TWI659265B - Black resin composition for light shielding film, substrate with light shielding film color filter and touch panel - Google Patents

Black resin composition for light shielding film, substrate with light shielding film color filter and touch panel Download PDF

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TWI659265B
TWI659265B TW104107270A TW104107270A TWI659265B TW I659265 B TWI659265 B TW I659265B TW 104107270 A TW104107270 A TW 104107270A TW 104107270 A TW104107270 A TW 104107270A TW I659265 B TWI659265 B TW I659265B
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light
black
shielding film
mass
shielding
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TW201535050A (en
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中島祥人
河野正範
柳本徹也
東学
齋藤亨
藤城光一
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日商日鐵化學材料股份有限公司
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

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  • Spectroscopy & Molecular Physics (AREA)
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Abstract

本發明提供用以獲得反射色具有無彩色的黑色或自無彩色起帶藍色調的黑色的色相的黑色硬化膜(遮光膜)的遮光膜用黑色樹脂組成物、在透明基板上形成有該遮光膜的帶遮光膜的基板、彩色濾光片及觸控面板。本發明是一種遮光膜用黑色樹脂組成物，其包含如下成分作為必須成分：(A)利用光或熱的硬化性樹脂、及/或利用光或熱的硬化性單體、(B)在分散介質中分散黑色遮光性粒子而成的含有黑色遮光性粒子的分散液、及(C)在分散介質中分散顏色調整用粒子而成的含有顏色調整用粒子的分散液。 The present invention provides a black resin composition for a light-shielding film for obtaining a black hardened film (light-shielding film) having a reflection color having an achromatic black or a hue with a black tint from blue. The light-shielding film is formed on a transparent substrate. Film substrate with light-shielding film, color filter and touch panel. The present invention is a black resin composition for a light-shielding film, which contains the following components as essential components: (A) a curable resin using light or heat, and / or a curable monomer using light or heat, (B) A dispersion liquid containing black light-shielding particles obtained by dispersing black light-shielding particles in a medium, and (C) a dispersion liquid containing color-adjusting particles obtained by dispersing color-adjusting particles in a dispersion medium.

Description

遮光膜用黑色樹脂組成物、帶遮光膜的基板、彩色 濾光片及觸控面板 Black resin composition for light-shielding film, substrate with light-shielding film, color Filters and touch panels

本發明涉及一種遮光膜用黑色樹脂組成物、在玻璃等透明基板上包含使該組成物硬化而成的遮光膜的帶遮光膜的基板，以及以該帶遮光膜的基板為構成元件的液晶顯示器(Liquid Crystal Display，LCD)等的顯示器用彩色濾光片及顯示裝置用觸控面板。詳細而言涉及一種適於在透明基板上形成微細的遮光膜的由於光或熱而硬化的黑色樹脂組成物，及一種在選擇的位置上形成該遮光膜的帶遮光膜的基板。 The present invention relates to a black resin composition for a light-shielding film, a substrate with a light-shielding film including a light-shielding film formed by curing the composition on a transparent substrate such as glass, and a liquid crystal display using the substrate with the light-shielding film as a constituent element. (Liquid Crystal Display, LCD) and other color filters for displays and touch panels for display devices. More specifically, it relates to a black resin composition suitable for forming a fine light-shielding film on a transparent substrate, which is hardened by light or heat, and a substrate with a light-shielding film which forms the light-shielding film at a selected position.

在液晶電視、液晶顯示器、彩色液晶行動電話等各種領域中使用彩色液晶面板。彩色液晶面板成為如下的結構：經由密封材料將形成有彩色濾光片的基板與對向基板(薄膜電晶體(Thin Film Transistor，TFT)基板)貼合，在兩個基板之間填充液晶。其中，彩色濾光片的製造方法通常使用如下方法：在玻璃、塑膠片材等透明基板的表面，形成黑色矩陣(所述黑色矩陣起到藉由 抑制紅、綠、藍各色之間的混色而提高對比度的作用)，繼而順次用條紋狀或馬賽克狀等彩色圖案形成起到表現出所有自然色的作用的紅、綠、藍的不同色相。而且，在觸控面板中，在前面玻璃上形成觸控面板電路的情況下，為了隱藏金屬等取出配線，採用在畫面的周邊部形成以邊框狀形成的遮光層的方法。 Color liquid crystal panels are used in various fields such as liquid crystal televisions, liquid crystal displays, and color liquid crystal mobile phones. The color liquid crystal panel has a structure in which a substrate on which a color filter is formed and a counter substrate (Thin Film Transistor (TFT) substrate) are bonded together via a sealing material, and liquid crystal is filled between the two substrates. Among them, a method for manufacturing a color filter generally uses the following method: a black matrix is formed on the surface of a transparent substrate such as glass or a plastic sheet (the black matrix functions by (Reduces the color mixing between red, green, and blue to increase the contrast), and then sequentially uses stripe or mosaic-like color patterns to form different hue of red, green, and blue, which play the role of all natural colors. Further, in the case of a touch panel, when a touch panel circuit is formed on a front glass, a method of forming a light-shielding layer formed in a frame shape on a peripheral portion of a screen in order to hide a metal or the like and take out wiring is adopted.

作為形成彩色濾光片的黑色矩陣或觸控面板的邊框的 遮光膜的遮光材料，主要使用遮光性高的碳黑。然而，產生如下的問題：碳黑的反射光通常並不成為並未著色的黑色、亦即無彩色的黑色，在多數情況下多少會著色為茶色系的色調，因此變得漏出該著色的光、亦即自無彩色偏離的光，因此在用彩色濾光片顯示黑色或亮度低的顏色的情況下，無法顯示所期望的顏色。而且，還存在如下問題：在電源關閉(OFF)時，與黑色嵌槽(液晶顯示裝置或觸控面板的顯示畫面的周圍的邊框部分)產生顏色偏差而造成設計性欠佳，在對設計性的要求多樣化中，調整黑色的色相的需求逐漸變高。另外，在碳黑以外的黑色遮光材料中，在多數情況下並不為無彩色的黑色，因此要求調整為無彩色的黑色的技術。近年來，為了使液晶面板的視認性提高及使其具有設計性，要求黑色矩陣為“中性黑”(並未著色的黑色：無彩色)。而且，在觸控面板中也存在需要使邊框部分與黑色嵌槽的色相一致的情況，在這種情況下，要求觸控面板邊框為中性黑。 As a black matrix forming a color filter or a frame of a touch panel As the light-shielding material of the light-shielding film, carbon black having high light-shielding properties is mainly used. However, the following problem arises: the reflected light of carbon black usually does not become uncolored black, that is, achromatic black. In most cases, it is colored to a brown hue, and therefore the colored light leaks out. That is, light that has no color deviation, so when a black color or a low-brightness color is displayed with a color filter, a desired color cannot be displayed. In addition, there is a problem that when the power is turned off (OFF), a color deviation occurs from a black recessed groove (a portion of a frame around a display screen of a liquid crystal display device or a touch panel), resulting in poor design performance. In the diversification of requirements, the need to adjust the hue of black is gradually increasing. In addition, in black light-shielding materials other than carbon black, in most cases, it is not achromatic black, so a technique for adjusting to achromatic black is required. In recent years, in order to improve the visibility and design of a liquid crystal panel, the black matrix is required to be “neutral black” (black without coloring: achromatic). Moreover, in the touch panel, there is also a case where the frame portion needs to be consistent with the color of the black recessed groove. In this case, the touch panel frame is required to be neutral black.

為了實現中性黑，在專利文獻1中記載了需要使C光源 或F10光源中的樹脂黑色矩陣的透射光及/或反射光的XYZ表色系 統中的色度坐標與光源的色度坐標一致。其中，具體記載的技術是使碳黑與有機顏料(相對於該碳黑帶自無彩色偏離的茶色系的色相而言，該有機顏料包含作為茶色系色相的補色的藍色系或紫色系的顏料)分散而調整色度的技術，需要加入較多的補色用顏料。然而，特別是在為了提高遮光性而使碳黑的含量在抗蝕劑中高的情況下，如果進一步大量加入補色用顏料，則有助於硬化性的黏合樹脂或硬化性單體成分等的調配比例相對變小，因此塗膜變得難以充分硬化，塗膜與玻璃基板的密接性降低，產生變得容易產生剝落等的問題，或者耐環境試驗後的電阻率、密接性降低等對可靠性特性的不良影響。而且，僅僅關於透射光的色度調整而加以記載，但關於反射光的色度調整，並未具體地表示。 In order to achieve neutral black, Patent Document 1 describes that it is necessary to make a C light source XYZ color system of transmitted light and / or reflected light of resin black matrix in F10 or F10 light source The chromaticity coordinates in the system are consistent with the chromaticity coordinates of the light source. Among them, the technology specifically described is that carbon black and organic pigments (compared to the brown hue of the carbon black belt from achromatic deviation, the organic pigment contains blue or purple based complementary colors of the brown hue. (Pigment) Dispersing and adjusting the chromaticity requires adding more pigments for color correction. However, especially in the case where the content of carbon black is high in the resist in order to improve the light-shielding property, if a large amount of a pigment for color supplementation is further added, it will contribute to the formulation of a curable adhesive resin or a curable monomer component. The ratio becomes relatively small, so it becomes difficult to sufficiently harden the coating film, the adhesion between the coating film and the glass substrate is reduced, problems such as peeling are likely to occur, or the resistivity and adhesion after the environmental resistance test are reduced. Adverse effects of characteristics. In addition, only the chromaticity adjustment of transmitted light is described, but the chromaticity adjustment of reflected light is not specifically shown.

而且，作為使反射色為中性黑的方法，揭示了在作為遮光材料的碳黑或氮化鈦中添加著色顏料的紅色顏料或黃色顏料而進行調色的技術(專利文獻2及專利文獻3)，但並未提及關於所使用的遮光材料與著色顏料的分散狀態，對於可確實地調整為目標的中性黑或具有優選的傾向的自中性黑稍許變藍的反射色的技術的要求變高。 In addition, as a method for making the reflection color neutral black, a technique of adding a red pigment or a yellow pigment of a coloring pigment to carbon black or titanium nitride as a light-shielding material and a technique for color adjustment have been disclosed (Patent Document 2 and Patent Document 3) ), But does not mention the technology of the dispersion of the light-shielding material and the coloring pigment used, and it can be adjusted to the target neutral black or the self-neutral black with a preferred tendency to reflect blue slightly. Demand becomes higher.

[現有技術文獻] [Prior Art Literature] [專利文獻] [Patent Literature]

[專利文獻1]WO95/35525號說明書 [Patent Document 1] WO95 / 35525 Specification

[專利文獻2]日本專利特開2011-227467號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2011-227467

[專利文獻3]日本專利特開2014-119640號公報 [Patent Document 3] Japanese Patent Laid-Open No. 2014-119640

本發明是鑒於該技術的諸多缺點而發明，其目的在於提供遮光膜及帶遮光膜的基板，所述遮光膜是遮光性高的黑色的遮光膜，且是反射光被調整為無彩色的黑色或稍許帶藍色調的黑色的色度的彩色濾光片用黑色矩陣等的遮光膜。亦即，其中一個目的是使用使遮光材料分散於樹脂中而成的特定的遮光膜用黑色樹脂組成物，獲得反射光的L*a*b*表色系統中的色度坐標(a*,b*)≒(0.0,0.0)的遮光膜，於實用上而言，重要的是可進行用以使色度與黑色嵌槽一致的色度調整，因此目的在於獲得對a*、b*進行色度調整為-側(負側)而使其與黑色嵌槽等的色相吻合的遮光膜。 The present invention has been made in view of many shortcomings of this technology, and an object thereof is to provide a light-shielding film which is a black light-shielding film with high light-shielding property and a black light-reflecting film whose reflected light is adjusted to be achromatic. Alternatively, a light-shielding film such as a black matrix is used for a color filter with a chromaticity of black with a blue tint. That is, one of the purposes is to use a specific black resin composition for a light-shielding film in which a light-shielding material is dispersed in a resin to obtain L * a * b * chromaticity coordinates (a * , b * ) ≒ (0.0,0.0) is a light-shielding film. Practically speaking, it is important to adjust the chromaticity to make the chromaticity consistent with the black slot. Therefore, the purpose is to obtain a * , b * A light-shielding film whose chromaticity is adjusted to the-side (negative side) so as to match the color of a black slot and the like.

本發明者等人為了解決所述現有技術的問題點而進行了努力研究，結果發現藉由除了碳黑、鈦黑等黑色遮光性粒子、及硬化性樹脂或硬化性單體以外，使用特定的顏色調整用粒子而製成黑色樹脂組成物，可將遮光膜的色度調整為無彩色化或帶藍色調的黑色。而且，發現在該黑色樹脂組成物中，通過將黑色遮光性粒子的平均二次粒徑與顏色調整用粒子的平均二次粒徑的比設為特定的範圍，且將黑色遮光性粒子的質量與顏色調整用粒子的質量的質量比設為特定的範圍，可確實地實現色度的調整。此 時，作為顏色調整粒子的色相，發現在碳黑為自無彩色偏離為茶色系的色相的情況下，並不調配與該偏離的色相處於補色(相反色)的關係的藍色或紫色的顏料，相反地含有少量的與偏離的色相為同系色的黃色或橙色的顏料，由此可維持硬化後的膜特性或可靠性，且將遮光膜的色度調整為無彩色化或帶藍色調的黑色，從而完成本發明。 The present inventors have made intensive research in order to solve the problems of the prior art, and as a result, they have found that by using a specific material other than black light-shielding particles such as carbon black and titanium black, and a hardening resin or hardening monomer, The particles for color adjustment are made into a black resin composition, and the chromaticity of the light-shielding film can be adjusted to achromatic or black with blue tint. Furthermore, it was found that in this black resin composition, the ratio of the average secondary particle diameter of the black light-shielding particles to the average secondary particle diameter of the particles for color adjustment was set to a specific range, and the mass of the black light-shielding particles was set. The mass ratio with respect to the mass of the color adjustment particles is set in a specific range, and the chromaticity can be adjusted reliably. this At this time, as the hue of the color adjustment particles, it was found that when carbon black is a hue that deviates from the achromatic color to a brown hue, blue or purple pigments that are in a complementary color (opposite color) relationship with the deviated hue are not prepared. Conversely, it contains a small amount of yellow or orange pigments that are in the same color as the deviation of the hue, thereby maintaining the film characteristics or reliability after hardening, and adjusting the chromaticity of the light-shielding film to be achromatic or blueish. Black, thus completing the present invention.

亦即，本發明的主旨如下所示。亦即， That is, the gist of the present invention is as follows. that is,

(1)本發明是一種遮光膜用黑色樹脂組成物，其包含如下成分作為必須成分：(A)利用光或熱的硬化性樹脂、及/或利用光或熱的硬化性單體、(B)在分散介質中分散黑色遮光性粒子而成的含有黑色遮光性粒子的分散液、及(C)在分散介質中分散顏色調整用粒子而成的含有顏色調整用粒子的分散液。 (1) The present invention is a black resin composition for a light-shielding film, which includes the following components as essential components: (A) a curable resin using light or heat, and / or a curable monomer using light or heat, (B ) A dispersion liquid containing black light-shielding particles obtained by dispersing black light-shielding particles in a dispersion medium; and (C) a dispersion liquid containing color-adjusting particles obtained by dispersing color-adjusting particles in a dispersion medium.

(2)本發明還是根據(1)的遮光膜用黑色樹脂組成物，其中(C)成分中的顏色調整用粒子的平均二次粒徑DC與(B)成分中的黑色遮光性粒子的平均二次粒徑DB的比DC/DB為0.2~1.2的範圍，且(C)成分中所含的顏色調整用粒子的質量mC與(B)成分中所含的黑色遮光性粒子的質量mB的比mC/mB為0.03~0.2的範圍。 (2) The present invention is also a black resin composition for a light-shielding film according to (1), wherein the average secondary particle diameter D C of the particles for color adjustment in the component (C) and the black light-shielding particles in the component (B) The ratio D C / D B of the average secondary particle diameter D B is in a range of 0.2 to 1.2, and the mass m C of the color-adjusting particles contained in the component (C) and the black light-shielding property contained in the component (B) The ratio m C / m B of the mass m B of the particles is in the range of 0.03 to 0.2.

(3)本發明還是根據(1)或(2)的遮光膜用黑色樹脂組成物，其中所述黑色遮光性粒子是碳黑粒子。 (3) The present invention is also a black resin composition for a light-shielding film according to (1) or (2), wherein the black light-shielding particles are carbon black particles.

(4)本發明還是根據(1)~(3)中任一項的遮光膜用黑色樹脂組成物，其中所述顏色調整用粒子是作為黃色顏料的C.I.顏料 黃139及/或作為橙色顏料的C.I.顏料橙61。 (4) The present invention is also a black resin composition for a light-shielding film according to any one of (1) to (3), wherein the particles for color adjustment are C.I. pigments as yellow pigments Yellow 139 and / or C.I. Pigment Orange 61 as an orange pigment.

(5)本發明還是一種遮光膜用黑色樹脂組成物，其特 徵在於：所述遮光膜用黑色樹脂組成物是使用含有聚合性不飽和基的鹼可溶性樹脂與具有乙烯性不飽和雙鍵的聚合性單體作為(A)成分，且進一步含有(D)溶劑及(E)光聚合引發劑的根據(1)~(4)中任一項所述的遮光膜用黑色樹脂組成物，且在包含光硬化後成為固形的聚合性單體的固體成分中，含有聚合性不飽和基的鹼可溶性樹脂為10質量%~60質量%，相對於含有聚合性不飽和基的鹼可溶性樹脂100質量份而言，具有乙烯性不飽和雙鍵的聚合性單體為10質量份~60質量份，相對於含有聚合性不飽和基的鹼可溶性樹脂與具有乙烯性不飽和雙鍵的聚合性單體的合計量100質量份而言，(E)為2質量份~50質量份，進一步在固體成分中，(B)成分中的黑色遮光性粒子為30質量%~60質量%，在固體成分中(C)成分中的顏色調整用粒子為1質量%~15質量%。 (5) The present invention is also a black resin composition for a light-shielding film. The black resin composition for a light-shielding film is characterized in that an alkali-soluble resin containing a polymerizable unsaturated group and a polymerizable monomer having an ethylenically unsaturated double bond are used as the (A) component, and the solvent (D) is further contained. And (E) the black resin composition for a light-shielding film according to any one of (1) to (4), and a photopolymerization initiator, and a solid component including a polymerizable monomer that becomes a solid after photocuring, The alkali-soluble resin containing a polymerizable unsaturated group is 10% to 60% by mass. The polymerizable monomer having an ethylenically unsaturated double bond is 100 parts by mass of the alkali-soluble resin containing a polymerizable unsaturated group. 10 to 60 parts by mass, (E) is 2 parts by mass to 100 parts by mass of the total amount of the alkali-soluble resin containing a polymerizable unsaturated group and the polymerizable monomer having an ethylenically unsaturated double bond. 50 parts by mass, and in the solid component, the black light-shielding particles in the component (B) are 30% to 60% by mass, and the particles for color adjustment in the component (C) are 1% to 15% by mass in the solid component. %.

(6)本發明還是根據(5)的遮光膜用黑色樹脂組成物，其中含有聚合性不飽和基的鹼可溶性樹脂使用使(a)二羧酸或三羧酸或其酸酐、及(b)四羧酸或其酸二酐和由雙酚類所衍生的具有2個縮水甘油醚基的環氧化合物與含有不飽和基的單羧酸的反應物進行反應而所得的含有聚合性不飽和基的鹼可溶性樹脂。 (6) The present invention is also a black resin composition for a light-shielding film according to (5), in which the alkali-soluble resin containing a polymerizable unsaturated group uses (a) a dicarboxylic acid or a tricarboxylic acid or an anhydride thereof, and (b) Tetracarboxylic acid or its acid dianhydride and an epoxy compound derived from bisphenols having two glycidyl ether groups react with a reactant of an unsaturated monocarboxylic acid-containing polymerizable unsaturated group Alkali-soluble resin.

(7)本發明還是一種帶遮光膜的基板，其特徵在於：所述帶遮光膜的基板是將根據(1)~(6)中任一項所述的遮光 膜用黑色樹脂組成物塗布於透明基板上的單面上，使其硬化而所得的帶遮光膜的基板，自所述透明基板的塗布有遮光膜的面的相反面側所測定的CIE Lab色彩空間表示系統中的帶遮光膜的基板的b*值滿足-1.0<b*<+0.2。 (7) The present invention is also a substrate with a light-shielding film, wherein the substrate with a light-shielding film is coated with the black resin composition for a light-shielding film according to any one of (1) to (6) on A light-shielding film-obtained substrate with a light-shielding film obtained by curing one side of a transparent substrate, and the light-shielding film in the CIE Lab color space measurement system measured from the opposite side of the surface of the transparent substrate coated with the light-shielding film. The b * value of the substrate satisfies -1.0 <b * <+ 0.2.

(8)本發明還是一種彩色濾光片，其特徵在於：包含根據(7)的帶遮光膜的基板。 (8) The present invention is also a color filter including the substrate with a light-shielding film according to (7).

(9)本發明還是一種觸控面板，其特徵在於：包含根據(7)的帶遮光膜的基板。 (9) The present invention is also a touch panel characterized by comprising a substrate with a light-shielding film according to (7).

藉由使用本發明的黑色樹脂組成物，可在透明基板上形成將反射色控制為無彩色的黑色或自無彩色起帶藍色調的黑色的色相的黑色硬化膜(遮光膜)，可將形成有該遮光膜的帶遮光膜的透明基板應用於顯示裝置用彩色濾光片或觸控面板中。亦即，藉由本發明，可設計即使在顯示畫面未點亮時，設計性也優異的彩色濾光片或觸控面板。 By using the black resin composition of the present invention, a black hardened film (light-shielding film) capable of controlling the reflection color to achromatic black or a hue with a blue hue from achromatic on a transparent substrate can be formed on a transparent substrate. The transparent substrate with a light-shielding film having the light-shielding film is applied to a color filter for a display device or a touch panel. That is, with the present invention, it is possible to design a color filter or a touch panel that is excellent in designability even when the display screen is not lit.

以下，對本發明加以詳細說明。 Hereinafter, the present invention will be described in detail.

本發明的黑色樹脂組成物中的作為(A)成分的利用光或熱的 硬化性樹脂、及/或利用光或熱的硬化性單體如果是在分子內具有至少1個以上由於熱或光而產生硬化反應的官能基(例如(甲基)丙烯醯基、乙烯基等具有乙烯性不飽和雙鍵的基，或環氧基、氧雜環丁烷基等環狀反應性基)的樹脂或單體，則可使用。 The (A) component in the black resin composition of the present invention uses light or heat. If the curable resin and / or the curable monomer using light or heat have at least one functional group (e.g. (meth) acrylfluorenyl group, vinyl group, etc.) in the molecule that causes a curing reaction due to heat or light A resin or monomer having a group having an ethylenically unsaturated double bond, or a cyclic reactive group such as an epoxy group or an oxetanyl group can be used.

作為(A)成分的具有乙烯性不飽和雙鍵的化合物存在 有(A-1)具有乙烯性不飽和雙鍵的樹脂與(A-2)具有乙烯性不飽和雙鍵的聚合性單體，考慮塗敷等處理條件、由於光或熱而使其硬化的條件、硬化物的物性等，可以單獨使用(A-1)或(A-2)，還可以以任意比例加以混合而使用。 (A) A compound having an ethylenically unsaturated double bond exists (A-1) a resin having an ethylenically unsaturated double bond and (A-2) a polymerizable monomer having an ethylenically unsaturated double bond, which are hardened by light or heat in consideration of processing conditions such as coating The conditions, physical properties of the cured product, and the like can be used alone (A-1) or (A-2), or they can be mixed and used at any ratio.

(A-1)成分例如可列舉使用包含1種以上具有羧基的 單體的3種~5種聚合性單體(所述單體選自丙烯酸、甲基丙烯酸、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸丁酯等丙烯酸烷基酯或甲基丙烯酸烷基酯(以下，有時將這些化合物匯總記載為“(甲基)丙烯酸烷基酯”等)、環狀的(甲基)丙烯酸環己酯、(甲基)丙烯酸羥基乙酯及苯乙烯等)而合成的共聚物的羧基，與具有環氧基或異氰酸酯基和至少1個以上乙烯性不飽和雙鍵的甲基丙烯酸縮水甘油酯、異氰酸酯基乙基丙烯酸酯或甲基丙烯醯基異氰酸酯等反應而所得的由於光或熱而硬化的具有不飽和雙鍵的硬化性樹脂。自耐熱性、顯影性的方面考慮，具有此種結構的硬化性樹脂優選使用重量平均分子量為5000~100000、酸值為50~150的硬化性樹脂。 (A-1) As the component, for example, one containing one or more types having a carboxyl group may be used. 3 to 5 types of polymerizable monomers (the monomers are selected from the group consisting of acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, and formazan Alkyl acrylates such as butyl acrylate or alkyl methacrylates (hereinafter, these compounds may be collectively described as "alkyl (meth) acrylates", etc.), cyclic (meth) acrylic acid cyclohexyl Ester, hydroxyethyl (meth) acrylate, styrene, etc.), carboxyl group of the copolymer, and glycidyl methacrylate having an epoxy group or an isocyanate group and at least one ethylenically unsaturated double bond, A hardening resin having an unsaturated double bond, which is hardened by light or heat and is obtained by reacting an isocyanate ethyl acrylate or a methacryl fluorenyl isocyanate. From the viewpoints of heat resistance and developability, a curable resin having such a structure is preferably a curable resin having a weight average molecular weight of 5000 to 100,000 and an acid value of 50 to 150.

而且，(A-1)成分的其它例可列舉雙酚A型環氧樹脂、 雙酚F型環氧樹脂、酚醛清漆型環氧樹脂、多羧酸縮水甘油酯、多元醇聚縮水甘油酯、脂肪族或脂環式環氧樹脂、胺型環氧樹脂、三苯酚甲烷型環氧樹脂或二羥基苯型環氧樹脂等環氧樹脂與(甲基)丙烯酸反應而所得的環氧(甲基)丙烯酸酯型硬化性樹脂。該環氧(甲基)丙烯酸酯型硬化性樹脂進一步與酸單酐及酸二酐反應而所得的環氧(甲基)丙烯酸酯酸加成物可以在製成用光微影法進行鹼性顯影的可形成圖案的樹脂組成物的情況下適宜地使用。這種情況下適宜的重量平均分子量是2000~20000，酸值是50~150。 Examples of the other component (A-1) include bisphenol A epoxy resin, Bisphenol F epoxy resin, novolac epoxy resin, glycidyl polycarboxylic acid, polyglycidyl polyol, aliphatic or alicyclic epoxy resin, amine epoxy resin, triphenol methane ring An epoxy (meth) acrylate type curable resin obtained by reacting an epoxy resin such as an oxygen resin or a dihydroxybenzene-type epoxy resin with (meth) acrylic acid. An epoxy (meth) acrylate acid adduct obtained by further reacting the epoxy (meth) acrylate type curable resin with an acid monoanhydride and an acid dianhydride can be made alkaline by photolithography. In the case of a developed patternable resin composition, it is suitably used. In this case, a suitable weight average molecular weight is 2,000 to 20,000, and an acid value is 50 to 150.

作為在光微影法中使用本發明的情況下的優選例子的 使所述環氧(甲基)丙烯酸酯型硬化性樹脂進一步與酸單酐及酸二酐反應而所得的環氧(甲基)丙烯酸酯酸加成物，是使(a)二羧酸或三羧酸或其酸酐、及(b)四羧酸或其酸二酐和由雙酚類所衍生的具有2個縮水甘油醚基的環氧化合物與含有不飽和基的單羧酸的反應物進行反應而所得的鹼可溶性樹脂。此處，(a)/(b)的莫耳比優選為0.01~10。 As a preferable example in the case where the present invention is used in a photolithography method The epoxy (meth) acrylate acid adduct obtained by further reacting the epoxy (meth) acrylate type curable resin with an acid monoanhydride and an acid dianhydride is (a) a dicarboxylic acid or Reactant of a tricarboxylic acid or an anhydride thereof, and (b) a tetracarboxylic acid or an acid dianhydride thereof and an epoxy compound derived from bisphenols having two glycidyl ether groups and an unsaturated monocarboxylic acid The alkali-soluble resin obtained by the reaction. Here, the molar ratio of (a) / (b) is preferably 0.01 to 10.

成為該環氧(甲基)丙烯酸酯酸加成物的原料的雙酚類的 例子可列舉雙(4-羥基苯基)酮、雙(4-羥基-3,5-二甲基苯基)酮、雙(4-羥基-3,5-二氯苯基)酮、雙(4-羥基苯基)碸、雙(4-羥基-3,5-二甲基苯基)碸、雙(4-羥基-3,5-二氯苯基)碸、雙(4-羥基苯基)六氟丙烷、雙(4-羥基-3,5-二甲基苯基)六氟丙烷、雙(4-羥基-3,5-二氯苯基)六氟丙烷、雙(4-羥基苯基)二甲基矽烷、雙(4-羥基-3,5-二甲基苯基)二甲基矽烷、雙(4-羥基-3,5-二氯苯基)二甲基矽烷、雙(4-羥基苯基) 甲烷、雙(4-羥基-3,5-二氯苯基)甲烷、雙(4-羥基-3,5-二溴苯基)甲烷、2,2-雙(4-羥基苯基)丙烷、2,2-雙(4-羥基-3,5-二甲基苯基)丙烷、2,2-雙(4-羥基-3,5-二氯苯基)丙烷、2,2-雙(4-羥基-3-甲基苯基)丙烷、2,2-雙(4-羥基-3-氯苯基)丙烷、雙(4-羥基苯基)醚、雙(4-羥基-3,5-二甲基苯基)醚、雙(4-羥基-3,5-二氯苯基)醚、9,9-雙(4-羥基苯基)芴、9,9-雙(4-羥基-3-甲基苯基)芴、9,9-雙(4-羥基-3-氯苯基)芴、9,9-雙(4-羥基-3-溴苯基)芴、9,9-雙(4-羥基-3-氟苯基)芴、9,9-雙(4-羥基-3,5-二甲基苯基)芴、9,9-雙(4-羥基-3,5-二氯苯基)芴、9,9-雙(4-羥基-3,5-二溴苯基)芴、4,4'-聯苯酚、3,3'-聯苯酚等及這些的衍生物。這些中特別適宜地利用具有芴-9,9-二基的化合物。 Bisphenols which are raw materials of the epoxy (meth) acrylate acid adduct Examples include bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, bis (4-hydroxy-3,5-dichlorophenyl) ketone, and bis ( 4-hydroxyphenyl) fluorene, bis (4-hydroxy-3,5-dimethylphenyl) fluorene, bis (4-hydroxy-3,5-dichlorophenyl) fluorene, bis (4-hydroxyphenyl ) Hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, bis (4-hydroxybenzene Dimethyl) silane, bis (4-hydroxy-3,5-dimethylphenyl) dimethyl silane, bis (4-hydroxy-3,5-dichlorophenyl) dimethyl silane, bis ( 4-hydroxyphenyl) Methane, bis (4-hydroxy-3,5-dichlorophenyl) methane, bis (4-hydroxy-3,5-dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4 -Hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3,5- Dimethylphenyl) ether, bis (4-hydroxy-3,5-dichlorophenyl) ether, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3 -Methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis ( 4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dichloro Phenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene, 4,4'-biphenol, 3,3'-biphenol, and derivatives thereof. Among these, a compound having a fluorene-9,9-diyl group is particularly suitably used.

其次，使所述雙酚類與表氯醇反應而獲得具有2個縮水 甘油醚基的環氧化合物。在該反應時，一般伴隨有二縮水甘油醚化合物的寡聚物化，因此獲得下述通式(I)的環氧化合物。 Next, the bisphenols are reacted with epichlorohydrin to obtain Glyceryl ether-based epoxy compound. In this reaction, an oligomerization of a diglycidyl ether compound is generally accompanied, and an epoxy compound of the following general formula (I) is obtained.

在通式(I)式中，R1、R2、R3及R4分別獨立地表示氫原子、碳數為1~5的烷基、鹵素原子或苯基，A表示-CO-、-SO2-、-C(CF3)2-、-Si(CH3)2-、-CH2-、-C(CH3)2-、-O-、芴-9,9-二基或直 接鍵結。l是0~10的數。優選的R1、R2、R3及R4是氫原子，優選的A是芴-9,9-二基。而且，l通常多個值混合存在，因此成為平均值0~10(並不限於整數)，優選的l的平均值是0~3。若l的值超過上限值，在製成使用鹼可溶性樹脂(所述鹼可溶性樹脂使用該環氧化合物而合成)的黑色樹脂組成物時，該組成物的黏度過於變大而變得不能很好地進行塗布，無法充分地賦予鹼可溶性，鹼性顯影性變得非常差。 In the general formula (I), R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and A represents -CO-,- SO 2- , -C (CF 3 ) 2- , -Si (CH 3 ) 2- , -CH 2- , -C (CH 3 ) 2- , -O-, 芴 -9,9-diyl or directly Bonding. l is a number from 0 to 10. Preferred R 1 , R 2 , R 3 and R 4 are hydrogen atoms, and preferred A is fluorene-9,9-diyl. In addition, since multiple values of l are usually mixed, the average value is 0 to 10 (not limited to an integer), and the average value of l is preferably 0 to 3. If the value of l exceeds the upper limit value, when a black resin composition using an alkali-soluble resin (the alkali-soluble resin is synthesized by using the epoxy compound) is prepared, the viscosity of the composition becomes too large to be very high. When the coating is performed well, alkali solubility cannot be sufficiently provided, and alkali developability becomes very poor.

其次，使通式(I)的化合物與作為含有不飽和基的單 羧酸的丙烯酸或甲基丙烯酸或這些兩種化合物反應而所得的具有羥基的反應物，與(a)二羧酸或三羧酸或其酸酐、及(b)四羧酸或其酸二酐在優選(a)/(b)的莫耳比成為0.01~10的範圍中進行反應，獲得具有下述通式(II)所表示的環氧(甲基)丙烯酸酯酸加成物結構的含有聚合性不飽和基的鹼可溶性樹脂。 Next, a compound of the general formula (I) Acrylic acid or methacrylic acid of carboxylic acid or a reactant having a hydroxyl group obtained by reacting these two compounds with (a) a dicarboxylic acid or a tricarboxylic acid or an anhydride thereof, and (b) a tetracarboxylic acid or an acid dianhydride thereof The reaction is preferably performed in a range of 0.01 to 10 in a molar ratio of (a) / (b) to obtain a content having an epoxy (meth) acrylate acid adduct structure represented by the following general formula (II). Alkali soluble resin with polymerizable unsaturated group.

(式中，R1、R2、R3、R4及A為與通式(I)相同的定義，R5表示氫原子或甲基，X表示4價的羧酸殘基，Y1及Y2分別獨立地 表示氫原子或-OC-Z-(COOH)m(其中，Z表示2價或3價的羧酸殘基，m表示1~2的數)，n表示1~20的數) (Wherein R 1 , R 2 , R 3 , R 4 and A have the same definitions as those of the general formula (I), R 5 represents a hydrogen atom or a methyl group, X represents a tetravalent carboxylic acid residue, and Y 1 and Y 2 independently represents a hydrogen atom or -OC-Z- (COOH) m (where Z represents a divalent or trivalent carboxylic acid residue, and m represents a number of 1 to 2), and n represents a number of 1 to 20 )

該環氧(甲基)丙烯酸酯酸加成物(II)是同時具有乙烯性不飽和雙鍵與羧基的含有聚合性不飽和基的鹼可溶性樹脂，因此作為在鹼性顯影型的光微影法中使用本發明的黑色樹脂組成物的情況下的(A-1)而賦予優異的光硬化性、良好的顯影性、圖案化特性，獲得良好的圖案形狀。 The epoxy (meth) acrylate acid adduct (II) is an alkali-soluble resin containing a polymerizable unsaturated group having both an ethylenically unsaturated double bond and a carboxyl group. Therefore, the epoxy (meth) acrylate acid adduct (II) is used as a photolithography in an alkaline development type. (A-1) in the case where the black resin composition of the present invention is used in the method imparts excellent photocurability, good developability, and patterning characteristics, and obtains a good pattern shape.

通式(II)的環氧(甲基)丙烯酸酯酸加成物中所利用的(a)二羧酸或三羧酸或其酸酐使用鏈式烴二羧酸或三羧酸或其酸酐或者脂環式二羧酸或三羧酸或其酸酐、芳香族二羧酸或三羧酸或其酸酐。此處，鏈式烴二羧酸或三羧酸或其酸酐例如存在有琥珀酸、乙醯基琥珀酸、馬來酸、己二酸、衣康酸、壬二酸、順式蘋果酸、丙二酸、戊二酸、檸檬酸、酒石酸、氧代戊二酸、庚二酸、癸二酸、辛二酸、二甘醇酸等化合物，還可以是進一步導入有任意取代基的二羧酸或三羧酸或其酸酐。而且，脂環式二羧酸或三羧酸或其酸酐例如存在有環丁烷二羧酸、環戊烷二羧酸、六氫鄰苯二甲酸、四氫鄰苯二甲酸、降冰片烷二羧酸等化合物，還可以是進一步導入有任意取代基的二羧酸或三羧酸或其酸酐。進一步而言，芳香族二羧酸或三羧酸或其酸酐例如存在有鄰苯二甲酸、間苯二甲酸、偏苯三甲酸等化合物，還可以是進一步導入有任意取代基的二羧酸或三羧酸或其酸酐。 The (a) dicarboxylic acid or tricarboxylic acid or anhydride used in the epoxy (meth) acrylate acid adduct of the general formula (II) uses a chain hydrocarbon dicarboxylic acid or tricarboxylic acid or anhydride thereof, or An alicyclic dicarboxylic acid or tricarboxylic acid or anhydride thereof, an aromatic dicarboxylic acid or tricarboxylic acid or anhydride thereof. Here, the chain hydrocarbon dicarboxylic acid or tricarboxylic acid or an anhydride thereof includes, for example, succinic acid, acetosuccinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, cis-malic acid, and propylene. Compounds such as diacid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, diethylene glycol acid, etc., or dicarboxylic acids with further introduced optional substituents Or tricarboxylic acid or its anhydride. Further, alicyclic dicarboxylic acid or tricarboxylic acid or anhydride thereof includes, for example, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid. A compound such as a carboxylic acid may be a dicarboxylic acid, a tricarboxylic acid, or an anhydride thereof to which an arbitrary substituent is further introduced. Furthermore, the aromatic dicarboxylic acid or tricarboxylic acid or its anhydride includes compounds such as phthalic acid, isophthalic acid, trimellitic acid, and the like, and it may be a dicarboxylic acid or a dicarboxylic acid further introduced with an optional substituent. Tricarboxylic acid or its anhydride.

而且，通式(II)的環氧(甲基)丙烯酸酯酸加成物中所 利用的(b)四羧酸或其酸二酐可使用鏈式烴四羧酸或其酸二酐或脂環式四羧酸或其酸二酐、或者芳香族多元羧酸或其酸二酐。此處，鏈式烴四羧酸或其酸二酐例如存在有丁烷四羧酸、戊烷四羧酸、己烷四羧酸等，還可以是進一步導入有取代基的四羧酸或其酸二酐。而且，脂環式四羧酸或其酸二酐例如存在有環丁烷四羧酸、環戊烷四甲酸、環己烷四羧酸、環庚烷四羧酸、降冰片烷四羧酸等，還可以是進一步導入有取代基的四羧酸或其酸二酐。另外，芳香族四羧酸或其酸二酐例如可列舉均苯四甲酸、二苯甲酮四羧酸、聯苯四羧酸、二苯醚四羧酸或其酸二酐，還可以是進一步導入有取代基的四羧酸或其酸二酐。 Moreover, the epoxy (meth) acrylate acid adduct of general formula (II) As the (b) tetracarboxylic acid or acid dianhydride to be used, a chain hydrocarbon tetracarboxylic acid or an acid dianhydride or an alicyclic tetracarboxylic acid or an acid dianhydride thereof, or an aromatic polycarboxylic acid or an acid dianhydride thereof can be used. . Here, the chain hydrocarbon tetracarboxylic acid or an acid dianhydride thereof may include, for example, butane tetracarboxylic acid, pentane tetracarboxylic acid, hexane tetracarboxylic acid, or the like, and may be a tetracarboxylic acid or a tetracarboxylic acid further introduced with a substituent. Acid dianhydride. Moreover, alicyclic tetracarboxylic acid or its acid dianhydride exists, for example, cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, norbornane tetracarboxylic acid, etc. It may also be a tetracarboxylic acid or an acid dianhydride in which a substituent is further introduced. Examples of the aromatic tetracarboxylic acid or an acid dianhydride thereof include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic acid, or an acid dianhydride thereof. A substituted tetracarboxylic acid or an acid dianhydride thereof is introduced.

通式(II)的環氧(甲基)丙烯酸酯酸加成物中所使用的 (a)二羧酸或三羧酸或其酸酐與(b)四羧酸或其酸二酐的莫耳比(a)/(b)優選為0.01~10，更優選成為0.1~3.0的範圍。如果莫耳比(a)/(b)偏離所述範圍則不能獲得最適宜的分子量，在作為(A-1)而使用的黑色樹脂組成物中，鹼性顯影性、耐熱性、耐溶劑性、圖案形狀等劣化，因此並不優選。另外，莫耳比(a)/(b)越小則分子量越大，存在鹼溶解性惡化的傾向。 Used in epoxy (meth) acrylate acid adducts of general formula (II) (a) The molar ratio (a) / (b) of the dicarboxylic acid or tricarboxylic acid or its anhydride to (b) the tetracarboxylic acid or its acid dianhydride is preferably from 0.01 to 10, and more preferably from 0.1 to 3.0. . If the molar ratio (a) / (b) deviates from the above range, the optimum molecular weight cannot be obtained. In the black resin composition used as (A-1), the alkali developability, heat resistance, and solvent resistance , Pattern shape, etc. are not preferable. In addition, the smaller the molar ratio (a) / (b), the larger the molecular weight, and the alkali solubility tends to deteriorate.

而且，通式(II)的環氧(甲基)丙烯酸酯酸加成物的重 量平均分子量(Mw)優選為2000~10000之間，特別優選為3000~7000之間。如果重量平均分子量(Mw)不滿2000，那麼作為(A-1)而使用的黑色樹脂組成物在顯影時無法維持圖案的密接性，產生圖案剝落，而且如果重量平均分子量(Mw)超過10000， 則變得容易殘留顯影殘渣或未曝光部的殘膜。另外，理想的是其酸值處於30mgKOH/g~200mgKOH/g的範圍。如果該值小於30mgKOH/g，則有作為(A-1)而使用的黑色樹脂組成物的鹼性顯影惡化的傾向，因此需要強鹼等特殊的顯影條件。另一方面，如果超過200mgKOH/g，則鹼性顯影液在作為(A-1)而使用的黑色樹脂組成物中的滲透變得過快，產生剝離顯影，因此均不優選。 Moreover, the weight of the epoxy (meth) acrylate acid adduct of general formula (II) The weight average molecular weight (Mw) is preferably between 2,000 and 10,000, and particularly preferably between 3,000 and 7,000. If the weight average molecular weight (Mw) is less than 2000, the black resin composition used as (A-1) cannot maintain the adhesion of the pattern during development, and the pattern peels off, and if the weight average molecular weight (Mw) exceeds 10,000, Then, it becomes easy to leave development residue or a residual film of an unexposed part. The acid value is preferably in a range of 30 mgKOH / g to 200 mgKOH / g. If the value is less than 30 mgKOH / g, the alkaline development of the black resin composition used as (A-1) tends to deteriorate, and special development conditions such as strong alkali are required. On the other hand, if it exceeds 200 mgKOH / g, the penetration of the alkaline developer into the black resin composition used as (A-1) becomes too fast and peeling development occurs, which is not preferred.

本發明中所利用的通式(II)的環氧(甲基)丙烯酸酯酸 加成物可藉由所述步驟，利用已知的方法(例如日本專利特開平8-278629號公報或日本專利特開2008-9401號公報等中所記載的方法)而製造。首先，使含有不飽和基的單羧酸與通式(I)的環氧化合物反應的方法例如存在有：將與環氧化合物的環氧基等莫耳的含有不飽和基的單羧酸添加於溶劑中，在催化劑(三乙基苄基氯化銨、2,6-二異丁基苯酚等)的存在下，一面吹入空氣一面在90℃~120℃下進行加熱、攪拌而使其反應的方法。其次，作為使酸酐與反應產物環氧丙烯酸酯化合物的羥基反應的方法存在有：將環氧丙烯酸酯化合物與酸二酐及酸單酐的規定量添加於溶劑中，在催化劑(四乙基溴化銨、三苯基膦等)的存在下，在90℃~130℃下進行加熱、攪拌而使其反應的方法。 Epoxy (meth) acrylate acid of general formula (II) used in the present invention The adduct can be produced by the above-mentioned steps by a known method (for example, a method described in Japanese Patent Laid-Open No. 8-278629 or Japanese Patent Laid-Open No. 2008-9401). First, a method for reacting an unsaturated group-containing monocarboxylic acid with an epoxy compound of the general formula (I) includes, for example, adding a mole-containing unsaturated group-containing monocarboxylic acid such as an epoxy group of an epoxy compound. In the presence of a catalyst (triethylbenzyl ammonium chloride, 2,6-diisobutylphenol, etc.) in a solvent, it is heated and stirred at 90 ° C to 120 ° C while blowing air. Method of reaction. Next, as a method for reacting an acid anhydride with a hydroxyl group of an epoxy acrylate compound as a reaction product, a predetermined amount of an epoxy acrylate compound, an acid dianhydride and an acid monoanhydride is added to a solvent, and a catalyst (tetraethyl bromide) is added. In the presence of ammonium chloride, triphenylphosphine, etc.), the method is performed by heating and stirring at 90 ° C to 130 ° C.

而且，(A-2)具有乙烯性不飽和雙鍵的聚合性單體(光或熱聚合性單體)例如可列舉：(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸-2-羥基丙酯、(甲基)丙烯酸-2-羥基己酯等具有羥基的(甲基)丙烯酸酯類，或乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯 酸酯、三乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、三羥甲基乙烷三(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇四(甲基)丙烯酸酯、甘油(甲基)丙烯酸酯、山梨糖醇五(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、或二季戊四醇六(甲基)丙烯酸酯、山梨糖醇六(甲基)丙烯酸酯、膦腈的環氧烷改性六(甲基)丙烯酸酯、己內酯改性二季戊四醇六(甲基)丙烯酸酯等(甲基)丙烯酸酯類，(A-2)成分可使用這些的1種或2種以上。而且，該具有乙烯性不飽和雙鍵的聚合性單體優選使用具有3個以上聚合性基而可使光或熱硬化性樹脂(在光微影法中使用的情況下為含有聚合性不飽和基的鹼可溶性樹脂)的分子彼此交聯的單體。另外，在將(A-2)具有乙烯性不飽和雙鍵的聚合性單體製成在光微影法中使用的黑色樹脂組成物的情況下，使用並不具有游離的羧基的化合物。 Examples of the polymerizable monomer (light or thermal polymerizable monomer) having (A-2) an ethylenically unsaturated double bond include (meth) acrylic acid 2-hydroxyethyl ester and (meth) acrylic acid- (Meth) acrylates having a hydroxyl group, such as 2-hydroxypropyl ester, 2-hydroxyhexyl (meth) acrylate, or ethylene glycol di (meth) acrylate, diethylene glycol di (methyl) Acrylic Acid ester, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate , Trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate Ester, glycerol (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, or dipentaerythritol hexa (meth) acrylate, sorbitol hexa (methyl) (Meth) acrylates such as acrylates, alkylene oxide-modified hexa (meth) acrylates of phosphazene, and caprolactone-modified dipentaerythritol hexa (meth) acrylates, (A-2) components can be used One or more of these. In addition, as the polymerizable monomer having an ethylenically unsaturated double bond, it is preferable to use a resin having three or more polymerizable groups to make it light or thermosetting (in the case of using a photolithography method, it contains a polymerizable unsaturated group). Monomers of which the molecules of the alkali-soluble resin) are crosslinked to each other. When the polymerizable monomer having an ethylenically unsaturated double bond (A-2) is used as a black resin composition used in a photolithography method, a compound having no free carboxyl group is used.

而且，(A)成分可列舉(A-3)在分子內具有至少1個 以上環氧基、氧雜環丁烷基等環狀反應性基的化合物。其具體例可列舉：雙酚A型環氧化合物、雙酚F型環氧化合物、雙酚芴型環氧化合物、苯酚酚醛清漆型環氧化合物、甲酚酚醛清漆型環氧化合物、多元醇的縮水甘油醚、多元羧酸的縮水甘油酯、包含(甲基)丙烯酸縮水甘油酯作為單元的聚合物、以3,4-環氧環己烷羧酸-(3',4'-環氧基環己基)甲酯為代表的脂環式環氧化合物、具有二環 戊二烯骨架的多官能環氧化合物(例如迪愛生(DIC)公司製造的HP7200系列)、2,2-雙(羥基甲基)-1-丁醇的1,2-環氧-4-(2-氧雜環丙基)環己烷加成物(例如大賽璐(DAICEL)公司製造的“EHPE3150”)、環氧化聚丁二烯(例如日本曹達公司製造的“尼索(NISSO)-PB．JP-100”)、具有矽酮骨架的環氧化合物等。 In addition, the (A) component can be exemplified by (A-3) having at least one in the molecule Compounds of the above cyclic reactive groups such as epoxy groups and oxetanyl groups. Specific examples thereof include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol fluorene type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, and polyhydric alcohols. Glycidyl ether, glycidyl ester of polycarboxylic acid, polymer containing glycidyl (meth) acrylate as unit, 3,4-epoxycyclohexanecarboxylic acid- (3 ', 4'-epoxy group Cyclohexyl) methyl esters are representative of alicyclic epoxy compounds Polyfunctional epoxy compounds with a pentadiene skeleton (e.g. HP7200 series manufactured by DIC), 1,2-epoxy-4- (2,2-bis (hydroxymethyl) -1-butanol) 2-oxetracyclyl) cyclohexane adduct (such as "EHPE3150" manufactured by DAICEL), epoxidized polybutadiene (such as "NISSO-PB" manufactured by Soda Japan) .JP-100 "), epoxy compounds with silicone skeleton, etc.

(A)成分可使用如(A-1)及(A-2)這樣的具有乙烯 性不飽和雙鍵的化合物、(A-3)具有環狀反應性基的化合物的僅僅一種，也可以將兩種化合物混合使用。 (A) As the component, it is possible to use a polymer having ethylene such as (A-1) and (A-2). Only one kind of the compound having an unsaturated double bond and the compound having a cyclic reactive group (A-3) may be used in combination.

另外，在使用具有乙烯性不飽和雙鍵的化合物作為(A) 成分的情況下，優選使由於紫外線或熱而產生自由基、陽離子、陰離子等的光聚合引發劑、熱聚合引發劑等共存而使用。而且，在使用(A-3)具有環狀反應基的化合物的情況下，優選使由於光或熱而與環狀反應基反應的化合物(例如具有羧基、胺基、羥基、硫醇基的化合物等)作為硬化劑共存而使用。 In addition, a compound having an ethylenically unsaturated double bond is used as (A) In the case of a component, it is preferable to use a photopolymerization initiator, a thermal polymerization initiator, etc. which generate | occur | produce radicals, a cation, an anion, etc. by ultraviolet or heat. When a compound having a cyclic reactive group (A-3) is used, a compound (for example, a compound having a carboxyl group, an amino group, a hydroxyl group, or a thiol group) that reacts with the cyclic reactive group by light or heat is preferably used. Etc.) Used together as a hardener.

優選選定所例示的(A)成分的硬化物的折射率處於1.48~1.6的範圍的化合物。例如在丙烯酸樹脂系硬化物的情況下，折射率為1.49~1.55，通過與在化學結構中具有芳香族基的苯乙烯單體等的共聚而調整。如果是環氧樹脂系，則折射率為1.50~1.60，如果使用雙酚系環氧樹脂或芳香族酸酐硬化劑，則折射率變高；如果使用脂肪族環氧樹脂、脂環式環氧樹脂或脂環式酸酐硬化劑，則折射率變得比較低。 It is preferable to select a compound whose refractive index of the exemplified cured component (A) is in the range of 1.48 to 1.6. For example, in the case of an acrylic resin-based cured product, the refractive index is 1.49 to 1.55, and it is adjusted by copolymerization with a styrene monomer or the like having an aromatic group in its chemical structure. In the case of epoxy resins, the refractive index is 1.50 to 1.60. In the case of bisphenol-based epoxy resins or aromatic acid anhydride hardeners, the refractive index becomes higher. In the case of aliphatic epoxy resins and alicyclic epoxy resins, Or an alicyclic acid anhydride hardener, the refractive index becomes relatively low.

另外，關於(A)成分的含量，只要在除溶劑成分外的 黑色樹脂組成物的固體成分(包含硬化後成為固體成分的硬化性單體成分)中為25質量%~60質量%的範圍即可，優選為35質量%~55質量%的範圍。 In addition, regarding the content of the (A) component, The solid content of the black resin composition (including the curable monomer component which becomes a solid content after curing) may be in the range of 25% by mass to 60% by mass, and is preferably in the range of 35% by mass to 55% by mass.

作為(B)成分中所含的黑色遮光性粒子，可並無特別 限制地使用黑色有機顏料或無機系顏料等。黑色有機顏料例如可列舉苝黑、花青黑、苯胺黑、內醯胺黑等。無機系顏料可列舉碳黑、氧化鉻、氧化鐵、鈦黑、氮氧化鈦、氮化鈦等。這些黑色遮光性粒子可單獨使用1種，也可以適宜選擇2種以上而使用。自目標薄膜的遮光率及遮光膜用組成物的保存穩定性的觀點考慮，主要使用其折射率超過1.6且吸收可見光的黑色顏料。本發明中所使用的黑色遮光性粒子優選為碳黑。碳黑可使用燈黑、乙炔黑、熱碳黑、槽法碳黑、爐法碳黑等任意者。另外，為了調整遮光性，可以使用黑色染料等其它遮光成分的1種或者將多種混合而使用，優選黑色遮光性粒子為遮光成分中的60%以上。例如如果較多地使用准黑色有機顏料系或染料系的遮光成分，則遮光率降低，變得難以獲得所期望的遮光率(OD)。 The black light-shielding particles contained in the component (B) are not particularly limited. The use of black organic pigments or inorganic pigments is restricted. Examples of the black organic pigment include perylene black, cyanine black, aniline black, and lactam black. Examples of the inorganic pigment include carbon black, chromium oxide, iron oxide, titanium black, titanium oxynitride, and titanium nitride. These black light-shielding particles may be used individually by 1 type, and may select and use 2 or more types suitably. From the viewpoint of the light-shielding rate of the target film and the storage stability of the composition for the light-shielding film, a black pigment whose refractive index exceeds 1.6 and which absorbs visible light is mainly used. The black light-shielding particles used in the present invention are preferably carbon black. As the carbon black, any of lamp black, acetylene black, thermal carbon black, channel black, and furnace black can be used. In addition, in order to adjust the light-shielding property, one kind of other light-shielding components such as a black dye may be used or a plurality of types may be mixed and used, and the black light-shielding particles are preferably 60% or more of the light-shielding components. For example, if a quasi-black organic pigment-based or dye-based light-shielding component is used in a large amount, the light-shielding ratio decreases, and it becomes difficult to obtain a desired light-shielding ratio (OD).

將這些黑色遮光性粒子或其它遮光成分與包含高分子 分散劑等分散劑及溶劑的分散介質一同在珠磨機中進行分散，製成含有黑色遮光性粒子的分散液(含有黑色遮光性粒子的分散液)，將其與(A)成分及後述的(C)成分加以混合，由此可製備本發明的遮光膜用黑色樹脂組成物。將該分散液中所分散的黑色遮光性粒子的平均二次粒徑DB製備為60nm~150nm、優選製備 為80nm~120nm。另外，在本發明中，所謂“平均二次粒徑”是指用分散溶劑或相當的溶劑加以稀釋，用動態光散射法進行測定，利用累積法而求出的平均粒徑的值。另外，黑色遮光性粒子如果是例如碳黑那樣微小的一次粒子連接為一串葡萄狀的形態，該形態中的粒徑(平均二次粒徑)表現出物性，因此重要；而且即便並不連接為一串葡萄狀，越是微小粒徑(平均一次粒徑)的粒子，越容易在分散液中凝聚，該凝聚狀態下的粒徑(平均二次粒徑)變重要。因此，在本發明中，將分散液中的粒徑設為平均二次粒徑。 These black light-shielding particles or other light-shielding components are dispersed in a bead mill together with a dispersion medium containing a dispersant such as a polymer dispersant and a solvent to prepare a dispersion liquid containing black light-shielding particles (a black light-shielding particle-containing dispersion). Dispersion liquid), and the black resin composition for a light-shielding film of the present invention can be prepared by mixing the component (A) and the component (C) described later. The dispersion of the dispersed particles of the black light-shielding average secondary particle diameter D B prepared as 60nm ~ 150nm, preferably prepared 80nm ~ 120nm. In addition, in the present invention, the "average secondary particle diameter" means a value obtained by diluting with a dispersing solvent or an equivalent solvent, measuring by a dynamic light scattering method, and obtaining the cumulative particle diameter by a cumulative method. In addition, if the black light-shielding particles are in the form of grape-like clusters where tiny primary particles such as carbon black are connected, the particle size (average secondary particle size) in this form exhibits physical properties and is therefore important; even if they are not connected It is a bunch of grapes, and the particles with a minute particle diameter (average primary particle diameter) are more likely to aggregate in the dispersion, and the particle diameter (average secondary particle diameter) in this aggregated state becomes important. Therefore, in the present invention, the particle diameter in the dispersion is the average secondary particle diameter.

例如如果是碳黑則是在丙二醇單甲醚乙酸酯溶劑中為 0.1質量%粒子濃度下所測定的值。如果平均二次粒徑DB不足60nm，則為了達成高遮光率而需要添加提高黑色遮光性粒子的濃度而所需的高分子分散劑，而且在保存時容易產生黏度增加。如果平均二次粒徑DB超過150nm，則所形成的遮光膜的表面平滑性並不優選，而且損及在用光微影而形成時的圖案邊緣的直線性。 For example, in the case of carbon black, it is a value measured at a particle concentration of 0.1% by mass in a propylene glycol monomethyl ether acetate solvent. If the average secondary particle diameter D B is less than 60 nm, in order to achieve a high light-shielding ratio, it is necessary to add a polymer dispersant required to increase the concentration of the black light-shielding particles, and the viscosity tends to increase during storage. If the average secondary particle diameter D B exceeds 150 nm, the surface smoothness of the formed light-shielding film is not preferable, and the linearity of the pattern edge when formed by photolithography is impaired.

亦即，觸控面板用遮光膜及彩色濾光片用黑色矩陣中的 遮光度(OD=-log[透射度])要求OD4以上，另一方面要求膜厚為3μm以下、優選為2μm以下的薄膜化。其理由是：在觸控面板中，用以在將觸控面板遮光膜上的金屬配線與觸控面板上的導電膜連接時防止斷線，在黑色矩陣中，用以彩色濾光片的平坦化。 為了即使在此種薄的遮光膜中也獲得高的遮光度，例如優選相對於組成物中的所有固體成分而言，將碳黑系黑色遮光性粒子設為 35質量%以上、70質量%以下。 That is, the light shielding film for a touch panel and the black matrix for a color filter are The light-shielding degree (OD = -log [transmittance]) is required to be OD4 or more, and on the other hand, a film thickness of 3 μm or less, and preferably 2 μm or less is required. The reason is that in the touch panel, it is used to prevent disconnection when the metal wiring on the touch panel light-shielding film is connected to the conductive film on the touch panel. In the black matrix, it is used to flatten the color filter. Into. In order to obtain a high light-shielding degree even in such a thin light-shielding film, for example, it is preferable to set carbon black-based black light-shielding particles to all solid components in the composition. 35 mass% or more and 70 mass% or less.

(C)成分中所含的顏色調整用粒子中所可使用的黃色顏料及橙色顏料例如可列舉：C.I.顏料黃(PY)20、C.I.顏料黃(PY)24、C.I.顏料黃(PY)31、C.I.顏料黃(PY)53、C.I.顏料黃(PY)83、C.I.顏料黃(PY)86、C.I.顏料黃(PY)93、C.I.顏料黃(PY)94、C.I.顏料黃(PY)109、C.I.顏料黃(PY)110、C.I.顏料黃(PY)117、C.I.顏料黃(PY)125、C.I.顏料黃(PY)137、C.I.顏料黃(PY)138、C.I.顏料黃(PY)139、C.I.顏料黃(PY)147、C.I.顏料黃(PY)148、C.I.顏料黃(PY)150、C.I.顏料黃(PY)153、C.I.顏料黃(PY)154、C.I.顏料黃(PY)166及C.I.顏料黃(PY)173等；C.I.顏料橙(PO)36、C.I.顏料橙(PO)43、C.I.顏料橙(PO)51、C.I.顏料橙(PO)55、C.I.顏料橙(PO)59、C.I.顏料橙(PO)61、C.I.顏料橙(PO)71、C.I.顏料橙(PO)73等；其中，C.I.顏料黃可將OD值保持為4.0以上，且可效率良好地使b*值變負因而優選。而且，可特別優選地用作顏色調整用粒子的具體例子可列舉PY139或PO61。 Examples of yellow pigments and orange pigments that can be used in the color-adjusting particles contained in the component (C) include CI Pigment Yellow (PY) 20, CI Pigment Yellow (PY) 24, CI Pigment Yellow (PY) 31, CI Pigment Yellow (PY) 53, CI Pigment Yellow (PY) 83, CI Pigment Yellow (PY) 86, CI Pigment Yellow (PY) 93, CI Pigment Yellow (PY) 94, CI Pigment Yellow (PY) 109, CI Pigment Yellow (PY) 110, CI Pigment Yellow (PY) 117, CI Pigment Yellow (PY) 125, CI Pigment Yellow (PY) 137, CI Pigment Yellow (PY) 138, CI Pigment Yellow (PY) 139, CI Pigment Yellow ( PY) 147, CI Pigment Yellow (PY) 148, CI Pigment Yellow (PY) 150, CI Pigment Yellow (PY) 153, CI Pigment Yellow (PY) 154, CI Pigment Yellow (PY) 166, and CI Pigment Yellow (PY) 173, etc .; CI Pigment Orange (PO) 36, CI Pigment Orange (PO) 43, CI Pigment Orange (PO) 51, CI Pigment Orange (PO) 55, CI Pigment Orange (PO) 59, CI Pigment Orange (PO) 61 , CI Pigment Orange (PO) 71, CI Pigment Orange (PO) 73, etc. Among them, CI Pigment Yellow is preferable because it can maintain an OD value of 4.0 or more and can efficiently decrease the b * value. Moreover, as a specific example which can be used especially suitably as a particle for color adjustment, PY139 or PO61 is mentioned.

例如在將碳黑用作黑色遮光性粒子的情況下，碳黑通常具有茶色系的反射色，因此優選同系色顏料的PY139、PY150。如果是該同系色則在黑色遮光性粒子為自無彩色偏離的色相．色度的情況下，顯示與偏離的色相．色度的同系色。例如，如果黑色遮光性粒子是向茶色系偏離的色相．色度，則在色相環上處於相同位置 的橙、黃色系的色相．色度為同系色。亦即，如果是遮光材的相反色，則在黑色遮光性粒子為自無彩色偏離的色相．色度的情況下，顯示與偏離的色相．色度的相反色。例如，如果遮光材是向茶色系偏離的色相．色度，則在色相環上位於對角線附近的藍、紫色系的色相．色度為相反色。亦即，黑色遮光性粒子之一的碳黑是自無彩色向茶色系偏離的色相，相對於此，以往考慮調配與該偏離的色相為補色(相反色)的顏料/染料的“藍色顏料/染料”或“紫色顏料/染料”。 For example, when carbon black is used as black light-shielding particles, carbon black usually has a brown reflection color, so PY139 and PY150, which are homogeneous color pigments, are preferred. If it is this homogeneous color, the black light-shielding particles are the hue that deviates from the achromatic color. In the case of chromaticity, the hue with deviation is displayed. Chromatic homolog. For example, if the black light-shielding particles have a hue deviating from the brown color system. Chroma, the same position on the hue ring Orange, yellow hue. Chroma is homologous. That is, if it is the opposite color of the light-shielding material, the black light-shielding particles have a hue that deviates from achromatic color. In the case of chromaticity, the hue with deviation is displayed. The opposite color of chroma. For example, if the shading material is a hue deviating from the brown color system. Chroma is the blue and purple hue near the diagonal on the hue ring. Chroma is the opposite color. In other words, carbon black, which is one of the black light-shielding particles, has a hue that deviates from achromatic to brown. In contrast, a “blue pigment” that has been considered to be a pigment / dye that complements (opposite) to the deviated hue. / Dye "or" purple pigment / dye ".

將這些顏色調整用粒子與包含高分子分散劑等分散劑 及溶劑的分散介質一同在珠磨機中進行分散，製成含有顏色調整用粒子的分散液(含有顏色調整用粒子的分散液)，將其與(A)成分及(B)成分加以混合，由此可製備本發明的遮光膜用黑色樹脂組成物。另外，關於該(C)成分中所分散的顏色調整用粒子的平均二次粒徑DC，使其與所述(B)成分中的黑色遮光性粒子的平均二次粒徑DB的比DC/DB成為0.2~1.2的範圍。該平均二次粒徑DC是用分散溶劑或相當的溶劑加以稀釋，用動態光散射法進行測定，利用累積法而求出的平均粒徑的值。 Dispersing these color-adjusting particles in a bead mill together with a dispersion medium containing a dispersant such as a polymer dispersant and a solvent to prepare a dispersion liquid containing the color-adjusting particles (a dispersion containing the color-adjusting particles), By mixing this with (A) component and (B) component, the black resin composition for light-shielding films of this invention can be prepared. Further, with respect to the component (C) dispersed in the color adjusting average secondary particle diameter D C of the particles, than the average secondary particle diameter D B is reacted with the component (B), the light-shielding black particles D C / D B is in the range of 0.2 to 1.2. The average secondary particle diameter D C is a value obtained by diluting with a dispersing solvent or a comparable solvent, measuring it by a dynamic light scattering method, and obtaining the average particle diameter by a cumulative method.

例如，如果是黃色顏料粒子，則是其分散液為0.1質量%~1.0質量%粒子濃度的測定值。如果平均二次粒徑的比DC/DB超過1.2，則變得實質上未發現使b*值變負的效果。而且，如果平均二次粒徑的比DC/DB低於0.2，則組成物中的分散穩定性降低。遮光膜用途中所使用的含有碳黑的分散液的平均二次粒徑DB為 60nm~150nm，因此難以製備DC為30nm以下的含有黃色顏料的分散液。DC的優選的平均二次粒徑是60nm~150nm，更優選為80nm~120nm。 For example, in the case of yellow pigment particles, the measured value is a particle concentration in which the dispersion is 0.1% to 1.0% by mass. When the ratio D C / D B of the average secondary particle diameter exceeds 1.2, the effect of negatively reducing the b * value becomes substantially not observed. When the ratio D C / D B of the average secondary particle diameter is less than 0.2, the dispersion stability in the composition is reduced. The average secondary particle diameter D B of the carbon black dispersion containing light-shielding film is used in applications 60nm ~ 150nm, D C is therefore difficult to prepare a dispersion containing less 30nm yellow pigment. Preferred average secondary particle diameter D C is 60nm ~ 150nm, more preferably 80nm ~ 120nm.

而且，在本發明中，在所述組成物中，使(C)成分中 所含的顏色調整用粒子(固體成分)的質量mC與(B)成分中所含的黑色遮光性粒子(固體成分)的質量mB的質量比mC/mB成為0.03~0.2的範圍。如果該mC/mB低於0.03，則未能發現b*的減低效果；如果超過0.2，則遮光率(OD/μm)降低。 In the present invention, in the composition, the mass m C of the color adjustment particles (solid content) contained in the component (C) and the black light-shielding particles (solid contained in the component (B)) The mass ratio m C / m B of the mass m B of the component) is in the range of 0.03 to 0.2. If this m C / m B is less than 0.03, the effect of reducing b * cannot be found, and if it exceeds 0.2, the light shielding rate (OD / μm) decreases.

然而，在將本組成物構成為硬化膜的帶遮光膜的基板 中，顏色調整用粒子表現出使b*減低的功能的機制可如下所述地設想。亦即，在帶遮光膜的基板中，自透明基板側入射的光的一部分主要被透明基板界面與其近旁的遮光膜內所分散的粒子反射及散射，自透明基板側射出。微粒子的散射在其粒徑低於光的波長的情況下產生，特別是在瑞利散射(Rayleigh scattering)區域中，相對於光入射至微粒子的方向的背向散射的波長相依性變顯著。由與碳黑粒子的粒徑為同等程度或其以下的黃色顏料或橙色顏料所引起的背向散射將處於其補色關係的藍色區域的光更多地散射至後方。 However, in a substrate with a light-shielding film in which the present composition is configured as a cured film, the mechanism by which the particles for color adjustment exhibit a function of reducing b * can be conceived as follows. That is, in a substrate with a light-shielding film, a part of the light incident from the transparent substrate side is mainly reflected and scattered by particles dispersed in the transparent substrate interface and the light-shielding film adjacent thereto, and is emitted from the transparent substrate side. Scattering of microparticles occurs when the particle diameter is lower than the wavelength of light, and particularly in the Rayleigh scattering region, the wavelength dependence of backscattering with respect to the direction in which light is incident on the microparticles becomes significant. Backscattering caused by a yellow pigment or an orange pigment having a particle size equal to or less than that of the carbon black particles scatters more of the light in the blue region in the complementary color relationship to the rear.

為了有效地發揮以上遮光膜的顏色調整(將b*調整至負 側)的機制，需要使黑色遮光性粒子以及顏色調整用粒子在組成物中及透明基板上所塗布的膜內均不自身凝聚地穩定地分散。因此，用珠磨機將本發明的黑色遮光性粒子及顏色調整用粒子在有 機溶劑中與高分子分散劑一同加以分散，且以分散液的形式進行供給。 In order to effectively make use of the above-mentioned mechanism of adjusting the color of the light-shielding film (adjusting b * to the negative side), it is necessary that the black light-shielding particles and the particles for color adjustment do not self-agglomerate in the composition and the film coated on the transparent substrate. Disperse stably. Therefore, the black light-shielding particles and the particles for color adjustment of the present invention are dispersed together with a polymer dispersant in an organic solvent using a bead mill, and supplied as a dispersion liquid.

在本發明的遮光膜用黑色樹脂組成物中，為了溶解利用 光或熱的硬化性樹脂等、及使黑色遮光性粒子或顏色調整粒子等分散，可含有1種或多種(D)溶劑，並無特別限定。例如可列舉甲醇、乙醇、正丙醇、異丙醇、乙二醇、丙二醇等醇類，α-松油醇或β-松油醇等萜烯類等，丙酮、甲基乙基酮、環己酮、N-甲基-2-吡咯烷酮等酮類，甲苯、二甲苯、四甲基苯等芳香族烴類，溶纖劑、甲基溶纖劑、乙基溶纖劑、卡必醇、甲基卡必醇、乙基卡必醇、丁基卡必醇、丙二醇單甲醚、丙二醇單***、二丙二醇單甲醚、二丙二醇單***、三乙二醇單甲醚、三乙二醇單***、二乙二醇二甲醚、二乙二醇乙基甲基醚、二乙二醇二***等二醇醚類，乙酸乙酯、乙酸丁酯、溶纖劑乙酸酯、乙基溶纖劑乙酸酯、丁基溶纖劑乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯等乙酸酯類，藉由使用數種這些溶劑進行溶解、混合，可製成使黑色遮光性粒子或顏色調整用粒子等穩定地分散的均一的組成物。 The black resin composition for a light-shielding film of the present invention is used for dissolution. Light or heat curable resin, etc., and black light-shielding particles or color-adjusting particles are dispersed, and they may contain one or more (D) solvents, and are not particularly limited. Examples include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol; terpenes such as α-terpineol or β-terpineol; acetone, methyl ethyl ketone, and cyclic Ketones such as hexanone, N-methyl-2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, Methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol Glycol ethers such as monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl Cellulose acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and other acetates can be dissolved and mixed using several of these solvents to make black A uniform composition that is stably dispersed, such as light-shielding particles or particles for color adjustment.

關於此種溶劑的含量，只要相對於黑色樹脂組成物100 質量份而言為5質量份~2000質量份的範圍即可，優選為50質量份~1000質量份，可出於根據在透明基板上塗布的方法而調整為適當的固體成分、溶液黏度等目的而使用。 As for the content of such a solvent, as long as it is 100% with respect to the black resin composition The mass part may be in the range of 5 to 2000 parts by mass, and preferably 50 to 1,000 parts by mass, and may be adjusted to an appropriate solid content, solution viscosity, etc. according to a method of coating on a transparent substrate. While using.

將本發明的黑色樹脂組成物作為光硬化性組成物(黑色 感光性樹脂組成物)而應用於光微影法等中的情況下，需要含有(E)光聚合引發劑。該(E)光聚合引發劑例如可列舉苯乙酮、2,2-二乙氧基苯乙酮、對二甲基苯乙酮、對二甲基胺基苯丙酮、二氯苯乙酮、三氯苯乙酮、對叔丁基苯乙酮等苯乙酮類，二苯甲酮、2-氯二苯甲酮、p,p'-雙二甲基胺基二苯甲酮等二苯甲酮類，苯偶醯、安息香、安息香甲醚、安息香異丙醚、安息香異丁醚等安息香醚類，2-(鄰氯苯基)-4,5-苯基聯咪唑、2-(鄰氯苯基)-4,5-二(間甲氧基苯基)聯咪唑、2-(鄰氟苯基)-4,5-二苯基聯咪唑、2-(鄰甲氧基苯基)-4,5-二苯基聯咪唑、2,4,5-三芳基聯咪唑等聯咪唑系化合物類，2-三氯甲基-5-苯乙烯基-1,3,4-噁二唑、2-三氯甲基-5-(對氰基苯乙烯基)-1,3,4-噁二唑、2-三氯甲基-5-(對甲氧基苯乙烯基)-1,3,4-噁二唑等鹵代甲基噻唑化合物類，2,4,6-三(三氯甲基)-1,3,5-三嗪、2-甲基-4,6-雙(三氯甲基)-1,3,5-三嗪、2-苯基-4,6-雙(三氯甲基)-1,3,5-三嗪、2-(4-氯苯基)-4,6-雙(三氯甲基)-1,3,5-三嗪、2-(4-甲氧基苯基)-4,6-雙(三氯甲基)-1,3,5-三嗪、2-(4-甲氧基萘基)-4,6-雙(三氯甲基)-1,3,5-三嗪、2-(4-甲氧基苯乙烯基)-4,6-雙(三氯甲基)-1,3,5-三嗪、2-(3,4,5-三甲氧基苯乙烯基)-4,6-雙(三氯甲基)-1,3,5-三嗪、2-(4-甲硫基苯乙烯基)-4,6-雙(三氯甲基)-1,3,5-三嗪等鹵代甲基-均三嗪系化合物類，1,2-辛二酮，1-[4-(苯硫基)苯基]-,2-(O-苯甲醯肟)、1-(4-苯硫基苯基)丁烷-1,2-二酮-2-肟-O-苯甲酸酯、1-(4-甲硫基苯基)丁烷-1,2-二酮-2-肟-O-乙酸酯、1-(4-甲硫基苯基)丁烷-1-酮肟-O-乙酸酯等O-醯基肟系化合物類，苯偶醯二 甲基縮酮、噻噸酮、2-氯噻噸酮、2,4-二乙基噻噸酮、2-甲基噻噸酮、2-異丙基噻噸酮等硫化合物，2-乙基蒽醌、八甲基蒽醌、1,2-苯并蒽醌、2,3-二苯基蒽醌等蒽醌類，偶氮雙異丁基腈、過氧化苯甲醯、過氧化枯烯等有機過氧化物，2-巰基苯并咪唑、2-巰基苯并噁唑、2-巰基苯并噻唑等硫醇化合物，三乙醇胺、三乙胺等叔胺等。其中，自容易獲得高感度的黑色感光性樹脂組成物的觀點考慮，優選使用O-醯基肟系化合物類。而且，還可以使用2種以上這些光聚合引發劑。另外，本發明中所謂的光聚合引發劑，以包含增感劑的含義而使用。 The black resin composition of the present invention was used as a photocurable composition (black When the photosensitive resin composition is used in a photolithography method or the like, it is necessary to contain a (E) photopolymerization initiator. Examples of the (E) photopolymerization initiator include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminophenylacetone, dichloroacetophenone, Acetophenones such as trichloroacetophenone, p-tert-butylacetophenone, diphenyls such as benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone Methyl ketones, benzoin, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin ethers, 2- (o-chlorophenyl) -4,5-phenylbiimidazole, 2- (ortho (Chlorophenyl) -4,5-bis (m-methoxyphenyl) biimidazole, 2- (o-fluorophenyl) -4,5-diphenylbiimidazole, 2- (o-methoxyphenyl) -4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole and other biimidazole compounds, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole , 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1, Halomethylthiazole compounds such as 3,4-oxadiazole, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-methyl-4,6-bis ( (Trichloromethyl) -1,3,5-triazine, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-chlorophenyl) -4,6-double (three (Chloromethyl) -1,3,5-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- ( 4-methoxynaphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (tri (Chloromethyl) -1,3,5-triazine, 2- (3,4,5-trimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-tri Halogenated methyl-mesytriazine compounds such as hydrazine, 2- (4-methylthiostyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 1, 2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzidine oxime), 1- (4-phenylthiophenyl) butane-1,2- Dione-2-oxime-O-benzoate, 1- (4-methylthiophenyl) butane-1,2-dione-2-oxime-O-acetate, 1- (4- O-fluorenyl oxime compounds such as methylthiophenyl) butane-1-one oxime-O-acetate, benzoin Sulfur compounds such as methylketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-ethyl Anthraquinones such as trimethyl anthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-diphenylanthraquinone, azobisisobutylnitrile, benzophenazine peroxide, Organic peroxides such as olefins, thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole; tertiary amines such as triethanolamine and triethylamine; and the like. Among these, from the viewpoint of easily obtaining a black photosensitive resin composition having high sensitivity, O-fluorenyl oxime-based compounds are preferably used. Furthermore, two or more of these photopolymerization initiators may be used. The photopolymerization initiator in the present invention is used to include a sensitizer.

而且，在本發明的遮光膜用黑色樹脂組成物中，可以視 需要調配硬化促進劑、熱聚合抑制劑、抗氧化劑、增塑劑、填充材料、流平劑、消泡劑、偶合劑、界面活性劑等添加劑。熱聚合抑制劑可列舉對苯二酚、對苯二酚單甲醚、鄰苯三酚、叔丁基兒茶酚、啡噻嗪等，抗氧化劑可列舉受阻酚系化合物等，增塑劑可列舉鄰苯二甲酸二丁酯、鄰苯二甲酸二辛酯、磷酸三甲苯酯等，填充材料可列舉玻璃纖維、二氧化矽、雲母、氧化鋁等，消泡劑或流平劑可列舉矽酮系、氟系、丙烯酸系化合物。而且，界面活性劑可列舉氟系界面活性劑、矽酮系界面活性劑等。 In the black resin composition for a light-shielding film of the present invention, Additives such as hardening accelerators, thermal polymerization inhibitors, antioxidants, plasticizers, fillers, leveling agents, defoamers, coupling agents, and surfactants need to be formulated. Examples of thermal polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, catechol, tert-butylcatechol, and phenothiazine. Examples of the antioxidant include hindered phenolic compounds. Plasticizers may Examples include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like. Filling materials include glass fiber, silicon dioxide, mica, and alumina. Examples of defoaming or leveling agents include silicon. Ketone, fluorine and acrylic compounds. Examples of the surfactant include a fluorine-based surfactant and a silicone-based surfactant.

而且，在要求自無彩色起帶藍色調的黑色的設計性的 LCD、觸控面板等顯示裝置的遮光膜等中，還存在藉由使該遮光膜的反射率為適當的範圍，增加設計性的要求。為了該目的，在本發明的組成物中可使用二氧化矽等無機粒子作為添加劑。 Furthermore, in the design that requires black with blue tones from achromatic In light-shielding films and the like of display devices such as LCDs and touch panels, there is also a need to increase the designability by making the reflectance of the light-shielding film in an appropriate range. To this end, inorganic particles such as silicon dioxide can be used as an additive in the composition of the present invention.

將遮光膜用黑色樹脂組成物塗布於透明基板上的方法 除了公知的溶液浸漬法、噴霧法以外，還可以採用使用噴墨機、輥塗機、砂塗機、狹縫塗布機或旋轉機的方法等任意方法。利用溶劑而調整為用以獲得良好的塗布膜的適當的黏度，通過這些方法而塗布為所期望的厚度後，在加熱或減壓下將溶劑除去(預烘烤)，形成乾燥塗膜。繼而藉由光及/或熱進行硬化，由此而製備作為目標的帶遮光膜的基板。 Method for coating black resin composition for light-shielding film on transparent substrate In addition to the known solution dipping method and spray method, any method such as a method using an inkjet machine, a roll coater, a sand coater, a slit coater, or a spinner can be used. The solvent is used to adjust the viscosity to obtain a good coating film, and after coating to a desired thickness by these methods, the solvent is removed (pre-baked) under heating or reduced pressure to form a dry coating film. Then, it is hardened by light and / or heat, thereby preparing a target substrate with a light-shielding film.

在透明基板上形成遮光膜圖案的印刷方法存在有光微 影法，亦即經由光罩對將本組成物塗布於透明基板上進行乾燥而成的塗膜照射紫外線，用顯影液將未曝光部分除去，進一步進行加熱處理。而且，存在有絲網印刷法、凹版印刷、凹板印刷法等使用轉印版而進行印刷的方法等，另外在近年來，噴墨印刷法作為無需罩幕或印刷版的數位印刷方法而受到關注。本發明的遮光膜用黑色樹脂組成物可應用於任意的圖案形成方法或印刷方法中，為了製成具有適合各印刷法的黏度、表面張力的樹脂組成物，選定所述硬化性樹脂/硬化性單體或溶劑或界面活性劑等添加劑。 而且，根據遮光膜圖案的印刷精度或解析度等而選定印刷機。 Printing method for forming light-shielding film pattern on transparent substrate In the shadow method, a coating film obtained by coating the composition on a transparent substrate and drying it is irradiated with ultraviolet rays through a photomask, and the unexposed portion is removed with a developing solution, and further heat treatment is performed. In addition, there are methods such as screen printing, gravure printing, and gravure printing that use a transfer plate to print, and in recent years, the inkjet printing method has been used as a digital printing method that does not require a mask or a printing plate. attention. The black resin composition for a light-shielding film of the present invention can be applied to any pattern forming method or printing method. In order to make a resin composition having viscosity and surface tension suitable for each printing method, the curable resin / curability is selected. Additives such as monomers or solvents or surfactants. The printer is selected based on the printing accuracy, resolution, and the like of the light-shielding film pattern.

例如，在用噴墨印刷法而形成遮光膜的情況下，本發明 的組成物所含有的遮光性黑色粒子或顏色調整用粒子等粒子再凝聚的現象少，因此間歇噴出時的噴墨噴嘴的閉塞少，且隨時間經過保存時的黏度穩定，因此有助於連續印刷時的圖案膜厚的穩定性。關於噴墨裝置，如果可以調整組成物的噴出液量，則並無特 別限制，在一般經常使用的壓電元件的噴墨頭中，穩定地形成液滴的墨水組成物的物性因噴頭的構成而異，在噴頭內部的溫度下，黏度為3mPa．sec~150mPa．sec即可，優選為4mPa．sec~30mPa．sec。如果黏度值變得比其大，則無法噴出液滴；相反地如果黏度值變得比其小，則液滴的噴出量並不穩定。而且，噴頭內部的溫度也因所使用的墨水組成物的穩定性而異，理想的是在20℃~45℃下使用。其中，為了使墨水組成物中的固體成分變多而使膜厚提高，為了設為可穩定進行噴出的黏度，一般採用35℃~40℃左右的溫度。 For example, when a light-shielding film is formed by an inkjet printing method, the present invention The composition contains few particles such as light-shielding black particles or particles for color adjustment. Therefore, the inkjet nozzles are blocked less during intermittent ejection, and the viscosity is stable during storage over time. Stability of the pattern film thickness during printing. Regarding the inkjet device, if the amount of liquid discharged from the composition can be adjusted, there is no special feature. Don't limit it. In the inkjet heads of piezoelectric elements that are often used, the physical properties of the ink composition that stably forms droplets vary depending on the structure of the nozzle. At the temperature inside the nozzle, the viscosity is 3 mPa. sec ~ 150mPa. sec is sufficient, preferably 4 mPa. sec ~ 30mPa. sec. If the viscosity value becomes larger than this, the droplet cannot be ejected; on the contrary, if the viscosity value becomes smaller than this, the ejection amount of the droplet is not stable. In addition, the temperature inside the printhead also varies depending on the stability of the ink composition used, and is preferably used at 20 ° C to 45 ° C. Among them, in order to increase the solid content in the ink composition and increase the film thickness, in order to set the viscosity for stable ejection, a temperature of about 35 ° C. to 40 ° C. is generally used.

如上所述的組成物的特性可主要藉由構成其的溶劑或 界面活性劑而調整，另外為了抑制連續印刷時的噴嘴部分的組成物的乾燥，溶劑以沸點為180℃以上的溶劑為主體，該沸點為180℃以上的溶劑能夠以在所有溶劑成分中為60%以上、優選為80%以上而單獨使用或使用多種。沸點為180℃以上的溶劑可使用乙二醇單甲醚乙酸酯等乙二醇單烷基醚乙酸酯類；二乙二醇單甲醚、二乙二醇單***等二乙二醇單烷基醚類；二乙二醇單正丁醚乙酸酯等二乙二醇單烷基醚乙酸酯類；丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯等丙二醇單烷基醚乙酸酯類；二乙二醇二甲醚等其它醚類、γ-丁內酯等高沸點溶劑類等。 The properties of the composition as described above can be mainly determined by the solvent or The surfactant is adjusted, and in order to suppress the drying of the composition of the nozzle part during continuous printing, the solvent is mainly a solvent having a boiling point of 180 ° C or higher. The solvent having a boiling point of 180 ° C or higher can be 60 in all solvent components. % Or more, preferably 80% or more, alone or in combination. For solvents with a boiling point of 180 ° C or higher, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate; diethylene glycol monomethyl ether such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether can be used. Alkyl ethers; diethylene glycol monoalkyl ether acetates such as diethylene glycol mono-n-butyl ether acetate; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Esters; other ethers such as diethylene glycol dimethyl ether, and high boiling point solvents such as γ-butyrolactone.

如果表示在噴墨法中使用的情況下的本發明的黑色樹 脂組成物的固體成分的構成比率的例子，則只要為(A)硬化性樹脂及/或硬化性單體為25質量%~60質量%，(B)成分中的黑色遮 光性粒子為35質量%~70質量%，(C)成分中的顏色調整用粒子為1質量%~14質量%的範圍即可，更優選為(A)成分為35質量%~55質量%，(B)成分中的黑色遮光性粒子為40質量%~60質量%，(C)成分中的顏色調整用粒子為1質量%~12質量%。而且，例如在併用具有乙烯性不飽和雙鍵的樹脂(A-1)與具有乙烯性不飽和雙鍵的單體(A-2)作為(A)成分的情況下，(A-1)/(A-2)只要為10/90~90/10的範圍即可，優選為30/70~70/30的範圍。 而且，在併用(A-1)與(A-2)的情況下，也可進一步併用具有2個以上的環氧基的環氧樹脂而調整硬化物的表面硬度或機械物性等物性，在這樣的情況下，相對於[(A-1)+(A-2)]的100質量份，優選在1質量份~60質量份的範圍使用環氧樹脂，更優選10質量份~50質量份的範圍。 If the black tree of the present invention is used in the case of inkjet method, An example of the composition ratio of the solid content of the fat composition is (A) 25% to 60% by mass of the curable resin and / or the curable monomer, and the black shading in the (B) component The optical particles are 35% to 70% by mass, and the color adjustment particles in the component (C) may be in a range of 1% to 14% by mass, and more preferably (A) is 35% to 55% by mass. The black light-shielding particles in the component (B) are 40% by mass to 60% by mass, and the particles for color adjustment in the component (C) are 1% by mass to 12% by mass. Furthermore, for example, when the resin (A-1) having an ethylenically unsaturated double bond and the monomer (A-2) having an ethylenically unsaturated double bond are used as the (A) component, (A-1) / (A-2) What is necessary is just to be the range of 10 / 90-90 / 10, and it is preferable that it is the range of 30 / 70-70 / 30. In addition, when (A-1) and (A-2) are used in combination, the physical properties such as the surface hardness and mechanical properties of the cured product may be adjusted by further using an epoxy resin having two or more epoxy groups in combination. In the case of 100% by mass of [(A-1) + (A-2)], an epoxy resin is preferably used in a range of 1 to 60 parts by mass, and more preferably 10 to 50 parts by mass. range.

另一方面，在光微影法中，(A)成分為光硬化性樹脂或 光硬化性單體，進一步混合用以使其溶解於鹼性顯影液中的鹼可溶性樹脂。而且，優選使用在分子內具有聚合性不飽和基與羧基等酸性基的含有不飽和基的鹼可溶性樹脂。例如，可使用以如下含有不飽和基的鹼可溶性樹脂為首的廣泛的樹脂，所述含有不飽和基的鹼可溶性樹脂是使如(甲基)丙烯酸縮水甘油酯這樣的在1分子中具有聚合性不飽和基與環氧基的化合物，和使(甲基)丙烯酸與(甲基)丙烯酸酯化合物進行自由基共聚而所得的樹脂的羧基的一部分反應而所得的樹脂。 On the other hand, in the photolithography method, the component (A) is a photocurable resin or The photocurable monomer is further mixed with an alkali-soluble resin for dissolving it in an alkaline developer. Further, an unsaturated group-containing alkali-soluble resin having a polymerizable unsaturated group and an acidic group such as a carboxyl group in the molecule is preferably used. For example, a wide range of resins including an unsaturated group-containing alkali-soluble resin, such as glycidyl (meth) acrylate, which is polymerizable in one molecule, can be used. A compound obtained by reacting a compound of an unsaturated group and an epoxy group with a part of a carboxyl group of a resin obtained by radical polymerization of (meth) acrylic acid and a (meth) acrylate compound.

形成在透明基板上的遮光膜的硬化方法以及硬化性樹 脂成分(A)以適合透明基板的耐熱性或所使用的環境、所要求的尺寸精度、可靠性的方式進行選定。 Method for hardening light-shielding film formed on transparent substrate and hardening tree The fat component (A) is selected so as to be suitable for the heat resistance of the transparent substrate, the environment to be used, and required dimensional accuracy and reliability.

關於如此所得的黑色硬化物(遮光膜)的色相、色度， 為了將黑色調整為無彩色或帶藍色調的黑色的目的，需要將CIE Lab色彩空間表示系統中的b*值調整為-1.0<b*<0.2，更優選為-1.0<b*<0.0。另外，作為本發明的這個b*值的測定方法，使用用於表示受日光照明的物體色彩的情況下的D65光源(JIS Z8720的日光標準光源(測色用的光))或C光源(JIS Z8720的日光輔助光源)，自上述所得的帶遮光膜的基板中的塗布有遮光膜的面的相反面側，而為在視野角2°或10°下測定的值。 Regarding the hue and chroma of the black hardened material (light-shielding film) thus obtained, in order to adjust black to achromatic or black with blue tint, it is necessary to adjust the b * value in the CIE Lab color space display system to -1.0. <b * <0.2, more preferably -1.0 <b * <0.0. In addition, as the method for measuring the b * value of the present invention, a D65 light source (JIS Z8720 daylight standard light source (light for color measurement)) or a C light source (JIS Z8720 daylight auxiliary light source) is a value measured at a viewing angle of 2 ° or 10 ° from the side opposite to the surface on which the light-shielding film is applied in the substrate with a light-shielding film obtained as described above.

關於在光微影法中使用本發明的遮光膜用黑色樹脂組 成物的情況下的黑色感光性樹脂組成物，若更具體地說明實施形態的例子，則該黑色感光性樹脂組成物含有上述(A)成分~(E)成分作為主成分。在該黑色感光性樹脂組成物中，優選在除(D)溶劑以外的固體成分(包含在光硬化後成為固體成分的聚合性單體成分)中，(A-1)含有聚合性不飽和基的鹼可溶性樹脂為10質量%~60質量%，相對於(A-1)100質量份而言，(A-2)光聚合性單體為10質量份~60質量份，相對於(A-1)與(A-2)的合計量100質量份而言，(E)光聚合引發劑為2質量份~50質量份。 更優選相對於(A-1)100質量份而言，(A-2)為15質量份~35質量份，相對於(A-1)與(A-2)的合計量100質量份而言，(E)為5質量份~30質量份。而且，關於(B)成分中的黑色遮光性 粒子，相對於除(D)溶劑以外的固體成分而言，其含量優選為30質量%~60質量%的範圍，更優選為40質量%~50質量%的範圍。而且，(C)成分中的顏色調整用粒子優選在除(D)溶劑以外的固體成分中為1質量%~15質量%，更優選為2質量%~7質量%的範圍。 About using the black resin set for the light-shielding film of the present invention in the photolithography method When the black photosensitive resin composition in the case of a product is more specifically described as an example of the embodiment, the black photosensitive resin composition contains the above-mentioned components (A) to (E) as a main component. In the black photosensitive resin composition, it is preferable that (A-1) contains a polymerizable unsaturated group in a solid component (including a polymerizable monomer component that becomes a solid component after photocuring) other than the (D) solvent. The alkali-soluble resin is 10% to 60% by mass, and (A-2) the photopolymerizable monomer is 10 to 60% by mass relative to 100% by mass of (A-1), relative to (A- 1) With respect to 100 parts by mass of the total amount with (A-2), the (E) photopolymerization initiator is 2 to 50 parts by mass. It is more preferably 15 to 35 parts by mass with respect to 100 parts by mass of (A-1), and 100 parts by mass with respect to the total amount of (A-1) and (A-2). (E) is 5 to 30 parts by mass. Further, regarding the black light-shielding property in the (B) component The content of the particles is preferably in the range of 30% to 60% by mass, and more preferably in the range of 40% to 50% by mass, with respect to the solid content other than the (D) solvent. The color-adjusting particles in the component (C) are preferably in a range of 1% to 15% by mass, and more preferably in a range of 2% to 7% by mass in the solid content other than the solvent (D).

使用本發明的黑色感光性樹脂組成物的硬化膜的形成 方法可列舉利用光微影法的方法。該形成方法可列舉如下的方法：首先，將黑色感光性樹脂組成物塗布於基板表面上，其次使溶劑乾燥(預烘烤)後，經由光罩對所得的塗膜照射紫外線而使曝光部硬化，進行使用鹼性水溶液使未曝光部溶出的顯影，由此而形成圖案，進一步進行熱硬化(後烘烤)。此處，塗布黑色感光性樹脂組成物的基板使用玻璃、透明膜(例如聚碳酸酯、聚對苯二甲酸乙二酯、聚醚碸等)等。 Formation of a cured film using the black photosensitive resin composition of the present invention Methods include a method using a photolithography method. Examples of the formation method include a method in which a black photosensitive resin composition is coated on the surface of a substrate, followed by drying (pre-baking) the solvent, and then irradiating the obtained coating film with ultraviolet rays through a photomask to harden the exposed portion. Then, development is performed using an alkaline aqueous solution to elute the unexposed portion, thereby forming a pattern, and further performing thermal curing (post-baking). Here, glass, a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether fluorene, etc.) etc. are used for the board | substrate which coats a black photosensitive resin composition.

將黑色感光性樹脂組成物塗布於基板上的方法除了公 知的溶液浸漬法、噴霧法以外，還可以採用使用輥塗機、砂塗機、狹縫塗布機或旋轉機的方法等任意方法。可藉由如下的方式而進行：利用這些方法，塗布為所期望的厚度後，將溶劑除去(預烘烤)，由此而形成塗膜。在預烘烤後，在20Pa~100Pa下進行15秒~60秒的減壓乾燥(VCD)，由此除去溶劑，其後用烘箱、加熱板等進行加熱。該預烘烤中的加熱溫度及加熱時間可根據所使用的溶劑而適宜選擇，例如在60℃~110℃的溫度下進行1分鐘~3分鐘。 A method for applying a black photosensitive resin composition to a substrate In addition to the known solution dipping method and spray method, any method such as a method using a roll coater, a sand coater, a slit coater, or a spinner may be used. This can be performed by forming a coating film by applying these methods to a desired thickness and then removing (pre-baking) the solvent. After the pre-baking, the solvent is removed under reduced pressure (VCD) at 20 Pa to 100 Pa for 15 to 60 seconds, and then heated in an oven, a hot plate, or the like. The heating temperature and heating time in the pre-baking can be appropriately selected according to the solvent used, and for example, it is performed at a temperature of 60 ° C. to 110 ° C. for 1 minute to 3 minutes.

預烘烤後所進行的曝光可用曝光機進行，經由光罩進行 曝光，由此使與圖案對應的部分的感光性樹脂及感光性單體感光。適宜選擇曝光機及其曝光照射條件，使用超高壓水銀燈、高壓水銀燈、金鹵燈、遠紫外線燈等光源而進行曝光。 The exposure after pre-baking can be performed with an exposure machine and through a photomask By exposing, the photosensitive resin and the photosensitive monomer in a portion corresponding to the pattern are exposed to light. It is suitable to choose an exposure machine and its exposure conditions, and use light sources such as ultra-high pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and far-ultraviolet lamps for exposure.

曝光後的鹼性顯影是出於將未曝光的部分的塗膜除去 的目的而進行，利用該顯影而形成所期望的圖案。適於該鹼性顯影的顯影液例如可列舉鹼金屬或鹼土類金屬的碳酸鹽的水溶液、鹼金屬的氫氧化物的水溶液等，特別優選使用含有0.03質量%~1質量%碳酸鈉、碳酸鉀等碳酸鹽的弱鹼性水溶液，在23℃~27℃的溫度下進行顯影，可使用市售的顯影機或超音波清洗機等精密地形成微細的圖像。 The alkaline development after exposure is to remove the coating film of the unexposed part The purpose is to use this development to form a desired pattern. Examples of the developing solution suitable for the alkaline development include an aqueous solution of a carbonate of an alkali metal or an alkaline earth metal, an aqueous solution of a hydroxide of an alkali metal, and the like, and it is particularly preferable to use 0.03% to 1% by mass of sodium carbonate and potassium carbonate. A weakly alkaline aqueous solution such as a carbonate is developed at a temperature of 23 ° C to 27 ° C, and a fine image can be precisely formed using a commercially available developing machine or an ultrasonic cleaner.

如上所述地進行顯影後，在200℃~240℃的溫度、20 分鐘~60分鐘的條件下進行熱處理(後烘烤)。以提高經圖案化的黑色膜與基板的密接性等目的而進行該後烘烤。其可藉由利用烘箱、加熱板等進行加熱而進行。而且，由此得到目標的帶遮光膜的基板。 After developing as described above, the temperature is 200 ° C to 240 ° C, 20 The heat treatment (post-baking) is performed under the conditions of minutes to 60 minutes. This post-baking is performed for the purpose of improving the adhesion between the patterned black film and the substrate. This can be performed by heating with an oven, a hot plate, or the like. Then, the target substrate with a light-shielding film was obtained.

關於如此所得的黑色硬化物(遮光膜)的色相、色度， 為了將黑色調整為無彩色或帶藍色調的黑色的目的，需要將CIE Lab色彩空間表示系統中的b*值調整為-1.0<b*<0.2，更優選為-1.0<b*<0.0。另外，作為本發明的這個b*值的測定方法，使用用於表示受日光照明的物體色彩的情況下的D65光源(JIS Z8720的日光標準光源(測色用的光))或C光源(JIS Z8720的日光輔助 光源)，自上述所得的帶遮光膜的基板中的塗布有遮光膜的面的相反面側，而測定的值。 Regarding the hue and chroma of the black hardened material (light-shielding film) thus obtained, in order to adjust black to achromatic or black with blue tint, it is necessary to adjust the b * value in the CIE Lab color space display system to -1.0. <b * <0.2, more preferably -1.0 <b * <0.0. In addition, as the method for measuring the b * value of the present invention, a D65 light source (JIS Z8720 daylight standard light source (light for color measurement)) or a C light source (JIS Z8720 daylight auxiliary light source), a value measured from the side opposite to the surface coated with the light-shielding film in the substrate with a light-shielding film obtained as described above.

以下，利用實施例對本發明加以更詳細的說明，但本發明並不限定於這些實施例。 Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples.

[實施例] [Example]

以下的實施例中的各種評價若無特別說明則如下所示地進行。 Various evaluations in the following examples were performed as described below unless otherwise specified.

[固體成分濃度] [Solid content concentration]

將後述的合成例中所得的樹脂溶液1g含浸於玻璃過濾器[質量：W0(g)]中而進行稱量[W1(g)]，根據在160℃下加熱2hr後的質量[W2(g)]，由下式而求出。 A glass filter [mass: W 0 (g)] was impregnated with 1 g of the resin solution obtained in the synthesis example described later and weighed [W 1 (g)], and the mass after heating at 160 ° C. for 2 hrs [W 2 (g)] is determined by the following formula.

固體成分濃度(質量%)=100×(W2-W0)/(W1-W0)。 Solid content concentration (% by mass) = 100 × (W 2 -W 0 ) / (W 1 -W 0 ).

[酸值] [Acid value]

使樹脂溶液溶解於二噁烷中，使用電位滴定裝置[平沼產業股份有限公司製造、商品名COM-1600]，用1/10N-KOH水溶液進行滴定而求出。 The resin solution was dissolved in dioxane, and it was determined by titration with a 1 / 10N-KOH aqueous solution using a potentiometric titration device [manufactured by Hiranuma Sangyo Co., Ltd., COM-1600].

[分子量] [Molecular weight]

用凝膠滲透色譜儀(gel permeation chromatography，GPC)[東曹(Tosoh)股份有限公司製造、商品名為HLC-8220GPC]、溶劑：四氫呋喃、管柱：TSKgelSuperH-2000(2根)+TSKgelSuperH-3000(1根)+TSKgelSuperH-4000(1根)+TSKgelSuper-H5000(1根) [東曹股份有限公司製造、溫度：40℃、速度：0.6ml/min]進行測定，設為標準聚苯乙烯[東曹股份有限公司製造、PS-寡聚物試劑盒]換算值而求出重量平均分子量(Mw)。 Gel permeation chromatography (GPC) [manufactured by Tosoh Corporation, trade name HLC-8220GPC], solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2) + TSKgelSuperH-3000 (1) + TSKgelSuperH-4000 (1) + TSKgelSuper-H5000 (1) [Manufactured by Tosoh Corporation, temperature: 40 ° C, speed: 0.6 ml / min] was measured and determined as a standard polystyrene [manufactured by Tosoh Corporation, PS-oligomer kit] and calculated Weight average molecular weight (Mw).

[平均二次粒徑測定] [Measurement of average secondary particle size]

關於所得的含有黑色遮光性粒子的分散液或含有顏色調整用粒子的分散液，利用動態光散射法的粒度分佈計(大塚電子股份有限公司製造、粒徑分析儀FPAR-1000)，分別測定利用累積法而求出的平均二次粒徑。以分散於丙二醇單甲醚乙酸酯中的粒子濃度成為0.1質量%~0.5質量%的方式對含有遮光性黑色粒子的分散液或含有顏色調整用粒子的分散液進行稀釋而製成測定用樣品。 The obtained dispersion liquid containing black light-shielding particles or the dispersion liquid containing particles for color adjustment was measured by a particle size distribution meter (manufactured by Otsuka Electronics Co., Ltd., particle size analyzer FPAR-1000) using a dynamic light scattering method. The average secondary particle diameter determined by the accumulation method. A dispersion liquid containing light-shielding black particles or a dispersion liquid containing particles for color adjustment is diluted to prepare a sample for measurement so that the particle concentration dispersed in propylene glycol monomethyl ether acetate becomes 0.1% by mass to 0.5% by mass. .

[黏度測定] [Viscosity measurement]

用E型黏度計(東機產業製造、RE80L)，在23℃下測定遮光膜用黑色樹脂組成物的黏度。 Using an E-type viscometer (manufactured by Toki Sangyo, RE80L), the viscosity of the black resin composition for a light-shielding film was measured at 23 ° C.

[遮光度(OD值)測定] [Measurement of shading degree (OD value)]

使用後烘烤後的帶遮光膜的玻璃基板，用大塚電子公司製造的OD計進行測定。 The glass substrate with a light-shielding film after baking was measured using an OD meter manufactured by Otsuka Electronics Co., Ltd.

[膜厚測定] [Measurement of film thickness]

使用觸針式膜厚計[科磊(Tencor)股份有限公司製造]對後烘烤後的帶遮光膜的玻璃基板進行測定。 The glass substrate with a light-shielding film after post-baking was measured using a stylus-type film thickness meter [manufactured by Tencor Corporation].

[噴墨吐出穩定性試驗] [Inkjet discharge stability test]

將遮光膜用黑色樹脂組成物裝入到柯尼卡美能達(Konica Minolta)IJ製造的壓電元件驅動型噴墨頭(14pL/滴；KM512M)中，實施沖洗、噴墨頭噴出面的清洗後，以30分鐘連續地用飛翔觀察照相機確認墨水組成物的噴出狀態，觀察是否存在不噴出液滴、飛翔軌道明顯地並不垂直等顯著的異常。進一步利用間歇噴出試驗(將噴墨頭噴出面清洗後靜置30分鐘，對再次噴出時的不噴出噴嘴的個數進行計數)，觀察所有512個噴嘴中的不吐出噴嘴的個數是否為良好(10個以內)。 The black resin composition for the light-shielding film was loaded into Konica Minolta. (Minolta) IJ's piezoelectric element-driven inkjet head (14pL / drop; KM512M), after performing flushing and cleaning of the ejection surface of the inkjet head, the flying state of the ink composition was continuously checked for 30 minutes using a flying observation camera. Observe whether there are significant anomalies such as no ejection of droplets, and apparently non-vertical orbits. Further using the intermittent ejection test (the inkjet head ejection surface was left to stand for 30 minutes after cleaning, and the number of non-ejection nozzles was counted when ejected again) to observe whether the number of non-ejection nozzles was good among all 512 nozzles (Within 10).

[顯影特性評價] [Evaluation of development characteristics]

使用旋塗機，以後烘烤後的膜厚成為1.2μm的方式將遮光膜用黑色樹脂組成物塗布於125mm×125mm的玻璃基板上，在80℃下進行1分鐘的預烘烤。其後，將曝光間隙調整為80μm，在乾燥塗膜上覆蓋線/空間=20μm/20μm的負型光罩，用I射線照度為30mW/cm2的超高壓水銀燈照射100mJ/cm2的紫外線，進行感光部分的光硬化反應。其次，將該曝光後的塗板在0.05%氫氧化鉀水溶液中、23℃下進行壓力為1kgf/cm2噴淋顯影，將觀察到圖案的時間作為顯影脫落時間(BT秒)，進一步進行20秒的顯影後，進行壓力為5kgf/cm2的噴霧水洗，將塗膜的未曝光部除去而在玻璃基板上形成像素圖案，其後使用熱風乾燥機而在230℃下進行30分鐘的後烘烤。各實施例、及比較例中所得的遮光膜的評價項目與方法如下所述。 Using a spin coater, a black resin composition for a light-shielding film was coated on a 125 mm × 125 mm glass substrate so that the film thickness after baking became 1.2 μm, and pre-baked at 80 ° C. for 1 minute. Thereafter, the exposure gap was adjusted to 80 μm, a dry mask was covered with a negative mask with a line / space = 20 μm / 20 μm, and an ultra-high pressure mercury lamp with an I-ray illumination of 30 mW / cm 2 was irradiated with 100 mJ / cm 2 of ultraviolet light. The photo-hardening reaction of the photosensitive part is performed. Next, the exposed coated plate was spray-developed in a 0.05% potassium hydroxide aqueous solution at a pressure of 1 kgf / cm 2 at 23 ° C., and the time at which the pattern was observed was taken as the development peeling time (BT seconds), and was further performed for 20 seconds. After image development, washing with spray water at a pressure of 5 kgf / cm 2 was performed to remove unexposed portions of the coating film to form a pixel pattern on a glass substrate. Thereafter, a hot air dryer was used for post-baking at 230 ° C. for 30 minutes. . The evaluation items and methods of the light-shielding films obtained in Examples and Comparative Examples are as follows.

圖案直線性及塗膜表面的平滑性：用顯微鏡以及掃描電子顯微鏡(Scanning Electron Microscope，SEM)觀察後烘烤後的20μ m的線，將觀測到鋸齒狀的情況判定為“不良”，將並無鋸齒狀的情況判定為“良好”。而且，在由於粗大粒子而造成在線膜厚上存在不均一的情況下，將平滑性判定為“不良”。 The linearity of the pattern and the smoothness of the coating film surface: 20 μm after baking, observed with a microscope and a scanning electron microscope (SEM) The line m is judged as "bad" when a jagged shape is observed, and is judged as "good" when a jagged shape is not observed. In addition, in the case where there is unevenness in the thickness of the line film due to the coarse particles, the smoothness is determined to be "poor".

而且，合成例等中所使用的省略符號如下所示。 The abbreviations used in the synthesis examples and the like are as follows.

BPFE：9,9-雙(4-羥基苯基)芴與氯甲基氧雜環丙烷的反應物。在通式(I)的化合物中，A為芴-9,9-二基、R1~R4為氫的化合物。 BPFE: reactant of 9,9-bis (4-hydroxyphenyl) fluorene and chloromethyloxane. Among the compounds of the general formula (I), compounds in which A is fluorene-9,9-diyl and R 1 to R 4 are hydrogen.

BPDA：3,3',4,4'-聯苯四羧酸二酐 BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride

THPA：1,2,3,6-四氫鄰苯二甲酸酐 THPA: 1,2,3,6-tetrahydrophthalic anhydride

TPP：三苯基膦 TPP: Triphenylphosphine

PGMEA：丙二醇單甲醚乙酸酯 PGMEA: propylene glycol monomethyl ether acetate

BDGAC：二乙二醇單丁醚乙酸酯 BDGAC: Diethylene glycol monobutyl ether acetate

DPHA：二季戊四醇六丙烯酸酯與二季戊四醇五丙烯酸酯的混合物[日本化藥股份有限公司製造的商品名DPHA] DPHA: a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate [trade name DPHA manufactured by Nippon Kayaku Co., Ltd.]

HDDA：1,6-己二醇二丙烯酸酯 HDDA: 1,6-hexanediol diacrylate

[合成例1] [Synthesis example 1]

在帶回流冷凝器的500ml四口燒瓶中裝入BPFE 78.63g(0.17mol)、丙烯酸24.50g(0.34mol)、TPP 0.45g、及PGMEA 114g，在100℃~105℃的加熱下進行12hr的攪拌而獲得反應產物。 A 500 ml four-necked flask with a reflux condenser was charged with 78.63 g (0.17 mol) of BPFE, 24.50 g (0.34 mol) of acrylic acid, 0.45 g of TPP, and 114 g of PGMEA, and was heated at 100 ° C to 105 ° C for 12 hours. Stir to obtain the reaction product.

其次，在所得的反應產物中裝入BPDA 25.01g(0.085mol)及THPA 12.93g(0.085mol)，在120℃~125℃的加熱下進行6hr的攪拌，獲得含有聚合性不飽和基的鹼可溶性樹脂溶液(A-1)-1。所得的樹脂溶液的固體成分濃度為55.8wt%，酸值(固 體成分換算)為103mgKOH/g，利用GPC分析的Mw為2600。 Next, 25.01 g (0.085 mol) of BPDA and 12.93 g (0.085 mol) of THPA were charged into the obtained reaction product, and stirred for 6 hr under heating at 120 ° C to 125 ° C to obtain alkali-solubility containing a polymerizable unsaturated group. Resin solution (A-1) -1. The solid content concentration of the obtained resin solution was 55.8 wt%, and the acid value (solid Body composition conversion) was 103 mgKOH / g, and Mw by GPC analysis was 2600.

[樹脂溶液的製備：A成分溶液] [Preparation of resin solution: A component solution]

製備以下的含有(A)成分的樹脂溶液A1及樹脂溶液A2。 The following resin solution A1 and resin solution A2 containing the component (A) were prepared.

(1)樹脂溶液A1(噴墨印刷用：熱硬化型樹脂組成物) (1) Resin solution A1 (for inkjet printing: thermosetting resin composition)

將BDGAC 82.9質量份、含有聚合性不飽和基的鹼可溶性樹脂溶液(A-1)-1 6.3質量份、苯酚酚醛清漆型環氧樹脂[三菱化學股份有限公司製造、商品名為JER154、環氧當量為178、1分子中的平均官能基數為3.0]3.2質量份、DPHA 4.0質量份、日本畢克化學(BYK-Chemie Japan)股份有限公司製造的商品名BYK(注冊商標)-333的10% BDGAC稀釋溶液1.24質量份、3-脲基丙基三乙氧基矽烷[信越化學工業股份有限公司製造、商品名為KBE-585]2.95質量份加以混合而製備樹脂溶液A1。 82.9 parts by mass of BDGAC, 6.3 parts by mass of an alkali-soluble resin solution (A-1) containing a polymerizable unsaturated group, a phenol novolac-type epoxy resin [manufactured by Mitsubishi Chemical Corporation, trade name JER154, epoxy Equivalent is 178, the average number of functional groups in one molecule is 3.0] 3.2 parts by mass, 4.0 parts by mass of DPHA, 10% of the product name BYK (registered trademark) -333 manufactured by BYK-Chemie Japan Co., Ltd. 1.24 parts by mass of the BDGAC diluted solution and 2.95 parts by mass of 3-ureidopropyltriethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBE-585] were mixed to prepare a resin solution A1.

(2)樹脂溶液A2(光微影印刷用：曝光/熱硬化型樹脂組成物) (2) Resin solution A2 (for photolithography: exposure / thermosetting resin composition)

將PGMEA 78.7質量份、鹼可溶性樹脂溶液(A-1)-1 12.3質量份、DPHA 2.41質量份、光聚合引發劑OXE-02(巴斯夫(BASF)公司製造)0.81質量份、日本畢克化學股份有限公司製造的商品名BYK(注冊商標)-333的10% BDGAC稀釋溶液1.24質量份、3-脲基丙基三乙氧基矽烷[信越化學工業股份有限公司製造、商品名為KBE-585]2.95質量份加以混合而製備樹脂溶液A2。 78.7 parts by mass of PGMEA, 12.3 parts by mass of the alkali-soluble resin solution (A-1) -1, 2.41 parts by mass of DPHA, 0.81 parts by mass of the photopolymerization initiator OXE-02 (manufactured by BASF), and BYK Chemical Co., Ltd. Co., Ltd.'s product name BYK (registered trademark) -333 10% BDGAC diluted solution 1.24 parts by mass, 3-ureidopropyltriethoxysilane [Made by Shin-Etsu Chemical Industry Co., Ltd., trade name is KBE-585] 2.95 parts by mass was mixed to prepare a resin solution A2.

[含有黑色遮光性粒子的分散液的製備：(B)成分] [Preparation of dispersion liquid containing black light-shielding particles: (B) component]

(1)含有黑色遮光性粒子的分散液B1(噴墨印刷用)： 以在BDGAC中碳黑濃度成為25wt%、高分子分散劑成為10wt%的方式在珠磨機中進行分散，製成含有黑色遮光性粒子的分散液B1。所得的分散液中的碳黑的平均二次粒徑為96nm。 (1) Dispersion B1 (for inkjet printing) containing black light-shielding particles: The carbon black concentration in BDGAC was 25% by weight, and the polymer dispersant was 10% by weight, and dispersed in a bead mill to prepare a dispersion liquid B1 containing black light-shielding particles. The average secondary particle diameter of the carbon black in the obtained dispersion was 96 nm.

(2)含有黑色遮光性粒子的分散液B2(光微影印刷用)：以在PGMEA中碳黑濃度成為25重量%、高分子分散劑成為10wt%的方式在珠磨機中進行分散，製成含有黑色遮光性粒子的分散液B2。所得的分散液中的碳黑的平均二次粒徑為111nm。 (2) Dispersion liquid B2 (for photolithography) containing black light-shielding particles: disperse in a bead mill so that the carbon black concentration in PGMEA becomes 25% by weight and the high-molecular dispersant becomes 10% by weight. A dispersion liquid B2 containing black light-shielding particles was formed. The average secondary particle diameter of carbon black in the obtained dispersion was 111 nm.

[含有顏色調整用粒子的分散液的製備：(C)成分] [Preparation of dispersion liquid containing particles for color adjustment: (C) component]

使用珠磨機將C.I.顏料黃顏料PY139與高分子分散劑在PGMEA或BDGAC中製備含有顏色調整用粒子的分散液C1~含有顏色調整用粒子的分散液C4。將各分散液的組成與特性示於表1中。 Using a bead mill, C.I. Pigment Yellow Pigment PY139 and a polymer dispersant were prepared in PGMEA or BDGAC to prepare a dispersion liquid C1 containing particles for color adjustment, and a dispersion liquid C4 containing particles for color adjustment. The composition and characteristics of each dispersion are shown in Table 1.

[遮光膜用黑色樹脂組成物及其遮光膜的製備、以及評價] [Preparation and evaluation of black resin composition for light-shielding film and light-shielding film] [實施例1~實施例2] [Examples 1 to 2]

將樹脂溶液A1 12.8質量份、碳黑分散液B1 13.5質量份、PY139分散液C1 3.8質量份、以及二氧化矽分散液S1(畢克(BYK)公司製造的奈米畢克(NANOBYK)-3605)0.5質量份加以混合，用1μm深層過濾器進行加壓過濾，製備遮光膜用墨水(遮光膜用黑色樹脂組成物)。所製作的墨水的初始黏度(室溫)為10.3mPa．sec[23℃、用E型黏度計(東機產業)測定]。利用旋塗改變轉速而將該遮光膜用墨水塗布於無鹼玻璃上，將這些在90℃下進行5分鐘乾燥，進一步在230℃下進行30分鐘後烘烤而製成帶遮光膜的玻璃基板。分別將膜厚1.1μm作為實施例1的樣品，將膜厚1.4μm作為實施例2的樣品。於表2中表示各樣品的組成，於表3中表示各樣品的評價結果。 12.8 parts by mass of resin solution A1, 13.5 parts by mass of carbon black dispersion B1, 3.8 parts by mass of PY139 dispersion C1, and silicon dioxide dispersion S1 (NANOBYK-3605 manufactured by BYK) ) 0.5 parts by mass were mixed, and pressure filtration was performed with a 1 μm depth filter to prepare an ink for a light-shielding film (a black resin composition for a light-shielding film). The initial viscosity (room temperature) of the prepared ink was 10.3 mPa. sec [23 ° C, measured with an E-type viscometer (Toki Sangyo)]. The light-shielding film ink was coated on an alkali-free glass by spin-coating to change the rotation speed, and these were dried at 90 ° C for 5 minutes, and further baked at 230 ° C for 30 minutes to prepare a glass substrate with a light-shielding film. . A film thickness of 1.1 μm was used as a sample in Example 1, and a film thickness of 1.4 μm was used as a sample in Example 2. The composition of each sample is shown in Table 2, and the evaluation result of each sample is shown in Table 3.

另外，表3中的反射光學特性的測定是用以下的方式進行。 The reflection optical characteristics in Table 3 were measured in the following manner.

[反射光學特性的測定] [Measurement of reflection optical characteristics]

使用後烘烤後的帶遮光膜的玻璃基板，自形成遮光膜的面的相反側的面側，使用柯尼卡美能達(Konica Minolta)製造的測色計CM2600d在D65光源、10°視野下進行測定。 After using the glass substrate with a light-shielding film after baking, from the side of the surface opposite to the surface on which the light-shielding film is formed, a color meter CM2600d manufactured by Konica Minolta is used under a D65 light source and a 10 ° field of view Perform the measurement.

[比較例1] [Comparative Example 1]

除了含有PY139的分散液以外，與實施例1同樣地進行，以表2中所示的質量份加以混合而製備遮光膜用墨水(遮光膜用黑色樹脂組成物)。將該遮光膜用墨水塗布於無鹼玻璃上，於90℃下進行5分鐘乾燥，進一步在230℃下進行30分鐘的後烘烤而製成帶遮光膜的玻璃基板。所作成的樣品膜厚是1.3μm。將樣品評價結果示於表3中。 Except that the dispersion liquid containing PY139 was carried out in the same manner as in Example 1, the parts by mass shown in Table 2 were mixed to prepare a light-shielding film ink (black resin composition for light-shielding film). This ink for a light-shielding film was coated on an alkali-free glass, dried at 90 ° C for 5 minutes, and further post-baked at 230 ° C for 30 minutes to prepare a glass substrate with a light-shielding film. The thickness of the prepared sample was 1.3 μm. The evaluation results of the samples are shown in Table 3.

如表3所示，在實施例1~實施例2中，帶遮光膜的基板也顯示遮光度3以上，b*也為-0.08而接近零，相對於此，在比較例1中，b*超過0.2。 As shown in Table 3, in Examples 1 to 2, the substrate with a light-shielding film also showed a light-shielding degree of 3 or more, and b * was also -0.08, which was close to zero. In contrast, in Comparative Example 1, b * More than 0.2.

[實施例3~實施例4、比較例2~比較例3] [Example 3 to Example 4, Comparative Example 2 to Comparative Example 3]

改變含有顏色調整用粒子的分散液中的PY139的平均二次粒徑，以表2中所示的組成比，除此以外與實施例1同樣地製備遮光性墨水(遮光膜用黑色樹脂組成物)，進一步與實施例1同樣地進行而在無鹼玻璃上形成遮光膜。將評價結果示於表3中。 A light-shielding ink (black resin composition for light-shielding film) was prepared in the same manner as in Example 1 except that the average secondary particle diameter of PY139 in the dispersion containing the particles for color adjustment was changed to the composition ratio shown in Table 2. ) Was further carried out in the same manner as in Example 1 to form a light-shielding film on an alkali-free glass. The evaluation results are shown in Table 3.

在PY139的平均二次粒徑低於碳黑的平均二次粒徑96nm的情況下，為-1.0<b*<0.2，相對於此，在PY139的平均二次粒徑超過碳黑的平均二次粒徑的各比較例的情況下，為b*超過0.2的 結果。 When the average secondary particle diameter of PY139 is lower than the average secondary particle diameter of carbon black at 96 nm, it is -1.0 <b * <0.2. In contrast, the average secondary particle diameter of PY139 exceeds the average secondary particle diameter of carbon black. In the case of each comparative example of the secondary particle diameter, it was a result that b * exceeded 0.2.

[實施例5~實施例6] [Example 5 to Example 6]

相對於碳黑粒子的質量，改變含有顏色調整用粒子的分散液中的PY139的添加質量，以表2中所示的組成比，除此以外與實施例1同樣地進行而製備遮光性墨水(遮光膜用黑色樹脂組成物)，進一步與實施例1同樣地進行而在無鹼玻璃上形成遮光膜。將評價結果示於表3中。在任意情況下，與並不共存PY139粒子的比較例1相比而言，b*向負側移動，顯示為-1.0<b*<0.2。 A light-shielding ink was prepared in the same manner as in Example 1 except that the added mass of PY139 in the dispersion containing the particles for color adjustment was changed with respect to the mass of the carbon black particles, with the composition ratio shown in Table 2. A black resin composition for a light-shielding film) was further carried out in the same manner as in Example 1 to form a light-shielding film on an alkali-free glass. The evaluation results are shown in Table 3. In any case, compared with Comparative Example 1 in which PY139 particles were not coexisted, b * moved to the negative side, and was displayed as -1.0 <b * <0.2.

[實施例7~實施例9、比較例4] [Example 7 to Example 9, Comparative Example 4]

使用光微影印刷用樹脂溶液(A2)，用表2中所示的組成製備遮光用墨水(遮光膜用黑色樹脂組成物)。使用旋塗機，以後烘烤後的膜厚成為1.0μm~1.3μm的方式將遮光膜用黑色樹脂組成物塗布於125mm×125mm的玻璃基板上，在80℃下進行1分鐘的預烘烤。其後，將曝光間隙調整為80μm，在乾燥塗膜上覆蓋線/空間=20μm/20μm的負型光罩，用I射線照度為30mW/cm2的超高壓水銀燈照射100mJ/cm2的紫外線，進行感光部分的光硬化反應。其次，將該曝光後的塗板在0.05%氫氧化鉀水溶液中、23℃下進行壓力為1kgf/cm2噴淋顯影，將觀察到圖案的時間作為顯影脫落時間(BT秒)，進一步進行20秒的顯影後，進行壓力為5kgf/cm2的噴霧水洗，將塗膜的未曝光部除去而在玻璃基板上形成像素圖案，其後使用熱風乾燥機而在230℃下進行30分鐘的後烘烤。 Using the resin solution (A2) for photolithographic printing, a light-shielding ink (black resin composition for light-shielding film) was prepared with the composition shown in Table 2. Using a spin coater, a black resin composition for a light-shielding film was coated on a 125 mm × 125 mm glass substrate so that the film thickness after baking was 1.0 μm to 1.3 μm, and pre-baked at 80 ° C. for 1 minute. Thereafter, the exposure gap was adjusted to 80 μm, a dry mask was covered with a negative mask with a line / space = 20 μm / 20 μm, and an ultra-high pressure mercury lamp with an I-ray illumination of 30 mW / cm 2 was irradiated with 100 mJ / cm 2 of ultraviolet light. The photo-hardening reaction of the photosensitive part is performed. Next, the exposed coated plate was spray-developed in a 0.05% potassium hydroxide aqueous solution at a pressure of 1 kgf / cm 2 at 23 ° C., and the time at which the pattern was observed was taken as the development peeling time (BT seconds), and was further performed for 20 seconds. After image development, washing with spray water at a pressure of 5 kgf / cm 2 was performed to remove unexposed portions of the coating film to form a pixel pattern on a glass substrate. Thereafter, a hot air dryer was used for post-baking at 230 ° C. for 30 minutes. .

在含有PY139粒子的帶遮光膜的基板中，b*顯示-1.0<b*<0.2，相對於此，在不含PY139的帶遮光膜的基板中，為b*超過0.2的結果。 In a substrate with a light-shielding film containing PY139 particles, b * shows -1.0 <b * <0.2, whereas in a substrate with a light-shielding film not containing PY139, b * exceeds 0.2.

[噴墨噴出性、顯影特性的評價] [Evaluation of inkjet ejectability and developing characteristics]

將實施例1~實施例6中所製備的遮光膜用黑色樹脂組成物裝入到柯尼卡美能達(konicaminolta)IJ製造的壓電元件驅動型噴墨頭(14pL/滴；KM512M)中，實施沖洗、噴墨頭噴出面的清洗後，以30分鐘連續地用飛翔觀察照相機確認墨水組成物的噴出狀態，未觀察到不噴出液滴、飛翔軌道明顯地並不垂直等顯著的異常。進一步根據間歇噴出試驗(將噴墨頭噴出面清洗後靜置30分鐘，對再次噴出時的不噴出噴嘴的個數進行計數)，所有512個噴嘴中的不吐出噴嘴的個數為2個以內，可知在噴墨噴出性上完全未發現問題。 The black resin composition for the light-shielding film prepared in Examples 1 to 6 was charged into a piezoelectric element-driven inkjet head (14pL / drop; KM512M) manufactured by Konicaminolta IJ, After rinsing and cleaning the ejection surface of the inkjet head, the ejection state of the ink composition was confirmed with a flying observation camera continuously for 30 minutes. No significant abnormalities such as no ejection of liquid droplets, and apparently non-vertical orbit were observed. According to the intermittent ejection test (the inkjet head ejection surface was left to stand for 30 minutes after cleaning, and the number of non-ejection nozzles was counted when ejected again), the number of non-ejection nozzles out of all 512 nozzles was within 2 It can be seen that no problem was found in the inkjet ejectability.

而且，關於實施例7~實施例9中所製備的遮光膜用黑色樹脂組成物，利用所述方法進行顯影特性(圖案直線性及塗膜表面的平滑性)的評價，結果確認直線性及平滑性均無問題。 In addition, regarding the black resin composition for a light-shielding film prepared in Examples 7 to 9, the development characteristics (pattern linearity and smoothness of the coating film surface) were evaluated by the method described above. As a result, linearity and smoothness were confirmed. No problem with sex.

進一步，關於光微影法用遮光膜用黑色感光性樹脂組成物，一併表示其評價。 Furthermore, the evaluation of the black photosensitive resin composition for light-shielding films for photolithography methods is also shown.

[黑色感光性樹脂組成物的製作] [Production of black photosensitive resin composition]

以表4所示的組成進行調配，製備實施例8~實施例10、及比較例5、比較例6的黑色感光性樹脂組成物。如下表示各組成中所使用的成分。 The black photosensitive resin compositions of Examples 8 to 10, and Comparative Examples 5 and 6 were prepared by blending the compositions shown in Table 4. The components used in each composition are shown below.

(A-1)鹼可溶性樹脂溶液：合成例1中所製備的含有聚合性不飽和基的鹼可溶性樹脂溶液(A-1)-1 (A-1) Alkali-soluble resin solution: Alkali-soluble resin solution (A-1) -1 containing a polymerizable unsaturated group prepared in Synthesis Example 1

(A-2)光聚合性單體：DPHA (A-2) Photopolymerizable monomer: DPHA

(B)黑色遮光性粒子分散液：碳黑為25質量%、高分子分散劑為6質量%的PGMEA溶劑的碳黑分散體 (B) Black light-shielding particle dispersion liquid: a carbon black dispersion of PGMEA solvent with 25% by mass of carbon black and 6% by mass of polymer dispersant

(C)顏色調整用粒子分散液： (C) Particle dispersion for color adjustment:

(C)-1：Y139(平均二次粒徑為108nm)為15質量%、高分子分散劑為9質量%的PGMEA溶劑的黃色顏料分散體 (C) -1: Yellow pigment dispersion of PGMEA solvent with 15% by mass of Y139 (average secondary particle size of 108nm) and 9% by mass of polymer dispersant

(C)-2：Y139(平均二次粒徑為123nm)為15質量%、高分子分散劑為9質量%的PGMEA溶劑的黃色顏料分散體 (C) -2: Yellow pigment dispersion of PGMEA solvent with 15% by mass of Y139 (average secondary particle diameter of 123nm) and a polymer dispersant of 9% by mass

(C)-3：Y139(平均二次粒徑為158nm)為15質量%、高分子分散劑為9質量%的PGMEA溶劑的黃色顏料分散體 (C) -3: Yellow pigment dispersion of PGMEA solvent with 15% by mass of Y139 (average secondary particle diameter of 158nm) and a polymer dispersant of 9% by mass

(C)-4：溶劑藍45(藍色染料：粉體) (C) -4: solvent blue 45 (blue dye: powder)

(D)溶劑：PGMEA、環己酮的混合溶劑 (D) Solvent: Mixed solvent of PGMEA and cyclohexanone

(E)光聚合引發劑：1-[9-乙基-6-(2-甲基苯甲醯基)咔唑-3-基]乙酮=O-乙醯肟(巴斯夫公司製造、商品名豔佳固(Irgacure)OXE02) (E) Photopolymerization initiator: 1- [9-ethyl-6- (2-methylbenzylidene) carbazol-3-yl] ethanone = O-acetamoxime (manufactured by BASF, trade name (IrgacureOXE02)

(F)界面活性劑：1%PGMEA溶液 (F) Surfactant: 1% PGMEA solution

(G)矽烷偶合劑 (G) Silane coupling agent

[反射色的評價] [Evaluation of reflection color]

將實施例8~實施例10、及比較例5、比較例6的黑色感光性樹脂組成物旋塗於玻璃板(5英寸見方)上，在90℃下用加熱板進行1分鐘乾燥後，在230℃下進行30分鐘的後烘烤。如上所述地進行而獲得厚度為1.45μm的黑色硬化物。 The black photosensitive resin composition of Examples 8 to 10, and Comparative Examples 5 and 6 was spin-coated on a glass plate (5 inches square), dried at 90 ° C for 1 minute using a hot plate, and then Post-baking was performed at 230 ° C for 30 minutes. This was performed as described above to obtain a black cured product having a thickness of 1.45 μm.

使用該黑色硬化物的整體基板，用日立高新技術股份有限公司製造的UH-4100進行反射色測定。光源是C光源(2°視野)或D65光源(10°視野)。 Using this black hardened monolithic substrate, the reflection color was measured using UH-4100 manufactured by Hitachi High-tech Co., Ltd. The light source is a C light source (2 ° field of view) or a D65 light source (10 ° field of view).

可知在比較例5中，顯示僅僅黑色遮光性粒子的反射色 的色度，但為了設為無彩色，存在使a*及b*接近0的必要性，特別是在反射色自無彩色起偏離若干的情況下，與茶色系相比而言，更加要求藍色系的色相，根據該狀況可知存在使b*為-的數值 的必要性。相對於此，可知在實施例8~實施例10中，藉由添加具有與黑色遮光性粒子為同系色的色度的黃色的顏色調整用粒子，可並不使反射色的a*大幅度變動地使b*向-側(負側)移動。 而且，可知為了使b*自黑色成為藍色系的色相，優選控制為-1.0<b*<0.2的範圍，在實施例8~實施例10中可藉由本發明而實現。另外，特別是為了使其為藍色系的色相，更優選調整為1.0<b*<0.0，可藉由控制黑色遮光性粒子與顏色調整用粒子的平均二次粒徑而控制。 It can be seen that Comparative Example 5 shows only the chromaticity of the reflection color of the black light-shielding particles. However, in order to make it achromatic, it is necessary to make a * and b * close to 0, especially when the reflection color deviates from the achromatic color. In some cases, the hue of the blue system is more demanded than that of the brown system, and it can be seen from this situation that there is a need to make b * a value of-. In contrast, in Examples 8 to 10, it was found that by adding yellow color-adjusting particles having a chromaticity of the same color as the black light-shielding particles, the reflection color a * could not be greatly changed. Ground b * to the-side (negative side). In addition, it was found that in order to make b * from black to a blue hue, it is preferable to control the range of -1.0 <b * <0.2, and it can be achieved by the present invention in Examples 8 to 10. In addition, in particular, in order to make it a blue hue, it is more preferably adjusted to 1.0 <b * <0.0, and can be controlled by controlling the average secondary particle diameter of the black light-shielding particles and the particles for color adjustment.

另一方面，可知如果像比較例6那樣添加具有黑色遮光 性粒子的相反色的色度的藍染料(溶解於溶劑中，在組成物中並非粒子)，則相反地b*的值變大而使反射色向無彩色的方向的相反方向移動，無法獲得所期望的無彩色或若干藍色系的色相。 On the other hand, it was found that if a blue dye having a chromaticity of the opposite color of the black light-shielding particles is added as in Comparative Example 6 (dissolved in a solvent, not particles in the composition), the value of b * will increase on the contrary. Moving the reflected color in the opposite direction to the achromatic direction makes it impossible to obtain the desired achromatic or some blue-based hue.

因此，如本發明所示，可知僅僅藉由選定與黑色遮光性粒子為同系色的顏色調整用粒子並少量添加，即可將黑色硬化物的反射色調整為無彩色化或所期望的色相。 Therefore, as shown in the present invention, it can be seen that the reflection color of the black hardened material can be adjusted to an achromatic color or a desired hue only by selecting and adding a small amount of color adjustment particles having the same color as the black light-shielding particles.

Claims (9)

一種遮光膜用黑色樹脂組成物，其特徵在於包含如下成分作為必須成分：(A)利用光或熱的硬化性樹脂、及/或利用光或熱的硬化性單體、(B)在分散介質中分散黑色遮光性粒子而成的含有黑色遮光性粒子的分散液、及(C)在分散介質中分散顏色調整用粒子而成的含有顏色調整用粒子的分散液。A black resin composition for a light-shielding film, comprising the following components as essential components: (A) a curable resin using light or heat, and / or a curable monomer using light or heat, and (B) a dispersion medium A black light-shielding particle-containing dispersion liquid in which black light-shielding particles are dispersed in the middle, and (C) a color-adjusting particle-containing dispersion liquid in which a color-adjusting particle is dispersed in a dispersion medium. 如申請專利範圍第1項所述的遮光膜用黑色樹脂組成物，其中(C)成分中的顏色調整用粒子的平均二次粒徑DC與(B)成分中的黑色遮光性粒子的平均二次粒徑DB的比DC/DB為0.2~1.2的範圍，且(C)成分中所含的顏色調整用粒子的質量mC與(B)成分中所含的黑色遮光性粒子的質量mB的比mC/mB為0.03~0.2的範圍。The black resin composition for a light-shielding film according to item 1 of the patent application scope, wherein the average secondary particle diameter D C of the color-adjusting particles in the component (C) and the average of the black light-shielding particles in the (B) component The ratio D C / D B of the secondary particle diameter D B is in the range of 0.2 to 1.2, and the mass m C of the color adjustment particles contained in the component (C) and the black light-shielding particles contained in the component (B) The ratio m C / m B of the mass m B is in the range of 0.03 to 0.2. 如申請專利範圍第1項或第2項所述的遮光膜用黑色樹脂組成物，其中所述黑色遮光性粒子是碳黑。The black resin composition for a light-shielding film according to item 1 or 2 of the scope of patent application, wherein the black light-shielding particles are carbon black. 如申請專利範圍第1項或第2項所述的遮光膜用黑色樹脂組成物，其中所述顏色調整用粒子是作為黃色顏料的C.I.顏料黃139及/或作為橙色顏料的C.I.顏料橙61。The black resin composition for a light-shielding film according to claim 1 or claim 2, wherein the particles for color adjustment are C.I. pigment yellow 139 as a yellow pigment and / or C.I. pigment orange 61 as an orange pigment. 一種遮光膜用黑色樹脂組成物，其特徵在於：所述遮光膜用黑色樹脂組成物是使用含有聚合性不飽和基的鹼可溶性樹脂與具有乙烯性不飽和雙鍵的聚合性單體作為(A)成分，且進一步含有(D)溶劑及(E)光聚合引發劑的如申請專利範圍第1項至第4項中任一項所述的遮光膜用黑色樹脂組成物，且在包含光硬化後成為固形的聚合性單體的固體成分中，含有聚合性不飽和基的鹼可溶性樹脂為10質量%~60質量%，相對於含有聚合性不飽和基的鹼可溶性樹脂100質量份而言，具有乙烯性不飽和雙鍵的聚合性單體為10質量份~60質量份，相對於含有聚合性不飽和基的鹼可溶性樹脂與具有乙烯性不飽和雙鍵的聚合性單體的合計量100質量份而言，(E)為2質量份~50質量份，進一步在固體成分中，(B)成分中的黑色遮光性粒子為30質量%~60質量%，在固體成分中(C)成分中的顏色調整用粒子為1質量%~15質量%。A black resin composition for a light-shielding film, wherein the black resin composition for a light-shielding film uses an alkali-soluble resin containing a polymerizable unsaturated group and a polymerizable monomer having an ethylenically unsaturated double bond as (A ) Component, further comprising (D) a solvent and (E) a photopolymerization initiator, the black resin composition for a light-shielding film according to any one of claims 1 to 4 in the scope of patent application, and including photocuring The solid content of the polymerizable monomer which will be solid in the future is 10% to 60% by mass of the alkali-soluble resin containing a polymerizable unsaturated group, and 100 parts by mass of the alkali-soluble resin containing a polymerizable unsaturated group. The polymerizable monomer having an ethylenically unsaturated double bond is 10 to 60 parts by mass, and the total amount of the polymerizable monomer having an ethylenically unsaturated double bond and the polymerizable monomer having an ethylenically unsaturated double bond is 100 to 100 parts by mass. In terms of parts by mass, (E) is 2 parts by mass to 50 parts by mass, and further in the solid content, the black light-shielding particles in the (B) component are 30% by mass to 60% by mass, and the (C) component is in the solid content 1 for color adjustment particles % By mass to 15%. 如申請專利範圍第5項所述的遮光膜用黑色樹脂組成物，其中含有聚合性不飽和基的鹼可溶性樹脂使用使(a)二羧酸或三羧酸或其酸酐、及(b)四羧酸或其酸二酐和由雙酚類所衍生的具有2個縮水甘油醚基的環氧化合物與含有不飽和基的單羧酸的反應物進行反應而所得的含有聚合性不飽和基的鹼可溶性樹脂。The black resin composition for a light-shielding film according to item 5 of the scope of application for a patent, wherein the alkali-soluble resin containing a polymerizable unsaturated group uses (a) a dicarboxylic acid or a tricarboxylic acid or an anhydride thereof, and (b) a tetracarboxylic acid. A polymerizable unsaturated group containing a carboxylic acid or an acid dianhydride thereof and an epoxy compound derived from bisphenols having two glycidyl ether groups and a reaction product of an unsaturated monocarboxylic acid-containing reactant Alkali soluble resin. 一種帶遮光膜的基板，其特徵在於：所述帶遮光膜的基板是將如申請專利範圍第1項至第6項中任一項所述的遮光膜用黑色樹脂組成物塗布於透明基板上的單面上，使其硬化而所得的帶遮光膜的基板，自所述透明基板的塗布有遮光膜的面的相反面側所測定的CIE Lab色彩空間表示系統中的帶遮光膜的基板的b*值滿足-1.0<b*<+0.2。A substrate with a light-shielding film, characterized in that: the substrate with a light-shielding film is coated on a transparent substrate with a black resin composition for a light-shielding film according to any one of claims 1 to 6 of the scope of patent application. The substrate with a light-shielding film obtained by curing the substrate with a light-shielding film on one side, the CIE Lab color space measured from the opposite side of the surface of the transparent substrate coated with the light-shielding film indicates the substrate with the light-shielding film in the system. The b * value satisfies -1.0 <b * <+ 0.2. 一種彩色濾光片，其特徵在於：包含如申請專利範圍第7項所述的帶遮光膜的基板。A color filter includes a substrate with a light-shielding film according to item 7 of the scope of patent application. 一種觸控面板，其特徵在於：包含如申請專利範圍第7項所述的帶遮光膜的基板。A touch panel, comprising: a substrate with a light-shielding film according to item 7 of the scope of patent application.
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