TW202041607A - Coloring composition and coloring resist composition - Google Patents
Coloring composition and coloring resist composition Download PDFInfo
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- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
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- G03F7/004—Photosensitive materials
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- H10K50/00—Organic light-emitting devices
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- H10K50/86—Arrangements for improving contrast, e.g. preventing reflection of ambient light
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Abstract
Description
本發明係關於一種著色組成物、及含有其之著色阻劑組成物。The present invention relates to a coloring composition and a coloring resist composition containing the same.
近年來，黑矩陣用著色組成物之用途涉及多個方面，例如，被用以於液晶或電漿等之平板顯示器中，於畫面之顯示區域內之著色圖案之間隙或顯示區域周邊部分之緣，又，於使用TFT之液晶顯示器中，於TFT之外光側等設置遮光膜（黑矩陣）。而且，發揮如下作用：於液晶顯示器中主要防止來自背光之漏光映現於畫面中，又，於電漿顯示器中主要防止因各色光之渾濁所引起之滲色映現於畫面中，而提高顯示特性（對比度及色純度）。In recent years, the use of coloring compositions for black matrices involves many aspects. For example, they are used in flat panel displays such as liquid crystal or plasma, in the gaps of colored patterns in the display area of the screen or the edges of the peripheral part of the display area. In addition, in a liquid crystal display using TFT, a light shielding film (black matrix) is provided on the light side of the TFT. Moreover, it plays the following role: in the liquid crystal display, the leakage of light from the backlight is mainly prevented from being reflected in the screen, and in the plasma display, the color bleeding caused by the turbidity of each color light is mainly prevented from being reflected in the screen, thereby improving the display characteristics ( Contrast and color purity).
例如，於用以將液晶顯示器之背光之白色光轉換為著色光之濾色器中，通常藉由在形成有黑矩陣之玻璃或塑膠片等透明基板表面依序以條紋狀或馬賽克狀等之圖案形成紅、綠、藍之不同色相之像素的方法來製造。For example, in a color filter used to convert the white light of the backlight of a liquid crystal display into colored light, it is usually done by sequentially forming stripes or mosaics on the surface of a transparent substrate such as glass or plastic sheet on which a black matrix is formed. The pattern is made by the method of forming pixels of different hues of red, green and blue.
又，於組合影像顯示裝置及位置輸入裝置而成之觸控面板中，亦同樣地利用形成有黑矩陣之濾色器作為遮光膜，迄今為止，一般隔著蓋玻璃形成於與感測器基板相反之側。但是，隨著對觸控面板之輕量化之要求提高，為了謀求更輕量化，正在開發一種於蓋玻璃之同一側同時形成遮光膜及觸控感測器之技術。In addition, in a touch panel formed by combining an image display device and a position input device, a color filter formed with a black matrix is also used as a light-shielding film. So far, it is generally formed on the sensor substrate via a cover glass. The opposite side. However, as the requirements for lighter weight of touch panels increase, in order to achieve lighter weight, a technology is being developed that simultaneously forms a light shielding film and a touch sensor on the same side of the cover glass.
例如，於專利文獻1中，揭示有一種技術，其係藉由在色間隔物形成用感光性著色組成物中，組合使用特定之顏料及碳黑作為著色劑，並且使碳黑之含有比率為特定範圍，而賦予遮蔽性等。For example, Patent Document 1 discloses a technique in which a specific pigment and carbon black are used in combination as a colorant in a photosensitive coloring composition for forming color spacers, and the content ratio of carbon black is A specific range is provided, and shielding properties are provided.
又，例如，於專利文獻2中，揭示有一種技術，其係藉由適當地組合光吸收特性不同之顏料種類，以確保紫外線區域與可見光區域之光吸收之平衡，而維持遮光性及液晶之電壓保持率。In addition, for example, Patent Document 2 discloses a technique that appropriately combines the types of pigments with different light absorption characteristics to ensure the balance of light absorption in the ultraviolet region and the visible light region, and maintain light-shielding properties and liquid crystal properties. Voltage retention rate.
然而，於構成影像顯示裝置之液晶層之黑矩陣等之著色組成物之耐溶劑性較低之情形時，會產生於像素圖案產生龜裂或缺損、或者著色成分自像素圖案溶出之問題。 於上述技術中，未針對耐溶劑性進行研究，期望開發出一種能夠獲得耐溶劑性優異之黑色阻劑圖案之黑矩陣用著色組成物。 [先前技術文獻] [專利文獻]However, when the solvent resistance of the coloring composition such as the black matrix of the liquid crystal layer constituting the image display device is low, the problem of cracks or defects in the pixel pattern or the elution of coloring components from the pixel pattern may occur. In the above technique, no research has been conducted on solvent resistance, and it is desired to develop a black matrix coloring composition capable of obtaining a black resist pattern with excellent solvent resistance. [Prior Technical Literature] [Patent Literature]
[專利文獻1]日本特開2016-177190號公報 [專利文獻2]國際公開第2013/115268號說明書[Patent Document 1] JP 2016-177190 A [Patent Document 2] International Publication No. 2013/115268 Specification
[發明所欲解決之課題][The problem to be solved by the invention]
因此，本發明之課題之目的在於提供一種能夠獲得遮光性優異且耐溶劑性亦優異之黑色阻劑圖案之著色組成物、及含有其之著色阻劑組成物。 [解決課題之技術手段]Therefore, the object of the subject of the present invention is to provide a coloring composition capable of obtaining a black resist pattern excellent in light-shielding and solvent resistance, and a coloring resist composition containing the same. [Technical means to solve the problem]
本發明人等發現藉由於含有顏料及黏合劑樹脂之著色組成物中組合使用特定之顏料，可獲得「能夠製作具有優異之遮蔽性並且耐溶劑性亦優異之黑色阻劑圖案」之著色組成物，從而完成了本發明。The inventors found that by combining specific pigments in a coloring composition containing a pigment and a binder resin, a coloring composition that "can produce a black resist pattern with excellent opacity and excellent solvent resistance" can be obtained , Thereby completing the present invention.
即，本發明係關於一種黑矩陣用著色組成物，其特徵在於：含有顏料及黏合劑樹脂，且上述顏料包含選自由C.I.顏料橙16及C.I.顏料黃139所組成之群中之1種以上、以及C.I.顏料藍60。That is, the present invention relates to a coloring composition for a black matrix, characterized in that it contains a pigment and a binder resin, and the pigment includes at least one selected from the group consisting of CI Pigment Orange 16 and CI Pigment Yellow 139, And CI Pigment Blue 60.
又，上述顏料較佳為進而包含選自由C.I.顏料紫23及C.I.顏料紫29所組成之群中之1種以上。 又，本發明亦係一種著色阻劑組成物，其係使用本發明之著色組成物而製造。 又，亦係一種被用作黑矩陣、黑色柱間隔物（black column spacer）或黑色間隔壁材料之本發明之著色組成物、或本發明之著色阻劑組成物。 以下，對本發明之著色組成物、及含有其之著色阻劑組成物詳細地進行說明。In addition, the above-mentioned pigment preferably further includes one or more selected from the group consisting of C.I. Pigment Violet 23 and C.I. Pigment Violet 29. In addition, the present invention is also a coloring resist composition, which is manufactured using the coloring composition of the present invention. In addition, it is also a coloring composition of the present invention or a coloring resist composition of the present invention that is used as a black matrix, black column spacer or black spacer material. Hereinafter, the coloring composition of the present invention and the coloring resist composition containing it will be described in detail.
（顏料） 本發明之著色組成物之顏料包含選自由C.I.顏料橙16及C.I.顏料黃139所組成之群中之1種以上、以及C.I.顏料藍60。 藉由使用上述顏料，可設為能夠獲得遮光性優異且耐溶劑性亦優異之黑色阻劑圖案之黑矩陣用著色組成物。就賦予耐溶劑性之觀點而言，上述顏料較佳為包含C.I.顏料黃139及C.I.顏料藍60。(pigment) The pigment of the coloring composition of the present invention includes one or more selected from the group consisting of C.I. Pigment Orange 16 and C.I. Pigment Yellow 139, and C.I. Pigment Blue 60. By using the above-mentioned pigment, it can be set as the coloring composition for black matrices which can obtain the black resist pattern excellent in light-shielding property and solvent resistance. From the viewpoint of imparting solvent resistance, the above-mentioned pigment preferably contains C.I. Pigment Yellow 139 and C.I. Pigment Blue 60.
關於選自由C.I.顏料橙16及C.I.顏料黃139所組成之群中之1種以上之顏料之含量，就遮光性之觀點而言，相對於顏料之總量，較佳為5～60質量%，更佳為8～50質量%，進而較佳為10～45質量%，尤佳為10～40質量%。 關於C.I.顏料藍60之含量，就遮光性之觀點而言，相對於顏料之總質量，較佳為5～70質量%，更佳為10～60質量%，進而較佳為15～55質量%，尤佳為20～50質量%。Regarding the content of one or more pigments selected from the group consisting of CI Pigment Orange 16 and CI Pigment Yellow 139, from the viewpoint of shading properties, it is preferably 5-60% by mass relative to the total amount of the pigment. It is more preferably 8 to 50% by mass, still more preferably 10 to 45% by mass, and particularly preferably 10 to 40% by mass. Regarding the content of CI Pigment Blue 60, from the viewpoint of light-shielding properties, relative to the total mass of the pigment, it is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and still more preferably 15 to 55% by mass , Particularly preferably 20-50% by mass.
上述顏料較佳為進而包含選自由C.I.顏料紫23及C.I.顏料紫29所組成之群中之1種以上。 藉由使上述顏料進而包含選自由C.I.顏料紫23及C.I.顏料紫29所組成之群中之1種以上，能夠對藉由著色組成物所獲得之黑色阻劑圖案賦予優異之遮蔽性。 就賦予耐溶劑性之觀點而言，上述顏料更佳為包含C.I.顏料紫29。The above-mentioned pigment preferably further contains one or more selected from the group consisting of C.I. Pigment Violet 23 and C.I. Pigment Violet 29. By making the above-mentioned pigment further include at least one selected from the group consisting of C.I. Pigment Violet 23 and C.I. Pigment Violet 29, it is possible to impart excellent masking properties to the black resist pattern obtained by the coloring composition. From the viewpoint of imparting solvent resistance, the above-mentioned pigment more preferably contains C.I. Pigment Violet 29.
關於選自由C.I.顏料紫23及C.I.顏料紫29所組成之群中之1種以上之顏料之含量，就遮光性之觀點而言，相對於顏料之總量，較佳為1～70質量%，更佳為10～60質量%。Regarding the content of one or more pigments selected from the group consisting of CI Pigment Violet 23 and CI Pigment Violet 29, from the viewpoint of shading properties, it is preferably 1 to 70% by mass relative to the total amount of the pigment. More preferably, it is 10 to 60% by mass.
於本發明之著色組成物中，相對於總固體成分，上述顏料以質量分率計較佳為20～90質量%，更佳為30～80質量%。In the coloring composition of the present invention, the pigment is preferably 20 to 90% by mass, more preferably 30 to 80% by mass relative to the total solid content.
於本發明之著色組成物中，上述顏料亦可於不損害本發明之效果之範圍內，包含碳黑、紅色顏料、橙色顏料、藍色顏料、綠色顏料等其他顏料。In the coloring composition of the present invention, the above-mentioned pigments may also include carbon black, red pigments, orange pigments, blue pigments, green pigments and other pigments within a range that does not impair the effects of the present invention.
（黏合劑樹脂） 本發明之著色組成物含有黏合劑樹脂。 作為上述黏合劑樹脂，只要為能夠用於濾色器之構件之樹脂，則可無特別限制地使用，可列舉：鹼可溶性樹脂、熱硬化性樹脂、熱塑性樹脂、光聚合性化合物（光聚合性樹脂、分子內具有1個以上之光聚合性不飽和鍵之單體、寡聚物等）等。其等可單獨或混合2種以上而使用。 於本發明之著色組成物中，相對於總固體成分，上述黏合劑樹脂以質量分率計較佳為1～40質量%，更佳為3～25質量%。(Adhesive resin) The coloring composition of the present invention contains a binder resin. As the above-mentioned binder resin, as long as it is a resin that can be used as a member of a color filter, it can be used without particular limitation. Examples include alkali-soluble resins, thermosetting resins, thermoplastic resins, and photopolymerizable compounds (photopolymerizable Resins, monomers and oligomers with more than one photopolymerizable unsaturated bond in the molecule), etc. These etc. can be used individually or in mixture of 2 or more types. In the coloring composition of the present invention, the binder resin is preferably 1-40% by mass, more preferably 3-25% by mass relative to the total solid content.
作為上述鹼可溶性樹脂，可例示鹼可溶性共聚物、鹼可溶性卡多樹脂（Cardo resin）等。 作為鹼可溶性共聚物，例如為使丙烯酸、甲基丙烯酸、伊康酸、順丁烯二酸、順丁烯二酸酐、順丁烯二酸單烷基酯、檸康酸、檸康酸酐、檸康酸單烷基酯等含羧基之不飽和單體，與選自由苯乙烯、丙烯酸2-羥基乙酯、甲基丙烯酸2-羥基乙酯、丙烯酸烯丙酯、甲基丙烯酸烯丙酯、丙烯酸苄酯、甲基丙烯酸苄酯、單丙烯酸甘油酯、甲基丙烯酸甘油酯、具有二環戊二烯骨架之單(甲基)丙烯酸酯、N-苯基順丁烯二醯亞胺、聚苯乙烯巨單體及聚甲基丙烯酸甲酯巨單體所組成之群中之至少1種進行反應所獲得之共聚物、及環氧丙烯酸酯樹脂。As said alkali-soluble resin, an alkali-soluble copolymer, an alkali-soluble cardo resin, etc. can be illustrated. As the alkali-soluble copolymer, for example, acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, monoalkyl maleate, citraconic acid, citraconic anhydride, citraconic acid Unsaturated monomers containing carboxyl group such as aconic acid monoalkyl ester, and selected from styrene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, acrylic acid Benzyl ester, benzyl methacrylate, glycerol monoacrylate, glycerol methacrylate, mono(meth)acrylate with dicyclopentadiene skeleton, N-phenylmaleimide, polyphenylene A copolymer obtained by reacting at least one of the group consisting of ethylene macromonomer and polymethyl methacrylate macromonomer, and epoxy acrylate resin.
作為上述鹼可溶性卡多樹脂，可列舉作為茀環氧(甲基)丙烯酸衍生物與二羧酸酐及/或四羧酸二酐之加成產物之具有茀骨架之環氧(甲基)丙烯酸酯酸加成物等。 上述鹼可溶性樹脂可單獨或併用2種以上而使用。關於鹼可溶性樹脂，就塗膜形成性、鹼性顯影性之方面而言，較佳為酸值為40～200 mgKOH/g，重量平均分子量為1000～5萬。 上述鹼可溶性樹脂可根據所要求之性能，而適當使用1種或組合使用2種以上。Examples of the above-mentioned alkali-soluble cardo resins include epoxy (meth)acrylates having a tetrakis skeleton as an addition product of epoxy (meth)acrylic acid derivatives and dicarboxylic anhydrides and/or tetracarboxylic dianhydrides Acid adducts, etc. The said alkali-soluble resin can be used individually or in combination of 2 or more types. The alkali-soluble resin preferably has an acid value of 40 to 200 mgKOH/g and a weight average molecular weight of 1,000 to 50,000 in terms of coating film formation properties and alkali developability. The above-mentioned alkali-soluble resin can be suitably used singly or in combination of two or more according to the required performance.
作為上述熱硬化性樹脂或熱塑性樹脂，例如可列舉：丁醛樹脂、苯乙烯-順丁稀二酸共聚物、氯化聚乙烯、氯化聚丙烯、聚氯乙烯、氯乙烯-乙酸乙烯酯共聚物、聚乙酸乙烯酯、聚胺酯（polyurethane）系樹脂、酚樹脂、聚酯樹脂、丙烯酸系樹脂、醇酸樹脂、苯乙烯樹脂、聚醯胺樹脂、橡膠系樹脂、環化橡膠、環氧樹脂、纖維素類、聚丁二烯、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、苯胍
作為上述光聚合性樹脂，可使用對具有羥基、羧基、胺基等反應性取代基之線性高分子經由異氰酸基、醛基、環氧基等，導入(甲基)丙烯酸化合物、桂皮酸等之光交聯性基而成之樹脂。亦使用將含有苯乙烯-順丁稀二酸酐共聚物或α-烯烴-順丁稀二酸酐共聚物等酸酐之線性高分子藉由(甲基)丙烯酸羥基烷基酯等具有羥基之(甲基)丙烯酸化合物半酯化而成之聚合物。As the above-mentioned photopolymerizable resin, it is possible to use (meth)acrylic compounds and cinnamic acid introduced into linear polymers with reactive substituents such as hydroxyl groups, carboxyl groups, and amino groups via isocyanate groups, aldehyde groups, epoxy groups, etc. It is a resin made of light-crosslinkable base. The linear polymer containing acid anhydrides such as styrene-maleic anhydride copolymer or α-olefin-maleic anhydride copolymer is also used to use (meth)acrylic acid hydroxyalkyl ester and other (methyl) ) A polymer formed by semi-esterification of acrylic compound.
於上述光聚合性化合物中，作為分子內具有1個上述光聚合性不飽和鍵之單體，例如可列舉：甲基丙烯酸甲酯、甲基丙烯酸丁酯、甲基丙烯酸2-乙基己酯、丙烯酸甲酯、丙烯酸丁酯、丙烯酸2-乙基己酯等甲基丙烯酸烷基酯或丙烯酸烷基酯；甲基丙烯酸苄酯、丙烯酸苄酯等甲基丙烯酸芳烷基酯或丙烯酸芳烷基酯；甲基丙烯酸丁氧基乙酯、丙烯酸丁氧基乙酯等甲基丙烯酸烷氧基烷基酯或丙烯酸烷氧基烷基酯；甲基丙烯酸N,N-二甲胺基乙酯、丙烯酸N,N-二甲胺基乙酯等甲基丙烯酸胺基烷基酯或丙烯酸胺基烷基酯；二乙二醇乙醚、三乙二醇丁醚、二丙二醇甲醚等聚伸烷基二醇烷基醚之甲基丙烯酸酯或丙烯酸酯；六乙二醇苯醚等聚伸烷基二醇芳基醚之甲基丙烯酸酯或丙烯酸酯；甲基丙烯酸異莰酯或丙烯酸異莰酯；甲基丙烯酸甘油酯或丙烯酸甘油酯；甲基丙烯酸2-羥基乙酯或丙烯酸2-羥基乙酯等。Among the above-mentioned photopolymerizable compounds, examples of monomers having one of the above-mentioned photopolymerizable unsaturated bonds in the molecule include: methyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate , Methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and other alkyl methacrylate or alkyl acrylate; benzyl methacrylate, benzyl acrylate and other aralkyl methacrylate or aralkyl acrylate Base ester; butoxyethyl methacrylate, butoxyethyl acrylate and other alkoxyalkyl methacrylate or alkoxyalkyl acrylate; N,N-dimethylaminoethyl methacrylate , N,N-dimethylamino ethyl acrylate and other amino alkyl methacrylate or amino alkyl acrylate; diethylene glycol ethyl ether, triethylene glycol butyl ether, dipropylene glycol methyl ether and other polyalkylenes Methacrylate or acrylate of base glycol alkyl ether; Methacrylate or acrylate of polyalkylene glycol aryl ether such as hexaethylene glycol phenyl ether; Isobornyl methacrylate or isobornyl acrylate Esters; glycerol methacrylate or glycerol acrylate; 2-hydroxyethyl methacrylate or 2-hydroxyethyl acrylate, etc.
於上述光聚合性化合物中，作為分子內具有2個以上之上述光聚合性不飽和鍵之單體，例如可列舉：雙酚A二甲基丙烯酸酯、1,4-丁二醇二甲基丙烯酸酯、1,3-丁二醇二甲基丙烯酸酯、二乙二醇二甲基丙烯酸酯、二甲基丙烯酸甘油酯、新戊二醇二甲基丙烯酸酯、聚乙二醇二甲基丙烯酸酯、聚丙二醇二甲基丙烯酸酯、四乙二醇二甲基丙烯酸酯、三羥甲基丙烷三甲基丙烯酸酯、新戊四醇三甲基丙烯酸酯、新戊四醇四甲基丙烯酸酯、二新戊四醇四甲基丙烯酸酯、二新戊四醇六甲基丙烯酸酯、二新戊四醇五甲基丙烯酸酯、雙酚A二丙烯酸酯、1,4-丁二醇二丙烯酸酯、1,3-丁二醇二丙烯酸酯、二乙二醇二丙烯酸酯、二丙烯酸甘油酯、新戊二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、聚丙二醇二丙烯酸酯、四乙二醇二丙烯酸酯、三羥甲基丙烷三丙烯酸酯、新戊四醇三丙烯酸酯、新戊四醇四丙烯酸酯、二新戊四醇四丙烯酸酯、二新戊四醇六丙烯酸酯、二新戊四醇五丙烯酸酯等。Among the photopolymerizable compounds, examples of monomers having two or more photopolymerizable unsaturated bonds in the molecule include bisphenol A dimethacrylate, 1,4-butanediol dimethyl Acrylate, 1,3-butanediol dimethacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethyl acrylate Acrylate, polypropylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, neopenteritol trimethacrylate, neopentaerythritol tetramethacrylate Esters, dineopentaerythritol tetramethacrylate, dineopentaerythritol hexamethacrylate, dineopentaerythritol pentamethacrylate, bisphenol A diacrylate, 1,4-butanediol two Acrylate, 1,3-butanediol diacrylate, diethylene glycol diacrylate, glycerol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, four Ethylene glycol diacrylate, trimethylolpropane triacrylate, neopentaerythritol triacrylate, neopentaerythritol tetraacrylate, dineopentaerythritol tetraacrylate, dineopentaerythritol hexaacrylate, Dineopentaerythritol pentaacrylate and so on.
（碳黑） 關於本發明之著色組成物，就調整色調之觀點而言，可含有碳黑。 作為上述碳黑，可列舉：乙炔黑、槽黑、爐黑、及科琴黑（Ketjen black）等。 作為上述碳黑之具體例，可列舉：三菱化學公司製造之MA7、MA8、MA11、MA14、＃1000、＃2350等；Orion Engineered Carbons公司製造之SpecialBlack350、SpecialBlack250、SpecialBlack550、NEROX2500、NEROX3500、NEROX305等；Cabot公司製造之MOGUL L、REGAL400R、TPK1101R、TPK1104R、TPK1227R等；Columbian Carbon公司製造之RAVEN1200、RAVEN1250、RAVEN1255、RAVEN1190U、RAVEN1170、RAVEN1035、RAVEN1080U、RAVEN1060U、RAVEN1100U等。 其中，較佳為pH為5以下且具有羧基等酸性基之酸性碳黑。又，較佳為粒徑為20～60 nm者。 作為滿足上述內容之酸性碳黑，可列舉：NEROX2500、NEROX3500、TPK1101R、TPK1104R、TPK1227R等。 再者，上述粒徑意指藉由顯微鏡觀察所測得或算出之平均一次粒徑。(Carbon black) Regarding the coloring composition of the present invention, from the viewpoint of adjusting the color tone, carbon black may be contained. As said carbon black, acetylene black, channel black, furnace black, and Ketjen black (Ketjen black) etc. are mentioned. Specific examples of the aforementioned carbon black include: MA7, MA8, MA11, MA14, #1000, #2350, etc. manufactured by Mitsubishi Chemical Corporation; SpecialBlack350, SpecialBlack250, SpecialBlack550, NEROX2500, NEROX3500, NEROX305, etc. manufactured by Orion Engineered Carbons; MOGUL L, REGAL400R, TPK1101R, TPK1104R, TPK1227R, etc. manufactured by Cabot; RAVEN1200, RAVEN1250, RAVEN1255, RAVEN1190U, RAVEN1170, RAVEN1035, RAVEN1080U, RAVEN1060U, RAVEN1100U, etc. manufactured by Columbia Carbon. Among them, acidic carbon black having a pH of 5 or less and having an acidic group such as a carboxyl group is preferred. Also, those having a particle diameter of 20 to 60 nm are preferred. As the acid carbon black satisfying the above content, NEROX2500, NEROX3500, TPK1101R, TPK1104R, TPK1227R, etc. can be cited. Furthermore, the above-mentioned particle size means the average primary particle size measured or calculated by microscope observation.
上述酸性碳黑之含量並無特別限定，但例如，相對於本發明之著色組成物之全部顏料之質量，較佳為含有70質量%以下。若上述酸性碳黑之含量超過70質量%，則存在引起電壓保持率下降、或曝光感光度下降之情況。 相對於本發明之著色組成物之全部顏料之質量，上述酸性碳黑之含量之更佳上限為50質量%。 再者，本發明之著色組成物亦可不含有上述酸性碳黑。The content of the acidic carbon black is not particularly limited, but, for example, it is preferably 70% by mass or less with respect to the mass of all the pigments of the coloring composition of the present invention. If the content of the above-mentioned acid carbon black exceeds 70% by mass, it may cause a decrease in the voltage retention rate or a decrease in the exposure sensitivity. With respect to the mass of all the pigments of the coloring composition of the present invention, the upper limit of the content of the acidic carbon black is more preferably 50% by mass. Furthermore, the coloring composition of the present invention may not contain the above-mentioned acid carbon black.
本發明之著色組成物較佳為進而含有顏料分散劑、下述之通式（1）及/或（2）所表示之顏料分散助劑、及/或作為銅酞青之磺化物（亦可被中和）之顏料分散助劑、及/或作為C.I.顏料黃138之磺化物（亦可被中和）之顏料分散助劑、黏合劑樹脂、以及有機溶劑。The coloring composition of the present invention preferably further contains a pigment dispersant, a pigment dispersing aid represented by the following general formula (1) and/or (2), and/or a copper phthalocyanine sulfonate (also Neutralized pigment dispersing aids, and/or pigment dispersing aids used as CI Pigment Yellow 138 sulfonates (also neutralized), binder resins, and organic solvents.
（顏料分散劑） 本發明之著色組成物較佳為含有顏料分散劑。 作為上述顏料分散劑，為含鹼性基之顏料分散劑，可使用：陰離子性界面活性劑、含鹼性基之聚酯系顏料分散劑、含鹼性基之丙烯酸系顏料分散劑、含鹼性基之胺酯（urethane）系顏料分散劑、含鹼性基之碳二醯亞胺系顏料分散劑、含酸性基之高分子顏料分散劑等。 該等含鹼性基之顏料分散劑可單獨使用，又，亦可使用2種以上之組合。其中，就可獲得良好之顏料分散性之方面而言，較佳為含鹼性基之高分子顏料分散劑。(Pigment Dispersant) The coloring composition of the present invention preferably contains a pigment dispersant. As the above-mentioned pigment dispersant, it is a basic group-containing pigment dispersant, which can be used: anionic surfactant, basic group-containing polyester pigment dispersant, basic group-containing acrylic pigment dispersant, alkali-containing Urethane based pigment dispersant, basic carbodiimide pigment dispersant, acidic polymer pigment dispersant, etc. These basic group-containing pigment dispersants can be used alone or in combination of two or more kinds. Among them, in terms of obtaining good pigment dispersibility, a basic group-containing polymer pigment dispersant is preferred.
作為含鹼性基之高分子顏料分散劑之具體例，可列舉： （1）聚胺化合物（例如，聚烯丙胺、聚乙烯胺、聚乙烯聚亞胺等聚（低級伸烷基胺）等）之胺基及/或亞胺基、與選自由具有游離之羧基之聚酯、聚醯胺及聚酯醯胺所組成之群中之至少1種之反應產物（日本特開2001-59906號公報）、 （2）聚（低級）伸烷基亞胺、甲基亞胺基雙丙基胺等低分子胺基化合物、與具有游離之羧基之聚酯之反應產物（日本特開昭54-37082號公報、日本特開平01-311177號公報）、 （3）使聚異氰酸酯化合物之異氰酸基依序與甲氧基聚乙二醇等醇類或己內酯聚酯等具有1個羥基之聚酯類、具有2～3個異氰酸基反應性官能基之化合物、具有異氰酸基反應性官能基及三級胺基之脂肪族或雜環式烴化合物進行反應而成之反應產物（日本特開平02-612號公報）、 （4）使具有醇性羥基之丙烯酸酯之聚合物與聚異氰酸酯化合物及具有胺基之烴化合物進行反應而成之化合物、 （5）使低分子胺基化合物與聚醚鏈加成而成之反應產物、 （6）使具有異氰酸基之化合物與具有胺基之化合物進行反應而成之反應產物（日本特開平04-210220號公報）、 （7）使聚環氧化合物與具有游離之羧基之線性聚合物及具有1個二級胺基之有機胺化合物進行反應而成之反應產物（日本特開平09-87537號公報）、 （8）於單末端具有可與胺基反應之官能基之聚碳酸酯化合物與聚胺化合物之反應產物（日本特開平09-194585號公報）、 （9）選自甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸丁酯、甲基丙烯酸硬脂酯、甲基丙烯酸苄酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、丙烯酸硬脂酯、丙烯酸苄酯等甲基丙烯酸酯或丙烯酸酯中之至少1種，與丙烯醯胺、甲基丙烯醯胺、N-羥甲基醯胺、乙烯基咪唑、乙烯基吡啶、具有胺基及聚己內酯骨架之單體等含鹼性基之聚合單體中之至少1種，與苯乙烯、苯乙烯衍生物、其他聚合性單體中之至少1種的共聚物（日本特開平01-164429號公報）、 （10）含鹼性基之碳二醯亞胺系顏料分散劑（國際公開WO04/000950號公報）、 （11）由具有三級胺基、四級銨鹽基等鹼性基之嵌段及不具有官能基之嵌段所構成之嵌段共聚物（參照日本特開2005-55814號之記載）、 （12）使聚烯丙胺與聚碳酸酯化合物進行麥可加成（Michael addition）反應而獲得之顏料分散劑（日本特開平09-194585號公報）、 （13）分別具有至少1個聚丁二烯鏈及含鹼性氮之基之碳二醯亞胺系化合物（日本特開2006-257243號公報）、 （14）分別具有至少1個於分子內具有醯胺基之側鏈、及含鹼性氮之基之碳二醯亞胺系化合物（日本特開2006-176657號公報）、 （15）具有含有鏈及環氧丙烷鏈之結構單元，且具有藉由四級化劑而四級化之胺基之聚胺酯系化合物（日本特開2009-175613號公報）、 （16）使分子內具有異氰脲酸酯環之異氰酸酯化合物之異氰酸基、與分子內具有活性氫基且具有咔唑環及/或偶氮苯骨架之化合物之活性氫基進行反應而獲得之化合物，且為該化合物之分子內之咔唑環及偶氮苯骨架之數量相對於源自具有異氰脲酸酯環之異氰酸酯化合物之異氰酸基及藉由異氰酸基與活性氫基之反應所產生之胺酯鍵及脲鍵之合計為15～85%之化合物（日本特願2009-220836）、 （17）對具有胺基之丙烯酸酯聚合物導入聚醚或聚酯側鏈而成之接枝共聚物等。As specific examples of the basic group-containing polymer pigment dispersant, one can cite: (1) The amine group and/or imine group of polyamine compounds (for example, poly(lower alkylene amine) such as polyallylamine, polyvinylamine, polyethylene polyimine, etc.), and selected from free carboxyl groups The reaction product of at least one of the group consisting of polyester, polyamide and polyesteramide (Japanese Patent Laid-Open No. 2001-59906), (2) Reaction products of low-molecular-weight amine compounds such as poly(lower) alkyleneimine, methyliminobispropylamine, and polyester with free carboxyl groups (Japanese Patent Laid-Open No. 54-37082) , Japanese Patent Publication No. 01-311177), (3) The isocyanate group of the polyisocyanate compound is sequentially combined with alcohols such as methoxy polyethylene glycol or polyesters with one hydroxyl group such as caprolactone polyester, and has 2 to 3 isocyanate groups A reaction product of a compound with a reactive functional group, an aliphatic or heterocyclic hydrocarbon compound with an isocyanate-reactive functional group and a tertiary amine group (Japanese Patent Laid-Open No. 02-612), (4) A compound obtained by reacting a polymer of acrylic ester having an alcoholic hydroxyl group with a polyisocyanate compound and a hydrocarbon compound having an amino group, (5) The reaction product formed by the addition of low-molecular-weight amine-based compounds and polyether chains, (6) A reaction product obtained by reacting a compound having an isocyanate group and a compound having an amine group (Japanese Patent Laid-Open No. 04-210220), (7) A reaction product formed by reacting a polyepoxy compound with a linear polymer having a free carboxyl group and an organic amine compound having a secondary amine group (Japanese Patent Laid-Open No. 09-87537), (8) The reaction product of a polycarbonate compound and a polyamine compound having a functional group that can react with an amine group at one end (Japanese Patent Laid-Open No. 09-194585), (9) Selected from methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, stearyl methacrylate, benzyl methacrylate, methyl acrylate, ethyl acrylate, At least one of methacrylates or acrylates such as propyl acrylate, butyl acrylate, stearyl acrylate, and benzyl acrylate, and acrylamide, methacrylamide, N-methylolamide, ethylene At least one of basic group-containing polymerizable monomers, such as base imidazole, vinyl pyridine, amine group and polycaprolactone skeleton, and styrene, styrene derivatives, and other polymerizable monomers At least one copolymer (Japanese Patent Application Laid-Open No. 01-164429), (10) Carbodiimide-based pigment dispersants containing basic groups (International Publication WO04/000950), (11) Block copolymers composed of blocks with basic groups such as tertiary amine groups and quaternary ammonium salt groups and blocks without functional groups (refer to the description of JP 2005-55814), (12) Pigment dispersant obtained by Michael addition reaction of polyallylamine and polycarbonate compound (Japanese Patent Laid-Open No. 09-194585), (13) Carbodiimide compounds each having at least one polybutadiene chain and a basic nitrogen-containing group (Japanese Patent Laid-Open No. 2006-257243), (14) Carbodiimide-based compounds each having at least one side chain having an amide group in the molecule and a basic nitrogen-containing group (Japanese Patent Laid-Open No. 2006-176657), (15) Polyurethane compounds having a structural unit containing a chain and a propylene oxide chain, and having an amine group quaternized by a quaternization agent (Japanese Patent Laid-Open No. 2009-175613), (16) The isocyanate group of an isocyanate compound having an isocyanurate ring in the molecule reacts with the active hydrogen group of a compound having an active hydrogen group in the molecule and a carbazole ring and/or azobenzene skeleton The obtained compound, and the number of the carbazole ring and the azobenzene skeleton in the molecule of the compound is relative to the isocyanate group derived from the isocyanate compound with the isocyanurate ring, and the isocyanate group and the active Compounds in which the total of amine ester bonds and urea bonds generated by the reaction of hydrogen groups is 15-85% (Japanese Patent Application 2009-220836), (17) Graft copolymers, etc. formed by introducing polyether or polyester side chains into an acrylate polymer having an amino group.
上述含鹼性基之高分子顏料分散劑之中，更佳為：含鹼性基之胺酯系高分子顏料分散劑、含鹼性基之聚酯系高分子顏料分散劑、含鹼性基之丙烯酸系高分子顏料分散劑，進而較佳為：含胺基之胺酯系高分子顏料分散劑、含胺基之聚酯系高分子顏料分散劑、含胺基之丙烯酸系高分子顏料分散劑。上述含鹼性基之高分子顏料分散劑之中，尤佳為具有選自由聚酯鏈、聚醚鏈、及聚碳酸酯鏈所組成之群中之至少1種之含鹼性基（胺基）之高分子顏料分散劑。Among the above-mentioned basic group-containing polymer pigment dispersants, more preferred are: basic group-containing urethane-based polymer pigment dispersants, basic group-containing polyester-based polymer pigment dispersants, and basic group-containing The acrylic polymer pigment dispersant is further preferably: amino ester polymer pigment dispersant containing amino group, polyester polymer pigment dispersant containing amino group, acrylic polymer pigment dispersing agent containing amino group Agent. Among the above-mentioned basic group-containing polymer pigment dispersants, it is particularly preferable to have at least one basic group (amine group) selected from the group consisting of polyester chains, polyether chains, and polycarbonate chains. ) The polymer pigment dispersant.
於本發明之著色組成物中，相對於上述顏料100質量份，上述顏料分散劑較佳為1～200質量份，更佳為5～100質量份。In the coloring composition of the present invention, relative to 100 parts by mass of the pigment, the pigment dispersant is preferably 1 to 200 parts by mass, more preferably 5 to 100 parts by mass.
（顏料分散助劑）
本發明之著色組成物較佳為含有下述通式（1）及/或（2）所表示之顏料分散助劑、及/或作為銅酞青之磺化物（亦可被中和）之顏料分散助劑、及/或作為C.I.顏料黃138之磺化物（亦可被中和）之顏料分散助劑。
上述顏料分散助劑用以使上述顏料分散。 於使上述顏料分散時，藉由併用上述顏料分散助劑及上述顏料分散劑，能獲得優異之流動性、經時穩定性。又，於將上述著色組成物用作著色阻劑組成物之情形時，能獲得較高之光學密度。The pigment dispersion aid is used to disperse the pigment. When dispersing the above-mentioned pigment, by using the above-mentioned pigment dispersing auxiliary agent and the above-mentioned pigment dispersant together, excellent fluidity and stability over time can be obtained. In addition, when the above-mentioned colored composition is used as a coloring resist composition, a higher optical density can be obtained.
上述通式（1）、（2）中，X及Y相同或者不同，表示可被F、Cl、Br、NO2 、CH3 或OCH3 取代之苯基。M表示H、Na、K、NH4 或NR1 R2 R3 R4 。 關於上述通式（1）、（2）之「NR1 R2 R3 R4 」（M），R1 、R2 、R3 及R4 相同或者不同，表示可被其他取代基取代之碳數1～10之飽和或不飽和之脂肪族烴基、或可被其他取代基取代之碳數6～10之芳香族烴基。此處，作為上述飽和或不飽和之脂肪族烴基，可列舉：甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基、戊基、己基、辛基、癸基等烷基；乙烯基、烯丙基、1-丁烯基等烯基；乙炔基、丙炔基等炔基等。作為上述芳香族烴基，可列舉：苯基、萘基等。又，作為上述其他取代基，可列舉：羥基、鹵素、羧基、胺基、低級烷基（碳數1～5）等。 再者，上述R1 、R2 、R3 及R4 既可1個被其他取代基取代，亦可2個以上被其他取代基取代。 進而，上述通式（1）、（2）之「m」為1以上之整數。In the above general formulas (1) and (2), X and Y are the same or different and represent a phenyl group that may be substituted by F, Cl, Br, NO 2 , CH 3 or OCH 3 . M represents H, Na, K, NH 4 or NR 1 R 2 R 3 R 4 . Regarding the "NR 1 R 2 R 3 R 4 "(M) of the above general formulas (1) and (2), R 1 , R 2 , R 3 and R 4 are the same or different, indicating a carbon that may be substituted by other substituents A saturated or unsaturated aliphatic hydrocarbon group of 1-10, or an aromatic hydrocarbon group of 6-10 that may be substituted by other substituents. Here, examples of the above-mentioned saturated or unsaturated aliphatic hydrocarbon groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, tertiary butyl, pentyl, Alkyl groups such as hexyl, octyl, and decyl; alkenyl groups such as vinyl, allyl, and 1-butenyl; alkynyl groups such as ethynyl and propynyl, etc. As said aromatic hydrocarbon group, a phenyl group, a naphthyl group, etc. are mentioned. Moreover, as said other substituent, a hydroxyl group, a halogen, a carboxyl group, an amino group, a lower alkyl group (carbon number 1 to 5), etc. are mentioned. In addition, one of the above-mentioned R 1 , R 2 , R 3 and R 4 may be substituted with another substituent, or two or more may be substituted with other substituents. Furthermore, "m" in the above general formulas (1) and (2) is an integer of 1 or more.
於上述化合物（顏料分散助劑）中，上述通式（1）所表示之化合物為烯醇型之互變異構物，上述通式（2）所表示之化合物為酮型之互變異構物，上述顏料分散助劑包含此兩種化合物。即，上述顏料分散助劑亦包含如下兩種情形：上述通式（1）或（2）所表示之化合物之情形、及由上述通式（1）及（2）所表示之化合物之兩者構成之情形。Among the above compounds (pigment dispersing aids), the compound represented by the above general formula (1) is an enol type tautomer, and the compound represented by the above general formula (2) is a ketone type tautomer, The above-mentioned pigment dispersion aid contains these two compounds. That is, the above-mentioned pigment dispersion auxiliary agent also includes the following two cases: the case of the compound represented by the above general formula (1) or (2), and both of the compound represented by the above general formula (1) and (2) Constitutional circumstances.
此種顏料分散助劑為新穎之化合物，例如，可將下述式（3）～（30）之單偶氮化合物溶解於濃硫酸、發煙硫酸、氯磺酸或其等之混合液中，加熱至室溫或80～90℃，繼而以大量之水進行稀釋而獲得懸濁液，將該懸濁液過濾後，進行水洗，對所獲得之濾餅進行乾燥、粉碎而製造，不存在市售品。This pigment dispersion aid is a novel compound. For example, the monoazo compound of the following formulas (3) to (30) can be dissolved in concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid or a mixture thereof, It is heated to room temperature or 80-90°C, and then diluted with a large amount of water to obtain a suspension. After filtering the suspension, it is washed with water, and the obtained filter cake is dried and pulverized. There is no market. For sale.
該等顏料分散助劑之中，就能夠獲得具有良好之流動性及經時穩定性，並且光學密度處於更高等級之著色阻劑組成物之方面而言，較佳為上述通式（1）及/或（2）之X為2,5-二氯苯基且Y為苯基之下述通式（31）所表示之化合物（使用上述式（3）之單偶氮化合物，藉由上述製法等所獲得之化合物：烯醇型）及/或下述通式（32）所表示之化合物（使用上述式（4）之單偶氮化合物，藉由上述製法等所獲得之化合物：酮型）。Among the pigment dispersion aids, in terms of obtaining a coloring resist composition with good fluidity and stability over time, and a higher optical density, the above general formula (1) is preferred And/or (2) X is 2,5-dichlorophenyl and Y is a compound represented by the following general formula (31) (using the monoazo compound of the above formula (3), by the above The compound obtained by the production method: enol type) and/or the compound represented by the following general formula (32) (using the monoazo compound of the above formula (4), the compound obtained by the above production method, etc.: ketone type ).
於本發明之著色組成物中，相對於上述顏料100質量份，上述顏料分散助劑較佳為30質量份以下，更佳為0.1～20質量份。 存在相對於上述顏料100質量份，即便上述顏料分散助劑超過30質量份，亦無法提高顏料分散效果之情況。In the coloring composition of the present invention, the pigment dispersion aid is preferably 30 parts by mass or less, and more preferably 0.1-20 parts by mass relative to 100 parts by mass of the pigment. There are cases where the pigment dispersion effect cannot be improved even if the pigment dispersion aid exceeds 30 parts by mass relative to 100 parts by mass of the pigment.
（有機溶劑） 本發明之著色組成物較佳為含有有機溶劑。 作為上述有機溶劑，較佳為常壓（1.013×102 kPa）之沸點為70～300℃之酯系有機溶劑、醚系有機溶劑、醚酯系有機溶劑、酮系有機溶劑、芳香族烴系有機溶劑、含氮系有機溶劑等。(Organic solvent) The coloring composition of the present invention preferably contains an organic solvent. As the above-mentioned organic solvent, ester-based organic solvents, ether-based organic solvents, ether-ester-based organic solvents, ketone-based organic solvents, aromatic hydrocarbon-based solvents with a boiling point of 70 to 300°C at atmospheric pressure (1.013×10 2 kPa) are preferred. Organic solvents, nitrogen-containing organic solvents, etc.
作為此種溶劑，具體而言，可例示：乙二醇單甲醚、乙二醇單乙醚、乙二醇單異丙醚、乙二醇單丁醚、二乙二醇單甲醚、二乙二醇單乙醚、丙二醇單甲醚、丙二醇單乙醚、丙二醇單丁醚、二乙二醇二乙醚、二乙二醇二甲醚、二乙二醇甲基乙基醚等醚系有機溶劑類、乙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、乙二醇單丁醚乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯等醚酯系有機溶劑類、甲基異丁基酮、環己酮、2-庚酮、δ-丁內酯等酮系有機溶劑類、2-羥基丙酸甲酯、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸乙酯、3-甲基-3-甲氧基丙酸丁酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙氧基乙酸乙酯、羥基乙酸酯、甲酸正戊酯等酯系有機溶劑類、N-甲基吡咯啶酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等含氮系有機溶劑類等，該等有機溶劑可單獨或混合2種以上而使用。Specific examples of such a solvent include: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethyl Glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and other ether-based organic solvents, Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and other ether ester organic solvents , Methyl isobutyl ketone, cyclohexanone, 2-heptanone, δ-butyrolactone and other ketone-based organic solvents, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2-hydroxy-2 -Ethyl methyl propionate, butyl 3-methyl-3-methoxy propionate, methyl 3-methoxy propionate, ethyl 3-methoxy propionate, 3-ethoxy propionic acid Ester organic solvents such as methyl ester, ethyl 3-ethoxypropionate, ethyl ethoxy acetate, hydroxyacetate, n-pentyl formate, N-methylpyrrolidone, N,N-dimethyl Nitrogen-containing organic solvents such as methamide and N,N-dimethylacetamide, etc. These organic solvents can be used alone or in combination of two or more.
該等有機溶劑之中，就沸點、溶解性、分散性、塗佈性等方面而言，較佳為：二乙二醇二甲醚、二乙二醇甲基乙基醚、乙二醇單甲醚乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、環己酮、2-庚酮、2-羥基丙酸乙酯、3-甲基-3-甲氧基丙酸丁酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、甲酸正戊酯等，更佳為丙二醇單甲醚乙酸酯。Among these organic solvents, in terms of boiling point, solubility, dispersibility, coating properties, etc., preferably: diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, ethylene glycol mono Methyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 2-heptanone, ethyl 2-hydroxypropionate, 3-methyl-3-methoxypropionic acid Butyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, n-pentyl formate, etc., more preferably propylene glycol monomethyl ether acetate.
（其他添加劑）
根據本發明之著色組成物之製造方法，可適當使用光聚合起始劑、熱聚合抑制劑、紫外線吸收劑、抗氧化劑等各種添加劑。
作為上述光聚合起始劑，並無特別限定，例如可使用：二苯甲酮、N,N'-四乙基-4,4'-二胺基二苯甲酮、4-甲氧基-4'-二甲胺基二苯甲酮、二苯乙二酮、2,2-二乙氧基苯乙酮、安息香、安息香甲醚、安息香異丁醚、苄基二甲基縮酮、α-羥基異丁基苯酮、9-氧硫𠮿
＜著色組成物之製造方法＞ 對使用以上材料製造著色組成物之方法之一例進行說明。 對上述各色之顏料，視需要添加黏合劑樹脂、碳黑、顏料分散劑、顏料分散助劑、有機溶劑及其他添加劑並進行混合，而獲得混合物。 將所獲得之混合物使用輥磨機、捏合機、高速攪拌裝置、珠磨機、球磨機、砂磨機、超音波分散機、高壓分散機等各種分散機進行混練，並進行分散處理，而獲得各色之顏料分散組成物。 繼而，將所獲得之各色之顏料分散組成物以成為疑似黑色化之方式按既定之組合進行摻合，並視需要添加黏合劑樹脂、有機溶劑、及其他添加劑，使用高速攪拌機等攪拌裝置均勻地混合之後，利用過濾器進行過濾，而獲得本發明之著色組成物。於上述製造方法中，黏合劑樹脂可於製作顏料分散組成物時添加。又，亦可於製作顏料分散組成物之後，於製作著色組成物時添加。＜Method of manufacturing colored composition＞ An example of a method of manufacturing a colored composition using the above materials will be described. For the above-mentioned pigments of various colors, binder resin, carbon black, pigment dispersant, pigment dispersing aid, organic solvent and other additives are added and mixed as necessary to obtain a mixture. The obtained mixture is kneaded using various dispersers such as roller mills, kneaders, high-speed stirring devices, bead mills, ball mills, sand mills, ultrasonic dispersers, and high-pressure dispersers, and then subjected to dispersion treatment to obtain various colors The pigment dispersion composition. Then, the obtained pigment dispersion composition of each color is blended in a predetermined combination in a manner that is suspected of blackening, and binder resin, organic solvent, and other additives are added as necessary, and a mixing device such as a high-speed mixer is used to uniformly After mixing, filter with a filter to obtain the colored composition of the present invention. In the above manufacturing method, the binder resin may be added when the pigment dispersion composition is manufactured. In addition, it may be added when the coloring composition is prepared after the pigment dispersion composition is prepared.
（共分散） 獲得由將各顏料以成為疑似黑色化之方式進行摻合所得之混合顏料、顏料分散劑、顏料分散助劑、有機溶劑、視需要之黏合劑樹脂、進一步視需要之其他添加劑所構成之混合物。將所獲得之混合物使用輥磨機、捏合機、高速攪拌裝置、珠磨機、球磨機、砂磨機、超音波分散機、高壓分散機等各種分散機進行混練，並進行分散處理，而獲得顏料分散組成物。 繼而，於所獲得之顏料分散組成物中，視需要添加黏合劑樹脂、有機溶劑、及其他添加劑，使用高速攪拌機等攪拌裝置均勻地混合之後，利用過濾器進行過濾，而獲得本發明之著色組成物。於上述製造方法中，黏合劑樹脂可於製作顏料分散組成物時添加。 又，亦可於製作顏料分散組成物之後，於製作著色組成物時添加。(Co-dispersion) Obtain a mixture of mixed pigments, pigment dispersants, pigment dispersion aids, organic solvents, binder resins as needed, and other additives as needed by blending each pigment in a manner that is suspected of blackening. The obtained mixture is kneaded with various dispersing machines such as roller mills, kneaders, high-speed stirring devices, bead mills, ball mills, sand mills, ultrasonic dispersers, and high-pressure dispersers, and then subjected to dispersion treatment to obtain pigments Disperse the composition. Then, to the obtained pigment dispersion composition, a binder resin, an organic solvent, and other additives are added as necessary, and the mixture is uniformly mixed with a stirring device such as a high-speed mixer, and then filtered with a filter to obtain the colored composition of the present invention Things. In the above manufacturing method, the binder resin may be added when the pigment dispersion composition is manufactured. In addition, it may be added when the coloring composition is prepared after the pigment dispersion composition is prepared.
本發明之著色組成物較佳為於25℃測定出之黏度為2.0～20.0 mPa·s。 若上述黏度未達2.0 mPa·s、或超過20.0 mPa·s，則存在對塗佈性造成不良影響之情況。 再者，上述黏度係將本發明之著色組成物緊塞於玻璃瓶等中，保存1日之後使用E型黏度計（東機產業公司製造）所測定出之黏度。The colored composition of the present invention preferably has a viscosity measured at 25°C of 2.0 to 20.0 mPa·s. If the above-mentioned viscosity does not reach 2.0 mPa·s or exceeds 20.0 mPa·s, it may adversely affect the coatability. In addition, the above-mentioned viscosity is the viscosity measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.) after tightly plugging the colored composition of the present invention in a glass bottle or the like and storing it for 1 day.
本發明之著色組成物較佳為經時穩定性為0.8～1.1。 若上述經時穩定性未達0.8、或超過1.1，則存在對塗佈性、顯影性造成不良影響之情況。 再者，上述經時穩定性係使用E型黏度計（東機產業公司製造）測定將本發明之著色組成物緊塞於玻璃瓶等中且於室溫（25℃）保存1日後之25℃之黏度、及將本發明之著色組成物緊塞於玻璃瓶等中且於40℃保存7日後之25℃之黏度，以（於40℃保存7日後之黏度）/（於室溫保存1日後之黏度）之形式求出者。The colored composition of the present invention preferably has a stability over time of 0.8 to 1.1. If the above-mentioned stability with time is less than 0.8 or exceeds 1.1, it may adversely affect coatability and developability. In addition, the above-mentioned stability with time was measured by using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.), when the colored composition of the present invention was tightly plugged into a glass bottle, etc. and stored at room temperature (25°C) for 1 day at 25°C The viscosity of the colored composition of the present invention is tightly plugged into a glass bottle, etc. and stored at 40°C for 7 days at 25°C, as (viscosity after storage at 40°C for 7 days)/(after 1 day at room temperature The form of the viscosity).
其次，對使用本發明之著色組成物作為著色阻劑組成物之例進行說明。 本發明之著色阻劑組成物含有本發明之著色組成物。 本發明之著色阻劑組成物較佳為除了本發明之著色組成物以外，亦含有鹼可溶性樹脂、光聚合性化合物、光聚合起始劑、有機溶劑，且視需要適當添加聚合抑制劑等各種添加劑而獲得者。Next, an example of using the coloring composition of the present invention as a coloring resist composition will be described. The coloring resist composition of the present invention contains the coloring composition of the present invention. The coloring resist composition of the present invention preferably contains, in addition to the coloring composition of the present invention, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, an organic solvent, and various polymerization inhibitors, etc., if necessary. Additives and winners.
＜著色阻劑組成物之構成材料＞ （著色組成物） 本發明之著色阻劑組成物係使用本發明之著色組成物來製造。 相對於本發明之著色阻劑組成物之總固體成分，本發明之著色組成物之含量以質量分率計較佳為20～90質量%，更佳為30～80質量%。＜Materials of coloring resist composition＞ (Coloring composition) The coloring resist composition of the present invention is manufactured using the coloring composition of the present invention. With respect to the total solid content of the coloring resist composition of the present invention, the content of the coloring composition of the present invention is preferably 20 to 90% by mass, and more preferably 30 to 80% by mass.
（顏料分散劑） 作為顏料分散劑，可較佳地使用上述本發明之著色組成物中所記載者。 於本發明之著色阻劑組成物中，相對於所使用之全部顏料100質量份，顏料分散劑之含量較佳為0.1～50質量份，更佳為1～20質量份。(Pigment Dispersant) As the pigment dispersant, those described in the above-mentioned coloring composition of the present invention can be preferably used. In the coloring resist composition of the present invention, the content of the pigment dispersant is preferably 0.1-50 parts by mass, more preferably 1-20 parts by mass relative to 100 parts by mass of all pigments used.
（黏合劑樹脂） 作為黏合劑樹脂，可較佳地使用本發明之著色組成物中所記載者。 於本發明之著色阻劑組成物中，黏合劑樹脂之含量較佳為於本發明之著色阻劑組成物之固體成分中為3～50質量%。(Adhesive resin) As the binder resin, those described in the coloring composition of the present invention can be preferably used. In the coloring resist composition of the present invention, the content of the binder resin is preferably 3-50% by mass in the solid content of the coloring resist composition of the present invention.
（光聚合起始劑）
作為光聚合起始劑，並無特別限定，例如可使用：二苯甲酮、N,N'-四乙基-4,4'-二胺基二苯甲酮、4-甲氧基-4'-二甲胺基二苯甲酮、二苯乙二酮、2,2-二乙氧基苯乙酮、安息香、安息香甲醚、安息香異丁醚、苄基二甲基縮酮、α-羥基異丁基苯酮、9-氧硫𠮿
（光聚合性單體） 作為光聚合性單體，可使用乙烯性不飽和化合物等。關於此處所使用之乙烯性不飽和化合物，就聚合性、交聯性等方面而言，較佳為於分子內具有2個以上之乙烯性不飽和鍵之化合物。該等光聚合性單體可單獨或併用2種以上而使用。(Photopolymerizable monomer) As the photopolymerizable monomer, ethylenically unsaturated compounds and the like can be used. Regarding the ethylenically unsaturated compound used here, in terms of polymerizability, crosslinkability, etc., a compound having two or more ethylenically unsaturated bonds in the molecule is preferred. These photopolymerizable monomers can be used alone or in combination of two or more kinds.
（有機溶劑） 作為有機溶劑，可較佳地使用本發明之著色組成物中所記載者。 於本發明之著色阻劑組成物中，關於有機溶劑之含量，就各材料之溶解性、顏料分散性、塗佈性等方面而言，相對於本發明之著色阻劑組成物之總量，較佳為5～90質量%。(Organic solvents) As the organic solvent, those described in the coloring composition of the present invention can be preferably used. In the coloring resist composition of the present invention, the content of the organic solvent is relative to the total amount of the coloring resist composition of the present invention in terms of the solubility of each material, pigment dispersibility, and coating properties, etc. Preferably it is 5 to 90% by mass.
（其他添加劑） 於本發明之著色阻劑組成物中，可視需要適當使用熱聚合抑制劑、紫外線吸收劑、抗氧化劑等各種添加劑。(Other additives) In the coloring resist composition of the present invention, various additives such as thermal polymerization inhibitors, ultraviolet absorbers, and antioxidants can be appropriately used as needed.
＜本發明之著色阻劑組成物之製造方法＞ 製造本發明之著色阻劑組成物之方法係本發明之較佳實施形態之一例，但本發明並非限定於此。 例如，可利用對本發明之著色組成物添加黏合劑樹脂、光聚合性化合物、光聚合起始劑、有機溶劑、及其他添加劑，並使用攪拌裝置等進行攪拌混合之方法。<The manufacturing method of the coloring resist composition of the present invention> The method of manufacturing the coloring resist composition of the present invention is an example of a preferred embodiment of the present invention, but the present invention is not limited to this. For example, a method of adding a binder resin, a photopolymerizable compound, a photopolymerization initiator, an organic solvent, and other additives to the coloring composition of the present invention, and using a stirring device for stirring and mixing can be used.
本發明之著色阻劑組成物較佳為於25℃測定出之黏度為1.0～30.0 mPa·s。 若上述黏度未達1.0 mPa·s、或超過30.0 mPa·s，則存在對塗佈性造成不良影響之情況。 再者，上述黏度係將本發明之著色阻劑組成物緊塞於玻璃瓶等中，保存1日之後之使用E型黏度計（東機產業公司製造）所測定出之黏度。The coloring resist composition of the present invention preferably has a viscosity measured at 25°C of 1.0 to 30.0 mPa·s. If the above viscosity does not reach 1.0 mPa·s or exceeds 30.0 mPa·s, it may adversely affect the coatability. In addition, the above-mentioned viscosity is the viscosity measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.) after the coloring resist composition of the present invention is tightly plugged into a glass bottle etc. and stored for 1 day.
本發明之著色阻劑組成物較佳為經時穩定性為0.8～1.2。 若上述經時穩定性未達0.8、或超過1.2，則存在對塗佈性、顯影性造成不良影響之情況。再者，上述經時穩定性係使用E型黏度計（東機產業公司製造）測定將本發明之著色阻劑組成物緊塞於遮光玻璃瓶等且於低溫（5℃）保存1日後之25℃之黏度、及將本發明之著色組成物緊塞於遮光玻璃瓶等中且於低溫（5℃）保存7日後之25℃之黏度，以（於5℃保存7日後之黏度）/（於5℃保存1日後之黏度）之形式求出者。The coloring resist composition of the present invention preferably has a stability over time of 0.8 to 1.2. If the above-mentioned stability with time is less than 0.8 or exceeds 1.2, it may adversely affect coatability and developability. In addition, the above-mentioned stability with time was measured by using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.) after the coloring resist composition of the present invention was tightly plugged into a light-shielding glass bottle, etc., and stored at a low temperature (5°C) for 1 day. ℃ viscosity, and the coloring composition of the present invention is tightly plugged into a light-shielding glass bottle, etc. and stored at a low temperature (5 ℃) for 7 days after the viscosity of 25 ℃, as (the viscosity after storage at 5 ℃ for 7 days) / (in Viscosity after storage at 5°C for 1 day).
本發明之著色阻劑組成物於形成厚度1 μm之阻劑圖案時之光學密度（OD值）較佳為1.00以上，更佳為1.20以上。 若上述光學密度（OD值）為1.25以上，則可認為遮蔽性充分。 再者，上述光學密度（OD值）係使用本發明之著色阻劑組成物形成1 μm之阻劑圖案，利用Macbeth濃度計（TD-931，商品名，Macbeth公司製造）所測定出之值。The optical density (OD value) of the colored resist composition of the present invention when forming a resist pattern with a thickness of 1 μm is preferably 1.00 or more, more preferably 1.20 or more. If the optical density (OD value) is 1.25 or more, it can be considered that the shielding property is sufficient. Furthermore, the above-mentioned optical density (OD value) is a value measured by using the coloring resist composition of the present invention to form a resist pattern of 1 μm and using a Macbeth densitometer (TD-931, trade name, manufactured by Macbeth).
本發明之著色阻劑組成物於形成厚度2 μm之硬化塗膜時之耐溶劑性較佳為0.6以下，更佳為0.5以下，進而較佳為0.4以下，尤佳為0.3以下，最佳為0.2以下。 再者，上述耐溶劑性係將厚度2 μm之硬化塗膜浸漬於被加熱至100℃之N-甲基吡咯啶酮中，並於100℃之烘箱內保溫10分鐘。其後，利用分光光度計（UV-2500PC）測定上述N-甲基吡咯啶酮之吸光度，將最大峰值之吸光度設為耐溶劑性之值。The solvent resistance of the coloring resist composition of the present invention when forming a hardened coating film with a thickness of 2 μm is preferably 0.6 or less, more preferably 0.5 or less, still more preferably 0.4 or less, particularly preferably 0.3 or less, most preferably 0.2 or less. Furthermore, the above-mentioned solvent resistance is achieved by immersing a hardened coating film with a thickness of 2 μm in N-methylpyrrolidone heated to 100°C and keeping it in an oven at 100°C for 10 minutes. Thereafter, the absorbance of the above-mentioned N-methylpyrrolidone was measured with a spectrophotometer (UV-2500PC), and the absorbance at the maximum peak was set as the value of the solvent resistance.
本發明之著色組成物及著色阻劑組成物具有上述特性，故而可較佳地用作影像顯示裝置或觸控面板等之黑矩陣、黑色柱間隔物或黑色間隔壁材料。 [發明之效果]The coloring composition and coloring resist composition of the present invention have the above-mentioned characteristics, so they can be preferably used as black matrix, black column spacer or black partition wall materials for image display devices or touch panels. [Effects of Invention]
根據本發明，可提供一種遮光性優異且耐溶劑性亦優異之著色組成物、及含有其之著色阻劑組成物。According to the present invention, it is possible to provide a coloring composition having excellent light-shielding properties and solvent resistance, and a coloring resist composition containing the same.
以下，使用實施例對本發明具體地進行說明，但本發明只要不脫離其主旨及應用範圍，則並非限定於該等。再者，只要未作特別說明，則於本實施例中，「份」及「%」分別表示「質量份」及「質量%」。Hereinafter, the present invention will be specifically described using examples, but the present invention is not limited to these unless it deviates from the spirit and scope of application. Furthermore, as long as there is no special description, in this embodiment, "parts" and "%" represent "parts by mass" and "% by mass" respectively.
以下之實施例1～10、比較例1～3中所使用之著色組成物之材料係如下所述。 ＜顏料＞ P.V.23（C.I.顏料紫23） P.V.29（C.I.顏料紫29） P.V.32（C.I.顏料紫32） P.Y.139（C.I.顏料黃139） P.Y.185（C.I.顏料黃185） P.O.16（C.I.顏料橙16） P.O.64（C.I.顏料橙64） P.R.254（C.I.顏料紅254） P.B.60（C.I.顏料藍60） P.B.15：6（C.I.顏料藍15：6） ＜碳黑＞ TPK1104R（Cabot公司製造，吸油量：38 ml/100 g，pH：2.7） ＜黏合劑樹脂＞ BzMA/MAA（鹼可溶性樹脂，甲基丙烯酸苄酯/甲基丙烯酸共聚物，理論酸值：120 mgKOH/g，質量平均分子量：10000） ＜顏料分散劑＞ BYK-LPN-22102（BYK-Chemie公司製造，由具有顏料親和性基之片段與具有黏合劑相溶性基之片段所構成之丙烯酸系嵌段共聚物） ＜顏料分散助劑＞ 於100 ml三角燒瓶中加入30 ml濃硫酸，一面利用電磁攪拌器進行攪拌，一面投入10 g顏料紅2（上述式（3）及/或（4）所表示之化合物），於室溫攪拌30分鐘。於1 L燒杯中加入水50 g與冰50 g之混合物，將上述反應物注入至該冰水中，利用電磁攪拌器攪拌30分鐘。將其於減壓下進行過濾、水洗，並使所獲得之固體乾燥，而獲得顏料分散助劑1（上述通式（31）及/或（32）所表示之化合物：M＝H）12 g。 ＜有機溶劑＞ PGMEA（丙二醇單甲醚乙酸酯）The materials of the coloring composition used in the following Examples 1-10 and Comparative Examples 1-3 are as follows. ＜Pigment＞ P.V.23 (C.I. Pigment Violet 23) P.V.29 (C.I. Pigment Violet 29) P.V.32 (C.I. Pigment Violet 32) P.Y.139 (C.I. Pigment Yellow 139) P.Y.185 (C.I. Pigment Yellow 185) P.O.16 (C.I. Pigment Orange 16) P.O.64 (C.I. Pigment Orange 64) P.R.254 (C.I. Pigment Red 254) P.B.60 (C.I. Pigment Blue 60) P.B.15: 6 (C.I. Pigment Blue 15: 6) ＜Carbon Black＞ TPK1104R (manufactured by Cabot, oil absorption: 38 ml/100 g, pH: 2.7) ＜Adhesive resin＞ BzMA/MAA (alkali-soluble resin, benzyl methacrylate/methacrylic acid copolymer, theoretical acid value: 120 mgKOH/g, mass average molecular weight: 10000) ＜Pigment Dispersant＞ BYK-LPN-22102 (manufactured by BYK-Chemie, an acrylic block copolymer composed of a segment with a pigment affinity group and a segment with a binder compatible group) ＜Pigment dispersion aids＞ Add 30 ml of concentrated sulfuric acid into a 100 ml Erlenmeyer flask. While stirring with an electromagnetic stirrer, add 10 g of Pigment Red 2 (the compound represented by the above formula (3) and/or (4)) and stir at room temperature for 30 minute. A mixture of 50 g of water and 50 g of ice was added to a 1 L beaker, the above reactant was poured into the ice water, and stirred with an electromagnetic stirrer for 30 minutes. This was filtered and washed with water under reduced pressure, and the obtained solid was dried to obtain pigment dispersion aid 1 (the compound represented by the above general formula (31) and/or (32): M=H) 12 g . ＜Organic solvent＞ PGMEA (Propylene Glycol Monomethyl Ether Acetate)
以下之實施例11～20、比較例4～6中所使用之著色阻劑組成物之材料係如下所述。
＜黏合劑樹脂＞
SPC-3500（鹼可溶性樹脂，含有碳＝碳不飽和鍵，理論酸值：60 mgKOH/g，質量平均分子量：11000）
＜光聚合起始劑＞
Irgacure907（BASF公司製造，2-甲基-1[4-(甲硫基)苯基]-2-
＜實施例1～10、比較例1～3之著色組成物之製備＞ 以成為表1之組成（表1中之各材料之使用量為質量%）之方式將各種材料混合，利用珠磨機研磨一晝夜，而製備出實施例1～10、比較例1～3之著色組成物。<Preparation of the colored composition of Examples 1 to 10 and Comparative Examples 1 to 3> Various materials were mixed so as to become the composition of Table 1 (the usage amount of each material in Table 1 is mass%), and the beads were ground for a whole day and night to prepare Examples 1 to 10 and Comparative Examples 1 to 3 Coloring composition.
＜實施例11～20、比較例4～6之著色阻劑組成物之製備＞ 使用高速攪拌機，將實施例1～10、比較例1～3之各著色組成物與其他材料以成為表2之組成（表2中之各材料之使用量為質量%）之方式均勻地混合之後，利用孔徑3 μm之過濾器進行過濾，而獲得實施例11～20、比較例4～6之著色阻劑組成物。<Preparation of coloring resist compositions of Examples 11-20 and Comparative Examples 4-6> Using a high-speed mixer, the coloring compositions of Examples 1 to 10 and Comparative Examples 1 to 3 and other materials were uniformly mixed to form the composition of Table 2 (the usage amount of each material in Table 2 is mass%) , Filtered with a filter with a pore size of 3 μm to obtain the coloring resist composition of Examples 11-20 and Comparative Examples 4-6.
（評價試驗） 針對實施例1～10、比較例1～3中所獲得之著色組成物、及實施例11～20、比較例4～6中所獲得之著色阻劑組成物，藉由下述之方法對流動性及經時穩定性進行評價，將其結果示於表1及2。 又，塗佈實施例11～20、比較例4～6中所獲得之著色阻劑組成物而形成阻劑圖案，對其光學密度及耐溶劑性進行評價，將其結果示於表2。(Evaluation test) Regarding the colored compositions obtained in Examples 1 to 10, Comparative Examples 1 to 3, and the colored resist compositions obtained in Examples 11 to 20 and Comparative Examples 4 to 6, the flow was controlled by the following method The properties and stability over time were evaluated, and the results are shown in Tables 1 and 2. In addition, the colored resist compositions obtained in Examples 11 to 20 and Comparative Examples 4 to 6 were applied to form resist patterns, and the optical density and solvent resistance were evaluated. The results are shown in Table 2.
＜流動性＞ 針對實施例1～10、比較例1～3中所獲得之著色組成物，分別取至玻璃瓶中，塞緊，並於室溫（25℃）保存1日之後，使用E型黏度計（東機產業公司製造）測定25℃之黏度[mPa·s]，而評價流動性。 針對實施例11～20、比較例4～6中所獲得之著色阻劑組成物，分別取至遮光玻璃瓶中，塞緊，並於低溫（5℃）保存1日之後，使用E型黏度計（東機產業公司製造）測定25℃之黏度[mPa·s]，而評價流動性。＜Liquidity＞ For the colored compositions obtained in Examples 1 to 10 and Comparative Examples 1 to 3, they were respectively taken into glass bottles, stoppered, and stored at room temperature (25°C) for 1 day, and then used the E-type viscometer (East (Manufactured by Ji Sangyo Co., Ltd.) to measure the viscosity [mPa·s] at 25°C to evaluate the fluidity. Regarding the coloring resist compositions obtained in Examples 11-20 and Comparative Examples 4-6, respectively take them into light-shielding glass bottles, stop them tightly, and store them at low temperature (5°C) for 1 day, then use an E-type viscometer (Manufactured by Toki Sangyo Co., Ltd.) Measure the viscosity [mPa·s] at 25°C to evaluate the fluidity.
＜經時穩定性＞ 針對實施例1～10、比較例1～3中所獲得之著色組成物，分別取至玻璃瓶中，使用E型黏度計（東機產業公司製造）測定將本發明之著色組成物緊塞於玻璃瓶等中且於室溫（25℃）保存1日後之25℃之黏度、及將本發明之著色組成物緊塞於玻璃瓶等中且於40℃保存7日後之25℃之黏度，以（於40℃保存7日後之黏度）/（於室溫保存1日後之黏度）之形式求出。 又，針對實施例11～20、比較例4～6中所獲得之著色阻劑組成物，使用E型黏度計（東機產業公司製造）測定緊塞於遮光玻璃瓶等中且於低溫（5℃）保存1日後之25℃之黏度、及將本發明之著色組成物緊塞於遮光玻璃瓶等中且於低溫（5℃）保存7日後之25℃之黏度，以（於5℃保存7日後之黏度）/（於5℃保存1日後之黏度）之形式求出。＜Stability with time＞ Regarding the colored compositions obtained in Examples 1-10 and Comparative Examples 1 to 3, they were taken into glass bottles, and measured with an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.). The colored composition of the present invention was tightly plugged in The viscosity at 25°C after 1 day in glass bottles, etc. and stored at room temperature (25°C), and the viscosity at 25°C after the colored composition of the present invention is tightly plugged in glass bottles, etc. and stored at 40°C for 7 days, to (Viscosity after storage at 40°C for 7 days)/(Viscosity after storage at room temperature for 1 day). In addition, the coloring resist compositions obtained in Examples 11 to 20 and Comparative Examples 4 to 6 were measured with an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.), which was tightly plugged in a light-shielding glass bottle, etc., and at low temperature (5 ℃) The viscosity of 25℃ after 1 day of storage, and the viscosity of 25℃ after storing the colored composition of the present invention tightly in a light-shielding glass bottle, etc. and stored at low temperature (5℃) for 7 days. Calculate the viscosity in the form of)/(viscosity after 1 day storage at 5℃).
＜光學密度（OD值）＞ 將實施例11～20、比較例4～6之著色阻劑組成物藉由旋轉塗佈機以成為膜厚1 μm之方式塗佈於玻璃基板上，以100℃預烤（prebake）3分鐘之後，利用高壓水銀燈進行曝光，進一步以230℃進行30分鐘後烘烤（post bake），而獲得僅於實體部形成之黑色阻劑圖案。利用Macbeth濃度計（TD-931，商品名，Macbeth公司製造）測定所獲得之各實體部之黑色阻劑圖案之光學密度（OD值）。＜Optical density (OD value)＞ The coloring resist compositions of Examples 11-20 and Comparative Examples 4-6 were coated on a glass substrate with a film thickness of 1 μm by a spin coater, and then prebakeed at 100°C for 3 minutes. , Use a high-pressure mercury lamp for exposure, and further post bake at 230°C for 30 minutes to obtain a black resist pattern formed only on the solid part. A Macbeth densitometer (TD-931, trade name, manufactured by Macbeth) was used to measure the optical density (OD value) of the black resist pattern of each physical part obtained.
＜耐溶劑性＞ 將實施例11～20、比較例4～6之著色阻劑組成物藉由旋轉塗佈機以成為膜厚1 μm之方式塗佈於玻璃基板上，以100℃預烤3分鐘之後，利用高壓水銀燈進行曝光，進一步以230℃進行30分鐘後烘烤，而獲得僅於實體部形成之硬化塗膜。 將所獲得之各實體部之硬化塗膜浸漬於被加熱至100℃之N-甲基吡咯啶酮中，於100℃之烘箱內保溫10分鐘。其後，利用分光光度計（UV-2500PC）測定上述N-甲基吡咯啶酮之吸光度，將最大峰值之吸光度設為耐溶劑性之值。＜Solvent resistance＞ The coloring resist compositions of Examples 11 to 20 and Comparative Examples 4 to 6 were coated on a glass substrate with a thickness of 1 μm by a spin coater, and then pre-baked at 100°C for 3 minutes, and then used high pressure Exposure with mercury lamp, and further post-baking at 230°C for 30 minutes to obtain a hardened coating film formed only on the solid part. The obtained hardened coating film of each physical part was immersed in N-methylpyrrolidone heated to 100°C, and kept in an oven at 100°C for 10 minutes. Thereafter, the absorbance of the above-mentioned N-methylpyrrolidone was measured with a spectrophotometer (UV-2500PC), and the absorbance at the maximum peak was set as the value of the solvent resistance.
[表1]
[表2]
確認到實施例之著色組成物及著色阻劑組成物之流動性及經時穩定性優異。 又，確認到實施例之著色阻劑組成物之OD值為1.25以上，且耐溶劑性為0.60以下，遮光性及耐溶劑性優異。 實施例之著色組成物及著色阻劑組成物具有上述特性，故而可較佳地用作影像顯示裝置或觸控面板等之黑矩陣、黑色柱間隔物或黑色間隔壁材料。 另一方面，於比較例之著色組成物及著色阻劑組成物中，無遮光性優異且耐溶劑性亦優異者。 [產業上之可利用性]It was confirmed that the coloring composition and the coloring resist composition of the examples were excellent in fluidity and stability over time. In addition, it was confirmed that the OD value of the coloring resist composition of the example was 1.25 or more, the solvent resistance was 0.60 or less, and it was excellent in light-shielding and solvent resistance. The coloring composition and coloring resist composition of the embodiment have the above-mentioned characteristics, and therefore can be preferably used as black matrix, black column spacer or black partition wall material for image display devices or touch panels. On the other hand, in the coloring composition and the coloring resist composition of the comparative example, there is no one having excellent light-shielding properties and excellent solvent resistance. [Industrial availability]
根據本發明，可提供一種遮光性優異且耐溶劑性亦優異之著色組成物、及含有其之著色阻劑組成物。According to the present invention, it is possible to provide a coloring composition having excellent light-shielding properties and solvent resistance, and a coloring resist composition containing the same.
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