JP2016161926A - Black resin composition for light blocking films, substrate with light blocking film obtained by curing composition, color filter having substrate with light blocking film, and touch panel - Google Patents

Black resin composition for light blocking films, substrate with light blocking film obtained by curing composition, color filter having substrate with light blocking film, and touch panel Download PDF

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JP2016161926A
JP2016161926A JP2015043999A JP2015043999A JP2016161926A JP 2016161926 A JP2016161926 A JP 2016161926A JP 2015043999 A JP2015043999 A JP 2015043999A JP 2015043999 A JP2015043999 A JP 2015043999A JP 2016161926 A JP2016161926 A JP 2016161926A
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light
shielding film
black
resin composition
particles
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JP6607682B2 (en
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齋藤　亨
Toru Saito
齋藤　　亨
藤城　光一
Koichi Fujishiro
光一 藤城
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Nippon Steel Chemical and Materials Co Ltd
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Nippon Steel and Sumikin Chemical Co Ltd
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Priority to KR1020160026529A priority patent/KR102614831B1/en
Priority to CN201610125576.XA priority patent/CN105938295B/en
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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
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • 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
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133512—Light shielding layers, e.g. black matrix
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—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
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—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
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means

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  • Optical Elements Other Than Lenses (AREA)
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Abstract

PROBLEM TO BE SOLVED: To provide a black resin composition for light blocking films which is used to obtain a light blocking film that offers reduced reflectance, and to provide a substrate with the light blocking film formed thereon.SOLUTION: A black resin composition for light blocking films contains essential ingredients of (A) a light- or heat-curable resin and/or light- or heat-curable monomer, (B) a black light blocking particle-containing dispersion liquid comprising black light-blocking particles dispersed in a dispersion medium, and (C) a transparent particle-containing dispersion liquid comprising transparent particles dispersed in a dispersion medium. The black resin composition is characterized in that: a ratio D/Dof an average secondary particle diameter Dof the transparent particles in the ingredient (C) to an average secondary particle diameter Dof the black light-blocking particles in the ingredient (B) is in a range of 0.2 to 1.0; a ratio m/mof a mass mof the transparent particles in the ingredient (C) to a mass mof the black light-blocking particles in the ingredient (B) is in a range of 0.015 to 0.20; and the transparent particles have a refractive index that is no greater than that of a hardened product of the ingredient (A).SELECTED DRAWING: None

Description

本発明は、遮光膜用黒色樹脂組成物、当該組成物を硬化させた遮光膜をガラス等の透明基板上に有した遮光膜付基板、並びに当該遮光膜付基板を構成要素とするＬＣＤ等のディスプレイ用カラーフィルター及び表示装置用タッチパネルに関する。詳しくは、透明基板上に微細な遮光膜を形成するのに適した光又は熱により硬化する黒色樹脂組成物、及び当該黒色樹脂組成物を硬化させて得られた遮光膜を選択的な位置に形成した遮光膜付基板に関する。   The present invention relates to a black resin composition for a light-shielding film, a substrate with a light-shielding film having a light-shielding film obtained by curing the composition on a transparent substrate such as glass, and an LCD having the light-shielding film-coated substrate as a component. The present invention relates to a color filter for display and a touch panel for display device. Specifically, a black resin composition that is cured by light or heat suitable for forming a fine light-shielding film on a transparent substrate, and a light-shielding film obtained by curing the black resin composition at selective positions. The present invention relates to the formed light-shielding film-coated substrate.

タッチパネル外枠には背面の液晶パネル周辺部の光漏れを遮光するために遮光膜（ベゼル）が設けられ、また液晶パネルにはカラーフィルター内にＴＦＴ素子を遮光するブラックマトリックスが設けられている。最近のモバイル端末の発達により、屋外や車載にて使用するタッチパネル及び液晶パネル等の表示装置が増加しており、パネル外部からの入射光に対してガラス基板やプラスチックフィルム基板上に設置された遮光膜からの反射光が、非点灯時の液晶表示装置等の見映えに影響するため、周囲の着色膜等からの反射光と同等の反射率にすることや、色相（反射色度）を制御することが新たな技術課題となっている。   The outer frame of the touch panel is provided with a light shielding film (bezel) for shielding light leakage around the liquid crystal panel on the back side, and the liquid crystal panel is provided with a black matrix for shielding the TFT elements in the color filter. Due to the recent development of mobile terminals, the number of display devices such as touch panels and liquid crystal panels used outdoors and in vehicles is increasing, and the light shielded on the glass substrate or plastic film substrate against incident light from outside the panel. The reflected light from the film affects the appearance of the liquid crystal display device, etc. when not lit, so the reflectance is equivalent to that of the reflected light from the surrounding colored film, etc., and the hue (reflection chromaticity) is controlled. It has become a new technical issue.

このような遮光膜は、硬化性樹脂と遮光材とを主体とした組成物を透明基板上に印刷して形成される（特許文献１，２）。遮光材としてカーボンブラックや黒色酸化チタンなど可視光を吸収する黒色顔料が多く用いられている。これら黒色顔料でもって遮光膜の遮光性を上げるため（遮光膜の光透過性を下げるため）に遮光膜中の黒色顔料濃度を高くしていくと、透明基板や硬化性樹脂に比較して黒色顔料の屈折率が高く、透明基板の遮光膜が形成された面とは反対の面側から見たときの反射率が高くなる。即ち、透明基板上に形成した遮光膜と透明基板の界面における反射が増加し、透明基板上の着色層と透明基板の界面での反射や着色べゼルと空気の界面での反射に比較して大きくなるような場合は遮光膜上の映り込みや、カラーフィルター着色部との反射率の差異でブラックマトリックス境界が目立つという課題が生じる。このため、高遮光にしようとするほど、遮光膜以外の着色層や着色ベゼルと同等の反射率にするという要求特性を両立させることが困難になる。   Such a light shielding film is formed by printing a composition mainly composed of a curable resin and a light shielding material on a transparent substrate (Patent Documents 1 and 2). A black pigment that absorbs visible light, such as carbon black or black titanium oxide, is often used as a light shielding material. In order to increase the light-shielding property of the light-shielding film with these black pigments (in order to reduce the light transmittance of the light-shielding film), the black pigment concentration in the light-shielding film increases as compared with transparent substrates and curable resins. The refractive index of the pigment is high, and the reflectance when viewed from the surface opposite to the surface on which the light-shielding film of the transparent substrate is formed is high. That is, the reflection at the interface between the light-shielding film formed on the transparent substrate and the transparent substrate increases, compared with the reflection at the interface between the colored layer on the transparent substrate and the transparent substrate and the reflection at the interface between the colored bezel and air. When it becomes larger, there arises a problem that the black matrix boundary is conspicuous due to reflection on the light shielding film and a difference in reflectance from the color filter coloring portion. For this reason, it is difficult to achieve both the required characteristics of a reflectance equivalent to that of a colored layer other than the light shielding film or a colored bezel as the light shielding is increased.

異種材料間の界面で生じる反射を低減させる手段として、例えば基板表面に外光反射を低減させる低屈折率フィルムを設置する方式（例えば1／4波長円偏光板）、基板表面を粗くするアンチグレア方式などがあり、また基板と遮光膜との中間の屈折率をもつ薄膜を形成する手段など、付加的手段を講じることが提案されている。その中間の屈折率を持つ薄膜の膜厚は、可視光波長の4分の１波長分に相当する100〜300μｍの透明膜もしくはこれらの多層膜で形成される（非特許文献１）。   As a means to reduce reflection that occurs at the interface between dissimilar materials, for example, a method of installing a low refractive index film that reduces external light reflection on the substrate surface (for example, 1/4 wavelength circularly polarizing plate), an anti-glare method that roughens the substrate surface In addition, it has been proposed to take additional measures such as a method of forming a thin film having an intermediate refractive index between the substrate and the light shielding film. The thin film having an intermediate refractive index is formed of a transparent film having a thickness of 100 to 300 μm corresponding to a quarter wavelength of visible light or a multilayer film thereof (Non-patent Document 1).

液晶パネルにおけるカラーフィルター上のブラックマトリックスやタッチパネル額縁用遮光膜では、必要な部位にのみ遮光膜をパターン形成する必要性があり、前述のような付加的手段を講じる場合は低反射化を目的とした薄膜（低反射膜）を透明基板と遮光膜との間にあらかじめ形成する、即ち、例えばフォトリソグラフィー法で低反射膜と遮光膜のパターン形成を個々に行い、低反射膜と遮光膜の二層構造を形成する必要がある。又は、透明薄膜を形成した上に遮光膜を形成し、遮光膜をフォトグラフィー法でパターン露光／現像し、これをフォトマスクとして使用して透明薄膜のパターン形成をする方法が考えられる。この方法では、あらかじめ形成した透明薄膜に対して遮光膜用黒色樹脂組成物が侵食しないことが必要である。   In the black matrix on the color filter in the liquid crystal panel and the shading film for the touch panel frame, it is necessary to pattern the shading film only on the necessary part, and when taking the above-mentioned additional measures, the purpose is to reduce the reflection The thin film (low reflection film) is formed in advance between the transparent substrate and the light shielding film, that is, the low reflection film and the light shielding film are individually formed by, for example, photolithography, and the low reflection film and the light shielding film are formed. It is necessary to form a layer structure. Alternatively, a method may be considered in which a light-shielding film is formed on a transparent thin film, the light-shielding film is subjected to pattern exposure / development by a photolithography method, and this is used as a photomask to form a pattern of the transparent thin film. In this method, it is necessary that the black resin composition for a light-shielding film does not erode with respect to a previously formed transparent thin film.

従来の遮光膜用黒色樹脂組成物は、硬化性樹脂成分と遮光材成分とを主体とするものであり、屈折率がより高い遮光材濃度を下げながら、所望の遮光度（ＯＤ値）4以上に見合う膜厚にて透明基板上に遮光膜を形成し、形成した遮光膜と透明基板の界面における反射率を下げることが可能とされている。しかしながら、フォトリソグラフィー法で1.5μｍを超える膜厚にてパターン遮光膜を形成しようとすると、露光／現像後の熱焼成過程において、露光された部分での膜厚方向に対する架橋密度の差があるため、塗膜表面と透明基板付近での熱硬化収縮に差が生じて塗膜表面粗度が増大し表面平滑性が悪化し、表面に皺が発生する課題が生じる。一方、特許文献３では、遮光膜組成物中に所定の平均一次粒径範囲を有するシリカ粒子を共存させることで、1.5μmを超える厚膜の場合でも、パターンのエッジ形状のシャープ性が良好なパターンを形成することができ、また、その後の熱焼成工程においても塗膜表面が平滑で熱硬化収縮による表面粗度の悪化が生じないという技術が開示されているが、その効果を得るためには遮光材に対してシリカを一定量以上添加する必要性があった。また、特許文献４ではアクリル樹脂微粒子とカーボンブラックとを含む樹脂組成物の技術が開示されているが、この場合も厚膜でのパターン形状を安定化させるために、遮光材に対してアクリル粒子を一定以上添加する必要性があった。   A conventional black resin composition for a light-shielding film is mainly composed of a curable resin component and a light-shielding material component, and a desired light shielding degree (OD value) of 4 or more while lowering the concentration of a light-shielding material having a higher refractive index. It is possible to form a light shielding film on the transparent substrate with a thickness suitable for the above, and to reduce the reflectance at the interface between the formed light shielding film and the transparent substrate. However, if an attempt is made to form a pattern light-shielding film with a film thickness exceeding 1.5 μm by the photolithography method, there is a difference in the cross-linking density with respect to the film thickness direction in the exposed portion in the thermal baking process after exposure / development. There is a difference in thermal curing shrinkage between the coating surface and the vicinity of the transparent substrate, the coating film surface roughness is increased, the surface smoothness is deteriorated, and the problem of generating wrinkles on the surface occurs. On the other hand, in Patent Document 3, by making silica particles having a predetermined average primary particle size range coexist in the light shielding film composition, the sharpness of the edge shape of the pattern is good even in the case of a thick film exceeding 1.5 μm. In order to obtain the effect, a pattern can be formed, and the surface of the coating film is smooth even in the subsequent thermal baking process and the surface roughness is not deteriorated due to thermal curing shrinkage. There was a need to add a certain amount or more of silica to the light shielding material. Patent Document 4 discloses a technique of a resin composition containing acrylic resin fine particles and carbon black. In this case as well, in order to stabilize the pattern shape in the thick film, acrylic particles are used with respect to the light shielding material. There was a need to add more than a certain amount.

近年インクジェット法によって透明基板上に直接硬化性樹脂組成物を印刷する方法が提案されている（特許文献５）。インクジェット印刷法では直接印刷パターンを形成するので、フォトリソグラフィー法のようなパターン形成のための露光・現像工程を基本的には必要とせず、信頼性を考慮した硬化物組成の検討のみをすればよい。熱硬化のみの場合、光硬化を併用する場合に比較してより厚膜時のしわ発生の懸念は少ないが、一方で硬化遮光膜の信頼性（透明電極や配線等のパターンエッチング時の耐薬品性）を担保するために熱硬化反応の硬化剤及び／又は硬化促進剤を共存させる必要があり、表面活性なシリカ粒子などの共存は熱硬化性樹脂組成物の保存安定性を低下させる懸念があった。   In recent years, a method of printing a curable resin composition directly on a transparent substrate by an inkjet method has been proposed (Patent Document 5). Since the inkjet printing method directly forms a print pattern, it does not basically require exposure and development processes for pattern formation like the photolithography method, but only by examining the cured product composition in consideration of reliability. Good. In the case of heat curing only, there is less concern about wrinkling when thicker than when using photocuring, but on the other hand, the reliability of the cured light-shielding film (chemical resistance during pattern etching of transparent electrodes, wiring, etc.) In order to ensure the property), it is necessary to coexist with a curing agent and / or a curing accelerator for the thermosetting reaction, and coexistence with surface active silica particles may decrease the storage stability of the thermosetting resin composition. there were.

特開平４−１７７２０２号公報JP-A-4-177202 特開平８−２７８６２９号公報JP-A-8-278629 特開２００８−３０４５８３号公報JP 2008-304583 A 特開２０１０−２５６５８９号公報JP 2010-256589 A ＷＯ２０１１／１５５４４６号公報WO2011 / 155446

光学薄膜ユーザーズハンドブック、James D.Rancourt著、小倉繁太郎訳、ｐｐ．１０Optical Thin Film User's Handbook, by James D. Rancourt, translated by Shigetaro Ogura, pp. 10

本発明は、かかる技術の諸欠点に鑑み、創案されたものであり、その目的とするところは、遮光性が高い黒色の遮光膜であり、かつ反射光をカラーフィルターの彩色（着色）部分並みに低減させることができる遮光膜を形成できる遮光膜用の黒色樹脂組成物及び当該遮光膜を提供することにある。さらに、当該遮光膜形成用の黒色樹脂組成物は、粘度安定性に優れ、また形成されたパターン遮光膜の表面平滑性に優れる。   The present invention has been invented in view of the drawbacks of such a technique. The object of the present invention is a black light-shielding film having a high light-shielding property, and the reflected light is similar to the coloring (coloring) portion of a color filter. An object of the present invention is to provide a black resin composition for a light shielding film capable of forming a light shielding film that can be reduced to a low level, and the light shielding film. Furthermore, the black resin composition for forming the light shielding film is excellent in viscosity stability and excellent in the surface smoothness of the formed pattern light shielding film.

本発明者らは、上記従来技術の問題点を解決すべく鋭意研究を行った結果、遮光膜用黒色樹脂組成物中の黒色遮光性粒子ならびに光もしくは熱により硬化される樹脂に比較して屈折率の低い透明粒子を加えることにより、本目的を達成可能なことを見出した。   As a result of diligent research to solve the above-mentioned problems of the prior art, the present inventors have refracted compared to the black light-shielding particles in the black resin composition for the light-shielding film and the resin cured by light or heat. It has been found that this object can be achieved by adding transparent particles having a low rate.

即ち、本発明の要旨は以下のとおりである。
（１） （A）光若しくは熱による硬化性樹脂、及び／又は光若しくは熱による硬化性単量体、（B）分散媒中に黒色遮光性粒子が分散されてなる黒色遮光性粒子含有分散液、並びに（C）透明粒子を分散媒中に分散されてなる透明粒子含有分散液を必須成分とし、（C）成分中の透明粒子の平均二次粒子径ＤＣと、（B）成分中の黒色遮光性粒子の平均二次粒子径ＤＢとの比ＤＣ／ＤＢが0.2〜1.0の範囲であり、且つ（C）成分中の透明粒子の質量ｍＣと、（B）成分の黒色遮光性粒子の質量ｍＢとの質量比ｍＣ／ｍＢが0.015〜0.20の範囲であり、また、前記透明粒子の屈折率が、前記(A)成分の硬化物の屈折率以下であることを特徴とする遮光膜用黒色樹脂組成物である。 That is, the gist of the present invention is as follows.
(1) (A) a curable resin by light or heat and / or a curable monomer by light or heat, (B) a black light-shielding particle-containing dispersion in which black light-shielding particles are dispersed in a dispersion medium and (C) a transparent particles as a dispersion medium essential components a transparent particle-containing dispersion is dispersed in an average secondary particle diameter D C of (C) transparent particles in component in component (B) The ratio D C / D B to the average secondary particle diameter D B of the black light-shielding particles is in the range of 0.2 to 1.0, and the mass m C of the transparent particles in the component (C) and the black component (B) The mass ratio m C / m B to the mass m B of the light-shielding particles is in the range of 0.015 to 0.20, and the refractive index of the transparent particles is not more than the refractive index of the cured product of the component (A). A black resin composition for a light-shielding film.

（２）本発明はまた、前記（C）成分中の透明粒子の屈折率が1.55以下であることを特徴とする（１）の遮光膜用黒色樹脂組成物である。
（３）本発明はまた、前記（B）成分中の黒色遮光性粒子がカーボンブラックであり、また、前記（C）成分中の透明粒子が分子内に反応性（メタ）アクリロイル基を有するシランカップリング剤により表面処理されたシリカであることを特徴とする（１）又は（２）の遮光膜用黒色樹脂組成物である。
（４）本発明はまた、前記（Ｃ）成分における前記分散媒が（メタ）アクリロイル基を有する硬化性単量体であると共に、前記透明粒子が分子内に（メタ）アクリロイル基を有するシランカップリング剤により表面処理されたシリカであることを特徴とする（１）〜（３）のいずれかの遮光膜用黒色樹脂組成物である。 (2) The black resin composition for a light shielding film according to (1), wherein the refractive index of the transparent particles in the component (C) is 1.55 or less.
(3) In the present invention, the black light-shielding particles in the component (B) are carbon black, and the transparent particles in the component (C) are silanes having a reactive (meth) acryloyl group in the molecule. The black resin composition for a light-shielding film according to (1) or (2), wherein the silica is surface-treated with a coupling agent.
(4) In the present invention, the dispersion medium in the component (C) is a curable monomer having a (meth) acryloyl group, and the transparent particles have a (meth) acryloyl group in the molecule. The black resin composition for a light shielding film according to any one of (1) to (3), wherein the silica is surface-treated with a ring agent.

（５）本発明はまた、光又は熱により硬化して得られた遮光膜の遮光率ＯＤが2.8／μｍ以上であることを特徴とする（１）〜（４）のいずれかの遮光膜用黒色樹脂組成物である。
（６）本発明はまた、前記遮光膜用黒色樹脂組成物は、前記（Ｂ）成分及び（Ｃ）成分中の分散媒として、及び／又は追加成分としての（Ｄ）溶剤を含み、尚且つ当該（Ｄ）溶剤が沸点180℃以上の溶剤を主成分として含むことにより、インクジェット印刷用の遮光膜用黒色樹脂組成物として使用されるものであることを特徴とする（１）〜（５）のいずれかの遮光膜用黒色樹脂組成物である。
（７）本発明はまた、前記遮光膜用黒色樹脂組成物は、前記（A)成分として光硬化性アルカリ可溶性樹脂及び／又は（E）アルカリ可溶性樹脂を含有することにより、フォトリソグラフィー法用の遮光膜用黒色樹脂組成物として使用されるものであることを特徴とする（１）〜（５）のいずれかの遮光膜用黒色樹脂組成物である。 (5) In the light-shielding film according to any one of (1) to (4), the light-shielding ratio OD of the light-shielding film obtained by curing with light or heat is 2.8 / μm or more. It is a black resin composition.
(6) In the present invention, the black resin composition for a light-shielding film contains a solvent (D) as a dispersion medium in the component (B) and the component (C) and / or as an additional component, and (1) to (5), wherein (D) the solvent contains a solvent having a boiling point of 180 ° C. or higher as a main component, so that the solvent is used as a black resin composition for a light-shielding film for inkjet printing. A black resin composition for a light-shielding film.
(7) In the present invention, the black resin composition for a light-shielding film contains a photocurable alkali-soluble resin and / or (E) an alkali-soluble resin as the component (A). The black resin composition for a light shielding film according to any one of (1) to (5), which is used as a black resin composition for a light shielding film.

（８）本発明はまた、（１）〜（７）のいずれかの遮光膜用黒色樹脂組成物を透明基板上の片面に塗布又は印刷し、更に硬化させて得られる遮光膜付基板であり、硬化後の遮光膜の膜厚が1〜3μｍであることを特徴とする遮光膜付基板である。
（９）本発明はまた、（８）の遮光膜付基板を有するカラーフィルターである。
（１０）本発明はまた、（８）の遮光膜付基板を有するタッチパネルである。 (8) The present invention is also a substrate with a light-shielding film obtained by applying or printing the black resin composition for a light-shielding film according to any one of (1) to (7) on one side of a transparent substrate and further curing it. The substrate with a light-shielding film is characterized in that the thickness of the light-shielding film after curing is 1 to 3 μm.
(9) The present invention is also a color filter having the substrate with a light-shielding film according to (8).
(10) The present invention is also a touch panel having the substrate with a light-shielding film according to (8).

本発明の遮光膜用黒色樹脂組成物によれば、黒色遮光性粒子の分散媒中での平均二次粒子径に対して、一定レベルの平均二次粒子径の透明粒子を、黒色遮光性粒子に対して比較的少量添加することにより、透明粒子を添加しない場合と比較して遮光膜の反射率を低減させることができる。ここで、透明粒子としては、屈折率が黒色遮光性粒子よりも小さい粒子を用いることが有効であり、特にシリカのような無機粒子を使用する場合は、特定の表面処理を行うことにより、有機溶剤中や、光又は熱により硬化する硬化性単量体中で所望の平均二次粒子径を有するように分散させることが有効である。このような遮光膜用黒色樹脂組成物を用いることにより、カラーフィルターやタッチパネル用の遮光膜として、高遮光率で意匠性にも優れた遮光膜を提供することができる。   According to the black resin composition for a light-shielding film of the present invention, transparent particles having a certain level of average secondary particle diameter with respect to the average secondary particle diameter in the dispersion medium of black light-shielding particles are converted into black light-shielding particles. By adding a relatively small amount, the reflectance of the light shielding film can be reduced as compared with the case where no transparent particles are added. Here, as the transparent particles, it is effective to use particles having a refractive index smaller than that of the black light-shielding particles. In particular, when inorganic particles such as silica are used, the organic particles can be obtained by performing a specific surface treatment. It is effective to disperse so as to have a desired average secondary particle size in a solvent or in a curable monomer that is cured by light or heat. By using such a black resin composition for a light-shielding film, a light-shielding film having a high light-shielding rate and excellent design can be provided as a light-shielding film for color filters and touch panels.

以下に、本発明を詳細に説明する。
本発明の遮光膜用黒色樹脂組成物における（Ａ）成分である光若しくは熱による硬化性樹脂及び／又は光若しくは熱による硬化性単量体としては、光若しくは熱により硬化反応を生じる官能基、即ち（メタ）アクリロイル基、ビニル基などのエチレン性不飽和二重結合、又はエポキシ基、オキセタン基などの環状反応性基を分子内に少なくとも１個以上有する樹脂又は単量体が好ましく用いられる。 The present invention is described in detail below.
The curable resin by light or heat and / or the curable monomer by light or heat that is the component (A) in the black resin composition for a light shielding film of the present invention includes a functional group that causes a curing reaction by light or heat, That is, a resin or monomer having at least one cyclic reactive group such as an epoxy group or oxetane group in the molecule, or an ethylenically unsaturated double bond such as a (meth) acryloyl group or a vinyl group is preferably used.

前記の光若しくは熱による硬化性樹脂としては、アクリル酸、メタクリル酸、メチルアクリレート、メチルメタクリレート、エチルアクリレート、エチルメタクリレート、ブチルアクリレート、ブチルメタクリレートなどのアルキルアクリレート又はアルキルメタクリレート（以下、これらをまとめて「アルキル（メタ）アクリレート」などのように記載する場合がある。）、環状のシクロヘキシルアクリレート又はメタクリレート、ヒドロキシエチルアクリレート又はメタクリレート、スチレンなどの内から３〜５種類程度のモノマーを用いて合成した、分子量５０００〜１０００００程度のポリマー（アクリル系樹脂）の側鎖及び／又は末端に、前述の熱又は光により硬化反応を生じる官能基を１個以上有するものが好ましい。例えば、アクリル系樹脂の一部に不飽和二重結合を付加させた樹脂として、上記のアクリル系樹脂においてカルボキシル基を有するモノマーを共重合させた樹脂に、イソシアネート基と少なくとも１個以上のエチレン性不飽和二重結合とを有するイソシアネートエチルアクリレート、メタクリロイルイソシアネートなどの化合物を反応させて得られる、酸価５０〜１５０の感光性共重合体が、耐熱性、現像性等の点から好ましく使用できる。   Examples of the curable resin by light or heat include acrylic acrylate, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, and other alkyl acrylates or alkyl methacrylates (hereinafter collectively referred to as “ May be described as “alkyl (meth) acrylate”, etc.), molecular weight synthesized from about 3 to 5 types of monomers from cyclic cyclohexyl acrylate or methacrylate, hydroxyethyl acrylate or methacrylate, styrene, etc. It is preferable to have one or more functional groups that cause a curing reaction by the above-described heat or light at the side chain and / or terminal of a polymer (acrylic resin) of about 5,000 to 100,000. For example, as a resin in which an unsaturated double bond is added to a part of an acrylic resin, a resin obtained by copolymerizing a monomer having a carboxyl group in the above acrylic resin with an isocyanate group and at least one ethylenic group A photosensitive copolymer having an acid value of 50 to 150 obtained by reacting a compound such as isocyanate ethyl acrylate or methacryloyl isocyanate having an unsaturated double bond can be preferably used from the viewpoints of heat resistance and developability.

更に、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ノボラック型エポキシ樹脂、ポリカルボン酸化合物のポリグリシジルエステル、ポリオール化合物のポリグリシジルエーテル、脂肪族又は脂環式エポキシ樹脂、グリシジルアミン型エポキシ樹脂、トリフェノールメタン型エポキシ樹脂、ジヒドロキシベンゼン型エポキシ樹脂などのエポキシ樹脂と（メタ）アクリル酸を反応させて得られるエポキシ（メタ）アクリレート等の通常の光重合可能な樹脂、さらにはエポキシ（メタ）アクリレートと酸無水物とを反応させることでフォトリソグラフィー法で現像パターン形成可能な樹脂組成物としても好適に使用可能である。   Furthermore, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, polyglycidyl ester of polycarboxylic acid compound, polyglycidyl ether of polyol compound, aliphatic or alicyclic epoxy resin, glycidylamine type epoxy resin, Usual photopolymerizable resins such as epoxy (meth) acrylate obtained by reacting epoxy resin such as triphenolmethane type epoxy resin and dihydroxybenzene type epoxy resin with (meth) acrylic acid, and also epoxy (meth) acrylate It can also be suitably used as a resin composition capable of forming a development pattern by a photolithography method by reacting an acid anhydride with an acid anhydride.

また、エチレン性不飽和二重結合を有する重合性の単量体としては、例えば、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート等の水酸基を有する（メタ）アクリル酸エステル類や、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、テトラメチレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールエタントリ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、グリセロール（メタ）アクリレート、ソルビトールペンタ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、又はジペンタエリスリトールヘキサ（メタ）アクリレート、ソルビトールヘキサ（メタ）アクリレート、フォスファゼンのアルキレンオキサイド変性ヘキサ（メタ）アクリレート、カプロラクトン変性ジペンタエリスリトールヘキサ（メタ）アクリレート等の（メタ）アクリル酸エステル類を挙げることができる。   Examples of the polymerizable monomer having an ethylenically unsaturated double bond include hydroxyl groups such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. (Meth) acrylic acid esters, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) ) Acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol Ritolol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, glycerol (meth) acrylate, sorbitol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol hexa ( (Meth) acrylates, phosphazene alkylene oxide-modified hexa (meth) acrylates, caprolactone-modified dipentaerythritol hexa (meth) acrylates and other (meth) acrylic esters.

エポキシ基、オキセタン基などの環状反応性基を分子内に少なくとも１個以上有する化合物の具体例としては、ビスフェノールＡ型エポキシ化合物、ビスフェノールＦ型エポキシ化合物、ビスフェノールフルオレン型エポキシ化合物、フェノールノボラック型エポキシ化合物、クレゾールノボラック型エポキシ化合物、多価アルコールのグリシジルエーテル、多価カルボン酸のグリシジルエステル、（メタ）アクリル酸グリシジルをユニットとして含む重合体、３，４−エポキシシクロヘキサンカルボン酸（３’，４’−エポキシシクロヘキシル）メチルに代表される脂環式エポキシ化合物、ジシクロペンタジエン骨格を有する多官能エポキシ化合物（例えばＤＩＣ社製ＨＰ７２００シリーズ）、２，２−ビス（ヒドロキシメチル）−１−ブタノールの１，２−エポキシ−４−（２−オキシラニル）シクロヘキサン付加物（例えばダイセル社製「ＥＨＰＥ３１５０」）、エポキシ化ポリブタジエン（例えば日本曹達社製「ＮＩＳＳＯ−ＰＢ・ＪＰ−１００」）、シリコーン骨格を有するエポキシ化合物等を挙げることができる。
これら光又は熱により硬化する樹脂や単量体は、単独で用いてもよく、また複数を混合することで信頼性などの特性を付与することが可能となる。 Specific examples of compounds having at least one cyclic reactive group such as an epoxy group or an oxetane group in the molecule include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol fluorene type epoxy compounds, and phenol novolac type epoxy compounds. , A cresol novolac type epoxy compound, a glycidyl ether of a polyhydric alcohol, a glycidyl ester of a polycarboxylic acid, a polymer containing glycidyl (meth) acrylate as a unit, 3,4-epoxycyclohexanecarboxylic acid (3 ′, 4′- Epoxycyclohexyl) methyl alicyclic epoxy compounds, polyfunctional epoxy compounds having a dicyclopentadiene skeleton (for example, HP7200 series manufactured by DIC), 2,2-bis (hydroxymethyl) -1-buta 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct (eg “EHPE3150” manufactured by Daicel), epoxidized polybutadiene (eg “NISSO-PB • JP-100” manufactured by Nippon Soda Co., Ltd.), silicone An epoxy compound having a skeleton can be given.
These resins and monomers that are cured by light or heat may be used singly, or by mixing a plurality of them, it is possible to impart characteristics such as reliability.

更に、通常これらと光又は熱により反応する化合物、例えばカルボキシル基、アミノ基、ヒドロキシ基、チオール基を有する化合物、及び紫外線や熱によりラジカル、カチオン、アニオンなどを発生する光重合開始剤、熱重合開始剤などを共存させて使用することが好ましい   Furthermore, compounds that react with these usually by light or heat, such as compounds having a carboxyl group, amino group, hydroxy group, thiol group, and photopolymerization initiators that generate radicals, cations, anions, etc. by ultraviolet light or heat, thermal polymerization It is preferable to use in the presence of an initiator, etc.

例示された（A）成分については、その硬化物の屈折率が1.48〜1.6の範囲となるものが選定されることが好ましい。例えば、アクリル樹脂系硬化物の場合、屈折率は1.48〜1.55であり、化学構造に芳香族基を含有させる、例えばスチレンモノマーとの共重合により屈折率が調整される。エポキシ樹脂系では1.50〜1.60であり、ビスフェノール系エポキシ樹脂や芳香族酸無水物硬化剤を用いると屈折率は高くなり、脂肪族エポキシ樹脂、脂環式エポキシ樹脂や脂環式酸無水物硬化剤を用いると比較的屈折率が低くなる。   About the (A) component illustrated, it is preferable that the refractive index of the cured product is selected 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 1.48 to 1.55, and the refractive index is adjusted by copolymerization with an aromatic group in the chemical structure, for example, with a styrene monomer. The epoxy resin type has a refractive index of 1.50 to 1.60, and the bisphenol type epoxy resin or aromatic acid curing agent increases the refractive index, and the aliphatic epoxy resin, alicyclic epoxy resin or alicyclic acid anhydride curing agent. If is used, the refractive index is relatively low.

（Ｂ）成分中の黒色遮光性粒子としては、その屈折率が1.6を超えるもので、可視光を吸収する黒色顔料が、目的とする薄膜における遮光率及び遮光膜用組成物の保存安定性の観点で主体的に用いられる。本発明に用いられる黒色顔料としては、カーボンブラックが好ましい。カーボンブラックとしては、ランプブラック、アセチレンブラック、サーマルブラック、チャンネルブラック、ファーネスブラック等のいずれのものを用いても良い。その他黒色染料などの遮光性を調整する目的で1種もしくは複数種混合して用いてもよいが、黒色遮光性粒子は全遮光材中の６０質量％以上が好ましい。例えば、有機顔料系／染料系の遮光材を多く用いると、遮光率が低下する。   The black light-shielding particles in the component (B) have a refractive index exceeding 1.6, and the black pigment that absorbs visible light has a light-shielding rate in the target thin film and the storage stability of the composition for the light-shielding film. Used mainly from the viewpoint. As the black pigment used in the present invention, carbon black is preferable. As carbon black, any of lamp black, acetylene black, thermal black, channel black, furnace black and the like may be used. In addition, for the purpose of adjusting the light-shielding property such as black dye, one kind or a mixture of two or more kinds may be used, but the black light-shielding particles are preferably 60% by mass or more based on the total light shielding material. For example, if a large amount of organic pigment / dye-based light-shielding material is used, the light-shielding rate decreases.

これら遮光材を、例えば、高分子分散剤や溶剤などの分散媒と共にビーズミル中で分散し、黒色遮光性粒子を含有する分散液とし、前記（Ａ）成分及び後述の（Ｃ）成分と混合することにより本目的の遮光膜用黒色樹脂組成物を調製する。分散液中の黒色遮光性粒子の平均二次粒径ＤＢは、60nm〜150nmに調製することが好ましく、より好ましくは80nm〜120nmに調製する。本発明において、「平均二次粒子径」とは、分散溶媒又は相当の溶媒にて希釈し、動的光散乱法で測定され、キュムラント法により求められる平均粒子径値を言う。例えば、カーボンブラックではPGMEA溶媒中0.1質量％粒子濃度で測定した値である。平均二次粒子径ＤＢが60nm未満であると、高遮光率を達成するために黒色遮光性粒子の濃度を高くするのに必要な高分子分散剤の添加が増えるか、また保存時に粘度増加が生じやすい。平均二次粒子径ＤＢが150nmを超えると、形成された遮光膜の表面平滑性の好ましくなく、またフォトリソグラフィー法で形成した際のパターンエッジの直線性が損なわれる。 These light shielding materials are dispersed, for example, in a bead mill together with a dispersion medium such as a polymer dispersant or a solvent to form a dispersion liquid containing black light shielding particles, and mixed with the component (A) and the component (C) described later. As a result, a black resin composition for a light-shielding film for this purpose is prepared. Average secondary particle size D B of the black light-shielding particles in the dispersion is preferably prepared from a 60 nm to 150 nm, more preferably adjusted to 80Nm～120nm. In the present invention, the “average secondary particle size” means an average particle size value obtained by diluting with a dispersion solvent or a corresponding solvent, measured by a dynamic light scattering method, and determined by a cumulant method. For example, for carbon black, it is a value measured at a 0.1% by mass particle concentration in a PGMEA solvent. When the average secondary particle diameter D B is less than 60 nm, viscosity increase or the addition of the polymeric dispersant necessary to increase the concentration of the black light-shielding particles in order to achieve a high light blocking ratio increases, also during storage Is likely to occur. When the average secondary particle diameter D B is more than 150 nm, undesirably the surface smoothness of the formed light-shielding film, also the linearity of the pattern edge when forming by photolithography is impaired.

因みに、タッチパネル用遮光膜及びカラーフィルター用ブラックマトリックスにおける遮光度（ＯＤ＝‐log[透過度]）はＯＤ4以上が要求され、一方で膜厚は3μｍ以下、好ましくは2μｍ以下の薄膜化が要求されている。理由はタッチパネルでは、遮光膜上の金属配線とタッチパネル上導電膜との接続に際する断線防止であり、カラーフィルターではブラックマトリックス上にＲＧＢ画素を形成した後の平坦性を確保するためである。このような薄い遮光膜でも高い遮光度を得る目的で、例えばカーボンブラックを組成物中の全固形分に対して35質量％以上70質量％以下とする。   Incidentally, the light shielding degree (OD = -log [transmittance]) in the light shielding film for the touch panel and the black matrix for the color filter is required to be OD4 or more, while the film thickness is required to be 3 μm or less, preferably 2 μm or less. ing. The reason is that in the touch panel, the disconnection is prevented when the metal wiring on the light shielding film and the conductive film on the touch panel are connected, and in the color filter, the flatness after forming the RGB pixels on the black matrix is ensured. In order to obtain a high light-shielding degree even with such a thin light-shielding film, for example, carbon black is made 35 mass% to 70 mass% with respect to the total solid content in the composition.

一方で、組成物の全固形分（硬化後に基板上に残存する全成分）中の黒色遮光性粒子の濃度を高くしていくと、透明基板上に形成した遮光膜と透明基板間における反射が増加し、遮光膜上の映り込みや、カラーフィルター着色部との反射率の差異で境界が目立つという課題があった。即ち、後述の（Ｃ）成分を含まない、硬化樹脂成分（Ａ）と遮光材成分（Ｂ）だけの場合、硬化・形成された遮光膜における遮光膜と透明基板間における反射率は、専ら（Ａ）成分と（Ｂ）成分中の黒色遮光性粒子との質量比に専ら依存し、質量比率が一定であれば遮光膜の膜厚を厚くしても反射率の低下は顕著ではなかった。   On the other hand, when the concentration of black light-shielding particles in the total solid content of the composition (all components remaining on the substrate after curing) is increased, reflection between the light-shielding film formed on the transparent substrate and the transparent substrate is caused. There has been a problem that the boundary is conspicuous due to the reflection on the light shielding film and the difference in reflectance from the colored portion of the color filter. That is, in the case of only the cured resin component (A) and the light shielding material component (B) that do not contain the component (C) described later, the reflectance between the light shielding film and the transparent substrate in the cured and formed light shielding film is exclusively ( The dependence on the mass ratio between the component A) and the black light-shielding particles in the component (B) depends exclusively, and if the mass ratio is constant, the decrease in reflectance is not significant even when the thickness of the light-shielding film is increased.

以上のような事実に鑑み、本発明者らは（A）成分の硬化物中に、（A）成分の硬化物の屈折率以下の屈折率を有する透明粒子を共存させることで、組成物の全固形分中の黒色遮光性粒子の濃度を同一にしながら（遮光度を維持しながら）反射率を低減可能なことを見出した。即ち、本発明では、（A）成分の硬化物の屈折率以下の屈折率を有する透明粒子を必須成分〔（C）成分として分散媒に分散した状態で使用〕とし、透明粒子としては、公知のシリカ等の金属酸化物等の無機系透明微粒子、アクリル樹脂、スチレン-アクリル樹脂、シリコーン樹脂、エポキシ樹脂又はメラミン樹脂等の樹脂系透明微粒子を例示できる。樹脂製の透明微粒子は、本発明の組成物中において有機溶剤に分散された分散溶液として供されることがあることから、有機溶剤に不溶な架橋樹脂で構成されることが好ましい。   In view of the above-mentioned facts, the present inventors coexisted transparent particles having a refractive index equal to or lower than the refractive index of the cured product of the component (A) in the cured product of the component (A). It was found that the reflectance can be reduced while maintaining the same concentration of black light-shielding particles in the total solid content (while maintaining the light-shielding degree). That is, in the present invention, transparent particles having a refractive index equal to or lower than the refractive index of the cured product of component (A) is an essential component [used in a state dispersed in a dispersion medium as component (C)]. Examples thereof include inorganic transparent fine particles such as metal oxides such as silica, and resin-based transparent fine particles such as acrylic resin, styrene-acrylic resin, silicone resin, epoxy resin or melamine resin. Since the resin-made transparent fine particles may be provided as a dispersion solution dispersed in an organic solvent in the composition of the present invention, it is preferably composed of a crosslinked resin that is insoluble in the organic solvent.

（A）成分として含まれ、（Ｂ）成分中の黒色遮光性粒子や（Ｃ）成分中の透明粒子のマトリックスとなる、光若しくは熱により硬化樹脂及び／又は硬化性単量体を硬化させた（Ａ）成分の硬化物は、その屈折率が化学構造に依存するものであり1.48〜1.6の範囲にあるものが好ましい。したがって、（C）成分の透明粒子を構成する成分の屈折率は、（A）成分の硬化物の屈折率以下であり、1.40〜1.60の範囲が好ましく、1.42〜1.55であることがより好ましい。なお、本発明において、「（Ａ）成分の硬化物の屈折率」とは、本発明の遮光膜用黒色樹脂組成物から（Ｂ）成分中の黒色遮光性粒子及び（Ｃ）成分中の透明粒子や硬化の過程で除かれる溶剤等を除いた、遮光膜の塗膜形成成分を硬化させた硬化物の屈折率であり、光又は熱で（Ａ）成分を硬化させるために硬化剤や重合開始剤等を共存させる場合には、それらを含めた硬化物の屈折率である。（C）成分中の透明粒子の屈折率が前記「（A）成分の硬化物の屈折率」を超えると、反射率の低減効果はなくなる。公知の透明粒子として用いられる成分の屈折率は、シリカでは1.44〜1.50、アクリル樹脂系やエポキシ樹脂系では1.47〜1.60、シリコーン樹脂系では1.40〜1.45である。これらを単独でも2種類以上用いてもよい。なお、透明粒子の透明性は全光線透過率で10％以上であり、透明性の光波長依存性は遮光膜の無彩色化に寄与するのであれば着色していても使用可能である。   The cured resin and / or curable monomer was cured by light or heat, which was included as the component (A) and became a matrix of black light-shielding particles in the component (B) and transparent particles in the component (C). The cured product of component (A) has a refractive index that depends on the chemical structure and is preferably in the range of 1.48 to 1.6. Accordingly, the refractive index of the component constituting the transparent particles of component (C) is not more than the refractive index of the cured product of component (A), preferably in the range of 1.40 to 1.60, more preferably 1.42 to 1.55. In the present invention, the “refractive index of the cured product of the component (A)” refers to the black light-shielding particles in the component (B) and the transparent in the component (C) from the black resin composition for the light-shielding film of the present invention. This is the refractive index of the cured product obtained by curing the coating film forming component of the light-shielding film, excluding particles and solvents that are removed during the curing process, and the curing agent and polymerization to cure the component (A) with light or heat. When an initiator or the like is allowed to coexist, it is the refractive index of the cured product including them. When the refractive index of the transparent particles in the component (C) exceeds the “refractive index of the cured product of the component (A)”, the effect of reducing the reflectance is lost. The refractive index of components used as known transparent particles is 1.44 to 1.50 for silica, 1.47 to 1.60 for acrylic resin and epoxy resin, and 1.40 to 1.45 for silicone resin. These may be used alone or in combination of two or more. It should be noted that the transparency of the transparent particles is 10% or more in terms of the total light transmittance, and the transparency can be used even if it is colored as long as it contributes to the achromatic color of the light shielding film.

更に、（C）成分中の透明粒子は、その平均二次粒子径ＤＣが、（B）成分中の黒色遮光性粒子の平均二次粒子径ＤＢとの比ＤＣ／ＤＢが0.2〜1.0の範囲であり、また、前記組成物中における（Ｃ）成分中の透明粒子の質量ｍＣと、（Ｂ）成分中の黒色遮光性粒子の質量ｍＢとの比ｍＣ／ｍＢが0.015〜0.20、好ましくは0.03〜0.10、より好ましくは0.03〜0.09の範囲で用いられる。平均二次粒子径ＤＣは、分散溶媒又は相当の溶媒にて希釈し動的光散乱法で測定され、キュムラント法により求められる平均粒子径の値である。例えば、シリカ粒子ではメタノール中1〜10質量％粒子濃度での測定値である。平均二次粒子径比ＤＣ／ＤＢが1.0を超えると、形成した遮光膜表面の平滑性に好ましくなく、また遮光率（OD／μｍ）が低下する。また、ＤＣ／ＤＢが0.2を下回ると形成した遮光膜の反射率低減効果が弱まる。組成物中における質量比ｍＣ／ｍＢが0.015を下回ると形成した遮光膜の反射率の低減効果は見られず、また、0.20を超えると遮光膜の遮光率（OD／μｍ）が低下する。なお、特に、遮光率（OD／μｍ）を大きくするために（Ｂ）成分を多く用いる場合には、（Ａ）の光若しくは熱により硬化する成分の構成比率が減少することになり、マトリックスの硬化物性が所望のレベルに達しないとか、フォトリソグラフィー法でのパターン形成が十分にできないといった問題が生じやすくなるので、本発明においては、（Ｃ）成分中の透明粒子の添加量が少なくても反射率を低減でき非常に有用である。 Further, the transparent particles in the component (C) has an average secondary particle diameter D C is the ratio D C / D B and the average secondary particle diameter D B of the black light-shielding particles in component (B) 0.2 The ratio m C / m B between the mass m C of the transparent particles in the component (C) and the mass m B of the black light-shielding particles in the component (B) in the composition. Is used in the range of 0.015-0.20, preferably 0.03-0.10, and more preferably 0.03-0.09. The average secondary particle diameter D C is measured by a dynamic light scattering method was diluted with a dispersion solvent or equivalent solvents, the average value of the particle diameter determined by cumulant method. For example, in the case of silica particles, the measured value is 1 to 10% by mass particle concentration in methanol. When the average secondary particle diameter ratio D C / D B exceeds 1.0, no preferable smoothness of the formed light-shielding film surface and the light blocking ratio (OD / [mu] m) is decreased. Further, D C / D B is weakened reflectance reducing effect of the light-shielding film formed to be below 0.2. When the mass ratio m C / m B in the composition is less than 0.015, the effect of reducing the reflectance of the formed light shielding film is not observed, and when it exceeds 0.20, the light shielding ratio (OD / μm) of the light shielding film is lowered. . In particular, when a large amount of the component (B) is used in order to increase the light shielding rate (OD / μm), the component ratio of the component (A) that is cured by light or heat decreases, In the present invention, the cured physical properties do not reach a desired level, or the problem that the pattern formation by the photolithography method cannot be sufficiently caused. Therefore, in the present invention, even if the addition amount of the transparent particles in the component (C) is small The reflectance can be reduced, which is very useful.

本組成物を硬化した遮光膜として構成される遮光膜付基板において反射低減効果を発現するするメカニズムとして以下が推測される。すなわち、遮光膜は溶剤を含む遮光性樹脂組成物を透明基板上片面に塗布し、乾燥後、硬化させて遮光膜を作成する。乾燥後の塗膜において、ムラがなく、また表面が平滑である場合、塗膜内部では低粘性体である（A）成分がマトリックスとなって、弾性体である（Ｂ）成分中の黒色遮光性粒子がそれに分散した形態となる。乾燥過程においては、塗膜内では溶剤が揮発するに従い、膜厚方向に体積収縮していくが、分散している粒子間の溶剤が排除されて粒子間距離が縮んでいく。透明基板と塗布された組成物との界面においても同様である。この時の硬化性樹脂及びモノマー成分は弾性体である黒色遮光性粒子に比較すると粘性が高い粘性体であるために分散している粒子間で変形・収縮し、最終的に硬化によって黒色遮光性粒子の位置が固定化される。このような遮光膜付基板において透明基板側から入射した光の一部は、専ら透明基板界面とその近傍の遮光膜内では黒色遮光性粒子〔カーボンブラックの屈折率は約２で（A）成分の硬化物の屈折率より十分に高い〕により反射及び散乱されて透明基板側に出てくる。したがって、組成物中の黒色遮光性粒子濃度を高めていくと、この黒色遮光性粒子による反射／散乱が増加していくことになる。一方、透明粒子を共存させると、黒色遮光性粒子と同様な弾性をもった透明粒子は（A）成分に比較して変形することなく黒色遮光性粒子間及び透明基板と黒色遮光性粒子間とに存在すると考える。したがって、黒色遮光性粒子よりも屈折率の低い透明粒子による反射／散乱は少なくなり、また透明基板界面に存在する透明粒子に入射した光はさらに周辺の黒色遮光性粒子により吸収されていくことになり、この吸収はある程度の膜厚が厚いほうが有効と想定される。   The following is presumed as a mechanism for exhibiting a reflection reducing effect in a substrate with a light shielding film configured as a light shielding film obtained by curing the present composition. That is, the light-shielding film is formed by applying a light-shielding resin composition containing a solvent on one side of a transparent substrate, drying and curing the light-shielding film. In the coating film after drying, when there is no unevenness and the surface is smooth, the (A) component which is a low-viscosity material becomes a matrix inside the coating film, and the black light shielding in the (B) component which is an elastic body The particles are dispersed in the particles. In the drying process, as the solvent volatilizes in the coating film, the volume shrinks in the film thickness direction, but the solvent between the dispersed particles is eliminated and the distance between the particles is reduced. The same applies to the interface between the transparent substrate and the applied composition. The curable resin and monomer component at this time is a viscous material having a higher viscosity than the black light-shielding particles that are elastic bodies. The position of the particles is fixed. In such a substrate with a light-shielding film, a part of light incident from the transparent substrate side is exclusively black light-shielding particles [carbon black has a refractive index of about 2 and component (A) in the light-shielding film at and near the transparent substrate interface. The refractive index of the cured product is sufficiently higher than the refractive index of the cured product, and the light is reflected and scattered and comes out to the transparent substrate side. Therefore, when the concentration of the black light-shielding particles in the composition is increased, the reflection / scattering by the black light-shielding particles increases. On the other hand, when the transparent particles coexist, the transparent particles having the same elasticity as the black light-shielding particles are not deformed as compared with the component (A) and between the black light-shielding particles and between the transparent substrate and the black light-shielding particles. I think that exists. Therefore, reflection / scattering by transparent particles having a refractive index lower than that of the black light-shielding particles is reduced, and light incident on the transparent particles existing at the transparent substrate interface is further absorbed by the surrounding black light-shielding particles. Thus, it is assumed that this absorption is more effective when the film is thick to some extent.

以上の反射率低減のメカニズムを有効に発揮させるには、黒色遮光性粒子と共に透明粒子を組成物中及び透明基板上に塗布された膜中においても自己凝集することなく安定的に分散させる必要があると想定される。したがって、黒色遮光性粒子及び透明粒子の分散安定性を向上させる手段が有効であり、組成物の粘度安定性はその指標となると考えられる。本発明に用いられる（Ｃ）成分における透明粒子においては、粒子表面処理をすることでその再凝集を抑制することが有効である。   In order to effectively exhibit the above-described reflectance reduction mechanism, it is necessary to disperse the transparent particles together with the black light-shielding particles in the composition and in the film coated on the transparent substrate without self-aggregation. It is assumed that there is. Therefore, a means for improving the dispersion stability of the black light-shielding particles and the transparent particles is effective, and the viscosity stability of the composition is considered to be an index thereof. In the transparent particles in the component (C) used in the present invention, it is effective to suppress reaggregation by performing particle surface treatment.

例えば、本発明の(C)成分中の透明粒子として使用されるシリカは、分子内に反応性（メタ）アクリロイル基を有するシランカップリング剤で表面処理されたシリカであることが好ましく、コロイダルシリカを表面処理したシリカは特開昭５７−１３１２１４号公報、特開２０００−２８９１７２号公報等に記載の周知の手段で調製される。これら表面処理されたシリカは、モノアルキルエーテル、モノアルキルエーテルアセテートなどの溶剤中にて高分子分散剤の共存で比較的安定に分散させることが可能であり、分散液〔（Ｃ）成分〕として本遮光膜用黒色樹脂組成物に好適に供される。更に、前述のエチレン性不飽和基を有する（メタ）アクリレートなどの硬化性単量体中においても同様に表面処理されたシリカの分散を比較的容易に行うことができるので、溶剤に限らず光又は熱により硬化する硬化性単量体中に透明粒子を分散した形態で（Ｃ）成分とすることもできる。また、溶剤と硬化性単量体の混合物中、さらに硬化性樹脂を溶解した溶液中に分散させて用いることもできる。この表面処理されたシリカに用いるシリカ粒子は、一般的な気相反応又は液相反応といった製造法で製造され、形状（球状、非球状）に制限されることはないが、その電子顕微鏡観察による一次粒子径は20〜40nmである。これらシリカ粒子を公知の方法で表面処理し、さらに表面処理されたシリカを有機溶剤中でビーズミルにて分散させた分散液をメタノール中１〜10wt％に希釈したサンプルを用い、動的光散乱法で測定してキュムラント法により求められる平均二次粒子径が30〜100nm、好ましくは30〜60nmであるものが比較的容易に製造でき、本発明の（Ｃ）成分中の透明粒子として処方することができる。   For example, the silica used as the transparent particles in the component (C) of the present invention is preferably silica surface-treated with a silane coupling agent having a reactive (meth) acryloyl group in the molecule, and colloidal silica. The surface-treated silica is prepared by known means described in JP-A-57-13214, JP-A-2000-289172, and the like. These surface-treated silicas can be dispersed relatively stably in the presence of a polymer dispersant in a solvent such as monoalkyl ether or monoalkyl ether acetate. As a dispersion (component (C)) The black resin composition for the light shielding film is suitably used. Furthermore, since the surface-treated silica can be dispersed relatively easily in the curable monomer such as (meth) acrylate having an ethylenically unsaturated group as described above, the light is not limited to the solvent. Or it can also be set as (C) component with the form which disperse | distributed transparent particles in the curable monomer hardened | cured with a heat | fever. Moreover, it can also be used by being dispersed in a solution in which a curable resin is dissolved in a mixture of a solvent and a curable monomer. The silica particles used for the surface-treated silica are manufactured by a general manufacturing method such as a gas phase reaction or a liquid phase reaction, and are not limited to a shape (spherical or non-spherical). The primary particle size is 20-40 nm. A dynamic light scattering method using a sample obtained by surface-treating these silica particles by a known method and further diluting a dispersion obtained by dispersing the surface-treated silica in an organic solvent with a bead mill to 1 to 10 wt% in methanol. An average secondary particle size determined by the cumulant method measured by the method of 30 to 100 nm, preferably 30 to 60 nm, can be produced relatively easily, and is formulated as transparent particles in the component (C) of the present invention. Can do.

一方、黒色遮光性粒子であるカーボンブラックの平均二次粒子径ＤＢは、遮光性を有効に発揮させ分散安定性を確保するには、前述の通り60nm〜150nm、好ましくは80〜120nmである。したがって、表面処理シリカの平均二次粒子径は、カーボンブラックの平均二次粒子径以下に比較的容易に処方可能である。 On the other hand, the average secondary particle diameter D B of the carbon black as a black light-shielding particles, to ensure the dispersion stability is effectively exhibited a light-shielding property, as described above 60 nm to 150 nm, is preferably 80~120nm . Therefore, the average secondary particle diameter of the surface-treated silica can be formulated relatively easily below the average secondary particle diameter of carbon black.

更に（C）成分中の透明粒子として、アクリル樹脂粒子も好適であり、アクリル樹脂粒子としては、製造法や形状（球状、非球状、単核構造、コアシェル構造など）に制限されることはないが、凝集性が少なく分散性に優れたものとして、日本ペイント製架橋アクリル微粒子ファインスフェアシリーズ、特開２０１０−２５６５８９号公報記載のアクリル微粒子などを利用できる。   Furthermore, acrylic resin particles are also suitable as the transparent particles in component (C), and the acrylic resin particles are not limited to the production method or shape (spherical, non-spherical, mononuclear structure, core-shell structure, etc.). However, as those having low cohesiveness and excellent dispersibility, cross-linked acrylic fine particle fine sphere series manufactured by Nippon Paint, acrylic fine particles described in JP2010-256589A, and the like can be used.

本発明の必須成分の溶解又は分散を目的に１種又は複数種類の溶剤を含有させることができ、特に限定されるものではない。例えば、メタノール、エタノール、ｎ−プロパノール、イソプロパノール、エチレングリコール、プロピレングリコール等のアルコール類、α−もしくはβ−テルピネオール等のテルペン類等、アセトン、メチルエチルケトン、シクロヘキサノン、Ｎ−メチル−２−ピロリドン等のケトン類、トルエン、キシレン、テトラメチルベンゼン等の芳香族炭化水素類、セロソルブ、メチルセロソルブ、エチルセロソルブ、カルビトール、メチルカルビトール、エチルカルビトール、ブチルカルビトール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールエチルメチルエーテル、ジエチレングリコールジエチルエーテル等のグリコールエーテル類、酢酸エチル、酢酸ブチル、セロソルブアセテート、エチルセロソルブアセテート、ブチルセロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート等の酢酸エステル類等が挙げられ、これらを数種類用いて溶解、混合させることにより、黒色遮光性粒子や透明粒子等を安定的に分散させた均一な組成物とすることが出来る。   One or more kinds of solvents can be contained for the purpose of dissolving or dispersing essential components of the present invention, and are not particularly limited. For example, alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, terpenes such as α- or β-terpineol, etc., ketones such as acetone, methyl ethyl ketone, cyclohexanone, 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 Cole monoethyl ether, glycol ethers such as diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Acetic acid esters and the like can be used, and by dissolving and mixing them using several kinds of these, a uniform composition in which black light-shielding particles, transparent particles and the like are stably dispersed can be obtained.

また、本発明の遮光膜用黒色樹脂組成物には、必要に応じて硬化促進剤、熱重合禁止剤、酸化防止剤、可塑剤、レベリング剤、消泡剤、カップリング剤、界面活性剤等の添加剤を配合することができる。熱重合禁止剤としては、ハイドロキノン、ハイドロキノンモノメチルエーテル、ピロガロール、ｔｅｒｔ−ブチルカテコール、フェノチアジン等を挙げることができ、酸化防止剤としてはヒンダートフェノール系化合物等を挙げることができ、可塑剤としては、ジブチルフタレート、ジオクチルフタレート、リン酸トリクレジル等を挙げることができ、消泡剤やレベリング剤としては、シリコーン系、フッ素系、アクリル系の化合物を挙げることができる。また、界面活性剤としてはフッ素系界面活性剤、シリコーン系界面活性剤等を挙げることができる。   In addition, the black resin composition for the light-shielding film of the present invention includes a curing accelerator, a thermal polymerization inhibitor, an antioxidant, a plasticizer, a leveling agent, an antifoaming agent, a coupling agent, a surfactant and the like as necessary. Additives can be blended. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine and the like, examples of the antioxidant include hindered phenol compounds, and the plasticizer includes: Examples include dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like. Examples of the antifoaming agent and leveling agent include silicone-based, fluorine-based, and acrylic compounds. Examples of the surfactant include a fluorine-based surfactant and a silicone-based surfactant.

遮光膜用黒色樹脂組成物を透明基板上に塗布する方法として、公知の溶液浸漬法、スプレー法の他、インクジェット機、ローラーコーター機、ランドコーター機、スリットコーター機やスピナー機を用いる方法等の何れかの方法を採用することができる。良好な塗布膜を得るための適正粘度に溶剤により調整し、これらの方法によって、所望の厚さに塗布した後、加熱もしくは減圧下で溶剤を除去する（プリベーク）ことにより、乾燥塗膜が形成される。引き続き光及び／又は熱により硬化することで目的とする遮光膜付基板を作製する。   As a method of applying the black resin composition for the light-shielding film on the transparent substrate, in addition to a known solution dipping method and spray method, a method using an inkjet machine, a roller coater machine, a land coater machine, a slit coater machine, a spinner machine, etc. Either method can be adopted. After adjusting the viscosity to a suitable viscosity for obtaining a good coating film and applying to the desired thickness by these methods, the solvent is removed under heating or reduced pressure (prebaking) to form a dry coating film Is done. Subsequently, the target substrate with a light-shielding film is produced by curing with light and / or heat.

前述の遮光膜用黒色樹脂組成物を光又は熱により硬化して得られた本発明における遮光膜は、その遮光率ＯＤが2.8／μｍ以上となることが好ましく、そのような特性を有するような遮光膜用樹脂組成物が好ましく用いられる。タッチパネル用遮光膜ならびにカラーフィルター用ブラックマトリックスにおける遮光度（ＯＤ＝‐log[透過度]）はＯＤ4以上が要求され、一方で膜厚は3μｍ以下が好ましく、2μｍ以下の薄膜がより好ましい。理由は、タッチパネルでは、タッチパネル遮光膜上の金属配線とタッチパネル上導電膜との接続に際する断線防止、カラーフィルターでは、ブラックマトリックス上にＲＧＢ画素を形成した後の平坦性確保のためである。このような薄い遮光膜でも高い遮光度を得る目的で、例えばカーボンブラックを組成物中の全固形分に対して35質量％以上とすることで、遮光度2.8／μm以上の遮光膜を調製できる。一方、OD/μｍが2.8未満の遮光膜では、透明基板と遮光膜間で反射L*は5.5以下となって実質的に問題とならない。   The light shielding film in the present invention obtained by curing the above black resin composition for a light shielding film with light or heat preferably has a light shielding ratio OD of 2.8 / μm or more, and has such characteristics. A resin composition for a light shielding film is preferably used. The light shielding degree (OD = −log [transmittance]) in the light shielding film for touch panel and the black matrix for color filter is required to be OD4 or more, while the film thickness is preferably 3 μm or less, and more preferably 2 μm or less. The reason for this is to prevent disconnection when the metal wiring on the touch panel light-shielding film and the conductive film on the touch panel are connected in the touch panel, and to ensure flatness after the RGB pixels are formed on the black matrix in the color filter. For the purpose of obtaining a high degree of light shielding even with such a thin light shielding film, for example, by making carbon black 35% by mass or more based on the total solid content in the composition, a light shielding film having a light shielding degree of 2.8 / μm or more can be prepared. . On the other hand, with a light shielding film having an OD / μm of less than 2.8, the reflection L * between the transparent substrate and the light shielding film is 5.5 or less, which is not substantially problematic.

透明基板上に遮光膜パターンを形成する方法として、本発明の遮光膜用黒色樹脂組成物を透明基板上に塗布、乾燥した塗膜にフォトマスクを介して紫外線を照射し、未露光部分を現像液により除去し、更に加熱処理を行うという、フォトリソグラフィー法がある。また、スクリーン印刷法、凹版印刷、グラビア印刷法など転写版を使用して印刷する方法などがあり、更に近年ではインクジェット印刷法は、マスクや印刷版必要としないデジタル印刷方法として着目されている。本発明の遮光膜用黒色樹脂組成物はいずれの遮光膜パターン形成方法にも適用可能であり、各々の方法に適合した粘度、表面張力を有する樹脂組成物とするために、硬化性樹脂樹／硬化性モノマー（単量体）、ならびに溶剤や界面活性剤脂組成物を選定する。また、遮光膜パターンの精度や解像度等によって形成方法、印刷機等が選定される。特に本発明の遮光膜用黒色樹脂組成物では黒色遮光性粒子や透明粒子が安定的に分散されており、分散粒子の凝集による粗大粒子の発生がなく、また保存時の粘度安定性に優れているので、特にインクジェット印刷法やフォトリソグラフィー法に対して好ましく用いることができる。   As a method for forming a light-shielding film pattern on a transparent substrate, the black resin composition for light-shielding film of the present invention is applied on the transparent substrate, the dried coating film is irradiated with ultraviolet rays through a photomask, and an unexposed portion is developed. There is a photolithography method in which removal is performed with a liquid and further heat treatment is performed. In addition, there are methods such as screen printing, intaglio printing, and gravure printing for printing using transfer plates. In recent years, ink jet printing has attracted attention as a digital printing method that does not require a mask or printing plate. The black resin composition for a light-shielding film of the present invention can be applied to any light-shielding film pattern forming method. In order to obtain a resin composition having a viscosity and a surface tension suitable for each method, a curable resin resin / A curable monomer (monomer), a solvent and a surfactant fat composition are selected. Further, a forming method, a printing machine, and the like are selected depending on the accuracy and resolution of the light shielding film pattern. In particular, in the black resin composition for a light-shielding film of the present invention, black light-shielding particles and transparent particles are stably dispersed, there is no generation of coarse particles due to aggregation of dispersed particles, and the viscosity stability during storage is excellent. Therefore, it can be preferably used particularly for the ink jet printing method and the photolithography method.

例えば、本発明の遮光膜用黒色樹脂組成物を用いてインクジェット印刷法で遮光膜を形成する場合、黒色遮光性粒子及び透明粒子が再凝集することが少ないために間欠吐出時のインクジェットノズルの閉塞が少なく、また保存時における粘度が安定しているために連続印刷時のパターン膜厚の安定性に寄与する。インクジェット装置については、組成物の吐出液量が調整可能なものであれば特に制限はないが、一般的によく用いられる圧電素子のインクジェットヘッドにおいて、安定的に液滴が形成されるインキ組成物の物性は、ヘッドの構成によっても異なるが、ヘッド内部における温度において、粘度が３mPa・sec〜１５０mPa・secであるのが良く、好ましくは４mPa・sec〜３０mPa・secであるのが良い。粘度の値がこれよりも大きくなると液滴を吐出ができなくなり、反対に、粘度の値がこれよりも小さくなると液滴の吐出量が安定しない。また、ヘッド内部の温度は、用いるインキ組成物の安定性によっても異なるが、室温２０℃〜４５℃で用いるのが望ましい。なかでも、インキ組成物中の固形分を多くして膜厚を向上させるためには、安定吐出可能な粘度にするために３５〜４０℃程度の温度が一般に採用される。   For example, when a light shielding film is formed by the inkjet printing method using the black resin composition for a light shielding film of the present invention, the black light shielding particles and the transparent particles are less likely to reaggregate, so that the inkjet nozzle is blocked during intermittent ejection. In addition, since the viscosity during storage is stable, it contributes to the stability of the pattern film thickness during continuous printing. The ink jet device is not particularly limited as long as the amount of the discharged liquid of the composition can be adjusted. However, an ink composition that stably forms droplets in an ink jet head of a commonly used piezoelectric element. The physical properties vary depending on the configuration of the head, but at the temperature inside the head, the viscosity is preferably 3 mPa · sec to 150 mPa · sec, and preferably 4 mPa · sec to 30 mPa · sec. When the viscosity value is larger than this, it becomes impossible to discharge the droplets. Conversely, when the viscosity value is smaller than this value, the discharge amount of the droplets is not stable. The temperature inside the head varies depending on the stability of the ink composition to be used, but it is desirable to use it at room temperature of 20 ° C to 45 ° C. In particular, in order to increase the solid content in the ink composition and improve the film thickness, a temperature of about 35 to 40 ° C. is generally employed in order to obtain a stable dischargeable viscosity.

以上のようなインクジェット印刷法のための遮光膜用黒色樹脂組成物の特性は、これを構成する溶剤や界面活性剤により主に調整され、さらに連続印刷時におけるノズル部分における当該組成物の乾燥を抑制するために、溶剤は沸点180℃以上のものを主体とし、それを全溶剤成分中60％以上、好ましくは80％以上で、単独もしくは複数種を用いることができる。沸点180℃以上の溶媒としてはエチレングリコールモノメチルエーテルアセテート等のエチレングリコールモノアルキルエーテルアセテート類；ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル等のジエチレングリコールモノアルキルエーテル類；ジエチレングリコールモノ−ｎ−ブチルエーテルアセテート等のジエチレングリコールモノアルキルエーテルアセテート類；プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート等のプロピレングリコールモノアルキルエーテルアセテート類；ジエチレングリコールジメチルエーテル等の他のエーテル類、γ−ブチロラクトン等の高沸点溶剤類等を用いることができる。   The characteristics of the black resin composition for a light-shielding film for the ink jet printing method as described above are mainly adjusted by the solvent and the surfactant constituting the light-shielding film, and further the drying of the composition in the nozzle portion during continuous printing. In order to suppress it, the solvent is mainly composed of a solvent having a boiling point of 180 ° C. or higher, and it is 60% or more, preferably 80% or more, based on the total solvent components, and a single kind or a plurality of kinds can be used. Solvents having a boiling point of 180 ° C. or higher include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate; diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; diethylene glycol monoalkyl such as diethylene glycol mono-n-butyl ether acetate. Alkyl ether acetates; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, high-boiling solvents such as γ-butyrolactone, etc. it can.

一方、フォトリソグラフィー法では、本発明の遮光膜用黒色樹脂組成物は、黒色遮光性粒子及び透明粒子の再凝集による粗大粒子発生が少ないため、現像後のパターンエッジ直線性を良好にすることができる。この粗大粒子の発生抑制は、他のパターン形成法、例えば印刷版上に載せた印刷インキを透明基板上に転写する場合や、印刷パターンの表面異物やクレーター等の欠陥を低減するにも好適である。   On the other hand, in the photolithographic method, the black resin composition for a light shielding film of the present invention is less likely to generate coarse particles due to reaggregation of black light shielding particles and transparent particles, so that the pattern edge linearity after development can be improved. it can. The suppression of the generation of coarse particles is also suitable for other pattern formation methods, for example, when transferring printing ink placed on a printing plate onto a transparent substrate, and reducing defects such as surface foreign matter and craters on the printing pattern. is there.

フォトリソグラフィー法で用いる本発明の遮光膜用黒色樹脂組成物においては、(A)成分は、光硬化性樹脂及び／又は光硬化性モノマーであり、さらにアルカリ現像液に溶解させるためのアルカリ可溶性樹脂を混合する。アルカリ可溶性樹脂としては、例えば、メチルアクリレート、メチルメタクリレート、エチルアクリレート、エチルメタクリレート、ブチルアクリレート、ブチルメタクリレートなどのアルキルアクリレート又はアルキルメタクリレート、環状の官能基有するシクロヘキシルアクリレート又はシクロヘキシルメタクリレート、水酸基を有するヒドロキシエチルアクリレート又はヒドロキシエチルメタクリレート、スチレン等のモノマーの中から選ばれる２〜５種類のモノマーと、アクリル酸、メタクリル酸等のカルボキシル基を有する単量体（モノマー）とを用いて合成した、分子量５０００〜１０００００の共重合体であって、光硬化性の官能基は有さない（Ｅ）アルカリ可溶性樹脂を挙げることができる。   In the black resin composition for a light-shielding film of the present invention used in the photolithography method, the component (A) is a photocurable resin and / or a photocurable monomer, and is further an alkali-soluble resin for dissolving in an alkali developer. Mix. Examples of the alkali-soluble resin include alkyl acrylate or alkyl methacrylate such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, and butyl methacrylate, cyclohexyl acrylate or cyclohexyl methacrylate having a cyclic functional group, and hydroxyethyl acrylate having a hydroxyl group. Alternatively, a molecular weight of 5,000 to 100,000 synthesized using 2 to 5 types of monomers selected from monomers such as hydroxyethyl methacrylate and styrene and a monomer (monomer) having a carboxyl group such as acrylic acid and methacrylic acid. And (E) an alkali-soluble resin that does not have a photocurable functional group.

更に、アルカリ可溶性樹脂の好適な例としては、重合性不飽和基とカルボキシル基等の酸性基を分子内に有する重合性不飽和基含有アルカリ可溶性樹脂を挙げることができ、（A）成分の一種である光硬化性樹脂それ自体が当該重合性不飽和基含有アルカリ可溶性樹脂である場合も好ましく使用される。この際、前記の光硬化性の官能基を有しない（Ｅ）アルカリ可溶性樹脂を併用して使用することも可能である。重合性不飽和基含有アルカリ可溶性樹脂としては、例えば、(メタ)アクリル酸と(メタ)アクリル酸エステル化合物をラジカル共重合して得られた樹脂のカルボキシル基の一部に、(メタ)アクリル酸グリシジルのような重合性不飽和基とエポキシ基を1分子中に有する化合物を反応させて得られる重合性不飽和基含有アルカリ可溶性樹脂や、エポキシ樹脂に(メタ)アクリル酸を反応させて得られるエポキシ（メタ）アクリレート樹脂に酸無水物を付加して得られる重合性不飽和基含有アルカリ可溶性樹脂を始めとして広範な樹脂を用いることができる。   Furthermore, preferred examples of the alkali-soluble resin include a polymerizable unsaturated group-containing alkali-soluble resin having an acidic group such as a polymerizable unsaturated group and a carboxyl group in the molecule, and is a kind of component (A). The photocurable resin itself is preferably used also when it is the polymerizable unsaturated group-containing alkali-soluble resin. Under the present circumstances, it is also possible to use together (E) alkali-soluble resin which does not have the said photocurable functional group. Examples of the polymerizable unsaturated group-containing alkali-soluble resin include, for example, (meth) acrylic acid in a part of the carboxyl group of a resin obtained by radical copolymerization of (meth) acrylic acid and a (meth) acrylic ester compound. Obtained by reacting a polymerizable unsaturated group-containing alkali-soluble resin obtained by reacting a polymerizable unsaturated group such as glycidyl and an epoxy group in one molecule, or (meth) acrylic acid with an epoxy resin. A wide range of resins can be used, including polymerizable unsaturated group-containing alkali-soluble resins obtained by adding acid anhydrides to epoxy (meth) acrylate resins.

透明基板上に印刷された遮光膜の硬化方法ならびに硬化性樹脂成分（A）は、透明基板の耐熱性や使用される環境、要求される寸法精度、信頼性に適合するように選定される。   The method of curing the light-shielding film printed on the transparent substrate and the curable resin component (A) are selected so as to suit the heat resistance of the transparent substrate, the environment in which it is used, the required dimensional accuracy, and reliability.

以下、実施例等を挙げて本発明をさらに詳細に説明するが、本発明はこれらの実施例に限定されるものではない。   EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated further in detail, this invention is not limited to these Examples.

以下の実施例における各種評価は断りのない限り以下の通りに行った。
［固形分濃度］
後述の合成例中で得られた樹脂溶液１ｇをガラスフィルター〔質量：Ｗ0（ｇ）〕に含浸させて秤量し〔Ｗ1（ｇ）〕、１６０℃にて２hr加熱した後の質量〔Ｗ2（ｇ）〕から次式より求めた。
固形分濃度（質量％）＝100×(Ｗ2−Ｗ0)／(Ｗ1−Ｗ0) Various evaluations in the following examples were performed as follows unless otherwise noted.
[Solid content]
A glass filter [mass: W 0 (g)] was impregnated with 1 g of the resin solution obtained in the synthesis examples described below, weighed [W 1 (g)], and the mass after heating at 160 ° C. for 2 hours [W 2 (g)] was obtained from the following equation.
Solid content concentration (% by mass) = 100 × (W 2 −W 0 ) / (W 1 −W 0 )

［酸価］
樹脂溶液をジオキサンに溶解させ、電位差滴定装置〔平沼産業（株）製 商品名COM-1600〕を用いて1/10N−KOH水溶液で滴定して求めた。 [Acid value]
The resin solution was dissolved in dioxane and titrated with a 1/10 N-KOH aqueous solution using a potentiometric titrator (trade name COM-1600, manufactured by Hiranuma Sangyo Co., Ltd.).

［分子量］
ゲルパーミュエーションクロマトグラフィー（GPC）｛東ソー(株)製HLC-8220GPC、溶媒：テトラヒドロフラン、カラム：TSKgelSuperH-2000（２本）＋TSKgelSuperH-3000（１本）＋TSKgelSuperH-4000（１本）＋TSKgelSuper-H5000（１本）〔東ソー(株)製〕、温度：40℃、速度：0.6ml/min｝にて測定し、標準ポリスチレン〔東ソー(株)製ＰＳ−オリゴマーキット〕換算値として重量平均分子量(Mw)を求めた値である。 [Molecular weight]
Gel permeation chromatography (GPC) {HLC-8220GPC manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2) + TSKgelSuperH-3000 (1) + TSKgelSuperH-4000 (1) + TSKgelSuper-H5000 ( 1) [Tosoh Co., Ltd.], temperature: 40 ° C., speed: 0.6 ml / min}, measured as standard polystyrene [Tosoh Co., Ltd. PS-oligomer kit] converted value, weight average molecular weight (Mw) Is the value obtained.

［一次粒子径測定］
粒子含有溶液を粒子濃度0.1wt％程度に溶剤で希釈し、得られた分散液をカーボン支持膜付き金属性メッシュへ滴下して作成した測定用サンプルを、透過型電子顕鏡（ＴＥＭ；日本電子社製、ＪＥＭ−２０００ＥＸ）により観測して得られた粒子径を一次粒子径とした。 [Primary particle size measurement]
A measurement sample prepared by diluting a particle-containing solution with a solvent to a particle concentration of about 0.1 wt% and dropping the obtained dispersion onto a metallic mesh with a carbon support film was used as a transmission electron microscope (TEM; JEOL). The particle diameter obtained by observation with JEM-2000EX (manufactured by Kogyo Co., Ltd.) was defined as the primary particle diameter.

［平均二次粒子径測定］
得られた黒色遮光性粒子含有分散液又は透明粒子含有分散液について、動的光散乱法の粒度分布計（大塚電子株式会社製、粒径アナライザーFPAR-1000）により、キュムラント法により求められる平均二次粒子径をそれぞれ測定した。黒色遮光性粒子含有分散液は、プロピレングリコールモノメチルエーテルアセテート（PGMEA）にて分散された粒子の濃度が0.1〜0.5質量％となるように希釈して測定用サンプルとした。また、透明粒子を含有する分散液では測定可能な散乱強度となるように、メタノールにて粒子濃度が1〜10ｗ％に希釈して測定用サンプルとした。 [Average secondary particle size measurement]
The obtained black light-shielding particle-containing dispersion or transparent particle-containing dispersion was subjected to a mean particle size obtained by a cumulant method using a dynamic light scattering particle size distribution meter (particle size analyzer FPAR-1000, manufactured by Otsuka Electronics Co., Ltd.). Each secondary particle size was measured. The black light-shielding particle-containing dispersion was diluted so that the concentration of particles dispersed with propylene glycol monomethyl ether acetate (PGMEA) was 0.1 to 0.5% by mass to obtain a measurement sample. In addition, a dispersion sample containing transparent particles was diluted with methanol to a particle concentration of 1 to 10% by weight so that a measurable scattering intensity was obtained.

［粘度測定］
遮光膜用黒色樹脂組成物の粘度をＥ型粘度計（東機産業製、RE80L）でもって23℃で測定した。測定は、当該組成物の調製直後に行い、その後密封できる容器に移し、5℃冷蔵1か月保管後ならびに40℃で一週間加速エージング後、同様の条件にて粘度を測定し、初期粘度よりの粘度上昇を判定した。 [Viscosity measurement]
The viscosity of the black resin composition for a light shielding film was measured at 23 ° C. with an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., RE80L). Measurement is performed immediately after preparation of the composition, then transferred to a container that can be sealed, stored at 5 ° C for 1 month, and after accelerated aging at 40 ° C for 1 week, the viscosity is measured under the same conditions. The viscosity increase was determined.

［遮光度（OD値）測定］
ポストベーク後の遮光膜付ガラス基板を用いて、大塚電子製OD計で測定した。 [Shading (OD value) measurement]
Using a glass substrate with a light-shielding film after post-baking, measurement was performed with an OD meter manufactured by Otsuka Electronics.

［膜厚測定］
ポストベーク後の遮光膜付きガラス基板を、触針式膜厚計〔テンコール（株）製〕を用いて測定した。 [Film thickness measurement]
The glass substrate with a light-shielding film after post-baking was measured using a stylus-type film thickness meter [manufactured by Tencor Corporation].

[屈折率の測定]
アッベの屈折率計を用いて測定した。 [Measurement of refractive index]
Measured using an Abbe refractometer.

［反射光学特性の測定］
ポストベーク後の遮光膜付ガラス基板を用いて、遮光膜を形成した面の反対側の面側からコニカミノルタ社製の測色計CM2600dを用いて、D65光源、10°視野にて測定を行った。
また、反射率は、当該反射光学特性の測定で得られたL*の測定値より、以下の計算式により求めた。
反射率（％）＝{（L*+16）/116}３×１００ [Measurement of reflection optical characteristics]
Using a glass substrate with a light-shielding film after post-baking, measurement is performed from the opposite side of the surface on which the light-shielding film is formed using a Konica Minolta colorimeter CM2600d with a D65 light source and a 10 ° field of view. It was.
The reflectance was obtained from the measured value of L * obtained by the measurement of the reflection optical characteristic by the following calculation formula.
Reflectivity (%) = {(L * + 16) / 116} 3 × 100

［インクジェット吐出安定性試験］
遮光膜用黒色樹脂組成物をコニカミノルタIJ製ピエゾ素子駆動型インクジェットヘッド（14pL/drop；KM512M）に仕込み、パージ、インクジェットヘッド吐出面の洗浄実施後、当該組成物の吐出状態を30分間連続で飛翔観察カメラにて確認し、液滴が吐出しない、飛翔軌道が明らかに垂直でない等、著しい不具合がなければ○とした。さらに間欠吐出試験（インクジェットヘッド吐出面洗浄後30分間静置し、再吐出したときの不吐出ノズルの数をカウント）にて、全512ノズル中不吐出ノズルの数が10個未満を○、30個未満を△、30個以上を×とした。 [Inkjet ejection stability test]
The black resin composition for the light shielding film is charged into a Konica Minolta IJ piezo element driven inkjet head (14pL / drop; KM512M), purged, and the ejection surface of the inkjet head is cleaned. It was confirmed with a flight observation camera. If there were no significant problems such as no droplets being ejected or the flight trajectory was not clearly vertical, it was rated as “Good”. Furthermore, in the intermittent discharge test (counting the number of non-discharge nozzles when standing for 30 minutes after cleaning the discharge surface of the inkjet head and re-discharge), the number of non-discharge nozzles in all 512 nozzles is less than 10 ○, 30 Less than the number was Δ, and 30 or more were marked X.

［現像特性評価］
遮光膜用黒色樹脂組成物を、スピンコーターを用いて125ｍｍ×125ｍｍのガラス基板上に、ポストベーク後の膜厚が1.2μｍとなるように塗布し、80℃で１分間プリベークした。その後、露光ギャップを80μmに調整し乾燥塗膜の上に、ライン/スペース=20μm/20μmのネガ型フォトマスクを被せ、I線照度30mW/cm2の超高圧水銀ランプで１００mJ/cm2の紫外線を照射し感光部分の光硬化反応を行った。次に、この露光済み塗板を0.05％水酸化カリウム水溶液中、23℃にて1kgf/cm2圧シャワー現像を行い、パターンが観察された時間を現像抜け時間（BT秒）とし、さらに20秒の現像を行った後、5kgf/cm2圧のスプレー水洗を行い、塗膜の未露光部を除去しガラス基板上に画素パターンを形成し、その後、熱風乾燥機を用いて230℃にて30分間熱ポストベークした。各実施例、及び比較例における得られた遮光膜の評価項目と方法は以下の通りである。
パターン直線性ならびに塗膜表面の平滑性：ポストベーク後の20μｍラインを顕微鏡ならびにSEMで観察し、ギザツキが観測された場合を×、ない場合を○とした。また、粗大粒子によるライン膜厚にばらつきがある場合は、平滑性×と判定した。 [Development characteristics evaluation]
The black resin composition for a light shielding film was applied on a 125 mm × 125 mm glass substrate using a spin coater so that the film thickness after post-baking was 1.2 μm, and prebaked at 80 ° C. for 1 minute. Then, on the dried coating to adjust the exposure gap in 80 [mu] m, covered with a negative type photomask having a line / space = 20 [mu] m / 20 [mu] m, an ultrahigh-pressure mercury lamp of I-line irradiance 30 mW / cm 2 for 100 mJ / cm 2 UV The photocuring reaction of the photosensitive part was performed. Next, this exposed coated plate was subjected to 1 kgf / cm 2 pressure shower development in a 0.05% aqueous potassium hydroxide solution at 23 ° C., and the time during which the pattern was observed was defined as the development omission time (BT seconds). After development, spray water washing with 5 kgf / cm 2 pressure, remove the unexposed part of the coating film to form a pixel pattern on the glass substrate, and then use a hot air dryer at 230 ° C. for 30 minutes Heat post-baked. Evaluation items and methods of the obtained light shielding film in each Example and Comparative Example are as follows.
Pattern linearity and smoothness of the coating film surface: The 20 μm line after post-baking was observed with a microscope and SEM. Moreover, when there was variation in the line film thickness due to coarse particles, it was determined as smoothness x.

次に、実施例で用いた樹脂の合成例を示すが、まず、以下の合成例、実施例中で用いる略号について示す。
BPFE：9,9-ビス（4-ヒドロキシフェニル）フルオレンとクロロメチルオキシランとの反応物。
BPDA：3,3',4,4'-ビフェニルテトラカルボン酸二無水物
THPA：1,2,3,6-テトラヒドロフタル酸無水物
TPP：トリフェニルホスフィン
PGMEA：プロピレングリコールモノメチルエーテルアセテート
BDGAC：ジエチレングリコールモノブチルエーテルアセテート
DPHA：ジペンタエリスリトールヘキサアクリレートとジペンタエリスリトールペンタアクリレートとの混合物〔日本化薬（株）製商品名DPHA〕
HDDA:1,6-ヘキサンジオールジアクリレート
TMPTA：トリメチロールプロパントリアクリレート Next, although the synthesis example of resin used in the Example is shown, first, the following synthesis examples and abbreviations used in the examples are shown.
BPFE: Reaction product of 9,9-bis (4-hydroxyphenyl) fluorene and chloromethyloxirane.
BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride
THPA: 1,2,3,6-tetrahydrophthalic anhydride
TPP: Triphenylphosphine
PGMEA: Propylene glycol monomethyl ether acetate
BDGAC: Diethylene glycol monobutyl ether acetate
DPHA: A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate [trade name DPHA manufactured by Nippon Kayaku Co., Ltd.]
HDDA: 1,6-hexanediol diacrylate
TMPTA: Trimethylolpropane triacrylate

［合成例１］
還留冷却器付き500ml四つ口フラスコ中に、BPFE 78.63g（0.17mol）、アクリル酸24.50g（0.34mol）、TPP 0.45g、及びPGMEA 114gを仕込み、100〜105℃の加熱下で12hr撹拌し、反応生成物を得た。
次いで、得られた反応生成物にBPDA 25.01g（0.085mol）及びTHPA 12.93g（0.085mol）を仕込み、120〜125℃の加熱下で6hr撹拌し、重合性不飽和基含有アルカリ可溶性樹脂溶液（A）-１を得た。得られた樹脂溶液の固形分濃度は55.8wt%であり、酸価（固形分換算）は103mgKOH/gであり、GPC分析によるMwは2600であった。 [Synthesis Example 1]
In a 500 ml four-necked flask with a reflux condenser, charge 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 stir for 12 hours under heating at 100 to 105 ° C. As a result, a reaction product was obtained.
Next, 25.01 g (0.085 mol) of BPDA and 12.93 g (0.085 mol) of THPA were added to the obtained reaction product, stirred for 6 hours under heating at 120 to 125 ° C., and an alkali-soluble resin solution containing a polymerizable unsaturated group ( A) -1 was obtained. The obtained resin solution had a solid content concentration of 55.8 wt%, an acid value (in terms of solid content) of 103 mg KOH / g, and an Mw of 2600 by GPC analysis.

［樹脂溶液の調製：A成分溶液］
以下の（A）成分を含有する樹脂溶液A1〜A3を調製した。この樹脂溶液A1〜A3をそれぞれ乾燥・硬化させた硬化物の屈折率は、いずれも1.50〜1.55であった。 [Preparation of resin solution: Component A solution]
Resin solutions A1 to A3 containing the following component (A) were prepared. The refractive indexes of the cured products obtained by drying and curing the resin solutions A1 to A3 were 1.50 to 1.55, respectively.

（１）樹脂溶液A1（インクジェット印刷用―１）：光硬化型樹脂組成物
BDGAC 86.9質量部、ウレタンアクリレート〔共栄社化学（株）製商品名UA-306H〕10.0質量部、光開始剤ＯＸＥ−０２（ＢＡＳＦ製）0.75質量部、ビックケミー・ジャパン（株）製商品名 BYK（登録商標）-333の10% BDGAC希釈溶液を1.23質量部、3-ウレイドプロピルトリエトキシシラン〔信越化学工業（株）製商品名 KBE-585〕1.14質量部を混合し、１μｍデプスフィルターによって加圧ろ過を行い、樹脂溶液A1を調製した。 (1) Resin solution A1 (for inkjet printing-1): photocurable resin composition
BDGAC 86.9 parts by mass, urethane acrylate [trade name UA-306H, manufactured by Kyoeisha Chemical Co., Ltd.] 10.0 parts by mass, photoinitiator OXE-02 (manufactured by BASF) 0.75 part by mass, product name BYK (registered by BYK Japan) Trademark) -333 10% BDGAC diluted solution 1.23 parts by mass, 3-ureidopropyltriethoxysilane (trade name KBE-585, manufactured by Shin-Etsu Chemical Co., Ltd.) 1.14 parts by mass, and pressure filtration through a 1 μm depth filter To prepare a resin solution A1.

（２）樹脂溶液A2（インクジェット印刷用−２）：熱硬化型樹脂組成物
BDGAC 82.9質量部、合成例１で得られた重合性不飽和基含有アルカリ可溶性樹脂溶液（A）-１ 6.3質量部、フェノールノボラック型エポキシ樹脂〔三菱化学（株）製商品名JER154、エポキシ当量１７８、１分子中の平均官能基数３．０〕3.2質量部、DPHA 4.0質量部、ビックケミー・ジャパン（株）製商品名 BYK（登録商標）-333の10% BDGAC希釈溶液を1.24質量部、3-ウレイドプロピルトリエトキシシラン〔信越化学工業（株）製商品名 KBE-585〕2.95質量部を混合し、樹脂溶液A2を調製した。 (2) Resin solution A2 (for inkjet printing-2): thermosetting resin composition
BDGAC 82.9 parts by mass, polymerizable unsaturated group-containing alkali-soluble resin solution (A) -1 obtained in Synthesis Example 1 6.3 parts by mass, phenol novolac type epoxy resin [trade name JER154 manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 178 Average number of functional groups in one molecule 3.0] 3.2 parts by mass, 4.0 parts by mass of DPHA, 1.24 parts by mass of 10% BDGAC diluted solution of BYK (registered trademark) -333 manufactured by BYK Japan KK 2.95 parts by mass of ureidopropyltriethoxysilane [trade name KBE-585, manufactured by Shin-Etsu Chemical Co., Ltd.] were mixed to prepare a resin solution A2.

（３）樹脂溶液A3（フォトリソグラフィー用）：光硬化型樹脂組成物
PGMEA 78.7質量部、合成例１で得られた重合性不飽和基含有アルカリ可溶性樹脂溶液（A）-１ 12.3質量部、DPHA 2.41質量部、光重合開始剤ＯＸＥ−０２（ＢＡＳＦ製）0.81質量部、ビックケミー・ジャパン（株）製商品名 BYK（登録商標）-333の10%BDGAC希釈溶液を1.24質量部、3-ウレイドプロピルトリエトキシシラン〔信越化学工業（株）製商品名 KBE-585〕2.95質量部を混合し、樹脂溶液A3を調製した。 (3) Resin solution A3 (for photolithography): photocurable resin composition
PGMEA 78.7 parts by mass, polymerizable unsaturated group-containing alkali-soluble resin solution (A) -1 obtained in Synthesis Example 1 12.3 parts by mass, DPHA 2.41 parts by mass, photopolymerization initiator OXE-02 (manufactured by BASF) 0.81 parts by mass 1.24 parts by weight of 10% BDGAC diluted solution of BYK (registered trademark) -333 manufactured by BYK Japan KK, 3-ureidopropyltriethoxysilane [trade name KBE-585 manufactured by Shin-Etsu Chemical Co., Ltd.] 2.95 Mass parts were mixed to prepare a resin solution A3.

[黒色遮光性粒子含有分散液の調製：B成分]
（１）カーボンブラック分散液B1(インクジェット印刷用)：BDGAC中でカーボンブラック濃度２５質量％、分散樹脂〔樹脂溶液（Ａ）−１中の樹脂成分〕として8質量％、高分子分散剤2質量％となるようにしてビーズミル中にて分散を行い、カーボンブラック分散液B1とした。得られた分散液中のカーボンブラック平均二次粒子径は106nmであった。
（２）カーボンブラック分散液B2（フォトリソグラフィー用）：PGMEA中でカーボンブラック濃度２５質量％、分散樹脂〔樹脂溶液（Ａ）−１中の樹脂成分〕8質量％、高分子分散剤２質量％となるようにしてビーズミル中にて分散を行い、カーボンブラック分散液B2とした。得られた分散液中のカーボンブラック平均二次粒子径は98nmであった。 [Preparation of dispersion containing black light-shielding particles: Component B]
(1) Carbon black dispersion B1 (for inkjet printing): carbon black concentration in BDGAC is 25% by mass, 8% by mass as dispersion resin [resin component in resin solution (A) -1], 2% polymer dispersant % Was dispersed in a bead mill to obtain a carbon black dispersion B1. The carbon black average secondary particle diameter in the obtained dispersion was 106 nm.
(2) Carbon black dispersion B2 (for photolithography): carbon black concentration in PGMEA 25% by mass, dispersion resin [resin component in resin solution (A) -1] 8% by mass, polymer dispersant 2% by mass In this manner, dispersion was performed in a bead mill to obtain a carbon black dispersion B2. The carbon black average secondary particle diameter in the obtained dispersion was 98 nm.

[透明粒子含有分散液の調製：C成分]
シリカの屈折率は1.45（文献値）、アルミナの屈折率は1.74（文献値）を用いた。調製した分散液の特性を表1に示した。
（１）シリカ分散液C１：日産化学工業（株）製コロイダルシリカをγ−メタクリロキシプロピルトリメトキシシランにて表面処理し、この表面処理されたシリカが50質量％濃度になるように高分子分散剤5質量％と共にHDDA中にビーズミルにて分散を行い、シリカ分散液C1とした。
（２）シリカ分散液C２：日産化学工業（株）製コロイダルシリカをγ−メタクリロキシプロピルトリメトキシシランにて表面処理し、この表面処理されたシリカが30質量％濃度になるように高分子分散剤3質量％と共にDPHA中にてビーズミルにて分散を行いシリカ分散液C２とした。
（３）シリカ分散液C3：日産化学工業（株）製コロイダルシリカをγ−メタクリロキシプロピルトリメトキシシランにて表面処理したシリカの濃度が30質量％になるように、高分子分散剤3質量％と共にTMPTA中にてビーズミルにて分散を行いシリカ分散液C4とした。
（４）シリカ分散液C3：粒状シリカ（日本アエロジル社製アエロジル）が濃度20質量％になるように高分子分散剤10質量％と共にPGMEA中にてビーズミルにて分散を行い、シリカ分散液C3とした。
（５）アルミナ分散液C5：日産化学工業（株）製コロイダルアルミナをγ−メタクリロキシプロピルトリメトキシシランにて表面処理し、表面処理されたコロイダルアルミナの濃度が30質量％になるように、高分子分散剤3質量％と共にHDDA中にてビーズミルにて分散を行いアルミナ分散液C5とした。 [Preparation of transparent particle-containing dispersion: Component C]
The refractive index of silica was 1.45 (reference value), and the refractive index of alumina was 1.74 (reference value). The characteristics of the prepared dispersion are shown in Table 1.
(1) Silica dispersion C1: Colloidal silica manufactured by Nissan Chemical Industries, Ltd. is surface-treated with γ-methacryloxypropyltrimethoxysilane, and polymer dispersion is performed so that the surface-treated silica has a concentration of 50% by mass. Dispersed in HDDA with a bead mill together with 5% by mass of the agent to obtain silica dispersion C1.
(2) Silica dispersion C2: Colloidal silica manufactured by Nissan Chemical Industries, Ltd. is surface-treated with γ-methacryloxypropyltrimethoxysilane, and polymer dispersion is performed so that the surface-treated silica has a concentration of 30% by mass. Dispersion was carried out in DPHA together with 3% by mass of the agent in a bead mill to obtain silica dispersion C2.
(3) Silica dispersion C3: 3% by mass of polymer dispersant so that the concentration of silica obtained by surface treatment of colloidal silica manufactured by Nissan Chemical Industries, Ltd. with γ-methacryloxypropyltrimethoxysilane is 30% by mass At the same time, it was dispersed in TMPTA with a bead mill to obtain silica dispersion C4.
(4) Silica dispersion C3: Disperse in a PGMEA using a bead mill with 10% by weight of a polymeric dispersant so that the granular silica (Aerosil manufactured by Nippon Aerosil Co., Ltd.) has a concentration of 20% by weight. did.
(5) Alumina dispersion C5: surface-treated colloidal alumina manufactured by Nissan Chemical Industries, Ltd. with γ-methacryloxypropyltrimethoxysilane, so that the concentration of the surface-treated colloidal alumina is 30% by mass. Alumina dispersion C5 was obtained by dispersing it in a bead mill in HDDA together with 3% by mass of molecular dispersant.

［遮光膜用黒色樹脂組成物およびその遮光膜の調製ならびに評価］
［実施例1］
樹脂溶液A2を14.5質量部、カーボンブラック分散液B1を15質量部、シリカ分散液C1を0.5質量部で混合し（全30質量部）、１μｍデプスフィルターによって加圧ろ過を行い、遮光膜用黒色樹脂組成物を調製した。調製した当該組成物の初期粘度（室温）は10.3mPa・secだった。この遮光膜用黒色樹脂組成物を無アルカリガラス上にスピンコートにて回転数を変えて塗布し、これらを90℃にて5分間乾燥、さらに230℃にて30分間ポストベークして遮光膜付ガラス基板を作成した。 [Black resin composition for light shielding film and preparation and evaluation of the light shielding film]
[Example 1]
Mix 14.5 parts by weight of resin solution A2, 15 parts by weight of carbon black dispersion B1, and 0.5 parts by weight of silica dispersion C1 (total 30 parts by weight). A resin composition was prepared. The prepared composition had an initial viscosity (room temperature) of 10.3 mPa · sec. This black resin composition for light-shielding film was applied on non-alkali glass by changing the number of rotation by spin coating, dried at 90 ° C for 5 minutes, and further post-baked at 230 ° C for 30 minutes to provide a light-shielding film. A glass substrate was created.

［実施例2〜3、比較例１〜３］
前述の樹脂溶液Ａ２及びカーボンブラック分散液B1と透明粒子含有分散液を表２〜３に示す質量部にて混合して遮光膜用黒色樹脂組成物を調製し、実施例1と同様にして粘度測定を行った。更にこの遮光膜用黒色樹脂組成物を無アルカリガラス上に塗布し、90℃にて5分間乾燥、さらに230℃にて30分間ポストベークして遮光膜付ガラス基板を作成した。結果を表２〜３に示す。
実施例１〜３における遮光膜付ガラス基板では、透明粒子を含まない比較例1の遮光膜付ガラス基板に比べ、同じカーボンブラック濃度にもかかわらず反射率を下げることができた。一方、アルミナ粒子（屈折率文献値1.74）を含有する比較例2の遮光膜付ガラス基板では反射率の低減は見られなかった。また平均二次粒子径がカーボンブラック粒子のそれよりも大きいシリカ粒子を用いた比較例３においては、遮光膜付ガラス基板の反射率は低減するものの、その硬化膜表面をSEMで観察したところ凝集粒子によるところの硬化膜表面の突起物が観察され、好ましくなく、膜厚にもばらつきがみられた。また遮光膜用黒色樹脂組成物においてはその40℃保管時の粘度が初期値に比較して著しい増粘があり、さらにインクジェット吐出試験においてノズルつまりが発生した。 [Examples 2 to 3, Comparative Examples 1 to 3]
A black resin composition for a light-shielding film was prepared by mixing the resin solution A2 and the carbon black dispersion B1 and the transparent particle-containing dispersion in parts by mass shown in Tables 2 to 3, and the viscosity was the same as in Example 1. Measurements were made. Further, this black resin composition for a light shielding film was applied on non-alkali 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 results are shown in Tables 2-3.
In the glass substrates with light-shielding films in Examples 1 to 3, the reflectance could be lowered in spite of the same carbon black concentration as compared with the glass substrate with light-shielding film in Comparative Example 1 that did not contain transparent particles. On the other hand, in the glass substrate with a light-shielding film of Comparative Example 2 containing alumina particles (refractive index document value 1.74), no reduction in reflectance was observed. In Comparative Example 3 using silica particles having an average secondary particle diameter larger than that of carbon black particles, the reflectance of the glass substrate with a light-shielding film was reduced, but the cured film surface was observed by SEM and aggregated. Protrusions on the surface of the cured film due to the particles were observed, which was not preferable and the film thickness varied. Further, in the black resin composition for a light shielding film, the viscosity at the time of storage at 40 ° C. was remarkably increased as compared with the initial value, and nozzle clogging occurred in the ink jet discharge test.

［実施例４］
樹脂溶液Ａ１を14.5質量部、カーボンブラック分散液B1を15質量部、シリカ分散液C1を0.5質量部で混合し（全30質量部）、１μｍデプスフィルターによって加圧ろ過を行い、遮光膜用黒色樹脂組成物を調製した。調製した当該組成物の初期粘度（室温）は10.0mPa・secだった。この遮光膜用黒色樹脂組成物を無アルカリガラス上にスピンコートにて回転数を変えて塗布し、90℃にて5分間乾燥、さらに紫外線露光1000mJ（365nm基準）、120℃にて30分ポストベークして遮光膜付ガラス基板を作成した。 [Example 4]
Mix 14.5 parts by weight of resin solution A1, 15 parts by weight of carbon black dispersion B1, and 0.5 parts by weight of silica dispersion C1 (total 30 parts by weight). A resin composition was prepared. The prepared composition had an initial viscosity (room temperature) of 10.0 mPa · sec. This black resin composition for light-shielding film was applied on non-alkali glass by changing the rotation speed by spin coating, dried at 90 ° C for 5 minutes, and further exposed to UV exposure 1000mJ (365nm standard), 120 ° C for 30 minutes. A glass substrate with a light shielding film was prepared by baking.

［実施例5〜6、比較例4〜6］
前述の樹脂溶液Ａ１及びカーボンブラック分散液B1と透明粒子含有分散液とを、表２〜３に示す質量部にて混合して遮光膜用黒色樹脂組成物を調製し、実施例１と同様にして粘度測定を行った。更にこの遮光膜用黒色樹脂組成物を無アルカリガラス上にスピンコートにて回転数を変えて塗布し、90℃にて5分間乾燥、さらに紫外線露光1000mJ（365nm基準）、120℃にて30分ポストベークして遮光膜付ガラス基板を作成した。
実施例4〜6における遮光膜付ガラス基板では、透明粒子を含まない比較例4に比べ、同じカーボンブラック濃度にもかかわらず反射率が低下した。一方、アルミナ粒子（屈折率文献値1.74）を含有する比較例5の遮光膜付ガラス基板では反射率の低減は見られなかった。また平均二次粒子径がカーボンブラック粒子のそれよりも大きいシリカ粒子を用いた比較例６においては、遮光膜付ガラス基板の反射率は低減するものの、その硬化膜表面の平滑性は好ましくなかった。 [Examples 5-6, Comparative Examples 4-6]
The resin solution A1 and the carbon black dispersion B1 and the transparent particle-containing dispersion were mixed in the parts by mass shown in Tables 2 to 3 to prepare a black resin composition for a light-shielding film. The viscosity was measured. Furthermore, this black resin composition for light-shielding film was applied on non-alkali glass by changing the number of rotations by spin coating, dried at 90 ° C for 5 minutes, further UV exposure 1000mJ (365nm standard), 120 ° C for 30 minutes A glass substrate with a light-shielding film was prepared by post-baking.
In the glass substrates with light-shielding films in Examples 4 to 6, the reflectance was lowered in spite of the same carbon black concentration as compared with Comparative Example 4 that did not contain transparent particles. On the other hand, in the glass substrate with a light-shielding film of Comparative Example 5 containing alumina particles (refractive index document value 1.74), no reduction in reflectance was observed. In Comparative Example 6 using silica particles having an average secondary particle diameter larger than that of carbon black particles, the reflectance of the glass substrate with a light-shielding film was reduced, but the smoothness of the cured film surface was not preferable. .

［実施例7、比較例7〜8］
全固形分濃度に対するカーボンブラック濃度を40質量％と変えて、実施例1ならびに比較例3及び比較例1と同様な遮光膜用黒色樹脂組成物を調製し、その粘度と遮光膜付ガラス基板の光学特性を評価した。結果を表２〜３に示す。
実施例7における遮光膜付ガラス基板では、透明粒子を含まない比較例8に比べ、同じカーボンブラック濃度にもかかわらず反射率を下げることができた。一方、平均二次粒子径がカーボンブラック粒子のそれよりも大きいシリカ粒子を用いた比較例7においては、遮光膜付ガラス基板の反射率は低減するものの、硬化膜表面をSEMで観察したところ凝集粒子によるところの硬化膜表面の突起物が観察され、好ましくなく、膜厚にばらつきがみられた。また遮光膜用黒色樹脂組成物においてはその40℃保管時の粘度が初期値に比較して著しい増粘があり、さらにインクジェット吐出試験においてノズルつまりが発生した。 [Example 7, Comparative Examples 7-8]
A black resin composition for a light shielding film similar to Example 1, Comparative Example 3 and Comparative Example 1 was prepared by changing the carbon black concentration relative to the total solid content concentration to 40% by mass. Optical properties were evaluated. The results are shown in Tables 2-3.
In the glass substrate with a light-shielding film in Example 7, the reflectance could be lowered despite the same carbon black concentration as compared with Comparative Example 8 that did not contain transparent particles. On the other hand, in Comparative Example 7 using silica particles whose average secondary particle diameter is larger than that of carbon black particles, the reflectance of the glass substrate with a light-shielding film is reduced, but when the cured film surface is observed with SEM, aggregation is observed. Protrusions on the surface of the cured film due to the particles were observed, which was not preferable and showed variations in film thickness. Further, in the black resin composition for a light shielding film, the viscosity at the time of storage at 40 ° C. was remarkably increased as compared with the initial value, and nozzle clogging occurred in the ink jet discharge test.

［実施例8及び比較例9〜10］
樹脂溶液A3及びカーボンブラック分散液B2としてフォトリソグラフィー向け遮光膜用黒色樹脂組成物を調製し、同様に粘度測定を行った。この遮光膜用黒色樹脂組成物を無アルカリガラス上にスピンコートにて塗布し、80℃にて5分間乾燥、石英マスクを通して紫外線露光100mJ（365nm基準）を行い、0.05％KOH水溶液中23℃にて40秒間浸漬／浸透し、更に230℃にて30分ポストベークして遮光膜付ガラス基板を作成した。結果を表４に示す。
実施例８における遮光膜付基板では、透明粒子を含まない比較例９に比べ、同じカーボンブラック濃度にもかかわらず反射率が低下した。一方、平均二次粒子径がカーボンブラック粒子のそれよりも大きいシリカ粒子を用いた比較例10においては、遮光膜付基板の反射率は低減するものの、硬化膜表面をSEMで観察したところ凝集粒子によるところの硬化膜表面の突起物が観察され、好ましくなく膜厚にばらつきがみられた。さらに20μｍラインのエッジ形状に、実施例8及び比較例9では観察されないギザツキが見られた。また遮光膜用黒色樹脂組成物においてはその40℃保管時の粘度が初期値に比較して増粘が見られた。 [Example 8 and Comparative Examples 9 to 10]
A black resin composition for a light-shielding film for photolithography was prepared as the resin solution A3 and the carbon black dispersion B2, and the viscosity was measured in the same manner. This black resin composition for a light-shielding film is applied onto an alkali-free glass by spin coating, dried at 80 ° C. for 5 minutes, exposed to ultraviolet light 100 mJ (365 nm standard) through a quartz mask, and kept at 23 ° C. in 0.05% KOH aqueous solution. For 40 seconds and then post-baked at 230 ° C. for 30 minutes to prepare a glass substrate with a light-shielding film. The results are shown in Table 4.
In the substrate with a light-shielding film in Example 8, the reflectance was lowered in spite of the same carbon black concentration as compared with Comparative Example 9 not including transparent particles. On the other hand, in Comparative Example 10 using silica particles having an average secondary particle size larger than that of carbon black particles, the reflectance of the substrate with the light shielding film was reduced, but the cured film surface was observed with an SEM. As a result, protrusions on the surface of the cured film were observed, and the film thickness was undesirably varied. Furthermore, a jaggedness that was not observed in Example 8 and Comparative Example 9 was observed in the edge shape of the 20 μm line. Further, in the black resin composition for a light shielding film, the viscosity when stored at 40 ° C. was increased compared to the initial value.

［実施例9〜１0］
樹脂溶液をA2及びカーボンブラック分散液B1とし、全固形分濃度に対するシリカ濃度（C1）を変えて遮光膜用黒色樹脂組成物を調製し、実施例1同様にして遮光膜付ガラス基板の光学特性を評価した。結果を表５に示す。いずれもシリカ分散液の添加により反射率が低下することが分かった。 [Examples 9 to 10]
The resin solution was A2 and carbon black dispersion B1, and the silica concentration (C1) with respect to the total solid content was changed to prepare a black resin composition for the light shielding film. The optical characteristics of the glass substrate with the light shielding film were the same as in Example 1. Evaluated. The results are shown in Table 5. In either case, it was found that the reflectance was lowered by the addition of the silica dispersion.

［実施例１１〜１２］
樹脂溶液をA3及びカーボンブラック分散液B2とし、全固形分濃度に対するシリカ濃度（C1）を変えて遮光膜用黒色樹脂組成物を調製し、実施例８と同様にして遮光膜付ガラス基板の光学特性を評価した。結果を表５に示す。いずれもシリカ分散液の添加により反射率が低下することが分かった。 [Examples 11 to 12]
The resin solution is A3 and the carbon black dispersion B2, and the silica concentration (C1) with respect to the total solid content is changed to prepare a black resin composition for the light shielding film. Characteristics were evaluated. The results are shown in Table 5. In either case, it was found that the reflectance was lowered by the addition of the silica dispersion.

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Claims (10)

（A）光若しくは熱による硬化性樹脂、及び／又は光若しくは熱による硬化性単量体、（B）分散媒中に黒色遮光性粒子が分散されてなる黒色遮光性粒子含有分散液、並びに（C）透明粒子を分散媒中に分散されてなる透明粒子含有分散液を必須成分とし、（C）成分中の透明粒子の平均二次粒子径ＤＣと、（B）成分中の黒色遮光性粒子の平均二次粒子径ＤＢとの比ＤＣ／ＤＢが0.2〜1.0の範囲であり、且つ（C）成分中の透明粒子の質量ｍＣと、（B）成分の黒色遮光性粒子の質量ｍＢとの質量比ｍＣ／ｍＢが0.015〜0.20の範囲であり、また、前記透明粒子の屈折率が、前記(A)成分の硬化物の屈折率以下であることを特徴とする遮光膜用黒色樹脂組成物。 (A) a curable resin by light or heat, and / or a curable monomer by light or heat, (B) a black light-shielding particle-containing dispersion in which black light-shielding particles are dispersed in a dispersion medium, and ( C) a transparent particles comprising the dispersed in a dispersion medium transparent particle-containing dispersion as an essential component, (C) an average secondary particle diameter D C of the transparent particles in component, (B) light shielding property in the component The ratio D C / D B to the average secondary particle diameter D B of the particles is in the range of 0.2 to 1.0, and the mass m C of the transparent particles in the component (C), and the black light-shielding particles of the component (B) The mass ratio m C / m B to the mass m B is 0.015 to 0.20, and the refractive index of the transparent particles is not more than the refractive index of the cured product of the component (A). A black resin composition for a light shielding film. 前記（C）成分中の透明粒子の屈折率が、1.55以下であることを特徴とする請求項１に記載の遮光膜用黒色樹脂組成物。   The black resin composition for a light-shielding film according to claim 1, wherein the refractive index of the transparent particles in the component (C) is 1.55 or less. 前記（B）成分中の黒色遮光性粒子がカーボンブラックであり、また、前記（C）成分中の透明粒子が、分子内に反応性（メタ）アクリロイル基を有するシランカップリング剤により表面処理されたシリカであることを特徴とする請求項１又は２に記載の遮光膜用黒色樹脂組成物。   The black light-shielding particles in the component (B) are carbon black, and the transparent particles in the component (C) are surface-treated with a silane coupling agent having a reactive (meth) acryloyl group in the molecule. The black resin composition for a light-shielding film according to claim 1, wherein the composition is silica. 前記（Ｃ）成分における前記分散媒が（メタ）アクリロイル基を有する硬化性単量体であると共に、前記透明粒子が分子内に（メタ）アクリロイル基を有するシランカップリング剤により表面処理されたシリカであることを特徴とする請求項１〜３のいずれかに記載の遮光膜用黒色樹脂組成物。   The silica in which the dispersion medium in the component (C) is a curable monomer having a (meth) acryloyl group, and the transparent particles are surface-treated with a silane coupling agent having a (meth) acryloyl group in the molecule. The black resin composition for a light-shielding film according to any one of claims 1 to 3. 光又は熱により硬化して得られた遮光膜の遮光率ＯＤが2.8／μｍ以上であることを特徴とする請求項１〜４のいずれかに記載の遮光膜用樹脂組成物。   5. The resin composition for a light shielding film according to claim 1, wherein a light shielding ratio OD of the light shielding film obtained by curing with light or heat is 2.8 / μm or more. 前記遮光膜用黒色樹脂組成物は、前記（Ｂ）成分及び（Ｃ）成分中の分散媒として、及び／又は追加成分としての（Ｄ）溶剤を含み、尚且つ当該（Ｄ）溶剤が沸点180℃以上の溶剤を主成分として含むことにより、インクジェット印刷用の遮光膜用黒色樹脂組成物として使用されるものであることを特徴とする請求項１〜５のいずれかに記載の遮光膜用黒色樹脂組成物。   The black resin composition for a light-shielding film contains a solvent (D) as a dispersion medium in the component (B) and the component (C) and / or an additional component, and the solvent (D) has a boiling point of 180. The black for a light-shielding film according to any one of claims 1 to 5, which is used as a black resin composition for a light-shielding film for ink-jet printing by containing a solvent at a temperature of ° C or higher as a main component. Resin composition. 前記遮光膜用黒色樹脂組成物は、前記（A)成分として光硬化性アルカリ可溶性樹脂及び／又は（E）アルカリ可溶性樹脂を含有することにより、フォトリソグラフィー法用の遮光膜用黒色樹脂組成物として使用されるものであることを特徴とする請求項１〜５のいずれかに記載の遮光膜用黒色樹脂組成物。   The black resin composition for a light-shielding film contains a photocurable alkali-soluble resin and / or (E) an alkali-soluble resin as the component (A), thereby providing a black resin composition for a light-shielding film for a photolithography method. The black resin composition for a light shielding film according to claim 1, wherein the black resin composition is used. 請求項１〜７のいずれかに記載の遮光膜用黒色樹脂組成物を透明基板上の片面に塗布又は印刷し、更に硬化させて得られる遮光膜付基板であり、硬化後の遮光膜の膜厚が1〜3μｍであることを特徴とする遮光膜付基板。   It is a board | substrate with a light shielding film obtained by apply | coating or printing the black resin composition for light shielding films in any one of Claims 1-7 on one side on a transparent substrate, and also making it harden | cure, The film | membrane of the light shielding film after hardening A substrate with a light-shielding film, wherein the thickness is 1 to 3 μm. 請求項８に記載の遮光膜付基板を有するカラーフィルター。   A color filter comprising the substrate with a light-shielding film according to claim 8. 請求項８に記載の遮光膜付基板を有するタッチパネル。   A touch panel comprising the substrate with a light-shielding film according to claim 8.
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