preferred to further add a leveling agent.

均染劑可使用與例如第1態樣之說明相同之物。使用均染劑時，其調配量宜與第1態樣之說明相同。 As the leveling agent, the same as the description of the first aspect, for example, can be used. When a leveling agent is used, the amount thereof is preferably the same as that described in the first aspect.

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。界面活性劑可單獨使用1種，或混合2種以上使用。該等界面活性劑可使用與例如第1態樣之說明相同之物。 Anionic, cationic, nonionic or amphoteric surfactants may also be added to the leveling agent. The surfactant may be used singly or in combination of two or more. As the surfactant, for example, the same as the description of the first aspect can be used.

<硬化劑及硬化促進劑> <hardener and hardening accelerator>

為了輔助熱硬化性樹脂之硬化，於該著色組成物中，亦可因應需要來含有硬化劑及硬化促進劑。硬化劑及硬化促進劑可使用與例如第1態樣之說明相同之物。使用硬化促進劑時，其調配量宜與第1態樣之說明相同。 In order to assist the hardening of the thermosetting resin, a curing agent and a curing accelerator may be contained in the colored composition as needed. As the curing agent and the hardening accelerator, the same as the description of the first aspect, for example, can be used. When a hardening accelerator is used, the amount thereof is preferably the same as that described in the first aspect.

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

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

儲藏安定劑可使用與例如第1態樣之說明相同之物。使用儲 藏安定劑及/或密貼提升劑時，其調配量宜與第1態樣之說明相同。 As the storage stabilizer, the same as the description of the first aspect, for example, can be used. Use storage When the stabilizer and/or the adhesion enhancer are used, the blending amount should be the same as that of the first aspect.

<去除粗粒子> <Remove coarse particles>

宜從該著色組成物，與第1態樣相同地去除粗粒子及混入微塵。亦即，該著色組成物實質上宜不含0.5mm以上之粒子，更宜實質上不含0.3mm以上之粒子。 It is preferable to remove the coarse particles and mix the fine dust from the colored composition in the same manner as in the first aspect. That is, the coloring composition is preferably substantially free of particles of 0.5 mm or more, and more preferably contains substantially no particles of 0.3 mm or more.

<<彩色濾光片>> <<Color filter>>

接著，說明關於本發明之第3態樣之彩色濾光片。 Next, a color filter according to a third aspect of the present invention will be described.

第2態樣之彩色濾光片包含吸收光譜不同、典型上規則地排列之複數個濾光片區段。一形態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。於第2態樣之彩色濾光片，至少1個藍色濾光片區段係由上述彩色濾光片用著色組成物所形成。 The color filter of the second aspect comprises a plurality of filter segments having different absorption spectra, typically regularly arranged. A color filter of one form includes at least one red filter segment, at least one green filter segment, and at least one blue filter segment. In the color filter of the second aspect, at least one of the blue filter segments is formed of the coloring composition for the color filter.

紅色著色組成物可使用例如包含紅色顏料及顏料載體之一般的紅色著色組成物來形成。紅色顏料可使用例如C.I.Pigment Red 7、C.I.Pigment Red 14、C.I.Pigment Red 41、C.I. Pigment Red 48：1、C.I.Pigment Red 48：2、C.I.Pigment Red 48：3、C.I.Pigment Red 48：4、C.I.Pigment Red 81：1、C.I.Pigment Red 81：2、C.I.Pigment Red 81：3、C.I.Pigment Red 81：4、C.I.Pigment Red 122、C.I.Pigment Red 146、C.I.Pigment Red 168、C.I.Pigment Red 177、C.I.Pigment Red 178、C.I.Pigment Red 184、C.I.Pigment Red 185、C.I.Pigment Red 187、C.I.Pigment Red 200、C.I.Pigment Red 202、C.I.Pigment Red 208、C.I.Pigment Red 210、C.I.Pigment Red 242、C.I.Pigment Red 246、C.I.Pigment Red 254、C.I.Pigment Red 255、C.I.Pigment Red 264、C.I.Pigment Red 270、C.I.Pigment Red 272、C.I.Pigment Red 273、C.I.Pigment Red 274、C.I.Pigment Red 276、C.I.Pigment Red 277、C.I.Pigment Red 278、C.I.Pigment Red 279、C.I.Pigment Red 280、C.I.Pigment Red 281、C.I.Pigment Red 282、C.I.Pigment Red 283、C.I.Pigment Red 284、C.I.Pigment Red 285、C.I.Pigment Red 286及C.I.Pigment Red 287等紅色顏料。亦可使用鹼性染料與酸性染料之呈現紅色之成鹽生成物。 The red coloring composition can be formed using, for example, a general red coloring composition comprising a red pigment and a pigment carrier. Red pigments can be used, for example, CIPigment Red 7, CIPigment Red 14, CIPigment Red 41, CI Pigment Red 48:1, CIPigment Red 48:2, CIPigment Red 48:3, CIPigment Red 48:4, CIPigment Red 81:1, CIPigment Red 81:2, CIPigment Red 81:3, CIPigment Red 81:4, CIPigment Red 122, CIPigment Red 146, CIPigment Red 168, CIPigment Red 177, CIPigment Red 178 , CIPigment Red 184, CIPigment Red 185, CIPigment Red 187, CIPigment Red 200, CIPigment Red 202, CIPigment Red 208, CIPigment Red 210, CIPigment Red 242, CIPigment Red 246, CIPigment Red 254 , CIPigment Red 255, CIPigment Red 264, CIPigment Red 270, CIPigment Red 272, CIPigment Red 273, CIPigment Red 274, CIPigment Red 276, CIPigment Red 277, CIPigment Red 278, CIPigment Red 279, CIPigment Red 280, CIPigment Red pigments such as Red 281, CIPigment Red 282, CIPigment Red 283, CIPigment Red 284, CIPigment Red 285, CIPigment Red 286 and CIPigment Red 287. It is also possible to use a salty product of a basic dye and an acid dye which exhibits a red color.

於紅色著色組成物，亦可並用C.I.Pigment Orange 43、71、73等橘色顏料、C.I.Pigment Yellow 1、C.I.Pigment Yellow 2、C.I.Pigment Yellow 3、C.I.Pigment Yellow 4、C.I.Pigment Yellow 5、C.I.Pigment Yellow 6、C.I.Pigment Yellow 10、C.I.Pigment Yellow 12、C.I.Pigment Yellow 13、C.I.Pigment Yellow 14、C.I.Pigment Yellow 15、C.I.Pigment Yellow 16、C.I.Pigment Yellow 17、C.I.Pigment Yellow 18、C.I.Pigment Yellow 24、C.I.Pigment Yellow 31、C.I.Pigment Yellow 32、C.I.Pigment Yellow 34、C.I.Pigment Yellow 35、C.I.Pigment Yellow 35：1、C.I.Pigment Yellow 36、C.I.Pigment Yellow 36：1、C.I.Pigment Yellow 37、C.I.Pigment Yellow 37：1、C.I.Pigment Yellow 40、C.I.Pigment Yellow 42、C.I.Pigment Yellow 43、C.I.Pigment Yellow 53、C.I.Pigment Yellow 55、C.I.Pigment Yellow 60、C.I.Pigment Yellow 61、C.I.Pigment Yellow 62、C.I.Pigment Yellow 63、C.I.Pigment Yellow 65、C.I.Pigment Yellow 73、C.I.Pigment Yellow 74、C.I.Pigment Yellow 77、C.I.Pigment Yellow 81、C.I.Pigment Yellow 83、C.I.Pigment Yellow 93、C.I.Pigment Yellow 95、C.I.Pigment Yellow 97、C.I.Pigment Yellow 98、C.I.Pigment Yellow 100、C.I.Pigment Yellow 101、C.I. Pigment Yellow 104、C.I.Pigment Yellow 106、C.I.Pigment Yellow 108、C.I.Pigment Yellow 109、C.I.Pigment Yellow 110、C.I.Pigment Yellow 113、C.I.Pigment Yellow 114、C.I.Pigment Yellow 115、C.I.Pigment Yellow 116、C.I.Pigment Yellow 117、C.I.Pigment Yellow 118、C.I.Pigment Yellow 119、C.I.Pigment Yellow 120、C.I.Pigment Yellow 123、C.I.Pigment Yellow 126、C.I.Pigment Yellow 127、C.I.Pigment Yellow 128、C.I.Pigment Yellow 129、C.I.Pigment Yellow 138、C.I.Pigment Yellow 147、C.I.Pigment Yellow 150、C.I.Pigment Yellow 151、C.I.Pigment Yellow 152、C.I.Pigment Yellow 153、C.I.Pigment Yellow 154、C.I.Pigment Yellow 155、C.I.Pigment Yellow 156、C.I.Pigment Yellow 161、C.I.Pigment Yellow 162、C.I.Pigment Yellow 164、C.I.Pigment Yellow 166、C.I.Pigment Yellow 167、C.I.Pigment Yellow 168、C.I.Pigment Yellow 169、C.I.Pigment Yellow 170、C.I.Pigment Yellow 171、C.I.Pigment Yellow 172、C.I.Pigment Yellow 173、C.I.Pigment Yellow 174、C.I.Pigment Yellow 175、C.I.Pigment Yellow 176、C.I.Pigment Yellow 177、C.I.Pigment Yellow 179、C.I.Pigment Yellow 180、C.I.Pigment Yellow 181、C.I.Pigment Yellow 182、C.I.Pigment Yellow 185、C.I.Pigment Yellow 187、C.I.Pigment Yellow 188、C.I.Pigment Yellow 193、C.I.Pigment Yellow 194、C.I.Pigment Yellow 198、C.I.Pigment Yellow 199、C.I.Pigment Yellow 213、C.I.Pigment Yellow 214、C.I.Pigment Yellow 218、C.I.Pigment Yellow 219、C.I.Pigment Yellow 220及C.I.Pigment Yellow 221等黃色顏料或其等之兩種以上之組合。又，亦可使用各個呈現橘色及/或黃色之鹼性染料與酸性染料之成鹽生成物。 For red coloring composition, it is also possible to use CIPigment Orange 43, 71, 73 and other orange pigments, CIPigment Yellow 1, CIPigment Yellow 2, CIPigment Yellow 3, CIPigment Yellow 4, CIPigment Yellow 5, CIPigment Yellow 6. CIPigment Yellow 10, CIPigment Yellow 12, CIPigment Yellow 13, CIPigment Yellow 14, CIPigment Yellow 15, CIPigment Yellow 16, CIPigment Yellow 17, CIPigment Yellow 18, CIPigment Yellow 24, CIPigment Yellow 31. CIPigment Yellow 32, CIPigment Yellow 34, CIPigment Yellow 35, CIPigment Yellow 35:1, CIPigment Yellow 36, CIPigment Yellow 36:1, CIPigment Yellow 37, CIPigment Yellow 37:1, CIPigment Yellow 40, CIPigment Yellow 42, CIPigment Yellow 43, CIPigment Yellow 53, CIPigment Yellow 55, CIPigment Yellow 60, CIPigment Yellow 61, CIPigment Yellow 62, CIPigment Yellow 63, CIPigment Yellow 65, CIPigment Yellow 73, CIPigment Yellow 74, CIPigment Yellow 77, CIPigment Yellow 81. C.I. Pigment Yellow 83, C.I. Pigment Yellow 93, C.I. Pigment Yellow 95, C.I. Pigment Yellow 97, C.I. Pigment Yellow 98, C.I. Pigment Yellow 100, C.I. Pigment Yellow 101, C.I. Pigment Yellow 104, CIPigment Yellow 106, CIPigment Yellow 108, CIPigment Yellow 109, CIPigment Yellow 110, CIPigment Yellow 113, CIPigment Yellow 114, CIPigment Yellow 115, CIPigment Yellow 116, CIPigment Yellow 117, CI Pigment Yellow 118, CIPigment Yellow 119, CIPigment Yellow 120, CIPigment Yellow 123, CIPigment Yellow 126, CIPigment Yellow 127, CIPigment Yellow 128, CIPigment Yellow 129, CIPigment Yellow 138, CIPigment Yellow 147, CI Pigment Yellow 150, CIPigment Yellow 151, CIPigment Yellow 152, CIPigment Yellow 153, CIPigment Yellow 154, CIPigment Yellow 155, CIPigment Yellow 156, CIPigment Yellow 161, CIPigment Yellow 162, CIPigment Yellow 164, CI Pigment Yellow 166, CIPigment Yellow 167, CIPigment Yellow 168, CIPigment Yellow 169, CIPigment Yellow 170, CIPigment Yellow 171, CIPigment Yellow 172, CIPigment Yellow 173, CIPigment Yellow 174, CIPigment Yellow 175, CI Pigment Yellow 176, CIPigment Yellow 177, CIPigment Yellow 179, CIPigment Yellow 180, CIPigment Yellow 181, CIPigment Yellow 182, CIPigment Yellow 185, CIPigment Yellow 187, CIPigment Yellow 188, CIPigment Yellow 193, CI Yellow pigment such as Pigment Yellow 194, CIPigment Yellow 198, CIPigment Yellow 199, CIPigment Yellow 213, CIPigment Yellow 214, CIPigment Yellow 218, CIPigment Yellow 219, CIPigment Yellow 220 and CIPigment Yellow 221 or the like A combination of two or more. Further, it is also possible to use a salt-forming product of each of an alkaline dye and an orange dye which exhibits an orange color and/or a yellow color.

綠色濾光片區段可使用例如包含綠色顏料及顏料載體之綠色著色組成物來形成。綠色顏料可使用例如C.I.Pigment Green 7、C.I.Pigment Green 10、C.I.Pigment Green 36、C.I.Pigment Green 37或C.I.Pigment Green 58。 The green filter segment can be formed using, for example, a green coloring composition comprising a green pigment and a pigment carrier. As the green pigment, for example, C.I. Pigment Green 7, C.I. Pigment Green 10, C.I. Pigment Green 36, C.I. Pigment Green 37 or C.I. Pigment Green 58 can be used.

綠色著色組成物亦可進一步包含黃色顏料。可並用的黃色顏料可舉出例如C.I.Pigment Yellow 1、C.I.Pigment Yellow 2、C.I.Pigment Yellow 3、C.I.Pigment Yellow 4、C.I.Pigment Yellow 5、C.I.Pigment Yellow 6、C.I.Pigment Yellow 10、C.I.Pigment Yellow 12、C.I.Pigment Yellow 13、C.I.Pigment Yellow 14、C.I.Pigment Yellow 15、C.I.Pigment Yellow 16、C.I.Pigment Yellow 17、C.I.Pigment Yellow 18、C.I.Pigment Yellow 24、C.I.Pigment Yellow 31、C.I.Pigment Yellow 32、C.I.Pigment Yellow 34、C.I.Pigment Yellow 35、C.I.Pigment Yellow 35：1、C.I.Pigment Yellow 36、C.I.Pigment Yellow 36：1、C.I.Pigment Yellow 37、C.I.Pigment Yellow 37：1、C.I.Pigment Yellow 40、C.I.Pigment Yellow 42、C.I.Pigment Yellow 43、C.I.Pigment Yellow 53、C.I.Pigment Yellow 55、C.I.Pigment Yellow 60、C.I.Pigment Yellow 61、C.I.Pigment Yellow 62、C.I.Pigment Yellow 63、C.I.Pigment Yellow 65、C.I.Pigment Yellow 73、C.I.Pigment Yellow 74、C.I.Pigment Yellow 77、C.I.Pigment Yellow 81、C.I.Pigment Yellow 83、C.I.Pigment Yellow 93、C.I.Pigment Yellow 95、C.I.Pigment Yellow 97、C.I.Pigment Yellow 98、C.I.Pigment Yellow 100、C.I.Pigment Yellow 101、C.I.Pigment Yellow 104、C.I.Pigment Yellow 106、C.I.Pigment Yellow 108、C.I.Pigment Yellow 109、C.I.Pigment Yellow 110、C.I.Pigment Yellow 113、C.I. Pigment Yellow 114、C.I.Pigment Yellow 115、C.I.Pigment Yellow 116、C.I.Pigment Yellow 117、C.I.Pigment Yellow 118、C.I.Pigment Yellow 119、C.I.Pigment Yellow 120、C.I.Pigment Yellow 123、C.I.Pigment Yellow 126、C.I.Pigment Yellow 127、C.I.Pigment Yellow 128、C.I.Pigment Yellow 129、C.I.Pigment Yellow 138、C.I.Pigment Yellow 147、C.I.Pigment Yellow 150、C.I.Pigment Yellow 151、C.I.Pigment Yellow 152、C.I.Pigment Yellow 153、C.I.Pigment Yellow 154、C.I.Pigment Yellow 155、C.I.Pigment Yellow 156、C.I.Pigment Yellow 161、C.I.Pigment Yellow 162、C.I.Pigment Yellow 164、C.I.Pigment Yellow 166、C.I.Pigment Yellow 167、C.I.Pigment Yellow 168、C.I.Pigment Yellow 169、C.I.Pigment Yellow 170、C.I.Pigment Yellow 171、C.I.Pigment Yellow 172、C.I.Pigment Yellow 173、C.I.Pigment Yellow 174、C.I.Pigment Yellow 175、C.I.Pigment Yellow 176、C.I.Pigment Yellow 177、C.I.Pigment Yellow 179、C.I.Pigment Yellow 180、C.I.Pigment Yellow 181、C.I.Pigment Yellow 182、C.I.Pigment Yellow 185、C.I.Pigment Yellow 187、C.I.Pigment Yellow 188、C.I.Pigment Yellow 193、C.I.Pigment Yellow 194、C.I.Pigment Yellow 198、C.I.Pigment Yellow 199、C.I.Pigment Yellow 213、C.I.Pigment Yellow 214、C.I.Pigment Yellow 218、C.I.Pigment Yellow 219、C.I.Pigment Yellow 220及C.I.Pigment Yellow 221。又，亦可並用各個呈現黃色之鹼性染料與酸性染料之成鹽生成物。 The green coloring composition may further comprise a yellow pigment. The yellow pigment which can be used in combination may, for example, be CIPigment Yellow 1, CIPigment Yellow 2, CIPigment Yellow 3, CIPigment Yellow 4, CIPigment Yellow 5, CIPigment Yellow 6, CIPigment Yellow 10, CIPigment Yellow 12, CI. Pigment Yellow 13, CIPigment Yellow 14, CIPigment Yellow 15, CIPigment Yellow 16, CIPigment Yellow 17, CIPigment Yellow 18, CIPigment Yellow 24, CIPigment Yellow 31, CIPigment Yellow 32, CIPigment Yellow 34, CI Pigment Yellow 35, CIPigment Yellow 35:1, CIPigment Yellow 36, CIPigment Yellow 36:1, CIPigment Yellow 37, CIPigment Yellow 37:1, CIPigment Yellow 40, CIPigment Yellow 42, CIPigment Yellow 43, CIPigment Yellow 53, CIPigment Yellow 60, CIPigment Yellow 61, CIPigment Yellow 62, CIPigment Yellow 63, CIPigment Yellow 65, CIPigment Yellow 73, CIPigment Yellow 74, CIPigment Yellow 77, CIPigment Yellow 81, CIPigment Yellow 83, CIPigment Yellow 93. CIPigment Yellow 95, CIPigment Yellow 97, CIPigment Yellow 98, CIPigment Yellow 100, CIPigment Yellow 101, CIPigment Yellow 104, CIPigment Yellow 106, CIPigment Yellow 108, CIPigment Yellow 109, CIPigment Yellow 110, CIPigment Yellow 113, CI Pigment Yellow 114, CIPigment Yellow 115, CIPigment Yellow 116, CIPigment Yellow 117, CIPigment Yellow 118, CIPigment Yellow 119, CIPigment Yellow 120, CIPigment Yellow 123, CIPigment Yellow 126, CIPigment Yellow 127, CI Pigment Yellow 128, CIPigment Yellow 129, CIPigment Yellow 138, CIPigment Yellow 147, CIPigment Yellow 150, CIPigment Yellow 151, CIPigment Yellow 152, CIPigment Yellow 153, CIPigment Yellow 154, CIPigment Yellow 155, CI Pigment Yellow 156, CIPigment Yellow 161, CIPigment Yellow 162, CIPigment Yellow 164, CIPigment Yellow 166, CIPigment Yellow 167, CIPigment Yellow 168, CIPigment Yellow 169, CIPigment Yellow 170, CIPigment Yellow 171, CI Pigment Yellow 172, CIPigment Yellow 173, CIPigment Yellow 174, CIPigment Yellow 175, CIPigment Yellow 176, CIPigment Yellow 177, CIPigment Yellow 179, CIPigment Yellow 180, CIPigment Yellow 181, CIPigment Yellow 182, CI Pigment Yellow 185, CIPigment Yellow 187, CIPigment Yellow 188, CIPigment Yellow 193, CIPigment Yellow 194, CIPigment Yellow 198, CIPigment Yellow 199, CIPigment Yellow 213, CIPigment Yellow 214, CIPigment Yellow 218, CI Pigment Yellow 219, CIPigment Yellow 220 and CIPigment Yellow 221. Further, a salt-forming product of each of the yellow-based basic dye and the acid dye may be used in combination.

青色濾光片區段可使用例如包含藍色顏料或青色顏料及顏料載體之青色著色組成物來形成。青色顏料可使用例如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 15：5、C.I.Pigment Blue 15：6、C.I.Pigment Blue 16、C.I.Pigment Blue 22、C.I.Pigment Blue 60或C.I.Pigment Blue 64。其中尤以銅酞菁系顏料之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 15：5及C.I.Pigment Blue 15：6為宜。又，亦可並用各個呈現藍色之鹼性染料與酸性染料之成鹽生成物。 The cyan filter section can be formed using, for example, a cyan coloring composition comprising a blue pigment or a cyan pigment and a pigment carrier. For cyan pigments, for example, 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 15:5, C.I. Pigment Blue 15:6, C.I. Pigment Blue 16, C.I. Pigment Blue 22, C.I. Pigment Blue 60 or C.I. Pigment Blue 64. Among them, CIPigment Blue 15 of Cyanide pigments, CIPigment Blue 15:1, CIPigment Blue 15:2, CIPigment Blue 15:3, CIPigment Blue 15:4, CIPigment Blue 15:5 and CI Pigment Blue 15:6 is appropriate. Further, a salt-forming product of each of the blue-based basic dye and the acid dye may be used in combination.

黃色濾光片區段可使用例如包含黃色顏料及顏料載體之黃色著色組成物來形成。黃色顏料可使用例如作為可與綠色顏料並用之黃色顏料而例示之顏料。又，亦可並用各個呈現黃色之鹼性染料與酸性染料之成鹽生成物。 The yellow filter segment can be formed using, for example, a yellow colored composition comprising a yellow pigment and a pigment carrier. As the yellow pigment, for example, a pigment exemplified as a yellow pigment which can be used in combination with a green pigment can be used. Further, a salt-forming product of each of the yellow-based basic dye and the acid dye may be used in combination.

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

該彩色濾光片可藉由與例如第1態樣之說明方法相同的方法來製造。 The color filter can be manufactured by the same method as the method of the first aspect, for example.

以下記載本發明之實施例，但本發明不受限於該等實施例。再者，只要未特別寫明，「部」係意味「重量部」。 The embodiments of the present invention are described below, but the present invention is not limited to the embodiments. In addition, as long as it is not specifically stated, "part" means "weight part".

首先，說明關於實施例及比較例中所進行的各種測定方法等。 First, various measurement methods and the like performed in the examples and comparative examples will be described.

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

成鹽生成物及玫瑰紅系化合物在粉碎後之平均粒徑係利用 Beckmancoulter公司製Multisizer 3，在光圈直徑100mm之條件下所獲得的體積平均粒徑。 The average particle size of the salt-forming product and the rose-red compound after pulverization Multi-layer 3 manufactured by Beckmancoulter Co., Ltd., volume average particle diameter obtained under the condition of an aperture diameter of 100 mm.

又，顏料之微細化度係以顏料粒子之相對表面積來評估。相對表面積之測定係利用自動蒸汽吸附量測定裝置(Bel Japan公司製「BELSORP18」)，藉由利用氮之BET(Brunauer-Emmett-Teller)法進行。 Further, the degree of refinement of the pigment is evaluated by the relative surface area of the pigment particles. The measurement of the relative surface area was carried out by using a nitrogen BET (Brunauer-Emmett-Teller) method using an automatic vapor adsorption amount measuring device ("BELSORP18" manufactured by Bel Japan Co., Ltd.).

接著，說明實施例及比較例所用之丙烯酸樹脂溶液、成鹽生成物及玫瑰紅系化學物之製造方法，以及顏料之微細化方法。 Next, the acrylic resin solution, the salt-forming product, and the method for producing the rose-red chemical used in the examples and the comparative examples, and a method for refining the pigment will be described.

<<試驗1>> <<Test 1>>

試驗1係關於第1態樣。於試驗1，對應於第1態樣之例子記載作「實施例」，其他例子記載作「比較例」。 Test 1 is about the first aspect. In the test 1, the examples corresponding to the first aspect are described as "examples", and the other examples are described as "comparative examples".

<丙烯酸樹脂溶液之製造方法> <Method for Producing Acrylic Resin Solution>

(丙烯酸樹脂溶液1之調製) (modulation of acrylic resin solution 1)

於分離式的4支燒瓶，安裝溫度計、冷卻管、氮氣導入管及攪拌裝置，於該反應容器放入環己酮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n-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部及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之丙烯酸樹脂溶液。冷卻至室溫後，將樹脂溶液取樣約2g，將其以180℃加熱歷經20分鐘以使其乾燥，測定未揮發成分。根據如此獲得之非揮發成分含有量，於先前合成之樹脂溶液添加丙二醇單乙基醚乙酯(PGMAC)，調製成丙烯酸樹脂溶液1。 A thermometer, a cooling tube, a nitrogen introduction tube, and a stirring device were attached to the four separate flasks, and 70.0 portions of cyclohexanone were placed in the reaction container. After the temperature was raised to 80 ° C and the reaction vessel was replaced with nitrogen, 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, and 4.3 parts of methacrylic acid were dropped by dropping the tube over 2 hours. A mixture of 7.4 parts of phenol epoxide modified acrylate ("ARONIX M110" manufactured by Toagosei Co., Ltd.) 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 an acrylic resin solution having a weight average molecular weight (Mw) of 26,000. After cooling to room temperature, the resin solution was sampled to about 2 g, and it was heated at 180 ° C for 20 minutes to be dried, and the nonvolatile component was measured. Based on the content of the nonvolatile component thus obtained, propylene glycol monoethyl ether ethyl ester (PGMAC) was added to the previously synthesized resin solution to prepare an acrylic resin solution 1.

<成鹽生成物之製造方法> <Method for Producing Salt-Forming Product>

(玫瑰紅系成鹽生成物1、1-1、1-2及1-3之生成) (Generation of rose red salt-forming products 1, 1-1, 1-2, and 1-3)

於7至15莫耳%之氫氧化鈉溶液中，添加2,8-二胺基-1-萘酚-5,7-二磺酸(分子量334)，充分攪拌該液體，藉此獲得其鈉鹽。將該2,8-二胺基-1-萘酚-5,7-二磺酸鈉鹽水溶液加熱到70至90℃後，於其逐次些許滴下玫瑰紅6GCP染料(C.I.基本紅1)。玫瑰紅6GCP染料亦可作為水溶液使用。玫瑰紅6GCP染料之滴下結束後，為了令其充分反應，以70至90℃，歷經40至60分鐘攪拌該溶液。反應的終點係於濾紙滴下反應液而已無滲液之時點。亦即，於已無滲液時，判斷獲得成鹽生成物。一面攪拌一面放冷至室溫後，進行吸取過濾，進一步予以水洗。水洗後，從殘留於濾紙上之成鹽生成物，利用乾燥機去除水分，獲得玫瑰紅6GCP染料與2,8-二胺基-1-萘酚-5,7-二磺酸之成鹽生成物，即玫瑰紅系成鹽生成物1。 2,8-diamino-1-naphthol-5,7-disulfonic acid (molecular weight 334) was added to a 7 to 15 mol% sodium hydroxide solution, and the liquid was sufficiently stirred to obtain sodium thereof. salt. After heating the aqueous solution of sodium 2,8-diamino-1-naphthol-5,7-disulfonate to 70 to 90 ° C, the rose red 6 GCP dye (C.I. Basic Red 1) was successively dropped therefrom. Rose red 6GCP dye can also be used as an aqueous solution. After the completion of the dropwise drop of the rose red 6GCP dye, the solution was stirred at 70 to 90 ° C for 40 to 60 minutes in order to allow sufficient reaction. The end point of the reaction is at the point when the filter paper drops the reaction solution without bleeding. That is, when the liquid has not been oozing, it is judged that the salt-forming product is obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt formation of rose red 6GCP dye and 2,8-diamino-1-naphthol-5,7-disulfonic acid. The substance, that is, rose red salt formation product 1.

接著，於100質量部之玫瑰紅系成鹽生成物1，添加松香改質順丁烯二酸樹脂(酸價130、重量平均分子量1000、荒川化學公司製MALKYD No.32)20質量部，以加壓捏合機予以混合。該混合係將材料溫度設定為120℃，歷經30分鐘進行。冷卻後，利用機械式粉碎機(Earthtechnica公司製KRYPTRON KTM1型)進行微粉碎，獲得平均粒徑10mm之粒子作為玫瑰紅系成鹽生成物1-1。 Then, 20 parts by mass of rosin-modified maleic acid resin (acid value 130, weight average molecular weight 1000, MALKYD No. 32 manufactured by Arakawa Chemical Co., Ltd.) was added to 100 parts by mass of rosin-based salt-forming product 1 to The pressure kneader was mixed. The mixing was carried out by setting the material temperature to 120 ° C for 30 minutes. After cooling, it was finely pulverized by a mechanical pulverizer (KRYPTRON KTM type 1 manufactured by Earthtechnica Co., Ltd.) to obtain particles having an average particle diameter of 10 mm as rosin-based salt-forming product 1-1.

又，於100質量部之玫瑰紅系成鹽生成物1，添加松香改質順丁烯二酸樹脂(酸價35、重量平均分子量3500、荒川化學公司製MALKYD No.8)20質量部，以加壓捏合機予以混合。該混合係將材料溫度設定為120℃，歷經30分鐘進行。冷卻後，利用機械式粉碎機(Earthtechnica公司製 KRYPTRON KTM1型)進行微粉碎，獲得平均粒徑10mm之粒子作為玫瑰紅系成鹽生成物1-2。 In addition, 20 parts by mass of rosin-modified maleic acid resin (acid value 35, weight average molecular weight 3,500, MALKYD No. 8 manufactured by Arakawa Chemical Co., Ltd.) was added to 100 parts by mass of rosin-based salt-forming product 1 The pressure kneader was mixed. The mixing was carried out by setting the material temperature to 120 ° C for 30 minutes. After cooling, use a mechanical pulverizer (manufactured by Earthtechnica) KRYPTRON KTM type 1) was finely pulverized to obtain particles having an average particle diameter of 10 mm as rosin-based salt-forming product 1-2.

進一步於100質量部之玫瑰紅系成鹽生成物1，添加熱塑性聚酯樹脂20質量部，以加壓捏合機予以混合。熱塑性聚酯樹脂係使用對苯二甲酸、異苯二甲酸、苯三甲酸、丙烯環氧附加雙酚A及乙二醇所構成的聚酯樹脂(酸價10mgKOH/g、OH價43mgKOH/g、重量平均分子量3500)。再者，該分子量係在與松香改質順丁烯二酸樹脂相同的條件下求出。又，該混合係將材料溫度設定為120℃，歷經30分鐘進行。冷卻後，利用機械式粉碎機(Earthtechnica公司製KRYPTRON KTM1型)進行微粉碎，獲得平均粒徑10mm之粒子作為玫瑰紅系成鹽生成物1-3。 Further, 20 parts by mass of the rose-red salt-forming product 1 was added to a mass fraction of a thermoplastic polyester resin, and the mixture was mixed by a pressure kneader. The thermoplastic polyester resin is a polyester resin composed of terephthalic acid, isophthalic acid, trimellitic acid, propylene epoxy, bisphenol A, and ethylene glycol (acid value: 10 mgKOH/g, OH price: 43 mgKOH/g, Weight average molecular weight 3,500). Further, the molecular weight was determined under the same conditions as those of the rosin-modified maleic acid resin. Further, the mixing was carried out by setting the material temperature to 120 ° C for 30 minutes. After cooling, it was finely pulverized by a mechanical pulverizer (KRYPTRON KTM type 1 manufactured by Earthtechnica Co., Ltd.) to obtain particles having an average particle diameter of 10 mm as rosin-based salt-forming products 1-3.

(玫瑰紅系成鹽生成物2及2-1之生成) (The formation of rose red salt-forming products 2 and 2-1)

於7至15莫耳%之氫氧化鈉溶液中，添加1-萘胺-3,6,8-二磺酸(分子量383)，充分攪拌該液體，藉此獲得其鈉鹽。將該1-萘胺-3,6,8-二磺酸鈉鹽水溶液加熱到70至90℃後，於其逐次些許滴下玫瑰紅6GCP染料(C.I.基本紅1)。玫瑰紅6GCP染料亦可作為水溶液使用。玫瑰紅6GCP染料之滴下結束後，為了令其充分反應，以70至90℃，歷經40至60分鐘攪拌該溶液。反應的終點係於濾紙滴下反應液而已無滲液之時點。亦即，於已無滲液時，判斷獲得成鹽生成物。一面攪拌一面放冷至室溫後，進行吸取過濾，進一步予以水洗。水洗後，從殘留於濾紙上之成鹽生成物，利用乾燥機去除水分，獲得玫瑰紅6GCP染料與1-萘胺-3,6,8-二磺酸之成鹽生成物，即玫瑰紅系成鹽生成物2。 To the sodium hydroxide solution of 7 to 15 mol%, 1-naphthylamine-3,6,8-disulfonic acid (molecular weight 383) was added, and the liquid was sufficiently stirred, thereby obtaining a sodium salt thereof. After heating the aqueous solution of sodium 1-naphthylamine-3,6,8-disulfonate to 70 to 90 ° C, the rose red 6 GCP dye (C.I. Basic Red 1) was successively dropped therefrom. Rose red 6GCP dye can also be used as an aqueous solution. After the completion of the dropwise drop of the rose red 6GCP dye, the solution was stirred at 70 to 90 ° C for 40 to 60 minutes in order to allow sufficient reaction. The end point of the reaction is at the point when the filter paper drops the reaction solution without bleeding. That is, when the liquid has not been oozing, it is judged that the salt-forming product is obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of rose red 6GCP dye and 1-naphthylamine-3,6,8-disulfonic acid, ie, rose red Salt formation product 2.

接著，於100質量部之玫瑰紅系成鹽生成物2，添加松香改 質順丁烯二酸樹脂(酸價100、重量平均分子量1600、荒川化學公司製MALKYD No.3002)20質量部，以加壓捏合機予以混合。該混合係將材料溫度設定為120℃，歷經30分鐘進行。冷卻後，利用機械式粉碎機(Earthtechnica公司製KRYPTRON KTM1型)進行微粉碎，獲得平均粒徑10mm之粒子作為玫瑰紅系成鹽生成物2-1。 Next, in the 100-mass portion of the rose red salt-forming product 2, add rosin to change A mass of maleic acid resin (acid value: 100, weight average molecular weight: 1600, MALKYD No. 3002, manufactured by Arakawa Chemical Co., Ltd.) was 20 parts by mass, and mixed by a pressure kneader. The mixing was carried out by setting the material temperature to 120 ° C for 30 minutes. After cooling, it was finely pulverized by a mechanical pulverizer (KRYPTRON KTM type 1 manufactured by Earthtechnica Co., Ltd.) to obtain particles having an average particle diameter of 10 mm as rosin-based salt-forming product 2-1.

(玫瑰紅系成鹽生成物3及3-1之生成) (The formation of rose red salt-forming products 3 and 3-1)

於7至15莫耳%之氫氧化鈉溶液中，添加蒽磺酸(分子量258)，充分攪拌該液體，藉此獲得其鈉鹽。將該蒽磺酸鈉鹽水溶液加熱到70至90℃後，於其逐次些許滴下玫瑰紅B染料(C.I.基本紫10)。玫瑰紅B染料亦可作為水溶液使用。玫瑰紅B染料之滴下結束後，為了令其充分反應，以70至90℃，歷經40至60分鐘攪拌該溶液。反應的終點係於濾紙滴下反應液而已無滲液之時點。亦即，於已無滲液時，判斷獲得成鹽生成物。一面攪拌一面放冷至室溫後，進行吸取過濾，進一步予以水洗。水洗後，從殘留於濾紙上之成鹽生成物，利用乾燥機去除水分，獲得玫瑰紅B染料與蒽磺酸之成鹽生成物，即玫瑰紅系成鹽生成物3。 To a solution of 7 to 15 mol% of sodium hydroxide, hydrazine sulfonic acid (molecular weight 258) was added, and the liquid was sufficiently stirred, thereby obtaining a sodium salt thereof. After heating the aqueous solution of the sodium sulfonate sodium salt to 70 to 90 ° C, the Rose Bengal B dye (C.I. Basic Violet 10) was successively dropped therefrom. Rose Bengal B dye can also be used as an aqueous solution. After the completion of the dropwise addition of the rose bengal B dye, the solution was stirred at 70 to 90 ° C for 40 to 60 minutes in order to allow sufficient reaction. The end point of the reaction is at the point when the filter paper drops the reaction solution without bleeding. That is, when the liquid has not been oozing, it is judged that the salt-forming product is obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the salt-forming product remaining on the filter paper was removed by a dryer to obtain a salt-forming product of rose bengal B dye and sulfonic acid, i.e., rose-red salt-forming product 3.

接著，於100質量部之玫瑰紅系成鹽生成物2，添加松香改質順丁烯二酸樹脂(酸價100、重量平均分子量1600、荒川化學公司製MALKYD No.3002)20質量部，以加壓捏合機予以混合。該混合係將材料溫度設定為120℃，歷經30分鐘進行。冷卻後，利用機械式粉碎機(Earthtechnica公司製KRYPTRON KTM1型)進行微粉碎，獲得平均粒徑10mm之粒子作為玫瑰紅系成鹽生成物3-1。 Then, 20 parts by mass of rosin-modified maleic acid resin (acid value of 100, weight average molecular weight of 1600, and MALKYD No. 3002 by Arakawa Chemical Co., Ltd.) was added to 100 parts by mass of rosin-based salt-forming product 2 to The pressure kneader was mixed. The mixing was carried out by setting the material temperature to 120 ° C for 30 minutes. After cooling, it was finely pulverized by a mechanical pulverizer (KRYPTRON KTM type 1 manufactured by Earthtechnica Co., Ltd.) to obtain particles having an average particle diameter of 10 mm as rosin-based salt-forming product 3-1.

(玫瑰紅系成鹽生成4及4-1之生成) (rose red is formed into salt 4 and 4-1)

於7至15莫耳%之氫氧化鈉溶液中，添加磷鎢酸(分子量2880)，充分攪拌該液體，藉此獲得其鈉鹽。將該磷鎢酸鈉鹽水溶液加熱到70至90℃後，於其逐次些許滴下玫瑰紅6GCP染料(C.I.基本紅1)。玫瑰紅6GCP染料亦可作為水溶液使用。玫瑰紅6GCP染料之滴下結束後，為了令其充分反應，以70至90℃，歷經40至60分鐘攪拌該溶液。反應的終點係於濾紙滴下反應液而已無滲液之時點。亦即，於已無滲液時，判斷獲得成鹽生成物。一面攪拌一面放冷至室溫後，進行吸取過濾，進一步予以水洗。水洗後，從殘留於濾紙上之成鹽生成物，利用乾燥機去除水分，獲得玫瑰紅6GCP染料與磷鎢酸之成鹽生成物，即玫瑰紅系成鹽生成物4。 To a sodium hydroxide solution of 7 to 15 mol%, phosphotungstic acid (molecular weight 2880) was added, and the liquid was sufficiently stirred, thereby obtaining a sodium salt thereof. After heating the aqueous solution of the sodium phosphotungstate to 70 to 90 ° C, the rose red 6 GCP dye (C.I. basic red 1) was successively dropped. Rose red 6GCP dye can also be used as an aqueous solution. After the completion of the dropwise drop of the rose red 6GCP dye, the solution was stirred at 70 to 90 ° C for 40 to 60 minutes in order to allow sufficient reaction. The end point of the reaction is at the point when the filter paper drops the reaction solution without bleeding. That is, when the liquid has not been oozing, it is judged that the salt-forming product is obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the salt-forming product remaining on the filter paper was removed by a dryer to obtain a salt-forming product of rose-red 6GCP dye and phosphotungstic acid, that is, rose-red salt-forming product 4.

接著，於100質量部之玫瑰紅系成鹽生成物4，添加松香改質順丁烯二酸樹脂(酸價100、重量平均分子量1600、荒川化學公司製MALKYD No.3002)20質量部，以加壓捏合機予以混合。該混合係將材料溫度設定為120℃，歷經30分鐘進行。冷卻後，利用機械式粉碎機(Earthtechnica公司製KRYPTRON KTM1型)進行微粉碎，獲得平均粒徑10mm之粒子作為玫瑰紅系成鹽生成物4-1。 Then, 20 parts by mass of rosin-modified maleic acid resin (acid value of 100, weight average molecular weight of 1600, and MALKYD No. 3002 by Arakawa Chemical Co., Ltd.) was added to 100 parts by mass of the rose-red salt-forming product 4 to The pressure kneader was mixed. The mixing was carried out by setting the material temperature to 120 ° C for 30 minutes. After cooling, it was finely pulverized by a mechanical pulverizer (KRYPTRON KTM type 1 manufactured by Earthtechnica Co., Ltd.) to obtain particles having an average particle diameter of 10 mm as rosin-based salt-forming product 4-1.

(玫瑰紅系成鹽生成物5及5-1之生成) (Formation of rose red salt-forming products 5 and 5-1)

於7至15莫耳%之氫氧化鈉溶液中，添加檸檬黃(食用黃色4號：C.I.酸性黃23)(分子量534)，充分攪拌該液體，藉此獲得其鈉鹽。將該檸檬黃鈉鹽水溶液加熱到70至90℃後，於其逐次些許滴下玫瑰紅6GCP染料(C.I.基本紅1)。玫瑰紅6GCP染料亦可作為水溶液使用。玫瑰紅6GCP染料之滴下結束後，為了令其充分反應，以70至90℃，歷經40至60分鐘攪拌該溶液。反應的終點係於濾紙滴下反應液而已無滲液之時點。亦即，於已無滲 液時，判斷獲得成鹽生成物。一面攪拌一面放冷至室溫後，進行吸取過濾，進一步予以水洗。水洗後，從殘留於濾紙上之成鹽生成物，利用乾燥機去除水分，獲得玫瑰紅6GCP染料與檸檬黃之成鹽生成物，即玫瑰紅系成鹽生成物5。 To a sodium hydroxide solution of 7 to 15 mol%, tartrazine (edible yellow No. 4: C.I. Acid Yellow 23) (molecular weight 534) was added, and the liquid was sufficiently stirred to obtain a sodium salt thereof. After heating the aqueous solution of the sodium citrate salt to 70 to 90 ° C, the rose red 6 GCP dye (C.I. Basic Red 1) was successively dropped therefrom. Rose red 6GCP dye can also be used as an aqueous solution. After the completion of the dropwise drop of the rose red 6GCP dye, the solution was stirred at 70 to 90 ° C for 40 to 60 minutes in order to allow sufficient reaction. The end point of the reaction is at the point when the filter paper drops the reaction solution without bleeding. That is, it has no seepage In the case of liquid, it was judged that a salt-forming product was obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the salt-forming product remaining on the filter paper was removed by a dryer to obtain a salt-forming product of rose red 6GCP dye and tartrazine, that is, rose-red salt-forming product 5.

接著，於100質量部之玫瑰紅系成鹽生成物5，添加松香改質順丁烯二酸樹脂(酸價100、重量平均分子量1600、荒川化學公司製MALKYD No.3002)20質量部，以加壓捏合機予以混合。該混合係將材料溫度設定為120℃，歷經30分鐘進行。冷卻後，利用機械式粉碎機(Earthtechnica公司製KRYPTRON KTM1型)進行微粉碎，獲得平均粒徑10mm之粒子作為玫瑰紅系成鹽生成物5-1。 Then, 20 parts by mass of rosin-modified maleic acid resin (acid value of 100, weight average molecular weight of 1600, and MALKYD No. 3002 by Arakawa Chemical Co., Ltd.) was added to 100 parts by mass of rose-red salt-forming product 5 The pressure kneader was mixed. The mixing was carried out by setting the material temperature to 120 ° C for 30 minutes. After cooling, it was finely pulverized by a mechanical pulverizer (KRYPTRON KTM type 1 manufactured by Earthtechnica Co., Ltd.) to obtain particles having an average particle diameter of 10 mm as rosin-based salt-forming product 5-1.

(玫瑰紅系成鹽生成物10及10-1之生成) (Formation of rose red salt-forming products 10 and 10-1)

於9莫耳%之氫氧化鈉溶液中，添加2-胺基-1-萘磺酸(吐氏酸)(分子量223)，充分攪拌該液體，藉此獲得其鈉鹽。將該2-胺基-1-萘磺酸鈉鹽水溶液加熱到85℃後，於其逐次些許滴下玫瑰紅6GCP染料(C.I.基本紅1)。玫瑰紅6GCP染料亦可作為水溶液使用。玫瑰紅6GCP染料之滴下結束後，為了令其充分反應，以85℃，歷經55分鐘攪拌該溶液。反應的終點係於濾紙滴下反應液而已無滲液之時點。亦即，於已無滲液時，判斷獲得成鹽生成物。一面攪拌一面放冷至室溫後，進行吸取過濾，進一步予以水洗。水洗後，從殘留於濾紙上之成鹽生成物，利用乾燥機去除水分，獲得玫瑰紅6GCP染料與2-胺基-1-萘磺酸(吐氏酸)之成鹽生成物，即玫瑰紅系成鹽生成物2。 2-Amino-1-naphthalenesulfonic acid (Tour acid) (molecular weight 223) was added to a 9 mol% sodium hydroxide solution, and the liquid was sufficiently stirred to obtain a sodium salt thereof. After heating the aqueous solution of the sodium 2-amino-1-naphthalenesulfonate to 85 ° C, the Rose Bengal 6 GCP dye (C.I. Basic Red 1) was successively dropped therefrom. Rose red 6GCP dye can also be used as an aqueous solution. After the dropwise addition of the rose red 6GCP dye, the solution was stirred at 85 ° C for 55 minutes in order to allow sufficient reaction. The end point of the reaction is at the point when the filter paper drops the reaction solution without bleeding. That is, when the liquid has not been oozing, it is judged that the salt-forming product is obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of Rose Bengal 6GCP dye and 2-amino-1-naphthalenesulfonic acid (Touric acid), namely rose red. It is formed into a salt product 2.

接著，於100質量部之玫瑰紅系成鹽生成物10，添加松香改 質順丁烯二酸樹脂(酸價100、重量平均分子量1600、荒川化學公司製MALKYD No.3002)20質量部，以加壓捏合機予以混合。該混合係將材料溫度設定為120℃，歷經30分鐘進行。冷卻後，利用機械式粉碎機(Earthtechnica公司製KRYPTRON KTM1型)進行微粉碎，獲得平均粒徑10mm之粒子作為玫瑰紅系成鹽生成物10-1。 Next, in the 100 parts by mass of the rose red salt-forming product 10, add rosin to change A mass of maleic acid resin (acid value: 100, weight average molecular weight: 1600, MALKYD No. 3002, manufactured by Arakawa Chemical Co., Ltd.) was 20 parts by mass, and mixed by a pressure kneader. The mixing was carried out by setting the material temperature to 120 ° C for 30 minutes. After cooling, it was finely pulverized by a mechanical pulverizer (KRYPTRON KTM type 1 manufactured by Earthtechnica Co., Ltd.) to obtain particles having an average particle diameter of 10 mm as the rosin-based salt-forming product 10-1.

(三芳基甲烷系成鹽生成物1及1-1之生成) (Formation of triaryl methane salt-forming products 1 and 1-1)

於7至15莫耳%之氫氧化鈉溶液中，添加2,8-二胺基-1-萘酚-5,7-二磺酸(分子量334)，充分攪拌該液體，藉此獲得其鈉鹽。將該2,8-二胺基-1-萘酚-5,7-二磺酸鈉鹽水溶液加熱到70至90℃後，於其逐次些許滴下維多利亞純藍染料(C.I.基本藍7)。維多利亞純藍染料亦可作為水溶液使用。維多利亞純藍染料之滴下結束後，為了令其充分反應，以70至90℃，歷經40至60分鐘攪拌該溶液。反應的終點係於濾紙滴下反應液而已無滲液之時點。亦即，於已無滲液時，判斷獲得成鹽生成物。一面攪拌一面放冷至室溫後，進行吸取過濾，進一步予以水洗。水洗後，從殘留於濾紙上之成鹽生成物，利用乾燥機去除水分，獲得維多利亞純藍染料與2,8-二胺基-1-萘酚-5,7-二磺酸之成鹽生成物，即三芳基甲烷系成鹽生成物1。 2,8-diamino-1-naphthol-5,7-disulfonic acid (molecular weight 334) was added to a 7 to 15 mol% sodium hydroxide solution, and the liquid was sufficiently stirred to obtain sodium thereof. salt. After heating the aqueous solution of sodium 2,8-diamino-1-naphthol-5,7-disulfonate to 70 to 90 ° C, a Victoria blue dye (C.I. Basic Blue 7) was successively dropped therefrom. Victoria Pure Blue Dye can also be used as an aqueous solution. After the end of the dropwise addition of the Victoria Pure Blue Dyestuff, the solution was stirred at 70 to 90 ° C for 40 to 60 minutes in order to allow it to react sufficiently. The end point of the reaction is at the point when the filter paper drops the reaction solution without bleeding. That is, when the liquid has not been oozing, it is judged that the salt-forming product is obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt formation of Victoria pure blue dye and 2,8-diamino-1-naphthol-5,7-disulfonic acid. The triarylmethane is formed into a salt product 1.

接著，於100質量部之三芳基甲烷系成鹽生成物1，添加松香改質順丁烯二酸樹脂(酸價130、重量平均分子量1000、荒川化學公司製MALKYD No.32)20質量部，以加壓捏合機予以混合。該混合係將材料溫度設定為120℃，歷經30分鐘進行。冷卻後，利用機械式粉碎機(Earthtechnica公司製KRYPTRON KTM1型)進行微粉碎，獲得平均粒徑10mm之粒子作為三芳基甲烷系成鹽生成物1-1。 Then, 20 parts by mass of the triarylmethane-based salt-forming product 1 was added, and 20 parts of rosin-modified maleic acid resin (acid value 130, weight average molecular weight 1000, MALKYD No. 32 manufactured by Arakawa Chemical Co., Ltd.) was added. It was mixed by a pressure kneader. The mixing was carried out by setting the material temperature to 120 ° C for 30 minutes. After cooling, it was finely pulverized by a mechanical pulverizer (KRYPTRON KTM type 1 manufactured by Earthtechnica Co., Ltd.) to obtain particles having an average particle diameter of 10 mm as a triarylmethane-based salt-forming product 1-1.

(三芳基甲烷系成鹽生成物2及2-1之生成) (Formation of triarylmethane salt formation products 2 and 2-1)

於7至15莫耳%之氫氧化鈉溶液中，添加1-萘胺-3,6,8-三磺酸(科赫酸)(分子量383)，充分攪拌該液體，藉此獲得其鈉鹽。將該1-萘胺-3,6,8-三磺酸(科赫酸)鈉鹽水溶液加熱到70至90℃後，於其逐次些許滴下孔雀綠染料(C.I.基本綠4)。孔雀綠染料亦可作為水溶液使用。孔雀綠染料之滴下結束後，為了令其充分反應，以70至90℃，歷經40至60分鐘攪拌該溶液。反應的終點係於濾紙滴下反應液而已無滲液之時點。亦即，於已無滲液時，判斷獲得成鹽生成物。一面攪拌一面放冷至室溫後，進行吸取過濾，進一步予以水洗。水洗後，從殘留於濾紙上之成鹽生成物，利用乾燥機去除水分，獲得孔雀綠染料與1-萘胺-3,6,8-三磺酸(科赫酸)之成鹽生成物，即三芳基甲烷系成鹽生成物2。 To 7 to 15 mol% of sodium hydroxide solution, 1-naphthylamine-3,6,8-trisulphonic acid (kohic acid) (molecular weight 383) was added, and the liquid was sufficiently stirred to obtain a sodium salt thereof. . After heating the aqueous solution of 1-naphthylamine-3,6,8-tris(sulfonic acid) sodium salt to 70 to 90 ° C, a malachite green dye (C.I. Basic Green 4) was successively dropped therefrom. Malachite green dye can also be used as an aqueous solution. After the end of the dropping of the malachite green dye, the solution was stirred at 70 to 90 ° C for 40 to 60 minutes in order to allow sufficient reaction. The end point of the reaction is at the point when the filter paper drops the reaction solution without bleeding. That is, when the liquid has not been oozing, it is judged that the salt-forming product is obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of the malachite green dye and 1-naphthylamine-3,6,8-trisulphonic acid (kohic acid). That is, the triarylmethane is a salt-forming product 2.

接著，於100質量部之三芳基甲烷系成鹽生成物2，添加松香改質順丁烯二酸樹脂(酸價200、重量平均分子量750、荒川化學公司製MALKYD No.31)20質量部，以加壓捏合機予以混合。該混合係將材料溫度設定為120℃，歷經30分鐘進行。冷卻後，利用機械式粉碎機(Earthtechnica公司製KRYPTRON KTM1型)進行微粉碎，獲得平均粒徑10mm之粒子作為三芳基甲烷系成鹽生成物2-1。 Then, 20 parts by mass of the triarylmethane-based salt-forming product 2 was added to the rosin-modified maleic acid resin (acid value 200, weight average molecular weight 750, MALKYD No. 31 manufactured by Arakawa Chemical Co., Ltd.). It was mixed by a pressure kneader. The mixing was carried out by setting the material temperature to 120 ° C for 30 minutes. After cooling, it was finely pulverized by a mechanical pulverizer (KRYPTRON KTM type 1 manufactured by Earthtechnica Co., Ltd.) to obtain particles having an average particle diameter of 10 mm as a triarylmethane-based salt-forming product 2-1.

(三芳基甲烷系成鹽生成物10及10-1之生成) (Production of triarylmethane-based salt-forming products 10 and 10-1)

於9莫耳%之氫氧化鈉溶液中，添加2-胺基-1-萘磺酸(吐氏酸)(分子量334)，充分攪拌該液體，藉此獲得其鈉鹽。將該2-胺基-1-萘磺酸(吐氏酸)鈉鹽水溶液加熱到85℃後，於其逐次些許滴下維多利亞純藍染料(C.I.基本藍7)。維多利亞純藍染料亦可作為水溶液使用。維多利亞純藍染料 之滴下結束後，為了令其充分反應，以85℃，歷經55分鐘攪拌該溶液。反應的終點係於濾紙滴下反應液而已無滲液之時點。亦即，於已無滲液時，判斷獲得成鹽生成物。一面攪拌一面放冷至室溫後，進行吸取過濾，進一步予以水洗。水洗後，從殘留於濾紙上之成鹽生成物，利用乾燥機去除水分，獲得維多利亞純藍染料與2-胺基-1-萘磺酸(吐氏酸)之成鹽生成物，即三芳基甲烷系成鹽生成物10。 2-Amino-1-naphthalenesulfonic acid (Tour acid) (molecular weight 334) was added to a 9 mol% sodium hydroxide solution, and the liquid was sufficiently stirred to obtain a sodium salt thereof. After heating the aqueous solution of the 2-amino-1-naphthalenesulfonic acid (Thronic acid) sodium salt to 85 ° C, the Victoria Pure Blue dye (C.I. Basic Blue 7) was successively dropped therefrom. Victoria Pure Blue Dye can also be used as an aqueous solution. Victoria Pure Blue Dye After the completion of the dropwise addition, the solution was stirred at 85 ° C for 55 minutes in order to allow sufficient reaction. The end point of the reaction is at the point when the filter paper drops the reaction solution without bleeding. That is, when the liquid has not been oozing, it is judged that the salt-forming product is obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of a Victoria pure blue dye and 2-amino-1-naphthalenesulfonic acid (Touric acid), that is, a triaryl group. Methane is a salt-forming product 10.

接著，於100質量部之三芳基甲烷系成鹽生成物10，添加松香改質順丁烯二酸樹脂(酸價200、重量平均分子量750、荒川化學公司製MALKYD No.31)20質量部，以加壓捏合機予以混合。該混合係將材料溫度設定為120℃，歷經30分鐘進行。冷卻後，利用機械式粉碎機(Earthtechnica公司製KRYPTRON KTM1型)進行微粉碎，獲得平均粒徑10mm之粒子作為三芳基甲烷系成鹽生成物10-1。 Then, 20 parts by mass of the triarylmethane-based salt-forming product 10 was added, and 20 parts of rosin-modified maleic acid resin (acid value 200, weight average molecular weight 750, MALKYD No. 31 manufactured by Arakawa Chemical Co., Ltd.) was added. It was mixed by a pressure kneader. The mixing was carried out by setting the material temperature to 120 ° C for 30 minutes. After cooling, it was finely pulverized by a mechanical pulverizer (KRYPTRON KTM type 1 manufactured by Earthtechnica Co., Ltd.) to obtain particles having an average particle diameter of 10 mm as a triarylmethane-based salt-forming product 10-1.

(三芳基甲烷系成鹽生成物11及11-1之生成) (Formation of triarylmethane-based salt-forming products 11 and 11-1)

於9莫耳%之氫氧化鈉溶液中，添加1-胺基-5-萘磺酸(羅倫茲酸、分子量223)(分子量223)，充分攪拌該液體，藉此獲得其鈉鹽。將該1-胺基-5-萘磺酸(羅倫茲酸、分子量223)鈉鹽水溶液加熱到85℃後，於其逐次些許滴下維多利亞純藍染料(C.I.基本藍7)。維多利亞純藍染料亦可作為水溶液使用。維多利亞純藍染料之滴下結束後，為了令其充分反應，以85℃，歷經55分鐘攪拌該溶液。反應的終點係於濾紙滴下反應液而已無滲液之時點。亦即，於已無滲液時，判斷獲得成鹽生成物。一面攪拌一面放冷至室溫後，進行吸取過濾，進一步予以水洗。水洗後，從殘留於濾紙上之成鹽生成物，利用乾燥機去除水分，獲得維多利亞純藍染料與1-胺基-5-萘磺酸(羅 倫茲酸、分子量223)之成鹽生成物，即三芳基甲烷系成鹽生成物11。 To the 9 mol% sodium hydroxide solution, 1-amino-5-naphthalenesulfonic acid (Lorentz acid, molecular weight 223) (molecular weight 223) was added, and the liquid was sufficiently stirred to obtain a sodium salt thereof. After heating the aqueous solution of 1-amino-5-naphthalenesulfonic acid (Lorentz acid, molecular weight 223) sodium salt to 85 ° C, a Victoria blue dye (C.I. Basic Blue 7) was successively dropped therefrom. Victoria Pure Blue Dye can also be used as an aqueous solution. After the end of the Victoria Pure Blue Dye, the solution was stirred at 85 ° C for 55 minutes in order to allow it to react adequately. The end point of the reaction is at the point when the filter paper drops the reaction solution without bleeding. That is, when the liquid has not been oozing, it is judged that the salt-forming product is obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain Victoria Pure Blue Dye and 1-Amino-5-naphthalenesulfonic acid (Ro) A salt formation product of lenz acid and a molecular weight of 223), that is, a triarylmethane-based salt-forming product 11.

接著，於100質量部之三芳基甲烷系成鹽生成物11，添加松香改質順丁烯二酸樹脂(酸價200、重量平均分子量750、荒川化學公司製MALKYD No.31)20質量部，以加壓捏合機予以混合。該混合係將材料溫度設定為120℃，歷經30分鐘進行。冷卻後，利用機械式粉碎機(Earthtechnica公司製KRYPTRON KTM1型)進行微粉碎，獲得平均粒徑10mm之粒子作為三芳基甲烷系成鹽生成物11-1。 Then, 20 parts by mass of the triarylmethane-based salt-forming product 11 was added, and 20 parts of rosin-modified maleic acid resin (acid value 200, weight average molecular weight 750, MALKYD No. 31 manufactured by Arakawa Chemical Co., Ltd.) was added. It was mixed by a pressure kneader. The mixing was carried out by setting the material temperature to 120 ° C for 30 minutes. After cooling, it was finely pulverized by a mechanical pulverizer (KRYPTRON KTM type 1 manufactured by Earthtechnica Co., Ltd.) to obtain particles having an average particle diameter of 10 mm as a triarylmethane-based salt-forming product 11-1.

(三芳基甲烷系成鹽生成物12及12-1之生成) (Formation of triarylmethane-forming salt products 12 and 12-1)

於9莫耳%之氫氧化鈉溶液中，添加1-羥基-4-萘磺酸(NW酸)(分子量224)，充分攪拌該液體，藉此獲得其鈉鹽。將該1-羥基-4-萘磺酸(NW酸)鈉鹽水溶液加熱到85℃後，於其逐次些許滴下維多利亞純藍染料(C.I.基本藍7)。維多利亞純藍染料亦可作為水溶液使用。維多利亞純藍染料之滴下結束後，為了令其充分反應，以85℃，歷經55分鐘攪拌該溶液。反應的終點係於濾紙滴下反應液而已無滲液之時點。亦即，於已無滲液時，判斷獲得成鹽生成物。一面攪拌一面放冷至室溫後，進行吸取過濾，進一步予以水洗。水洗後，從殘留於濾紙上之成鹽生成物，利用乾燥機去除水分，獲得維多利亞純藍染料與1-羥基-4-萘磺酸(NW酸)之成鹽生成物，即三芳基甲烷系成鹽生成物12。 To a 9 mol% sodium hydroxide solution, 1-hydroxy-4-naphthalenesulfonic acid (NW acid) (molecular weight 224) was added, and the liquid was sufficiently stirred to obtain a sodium salt thereof. After heating the aqueous solution of 1-hydroxy-4-naphthalenesulfonic acid (NW acid) sodium salt to 85 ° C, the Victoria Pure Blue dye (C.I. Basic Blue 7) was successively dripped. Victoria Pure Blue Dye can also be used as an aqueous solution. After the end of the Victoria Pure Blue Dye, the solution was stirred at 85 ° C for 55 minutes in order to allow it to react adequately. The end point of the reaction is at the point when the filter paper drops the reaction solution without bleeding. That is, when the liquid has not been oozing, it is judged that the salt-forming product is obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of Victoria pure blue dye and 1-hydroxy-4-naphthalenesulfonic acid (NW acid), that is, a triarylmethane system. Salt formation product 12.

接著，於100質量部之三芳基甲烷系成鹽生成物12，添加松香改質順丁烯二酸樹脂(酸價200、重量平均分子量750、荒川化學公司製MALKYD No.31)20質量部，以加壓捏合機予以混合。該混合係將材料溫度設定為120℃，歷經30分鐘進行。冷卻後，利用機械式粉碎機(Earthtechnica 公司製KRYPTRON KTM1型)進行微粉碎，獲得平均粒徑10mm之粒子作 三芳基甲烷系成鹽生成物12-1。 Then, 20 parts by mass of the triarylmethane-based salt-forming product 12 was added to the rosin-modified maleic acid resin (acid value 200, weight average molecular weight 750, MALKYD No. 31 manufactured by Arakawa Chemical Co., Ltd.). It was mixed by a pressure kneader. The mixing was carried out by setting the material temperature to 120 ° C for 30 minutes. After cooling, use a mechanical pulverizer (Earthtechnica The company's KRYPTRON KTM1 type) is micro-pulverized to obtain particles with an average particle size of 10 mm. The triarylmethane is a salt-forming product 12-1.

(黃素系成鹽生成物1及1-1之生成) (Formation of flavin-forming salt formation products 1 and 1-1)

於7至15莫耳%之氫氧化鈉溶液中，添加蒽磺酸(分子量258)，充分攪拌該液體，藉此獲得其鈉鹽。將該蒽磺酸鈉鹽水溶液加熱到70至90℃後，於其逐次些許滴下黃素染料(C.I.基本黃1)。黃素染料亦可作為水溶液使用。維多利亞純藍染料之滴下結束後，為了令其充分反應，以70至90℃，歷經40至60分鐘攪拌該溶液。反應的終點係於濾紙滴下反應液而已無滲液之時點。亦即，於已無滲液時，判斷獲得成鹽生成物。一面攪拌一面放冷至室溫後，進行吸取過濾，進一步予以水洗。水洗後，從殘留於濾紙上之成鹽生成物，利用乾燥機去除水分，獲得黃素染料與蒽磺酸之成鹽生成物，即黃素系成鹽生成物1。 To a solution of 7 to 15 mol% of sodium hydroxide, hydrazine sulfonic acid (molecular weight 258) was added, and the liquid was sufficiently stirred, thereby obtaining a sodium salt thereof. After heating the aqueous sodium sulfonate solution to 70 to 90 ° C, the flavin dye (C.I. Basic Yellow 1) was successively dripped. The flavin dye can also be used as an aqueous solution. After the end of the dropwise addition of the Victoria Pure Blue Dyestuff, the solution was stirred at 70 to 90 ° C for 40 to 60 minutes in order to allow it to react sufficiently. The end point of the reaction is at the point when the filter paper drops the reaction solution without bleeding. That is, when the liquid has not been oozing, it is judged that the salt-forming product is obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of a flavin dye and an oxime sulfonic acid, that is, a flavin-forming salt-forming product 1.

接著，於100質量部之黃素系成鹽生成物1，添加松香改質順丁烯二酸樹脂(酸價300、重量平均分子量450、荒川化學公司製MALKYD No.33)20質量部，以加壓捏合機予以混合。該混合係將材料溫度設定為120℃，歷經30分鐘進行。冷卻後，利用機械式粉碎機(Earthtechnica公司製KRYPTRON KTM1型)進行微粉碎，獲得平均粒徑10mm之粒子作為黃素系成鹽生成物1-1。 Then, 20 parts by mass of rosin-modified maleic acid resin (acid value 300, weight average molecular weight 450, MALKYD No. 33 manufactured by Arakawa Chemical Co., Ltd.) was added to 100 parts by mass of flavonoid salt-forming product 1 to The pressure kneader was mixed. The mixing was carried out by setting the material temperature to 120 ° C for 30 minutes. After cooling, it was finely pulverized by a mechanical pulverizer (KRYPTRON KTM type 1 manufactured by Earthtechnica Co., Ltd.) to obtain particles having an average particle diameter of 10 mm as the flavin-based salt-forming product 1-1.

(亞甲藍系成鹽生成物1及1-1之生成) (Formation of methylene blue salt-forming products 1 and 1-1)

於7至15莫耳%之氫氧化鈉溶液中，添加2,8-二胺基-1-萘酚-5,7-二磺酸(分子量334)，充分攪拌該液體，藉此獲得其鈉鹽。將該2,8-二胺基-1-萘酚-5,7-二磺酸鈉鹽水溶液加熱到70至90℃後，於其逐次些許滴下亞 甲藍FZ染料(C.I.基本藍9)。亞甲藍FZ染料亦可作為水溶液使用。亞甲藍FZ染料之滴下結束後，為了令其充分反應，以70至90℃，歷經40至60分鐘攪拌該溶液。反應的終點係於濾紙滴下反應液而已無滲液之時點。亦即，於已無滲液時，判斷獲得成鹽生成物。一面攪拌一面放冷至室溫後，進行吸取過濾，進一步予以水洗。水洗後，從殘留於濾紙上之成鹽生成物，利用乾燥機去除水分，獲得亞甲藍FZ染料與2,8-二胺基-1-萘酚-5,7-二磺酸之成鹽生成物，即亞甲藍系成鹽生成物1。 2,8-diamino-1-naphthol-5,7-disulfonic acid (molecular weight 334) was added to a 7 to 15 mol% sodium hydroxide solution, and the liquid was sufficiently stirred to obtain sodium thereof. salt. The aqueous solution of 2,8-diamino-1-naphthol-5,7-disulfonic acid sodium salt is heated to 70 to 90 ° C, and then it is sub-dropped. Blue-blue FZ dye (C.I. Basic Blue 9). Methylene blue FZ dye can also be used as an aqueous solution. After the completion of the dropwise addition of the methylene blue FZ dye, the solution was stirred at 70 to 90 ° C for 40 to 60 minutes in order to allow sufficient reaction. The end point of the reaction is at the point when the filter paper drops the reaction solution without bleeding. That is, when the liquid has not been oozing, it is judged that the salt-forming product is obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt of methylene blue FZ dye and 2,8-diamino-1-naphthol-5,7-disulfonic acid. The product, that is, the methylene blue salt-forming product 1.

於100質量部之亞甲藍系成鹽生成物1，添加松香改質順丁烯二酸樹脂(酸價130、重量平均分子量1000、荒川化學公司製MALKYD No.32)20質量部，以加壓捏合機予以混合。該混合係將材料溫度設定為120℃，歷經30分鐘進行。冷卻後，利用機械式粉碎機(Earthtechnica公司製KRYPTRON KTM1型)進行微粉碎，獲得平均粒徑10mm之粒子作為亞甲藍系成鹽生成物1-1。 In the methylene blue salt-forming product 1 of 100 parts by mass, 20 mass parts of rosin-modified maleic acid resin (acid value 130, weight average molecular weight 1000, MALKYD No. 32 manufactured by Arakawa Chemical Co., Ltd.) was added to add The kneading machine is mixed. The mixing was carried out by setting the material temperature to 120 ° C for 30 minutes. After cooling, it was finely pulverized by a mechanical pulverizer (KRYPTRON KTM type 1 manufactured by Earthtechnica Co., Ltd.) to obtain particles having an average particle diameter of 10 mm as the methylene blue-based salt-forming product 1-1.

(玫瑰紅系成鹽生成物5及5-1之生成) (Formation of rose red salt-forming products 5 and 5-1)

於7至15莫耳%之氫氧化鈉溶液中，添加檸檬黃(食用黃色4號：C.I.酸性黃23)(分子量534)，充分攪拌該液體，藉此獲得其鈉鹽。將該檸檬黃鈉鹽水溶液加熱到70至90℃後，於其逐次些許滴下玫瑰紅6GCP染料(C.I.基本紅1)。玫瑰紅6GCP染料亦可作為水溶液使用。玫瑰紅6GCP染料之滴下結束後，為了令其充分反應，以70至90℃，歷經40至60分鐘攪拌該溶液。反應的終點係於濾紙滴下反應液而已無滲液之時點。亦即，於已無滲液時，判斷獲得成鹽生成物。一面攪拌一面放冷至室溫後，進行吸取過濾，進一步予以水洗。水洗後，從殘留於濾紙上之成鹽生成物，利用乾燥機去 除水分，獲得玫瑰紅6GCP染料與檸檬黃之成鹽生成物，即玫瑰紅系成鹽生成物5。 To a sodium hydroxide solution of 7 to 15 mol%, tartrazine (edible yellow No. 4: C.I. Acid Yellow 23) (molecular weight 534) was added, and the liquid was sufficiently stirred to obtain a sodium salt thereof. After heating the aqueous solution of the sodium citrate salt to 70 to 90 ° C, the rose red 6 GCP dye (C.I. Basic Red 1) was successively dropped therefrom. Rose red 6GCP dye can also be used as an aqueous solution. After the completion of the dropwise drop of the rose red 6GCP dye, the solution was stirred at 70 to 90 ° C for 40 to 60 minutes in order to allow sufficient reaction. The end point of the reaction is at the point when the filter paper drops the reaction solution without bleeding. That is, when the liquid has not been oozing, it is judged that the salt-forming product is obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the salt-forming product remaining on the filter paper is dried by a dryer. In addition to moisture, a salt-forming product of Rose Bengal 6GCP dye and tartrazine is obtained, that is, rose-red salt-forming product 5.

接著，於100質量部之玫瑰紅系成鹽生成物5，添加松香改質順丁烯二酸樹脂(酸價100、重量平均分子量1600、荒川化學公司製MALKYD No.3002)20質量部，以加壓捏合機予以混合。該混合係將材料溫度設定為120℃，歷經30分鐘進行。冷卻後，利用機械式粉碎機(Earthtechnica公司製KRYPTRON KTM1型)進行微粉碎，獲得平均粒徑10mm之粒子作為玫瑰紅系成鹽生成物5-1。 Then, 20 parts by mass of rosin-modified maleic acid resin (acid value of 100, weight average molecular weight of 1600, and MALKYD No. 3002 by Arakawa Chemical Co., Ltd.) was added to 100 parts by mass of rose-red salt-forming product 5 The pressure kneader was mixed. The mixing was carried out by setting the material temperature to 120 ° C for 30 minutes. After cooling, it was finely pulverized by a mechanical pulverizer (KRYPTRON KTM type 1 manufactured by Earthtechnica Co., Ltd.) to obtain particles having an average particle diameter of 10 mm as rosin-based salt-forming product 5-1.

(玫瑰紅系成鹽生成物6及6-1之生成) (The formation of rose red salt-forming products 6 and 6-1)

於7至15莫耳%之氫氧化鈉溶液中，添加3-羥基-2-萘酸(分子量177)，充分攪拌該液體，藉此獲得其鈉鹽。將該3-羥基-2-萘酸鈉鹽水溶液加熱到70至90℃後，於其逐次些許滴下玫瑰紅6GCP染料(C.I.基本紅1)。玫瑰紅6GCP染料亦可作為水溶液使用。玫瑰紅6GCP染料之滴下結束後，為了令其充分反應，以70至90℃，歷經40至60分鐘攪拌該溶液。反應的終點係於濾紙滴下反應液而已無滲液之時點。亦即，於已無滲液時，判斷獲得成鹽生成物。一面攪拌一面放冷至室溫後，進行吸取過濾，進一步予以水洗。水洗後，從殘留於濾紙上之成鹽生成物，利用乾燥機去除水分，獲得玫瑰紅6GCP染料與3-羥基-2-萘酸之成鹽生成物，即玫瑰紅系成鹽生成物6。接著，於100質量部之玫瑰紅系成鹽生成物6，添加松香改質順丁烯二酸樹脂(酸價130、重量平均分子量1000、荒川化學公司製MALKYD No.32)20質量部，以加壓捏合機予以混合。該混合係將材料溫度設定為120℃，歷經30分鐘進行。冷卻後，利用機械式粉碎機(Earthtechnica公司製KRYPTRON KTM1型)進行微粉碎，獲得平均粒徑10mm之粒子作為玫瑰紅系成鹽生成物6-1。 To the sodium hydroxide solution of 7 to 15 mol%, 3-hydroxy-2-naphthoic acid (molecular weight 177) was added, and the liquid was sufficiently stirred, thereby obtaining a sodium salt thereof. After heating the aqueous solution of sodium 3-hydroxy-2-naphthalate to 70 to 90 ° C, the rose red 6 GCP dye (C.I. Basic Red 1) was successively dropped therefrom. Rose red 6GCP dye can also be used as an aqueous solution. After the completion of the dropwise drop of the rose red 6GCP dye, the solution was stirred at 70 to 90 ° C for 40 to 60 minutes in order to allow sufficient reaction. The end point of the reaction is at the point when the filter paper drops the reaction solution without bleeding. That is, when the liquid has not been oozing, it is judged that the salt-forming product is obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the salt-forming product remaining on the filter paper was removed by a dryer to obtain a salt-forming product of rose red 6GCP dye and 3-hydroxy-2-naphthoic acid, that is, rose-red salt-forming product 6. Then, 20 parts by mass of rosin-modified maleic acid resin (acid value 130, weight average molecular weight 1000, MALKYD No. 32 manufactured by Arakawa Chemical Co., Ltd.) was added to 100 parts by mass of rosin-based salt-forming product 6 to The pressure kneader was mixed. The mixing was carried out by setting the material temperature to 120 ° C for 30 minutes. After cooling, use a mechanical pulverizer (KRYPTRON, manufactured by Earthtechnica) KTM1 type) was finely pulverized to obtain particles having an average particle diameter of 10 mm as rosin-based salt-forming product 6-1.

<玫瑰紅系化合物之製造> <Manufacture of rose red compound>

(玫瑰紅系化合物1-1之生成) (production of rose red compound 1-1)

於玫瑰紅6GCP染料(C.I.基本紅1)100質量部，添加松香改質順丁烯二酸樹脂(酸價35、重量平均分子量3600、荒川化學公司製MALKYD No.8)50質量部，以加壓捏合機予以混合。該混合係將材料溫度設定為120℃，歷經45分鐘進行。冷卻後，利用機械式粉碎機(Earthtechnica公司製KRYPTRON KTM1型)進行微粉碎，獲得平均粒徑10mm之粒子作為玫瑰紅系化合物1-1。 Adding 50 parts of rosin-modified maleic acid resin (acid price 35, weight average molecular weight 3600, MALKYD No. 8 manufactured by Arakawa Chemical Co., Ltd.) to 100 parts of rose red 6GCP dye (CI basic red 1) The kneading machine is mixed. The mixing was carried out by setting the material temperature to 120 ° C for 45 minutes. After cooling, it was finely pulverized by a mechanical pulverizer (KRYPTRON KTM type 1 manufactured by Earthtechnica Co., Ltd.) to obtain particles having an average particle diameter of 10 mm as rose erythroid compound 1-1.

<微細化顏料之製造方法> <Method for Producing Micronized Pigment>

(紅色微細顏料1之生成) (production of red fine pigment 1)

將二酮吡咯並吡咯系紅色顏料之C.I.Pigment Red 254(日本千葉公司製「IRGAZIN RED 2030」、相對表面積65m²/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℃歷經6小時予以混合攪拌。接著，將該混合攪拌物放入8公升的溫水中，一面加熱至80℃，一面歷經2小時予以攪拌而製成漿狀。重複過濾及水洗以去除氯化鈉及二乙二醇後，以85℃乾燥一晝夜，獲得190部的紅色微細顏料1。紅色微細顏料1之相對表面積為80m²/g。 CIPigment Red 254 (IRGAZIN RED 2030, manufactured by Chiba Corporation, Japan, relative surface area 65 m ² /g), 200 parts of sodium chloride, 1400 parts of diamethylene glycol, and 360 parts of diethylene glycol were placed in stainless steel. A 1 gallon kneader (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, and heated to 80 ° C, and stirred for 2 hours to prepare a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 85 ° C for one day and night to obtain 190 red fine pigments 1. The red fine pigment 1 has a relative surface area of 80 m ² /g.

(綠色微細顏料1之生成) (production of green fine pigment 1)

將酞菁系綠色顏料之C.I.Pigment Green 36(東洋墨水製造股份有限公司製「Lionol Green 6YK」、相對表面積60m²/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℃歷經6小時予以混合攪拌。接著，將該混合攪拌物放入8公升的溫水中，一面加熱至80℃，一面歷經2小時予以攪拌而製成漿狀。重複過濾及水洗以去除氯化鈉及二乙二醇後，以85℃乾燥一晝夜，獲得190部的綠色微細顏料1。綠色微細顏料1之相對表面積為75m²/g。 CIPigment Green 36 ("Leonol Green 6YK" manufactured by Toyo Ink Co., Ltd., relative surface area 60 m ² /g), 200 parts of sodium chloride, 1400 parts of diamethylene glycol, and 360 parts of diethylene glycol were placed in stainless steel. A 1 gallon kneader (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, and heated to 80 ° C, and stirred for 2 hours to prepare a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 85 ° C for one day and night to obtain 190 green fine pigments 1. The green fine pigment 1 has a relative surface area of 75 m ² /g.

(黃色微細顏料1之生成) (production of yellow fine pigment 1)

將鎳錯合物系黃色顏料之C.I.Pigment Yellow 150(LANXESS公司「E-4GN」、相對表面積100m²/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℃歷經6小時予以混合攪拌。接著，將該混合攪拌物放入8公升的溫水中，一面加熱至80℃，一面歷經2小時予以攪拌而製成漿狀。重複過濾及水洗以去除氯化鈉及二乙二醇後，以85℃乾燥一晝夜，獲得190部的黃色微細顏料1。黃色微細顏料1之相對表面積為130m²/g。 200 parts of CIPigment Yellow 150 (LANXESS "E-4GN", relative surface area 100 m ² /g), 1400 parts of sodium chloride and 360 parts of diethylene glycol of nickel complex yellow pigment were placed in a 1 gallon kneading process made of stainless steel. The machine (manufactured by Inoue Works Co., Ltd.) was mixed and stirred at 80 ° C for 6 hours. Next, the kneaded material was placed in 8 liters of warm water, and heated to 80 ° C, and stirred for 2 hours to prepare a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 85 ° C for one day and night to obtain 190 yellow fine pigments 1. The yellow fine pigment 1 has a relative surface area of 130 m ² /g.

(藍色微細顏料1之生成) (production of blue fine pigment 1)

將酞菁系藍色顏料之C.I.Pigment Blue 15：6(東洋墨水製造公司製「Lionol Blue ES」、相對表面積60m²/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℃歷經6小時予以混合攪拌。接著，將該混合攪拌物放入8公升的溫水中，一面加熱至80℃，一面歷經2小時予以攪拌而製成漿狀。重複過濾及水洗以去除氯化鈉及二乙二醇後，以85℃乾燥一晝夜，獲得190部的藍色微細顏料1。藍色微細顏料1之相對表面積為80m²/g。 CIPigment Blue 15:6 ("Lionol Blue ES" manufactured by Toyo Ink Co., Ltd., relative surface area 60 m ² /g), 200 parts of sodium chloride, 1400 parts of diamethylene glycol, and 360 parts of diethylene glycol were placed in stainless steel. A one-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) was prepared and mixed and stirred at 80 ° C for 6 hours. Next, the kneaded material was placed in 8 liters of warm water, and heated to 80 ° C, and stirred for 2 hours to prepare a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 85 ° C for one day and night to obtain 190 blue fine pigments 1. The relative surface area of the blue fine pigment 1 was 80 m ² /g.

(紫色微細顏料1之生成) (production of purple fine pigment 1)

將二噁嗪系紫色色顏料之C.I.Pigment Violet 23(東洋墨水製造公司製「LIONOGEN VIOLET RL」、相對表面積75m²/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℃歷經6小時予以混合攪拌。接著，將該混合攪拌物放入8公升的溫水中，一面加熱至80℃，一面歷經2小時予以攪拌而製成漿狀。重複過濾及水洗以去除氯化鈉及二乙二醇後，以85℃乾燥一晝夜，獲得190部的紫色微細顏料1。紫色微細顏料1之相對表面積為95m²/g。 CIPigment Violet 23 ("LIONOGEN VIOLET RL" manufactured by Toyo Ink Co., Ltd., relative surface area: 75 m ² /g), 200 parts of sodium chloride, 1400 parts of diamethylene glycol, and 360 parts of diethylene glycol were placed in stainless steel. A 1 gallon kneader (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, and heated to 80 ° C, and stirred for 2 hours to prepare a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 85 ° C for one day and night to obtain 190 purple fine pigments 1. The purple fine pigment 1 has a relative surface area of 95 m ² /g.

[實施例1至16及比較例1至7] [Examples 1 to 16 and Comparative Examples 1 to 7]

(實施例1：彩色濾光片用著色組成物(D-1)) (Example 1: Coloring composition (D-1) for color filter)

將下述混合物攪拌均勻後，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」)，歷經5小時進行分散處理後，以5.0mm的過濾器過濾分散液，獲得彩色濾光片用著色組成物(D-1)。 After the following mixture was stirred uniformly, a zirconia bead having a diameter of 0.5 mm was used, and an IGER mill ("Mini Model M-250 MKII" manufactured by Iger Japan Co., Ltd.) was subjected to dispersion treatment for 5 hours, and then filtered at 5.0 mm. The dispersion was filtered to obtain a colored composition (D-1) for a color filter.

玫瑰紅系成鹽生成物1：11.0部 Rose red salt formation product 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)：48.0部 Propylene glycol monoethyl ether ethyl ester (PGMAC): 48.0

樹脂型分散劑(EFKA4300)：1.0部 Resin type dispersant (EFKA4300): 1.0

(實施例2至16及比較例1至7：彩色濾光片用著色組成物(D-2)至(D-23)) (Examples 2 to 16 and Comparative Examples 1 to 7: Coloring Compositions (D-2) to (D-23) for Color Filters)

除了以表1所示之著色劑置換玫瑰紅系成鹽生成物1以外，其他均與實施例1之著色組成物(D-1)同樣地調製著色組成物(D-2)至(D-23)。 The coloring compositions (D-2) to (D-) were prepared in the same manner as in the coloring composition (D-1) of Example 1, except that the rose erythroid salt-forming product 1 was replaced with the coloring agent shown in Table 1. twenty three).

表1 Table 1

[著色組成物之評估] [Evaluation of coloring composition]

採下述方法進行著色組成物(D-1)至(D-23)之色彩特性評估及耐熱性試驗。 The color characteristics evaluation and heat resistance test of the coloring compositions (D-1) to (D-23) were carried out by the following methods.

(色彩特性及耐熱性之評估方法) (Methods for evaluating color characteristics and heat resistance)

於玻璃基板上，於C光源下，將著色組成物(D-1)至(D-23)之各個塗布呈現表2所示之色相，以230℃歷經20分鐘加熱基板。其後，利用顯微分光光度計(Olympus光學公司製「OSP-SP200」)測定如此形成著色層之基板之亮度Y。 On the glass substrate, each of the colored compositions (D-1) to (D-23) was coated with a hue shown in Table 2 under a C light source, and the substrate was heated at 230 ° C for 20 minutes. Thereafter, the luminance Y of the substrate on which the colored layer was formed was measured by a microscopic spectrophotometer ("OSP-SP200" manufactured by Olympus Optics Co., Ltd.).

表2 Table 2

又，針對形成於著色層之上述基板，利用顯微分光光度計(Olympus光學公司製「OSP-SP200」)測定於C光源下之色差1(L*(1)、a*(1)、b*(1))。其後，將已形成著色層之上述基板，供作於烤箱內、以250℃歷經1小時加熱之耐熱試驗，進一步測定於C光源下之色差2(L*(2)、a*(2)、b*(2))。 Further, the color difference 1 (L*(1), a*(1), b) measured under a C light source was measured by a microscopic spectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.) on the substrate formed on the colored layer. *(1)). Thereafter, the substrate on which the colored layer has been formed is subjected to a heat resistance test in an oven at 250 ° C for 1 hour, and the color difference 2 under the C light source is further measured (L*(2), a*(2) , b*(2)).

利用該等色差值，藉由下述計算式算出色差變化率△Eab*。然後，根據該色差變化率△Eab*，採下述4階段評估塗膜之耐熱性。 Using the color difference values, the color difference change rate ΔEab* is calculated by the following calculation formula. Then, based on the color change rate ΔEab*, the heat resistance of the coating film was evaluated in the following four stages.

◎：△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3表示色彩特性及耐熱性之評估結果。 Table 3 shows the evaluation results of color characteristics and heat resistance.

(色彩特性及耐熱性之評估結果) (Evaluation results of color characteristics and heat resistance)

使用含成鹽生成物作為著色劑之著色組成物(D-1)至(D-12)及著色組成物(D-20)至(D-23)時，與使用僅含顏料作為著色劑之著色組成物(D-15)至(D-19)時相比較，可獲得較高亮度Y。比較例2之著色組成物(D-14)係由於使用未與相對化合物(陰離子成分)成鹽之著色劑，因此呈色弱，不具著色力，故結果其亮度低。 When the coloring compositions (D-1) to (D-12) and the coloring compositions (D-20) to (D-23) containing the salt-forming product as a coloring agent are used, and only the pigment is used as the coloring agent. A higher luminance Y can be obtained by comparing the coloring compositions (D-15) to (D-19). In the coloring composition (D-14) of Comparative Example 2, since a coloring agent which does not form a salt with a relative compound (anionic component) is used, the color is weak and does not have a coloring power, so that the brightness is low.

又，針對耐熱性而言，使用含成鹽生成物作為著色劑之著色組成物(D-1)至(D-12)及著色組成物(D-20)至(D-23)時，可獲得良好結果。若與使用含玫瑰紅系成鹽生成物1之著色組成物(D-1)至(D-4)時所獲得的結果相比較，使用酸價在100至300mgKOH/mg範圍內之松香改質順丁烯二酸 樹脂時，可達成與其他情況大致同等的亮度，可達成較良好的耐熱性。從上述結果可知，含特性成鹽生成物之著色組成物係於色彩特性及耐熱性兩方面，發揮良好的性能。 Moreover, when the coloring compositions (D-1) to (D-12) and the coloring compositions (D-20) to (D-23) containing a salt-forming product as a coloring agent are used, the heat resistance can be used. Get good results. When compared with the results obtained when using the coloring compositions (D-1) to (D-4) containing the rose-red salt-forming product 1, rosin-modified with an acid value in the range of 100 to 300 mgKOH/mg is used. Maleic acid In the case of a resin, brightness equivalent to that of other cases can be achieved, and excellent heat resistance can be achieved. From the above results, it is understood that the colored composition containing the salt-forming product exhibits excellent performance in both color characteristics and heat resistance.

[實施例17至46及比較例8至12] [Examples 17 to 46 and Comparative Examples 8 to 12]

(實施例13：抗蝕劑材料(R-1)) (Example 13: resist material (R-1))

將下述混合物攪拌均勻後，以1.0μm的過濾器過濾分散液，獲得鹼顯影型抗蝕劑材料(R-1)。 After the following mixture was stirred uniformly, the dispersion was filtered through a 1.0 μm filter to obtain an alkali-developable resist material (R-1).

著色組成物(D-8)：50.0部 Coloring composition (D-8): 50.0 parts

著色組成物(D-11)：10.0部 Coloring composition (D-11): 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

丙二醇單乙基醚乙酯(PGMAC)：23.2部 Propylene glycol monoethyl ether ethyl ester (PGMAC): 23.2

(實施例17至46及比較例8至12：抗蝕劑材料(R-2)至(R-35)) (Examples 17 to 46 and Comparative Examples 8 to 12: Resist materials (R-2) to (R-35))

除了以表4所示之著色組成物置換著色組成物，如表4變更其調配量以外，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)至(R-35)。再者，並用複數種著色組成物，抗蝕劑材料全體設為100部時，著色組成物之合計量為60部。 An alkali-developing resist material (R-2) was obtained in the same manner as the resist material (R-1) except that the coloring composition was replaced with the colored composition shown in Table 4, and the blending amount was changed as shown in Table 4. ) to (R-35). In addition, when a plurality of coloring compositions were used in combination, and the total amount of the resist material was 100, the total amount of the coloring compositions was 60.

表4 Table 4

[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)至(R-35)之色彩特性評估及耐受性(耐熱性、耐光性及耐溶劑性)試驗。 The color property evaluation and the resistance (heat resistance, light resistance, and solvent resistance) of the resist materials (R-1) to (R-35) were tested by the following methods.

(色彩特性評估) (color characterization)

於玻璃基板上，塗布抗蝕劑材料。具體而言，將紅色抗蝕劑材料(R-1)至(R-12)、(R-27)至(R-29)及(R-32)，塗布為在C光源下之色度會成為x=0.640、y=0.330之膜厚。將綠色抗蝕劑材料(R-13)至(R-18)及(R-30)，塗布為在C光源下之色度會成為x=0.300、y=0.600之膜厚。將藍色抗蝕劑材 料(R-19)至(R-26)、(R-31)至(R-33)及(R-35)，塗布為在C光源下之色度會成為x=0.150、y=0.060之膜厚。接著，以230℃歷經20分鐘加熱基板，藉此於基板上形成著色層。其後，利用顯微分光光度計(Olympus光學公司製「OSP-SP200」)測定形成有著色層之基板之亮度Y。於表5表示評估結果。 A resist material is applied on the glass substrate. Specifically, the red resist materials (R-1) to (R-12), (R-27) to (R-29), and (R-32) are coated as chromaticity under the C light source. The film thickness was x=0.640 and y=0.330. The green resist materials (R-13) to (R-18) and (R-30) were coated so that the chromaticity under the C light source became a film thickness of x=0.300 and y=0.600. Blue resist Materials (R-19) to (R-26), (R-31) to (R-33) and (R-35), coated with a chromaticity under C light source will become x = 0.150, y = 0.060 Film thickness. Next, the substrate was heated at 230 ° C for 20 minutes to form a colored layer on the substrate. Thereafter, the luminance Y of the substrate on which the colored layer was formed was measured by a microscopic spectrophotometer ("OSP-SP200" manufactured by Olympus Optics Co., Ltd.). The evaluation results are shown in Table 5.

針對紅色抗蝕劑材料(R-1)至(R-12)、(R-27)至(R-29)及(R-32)，採以下程序進行耐受性(耐熱性、耐光性及耐溶劑性)之試驗。 For the red resist materials (R-1) to (R-12), (R-27) to (R-29) and (R-32), the following procedures are used for resistance (heat resistance, light resistance, and Solvent resistance test.

(塗膜耐熱性試驗之方法) (Method of coating 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，以紫外線將該塗膜進行曝光。於該塗膜噴霧鹼顯影液，去除未硬化部分，藉此形成所需圖案。其後，於烤箱內，以230℃歷經1小時加熱之。放冷後，利用顯微分光光度計(Olympus光學公司製「OSP-SP200」)，測定所獲得的塗膜在C光源下之色差1(L*(1)、a*(1)、b*(1))。其後，將其供作於烤箱內、以250℃歷經1小時加熱之耐熱試驗，進一步測定於C光源下之色差2(L*(2)、a*(2)、b*(2))。 On the transparent substrate, the resist material was applied so that the dried coating film was 2.5 μm, and a mask having a specific pattern was interposed, and the coating film was exposed to ultraviolet rays. The alkali developer is sprayed on the coating film to remove the uncured portion, thereby forming a desired pattern. Thereafter, it was heated in an oven at 230 ° C for 1 hour. After cooling, the color difference 1 (L*(1), a*(1), b* 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)). Thereafter, it was subjected to a heat resistance test in an oven at 250 ° C for 1 hour, and the color difference 2 (L*(2), a*(2), b*(2)) under the C light source was further measured. .

利用該等色差值，藉由下述計算式算出色差變化率△Eab*。然後，根據該色差變化率△Eab*，採下述4階段評估塗膜之耐熱性。 Using the color difference values, the color difference change rate ΔEab* is calculated by the following calculation formula. Then, based on the color change rate ΔEab*, the heat resistance of the coating film was evaluated in the following four stages.

◎：△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

(塗膜耐光性試驗之方法) (Method of coating film 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光源下之色差1(L*(1)、a*(1)、b*(1))。其後，將基板放入於耐光性試驗機(TOYOSEIKI公司製「SUNTEST CPS+」)，放置500小時。取出基板後，測定C光源下之色差2(L*(2)、a*(2)、b*(2))。利用該等色差值，與塗膜耐熱性同樣地算出色差 變化率△Eab*，依據與耐熱性相同的基準，採4階段評估塗膜之耐光性。於表6表示耐受性(耐熱性、耐光性及耐溶劑性)試驗之結果。 The test substrate was prepared by the same procedure as the coating film heat resistance test, and the color difference 1 (L*(1), a*(1) under the C light source was measured by a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optics Co., Ltd.). ), 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 color difference 2 (L*(2), a*(2), b*(2)) under the C light source was measured. Using these color difference values, the color difference is calculated in the same manner as the heat resistance of the coating film. The rate of change ΔEab* was evaluated in accordance with the same heat resistance as the four-stage evaluation of the light resistance of the coating film. Table 6 shows the results of the tests for resistance (heat resistance, light resistance, and solvent resistance).

(色彩特性及耐受性之評估結果) (Evaluation results of color characteristics and tolerance)

若比較針對紅色抗蝕劑材料(R-1)至(R-12)、(R-27)至(R-29)及(R-32)所獲得的結果，使用抗蝕劑材料(R-1)至(R-12)、(R-27)及(R-32)時，與使用著色劑僅有顏料之抗蝕劑材料(R-29)時相比較，亮度Y為較高值。針對綠色抗蝕劑材料(R-13)至(R-18)及(R-18)，使用著色劑僅以顏料構成之抗蝕劑材料時，與使用著色劑含成鹽生成物之抗蝕劑材料時相比較，亮度較低。同樣地，針對藍色抗蝕劑材料(R-19)至(R-26)、(R-31)及(R-33)至(R-35)，使用著色劑僅以顏料構成之抗蝕劑材料時，與使用著色劑含成鹽生成物之抗蝕劑材料時相比較，亮度較低。又，使用抗蝕劑材料(R-28)時，由於使用未與相對化合物(陰離子成分)成鹽之著色劑，因此呈色弱，不具著色力，故結果其亮度低。 If the results obtained for the red resist materials (R-1) to (R-12), (R-27) to (R-29) and (R-32) are compared, a resist material (R- is used). 1) To (R-12), (R-27), and (R-32), the luminance Y is a higher value than when the colorant-only pigment resist material (R-29) is used. For the green resist materials (R-13) to (R-18) and (R-18), when a resist material composed of only a pigment is used as a resist material, a resist formed by using a colorant is formed. The brightness of the material is lower when compared to the material. Similarly, for the blue resist materials (R-19) to (R-26), (R-31), and (R-33) to (R-35), a resist composed of a pigment only using a pigment is used. In the case of the agent material, the brightness is lower than when the resist material containing the salt-forming product is used. Further, when the resist material (R-28) is used, since a coloring agent which does not form a salt with the relative compound (anionic component) is used, the color is weak and the coloring power is not obtained, so that the brightness is low.

又，使用抗蝕劑材料(R-1)至(R-12)、(R-27)至(R-29)及(R-32)時，針對耐熱性亦獲得良好結果。若比較針對抗蝕劑材料(R-3)至(R-6)所獲得的結果，使用包含含有酸價在100至300mgKOH/mg範圍內之松香改質順丁烯二酸樹脂之著色組成物(D-2)之抗蝕劑材料(R-4)時，可達成較使用抗蝕劑材料(R-3)、(R-5)及(R-6)時更良好的亮度及耐熱性。使用抗蝕劑材料(R-27)時，雖可達成良好的色彩特性，但由於用在成鹽之相對化合物之分子量低於250，因此耐受性不佳。使用抗蝕劑材料(R-28)時，雖可達成稍微優於使用抗蝕劑材料(R-27)時之耐受性，但如前述，其亮度為較低值。又，使用抗蝕劑材料(R-29)時，雖可達成良好的耐受性，但亮度低、色彩特性不佳。 Further, when the resist materials (R-1) to (R-12), (R-27) to (R-29), and (R-32) were used, good results were obtained for heat resistance. If the results obtained for the resist materials (R-3) to (R-6) are compared, a coloring composition containing a rosin-modified maleic acid resin having an acid value in the range of 100 to 300 mgKOH/mg is used. (D-4) Resist material (R-4), which achieves better brightness and heat resistance than when resist materials (R-3), (R-5), and (R-6) are used. . When the resist material (R-27) is used, good color characteristics can be achieved, but since the molecular weight of the relative compound used for salt formation is less than 250, the resistance is not good. When the resist material (R-28) is used, although it is slightly better than the resistance when the resist material (R-27) is used, as described above, the luminance is a low value. Further, when a resist material (R-29) is used, good resistance can be achieved, but the brightness is low and the color characteristics are not good.

(製作彩色濾光片) (Making color filters)

於彩色基板上，形成遮光圖案之黑矩陣，接著利用旋轉塗布機塗布紅色抗蝕劑材料(抗蝕劑材料(R-1))。紅色抗蝕劑材料係塗布為在C光源下之色度會成為x=0.640、y=0.330之膜厚。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。其後，使用由0.2重量%碳酸鈉水溶液所組成的鹼顯影液供作噴霧顯影，去除未曝光部分，以離子交換水洗淨。進而以230℃歷經20分鐘加熱該基板，形成紅色濾光片區段。 A black matrix of a light-shielding pattern was formed on the color substrate, and then a red resist material (resist material (R-1)) was applied by a spin coater. The red resist material is applied such that the chromaticity under the C light source becomes a film thickness of x=0.640 and y=0.330. In the coating film, an ultraviolet ray of 300 mJ/cm ^{2 was} irradiated with an ultrahigh pressure mercury lamp by interposing a photomask. Thereafter, an alkali developing solution composed of a 0.2% by weight aqueous sodium carbonate solution was used for spray development, and the unexposed portion was removed, and washed with ion-exchanged water. Further, the substrate was heated at 230 ° C for 20 minutes to form a red filter segment.

接著，於該基板上，藉由與上述同樣的方法塗布綠色抗蝕劑材料(抗蝕劑材料(R-13))。綠色抗蝕劑材料係塗布為在C光源下之色度會成為x=0.300、y=0.600之膜厚。將該塗膜供作針對紅色抗蝕劑材料已於上面敘述同樣之曝光、顯影、洗淨及燒成，形成綠色濾光片區段。進而於該基板上，藉由與上述同樣的手法，塗布藍色抗蝕劑材料(抗蝕劑材料(R-19))。藍色抗蝕劑材料係塗布為在C光源下之色度會成為x=0.150、y=0.006之膜 厚。將該塗膜供作針對紅色抗蝕劑材料已於上面敘述同樣之曝光、顯影、洗淨及燒成，形成藍色濾光片區段。如以上獲得彩色濾光片。 Next, a green resist material (resist material (R-13)) was applied onto the substrate by the same method as described above. The green resist material is applied such that the chromaticity under the C light source becomes a film thickness of x=0.300 and y=0.600. The coating film was applied to the red resist material as described above for the same exposure, development, washing and firing to form a green filter segment. Further, a blue resist material (resist material (R-19)) was applied onto the substrate by the same method as described above. The blue resist material is coated as a film having a chromaticity of C=0.150 and y=0.006 under a C light source. thick. The coating film was applied to the red resist material as described above for exposure, development, washing, and firing to form a blue filter segment. A color filter is obtained as above.

如以上，藉由使用特定成鹽生成物，可獲得色彩特性及耐熱性、耐光性及耐溶劑性均良好的彩色濾光片。 As described above, by using a specific salt-forming product, a color filter excellent in color characteristics, heat resistance, light resistance, and solvent resistance can be obtained.

<<試驗2>> <<Test 2>>

試驗2係關於第2態樣。於試驗2，對應於第2態樣之例子記載作「實施例」，其他例子記載作「比較例」。 Test 2 is about the second aspect. In the test 2, the example corresponding to the second aspect is described as "example", and the other example is described as "comparative example".

<丙烯酸樹脂溶液之製造方法> <Method for Producing Acrylic Resin Solution>

(丙烯酸樹脂溶液1A之調製) (modulation of acrylic resin solution 1A)

於分離式的4支燒瓶，安裝溫度計、冷卻管、氮氣導入管及攪拌裝置，於該反應容器放入環己酮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n-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部及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之丙烯酸樹脂溶液。冷卻至室溫後，將樹脂溶液取樣約2g。將其以180℃加熱歷經20分鐘以使其乾燥，測定未揮發成分。根據如此獲得之非揮發成分含有量，於先前合成之樹脂溶液添加丙二醇單乙基醚乙酯(PGMAC)，調製成丙烯酸樹脂溶液1A。 A thermometer, a cooling tube, a nitrogen introduction tube, and a stirring device were attached to the four separate flasks, and 70.0 portions of cyclohexanone were placed in the reaction container. After the temperature was raised to 80 ° C and the reaction vessel was replaced with nitrogen, 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, and 4.3 parts of methacrylic acid were dropped by dropping the tube over 2 hours. A mixture of 7.4 parts of phenol epoxide modified acrylate ("ARONIX M110" manufactured by Toagosei Co., Ltd.) 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 an acrylic resin solution having a weight average molecular weight (Mw) of 26,000. After cooling to room temperature, the resin solution was sampled to about 2 g. This was heated at 180 ° C for 20 minutes to be dried, and the nonvolatile component was measured. Based on the content of the nonvolatile component thus obtained, propylene glycol monoethyl ether ethyl ester (PGMAC) was added to the previously synthesized resin solution to prepare an acrylic resin solution 1A.

<成鹽生成物之製造方法> <Method for Producing Salt-Forming Product>

(成鹽生成物1A) (salt formation product 1A)

採下述程序合成由維多利亞藍染料(C.I.基本藍7)與呫噸系 酸性染料(C.I.基本紅289)所組成的成鹽生成物1A。 Synthetic by Victoria Blue Dye (C.I. Basic Blue 7) and xanthene A salt-forming product 1A composed of an acid dye (C.I. Basic Red 289).

於7至15莫耳%之氫氧化鈉溶液中，添加呫噸系酸性染料(C.I.基本紅289)，充分攪拌該液體，藉此獲得其鈉鹽。將該呫噸系酸性染料鈉鹽水溶液加熱到70至90℃後，於其逐次些許滴下維多利亞藍染料(C.I.基本藍7)。維多利亞藍染料亦可作為水溶液使用。維多利亞藍染料之滴下結束後，為了令其充分反應，以70至90℃，歷經40至60分鐘攪拌該溶液。反應的終點係於濾紙滴下反應液而已無滲液之時點。亦即，於已無滲液時，判斷獲得成鹽生成物。一面攪拌一面放冷至室溫後，進行吸取過濾，進一步予以水洗。水洗後，從殘留於濾紙上之成鹽生成物，利用乾燥機去除水分，獲得維多利亞藍染料(C.I.基本藍7)與呫噸系酸性染料(C.I.基本紅289)之成鹽生成物，即成鹽生成物1A。 To a sodium hydroxide solution of 7 to 15 mol%, a xanthene-based acid dye (C.I. Basic Red 289) was added, and the liquid was sufficiently stirred, thereby obtaining a sodium salt thereof. After heating the xanthene acid dye sodium salt aqueous solution to 70 to 90 ° C, the Victoria blue dye (C.I. Basic Blue 7) was successively dropped. Victoria blue dye can also be used as an aqueous solution. After the end of the dropping of the Victoria blue dye, the solution was stirred at 70 to 90 ° C for 40 to 60 minutes in order to allow it to react sufficiently. The end point of the reaction is at the point when the filter paper drops the reaction solution without bleeding. That is, when the liquid has not been oozing, it is judged that the salt-forming product is obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of Victoria Blue dye (CI Basic Blue 7) and xanthene-based acid dye (CI Basic Red 289). Salt product 1A.

(成鹽生成物2A) (salt formation product 2A)

採下述程序合成由維多利亞藍染料(C.I.基本藍7)與玫瑰紅系酸性染料(C.I.酸性紅52：酸性玫瑰紅B)所組成的成鹽生成物2A。 The salt-forming product 2A consisting of Victoria blue dye (C.I. Basic Blue 7) and rose red acid dye (C.I. Acid Red 52: Acid Rose Red B) was synthesized by the following procedure.

於7至15莫耳%之氫氧化鈉溶液中，添加玫瑰紅系酸性染料(C.I.酸性紅52)，充分攪拌該液體，藉此獲得其鈉鹽。將該玫瑰紅系酸性染料鈉鹽水溶液加熱到70至90℃後，於其逐次些許滴下維多利亞藍染料(C.I.基本藍7)。維多利亞藍染料亦可作為水溶液使用。維多利亞藍染料之滴下結束後，為了令其充分反應，以70至90℃，歷經40至60分鐘攪拌該溶液。反應的終點係於濾紙滴下反應液而已無滲液之時點。亦即，於已無滲液時，判斷獲得成鹽生成物。一面攪拌一面放冷至室溫後，進行吸取過濾，進一步予以水洗。水洗後，從殘留於濾紙上之成鹽生成物，利用乾燥機去除水 分，獲得維多利亞藍染料(C.I.基本藍7)與玫瑰紅系酸性染料(C.I.酸性紅52)之成鹽生成物，即成鹽生成物2A。 To a sodium hydroxide solution of 7 to 15 mol%, a rose-red acid dye (C.I. Acid Red 52) was added, and the liquid was sufficiently stirred to obtain a sodium salt thereof. After heating the aqueous solution of the rose red acid dye sodium salt to 70 to 90 ° C, the Victoria blue dye (C.I. Basic Blue 7) was successively dropped therefrom. Victoria blue dye can also be used as an aqueous solution. After the end of the dropping of the Victoria blue dye, the solution was stirred at 70 to 90 ° C for 40 to 60 minutes in order to allow it to react sufficiently. The end point of the reaction is at the point when the filter paper drops the reaction solution without bleeding. That is, when the liquid has not been oozing, it is judged that the salt-forming product is obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the salt-forming product remains on the filter paper, and the water is removed by a dryer. A salt formation product of a Victoria blue dye (C.I. Basic Blue 7) and a rose red acid dye (C.I. Acid Red 52), that is, a salt-forming product 2A was obtained.

(成鹽生成物3A) (salt formation product 3A)

採下述程序合成由維多利亞藍染料(C.I.基本藍7)與呫噸系酸性染料(C.I.酸性紅：曙紅)所組成的成鹽生成物3A。 The salt-forming product 3A consisting of Victoria blue dye (C.I. Basic Blue 7) and xanthene acid dye (C.I. Acid Red: Eosin) was synthesized by the following procedure.

於7至15莫耳%之氫氧化鈉溶液中，添加呫噸系酸性染料(C.I.酸性紅87)，充分攪拌該液體，藉此獲得其鈉鹽。將該呫噸系酸性染料鈉鹽水溶液加熱到70至90℃後，於其逐次些許滴下維多利亞藍染料(C.I.基本藍7)。維多利亞藍染料亦可作為水溶液使用。維多利亞藍染料之滴下結束後，為了令其充分反應，以70至90℃，歷經40至60分鐘攪拌該溶液。反應的終點係於濾紙滴下反應液而已無滲液之時點。亦即，於已無滲液時，判斷獲得成鹽生成物。一面攪拌一面放冷至室溫後，進行吸取過濾，進一步予以水洗。水洗後，從殘留於濾紙上之成鹽生成物，利用乾燥機去除水分，獲得維多利亞藍染料(C.I.基本藍7)與呫噸系酸性染料(C.I.酸性紅87)之成鹽生成物，即成鹽生成物3A。 To a sodium hydroxide solution of 7 to 15 mol%, a xanthene-based acid dye (C.I. Acid Red 87) was added, and the liquid was sufficiently stirred to obtain a sodium salt thereof. After heating the xanthene acid dye sodium salt aqueous solution to 70 to 90 ° C, the Victoria blue dye (C.I. Basic Blue 7) was successively dropped. Victoria blue dye can also be used as an aqueous solution. After the end of the dropping of the Victoria blue dye, the solution was stirred at 70 to 90 ° C for 40 to 60 minutes in order to allow it to react sufficiently. The end point of the reaction is at the point when the filter paper drops the reaction solution without bleeding. That is, when the liquid has not been oozing, it is judged that the salt-forming product is obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of a Victoria blue dye (CI Basic Blue 7) and a xanthene-based acid dye (CI Acid Red 87). Salt product 3A.

(成鹽生成物4A) (salt formation product 4A)

採下述程序合成由維多利亞藍染料(C.I.基本藍7)與呫噸系酸性染料(C.I.酸性紅92：夾竹桃紅B)所組成的成鹽生成物4A。 The salt-forming product 4A consisting of Victoria blue dye (C.I. Basic Blue 7) and xanthene acid dye (C.I. Acid Red 92: Oleander Red B) was synthesized by the following procedure.

於7至15莫耳%之氫氧化鈉溶液中，添加呫噸系酸性染料(C.I.酸性紅92)，充分攪拌該液體，藉此獲得其鈉鹽。將該呫噸系酸性染料鈉鹽水溶液加熱到70至90℃後，於其逐次些許滴下維多利亞藍染料(C.I.基本藍7)。維多利亞藍染料亦可作為水溶液使用。維多利亞藍染料之滴下結束 後，為了令其充分反應，以70至90℃，歷經40至60分鐘攪拌該溶液。反應的終點係於濾紙滴下反應液而已無滲液之時點。亦即，於已無滲液時，判斷獲得成鹽生成物。一面攪拌一面放冷至室溫後，進行吸取過濾，進一步予以水洗。水洗後，從殘留於濾紙上之成鹽生成物，利用乾燥機去除水分，獲得維多利亞藍染料(C.I.基本藍7)與呫噸系酸性染料(C.I.酸性紅92)之成鹽生成物，即成鹽生成物4A。 To a sodium hydroxide solution of 7 to 15 mol%, a xanthene-based acid dye (C.I. Acid Red 92) was added, and the liquid was sufficiently stirred to obtain a sodium salt thereof. After heating the xanthene acid dye sodium salt aqueous solution to 70 to 90 ° C, the Victoria blue dye (C.I. Basic Blue 7) was successively dropped. Victoria blue dye can also be used as an aqueous solution. The end of the Victoria Blue Dye Thereafter, in order to allow sufficient reaction, the solution was stirred at 70 to 90 ° C for 40 to 60 minutes. The end point of the reaction is at the point when the filter paper drops the reaction solution without bleeding. That is, when the liquid has not been oozing, it is judged that the salt-forming product is obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of Victoria blue dye (CI basic blue 7) and xanthene acid dye (CI acid red 92). Salt product 4A.

(成鹽生成物5A) (salt formation product 5A)

採下述程序合成由玫瑰紅6G染料(C.I.基本紅1)與三苯基甲烷系酸性染料(C.I.酸性藍1)所組成的成鹽生成物5A。 The salt-forming product 5A composed of Rose Bengal 6G dye (C.I. Basic Red 1) and triphenylmethane-based acid dye (C.I. Acid Blue 1) was synthesized by the following procedure.

於7至15莫耳%之氫氧化鈉溶液中，添加三苯基甲烷系酸性染料(C.I.酸性藍1)，充分攪拌該液體，藉此獲得其鈉鹽。將該呫噸系酸性染料鈉鹽水溶液加熱到70至90℃後，於其逐次些許滴下玫瑰紅6G染料(C.I.基本紅1)。玫瑰紅6G染料亦可作為水溶液使用。玫瑰紅6G染料之滴下結束後，為了令其充分反應，以70至90℃，歷經40至60分鐘攪拌該溶液。反應的終點係於濾紙滴下反應液而已無滲液之時點。亦即，於已無滲液時，判斷獲得成鹽生成物。一面攪拌一面放冷至室溫後，進行吸取過濾，進一步予以水洗。水洗後，從殘留於濾紙上之成鹽生成物，利用乾燥機去除水分，獲得玫瑰紅6G染料(C.I.基本紅1)與三苯基甲烷系酸性染料(C.I.酸性藍1)之成鹽生成物，即成鹽生成物5A。 To a sodium hydroxide solution of 7 to 15 mol%, a triphenylmethane-based acid dye (C.I. Acid Blue 1) was added, and the liquid was sufficiently stirred to obtain a sodium salt thereof. After heating the xanthene acid dye sodium salt aqueous solution to 70 to 90 ° C, the rose red 6G dye (C.I. Basic Red 1) was successively dropped thereon. Rose red 6G dye can also be used as an aqueous solution. After the completion of the dropwise addition of the rose red 6G dye, the solution was stirred at 70 to 90 ° C for 40 to 60 minutes in order to allow sufficient reaction. The end point of the reaction is at the point when the filter paper drops the reaction solution without bleeding. That is, when the liquid has not been oozing, it is judged that the salt-forming product is obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of rose red 6G dye (CI basic red 1) and triphenylmethane-based acid dye (CI acid blue 1). , the salt formation product 5A.

(成鹽生成物6A) (salt formation product 6A)

採下述程序合成由玫瑰紅6G染料(C.I.基本紅1)與三苯基甲烷系酸性染料(C.I.酸性藍93)所組成的成鹽生成物6A。 The salt-forming product 6A composed of Rose Bengal 6G dye (C.I. Basic Red 1) and triphenylmethane-based acid dye (C.I. Acid Blue 93) was synthesized by the following procedure.

於7至15莫耳%之氫氧化鈉溶液中，添加三苯基甲烷系酸性染料(C.I.酸性藍93)，充分攪拌該液體，藉此獲得其鈉鹽。將該三苯基甲烷系酸性染料鈉鹽水溶液加熱到70至90℃後，於其逐次些許滴下玫瑰紅6G染料(C.I.基本紅1)。玫瑰紅6G染料亦可作為水溶液使用。玫瑰紅6G染料之滴下結束後，為了令其充分反應，以70至90℃，歷經40至60分鐘攪拌該溶液。反應的終點係於濾紙滴下反應液而已無滲液之時點。亦即，於已無滲液時，判斷獲得成鹽生成物。一面攪拌一面放冷至室溫後，進行吸取過濾，進一步予以水洗。水洗後，從殘留於濾紙上之成鹽生成物，利用乾燥機去除水分，獲得玫瑰紅6G染料(C.I.基本紅1)與三苯基甲烷系酸性染料(C.I.酸性藍93)之成鹽生成物，即成鹽生成物6A。 To a sodium hydroxide solution of 7 to 15 mol%, a triphenylmethane-based acid dye (C.I. Acid Blue 93) was added, and the liquid was sufficiently stirred to obtain a sodium salt thereof. After heating the aqueous solution of the triphenylmethane-based acid dye sodium salt to 70 to 90 ° C, the rose red 6G dye (C.I. Basic Red 1) was successively dropped therefrom. Rose red 6G dye can also be used as an aqueous solution. After the completion of the dropwise addition of the rose red 6G dye, the solution was stirred at 70 to 90 ° C for 40 to 60 minutes in order to allow sufficient reaction. The end point of the reaction is at the point when the filter paper drops the reaction solution without bleeding. That is, when the liquid has not been oozing, it is judged that the salt-forming product is obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of rose red 6G dye (CI basic red 1) and triphenylmethane-based acid dye (CI acid blue 93). , the salt formation product 6A.

(成鹽生成物7A) (salt formation product 7A)

採下述程序合成由玫瑰紅B染料(C.I.基本紫10)與三苯基甲烷系酸性染料(C.I.酸性藍93)所組成的成鹽生成物7A。 The salt-forming product 7A composed of Rose Bengal B dye (C.I. Basic Violet 10) and triphenylmethane-based acid dye (C.I. Acid Blue 93) was synthesized by the following procedure.

於7至15莫耳%之氫氧化鈉溶液中，添加三苯基甲烷系酸性染料(C.I.酸性藍1)，充分攪拌該液體，藉此獲得其鈉鹽。將該三苯基甲烷系酸性染料鈉鹽水溶液加熱到70至90℃後，於其逐次些許滴下玫瑰紅B染料(C.I.基本紫10)。玫瑰紅B染料亦可作為水溶液使用。玫瑰紅B染料之滴下結束後，為了令其充分反應，以70至90℃，歷經40至60分鐘攪拌該溶液。反應的終點係於濾紙滴下反應液而已無滲液之時點。亦即，於已無滲液時，判斷獲得成鹽生成物。一面攪拌一面放冷至室溫後，進行吸取過濾，進一步予以水洗。水洗後，從殘留於濾紙上之成鹽生成物，利用乾燥機去除水分，獲得玫瑰紅6G染料(C.I.基本紅1)與三苯基甲烷系酸性染料(C.I.酸性藍1) 之成鹽生成物，即成鹽生成物7A。 To a sodium hydroxide solution of 7 to 15 mol%, a triphenylmethane-based acid dye (C.I. Acid Blue 1) was added, and the liquid was sufficiently stirred to obtain a sodium salt thereof. After heating the aqueous solution of the triphenylmethane-based acid dye sodium salt to 70 to 90 ° C, the Rose Bengal B dye (C.I. Basic Violet 10) was successively dropped therefrom. Rose Bengal B dye can also be used as an aqueous solution. After the completion of the dropwise addition of the rose bengal B dye, the solution was stirred at 70 to 90 ° C for 40 to 60 minutes in order to allow sufficient reaction. The end point of the reaction is at the point when the filter paper drops the reaction solution without bleeding. That is, when the liquid has not been oozing, it is judged that the salt-forming product is obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain Rose Bengal 6G dye (C.I. Basic Red 1) and triphenylmethane-based acid dye (C.I. Acid Blue 1). The salt-forming product, that is, the salt-forming product 7A.

(成鹽生成物8A及9A) (salt formation products 8A and 9A)

採下述程序合成由玫瑰紅6G染料(C.I.基本紅1)與三苯基甲烷系酸性染料(C.I.酸性藍3)所組成的成鹽生成物8A。 The salt-forming product 8A composed of Rose Bengal 6G dye (C.I. Basic Red 1) and triphenylmethane-based acid dye (C.I. Acid Blue 3) was synthesized by the following procedure.

於7至15莫耳%之氫氧化鈉溶液中，添加三苯基甲烷系酸性染料(C.I.酸性藍3)，充分攪拌該液體，藉此獲得其鈉鹽。將該三苯基甲烷系酸性染料鈉鹽水溶液加熱到70至90℃後，於其逐次些許滴下玫瑰紅6G染料(C.I.基本紅1)。玫瑰紅6G染料亦可作為水溶液使用。玫瑰紅6G染料之滴下結束後，為了令其充分反應，以70至90℃，歷經40至60分鐘攪拌該溶液。反應的終點係於濾紙滴下反應液而已無滲液之時點。亦即，於已無滲液時，判斷獲得成鹽生成物。一面攪拌一面放冷至室溫後，進行吸取過濾，進一步予以水洗。水洗後，從殘留於濾紙上之成鹽生成物，利用乾燥機去除水分，獲得玫瑰紅6G染料(C.I.基本紅1)與三苯基甲烷系酸性染料(C.I.酸性藍3)之成鹽生成物，即成鹽生成物8A。 To a sodium hydroxide solution of 7 to 15 mol%, a triphenylmethane-based acid dye (C.I. Acid Blue 3) was added, and the liquid was sufficiently stirred to obtain a sodium salt thereof. After heating the aqueous solution of the triphenylmethane-based acid dye sodium salt to 70 to 90 ° C, the rose red 6G dye (C.I. Basic Red 1) was successively dropped therefrom. Rose red 6G dye can also be used as an aqueous solution. After the completion of the dropwise addition of the rose red 6G dye, the solution was stirred at 70 to 90 ° C for 40 to 60 minutes in order to allow sufficient reaction. The end point of the reaction is at the point when the filter paper drops the reaction solution without bleeding. That is, when the liquid has not been oozing, it is judged that the salt-forming product is obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of rose red 6G dye (CI basic red 1) and triphenylmethane-based acid dye (CI acid blue 3). , that is, salt formation product 8A.

接著，於100質量部之成鹽生成物8A，添加松香改質順丁烯二酸樹脂(酸價130、荒川化學公司製MALKYD No.32)30質量部，以加壓捏合機予以混合。該混合係將材料溫度設定為120℃，歷經30分鐘進行。冷卻後，利用噴射氣流式粉碎機(Nippon Pneumatic工業公司製IDS-2型)進行微粉碎，獲得平均粒徑10mm之粒子作為成鹽生成物9A。 Then, 30 parts by mass of the rosin-modified maleic acid resin (acid price 130, MALKYD No. 32 manufactured by Arakawa Chemical Co., Ltd.) was added to the salt-forming product 8A of 100 parts by mass, and the mixture was mixed by a pressure kneader. The mixing was carried out by setting the material temperature to 120 ° C for 30 minutes. After cooling, it was finely pulverized by a jet flow type pulverizer (IDS-2 type manufactured by Nippon Pneumatic Co., Ltd.) to obtain particles having an average particle diameter of 10 mm as the salt-forming product 9A.

(成鹽生成物10A) (salt formation product 10A)

採下述程序合成由維多利亞藍染料(C.I.基本藍7)與1-萘磺酸所組成的成鹽生成物10A。 The salt-forming product 10A consisting of Victoria blue dye (C.I. Basic Blue 7) and 1-naphthalenesulfonic acid was synthesized by the following procedure.

於7至15莫耳%之氫氧化鈉溶液中，添加1-萘磺酸，充分攪拌該液體，藉此獲得其鈉鹽。將該1-萘磺酸鈉鹽水溶液加熱到70至90℃後，於其逐次些許滴下維多利亞藍染料(C.I.基本藍7)。維多利亞藍染料亦可作為水溶液使用。維多利亞藍染料之滴下結束後，為了令其充分反應，以70至90℃，歷經40至60分鐘攪拌該溶液。反應的終點係於濾紙滴下反應液而已無滲液之時點。亦即，於已無滲液時，判斷獲得成鹽生成物。一面攪拌一面放冷至室溫後，進行吸取過濾，進一步予以水洗。水洗後，從殘留於濾紙上之成鹽生成物，利用乾燥機去除水分，獲得維多利亞藍染料與1-萘磺酸之成鹽生成物，即成鹽生成物10A。 To the sodium hydroxide solution of 7 to 15 mol%, 1-naphthalenesulfonic acid was added, and the liquid was sufficiently stirred, thereby obtaining a sodium salt thereof. After heating the aqueous solution of sodium 1-naphthalenesulfonate to 70 to 90 ° C, a Victoria blue dye (C.I. Basic Blue 7) was successively dropped therefrom. Victoria blue dye can also be used as an aqueous solution. After the end of the dropping of the Victoria blue dye, the solution was stirred at 70 to 90 ° C for 40 to 60 minutes in order to allow it to react sufficiently. The end point of the reaction is at the point when the filter paper drops the reaction solution without bleeding. That is, when the liquid has not been oozing, it is judged that the salt-forming product is obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the salt-forming product remaining on the filter paper was removed by a dryer to obtain a salt-forming product of Victoria blue dye and 1-naphthalenesulfonic acid, that is, a salt-forming product 10A.

(成鹽生成物11A) (salt formation product 11A)

採下述程序合成由玫瑰紅6G染料(C.I.基本紅1)與1-萘磺酸所組成的成鹽生成物11A。 The salt-forming product 11A composed of Rose Bengal 6G dye (C.I. Basic Red 1) and 1-naphthalenesulfonic acid was synthesized by the following procedure.

於7至15莫耳%之氫氧化鈉溶液中，添加1-萘磺酸，充分攪拌該液體，藉此獲得其鈉鹽。將該1-萘磺酸鈉鹽水溶液加熱到70至90℃後，於其逐次些許滴下玫瑰紅6G染料(C.I.基本紅1)。玫瑰紅6G染料亦可作為水溶液使用。玫瑰紅6G染料之滴下結束後，為了令其充分反應，以70至90℃，歷經40至60分鐘攪拌該溶液。反應的終點係於濾紙滴下反應液而已無滲液之時點。亦即，於已無滲液時，判斷獲得成鹽生成物。一面攪拌一面放冷至室溫後，進行吸取過濾，進一步予以水洗。水洗後，從殘留於濾紙上之成鹽生成物，利用乾燥機去除水分，獲得玫瑰紅6G染料與1-萘磺酸之成鹽生成物，即成鹽生成物11A。 To the sodium hydroxide solution of 7 to 15 mol%, 1-naphthalenesulfonic acid was added, and the liquid was sufficiently stirred, thereby obtaining a sodium salt thereof. After heating the aqueous solution of sodium 1-naphthalenesulfonate to 70 to 90 ° C, a rose red 6G dye (C.I. Basic Red 1) was successively dropped therefrom. Rose red 6G dye can also be used as an aqueous solution. After the completion of the dropwise addition of the rose red 6G dye, the solution was stirred at 70 to 90 ° C for 40 to 60 minutes in order to allow sufficient reaction. The end point of the reaction is at the point when the filter paper drops the reaction solution without bleeding. That is, when the liquid has not been oozing, it is judged that the salt-forming product is obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the salt-forming product remaining on the filter paper was removed by a dryer to obtain a salt-forming product of rose-red 6G dye and 1-naphthalenesulfonic acid, that is, a salt-forming product 11A.

<微細化顏料之製造方法> <Method for Producing Micronized Pigment>

(藍色微細顏料1A之生成) (production of blue fine pigment 1A)

將酞菁系藍色顏料之C.I.Pigment Blue 15：6(東洋墨水製造公司製「Lionol Blue ES」、相對表面積60m²/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℃歷經6小時予以混合攪拌。接著，將該混合攪拌物放入8公升的溫水中，一面加熱至80℃，一面歷經2小時予以攪拌而製成漿狀。重複過濾及水洗以去除氯化鈉及二乙二醇後，以85℃乾燥一晝夜，獲得190部的藍色微細顏料1A。藍色微細顏料1A之相對表面積為80m²/g。 CIPigment Blue 15:6 ("Lionol Blue ES" manufactured by Toyo Ink Co., Ltd., relative surface area 60 m ² /g), 200 parts of sodium chloride, 1400 parts of diamethylene glycol, and 360 parts of diethylene glycol were placed in stainless steel. A one-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) was prepared and mixed and stirred at 80 ° C for 6 hours. Next, the kneaded material was placed in 8 liters of warm water, and heated to 80 ° C, and stirred for 2 hours to prepare a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 85 ° C for one day and night to obtain 190 blue fine pigment 1A. The relative surface area of the blue fine pigment 1A was 80 m ² /g.

(紫色微細顏料1A之生成) (Production of purple fine pigment 1A)

將二噁嗪系紫色色顏料之C.I.Pigment Violet 23(東洋墨水製造公司製「LIONOGEN VIOLET RL」、相對表面積75m²/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℃歷經6小時予以混合攪拌。接著，將該混合攪拌物放入8公升的溫水中，一面加熱至80℃，一面歷經2小時予以攪拌而製成漿狀。重複過濾及水洗以去除氯化鈉及二乙二醇後，以85℃乾燥一晝夜，獲得190部的紫色微細顏料1A。紫色微細顏料1A之相對表面積為95m²/g。 CIPigment Violet 23 ("LIONOGEN VIOLET RL" manufactured by Toyo Ink Co., Ltd., relative surface area: 75 m ² /g), 200 parts of sodium chloride, 1400 parts of diamethylene glycol, and 360 parts of diethylene glycol were placed in stainless steel. A 1 gallon kneader (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, and heated to 80 ° C, and stirred for 2 hours to prepare a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 85 ° C for one day and night to obtain 190 purple fine pigment 1A. The relative surface area of the purple fine pigment 1A was 95 m ² /g.

(紅色微細顏料1A之生成) (generation of red fine pigment 1A)

將二酮吡咯並吡咯系紅色顏料之C.I.Pigment Red 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℃歷經6小時予以混合攪拌。接著，將該混合攪拌物放入8公升的溫水中，一面加熱至80℃，一面歷經2小時予以攪拌而製成漿狀。重複過濾及水洗以去除氯化鈉及二乙二醇 後，以85℃乾燥一晝夜，獲得190部的紅色微細顏料1A。 200 parts of CIPigment 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 stainless steel 1 gallon kneader (in the well) of the diketopyrrolopyrrole red pigment. The production system was mixed and stirred at 80 ° C for 6 hours. Next, the kneaded material was placed in 8 liters of warm water, and heated to 80 ° C, and stirred for 2 hours to prepare a slurry. Repeat filtration and water washing to remove sodium chloride and diethylene glycol Thereafter, it was dried at 85 ° C for one day and night to obtain 190 red fine pigments 1A.

(綠色微細顏料1A之生成) (Production of green fine pigment 1A)

將酞菁系綠色顏料之C.I.Pigment Green 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℃歷經6小時予以混合攪拌。接著，將該混合攪拌物放入8公升的溫水中，一面加熱至80℃，一面歷經2小時予以攪拌而製成漿狀。重複過濾及水洗以去除氯化鈉及二乙二醇後，以85℃乾燥一晝夜，獲得190部的綠色微細顏料1A。 200 pieces of CIPigment 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 production system was mixed and stirred at 80 ° C for 6 hours. Next, the kneaded material was placed in 8 liters of warm water, and heated to 80 ° C, and stirred for 2 hours to prepare a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 85 ° C for one day and night to obtain 190 green fine pigment 1A.

(黃色微細顏料1A之生成) (production of yellow fine pigment 1A)

將異吲哚啉系黃色顏料之C.I.Pigment Yellow 150(LANXESS公司「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℃歷經6小時予以混合攪拌。接著，將該混合攪拌物放入8公升的溫水中，一面加熱至80℃，一面歷經2小時予以攪拌而製成漿狀。重複過濾及水洗以去除氯化鈉及二乙二醇後，以85℃乾燥一晝夜，獲得190部的黃色微細顏料1A。 200 parts of CIPigment Yellow 150 (LANXESS "E-4GN"), 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.). It was mixed and stirred at 80 ° C for 6 hours. Next, the kneaded material was placed in 8 liters of warm water, and heated to 80 ° C, and stirred for 2 hours to prepare a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 85 ° C for one day and night to obtain 190 yellow fine pigment 1A.

(黃色微細顏料2A之生成) (production of yellow fine pigment 2A)

將鎳錯合物系黃色顏料之C.I.Pigment Yellow 150(LANXESS公司「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℃歷經6小時予以混合攪拌。接著，將該混合攪拌物放入8公升的溫水中，一面加熱至80℃，一面歷經2小時予以攪拌而製成漿狀。重複過濾及水洗以去除氯化鈉及二乙二醇後，以85℃乾燥一晝夜，獲得190部的黃色微細顏料2A。 200 pieces of CIPigment Yellow 150 (LANXESS "E-4GN") of nickel complex yellow pigment, 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.) It was mixed and stirred at 80 ° C for 6 hours. Next, the kneaded material was placed in 8 liters of warm water, and heated to 80 ° C, and stirred for 2 hours to prepare a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 85 ° C for one day and night to obtain 190 yellow fine pigment 2A.

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

(顏料分散體(P-1A)之調製) (Modulation of pigment dispersion (P-1A))

將下述混合物攪拌均勻後，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」)，歷經5小時進行分散處理。其後，以5.0mm的過濾器過濾分散液，獲得顏料分散體(P-1A)。 After the mixture was stirred well, the zirconia beads having a diameter of 0.5 mm were used for dispersion treatment by an IGER mill ("Mini Model M-250 MKII" manufactured by Iger Japan Co., Ltd.) over 5 hours. Thereafter, the dispersion was filtered with a 5.0 mm filter to obtain a pigment dispersion (P-1A).

藍色微細顏料1A：11.0部 Blue fine pigment 1A: 11.0

(C.I.Pigment Blue 15：6) (C.I.Pigment Blue 15:6)

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

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：1.0部 Resin type dispersant: 1.0

(日本千葉公司製「EFKA4300」) ("EFKA4300" manufactured by Chiba Corporation, Japan)

(顏料分散體(P-2A)至(P-6A)之調製) (Preparation of pigment dispersions (P-2A) to (P-6A))

除了將藍色微細顏料1A變更為表7所示之顏料以外，其他均與上述顏料分散體(P-1A)同樣地獲得顏料分散體(P-2A)至(P-6A)。 Pigment dispersions (P-2A) to (P-6A) were obtained in the same manner as in the above pigment dispersion (P-1A) except that the blue fine pigment 1A was changed to the pigment shown in Table 7.

<紅色及綠色抗蝕劑材料之製造方法> <Method of Manufacturing Red and Green Resist Material>

(紅色抗蝕劑材料之調製) (modulation of red resist material)

將下述混合物攪拌均勻後，以1.0μm的過濾器過濾分散液，獲得紅色抗蝕劑材料。 After the following mixture was stirred uniformly, the dispersion was filtered through a 1.0 μm filter to obtain a red resist material.

顏料分散體(P-3A)：50.0部 Pigment dispersion (P-3A): 50.0 parts

顏料分散體(P-4A)：10.0部 Pigment dispersion (P-4A): 10.0

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

丙二醇單乙基醚乙酯(PGMAC)：23.2部 Propylene glycol monoethyl ether ethyl ester (PGMAC): 23.2

(綠色抗蝕劑材料之調製) (modulation of green resist material)

將下述混合物攪拌均勻後，以1.0μm的過濾器過濾分散液，獲得綠色抗蝕劑材料。 After the following mixture was stirred uniformly, the dispersion was filtered through a 1.0 μm filter to obtain a green resist material.

顏料分散體(P-5A)：45.0部 Pigment dispersion (P-5A): 45.0 parts

顏料分散體(P-6A)：15.0部 Pigment dispersion (P-6A): 15.0 parts

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

丙二醇單乙基醚乙酯(PGMAC)：23.2部 Propylene glycol monoethyl ether ethyl ester (PGMAC): 23.2

[實施例47至55及比較例13至16] [Examples 47 to 55 and Comparative Examples 13 to 16]

(實施例47：彩色濾光片用藍色著色組成物(D-1A)) (Example 47: Blue coloring composition (D-1A) for color filter)

將下述混合物攪拌均勻後，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」)，歷經5小時進行分散處理。其後，以5.0mm的過濾器過濾分散液，獲得顏料分散體(D-1A)。 After the mixture was stirred well, the zirconia beads having a diameter of 0.5 mm were used for dispersion treatment by an IGER mill ("Mini Model M-250 MKII" manufactured by Iger Japan Co., Ltd.) over 5 hours. Thereafter, the dispersion was filtered through a 5.0 mm filter to obtain a pigment dispersion (D-1A).

成鹽生成物：11.0部 Salt formation product: 11.0

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

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：1.0部 Resin type dispersant: 1.0

(日本千葉公司製「EFKA4300」) ("EFKA4300" manufactured by Chiba Corporation, Japan)

(實施例48至55及比較例13至16：彩色濾光片用藍色著色組成物(D-2A)至(D-13A)) (Examples 48 to 55 and Comparative Examples 13 to 16: Blue coloring compositions (D-2A) to (D-13A) for color filters)

除了將成鹽生成物1A變更為表8所示之著色劑以外，其他均與彩色濾光片用藍色著色組成物(D-1A))同樣地獲得彩色濾光片用藍色著色組成物(D-2A)至(D-13A)。 A blue coloring composition for a color filter was obtained in the same manner as the blue coloring composition (D-1A) of the color filter, except that the salt-forming product 1A was changed to the coloring agent shown in Table 8. (D-2A) to (D-13A).

表8 Table 8

[彩色濾光片用藍色著色組成物之評估] [Evaluation of Blue Coloring Compositions for Color Filters]

採下述方法進行彩色濾光片用藍色著色組成物(D-1A)至(D-13A)之耐熱性試驗。 The heat resistance test of the blue coloring compositions (D-1A) to (D-13A) for color filters was carried out by the following method.

(耐熱性試驗之方法) (Method of heat resistance test)

於透明基板上，將著色組成物(D-1A)至(D-13A)之各者塗布為乾燥塗膜成為2.0μm，以230℃歷經20分鐘加熱基板。針對形成有著色層之上述基板，利用顯微分光光度計(Olympus光學公司製「OSP-SP200」)，測定在C光源下之色差1(L*(1)、a*(1)、b*(1))。其後，將形成有著色層之上述基板，供作於烤箱內、以250℃歷經1小時加熱之耐熱試驗，進一步測定於C光源下之色差2(L*(2)、a*(2)、b*(2))。 Each of the colored compositions (D-1A) to (D-13A) was applied as a dry coating film to a thickness of 2.0 μm on a transparent substrate, and the substrate was heated at 230 ° C for 20 minutes. The color difference 1 (L*(1), a*(1), b* under the C light source was measured by a microscopic spectrophotometer ("OSP-SP200" manufactured by Olympus Optics Co., Ltd.) for the above-mentioned substrate on which the colored layer was formed. (1)). Thereafter, the substrate on which the colored layer was formed was subjected to a heat resistance test in an oven at 250 ° C for 1 hour, and the color difference 2 under the C light source was further measured (L*(2), a*(2) , b*(2)).

利用該等色差值，藉由下述計算式算出色差變化率△Eab*。然後，根據該色差變化率△Eab*，採下述4階段評估塗膜之耐熱性。 Using the color difference values, the color difference change rate ΔEab* is calculated by the following calculation formula. Then, based on the color change rate ΔEab*, the heat resistance of the coating film was evaluated in the following four stages.

◎：△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9表示色彩特性及耐熱性之評估結果。 Table 9 shows the evaluation results of color characteristics and heat resistance.

(耐熱性之評估結果) (Evaluation results of heat resistance)

使用含特定成鹽生成物作為著色劑之著色組成物(D-1A)至(D-9A)時，針對耐熱性獲得良好結果。然後，使用從玫瑰紅系染料獲得之成鹽生成物時，尤其獲得良好結果。相對於此，使用含染料及無色之相對成分之成鹽生成物，或含染料作為著色劑之著色組成物(D-10A)至(D-13A)時，色差變化超過5，耐熱性相對較低。 When the coloring compositions (D-1A) to (D-9A) containing a specific salt-forming product as a coloring agent were used, good results were obtained for heat resistance. Then, particularly good results were obtained when a salt-forming product obtained from a rose-red dye was used. On the other hand, when a salt-forming product containing a dye and a colorless relative component or a coloring composition containing a dye as a colorant (D-10A) to (D-13A) is used, the color difference changes by more than 5, and the heat resistance is relatively high. low.

從上述結果可知，含特定成鹽生成物之著色組成物係於耐熱性達到良好的性能。 From the above results, it is understood that the coloring composition containing a specific salt-forming product is excellent in heat resistance.

[實施例56至67及比較例17至21] [Examples 56 to 67 and Comparative Examples 17 to 21]

(實施例56：抗蝕劑材料(R-1A)) (Example 56: resist material (R-1A))

將下述混合物攪拌均勻後，以1.0μm的過濾器過濾分散 液，獲得鹼顯影型抗蝕劑材料(R-1A)。 After the following mixture was stirred uniformly, it was filtered and dispersed by a 1.0 μm filter. Liquid, an alkali-developable resist material (R-1A) was obtained.

著色組成物(D-1A)：60.0部 Coloring composition (D-1A): 60.0

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

丙二醇單乙基醚乙酯(PGMAC)：23.2部 Propylene glycol monoethyl ether ethyl ester (PGMAC): 23.2

(實施例57至67及比較例17至21：抗蝕劑材料(R-2A)至(R-17A)) (Examples 57 to 67 and Comparative Examples 17 to 21: Resist materials (R-2A) to (R-17A))

除了以表10所示之著色組成物或顏料分散體置換著色組成物，如表10變更其調配量以外，其他均與抗蝕劑材料(R-1A)同樣地獲得鹼顯影型抗蝕劑材料(R-2A)至(R-17A)。再者，於一部分抗蝕劑材料，將顏料作為著色劑使用，抗蝕劑材料全體設為100部時，著色組成物及/或顏料分散體之合計量為60部。 An alkali-developing resist material was obtained in the same manner as the resist material (R-1A) except that the colored composition or the pigment dispersion shown in Table 10 was substituted for the coloring composition, and the blending amount was changed as shown in Table 10. (R-2A) to (R-17A). In addition, when a part of the resist material is used as a coloring agent, and the entire resist material is 100 parts, the total amount of the coloring composition and/or the pigment dispersion is 60 parts.

表10 Table 10

[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-1A)至(R-17A)之色彩特性(亮度)評估及耐受性(耐熱性、耐光性及耐溶劑性)試驗。 The color characteristics (brightness) evaluation and the resistance (heat resistance, light resistance, and solvent resistance) of the resist materials (R-1A) to (R-17A) were tested by the following methods.

(色彩特性評估) (color characterization)

於玻璃基板上，塗布抗蝕劑材料。具體而言，將抗蝕劑材料(R-1A)至(R-17A)塗布為在C光源下之色度會成為x=0.150、y=0.060之膜厚。將該等基板以230℃歷經20分鐘加熱，藉此於基板上形成著色層。其後，利用顯微分光光度計(Olympus光學公司製「OSP-SP200」)測定形成有著色層之基板之亮度Y。 A resist material is applied on the glass substrate. Specifically, the resist materials (R-1A) to (R-17A) are coated so that the chromaticity under the C light source becomes a film thickness of x=0.150 and y=0.060. The substrates were heated at 230 ° C for 20 minutes to form a colored layer on the substrate. Thereafter, the luminance Y of the substrate on which the colored layer was formed was measured by a microscopic spectrophotometer ("OSP-SP200" manufactured by Olympus Optics Co., Ltd.).

(塗膜耐熱性試驗之方法) (Method of coating 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，以紫外線將該塗膜進行曝光。於該塗膜噴霧鹼顯影液，去除未硬化部分，藉此形成所需圖案。其後，於烤箱內，以230℃歷經1小時加熱之。放冷後，利用顯微分光光度計(Olympus光學公司製 「OSP-SP200」)，測定所獲得的塗膜在C光源下之色差1(L*(1)、a*(1)、b*(1))。其後，將其供作於烤箱內、以250℃歷經1小時加熱之耐熱試驗，進一步測定於C光源下之色差2(L*(2)、a*(2)、b*(2))。 On the transparent substrate, the resist material was applied so that the dried coating film was 2.5 μm, and a mask having a specific pattern was interposed, and the coating film was exposed to ultraviolet rays. The alkali developer is sprayed on the coating film to remove the uncured portion, thereby forming a desired pattern. Thereafter, it was heated in an oven at 230 ° C for 1 hour. After cooling, use a microscopic spectrophotometer (Olympus Optical Co., Ltd. "OSP-SP200"), the color difference 1 (L*(1), a*(1), b*(1)) of the obtained coating film under the C light source was measured. Thereafter, it was subjected to a heat resistance test in an oven at 250 ° C for 1 hour, and the color difference 2 (L*(2), a*(2), b*(2)) under the C light source was further measured. .

利用該等色差值，藉由下述計算式算出色差變化△Eab*。然後，根據該色差變化率△Eab*，採下述4階段評估塗膜之耐熱性。 Using the color difference values, the color difference change ΔEab* is calculated by the following calculation formula. Then, based on the color change rate ΔEab*, the heat resistance of the coating film was evaluated in the following four stages.

◎：△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

(塗膜耐光性試驗之方法) (Method of coating film 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光源下之色差1(L*(1)、a*(1)、b*(1))。其後，將基板放入於耐光性試驗機(TOYOSEIKI公司製「SUNTEST CPS+」)，放置500小時。取出基板後，測定C光源下之色差2(L*(2)、a*(2)、b*(2))。利用該等色差值，與塗膜耐熱性同樣地算出色差變化率△Eab*，依據與耐熱性相同的基準，採4階段評估塗膜之耐光性。 The test substrate was prepared by the same procedure as the coating film heat resistance test, and the color difference 1 (L*(1), a*(1) under the C light source was measured by a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optics Co., Ltd.). ), 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 color difference 2 (L*(2), a*(2), b*(2)) under the C light source was measured. Using the color difference values, the color difference change rate ΔEab* was calculated in the same manner as the heat resistance of the coating film, and the light resistance of the coating film was evaluated in four stages in accordance with the same criteria as the heat resistance.

(塗膜耐溶劑性試驗之方法) (Method of film 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光源下之色差1(L*(1)、a*(1)、b*(1))。其後，將基板歷經30分鐘浸漬於N-甲基砒喀烷酮。取出基板後，測定C光源下之色差2(L*(2)、a*(2)、b*(2))。利用該等色差值，與塗膜耐熱性同樣地算出色差變化率△Eab*，依據與耐熱性相同的基準， 採4階段評估塗膜之耐溶劑性。 The test substrate was prepared by the same procedure as the coating film heat resistance test, and the color difference 1 (L*(1), a*(1) under the C light source was measured by a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optics Co., Ltd.). ), b*(1)). Thereafter, the substrate was immersed in N-methylxanthone over 30 minutes. After the substrate was taken out, the color difference 2 (L*(2), a*(2), b*(2)) under the C light source was measured. Using the color difference values, the color difference change rate ΔEab* is calculated in the same manner as the heat resistance of the coating film, and based on the same criteria as the heat resistance. The solvent resistance of the coating film was evaluated in the fourth stage.

於表11表示耐受性(耐熱性、耐光性及耐溶劑性)試驗之結果。 Table 11 shows the results of the tests for resistance (heat resistance, light resistance, and solvent resistance).

(色彩特性及耐受性之評估結果) (Evaluation results of color characteristics and tolerance)

使用成鹽生成物及染料之抗蝕劑材料(R-1A)至(R-15A)時，與使用著色劑僅以顏料構成之抗蝕劑材料(R-17A)時相比較，亮度Y為較高值。然後，使用抗蝕劑材料(R-9A)時，亮度特別高。推測此係由於將著色劑表面予以樹脂處理，著色劑之分散性及溶解性提升，可獲得高亮度。 When the salt-forming product and the dye resist material (R-1A) to (R-15A) are used, the brightness Y is compared with the case where the colorant is only a resist material (R-17A) composed of a pigment. Higher value. Then, when a resist material (R-9A) is used, the brightness is particularly high. It is presumed that this is because the surface of the colorant is subjected to resin treatment, and the dispersibility and solubility of the colorant are improved, and high brightness can be obtained.

又，使用抗蝕劑材料(R-1A)至(R-12A)時，針對耐熱性亦獲得良好結果。然後，使用利用玫瑰紅系染料所獲得的成鹽生成物時，針對耐熱性尤其獲得良好結果。 Further, when the resist materials (R-1A) to (R-12A) were used, good results were obtained for heat resistance. Then, when a salt-forming product obtained by using a rose-red dye is used, particularly good results are obtained for heat resistance.

再者，使用著色劑僅以顏料構成之抗蝕劑材料(R-17)時，針對耐熱性亦獲得良好結果。相對於此，使用含染料及無色之相對成分之成 鹽生成物，或含染料作為著色劑之著色組成物(R-13A)至(R-16A)時，色差變化超過5，耐熱性相對較低。 Further, when a resist material (R-17) composed only of a pigment was used, good results were obtained for heat resistance. In contrast, the use of dye-containing and colorless relative components When a salt product or a coloring composition (R-13A) to (R-16A) containing a dye as a colorant, the color difference changes by more than 5, and the heat resistance is relatively low.

從上述結果可知，含特定成鹽生成物之抗蝕劑材料係於色彩特性(亮度)及耐候性兩方面發揮良好的性能。 From the above results, it is understood that the resist material containing a specific salt-forming product exhibits excellent performance in terms of both color characteristics (brightness) and weather resistance.

[實施例68至79及比較例22至26] [Examples 68 to 79 and Comparative Examples 22 to 26]

藉由以下方法製作彩色濾光片。 A color filter was produced by the following method.

(實施例68：彩色濾光片(CF-1A)) (Example 68: Color filter (CF-1A))

於彩色基板上，形成遮光圖案之黑矩陣，接著利用旋轉塗布機塗布紅色抗蝕劑材料。紅色抗蝕劑材料係塗布為在C光源下之色度會成為x=0.640、y=0.330之膜厚。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。其後，使用由0.2重量%碳酸鈉水溶液所組成的鹼顯影液供作噴霧顯影，去除未曝光部分，以離子交換水洗淨。進而以230℃歷經20分鐘加熱該基板，形成紅色濾光片區段。 A black matrix of a light-shielding pattern was formed on the color substrate, and then a red resist material was applied by a spin coater. The red resist material is applied such that the chromaticity under the C light source becomes a film thickness of x=0.640 and y=0.330. In the coating film, an ultraviolet ray of 300 mJ/cm ^{2 was} irradiated with an ultrahigh pressure mercury lamp by interposing a photomask. Thereafter, an alkali developing solution composed of a 0.2% by weight aqueous sodium carbonate solution was used for spray development, and the unexposed portion was removed, and washed with ion-exchanged water. Further, the substrate was heated at 230 ° C for 20 minutes to form a red filter segment.

接著，於該基板上，藉由與上述同樣的方法塗布綠色抗蝕劑材料。綠色抗蝕劑材料係塗布為在C光源下之色度會成為x=0.300、y=0.600之膜厚。將該塗膜供作針對紅色抗蝕劑材料已於上面敘述同樣之曝光、顯影、洗淨及燒成，形成綠色濾光片區段。進而於該基板上，藉由與上述同樣的手法，塗布藍色抗蝕劑材料。藍色抗蝕劑材料係塗布為在C光源下之色度會成為x=0.150、y=0.06之膜厚。將該塗膜供作針對紅色抗蝕劑材料已於上面敘述同樣之曝光、顯影、洗淨及燒成，形成藍色濾光片區段。如以上獲得彩色濾光片(CF-1A)。 Next, a green resist material was applied on the substrate by the same method as described above. The green resist material is applied such that the chromaticity under the C light source becomes a film thickness of x=0.300 and y=0.600. The coating film was applied to the red resist material as described above for the same exposure, development, washing and firing to form a green filter segment. Further, a blue resist material was applied onto the substrate by the same method as described above. The blue resist material is applied such that the chromaticity under the C light source becomes a film thickness of x=0.150 and y=0.06. The coating film was applied to the red resist material as described above for exposure, development, washing, and firing to form a blue filter segment. A color filter (CF-1A) was obtained as above.

(液晶顯示裝置之製作) (Production of liquid crystal display device)

於彩色濾光片(CF-1A)上，形成由銦錫氧化物(ITO)所組成的電極，於其上形成由聚醯亞胺所組成的配向層。又，於另外準備的玻璃基板之一面，形成TFT陣列及像素電極，於其上形成由聚醯亞胺所組成的配向層。 On the color filter (CF-1A), an electrode composed of indium tin oxide (ITO) was formed, on which an alignment layer composed of polyimine was formed. Further, a TFT array and a pixel electrode were formed on one surface of a separately prepared glass substrate, and an alignment layer composed of polyimide was formed thereon.

接著，於玻璃基板之設有電極之一面，利用密封劑形成具有連通框體內側與外側之通路之框狀圖案。接下來，以電極彼此相面對之方式，於其間隔著間隔珠而黏合該等基板。 Next, a frame-like pattern having a passage that communicates the inside and the outside of the casing is formed by a sealant on one surface of the glass substrate on which the electrode is provided. Next, the electrodes are bonded to each other with the spacers interposed therebetween in such a manner that the electrodes face each other.

接著，於如此獲得之胞(cell)之內部空間，從先前的通路注入液晶組成物。密封通路後，於胞之雙面黏貼偏光板，獲得液晶顯示面板。其後，組合液晶顯示面板及背光單元等，完成液晶顯示裝置。 Next, in the inner space of the cell thus obtained, the liquid crystal composition was injected from the previous via. After sealing the passage, the polarizing plate is adhered to both sides of the cell to obtain a liquid crystal display panel. Thereafter, the liquid crystal display panel, the backlight unit, and the like are combined to complete the liquid crystal display device.

(實施例69至79及比較例22至26：彩色濾光片(CF-2A)至(CF-17A)) (Examples 69 to 79 and Comparative Examples 22 to 26: Color Filters (CF-2A) to (CF-17A))

除了將抗蝕劑材料變更為表6所示之抗蝕劑材料以外，其他均與彩色濾光片(CF-1A)及上述液晶顯示裝置同樣，分別製造彩色濾光片(CF-2A)至(CF-17A)。再者，於第1圖表示所使用的背光之發光光譜。 A color filter (CF-2A) was separately produced in the same manner as the color filter (CF-1A) and the liquid crystal display device except that the resist material was changed to the resist material shown in Table 6. (CF-17A). Furthermore, Fig. 1 shows the luminescence spectrum of the backlight used.

[彩色濾光片(CF-1A)至(CF-17A)之評估] [Evaluation of Color Filters (CF-1A) to (CF-17A)]

於上述液晶顯示裝置顯示彩色圖像，利用顯微分光光度計(Olympus光學公司製「OSP-SP200」)測定對應於紅色、綠色及藍色彩色濾光片之區域之亮度。然後，從其等亮度求出白色顯示之亮度。於表12表示白色顯示之亮度。 A color image was displayed on the liquid crystal display device, and the luminance of the region corresponding to the red, green, and blue color filters was measured by a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.). Then, the brightness of the white display is obtained from the equal brightness. Table 12 shows the brightness of the white display.

表12 Table 12

於彩色濾光片(CF-17A)之藍色濾光片區段，使用自以往適宜使用於該類濾光片區段之銅酞菁顏料及二噁嗪系顏料之組合。另，於彩色濾光片(CF-1A)至(CF-12A)之藍色濾光片區段，使用特定成鹽生成物。若比較彩色濾光片(CF-1A)至(CF-12A)及彩色濾光片(CF-17A)，於彩色濾光片(CF-1A)至(CF-12A)，針對藍色及白色之各者，獲得與彩色濾光片(CF-17A)相比較更高之亮度。 In the blue filter section of the color filter (CF-17A), a combination of a copper phthalocyanine pigment and a dioxazine-based pigment which have been conventionally used for such a filter section is used. Further, a specific salt-forming product is used for the blue filter segments of the color filters (CF-1A) to (CF-12A). Compare color filters (CF-1A) to (CF-12A) and color filters (CF-17A) to color filters (CF-1A) to (CF-12A) for blue and white Each of them obtained a higher brightness than the color filter (CF-17A).

又，於彩色濾光片(CF-13A)至(CF-16A)之藍色濾光片區段，使用染料與無色之相對成分之成鹽生成物、與染料之組合。因此，亮度雖高，但耐受性相對較低。 Further, in the blue filter segments of the color filters (CF-13A) to (CF-16A), a salt-forming product of a dye and a colorless component and a combination with a dye are used. Therefore, although the brightness is high, the tolerance is relatively low.

如以上，藉由使用特定成鹽生成物，可獲得色彩特性(亮度)以及耐熱性、耐光性及耐溶劑性均良好的藍色濾光片區段。 As described above, by using a specific salt-forming product, a blue filter segment having excellent color characteristics (brightness) and heat resistance, light resistance, and solvent resistance can be obtained.

<<試驗3>> <<Trial 3>>

試驗33係關於第3態樣。於試驗3，對應於第3態樣之例子記 載作「實施例」，其他例子記載作「比較例」。 Test 33 is about the third aspect. In Experiment 3, an example corresponding to the third aspect It is described as "Example", and other examples are described as "Comparative Examples".

<丙烯酸樹脂溶液之製造方法> <Method for Producing Acrylic Resin Solution>

(丙烯酸樹脂溶液1B之調製) (Modulation of Acrylic Resin Solution 1B)

於分離式的4支燒瓶，安裝溫度計、冷卻管、氮氣導入管及攪拌裝置，於該反應容器放入環己酮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n-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部及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之丙烯酸樹脂溶液。冷卻至室溫後，將樹脂溶液取樣約2g。將其以180℃加熱歷經20分鐘以使其乾燥，測定未揮發成分。根據如此獲得之非揮發成分含有量，於先前合成之樹脂溶液添加環己酮以使非揮發成分成為20重量%，調製成丙烯酸樹脂溶液1B。 A thermometer, a cooling tube, a nitrogen introduction tube, and a stirring device were attached to the four separate flasks, and 70.0 portions of cyclohexanone were placed in the reaction container. After the temperature was raised to 80 ° C and the reaction vessel was replaced with nitrogen, 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, and 4.3 parts of methacrylic acid were dropped by dropping the tube over 2 hours. A mixture of 7.4 parts of phenol epoxide modified acrylate ("ARONIX M110" manufactured by Toagosei Co., Ltd.) 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 an acrylic resin solution having a weight average molecular weight (Mw) of 26,000. After cooling to room temperature, the resin solution was sampled to about 2 g. This was heated at 180 ° C for 20 minutes to be dried, and the nonvolatile component was measured. Based on the content of the nonvolatile component thus obtained, cyclohexanone was added to the previously synthesized resin solution to have a nonvolatile content of 20% by weight to prepare an acrylic resin solution 1B.

(丙烯酸樹脂溶液2B之調製) (modulation of acrylic resin solution 2B)

於安裝有溫度計、冷卻管、氮氣導入管及攪拌裝置之分離式的4支燒瓶中，注入環己酮207部，將此升溫至80℃。以氮氣置換燒瓶內之氣體後，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，獲得共聚物溶液。 In a separate four-stage flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device, 207 portions of cyclohexanone were injected, and the temperature was raised to 80 °C. After the gas in the flask was replaced with nitrogen gas, 20 parts of methacrylic acid and 20 parts of p-cumyl epoxide ethylene oxide modified acrylate ("ARONIX M110" manufactured by Toagosei Co., Ltd.) and methyl group were dropped by dropping the tube over 2 hours. 45 parts of methyl acrylate, 8.5 parts of 2-hydroxyethyl methacrylate 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 copolymer solution.

接著，停止對燒瓶內供給氮氣，對於該共聚物溶液之總量，一面攪拌一面注入乾燥空氣1小時。其後，冷卻至室溫，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 to the flask was stopped, and dry air was injected for 1 hour while stirring the total amount of the copolymer solution. Thereafter, it was cooled to room temperature and dried at 70 ° C for 3 hours. A mixture of 6.5 parts of 2-methyl propylene oxirane ethyl isocyanate (Karenz MOI, manufactured by Showa Denko Co., Ltd.), 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone was dropped.

將該樹脂溶液取樣約2g。將其以180℃加熱歷經20分鐘以使其乾燥，測定未揮發成分。根據如此獲得之非揮發成分含有量，於先前合成之樹脂溶液添加環己酮以使非揮發成分成為20重量%，調製成丙烯酸樹脂溶液2B。再者，該樹脂溶液2B所含之丙烯酸樹脂之重量平均分子量(Mw)為18000。 The resin solution was sampled at about 2 g. This was heated at 180 ° C for 20 minutes to be dried, and the nonvolatile component was measured. Based on the content of the nonvolatile component thus obtained, cyclohexanone was added to the previously synthesized resin solution to make the nonvolatile component 20% by weight, and the acrylic resin solution 2B was prepared. Further, the weight average molecular weight (Mw) of the acrylic resin contained in the resin solution 2B was 18,000.

(丙烯酸樹脂溶液3B之調製) (Modulation of Acrylic Resin Solution 3B)

於安裝有溫度計、冷卻管、氮氣導入管及攪拌裝置之分離式的4支燒瓶中，注入環己酮207部，將此升溫至80℃。以氮氣置換燒瓶內之氣體後，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，獲得共聚物溶液。 In a separate four-stage flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device, 207 portions of cyclohexanone were injected, and the temperature was raised to 80 °C. After the gas in the flask was replaced with nitrogen gas, 20 parts of methacrylic acid and 20 parts of p-cumyl epoxide ethylene oxide modified acrylate ("ARONIX M110" manufactured by Toagosei Co., Ltd.) and methyl group were dropped by dropping the tube over 2 hours. 45 parts of methyl acrylate, 8.5 parts of 2-hydroxyethyl methacrylate 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 copolymer solution.

停止對燒瓶內供給氮氣，對於該共聚物溶液之總量，一面攪拌一面注入乾燥空氣1小時。其後，冷卻至室溫，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。 Nitrogen gas was supplied to the flask, and dry air was injected for 1 hour while stirring the total amount of the copolymer solution. Thereafter, the mixture was cooled to room temperature, and 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.

將該樹脂溶液取樣約2g。將其以180℃加熱歷經20分鐘以使其乾燥，測定未揮發成分。根據如此獲得之非揮發成分含有量，於先前合成之樹脂溶液添加環己酮以使非揮發成分成為20重量%，調製成丙烯酸樹脂溶液3B。再者，該樹脂溶液3B所含之丙烯酸樹脂之重量平均分子量(Mw) 為19000。 The resin solution was sampled at about 2 g. This was heated at 180 ° C for 20 minutes to be dried, and the nonvolatile component was measured. Based on the content of the nonvolatile component thus obtained, cyclohexanone was added to the previously synthesized resin solution to make the nonvolatile component 20% by weight, and the acrylic resin solution 3B was prepared. Further, the weight average molecular weight (Mw) of the acrylic resin contained in the resin solution 3B It is 19000.

(丙烯酸樹脂溶液4B之調製) (modulation of acrylic resin solution 4B)

於安裝有溫度計、冷卻管、氮氣導入管及攪拌裝置之分離式的4支燒瓶中，注入環己酮370部，將此升溫至80℃。以氮氣置換燒瓶內之氣體後，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。滴下結束後，以110℃進一步使其反應3小時。接著，於該溶液，添加令偶氮雙異丁腈1.0部溶解於環己酮50部而成之溶液，以100℃進一步使其反應1小時。其後，以空氣置換反應容器內，對該容器內放入丙烯酸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℃歷經6小時繼續反應，於固體成分之酸值成為0.5時結束反應。接下來，於如此獲得之溶液，加入四氫苯二酸酐19.5部(生成之羥基之100%)及三乙基胺0.5部，以120℃歷經3.5小時使其反應，藉此獲得丙烯酸樹脂。 In a separate four-stage flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device, 370 parts of cyclohexanone were injected, and the temperature was raised to 80 °C. After replacing the gas in the flask with nitrogen gas, 20 parts of methacrylic acid and 18 parts of cumyl phenol ethylene oxide modified acrylate ("ARONIX M110" manufactured by Toagosei Co., Ltd.) and benzyl group were dropped by dropping the tube over 2 hours. A mixture of 10 parts of methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2.0 parts of 2,2'-azobisisobutyronitrile. After completion of the dropwise addition, the mixture was further reacted at 110 ° C for 3 hours. Next, a solution obtained by dissolving 1.0 part of azobisisobutyronitrile in 50 parts of cyclohexanone was added to the solution, and the mixture was further reacted at 100 ° C for 1 hour. Thereafter, the inside of the reaction vessel was replaced with air, and 9.3 parts of the acrylic acid (100% of the glycerol group), 0.5 part of trimethylaminophenol, and 0.1 part of hydroquinone were placed in the container. The reaction was continued at 120 ° C for 6 hours, and the reaction was terminated when the acid value of the solid component became 0.5. Next, in the solution thus obtained, 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 an acrylic resin.

將該樹脂溶液取樣約2g。將其以180℃加熱歷經20分鐘以使其乾燥，測定未揮發成分。根據如此獲得之非揮發成分含有量，於先前合成之樹脂溶液添加環己酮以使非揮發成分成為20重量%，調製成丙烯酸樹脂溶液4B。再者，該樹脂溶液4B所含之丙烯酸樹脂之重量平均分子量(Mw)為19000。 The resin solution was sampled at about 2 g. This was heated at 180 ° C for 20 minutes to be dried, and the nonvolatile component was measured. Based on the content of the nonvolatile component thus obtained, cyclohexanone was added to the previously synthesized resin solution to make the nonvolatile component 20% by weight, and the acrylic resin solution 4B was prepared. Further, the weight average molecular weight (Mw) of the acrylic resin contained in the resin solution 4B was 19,000.

<成鹽生成物之製造方法> <Method for Producing Salt-Forming Product>

(成鹽生成物1B) (salt formation product 1B)

採下述程序合成由玫瑰紅6GCP染料(C.I.基本紅1)與呫噸系酸性染料(C.I.酸性紅289)所組成的成鹽生成物1B。 The salt-forming product 1B composed of Rose Bengal 6GCP dye (C.I. Basic Red 1) and a xanthene-based acid dye (C.I. Acid Red 289) was synthesized by the following procedure.

於7至15莫耳%之氫氧化鈉溶液中，添加呫噸系酸性染料(C.I.酸性紅289)，充分攪拌該液體。將該溶液加熱到70至90℃後，於其逐次些許滴下玫瑰紅6GCP染料(C.I.基本紅1)。玫瑰紅6GCP染料亦可作為水溶液使用。玫瑰紅6GCP染料之滴下結束後，為了令其充分反應，以70至90℃，歷經40至60分鐘攪拌該溶液。反應的終點係於濾紙滴下反應液而已無滲液之時點。亦即，於已無滲液時，判斷獲得成鹽生成物。一面攪拌一面放冷至室溫後，進行吸取過濾，進一步予以水洗。水洗後，從殘留於濾紙上之成鹽生成物，利用乾燥機去除水分，獲得玫瑰紅6GCP染料(C.I.基本紅1)與呫噸系酸性染料(C.I.酸性紅289)之成鹽生成物，即成鹽生成物1B。 To a sodium hydroxide solution of 7 to 15 mol%, a xanthene-based acid dye (C.I. Acid Red 289) was added, and the liquid was thoroughly stirred. After the solution was heated to 70 to 90 ° C, Rose Bengal 6 GCP dye (C.I. Basic Red 1) was successively dropped therefrom. Rose red 6GCP dye can also be used as an aqueous solution. After the completion of the dropwise drop of the rose red 6GCP dye, the solution was stirred at 70 to 90 ° C for 40 to 60 minutes in order to allow sufficient reaction. The end point of the reaction is at the point when the filter paper drops the reaction solution without bleeding. That is, when the liquid has not been oozing, it is judged that the salt-forming product is obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of rose red 6GCP dye (CI basic red 1) and xanthene acid dye (CI acid red 289). Salt formation product 1B.

(成鹽生成物2B) (salt formation product 2B)

採下述程序合成由玫瑰紅6GCP染料(C.I.基本紅1)與酸性玫瑰紅(C.I.酸性紅52)所組成的成鹽生成物2B。 The salt-forming product 2B composed of rose red 6GCP dye (C.I. basic red 1) and acid rose red (C.I. acid red 52) was synthesized by the following procedure.

於7至15莫耳%之氫氧化鈉溶液中，添加酸性玫瑰紅(C.I.酸性紅52)，充分攪拌該液體。將該溶液加熱到70至90℃後，於其逐次些許滴下玫瑰紅6GCP染料(C.I.基本紅1)。玫瑰紅6GCP染料亦可作為水溶液使用。玫瑰紅6GCP染料之滴下結束後，為了令其充分反應，以70至90℃，歷經40至60分鐘攪拌該溶液。反應的終點係於濾紙滴下反應液而已無滲液之時點。亦即，於已無滲液時，判斷獲得成鹽生成物。一面攪拌一面放冷至室溫後，進行吸取過濾，進一步予以水洗。水洗後，從殘留於濾紙上之成鹽生成物，利用乾燥機去除水分，獲得玫瑰紅6GCP染料(C.I.基本紅1)與酸性 玫瑰紅(C.I.酸性紅52)之成鹽生成物，即成鹽生成物2B。 Acid rose red (C.I. Acid Red 52) was added to a 7 to 15 mol% sodium hydroxide solution, and the liquid was thoroughly stirred. After the solution was heated to 70 to 90 ° C, Rose Bengal 6 GCP dye (C.I. Basic Red 1) was successively dropped therefrom. Rose red 6GCP dye can also be used as an aqueous solution. After the completion of the dropwise drop of the rose red 6GCP dye, the solution was stirred at 70 to 90 ° C for 40 to 60 minutes in order to allow sufficient reaction. The end point of the reaction is at the point when the filter paper drops the reaction solution without bleeding. That is, when the liquid has not been oozing, it is judged that the salt-forming product is obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain rose red 6GCP dye (C.I. basic red 1) and acid. A salt-forming product of rose red (C.I. Acid Red 52), that is, a salt-forming product 2B.

(成鹽生成物3B) (salt formation product 3B)

採下述程序合成由玫瑰紅6GCP染料(C.I.基本紅1)與曙紅(C.I.酸性紅87)所組成的成鹽生成物3B。 The salt-forming product 3B composed of Rose Bengal 6GCP dye (C.I. Basic Red 1) and Eosin (C.I. Acid Red 87) was synthesized by the following procedure.

於7至15莫耳%之氫氧化鈉溶液中，添加曙紅(C.I.酸性紅87)，充分攪拌該液體。將該溶液加熱到70至90℃後，於其逐次些許滴下玫瑰紅6GCP染料(C.I.基本紅1)。玫瑰紅6GCP染料亦可作為水溶液使用。玫瑰紅6GCP染料之滴下結束後，為了令其充分反應，以70至90℃，歷經40至60分鐘攪拌該溶液。反應的終點係於濾紙滴下反應液而已無滲液之時點。亦即，於已無滲液時，判斷獲得成鹽生成物。一面攪拌一面放冷至室溫後，進行吸取過濾，進一步予以水洗。水洗後，從殘留於濾紙上之成鹽生成物，利用乾燥機去除水分，獲得玫瑰紅6GCP染料(C.I.基本紅1)與曙紅(C.I.酸性紅87)之成鹽生成物，即成鹽生成物3B。 To the sodium hydroxide solution of 7 to 15 mol%, eosin (C.I. Acid Red 87) was added, and the liquid was thoroughly stirred. After the solution was heated to 70 to 90 ° C, Rose Bengal 6 GCP dye (C.I. Basic Red 1) was successively dropped therefrom. Rose red 6GCP dye can also be used as an aqueous solution. After the completion of the dropwise drop of the rose red 6GCP dye, the solution was stirred at 70 to 90 ° C for 40 to 60 minutes in order to allow sufficient reaction. The end point of the reaction is at the point when the filter paper drops the reaction solution without bleeding. That is, when the liquid has not been oozing, it is judged that the salt-forming product is obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of rose red 6GCP dye (CI basic red 1) and blush (CI acid red 87), that is, salt formation. 3B.

(成鹽生成物4B) (salt formation product 4B)

採下述程序合成由玫瑰紅6GCP染料(C.I.基本紅1)與C.I酸性紅388所組成的成鹽生成物4B。 The salt-forming product 4B composed of Rose Bengal 6GCP dye (C.I. Basic Red 1) and C.I Acid Red 388 was synthesized by the following procedure.

於7至15莫耳%之氫氧化鈉溶液中，添加C.I酸性紅388，充分攪拌該液體。將該溶液加熱到70至90℃後，於其逐次些許滴下玫瑰紅6GCP染料(C.I.基本紅1)。玫瑰紅6GCP染料亦可作為水溶液使用。玫瑰紅6GCP染料之滴下結束後，為了令其充分反應，以70至90℃，歷經40至60分鐘攪拌該溶液。反應的終點係於濾紙滴下反應液而已無滲液之時點。亦即，於已無滲液時，判斷獲得成鹽生成物。一面攪拌一面放冷至室溫後，進行 吸取過濾，進一步予以水洗。水洗後，從殘留於濾紙上之成鹽生成物，利用乾燥機去除水分，獲得玫瑰紅6GCP染料(C.I.基本紅1)與C.I酸性紅388之成鹽生成物，即成鹽生成物4B。 To a sodium hydroxide solution of 7 to 15 mol%, C.I Acid Red 388 was added, and the liquid was thoroughly stirred. After the solution was heated to 70 to 90 ° C, Rose Bengal 6 GCP dye (C.I. Basic Red 1) was successively dropped therefrom. Rose red 6GCP dye can also be used as an aqueous solution. After the completion of the dropwise drop of the rose red 6GCP dye, the solution was stirred at 70 to 90 ° C for 40 to 60 minutes in order to allow sufficient reaction. The end point of the reaction is at the point when the filter paper drops the reaction solution without bleeding. That is, when the liquid has not been oozing, it is judged that the salt-forming product is obtained. After stirring and letting it cool to room temperature, proceed The filtrate was suctioned and further washed with water. After washing with water, the salt-forming product remaining on the filter paper was removed by a dryer to obtain a salt-forming product of rose red 6GCP dye (C.I. basic red 1) and C.I acid red 388, that is, salt-forming product 4B.

(成鹽生成物5B) (salt formation product 5B)

採下述程序合成由玫瑰紅B染料(C.I.基本紫10)與呫噸系酸性染料(C.I.酸性紅289)所組成的成鹽生成物5B。 The salt-forming product 5B composed of Rose Bengal B dye (C.I. Basic Violet 10) and a xanthene-based acid dye (C.I. Acid Red 289) was synthesized by the following procedure.

於7至15莫耳%之氫氧化鈉溶液中，添加呫噸系酸性染料(C.I.酸性紅289)，充分攪拌該液體。將該溶液加熱到70至90℃後，於其逐次些許滴下玫瑰紅B染料(C.I.基本紫10)。玫瑰紅B染料染料亦可作為水溶液使用。玫瑰紅B染料之滴下結束後，為了令其充分反應，以70至90℃，歷經40至60分鐘攪拌該溶液。反應的終點係於濾紙滴下反應液而已無滲液之時點。亦即，於已無滲液時，判斷獲得成鹽生成物。一面攪拌一面放冷至室溫後，進行吸取過濾，進一步予以水洗。水洗後，從殘留於濾紙上之成鹽生成物，利用乾燥機去除水分，獲得玫瑰紅B染料(C.I.基本紫10)與呫噸系酸性染料(C.I.酸性紅289)之成鹽生成物，即成鹽生成物5B。 To a sodium hydroxide solution of 7 to 15 mol%, a xanthene-based acid dye (C.I. Acid Red 289) was added, and the liquid was thoroughly stirred. After the solution was heated to 70 to 90 ° C, Rose Bengal B dye (C.I. Basic Violet 10) was successively dropped therefrom. Rose Bengal B dye can also be used as an aqueous solution. After the completion of the dropwise addition of the rose bengal B dye, the solution was stirred at 70 to 90 ° C for 40 to 60 minutes in order to allow sufficient reaction. The end point of the reaction is at the point when the filter paper drops the reaction solution without bleeding. That is, when the liquid has not been oozing, it is judged that the salt-forming product is obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of rose bengal B dye (CI basic violet 10) and xanthene acid dye (CI acid red 289). Salt formation product 5B.

(成鹽生成物6B) (salt formation product 6B)

採下述程序合成由玫瑰紅B染料(C.I.基本紫10)與呫噸系酸性染料(酸性夾竹桃紅：C.I.酸性紅92)所組成的成鹽生成物6B。 The salt-forming product 6B composed of Rose Bengal B dye (C.I. Basic Violet 10) and a xanthene-based acid dye (acid oleander red: C.I. Acid Red 92) was synthesized by the following procedure.

於7至15莫耳%之氫氧化鈉溶液中，添加酸性夾竹桃紅PB染料(C.I.酸性紅92)，充分攪拌該液體。將該溶液加熱到70至90℃後，於其逐次些許滴下玫瑰紅B染料(C.I.基本紫10)。玫瑰紅B染料染料亦可作為水溶液使用。玫瑰紅B染料之滴下結束後，為了令其充分反應，以70至90℃，歷經 40至60分鐘攪拌該溶液。反應的終點係於濾紙滴下反應液而已無滲液之時點。亦即，於已無滲液時，判斷獲得成鹽生成物。一面攪拌一面放冷至室溫後，進行吸取過濾，進一步予以水洗。水洗後，從殘留於濾紙上之成鹽生成物，利用乾燥機去除水分，獲得玫瑰紅B染料(C.I.基本紫10)與酸性夾竹桃紅PB染料(C.I.酸性紅92)之成鹽生成物，即成鹽生成物6B。 An acidic oleander red PB dye (C.I. Acid Red 92) was added to a 7 to 15 mol% sodium hydroxide solution, and the liquid was thoroughly stirred. After the solution was heated to 70 to 90 ° C, Rose Bengal B dye (C.I. Basic Violet 10) was successively dropped therefrom. Rose Bengal B dye can also be used as an aqueous solution. After the end of the drop of the rose red B dye, in order to make it fully react, at 70 to 90 ° C, after going through The solution was stirred for 40 to 60 minutes. The end point of the reaction is at the point when the filter paper drops the reaction solution without bleeding. That is, when the liquid has not been oozing, it is judged that the salt-forming product is obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of rose bengal B dye (CI basic purple 10) and acidic oleander red PB dye (CI acid red 92). Salt formation product 6B.

(成鹽生成物7B) (salt formation product 7B)

採下述程序合成由玫瑰紅G染料(C.I.基本紅8)與呫噸系酸性染料(C.I.酸性紅289)所組成的成鹽生成物7B。 The salt-forming product 7B composed of Rose Bengal G dye (C.I. Basic Red 8) and a xanthene-based acid dye (C.I. Acid Red 289) was synthesized by the following procedure.

於7至15莫耳%之氫氧化鈉溶液中，添加呫噸系酸性染料(C.I.酸性紅289)，充分攪拌該液體。將該溶液加熱到70至90℃後，於其逐次些許滴下玫瑰紅G染料(C.I.基本紅8)。玫瑰紅G染料染料亦可作為水溶液使用。玫瑰紅G染料之滴下結束後，為了令其充分反應，以70至90℃，歷經40至60分鐘攪拌該溶液。反應的終點係於濾紙滴下反應液而已無滲液之時點。亦即，於已無滲液時，判斷獲得成鹽生成物。一面攪拌一面放冷至室溫後，進行吸取過濾，進一步予以水洗。水洗後，從殘留於濾紙上之成鹽生成物，利用乾燥機去除水分，獲得玫瑰紅G染料(C.I.基本紅8)與呫噸系酸性染料(C.I.酸性紅289)之成鹽生成物，即成鹽生成物7B。 To a sodium hydroxide solution of 7 to 15 mol%, a xanthene-based acid dye (C.I. Acid Red 289) was added, and the liquid was thoroughly stirred. After the solution was heated to 70 to 90 ° C, Rose Bengal G dye (C.I. Basic Red 8) was successively dropped therefrom. Rose red G dye can also be used as an aqueous solution. After the completion of the dropwise drop of the rose red G dye, the solution was stirred at 70 to 90 ° C for 40 to 60 minutes in order to allow sufficient reaction. The end point of the reaction is at the point when the filter paper drops the reaction solution without bleeding. That is, when the liquid has not been oozing, it is judged that the salt-forming product is obtained. After cooling to room temperature while stirring, the mixture was suction filtered and further washed with water. After washing with water, the salt-forming product remaining on the filter paper is removed by a dryer to obtain a salt-forming product of Rose Bengal G dye (CI Basic Red 8) and xanthene-based acid dye (CI Acid Red 289). Salt formation product 7B.

(成鹽生成物8B) (salt formation product 8B)

於100質量部之成鹽生成物1B，添加松香改質順丁烯二酸樹脂(酸價130mgKOH/g、荒川化學公司製MALKYD No.32)30質量部，以加壓捏合機予以混合。該混合係將材料溫度設定為120℃，歷經30分鐘進行。冷卻後，利用噴射氣流式粉碎機(Nippon Pneumatic工業公司製IDS-2型)進行微 粉碎，獲得平均粒徑8mm之粒子作為成鹽生成物8B。 To the salt-forming product 1B of 100 parts by mass, 30 parts by mass of rosin-modified maleic acid resin (acid value: 130 mgKOH/g, MALKYD No. 32, manufactured by Arakawa Chemical Co., Ltd.) was added, and the mixture was mixed by a pressure kneader. The mixing was carried out by setting the material temperature to 120 ° C for 30 minutes. After cooling, the jet flow type pulverizer (IDS-2 type manufactured by Nippon Pneumatic Industries Co., Ltd.) was used for microfiltration. After pulverization, particles having an average particle diameter of 8 mm were obtained as the salt-forming product 8B.

<微細化顏料之製造方法> <Method for Producing Micronized Pigment>

(紅色微細顏料1B之生成) (generation of red fine pigment 1B)

將二酮吡咯並吡咯系紅色顏料之C.I.Pigment Red 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℃歷經6小時予以混合攪拌。接著，將該混合攪拌物放入8公升的溫水中，一面加熱至80℃，一面歷經2小時予以攪拌而製成漿狀。重複過濾及水洗以去除氯化鈉及二乙二醇後，以85℃乾燥一晝夜，獲得190部的紅色微細顏料。紅色微細顏料之相對表面積為65m²/g。 200 parts of CIPigment 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 stainless steel 1-gallon kneader (Inoue Co., Ltd.) The system was mixed and stirred at 80 ° C for 6 hours. Next, the kneaded material was placed in 8 liters of warm water, and heated to 80 ° C, and stirred for 2 hours to prepare a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 85 ° C for one day and night to obtain 190 red fine pigments. The red fine pigment has a relative surface area of 65 m ² /g.

(紅色微細顏料1B之生成) (generation of red fine pigment 1B)

將二酮吡咯並吡咯系紅色顏料之C.I.Pigment Red 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℃歷經6小時予以混合攪拌。接著，將該混合攪拌物放入8公升的溫水中，一面加熱至80℃，一面歷經2小時予以攪拌而製成漿狀。重複過濾及水洗以去除氯化鈉及二乙二醇後，以85℃乾燥一晝夜，獲得190部的紅色微細顏料。紅色微細顏料之相對表面積為65m²/g。 200 parts of CIPigment 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 stainless steel 1-gallon kneader (Inoue Co., Ltd.) The system was mixed and stirred at 80 ° C for 6 hours. Next, the kneaded material was placed in 8 liters of warm water, and heated to 80 ° C, and stirred for 2 hours to prepare a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 85 ° C for one day and night to obtain 190 red fine pigments. The red fine pigment has a relative surface area of 65 m ² /g.

(洋紅色微細顏料1B之生成) (generation of magenta fine pigment 1B)

將喹吖酮系紅色顏料之C.I.Pigment Red 122(Clariant公司製「HOSTAPERM Pink E」)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℃歷經6小時予以混合攪拌。接著， 將該混合攪拌物放入8公升的溫水中，一面加熱至80℃，一面歷經2小時予以攪拌而製成漿狀。重複過濾及水洗以去除氯化鈉及二乙二醇後，以85℃乾燥一晝夜，獲得190部的洋紅色微細顏料。洋紅色微細顏料之相對表面積為90m²/g。 200 parts of CIPigment Red 122 ("HOSTAPERM Pink E" by Clariant 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 at 80 ° C for 6 hours. Next, the kneaded material was placed in 8 liters of warm water, and heated to 80 ° C, and stirred for 2 hours to form a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 85 ° C for one day and night to obtain 190 magenta fine pigments. The relative surface area of the magenta fine pigment is 90 m ² /g.

(綠色微細顏料1B之生成) (Generation of green fine pigment 1B)

將酞菁系綠色顏料之C.I.Pigment Green 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℃歷經6小時予以混合攪拌。接著，將該混合攪拌物放入8公升的溫水中，一面加熱至80℃，一面歷經2小時予以攪拌而製成漿狀。重複過濾及水洗以去除氯化鈉及二乙二醇後，以85℃乾燥一晝夜，獲得190部的綠色微細顏料1B。綠色微細顏料1B之相對表面積為75m²/g。 200 pieces of CIPigment 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 Co., Ltd.) The system was mixed and stirred at 80 ° C for 6 hours. Next, the kneaded material was placed in 8 liters of warm water, and heated to 80 ° C, and stirred for 2 hours to prepare a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 85 ° C for one day and night to obtain 190 green fine pigments 1B. The relative surface area of the green fine pigment 1B was 75 m ² /g.

(藍色微細顏料1B之生成) (production of blue fine pigment 1B)

將酞菁系藍色顏料之C.I.Pigment Blue 15：6(東洋墨水製造公司製「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℃歷經6小時予以混合攪拌。接著，將該混合攪拌物放入8公升的溫水中，一面加熱至80℃，一面歷經2小時予以攪拌而製成漿狀。重複過濾及水洗以去除氯化鈉及二乙二醇後，以85℃乾燥一晝夜，獲得190部的藍色微細顏料1B。藍色微細顏料1B之相對表面積為80m²/g。 200 pieces of CIPigment 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 1 gallon kneading machine made of stainless steel (Inoue) The production system was mixed and stirred at 80 ° C for 6 hours. Next, the kneaded material was placed in 8 liters of warm water, and heated to 80 ° C, and stirred for 2 hours to prepare a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 85 ° C for one day and night to obtain 190 blue fine pigments 1B. The relative surface area of the blue fine pigment 1B was 80 m ² /g.

(青色微細顏料1B之生成) (production of cyan fine pigment 1B)

將酞菁系藍色顏料之C.I.Pigment Blue 15：3(東洋墨水製造 公司製「Lionol Blue FG-7351」)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℃歷經6小時予以混合攪拌。接著，將該混合攪拌物放入8公升的溫水中，一面加熱至80℃，一面歷經2小時予以攪拌而製成漿狀。重複過濾及水洗以去除氯化鈉及二乙二醇後，以85℃乾燥一晝夜，獲得190部的青色微細顏料1B。青色微細顏料1B之相對表面積為85m²/g。 200 pieces of CIPigment Blue 15:3 ("Lionol Blue FG-7351" manufactured by Toyo Ink Co., Ltd.), 1400 parts of sodium chloride and 360 parts of diethylene glycol were placed in a 1 gallon kneading machine made of stainless steel. (manufactured by Inoue Seisakusho Co., Ltd.), mixing and stirring at 80 ° C for 6 hours. Next, the kneaded material was placed in 8 liters of warm water, and heated to 80 ° C, and stirred for 2 hours to prepare a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 85 ° C for one day and night to obtain 190 parts of cyan fine pigment 1B. The relative surface area of the cyan fine pigment 1B was 85 m ² /g.

(黃色微細顏料1B之生成) (generation of yellow fine pigment 1B)

將異吲哚啉系黃色顏料之C.I.Pigment Yellow 139(日本千葉公司製「IRGA For Yellow 2R-CF」)500部、氯化鈉500部及二乙二醇250部放入不銹鋼製1加侖捏合機(井上製作所製)，以120℃歷經8小時予以混合攪拌。接著，將該混合攪拌物放入5公升的溫水中，一面加熱至70℃，一面歷經1小時予以攪拌而製成漿狀。重複過濾及水洗以去除氯化鈉及二乙二醇後，以80℃乾燥一晝夜，獲得490部的黃色微細顏料1B。黃色微細顏料1B之相對表面積為80m²/g。 500 parts of CIPigment Yellow 139 ("IRGA For Yellow 2R-CF" manufactured by Chiba Corporation, Japan), 500 parts of sodium chloride, and 250 parts of diethylene glycol were placed in a 1-gallon kneader made of stainless steel ( It was mixed and stirred at 120 ° C for 8 hours. Next, the kneaded material was placed in 5 liters of warm water, and heated to 70 ° C, and stirred for 1 hour to form a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80 ° C for one day and night to obtain 490 yellow fine pigments 1B. The yellow fine pigment 1B has a relative surface area of 80 m ² /g.

(黃色微細顏料2B之生成) (generation of yellow fine pigment 2B)

將鎳錯合物系黃色顏料之C.I.Pigment Yellow 150(LANXESS公司「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℃歷經6小時予以混合攪拌。接著，將該混合攪拌物放入8公升的溫水中，一面加熱至80℃，一面歷經2小時予以攪拌而製成漿狀。重複過濾及水洗以去除氯化鈉及二乙二醇後，以85℃乾燥一晝夜，獲得190部的黃色微細顏料2B。黃色微細顏料2B之相對表面積為70m²/g。 200 parts of CIPigment Yellow 150 (LANXESS "E-4GN") of nickel complex yellow pigment, 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.). The mixture was stirred at 80 ° C for 6 hours. Next, the kneaded material was placed in 8 liters of warm water, and heated to 80 ° C, and stirred for 2 hours to prepare a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 85 ° C for one day and night to obtain 190 yellow fine pigment 2B. The yellow fine pigment 2B has a relative surface area of 70 m ² /g.

(紫色微細顏料1B之生成) (Production of purple fine pigment 1B)

將二噁嗪系紫色色顏料之C.I.Pigment Violet 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℃歷經6小時予以混合攪拌。接著，將該混合攪拌物放入8公升的溫水中，一面加熱至80℃，一面歷經2小時予以攪拌而製成漿狀。重複過濾及水洗以去除氯化鈉及二乙二醇後，以85℃乾燥一晝夜，獲得190部的紫色微細顏料1B。紫色微細顏料1B之相對表面積為95m²/g。 200 pieces of CIPigment Violet 23 ("LIONOGEN VIOLET RL" 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 Co., Ltd.) The system was mixed and stirred at 80 ° C for 6 hours. Next, the kneaded material was placed in 8 liters of warm water, and heated to 80 ° C, and stirred for 2 hours to prepare a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 85 ° C for one day and night to obtain 190 purple fine pigment 1B. The relative surface area of the purple fine pigment 1B was 95 m ² /g.

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

(顏料分散體(P-1B)之調製) (Modulation of pigment dispersion (P-1B))

將下述混合物攪拌均勻後，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」)，歷經5小時進行分散處理。其後，以5.0mm的過濾器過濾分散液，獲得顏料分散體(P-1B)。 After the mixture was stirred well, the zirconia beads having a diameter of 0.5 mm were used for dispersion treatment by an IGER mill ("Mini Model M-250 MKII" manufactured by Iger Japan Co., Ltd.) over 5 hours. Thereafter, the dispersion was filtered through a 5.0 mm filter to obtain a pigment dispersion (P-1B).

紅色微細顏料1B：11.0部 Red fine pigment 1B: 11.0

(C.I.Pigment Red 254) (C.I.Pigment Red 254)

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

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：1.0部 Resin type dispersant: 1.0

(日本千葉公司製「EFKA4300」) ("EFKA4300" manufactured by Chiba Corporation, Japan)

(顏料分散體(P-2B)至(P-8B)之調製) (Preparation of pigment dispersions (P-2B) to (P-8B))

除了將紅色微細顏料1B變更為表13所示之顏料以外，其他 均與上述顏料分散體(P-1B)同樣地獲得顏料分散體(P-2B)至(P-8B)。 In addition to changing the red fine pigment 1B to the pigment shown in Table 13, the other Pigment dispersions (P-2B) to (P-8B) were obtained in the same manner as in the above pigment dispersion (P-1B).

<抗蝕劑材料之製造方法> <Method of Manufacturing Resist Material>

(紅色抗蝕劑材料之調製) (modulation of red resist material)

將下述混合物攪拌均勻後，以1.0μm的過濾器過濾分散液，獲得紅色抗蝕劑材料。 After the following mixture was stirred uniformly, the dispersion was filtered through a 1.0 μm filter to obtain a red resist material.

顏料分散體(P-1B)：50.0部 Pigment dispersion (P-1B): 50.0 parts

顏料分散體(P-6B)：10.0部 Pigment dispersion (P-6B): 10.0

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

(綠色抗蝕劑材料之調製) (modulation of green resist material)

將下述混合物攪拌均勻後，以1.0μm的過濾器過濾分散液，獲得綠色抗蝕劑材料。 After the following mixture was stirred uniformly, the dispersion was filtered through a 1.0 μm filter to obtain a green resist material.

顏料分散體(P-3B)：45.0部 Pigment dispersion (P-3B): 45.0 parts

顏料分散體(P-7B)：15.0部 Pigment Dispersion (P-7B): 15.0

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

(青色抗蝕劑材料之調製) (modulation of cyan resist material)

將下述混合物攪拌均勻後，以1.0μm的過濾器過濾分散液，獲得青色抗蝕劑材料。 After the following mixture was stirred uniformly, the dispersion was filtered through a 1.0 μm filter to obtain a cyan resist material.

顏料分散體(P-5B)：60.0部 Pigment dispersion (P-5B): 60.0

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

(黃色抗蝕劑材料之調製) (modulation of yellow resist material)

將下述混合物攪拌均勻後，以1.0μm的過濾器過濾分散液，獲得黃色抗蝕劑材料。 After the following mixture was stirred uniformly, the dispersion was filtered through a 1.0 μm filter to obtain a yellow resist material.

顏料分散體(P-6B)：45.0部 Pigment dispersion (P-6B): 45.0 parts

顏料分散體(P-7B)：15.0部 Pigment Dispersion (P-7B): 15.0

丙烯酸樹脂溶液1B：11.0部 Acrylic resin solution 1B: 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80至87及比較例27至28] [Examples 80 to 87 and Comparative Examples 27 to 28]

(實施例80：彩色濾光片用藍色著色組成物(D-1B)) (Example 80: Blue coloring composition (D-1B) for color filter)

將下述混合物攪拌均勻後，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」)，歷經5小時進行分散處理。其後，以5.0mm的過濾器過濾分散液，獲得顏料分散體(D-1B)。 After the mixture was stirred well, the zirconia beads having a diameter of 0.5 mm were used for dispersion treatment by an IGER mill ("Mini Model M-250 MKII" manufactured by Iger Japan Co., Ltd.) over 5 hours. Thereafter, the dispersion was filtered through a 5.0 mm filter to obtain a pigment dispersion (D-1B).

成鹽生成物1B：11.0部 Salt-forming product 1B: 11.0

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

環己酮：48.0部 Cyclohexanone: 48.0

樹脂型分散劑：1.0部 Resin type dispersant: 1.0

(日本千葉公司製「EFKA4300」) ("EFKA4300" manufactured by Chiba Corporation, Japan)

(實施例81至87及比較例27及28：彩色濾光片用著色組成物(D-2B)至(D-10B)) (Examples 81 to 87 and Comparative Examples 27 and 28: Colored Compositions (D-2B) to (D-10B) for Color Filters)

除了將成鹽生成物1B變更為表14所示之著色劑以外，其他均與彩色濾光片用藍色著色組成物(D-1B))同樣地獲得彩色濾光片用藍色著色組成物(D-2B)至(D-10B)。 A blue coloring composition for a color filter was obtained in the same manner as the blue coloring composition (D-1B) of the color filter, except that the salt-forming product 1B was changed to the coloring agent shown in Table 14. (D-2B) to (D-10B).

[彩色濾光片用著色組成物之評估] [Evaluation of coloring composition for color filters]

採與試驗2同樣的方法進行彩色濾光片用著色組成物(D-1B)至(D-10B)之耐熱性試驗。於表15表示耐熱性試驗之結果。 The heat resistance test of the coloring compositions for color filters (D-1B) to (D-10B) was carried out in the same manner as in Test 2. Table 15 shows the results of the heat resistance test.

表15 Table 15

使用含特定成鹽生成物之著色組成物(D-1B)至(D-8B)時，可達成良好的耐熱性。然後，使用含已藉由松香改質順丁烯二酸樹脂進行處理之著色劑之著色組成物(D-8B)時，尤其可達成良好的性能。相對於此，使用含染料作為著色劑之著色組成物(D-9B)至(D-10B)時，色度變化超過5，耐熱性低。 When the coloring compositions (D-1B) to (D-8B) containing a specific salt-forming product are used, good heat resistance can be achieved. Then, when a coloring composition (D-8B) containing a coloring agent which has been treated with rosin-modified maleic acid resin is used, particularly good performance can be attained. On the other hand, when the coloring composition (D-9B) to (D-10B) containing a dye as a coloring agent is used, the chromaticity change exceeds 5, and heat resistance is low.

從上述結果可知，含特定成鹽生成物之著色組成物係於耐熱性達到良好的性能。 From the above results, it is understood that the coloring composition containing a specific salt-forming product is excellent in heat resistance.

[實施例88至108及比較例29至32] [Examples 88 to 108 and Comparative Examples 29 to 32]

(實施例88：抗蝕劑材料(R-1B)) (Example 88: resist material (R-1B))

將下述混合物攪拌均勻後，以1.0μm的過濾器過濾分散液，獲得抗蝕劑材料(R-1B)。 After the following mixture was stirred uniformly, the dispersion was filtered through a 1.0 μm filter to obtain a resist material (R-1B).

著色組成物(D-1B)：10.0部 Coloring composition (D-1B): 10.0

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

丙烯酸樹脂溶液1B：11.0部 Acrylic resin solution 1B: 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89至108及比較例29至32：抗蝕劑材料(R-2B)至(R-25B)) (Examples 89 to 108 and Comparative Examples 29 to 32: Resist materials (R-2B) to (R-25B))

除了以表16所示之著色組成物或顏料分散體置換著色組成物(D-1B)及顏料分散體(P-4B)，如表16變更其調配量以外，其他均與抗蝕劑材料(R-1B)同樣地獲得鹼顯影型抗蝕劑材料(R-2B)至(R-12B)、(R-24B)至(R-26B)、及(R-23B)至(R-25B)。再者，於一部分抗蝕劑材料，並用著色組成物及顏料分散體，抗蝕劑材料全體設為100部時，著色組成物及/或顏料分散體之合計量為60部。 Except that the coloring composition or the pigment dispersion shown in Table 16 was substituted for the coloring composition (D-1B) and the pigment dispersion (P-4B), as shown in Table 16, the amount of the composition was changed, and the other was combined with the resist material ( R-1B) Similarly, alkali-developing resist materials (R-2B) to (R-12B), (R-24B) to (R-26B), and (R-23B) to (R-25B) are obtained. . In addition, when a part of the resist material and the coloring composition and the pigment dispersion were used in combination, and the total amount of the resist material was 100, the total amount of the coloring composition and/or the pigment dispersion was 60.

又，除了將以丙烯酸樹脂溶液2B至4B置換丙烯酸樹脂溶液1B以外，其他均與抗蝕劑材料(R-1B)同樣地分別獲得鹼顯影型抗蝕劑材料(R-13B)至(R-15B)。進而除了將以丙烯酸樹脂溶液2B至4B置換丙烯酸樹脂溶液1B以外，其他均與抗蝕劑材料(R-16B)同樣地分別獲得鹼顯影型抗蝕劑材料(R-19B)至(R-21B)。 In addition, the alkali-developing resist materials (R-13B) to (R-) were obtained in the same manner as the resist material (R-1B) except that the acrylic resin solution 2B was replaced with the acrylic resin solution 2B to 4B. 15B). Further, the alkali-developing resist materials (R-19B) to (R-21B) were obtained in the same manner as the resist material (R-16B) except that the acrylic resin solution 2B was replaced with the acrylic resin solution 2B to 4B. ).

[抗蝕劑材料(R-1B)至(R-25B)之評估] [Evaluation of resist materials (R-1B) to (R-25B)]

採下述方法進行抗蝕劑材料(R-1B)至(R-25B)之色彩特性(亮度)評估及耐受性(耐熱性、耐光性及耐溶劑性)試驗。 The color characteristics (brightness) evaluation and the resistance (heat resistance, light resistance, and solvent resistance) of the resist materials (R-1B) to (R-25B) were tested by the following methods.

(色彩特性評估) (color characterization)

於玻璃基板上，塗布抗蝕劑材料。具體而言，藍色抗蝕劑材料係塗布為在C光源下之色度會成為y=0.060之膜厚。洋紅色抗蝕劑材料係塗布為在C光源下之色度會成為x=0.348之膜厚。將該等基板以230℃歷經20分鐘加熱，藉此於基板上形成著色層。其後，利用顯微分光光度計(Olympus光學公司製「OSP-SP200」)測定形成有著色層之基板之亮度Y。 A resist material is applied on the glass substrate. Specifically, the blue resist material is applied such that the chromaticity under the C light source becomes a film thickness of y=0.060. The magenta resist material is applied such that the chromaticity under the C light source becomes a film thickness of x = 0.348. The substrates were heated at 230 ° C for 20 minutes to form a colored layer on the substrate. Thereafter, the luminance Y of the substrate on which the colored layer was formed was measured by a microscopic spectrophotometer ("OSP-SP200" manufactured by Olympus Optics Co., Ltd.).

(耐受性試驗) (tolerance test)

進行與試驗2所進行者相同之塗膜耐熱性試驗、塗膜耐光性試驗及塗膜耐溶劑性試驗。 The coating film heat resistance test, the coating film light resistance test, and the coating film solvent resistance test were performed in the same manner as in Test 2.

(抗蝕劑材料之評估結果) (evaluation result of resist material)

於表17表示抗蝕劑材料(R-1B)至(R-25B)之評估結果 Table 17 shows the evaluation results of the resist materials (R-1B) to (R-25B).

表17 Table 17

使用含成鹽生成物及染料之抗蝕劑材料(R-1B)至(R-22B)及(R-24B)時，與使用著色劑僅含顏料之抗蝕劑材料(R-23B)及(R-25B)時相比較，可達成較高亮度Y。然後，使用抗蝕劑材料(R-8B)時，尤其可達成高亮度。推測此係由於將著色劑表面予以樹脂處理，著色劑之分散性及溶解性提升，可獲得高亮度。 When a resist material (R-1B) to (R-22B) and (R-24B) containing a salt-forming product and a dye is used, a resist material (R-23B) containing only a pigment and a colorant is used. (R-25B) The higher brightness Y can be achieved by comparing the phases. Then, when a resist material (R-8B) is used, high brightness can be achieved in particular. It is presumed that this is because the surface of the colorant is subjected to resin treatment, and the dispersibility and solubility of the colorant are improved, and high brightness can be obtained.

又，使用含特定成鹽生成物之抗蝕劑材料(R-1B)至(R-21B)時，於耐受性試驗亦得到良好結果。然後，使用含成鹽生成物及顏料之抗蝕劑材料時，尤其獲得良好結果。再者，使用含成鹽生成物及染料之抗蝕劑材料(R-12B)及(R-18B)時，耐受性試驗之結果稍差，但為實用上不構成問題的程度。 Further, when the resist materials (R-1B) to (R-21B) containing the specific salt-forming products were used, good results were obtained in the resistance test. Then, when a resist material containing a salt-forming product and a pigment is used, particularly good results are obtained. In addition, when the resist materials (R-12B) and (R-18B) containing a salt-forming product and a dye were used, the results of the resistance test were slightly inferior, but they did not pose a problem in practical use.

又，使用僅含顏料作為著色劑之抗蝕劑材料(R-23B)及(R-25B)時，耐受性試驗之結果良好，但亮度Y低。相對於此，使用僅含染料作為著色劑之抗蝕劑材料(R-22B)及(R-24B)時，色差變化超過5，耐受性較低。 Further, when resist materials (R-23B) and (R-25B) containing only a pigment as a colorant were used, the results of the resistance test were good, but the luminance Y was low. On the other hand, when the resist materials (R-22B) and (R-24B) containing only a dye as a colorant are used, the chromatic aberration changes by more than 5, and the resistance is low.

又，使用抗蝕劑材料(R-13B)至(R-15B)及(R-19B)至(R-21B)時，耐受性試驗之結果亦良好。據判此係由於藉由使用具有乙烯結合之活性能量線硬化樹脂，塗膜的硬化性提升。 Further, when the resist materials (R-13B) to (R-15B) and (R-19B) to (R-21B) were used, the results of the resistance test were also good. It is said that this is because the hardenability of the coating film is improved by using an active energy ray-curable resin having ethylene bonding.

從上述結果可知，含特定成鹽生成物之抗蝕劑材料係於色彩特性(亮度)及耐受性兩方面發揮良好的性能。 From the above results, it is understood that the resist material containing a specific salt-forming product exhibits excellent performance in terms of both color characteristics (brightness) and resistance.

[實施例109至129及比較例36至39] [Examples 109 to 129 and Comparative Examples 36 to 39]

藉由以下所記載的方法製作原色系及補色系彩色濾光片。 A primary color system and a complementary color system color filter were produced by the method described below.

(實施例100：原色系彩色濾光片(CF-1B)) (Example 100: primary color system color filter (CF-1B))

於彩色基板上，形成遮光圖案之黑矩陣，接著利用旋轉塗布機塗布紅色抗蝕劑材料。紅色抗蝕劑材料係塗布為在C光源下之色度會成為x=0.640之膜厚。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。其後，使用由0.2重量%碳酸鈉水溶液所組成的鹼顯影液供作噴霧顯影，去除未曝光部分，以離子交換水洗淨。進而以230℃歷經20分鐘加熱該基板，形成紅色濾光片區段。 A black matrix of a light-shielding pattern was formed on the color substrate, and then a red resist material was applied by a spin coater. The red resist material is applied such that the chromaticity under the C light source becomes a film thickness of x = 0.640. In the coating film, an ultraviolet ray of 300 mJ/cm ^{2 was} irradiated with an ultrahigh pressure mercury lamp by interposing a photomask. Thereafter, an alkali developing solution composed of a 0.2% by weight aqueous sodium carbonate solution was used for spray development, and the unexposed portion was removed, and washed with ion-exchanged water. Further, the substrate was heated at 230 ° C for 20 minutes to form a red filter segment.

接著，於該基板上，藉由與上述同樣的方法塗布綠色抗蝕劑材料。綠色抗蝕劑材料係塗布為在C光源下之色度會成為y=0.600之膜厚。將該塗膜供作針對紅色抗蝕劑材料已於上面敘述同樣之曝光、顯影、洗淨及燒成，形成綠色濾光片區段。進而於該基板上，藉由與上述同樣的手法，塗布藍色抗蝕劑材料(R-1B)。藍色抗蝕劑材料係塗布為在C光源下之色度會成為y=0.06之膜厚。將該塗膜供作針對紅色抗蝕劑材料已於上面敘述同樣之曝光、顯影、洗淨及燒成，形成藍色濾光片區段。如以上獲得彩色濾光片(CF-1B)。 Next, a green resist material was applied on the substrate by the same method as described above. The green resist material is applied such that the chromaticity under the C light source becomes a film thickness of y = 0.600. The coating film was applied to the red resist material as described above for the same exposure, development, washing and firing to form a green filter segment. Further, a blue resist material (R-1B) was applied onto the substrate by the same method as described above. The blue resist material is applied such that the chromaticity under the C light source becomes a film thickness of y=0.06. The coating film was applied to the red resist material as described above for exposure, development, washing, and firing to form a blue filter segment. A color filter (CF-1B) was obtained as above.

(液晶顯示裝置之製作) (Production of liquid crystal display device)

除了使用彩色濾光片(CF-1B)取代彩色濾光片(CF-1A)以外，其他均藉由與實施例68所說明之方法相同的方法製作液晶顯示裝置。(實施例110至123及比較例36及37：原色系彩色濾光片(CF-2B)至(CF-17B))除了將抗蝕劑材料變更為表18所示之抗蝕劑材料以外，其他均與彩色濾光片(CF-1B)及上述液晶顯示裝置相同，分別製作原色系彩色濾光片(CF-2B)至(CF-17B)。 A liquid crystal display device was produced by the same method as that described in Example 68, except that a color filter (CF-1B) was used instead of the color filter (CF-1A). (Examples 110 to 123 and Comparative Examples 36 and 37: primary color system color filters (CF-2B) to (CF-17B)) except that the resist material was changed to the resist material shown in Table 18, Others were the same as the color filter (CF-1B) and the above liquid crystal display device, and primary color system color filters (CF-2B) to (CF-17B) were produced, respectively.

(實施例124：補色系彩色濾光片(CF-18B)) (Example 124: complementary color system color filter (CF-18B))

於彩色基板上，形成遮光圖案之黑矩陣，接著利用旋轉塗布機塗布洋紅色抗蝕劑材料(R-16B)。洋紅色抗蝕劑材料(R-16B)係塗布為在C光源下之色度會成為x=0.348之膜厚。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。其後，使用由0.2重量%碳酸鈉水溶液所組成的鹼顯影液供作噴霧顯影，去除未曝光部分，以離子交換水洗淨。進而以230℃歷經20分鐘加熱該基板，形成洋紅色濾光片區段。 A black matrix of a light-shielding pattern was formed on the color substrate, and then a magenta resist material (R-16B) was applied by a spin coater. The magenta resist material (R-16B) was applied such that the chromaticity under the C light source became a film thickness of x=0.348. In the coating film, an ultraviolet ray of 300 mJ/cm ^{2 was} irradiated with an ultrahigh pressure mercury lamp by interposing a photomask. Thereafter, an alkali developing solution composed of a 0.2% by weight aqueous sodium carbonate solution was used for spray development, and the unexposed portion was removed, and washed with ion-exchanged water. Further, the substrate was heated at 230 ° C for 20 minutes to form a magenta filter segment.

接著，於該基板上，藉由與上述同樣的方法塗布黃色抗蝕劑材料。黃色抗蝕劑材料係塗布為在C光源下之色度會成為x=0.440之膜厚。將該塗膜供作針對洋紅色抗蝕劑材料已於上面敘述同樣之曝光、顯影、洗淨及燒成，形成黃色濾光片區段。進而於該基板上，藉由與上述同樣的手法，塗布青色抗蝕劑材料。青色抗蝕劑材料係塗布為在C光源下之色度會成為y=0.06之膜厚。將該塗膜供作針對洋紅色抗蝕劑材料已於上面敘述同樣之曝光、顯影、洗淨及燒成，形成青色濾光片區段。如以上獲得彩色濾光片(CF-18B)。 Next, a yellow resist material was applied on the substrate by the same method as described above. The yellow resist material is applied such that the chromaticity under the C light source becomes a film thickness of x = 0.440. The coating film was applied to the magenta resist material as described above for the same exposure, development, washing and firing to form a yellow filter segment. Further, a cyan resist material was applied onto the substrate by the same method as described above. The cyan resist material is applied such that the chromaticity under the C light source becomes a film thickness of y=0.06. The coating film was applied to the magenta resist material as described above for the same exposure, development, washing and firing to form a cyan filter segment. A color filter (CF-18B) was obtained as above.

(液晶顯示裝置之製作) (Production of liquid crystal display device)

除了使用彩色濾光片(CF-18B)取代彩色濾光片(CF-1A)以外，其他均藉由與實施例68所說明之方法相同的方法製作液晶顯示裝置。 A liquid crystal display device was produced by the same method as that described in Example 68, except that a color filter (CF-18B) was used instead of the color filter (CF-1A).

(實施例125至129及比較例38及39：補色系彩色濾光片(CF-19B)至(CF-25B)) (Examples 125 to 129 and Comparative Examples 38 and 39: complementary color system color filters (CF-19B) to (CF-25B))

除了將抗蝕劑材料變更為表19所示之抗蝕劑材料以外，其他均與彩色濾光片(CF-18B)及上述液晶顯示裝置相同，分別製作補色系彩色濾光片(CF-1B)至(CF-25B)。 A complementary color system color filter (CF-1B) was produced in the same manner as the color filter (CF-18B) and the liquid crystal display device except that the resist material was changed to the resist material shown in Table 19. ) to (CF-25B).

[彩色濾光片(CF-1B)至(CF-25B)之評估] [Evaluation of Color Filters (CF-1B) to (CF-25B)]

於上述液晶顯示裝置顯示彩色圖像。然後，針對含原色系彩色濾光片之液晶顯示，利用顯微分光光度計(Olympus光學公司製「OSP-SP200」)測定對應於紅色、綠色及藍色彩色濾光片之區域之亮度。又，針對含補色系彩色濾光片之液晶顯示，利用顯微分光光度計(Olympus光學公司製「OSP-SP200」)測定對應於紅色、綠色及藍色彩色濾光片之區域之亮度。然後，從該等亮度求出白色顯示之亮度。 A color image is displayed on the liquid crystal display device described above. Then, for the liquid crystal display containing the primary color filter, the luminance corresponding to the regions of the red, green, and blue color filters was measured by a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.). Further, for the liquid crystal display containing the complementary color system color filter, the luminance corresponding to the regions of the red, green, and blue color filters was measured by a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.). Then, the brightness of the white display is obtained from the brightness.

於表18表示針對含原色系彩色濾光片之液晶顯示裝置所獲得的結果。又，於表19表示針對含補色系彩色濾光片之液晶顯示裝置所獲得的結果。 Table 18 shows the results obtained for the liquid crystal display device including the primary color filter. Further, Table 19 shows the results obtained for the liquid crystal display device containing the complementary color system color filter.

表18 Table 18

於原色系彩色濾光片(CF-17B)之藍色濾光片區段，使用自以往適宜使用於該類濾光片區段之銅酞菁顏料及二噁嗪系顏料之組合。另，於彩色濾光片(CF-1B)至(CF-15B)，在藍色濾光片區段使用特定成鹽生成物。若比較彩色濾光片(CF-1B)至(CF-15B)及彩色濾光片(CF-17B)，於彩色濾光片(CF-1B)至(CF-15B)，針對藍色及白色之各者，獲得與彩色濾光片(CF-17B)相比較更高之亮度。 In the blue filter section of the primary color filter (CF-17B), a combination of a copper phthalocyanine pigment and a dioxazine-based pigment which have been conventionally used for such a filter section is used. Further, in the color filters (CF-1B) to (CF-15B), a specific salt-forming product is used in the blue filter section. Compare color filters (CF-1B) to (CF-15B) and color filters (CF-17B) to color filters (CF-1B) to (CF-15B) for blue and white Each of them obtained a higher brightness than the color filter (CF-17B).

又，於彩色濾光片(CF-17B)之藍色濾光片區段，使用染料作為著色劑。因此，亮度雖高，但耐受性相對較低。關於補色系彩色濾光片之洋紅色濾光片區段，亦獲得與針對原色系彩色濾光片之濾光片區段之說明同樣的結果。 Further, a dye was used as a colorant in the blue filter section of the color filter (CF-17B). Therefore, although the brightness is high, the tolerance is relatively low. Regarding the magenta filter segment of the complementary color filter, the same results as those for the filter segment of the primary color filter were obtained.

如以上，藉由使用特定成鹽生成物，可獲得色彩特性(亮度)以及耐熱性、耐光性及耐溶劑性均良好的藍色濾光片區段。 As described above, by using a specific salt-forming product, a blue filter segment having excellent color characteristics (brightness) and heat resistance, light resistance, and solvent resistance can be obtained.

Claims (20)

一種彩色濾光片用著色組成物，其係含有透明樹脂及著色劑；前述著色劑包含由鹼性染料及陰離子成分之相對化合物所組成的成鹽生成物；前述相對化合物之分子量係在200至3500之範圍內，且前述相對化合物係從由雜多酸、有機磺酸及有機羧酸所組成的群組選擇之至少一者。 A coloring composition for a color filter, comprising a transparent resin and a coloring agent; the coloring agent comprising a salt-forming product composed of a relative compound of a basic dye and an anionic component; the molecular weight of the relative compound is 200 to Within the scope of 3500, the aforementioned relative compound is selected from at least one of the group consisting of heteropolyacids, organic sulfonic acids, and organic carboxylic acids. 如申請專利範圍第1項之彩色濾光片用著色組成物，其中前述相對化合物之分子量係在250至3500之範圍內。 The coloring composition for a color filter according to the first aspect of the invention, wherein the molecular weight of the aforementioned relative compound is in the range of 250 to 3,500. 如申請專利範圍第1項之彩色濾光片用著色組成物，包含前述有機磺酸，前述有機磺酸係萘胺磺酸。 The coloring composition for a color filter according to the first aspect of the invention, comprising the organic sulfonic acid, the organic sulfonic acid naphthylamine sulfonic acid. 如申請專利範圍第1項之彩色濾光片用著色組成物，其中前述著色劑進一步包含具有酸基之樹脂。 The coloring composition for a color filter according to the first aspect of the invention, wherein the coloring agent further comprises a resin having an acid group. 如申請專利範圍第4項之彩色濾光片用著色組成物，其中前述具有酸基之樹脂之重量平均分子量係在400至12000之範圍內。 The coloring composition for a color filter according to the fourth aspect of the invention, wherein the weight average molecular weight of the resin having an acid group is in the range of 400 to 12,000. 如申請專利範圍第4項之彩色濾光片用著色組成物，其中前述具有酸基之樹脂係松香改質順丁烯二酸樹脂。 A coloring composition for a color filter according to the fourth aspect of the invention, wherein the resin having an acid group is a rosin-modified maleic acid resin. 如申請專利範圍第4項之彩色濾光片用著色組成物，其中前述具有酸基之樹脂之酸價係在100至300mgKOH/g之範圍內。 The coloring composition for a color filter according to the fourth aspect of the invention, wherein the acid value of the acid group-containing resin is in the range of 100 to 300 mgKOH/g. 如申請專利範圍第1項之彩色濾光片用著色組成物，其中前述鹼性染料係從由三芳基甲烷系染料、玫瑰紅系染料、亞甲藍系染料及黃素系染料所組成的群組選擇之至少一者。 The coloring composition for a color filter according to the first aspect of the invention, wherein the basic dye is a group consisting of a triarylmethane dye, a rose red dye, a methylene blue dye, and a flavin dye. At least one of the group selections. 如申請專利範圍第1項之彩色濾光片用著色組成物，其中進一步含有光聚合性組成物及光聚合起始劑之至少一方。 The coloring composition for a color filter according to the first aspect of the invention, further comprising at least one of a photopolymerizable composition and a photopolymerization initiator. 一種彩色濾光片用著色組成物，其係含有透明樹脂及著色劑；前述著色劑包含由鹼性染料及陰離子成分之相對化合物所組成的成鹽生成物；前述相對化合物之分子量係在200至3500之範圍內；前述彩色濾光片用著色組成物係彩色濾光片用藍色著色組成物；前述成鹽生成物包含由三芳基甲烷系染料及呫噸系染料所組成的成鹽生成物。 A coloring composition for a color filter, comprising a transparent resin and a coloring agent; the coloring agent comprising a salt-forming product composed of a relative compound of a basic dye and an anionic component; the molecular weight of the relative compound is 200 to In the range of 3500, the coloring component coloring component is a blue coloring composition for a color filter, and the salt-forming product contains a salt-forming product composed of a triarylmethane dye and a xanthene dye. . 如申請專利範圍第10項之彩色濾光片用著色組成物，其中前述三芳基甲烷系染料係三芳基甲烷系鹼性染料；前述呫噸系染料係呫噸系酸性染料。 The coloring composition for a color filter according to claim 10, wherein the triarylmethane-based dye is a triarylmethane-based basic dye; and the xanthene-based dye is a xanthene-based acid dye. 如申請專利範圍第10項之彩色濾光片用著色組成物，其中前述三芳基甲烷系染料係三芳基甲烷系酸性染料；前述呫噸系染料係呫噸系鹼性染料。 The colored composition for a color filter according to claim 10, wherein the triarylmethane-based dye is a triarylmethane-based acid dye; and the xanthene-based dye is a xanthene-based basic dye. 如申請專利範圍第10項之彩色濾光片用著色組成物，其中前述呫噸系染料係玫瑰紅系染料。 The coloring composition for a color filter according to claim 10, wherein the xanthene dye is a rose red dye. 如申請專利範圍第10項之彩色濾光片用著色組成物，其中前述著色劑進一步包含酞菁系顏料。 The coloring composition for a color filter according to claim 10, wherein the coloring agent further comprises a phthalocyanine-based pigment. 如申請專利範圍第10項之彩色濾光片用著色組成物，其中前述著色劑進一步包含二噁嗪系顏料。 The coloring composition for a color filter according to claim 10, wherein the coloring agent further comprises a dioxazine-based pigment. 一種彩色濾光片用著色組成物，其係含有透明樹脂及著色劑；前述著色劑包含由鹼性染料及陰離子成分之相對化合物所組成的成鹽生成物；前述相對化合物之分子量係在200至3500之範圍內；前述成鹽生成物包含由呫噸系鹼性染料及呫噸系酸性染料所組成的成鹽生成物。 A coloring composition for a color filter, comprising a transparent resin and a coloring agent; the coloring agent comprising a salt-forming product composed of a relative compound of a basic dye and an anionic component; the molecular weight of the relative compound is 200 to In the range of 3,500, the salt-forming product includes a salt-forming product composed of a xanthene-based basic dye and a xanthene-based acid dye. 如申請專利範圍第16項中任一項之彩色濾光片用著色組成物，其中前述呫噸系鹼性染料係玫瑰紅系染料。 The coloring composition for a color filter according to any one of claims 16, wherein the xanthene-based basic dye is a rose red dye. 如申請專利範圍第16項之彩色濾光片用著色組成物，其中前述著色劑進一步含有酞菁系顏料。 The coloring composition for a color filter according to claim 16, wherein the coloring agent further contains a phthalocyanine-based pigment. 如申請專利範圍第16項之彩色濾光片用著色組成物，其中前述著色劑進一步包含二噁嗪系顏料。 The coloring composition for a color filter according to claim 16, wherein the coloring agent further comprises a dioxazine-based pigment. 一種彩色濾光片，其係具備由如申請專利範圍第1至19項中任一項之彩色濾光片用著色組成物所形成的濾光片區段。 A color filter comprising a filter segment formed of a coloring composition for a color filter according to any one of claims 1 to 19.