JP4712516B2 - Fine particle-containing composition, ink for forming colored film for display device, light shielding film for display device, light shielding material, substrate with light shielding film, color filter, liquid crystal display element, and liquid crystal display device - Google Patents
Fine particle-containing composition, ink for forming colored film for display device, light shielding film for display device, light shielding material, substrate with light shielding film, color filter, liquid crystal display element, and liquid crystal display device Download PDFInfo
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- JP4712516B2 JP4712516B2 JP2005305025A JP2005305025A JP4712516B2 JP 4712516 B2 JP4712516 B2 JP 4712516B2 JP 2005305025 A JP2005305025 A JP 2005305025A JP 2005305025 A JP2005305025 A JP 2005305025A JP 4712516 B2 JP4712516 B2 JP 4712516B2
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- display device
- fine particle
- fine particles
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- GBECUEIQVRDUKB-UHFFFAOYSA-M thallium monochloride Chemical compound [Tl]Cl GBECUEIQVRDUKB-UHFFFAOYSA-M 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/38—Esters containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/38—Esters containing sulfur
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/38—Esters containing sulfur
- C08F220/382—Esters containing sulfur and containing oxygen, e.g. 2-sulfoethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
-
- 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
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
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- Spectroscopy & Molecular Physics (AREA)
- Polymers & Plastics (AREA)
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- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Mathematical Physics (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials For Photolithography (AREA)
- Optical Filters (AREA)
- Liquid Crystal (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Description
本発明は、プラズマディスプレイ表示装置、EL表示装置、CRT表示装置など表示装置の内部に設けられる遮光用の膜(遮光膜)を作製するのに好適な微粒子含有組成物並びに、該微粒子含有組成物を用いた表示装置用着色膜形成用インク、表示装置用遮光膜、遮光材料、遮光膜付き基板、カラーフィルタ、液晶表示素子、及び液晶表示装置に関する。 The present invention relates to a fine particle-containing composition suitable for producing a light-shielding film (light-shielding film) provided inside a display device such as a plasma display device, EL display device, or CRT display device, and the fine particle-containing composition. The present invention relates to a colored film forming ink for display device, a light shielding film for display device, a light shielding material, a substrate with a light shielding film, a color filter, a liquid crystal display element, and a liquid crystal display device.
表示装置用途の遮光膜は、液晶表示装置、プラズマディスプレイ表示装置、EL表示装置、CRT表示装置などの装置内部に、黒色の縁や画素周囲の格子状、ストライプ状の黒色の縁部(いわゆるブラックマトリックス)、薄膜トランジスター(TFT)遮光のためのドット状、線状の黒色パターンなどとして設けられている。 A light-shielding film for use in a display device has a black edge, a grid around a pixel, a stripe-like black edge (so-called black edge) inside a liquid crystal display device, a plasma display device, an EL display device, a CRT display device, or the like. Matrix), thin film transistors (TFTs), which are provided as dot-like or linear black patterns for light shielding.
例えばブラックマトリックスは、液晶表示装置等を構成する遮光膜の例であり、液晶表示装置の内部に備えられたカラーフィルタの各着色画素(赤、緑、青)を取り囲むように設けられており、各画素間の光漏れによるコントラストの低下を防止するものである。また、他の例として、TFTを用いたアクティブマトリックス駆動方式の液晶表示素子において、光によるTFTの電流リークに伴なう画質低下を防ぐためにTFT上に設ける遮光膜がある。
これらの遮光膜には一般に、光学濃度2以上の遮光性が要求されており、遮光膜の色調は表示装置の表示品位の点から黒色が好ましい。
For example, a black matrix is an example of a light shielding film that constitutes a liquid crystal display device or the like, and is provided so as to surround each colored pixel (red, green, blue) of a color filter provided inside the liquid crystal display device. This prevents a decrease in contrast due to light leakage between pixels. As another example, in a liquid crystal display element of an active matrix driving system using TFTs, there is a light shielding film provided on the TFTs in order to prevent image quality degradation due to TFT current leakage due to light.
These light-shielding films are generally required to have a light-shielding property having an optical density of 2 or more, and the color tone of the light-shielding film is preferably black from the viewpoint of display quality of the display device.
上記に関連して、金属微粒子の分散物を利用して遮光膜を作製する方法に関する開示がある(例えば、特許文献1参照)。この方法では、金属微粒子の分散には一般に広く知られている分散剤が用いられている。 In relation to the above, there is a disclosure relating to a method of producing a light shielding film using a dispersion of metal fine particles (see, for example, Patent Document 1). In this method, a widely known dispersant is used for dispersing the metal fine particles.
また、ハロゲン化銀粒子の保護コロイドとして、ハロゲン化銀粒子と共にチオエーテル基を有する高分子化合物を用いた例がある(例えば、特許文献2〜4参照)。
しかしながら、上記した遮光膜の作製方法では、金属微粒子の分散に用いる分散剤は通常広く用いられるものであり、表示装置用遮光膜の用途としては、金属微粒子の分散が不充分で満足できる遮光性能は得られない。 However, in the above-described method for producing a light-shielding film, the dispersant used for dispersing the metal fine particles is usually widely used, and as a use for the light-shielding film for a display device, the light-shielding performance is satisfactory because the dispersion of the metal fine particles is insufficient. Cannot be obtained.
また、表示装置用途で遮光膜を作製する場合、製造工程上、高温に曝されること(例えば現像後のポストベーク)があるが、従来から広く知られた分散剤を用いた金属微粒子の分散系では、高温下で膜の色味が変化しやすく、所期の遮光性能や表示コントラストが得られないとの課題もある。 In addition, when producing a light-shielding film for use in a display device, it may be exposed to a high temperature in the manufacturing process (for example, post-baking after development), but dispersion of metal fine particles using a conventionally well-known dispersant. In the system, there is a problem that the color of the film is likely to change at a high temperature, and the desired light shielding performance and display contrast cannot be obtained.
本発明は、上記に鑑みなされたものであり、薄膜で優れた遮光性能が得られ、高温環境に曝された場合の色味変化が抑えられた微粒子含有組成物、表示装置用着色膜形成用インク、表示装置用遮光膜、遮光材料、及び遮光膜付き基板、並びに、高コントラストで鮮やかな画像表示が可能なカラーフィルタ、液晶表示素子、及び液晶表示装置を提供することを目的とし、該目的を達成することを課題とする。 The present invention has been made in view of the above, and a fine particle-containing composition capable of obtaining excellent light-shielding performance with a thin film and suppressing color change when exposed to a high-temperature environment, for forming a colored film for a display device An object of the present invention is to provide ink, a light shielding film for a display device, a light shielding material, a substrate with a light shielding film, a color filter capable of displaying a high-contrast and vivid image, a liquid crystal display element, and a liquid crystal display device. The goal is to achieve this.
本発明は、金属系の微粒子の分散剤としてチオエーテル構造を有する高分子を用いることが、分散した際の分散性及び分散後の分散安定性、並びに高温環境下における色味変化の抑止に有効であるとの知見を得、かかる知見に基づいて達成されたものである。前記課題を達成するための具体的手段は以下の通りである。 In the present invention, use of a polymer having a thioether structure as a dispersing agent for metal-based fine particles is effective for dispersibility when dispersed, dispersion stability after dispersion, and suppression of color change in a high temperature environment. It has been achieved based on such knowledge. Specific means for achieving the above object are as follows.
<1> 少なくとも、金属微粒子及び/又は金属化合物微粒子と、少なくとも1つのチオエーテル基を有する高分子化合物(以下、「本発明に係る高分子分散剤」ということがある。)と、熱もしくは光で硬化する化合物とを含有することを特徴とする微粒子含有組成物である。 <1> At least metal fine particles and / or metal compound fine particles, a polymer compound having at least one thioether group (hereinafter sometimes referred to as “polymer dispersant according to the present invention”), and heat or light. A fine particle-containing composition comprising a curing compound.
<2> 前記高分子化合物が、少なくとも一種のチオエーテル構造を側鎖に含むエチレン性不飽和単量体から誘導される繰り返し単位を有する前記<1>に記載の微粒子含有組成物である。
<3> 前記高分子化合物が、下記一般式(1)で表される繰り返し単位を少なくとも有する前記<1>又は<2>に記載の微粒子含有組成物である。
<2> The fine particle-containing composition according to <1>, wherein the polymer compound has a repeating unit derived from an ethylenically unsaturated monomer containing at least one thioether structure in the side chain.
<3> The fine particle-containing composition according to <1> or <2>, wherein the polymer compound has at least a repeating unit represented by the following general formula (1).
前記一般式(1)において、R1は、水素原子又は総炭素数1〜4のアルキル基を表し、R2は水素原子、総炭素数1〜18のアルキル基、総炭素数6〜14のアリール基、又は総炭素数7〜16のアラルキル基を表す。Zは、−O−又は−NH−を表し、Yは総炭素数1〜8の2価の連結基を表す。 In the general formula (1), R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms in total, R 2 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms in total, and 6 to 14 carbon atoms in total. An aryl group or an aralkyl group having 7 to 16 carbon atoms in total is represented. Z represents —O— or —NH—, and Y represents a divalent linking group having 1 to 8 carbon atoms in total.
<4> 前記高分子化合物が、酸基を更に有する前記<1>〜<3>のいずれか1つに記載の微粒子含有組成物である。
<5> 前記酸基が、カルボン酸基である前記<4>に記載の微粒子含有組成物である。
<6> 前記金属微粒子及び/又は金属化合物微粒子は、アスペクト比が2〜100である前記<1>〜<5>のいずれか1つに記載の微粒子含有組成物である。
<7> 多官能モノマーを更に含有する前記<1>〜<6>のいずれか1つに記載の微粒子含有組成物である。
<8> 光重合開始剤を更に含有する前記<1>〜<7>のいずれか1つに記載の微粒子含有組成物である。
<4> The fine particle-containing composition according to any one of <1> to <3>, wherein the polymer compound further has an acid group.
<5> The fine particle-containing composition according to <4>, wherein the acid group is a carboxylic acid group.
<6> The fine particle-containing composition according to any one of <1> to <5>, wherein the metal fine particles and / or the metal compound fine particles have an aspect ratio of 2 to 100.
<7> The fine particle-containing composition according to any one of <1> to <6>, further including a polyfunctional monomer.
<8> The fine particle-containing composition according to any one of <1> to <7>, further including a photopolymerization initiator.
<9> 前記<1>〜<8>のいずれか1つに記載の微粒子含有組成物を用いてなることを特徴とする表示装置用着色膜形成用インクである。
<10> 前記<1>〜<8>のいずれか1つに記載の微粒子含有組成物又は前記<9>に記載の表示装置用着色膜形成用インクを用いてなることを特徴とする表示装置用遮光膜である。
<11> 表示装置用遮光膜の形成に用いられる遮光材料であって、
支持体上に、アスペクト比が2〜100の金属微粒子及び/又は金属化合物微粒子と、少なくとも1つのチオエーテル基を有する高分子化合物と、熱もしくは光で硬化する化合物とを少なくとも含有する微粒子含有層を少なくとも1層有することを特徴とする遮光材料である。
<12> 多官能モノマーを更に含有する前記<11>に記載の遮光材料である。
<13> 光重合開始剤を更に含有する前記<11>又は<12>に記載の遮光材料である。
<14> 前記微粒子含有層が、被転写体への転写が可能な層である前記<11>〜<13>のいずれか1つに記載の遮光材料である。
<9> A colored film forming ink for a display device, comprising the fine particle-containing composition according to any one of <1> to <8>.
<10> A display device comprising the fine particle-containing composition according to any one of <1> to <8> or the colored film forming ink for display device according to <9>. It is a shading film for use.
<11> A light shielding material used for forming a light shielding film for a display device,
On a support, a fine particle-containing layer containing at least metal fine particles and / or metal compound fine particles having an aspect ratio of 2 to 100, a polymer compound having at least one thioether group, and a compound curable by heat or light. It is a light-shielding material having at least one layer.
<12> The light-shielding material according to <11>, further including a polyfunctional monomer.
<13> The light-shielding material according to <11> or <12>, further including a photopolymerization initiator.
<14> The light shielding material according to any one of <11> to <13>, wherein the fine particle-containing layer is a layer that can be transferred to a transfer target.
<15> 前記<1>〜<8>のいずれか1つに記載の微粒子含有組成物、前記<9>に記載の表示装置用着色膜形成用インク、又は前記<11>〜<14>のいずれか1つに記載の遮光材料を用いてなる遮光膜を有することを特徴とする遮光膜付き基板である。
<16> 光透過性の基板上に、互いに異なる色相を呈する複数の画素を含む画素群と、前記画素群を構成する各画素を離隔する遮光画像とを有するカラーフィルタにおいて、前記遮光画像が、前記<10>に記載の表示装置用遮光膜であることを特徴とするカラーフィルタである。
<17> 前記<15>に記載の遮光膜付き基板を備えたことを特徴とするカラーフィルタである。
<18> 前記<15>に記載の遮光膜付き基板を備えたことを特徴とする液晶表示素子である。
<19> 前記<18>に記載の液晶表示素子を備えたことを特徴とする液晶表示装置である。
<15> The fine particle-containing composition according to any one of <1> to <8>, the colored film forming ink for a display device according to <9>, or the <11> to <14>. A substrate with a light-shielding film, comprising a light-shielding film using the light-shielding material according to any one of the above.
<16> On a light-transmitting substrate, a color filter having a pixel group including a plurality of pixels exhibiting different hues and a light-shielding image separating each pixel constituting the pixel group, the light-shielding image is A color filter comprising the light shielding film for a display device according to <10>.
<17> A color filter comprising the light-shielding film-coated substrate according to <15>.
<18> A liquid crystal display device comprising the substrate with a light-shielding film according to <15>.
<19> A liquid crystal display device comprising the liquid crystal display element according to <18>.
本発明によれば、薄膜で優れた遮光性能が得られ、高温環境に曝された場合の色味変化が抑えられた微粒子含有組成物、表示装置用着色膜形成用インク、表示装置用遮光膜、遮光材料、及び遮光膜付き基板、並びに、高コントラストで鮮やかな画像表示が可能なカラーフィルタ、液晶表示素子、及び液晶表示装置を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the fine particle containing composition by which the outstanding light-shielding performance was obtained with the thin film, and the color change when exposed to high temperature environment was suppressed, the coloring film forming ink for display apparatuses, the light shielding film for display apparatuses In addition, a light shielding material, a substrate with a light shielding film, a color filter capable of displaying a high-contrast and vivid image, a liquid crystal display element, and a liquid crystal display device can be provided.
以下、本発明の微粒子含有組成物について詳細に説明すると共に、該説明を通じて本発明の表示装置用着色膜形成用インク、表示装置用遮光膜、遮光材料、遮光膜付き基板、カラーフィルタ、液晶表示素子、液晶表示装置の詳細についても詳述することとする。 Hereinafter, the fine particle-containing composition of the present invention will be described in detail. Through the description, the colored film forming ink for display device, the light shielding film for display device, the light shielding material, the substrate with the light shielding film, the color filter, and the liquid crystal display Details of the element and the liquid crystal display device will also be described in detail.
<微粒子含有組成物>
本発明の微粒子含有組成物は、金属微粒子及び/又は金属化合物微粒子と、少なくとも1つのチオエーテル基を有する高分子化合物と、熱もしくは光で硬化する化合物とを少なくとも含有してなり、必要に応じて、他の成分を用いて構成することができる。
<Fine particle-containing composition>
The fine particle-containing composition of the present invention contains at least metal fine particles and / or metal compound fine particles, a polymer compound having at least one thioether group, and a compound that is cured by heat or light, and as necessary. It can be configured using other components.
本発明においては、着色剤(特に黒色系の着色剤)として、金属微粒子及び/又は金属化合物微粒子を分散して用いると共に、該金属微粒子等の分散に分散剤として、本発明に係る高分子分散剤(チオエーテル基を有する高分子化合物)を用いることで、金属系の微粒子の凝集防止等の粒子挙動に寄与し、製造工程上高温に曝されるような場合など、高温環境での樹脂成分、微粒子の変質に伴なう色味変化が抑制されるので、分散時の分散性及び分散後の分散安定性が向上し、色相が良好で高い光学濃度を確保することができる。 In the present invention, metal fine particles and / or metal compound fine particles are dispersed and used as a colorant (particularly a black colorant), and the polymer dispersion according to the present invention is used as a dispersant for dispersing the metal fine particles. By using an agent (polymer compound having a thioether group), it contributes to particle behavior such as prevention of aggregation of metal-based fine particles, such as when exposed to high temperatures in the production process, resin components in high-temperature environments, Since the color change accompanying the change of fine particles is suppressed, the dispersibility during dispersion and the dispersion stability after dispersion are improved, and the hue is good and a high optical density can be ensured.
本発明の微粒子含有組成物は、金属微粒子及び/又は金属化合物微粒子が、後述するチオエーテル基を有する高分子化合物(本発明に係る高分子分散剤)中に分散されていることが好ましい。 In the fine particle-containing composition of the present invention, the metal fine particles and / or the metal compound fine particles are preferably dispersed in a polymer compound having a thioether group described later (the polymer dispersant according to the present invention).
−金属微粒子及び/又は金属化合物微粒子−
本発明の微粒子含有組成物は、(特に黒色の)着色剤として、金属微粒子及び金属化合物微粒子の少なくとも1種を含有する。金属系の微粒子を着色剤として用いることで、薄膜で高濃度の像形性が可能であり、特に遮光画像(ブラックマトリクスを含む。)などの黒色像の形成に有効である。
-Metal fine particles and / or metal compound fine particles-
The fine particle-containing composition of the present invention contains at least one of metal fine particles and metal compound fine particles as a (particularly black) colorant. By using metallic fine particles as a colorant, a high-density image formability is possible with a thin film, which is particularly effective for forming a black image such as a light-shielded image (including a black matrix).
本発明において、金属微粒子における「金属」とは、「岩波理化学辞典(第5版)」(1998年、岩波書店発行)に記載の「金属」(352頁)による。また、「金属化合物」とは、金属と金属以外の元素との化合物であり、ここでの金属も前記金属微粒子における金属と同義である。 In the present invention, the “metal” in the metal fine particles is based on the “metal” (page 352) described in “Iwanami Physical and Chemical Dictionary (5th edition)” (1998, published by Iwanami Shoten). Further, the “metal compound” is a compound of a metal and an element other than the metal, and the metal here is also synonymous with the metal in the metal fine particles.
金属微粒子としては、特に限定はなく適宜選択することができ、例えば、長周期型周期表(IUPAC 1991)の第4周期、第5周期、及び第6周期に含まれる金属群より選択される金属を主成分として含むことが好ましく、また、第2族、第8族、第9族、第10族、第11族、第12族、第13族、及び第14族に含まれる金属群から選ばれる金属を主成分として含むことが好ましい。
これら金属のうち、金属微粒子として、第4周期、第5周期、又は第6周期の金属であって、第2族、第10族、第11族、第12族、又は第14族の金属がさらに好ましい。
The metal fine particles are not particularly limited and can be appropriately selected. For example, a metal selected from a metal group included in the fourth period, the fifth period, and the sixth period of the long-period periodic table (IUPAC 1991). Is preferably selected from the group of metals included in Group 2, Group 8, Group 9, Group 10, Group 11, Group 12, Group 13, and Group 14. It is preferable to contain a metal as a main component.
Among these metals, the metal fine particles are metals of the fourth period, the fifth period, or the sixth period, and the metals of Group 2, Group 10, Group 11, Group 12, or Group 14 are Further preferred.
金属微粒子の形状には、特に制限はなく、アンパン状、ジャガイモ状、棒状(針状、円柱状、直方体等の角柱形、ラグビーボール形等)、平板状(鱗片状、楕円板状、板状)、繊維状、金平糖状、コイル状等であってもよい。好ましくは、板状粒子、棒状(ロッド状)である。 The shape of the metal fine particles is not particularly limited, and is an amp shape, a potato shape, a rod shape (a needle shape, a cylindrical shape, a rectangular column shape such as a rectangular parallelepiped, a rugby ball shape, etc.), a flat shape (a scale shape, an elliptical plate shape, a plate shape). ), Fibrous, confetti, coiled, etc. Preferred are plate-like particles and rod-like (rod-like) shapes.
前記金属微粒子の好ましい例としては、銅、銀、金、白金、パラジウム、ニッケル、錫、コバルト、ロジウム、イリジウム、鉄、ルテニウム、オスミウム、マンガン、モリブデン、タングステン、ニオブ、タンタル、カルシウム、チタン、ビスマス、アンチモン、鉛、又はこれらの合金より選ばれる少なくとも一種を挙げることができる。さらに、好ましい金属微粒子の例として、銅、銀、金、白金、パラジウム、ニッケル、錫、コバルト、ロジウム、イリジウム、又はこれらの合金が挙げられ、特に好ましい金属微粒子の例として、銅、銀、金、白金、錫、又はこれらの合金より選ばれる少なくとも一種が挙げられる。 Preferred examples of the fine metal particles include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, calcium, titanium, and bismuth. And at least one selected from antimony, lead, and alloys thereof. Further, examples of preferable metal fine particles include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, or alloys thereof, and examples of particularly preferable metal fine particles include copper, silver, gold, and the like. And at least one selected from platinum, tin, and alloys thereof.
中でも、容易に微粒子が得られやすいという点で、金、銀、銅、錫が好ましく、とりわけ銀が好ましい。本発明における金属微粒子は、前記金属の合金であってもよく、好ましい合金として銀とスズの合金が挙げられる。 Among these, gold, silver, copper, and tin are preferable, and silver is particularly preferable because fine particles can be easily obtained. The metal fine particles in the present invention may be an alloy of the metal, and a preferable alloy is an alloy of silver and tin.
金属微粒子の数平均粒径は、膜厚を超えない限り特に制限はないが、10〜1000nmの範囲が好ましく、10〜500nmの範囲がより好ましく、10〜200nmの範囲が更に好ましい。該数平均粒径が前記範囲内であると、生成が容易で、かかる範囲内の金属微粒子を用いてカラーフィルタを作製した場合に、特性上目視により良好な黒色(茶褐色がかった色相にならない)に見えるブラックマトリクス等の黒色像部が得られ、粒子径が大きすぎて金属微粒子分散後の分散物の安定性が低下して、遮光性が悪化することもない。 The number average particle diameter of the metal fine particles is not particularly limited as long as it does not exceed the film thickness, but is preferably in the range of 10 to 1000 nm, more preferably in the range of 10 to 500 nm, and still more preferably in the range of 10 to 200 nm. When the number average particle diameter is within the above range, the production is easy, and when a color filter is produced using metal fine particles within such a range, a black color which is visually good in terms of characteristics (not a brownish hue) A black image portion such as a black matrix can be obtained, and the particle size is not too large, so that the stability of the dispersion after dispersion of the metal fine particles is lowered, and the light shielding property is not deteriorated.
ここで、「粒径」とは、粒子の電子顕微鏡写真画像を同面積の円とした時の直径をいい、「数平均粒径」とは、多数の粒子について前記粒径を求め、求められた粒径の100個の平均値をいう。なお、粒径分布については特に制約はない。 Here, “particle size” means the diameter when the electron micrograph image of the particle is a circle of the same area, and “number average particle size” is obtained by determining the particle size for a number of particles. The average value of 100 particles having a particle diameter. The particle size distribution is not particularly limited.
また、金属微粒子は、均一な組成でも不均一な組成でもよい。不均一な組成の例として、表面に内部と異なる組成のコーティング層を設けたもの等が挙げられる。 The metal fine particles may have a uniform composition or a non-uniform composition. As an example of a non-uniform composition, there may be mentioned a coating layer having a composition different from the inside on the surface.
前記金属化合物微粒子は、金属と金属以外の他の元素との化合物であり、例えば、金属の酸化物、硫化物、硫酸塩、炭酸塩などが挙げられる。このうち、色調や微粒子形成のしやすさの点で、硫化物が特に好ましい。具体的には、金属化合物の例として、酸化銅(II)、硫化鉄、硫化銀、硫化銅(II)、チタンブラックなどが挙げられ、色調、微粒子形成のしやすさ、安定性の点で、硫化銀が特に好ましい。 The metal compound fine particles are a compound of a metal and an element other than the metal, and examples thereof include metal oxides, sulfides, sulfates, and carbonates. Of these, sulfides are particularly preferable in terms of color tone and ease of forming fine particles. Specifically, examples of the metal compound include copper oxide (II), iron sulfide, silver sulfide, copper sulfide (II), titanium black, etc., in terms of color tone, ease of fine particle formation, and stability. Silver sulfide is particularly preferred.
また、前記金属化合物微粒子は、均一な組成でも不均一な組成でもよい。不均一な組成の例としては、表面に内部と異なる組成のコーティング層を設けたものを挙げることができる。 The metal compound fine particles may have a uniform composition or a non-uniform composition. As an example of the non-uniform composition, there can be mentioned a coating layer having a composition different from the inside on the surface.
本発明における金属微粒子及び金属化合物微粒子は、特に制限はなく、気相法、液相法などの公知の方法で作製することができる。金属化合物微粒子の作製方法については、例えば、「超微粒子の技術と応用における最新動向II」(住ベテクノリサーチ(株)、2002年発行)に記載されている。 The metal fine particles and metal compound fine particles in the present invention are not particularly limited, and can be produced by a known method such as a gas phase method or a liquid phase method. The method for producing metal compound fine particles is described in, for example, “Latest Trends in Technology and Application of Ultrafine Particles II” (Sumibe Techno Research Co., Ltd., issued in 2002).
金属微粒子は、市販のものを用いることができるほか、金属イオンの化学的還元法、無電解メッキ法、金属の蒸発法等により調製することが可能である。
特にロッド状の銀微粒子については、例えばAdv.Mater.2002,14,80−82の記載を参照することができ、すなわち、球形の銀微粒子を種粒子としてその後、更に銀塩を添加し、CTAB(セチルトリメチルアンモニウムブロマイド)等の界面活性剤の存在下で、アスコルビン酸などの比較的還元力の弱い還元剤を用いることにより、銀ロッドやワイヤーを得ることができる。また、同様の記載が、Mater.Chem.Phys.2004,84,197−204、Adv.Funct.Mater.2004,14,183−189にある。
As the metal fine particles, commercially available ones can be used, and the metal fine particles can be prepared by a chemical reduction method of metal ions, an electroless plating method, a metal evaporation method, or the like.
For rod-shaped silver fine particles, for example, see Adv. Mater. The description of 2002, 14, 80-82 can be referred to, that is, in the presence of a surfactant such as CTAB (cetyltrimethylammonium bromide) after adding further silver salt using spherical silver fine particles as seed particles. Thus, a silver rod or a wire can be obtained by using a reducing agent having a relatively low reducing power such as ascorbic acid. In addition, the same description is described in Mater. Chem. Phys. 2004, 84, 197-204, Adv. Funct. Mater. 2004, 14, 183-189.
また、Mater.Lett.2001,49,91−95には、電気分解を用いた方法が、J.Mater.Res.2004,19,469−473には、マイクロ波を照射することにより銀ロッドを生成する方法が、それぞれ記載されている。また、逆ミセルと超音波を併用した例について、J.Phys.Chem.B,2003,107,3679−3683に記載がある。
金に関しても、同様に、J.Phys.Chem.B 1999,103、3073−3077及びLangmuir 1999,15,701−709、J.Am.Chem.Soc.2002,124,14316−14317に記載されている。
Also, Mater. Lett. 2001, 49, 91-95, a method using electrolysis is described in J. Org. Mater. Res. 2004, 19, 469-473 describe a method for producing a silver rod by irradiating microwaves, respectively. In addition, for an example in which reverse micelles and ultrasonic waves are used in combination, J. et al. Phys. Chem. B, 2003, 107, 3679-3683.
As for gold, J. Phys. Chem. B 1999, 103, 3073-3077 and Langmuir 1999, 15, 701-709; Am. Chem. Soc. 2002, 124, 14316-14317.
ロッド状の粒子は、界面活性剤の存在下で還元法により作製することができる。基本的には、界面活性剤の種類や還元剤の種類、添加量調整、pH制御により、種々のロッド状粒子の調製が可能である。具体的には、金属との相互作用の少ない界面活性剤をはじめに用い、還元して粒子成長させた段階で、金属と大きく相互作用する界面活性剤を添加し、それ以上の粒子の成長を抑える。つまり、還元剤の種類と時間で形状制御することができる。 Rod-shaped particles can be prepared by a reduction method in the presence of a surfactant. Basically, various rod-shaped particles can be prepared by controlling the type of surfactant, the type of reducing agent, adjusting the amount of addition, and controlling the pH. Specifically, a surfactant that has little interaction with the metal is used first, and at the stage of reduction and particle growth, a surfactant that interacts greatly with the metal is added to suppress further particle growth. . That is, the shape can be controlled by the type and time of the reducing agent.
金属化合物微粒子については、ロッド状の粒子を酸化や硫化することによって調製することができる。 The metal compound fine particles can be prepared by oxidizing or sulfurating rod-shaped particles.
本発明において、前記金属微粒子には、金属と金属との複合微粒子が含まれ、前記金属化合物微粒子には、金属と金属化合物との複合微粒子、金属化合物と金属化合物との複合微粒子が含まれる。 In the present invention, the metal fine particles include composite fine particles of metal and metal, and the metal compound fine particles include composite fine particles of a metal and a metal compound, and composite fine particles of a metal compound and a metal compound.
複合微粒子の形状には、特に制限はなく、例えば、粒子の内部と表面で組成の異なるもの、2種類の粒子が合一したもの等を挙げることができる。また、複合微粒子を構成する金属化合物、金属はそれぞれ、1種でも2種以上であってもよい。
前記「金属と金属化合物との複合微粒子」の具体例としては、銀と硫化銀との複合微粒子、銀と酸化銅(II)との複合微粒子などが挙げられる。
The shape of the composite fine particles is not particularly limited, and examples thereof include those having different compositions between the inside and the surface of the particles, and those obtained by combining two types of particles. Further, each of the metal compound and the metal constituting the composite fine particle may be one type or two or more types.
Specific examples of the “composite fine particles of metal and metal compound” include composite fine particles of silver and silver sulfide, and composite fine particles of silver and copper (II) oxide.
上記以外に、本発明における金属微粒子及び金属化合物微粒子は、コア・シェル構造を有する複合粒子であってもよい。コア・シェル構造を有する複合粒子とは、コア材料の表面がシェル材料でコートされたものである。コア・シェル構造を有する複合粒子を用いる場合、シェル材料としては、例えば、Si、Ge、AlSb、InP 、Ga、As、GaP 、ZnS 、ZnSe、ZnTe、CdS 、CdSe、CdTe、PbS 、PbSe、PbTe、Se、Te、CuCl、CuBr、CuI 、TlCl、TlBr、TlI、及びこれらの固溶体もしくはこれらを90mol%以上含む固溶体より選択される少なくとも一種の半導体、又は銅、銀、金、白金、パラジウム、ニッケル、錫、コバルト、ロジウム、イリジウム、鉄、ルテニウム、オスミウム、マンガン、モリブデン、タングステン、ニオブ、タンタル、チタン、ビスマス、アンチモン、鉛、又はこれらの合金より選択される少なくとも一種の金属を挙げることができる。これらシェル材料は、利用される波長域である300〜800nmにおいて、量子閉じ込め効果により離散化した量子レベル間に共鳴する光吸収ピークを有するという点で好ましい。 In addition to the above, the metal fine particles and metal compound fine particles in the present invention may be composite particles having a core-shell structure. The composite particles having a core / shell structure are those in which the surface of the core material is coated with the shell material. When using composite particles having a core-shell structure, examples of the shell material include Si, Ge, AlSb, InP, Ga, As, GaP, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, PbS, PbSe, and PbTe. , Se, Te, CuCl, CuBr, CuI, TlCl, TlBr, TlI and at least one semiconductor selected from these solid solutions or solid solutions containing 90 mol% or more of these, or copper, silver, gold, platinum, palladium, nickel And at least one metal selected from tin, cobalt, rhodium, iridium, iron, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, titanium, bismuth, antimony, lead, or alloys thereof. . These shell materials are preferable in that they have a light absorption peak that resonates between quantum levels discretized by the quantum confinement effect in the wavelength range of 300 to 800 nm used.
上記のうち、好ましいコア材料は、銅、銀、金、パラジウム、ニッケル、錫、ビスマス、アンモチン、鉛、又はこれらの合金より選択される少なくとも一種である。
前記シェル材料は、反射率を低下させる目的で、屈折率の調整剤としても好適に用いられる。
Among the above, a preferable core material is at least one selected from copper, silver, gold, palladium, nickel, tin, bismuth, ammotin, lead, or an alloy thereof.
The shell material is also preferably used as a refractive index adjusting agent for the purpose of reducing the reflectance.
コアシェル構造を有する複合粒子のコア材料としては、例えば、銅、銀、金、パラジウム、又はこれらの合金より選択される少なくとも一種の金属を用いることができる。 As a core material of the composite particles having a core-shell structure, for example, at least one metal selected from copper, silver, gold, palladium, or an alloy thereof can be used.
コアシェル構造を有する複合粒子の作製方法には、特に制限はなく、代表的な方法を以下に示す。
(1)公知の方法で作製した金属微粒子の表面に、酸化、硫化などにより金属化合物のシェルを形成する方法である。例えば、金属微粒子を水などの分散媒に分散させて、硫化ナトリウムや硫化アンモニウムなどの硫化物を添加する方法がある。この方法により、粒子表面が硫化されてコアシェル複合粒子が形成される。
この場合、用いる金属微粒子は、気相法、液相法などの公知の方法で作製することができ、金属微粒子の作製方法については、例えば「超微粒子の技術と応用における最新動向II」(住ベテクノリサーチ(株)、2002年発行)に記載がある。
(2)金属微粒子を作製する過程で連続的に表面に金属化合物のシェルを形成する方法である。例えば、金属塩溶液に還元剤を添加し、金属イオンの一部を還元して金属微粒子を作製し、これに硫化物を添加し、作製した金属微粒子の周囲に金属硫化物を形成することにより、コアシェル複合粒子が形成される。
There is no restriction | limiting in particular in the preparation methods of the composite particle which has a core-shell structure, A typical method is shown below.
(1) A method of forming a metal compound shell on the surface of a metal fine particle produced by a known method by oxidation, sulfurization, or the like. For example, there is a method in which metal fine particles are dispersed in a dispersion medium such as water and sulfides such as sodium sulfide and ammonium sulfide are added. By this method, the particle surface is sulfided to form core-shell composite particles.
In this case, the metal fine particles to be used can be prepared by a known method such as a gas phase method or a liquid phase method. Betechno Research Co., Ltd., published in 2002).
(2) A method of continuously forming a metal compound shell on the surface in the process of producing metal fine particles. For example, by adding a reducing agent to a metal salt solution, reducing part of the metal ions to produce metal fine particles, adding sulfide to this, and forming metal sulfides around the produced metal fine particles Core-shell composite particles are formed.
上記した金属微粒子及び金属化合物微粒子のうち、アスペクト比(粒子の長軸長/粒子の短軸長の比)が2〜100である微粒子が、吸収スペクトルの制御ができ、色相を黒色に近づけることができる点で好ましい。中でも、吸収スペクトルの制御ができ、色相をより黒色に近づけることができる点で、前記アスペクト比は、4〜80が好ましく、10〜60が更に好ましく、15〜50が特に好ましい。アスペクト比が前記範囲内であると、黒色粒子を得るのが比較的容易であり、可視光域の吸収が良好で画質(解像力)の低下を招来することもない。 Among the fine metal particles and fine metal compound particles described above, fine particles having an aspect ratio (ratio of major axis length / minor axis length) of 2 to 100 can control the absorption spectrum and bring the hue closer to black. It is preferable in that Among these, the aspect ratio is preferably 4 to 80, more preferably 10 to 60, and particularly preferably 15 to 50 in that the absorption spectrum can be controlled and the hue can be made closer to black. When the aspect ratio is within the above range, it is relatively easy to obtain black particles, absorption in the visible light region is good, and image quality (resolution) is not reduced.
アスペクト比とは、金属微粒子又は金属化合物微粒子の、後述のように定義された長軸長を短軸長で割った値を意味し、100個の金属微粒子及び/又は金属化合物微粒子を測定した値の平均値である。なお、粒子の投影面積は電子顕微鏡写真上での面積を測定し、撮影倍率を補正することにより得られる。 The aspect ratio means a value obtained by dividing a major axis length defined as described later by a minor axis length of a metal fine particle or metal compound fine particle, and a value obtained by measuring 100 metal fine particles and / or metal compound fine particles. Is the average value. The projected area of the particles can be obtained by measuring the area on the electron micrograph and correcting the photographing magnification.
次に、径(長軸長、短軸長)について金属微粒子を例に説明する。
金属微粒子の粒子径を三軸径とする。そして、1個の金属粒子がちょうど(きっちりと)収まる箱(直方体)を考え、この箱の長さL、幅b、高さ又は厚みtをもってこの金属粒子の寸法と定義する仕方である。金属粒子を箱に収める場合、いくつかの仕方があるが、本発明では以下の方法を採用する。
まず、平面上に金属粒子を、最も重心が低くて安定に静止するように置く。次に、平面に対し直角に立てた2枚の平行な平板により金属粒子を挟み、その平板間隔が最も短くなる位置の平板間隔を「幅b」とする。次に、前記幅bを決する2枚の平板に対し直角で前記平面に対しても直角の2枚の平行な平板により金属粒子を挟み、この2枚の平板間隔を「長さL」とする。最後に金属粒子の最も高い位置に接触するように天板を前記平面に平行に載せ、天板と平面との間隔を高さ又は厚みtとする。(この方法により平面、各2枚の平板及び天板によって画される直方体が形成される。)また、金属粒子の三軸径b、L及びtの最も長いものに該当する軸を「長軸」と定義し、長軸方向における長さを「長軸長」と、また、長軸に平行な光を金属粒子に照射して得られる投影面積を真円換算した場合の直径を「短軸長」と定義する。
Next, the diameter (major axis length, minor axis length) will be described using metal fine particles as an example.
The particle diameter of the metal fine particles is defined as a triaxial diameter. Then, a box (a rectangular parallelepiped) in which one metal particle just fits exactly is considered, and the length L, width b, height or thickness t of the box is defined as the dimension of the metal particle. There are several ways to store the metal particles in the box. In the present invention, the following method is adopted.
First, the metal particles are placed on a flat surface so that the center of gravity is the lowest and is stable. Next, the metal particles are sandwiched between two parallel flat plates standing at right angles to the plane, and the flat plate interval at the position where the flat plate interval is the shortest is defined as “width b”. Next, metal particles are sandwiched between two parallel flat plates that are perpendicular to the two flat plates that determine the width b and also perpendicular to the flat surface, and the distance between the two flat plates is defined as “length L”. . Finally, the top plate is placed parallel to the plane so as to contact the highest position of the metal particles, and the distance between the top plate and the plane is defined as the height or thickness t. (This method forms a rectangular parallelepiped defined by a plane, two flat plates and a top plate.) Also, the axis corresponding to the longest three-axis diameters b, L, and t of the metal particles is defined as “long axis. ``, The length in the major axis direction is `` major axis length '', and the diameter when the projected area obtained by irradiating metal particles with light parallel to the major axis is converted to a perfect circle is `` minor axis '' Long ”is defined.
金属微粒子又は金属化合物微粒子の短軸長は、4〜50nmの範囲内が好ましく、15〜50nmの範囲内がより好ましく、15〜30nmの範囲内が最も好ましい。また、金属微粒子又は金属化合物微粒子の長軸長(最大長)は、10〜1000nmの範囲内が好ましく、更には100〜1000nmの範囲内がより好ましく、400〜800nmの範囲内が好ましい。 The short axis length of the metal fine particles or metal compound fine particles is preferably within the range of 4 to 50 nm, more preferably within the range of 15 to 50 nm, and most preferably within the range of 15 to 30 nm. The major axis length (maximum length) of the metal fine particles or metal compound fine particles is preferably in the range of 10 to 1000 nm, more preferably in the range of 100 to 1000 nm, and preferably in the range of 400 to 800 nm.
金属微粒子及び/又は金属化合物微粒子は、アスペクト比を調整(異なるアスペクト比の粒子を混合)することにより、すなわち同一金属で異なるアスペクト比の微粒子を併用することにより、吸収スペクトルを制御でき、色相を黒色に近づけることもできる。黒色に近づけるためには、他の金属や金属化合物微粒子など、種々のアスペクト比を持つ粒子を組み合わせることにより得ることもできる。 Metal fine particles and / or metal compound fine particles can control the absorption spectrum by adjusting the aspect ratio (mixing particles of different aspect ratios), that is, by using fine particles of the same metal with different aspect ratios, and controlling the hue. It can also be close to black. In order to approach black, it can also be obtained by combining particles having various aspect ratios such as other metals and metal compound fine particles.
本発明における金属微粒子又は金属化合物微粒子を、球形から例えばロッド形状へ変化させると、可視光線の吸収量も約2倍高められ、球状粒子の場合よりトータルの吸収係数が大きくなり、透過濃度を高めることが可能である。これにより、高濃度を保持しながら薄膜化することができる。 When the metal fine particles or metal compound fine particles in the present invention are changed from a spherical shape to, for example, a rod shape, the amount of absorption of visible light is also increased by about twice, and the total absorption coefficient is larger than that of spherical particles, and the transmission density is increased. It is possible. Thereby, it is possible to reduce the thickness while maintaining a high concentration.
金属微粒子及び/又は金属化合物微粒子の微粒子含有組成物中における含有量としては、微粒子の種類や性状により異なるが、該組成物の全固形分に対して、10〜98質量%が好ましく、20〜95質量%がより好ましく、30〜93質量%が好ましい。該含有量が前記範囲内であると、薄膜で高濃度が得られ、現像性に支障を来すこともない。 The content of the metal fine particles and / or metal compound fine particles in the fine particle-containing composition varies depending on the type and properties of the fine particles, but is preferably 10 to 98% by mass with respect to the total solid content of the composition. 95 mass% is more preferable, and 30-93 mass% is preferable. When the content is within the above range, a high concentration can be obtained with a thin film, and developability is not hindered.
−高分子化合物−
本発明の微粒子含有組成物は、前記金属微粒子及び/又は金属化合物微粒子の分散剤として、少なくとも1つのチオエーテル基を有する高分子化合物の少なくとも1種(本発明に係る高分子分散剤)を含有する。チオエーテル基を有する高分子化合物を分散剤とするので、既述の金属系の微粒子を分散して含有する場合に、分散時の分散性及び分散後の分散安定性が向上し、色相(特に黒色相)が良好で、高い光学濃度の画像形成が可能となる。
-Polymer compound-
The fine particle-containing composition of the present invention contains at least one polymer compound having at least one thioether group (polymer dispersant according to the present invention) as a dispersant for the metal fine particles and / or metal compound fine particles. . Since the polymer compound having a thioether group is used as a dispersant, when the above-mentioned metal-based fine particles are dispersed and contained, the dispersibility during dispersion and the dispersion stability after dispersion are improved, and the hue (particularly black Phase) is good, and an image having a high optical density can be formed.
本発明に係る高分子分散剤は、分子中に少なくとも一つのチオエーテル基を有する高分子化合物の中から選択して用いることができ、特に高分子の側鎖部分にチオエーテル基を有する化合物が好適である。 The polymer dispersant according to the present invention can be used by selecting from among polymer compounds having at least one thioether group in the molecule, and particularly preferred are compounds having a thioether group in the side chain portion of the polymer. is there.
中でも、高分子の構成単位として、少なくとも一種のチオエーテル構造を側鎖に含むエチレン性不飽和単量体から誘導される繰り返し単位を分子中に有する高分子化合物が好ましく、下記一般式(1)で表される繰り返し単位の少なくとも1種を有する高分子化合物が特に好ましい。 Among these, a polymer compound having a repeating unit derived from an ethylenically unsaturated monomer containing at least one thioether structure in the side chain as the polymer structural unit is preferable, represented by the following general formula (1). A polymer compound having at least one type of repeating unit represented is particularly preferable.
前記一般式(1)において、R1は、水素原子、又は総炭素数1〜4のアルキル基を表す。
総炭素数1〜4のアルキル基としては、例えば、メチル基、エチル基、ノルマルプロピル基、イソプロピル基、ノルマルブチル基、secブチル基、イソブチル基、tert−ブチル基等が挙げられ、中でも、メチル基が好ましい。
In the general formula (1), R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a sec butyl group, an isobutyl group, and a tert-butyl group. Groups are preferred.
前記一般式(1)において、R2は、水素原子、総炭素数1〜18のアルキル基、総炭素数6〜14のアリール基、又は総炭素数7〜16のアラルキル基を表し、このアルキル基、アリール基、及びアラルキル基は各々独立に、無置換でも置換基を有していてもよく、飽和又は不飽和の環状構造を形成していてもよい。 In the general formula (1), R 2 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 16 carbon atoms. The group, the aryl group, and the aralkyl group may each independently be unsubstituted or substituted, and may form a saturated or unsaturated cyclic structure.
前記R2で表される総炭素数1〜18のアルキル基は、無置換でも置換基を有していてもよく、例えば、メチル基、エチル基、ノルマルプロピル基、イソプロピル基、ノルマルブチル基、sec−ブチル基、イソブチル基、tert−ブチル基、ヘキシル基、オクチル基、ドデシル基、ステアリル基等のアルキル基が挙げられる。置換基を有する場合の置換基としては、例えば、ハロゲン原子、水酸基、アミノ基、アミド基、カルボキシル基、エステル基、スルホニル基等が好適である。 The alkyl group having 1 to 18 carbon atoms represented by R 2 may be unsubstituted or substituted, for example, a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, Examples thereof include alkyl groups such as sec-butyl group, isobutyl group, tert-butyl group, hexyl group, octyl group, dodecyl group and stearyl group. As the substituent in the case of having a substituent, for example, a halogen atom, a hydroxyl group, an amino group, an amide group, a carboxyl group, an ester group, a sulfonyl group and the like are preferable.
上記のうち、総炭素数1〜12のアルキル基が好ましく、総炭素数1〜8のアルキル基がより好ましく、メチル基、エチル基、ノルマルプロピル基、イソプロピル基、ノルマルブチル基、tert−ブチル基は特に好ましい。 Among the above, an alkyl group having 1 to 12 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a tert-butyl group. Is particularly preferred.
前記R2で表される総炭素数6〜14のアリール基は、無置換でも置換基を有していてもよく、例えば、フェニル基、トルイル基、キシリル基、ナフチル基、アントラセニル基等のアリール基が挙げられる。置換基を有する場合の置換基としては、例えば、ハロゲン原子、水酸基、アミノ基、アミド基、カルボキシル基、エステル基、スルホニル基等が好適である。
上記のうち、総炭素数6〜10のアリール基が好ましく、フェニル基は特に好ましい。
The aryl group having 6 to 14 carbon atoms in total represented by R 2 may be unsubstituted or substituted, for example, aryl such as phenyl group, toluyl group, xylyl group, naphthyl group, anthracenyl group, etc. Groups. As the substituent in the case of having a substituent, for example, a halogen atom, a hydroxyl group, an amino group, an amide group, a carboxyl group, an ester group, a sulfonyl group and the like are preferable.
Among the above, an aryl group having 6 to 10 carbon atoms is preferable, and a phenyl group is particularly preferable.
前記R2で表される総炭素数7〜16のアラルキル基は、無置換でも置換基を有していてもよく、例えば、ベンジル基、フェネチル基、ナフチルメチル基、アントラセニルメチル基等のアラルキル基が挙げられる。置換基を有する場合の置換基としては、例えば、ハロゲン原子、水酸基、アミノ基、アミド基、カルボキシル基、エステル基、スルホニル基等が好適である。
上記のうち、総炭素数7〜11のアラルキル基が好ましく、ベンジル基は特に好ましい。
The aralkyl group having 7 to 16 carbon atoms represented by R 2 may be unsubstituted or substituted, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, and an anthracenylmethyl group. An aralkyl group is mentioned. As the substituent in the case of having a substituent, for example, a halogen atom, a hydroxyl group, an amino group, an amide group, a carboxyl group, an ester group, a sulfonyl group and the like are preferable.
Among the above, an aralkyl group having 7 to 11 carbon atoms is preferable, and a benzyl group is particularly preferable.
前記一般式(1)において、Zは、−O−又は−NH−を表す。また、Yは、総炭素数1〜8の2価の連結基を表す。
Yで表される総炭素数1〜8の2価の連結基は、例えば、アルキレン基(例、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンチレン基)、アルケニレン基(例、エテニレン基、プロぺニレン基)、アルキニレン基(例、エチニレン基、プロピニレン基)、アリーレン基(例、フェニレン基)、二価のヘテロ環基(例、6−クロロ−1,3,5−トリアジン−2,4−ジイル基、ピリミジン−2,4−ジイル基、キノキサリン−2,3−ジイル基、ピリダジン−3,6−ジイル基)、−O−、−CO−、−NR−(Rは水素原子、アルキル基、又はアリール基を表す。)、又はこれらの組み合わせ(例えば、−NHCH2CH2NH−、−NHCONH−等)であることが好ましい。
In the general formula (1), Z represents —O— or —NH—. Y represents a divalent linking group having 1 to 8 carbon atoms in total.
The divalent linking group having 1 to 8 carbon atoms represented by Y is, for example, an alkylene group (eg, methylene group, ethylene group, propylene group, butylene group, pentylene group), alkenylene group (eg, ethenylene group, Propenylene group), alkynylene group (eg, ethynylene group, propynylene group), arylene group (eg, phenylene group), divalent heterocyclic group (eg, 6-chloro-1,3,5-triazine-2, 4-diyl group, pyrimidine-2,4-diyl group, quinoxaline-2,3-diyl group, pyridazine-3,6-diyl group), -O-, -CO-, -NR- (R is a hydrogen atom, Represents an alkyl group or an aryl group), or a combination thereof (for example, —NHCH 2 CH 2 NH—, —NHCONH—, etc.).
前記Yで表されるアルキレン基、アルケニレン基、アルキニレン基、アリーレン基、二価のヘテロ環基、並びにRで表されるアルキル基又はアリール基は、置換基を有していてもよい。該置換基の例としては、前記R2で表されるアリール基の置換基と同じである。Rで表されるアルキル基及びアリール基は、既述のR2で表されるアルキル基及びアリール基と同義である。 The alkylene group, alkenylene group, alkynylene group, arylene group, divalent heterocyclic group represented by Y, and the alkyl group or aryl group represented by R may have a substituent. Examples of the substituent are the same as those of the aryl group represented by R 2 . The alkyl group and aryl group represented by R are synonymous with the alkyl group and aryl group represented by R 2 described above.
Yで表される総炭素数1〜8の2価の連結基のうち、総炭素数1〜6の2価の連結基が好ましく、中でも、エチレン基、プロピレン基、ブチレン基、ヘキシレン基、−CH2−CH(OH)−CH2−、−C2H4−O−C2H4−は特に好ましい。 Of the divalent linking groups having 1 to 8 carbon atoms represented by Y, divalent linking groups having 1 to 6 carbon atoms are preferred, and among them, an ethylene group, a propylene group, a butylene group, a hexylene group,- CH 2 —CH (OH) —CH 2 — and —C 2 H 4 —O—C 2 H 4 — are particularly preferred.
本発明に係る高分子分散剤は、前記一般式(1)で表される繰り返し単位を1種のみならず、2種以上を共重合して硫黄原子を2以上含む高分子化合物であってもよい。また、側鎖を構成するチオエーテル構造は、硫黄原子を1つのみならず、前記Z、R2を硫黄原子を有する基で構成することにより、2つ以上の硫黄原子を有する側鎖とすることができる。 The polymer dispersant according to the present invention may be a polymer compound containing two or more sulfur atoms by copolymerizing not only one type of repeating unit represented by the general formula (1) but also two or more types. Good. In addition, the thioether structure constituting the side chain is not only one sulfur atom but also a side chain having two or more sulfur atoms by constituting Z and R 2 with a group having a sulfur atom. Can do.
本発明に係る高分子分散剤は、所望の高分子化合物に(好ましくは側鎖として)チオエーテル構造を導入する、あるいはチオエーテル基を(好ましくは側鎖に)持つ単量体の単独重合、又はチオエーテル基を(好ましくは側鎖に)持つ単量体と他の単量体との共重合により得ることができる。好ましくは、エチレン性不飽和単量体の側鎖にチオエーテル構造を導入する、あるいはチオエーテル構造を側鎖に含むエチレン性不飽和単量体の単独重合、又はチオエーテル構造を側鎖に含むエチレン性不飽和単量体と他の共重合成分との共重合により得ることができる。 The polymer dispersant according to the present invention introduces a thioether structure into a desired polymer compound (preferably as a side chain), or homopolymerization of a monomer having a thioether group (preferably in a side chain), or thioether It can be obtained by copolymerization of a monomer having a group (preferably in the side chain) with another monomer. Preferably, a thioether structure is introduced into the side chain of the ethylenically unsaturated monomer, or homopolymerization of an ethylenically unsaturated monomer containing a thioether structure in the side chain, or an ethylenically unsaturated group containing a thioether structure in the side chain. It can be obtained by copolymerization of a saturated monomer and another copolymer component.
以下、前記一般式(1)で表される繰り返し単位の具体例を示す。但し、本発明においては、これらに制限されるものではない。 Specific examples of the repeating unit represented by the general formula (1) are shown below. However, the present invention is not limited to these.
上記した中でも、特に、R1が水素原子又はメチル基であって、R2がメチル基、エチル基、ノルマルプロピル基、ノルマルブチル基、tert−ブチル基、又はフェニル基であって、Zが−O−であって、Yがエチレン基である化合物が好ましい。 Among the above, in particular, R 1 is a hydrogen atom or a methyl group, R 2 is a methyl group, an ethyl group, a normal propyl group, a normal butyl group, a tert-butyl group, or a phenyl group, and Z is − A compound that is O- and Y is an ethylene group is preferred.
本発明に係る高分子分散剤は、前記一般式(1)で表される繰り返し単位と、他のビニルモノマーとの共重合体であってもよい。
他のビニルモノマーとしては、芳香族ビニル化合物(例、スチレン、α−メチルスチレン、p−ヒドロキシスチレン、クロロメチルスチレン、及びビニルトルエンなど)、シアン化ビニル(例、(メタ)アクリロニトリル、及びα−クロロアクリロニトリルなど)、カルボン酸ビニルエステル(例、酢酸ビニル、安息香酸ビニル、ギ酸ビニルなど)、脂肪族共役ジエン(例、1,3‐ブタジエン、及びイソプレンなど)、(メタ)アクリル酸アルキルエステル(例、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n−ブチル(メタ)アクリレート、i−ブチル(メタ)アクリレート、及び2‐エチルヘキシル(メタ)アクリレートなど)、(メタ)アクリル酸アルキルアリールエステル(例、ベンジル(メタ)アクリレートなど)、(メタ)アクリル酸置換アルキルエステル(例、グリシジル(メタ)アクリレート、2−ヒドロキシエチル(メタ)アクリレート、ジメチルアミノエチル(メタ)アクリレート、及びジメチルアミノプロピル(メタ)アクリレートなど)、アルキル(メタ)アクリルアミド(例、(メタ)アクリルアミド、ジメチル(メタ)アクリルアミド、N−イソプロピル(メタ)アクリルアミド、n−ブチル(メタ)アクリルアミド、tert−ブチル(メタ)アクリルアミド、及びtert−オクチル(メタ)アクリルアミドなど)、置換アルキル(メタ)アクリルアミド(例、ジメチルアミノエチル(メタ)アクリルアミド、及びジメチルアミノプロピル(メタ)アクリルアミドなど)、重合性オリゴマー(例、片末端メタクリロイル化ポリメチルメタクリレートオリゴマー、片末端メタクリロイル化ポリスチレンオリゴマー、及び片末端メタクリロイル化ポリエチレングリコールなど)等が好ましく用いられる。
The polymer dispersant according to the present invention may be a copolymer of the repeating unit represented by the general formula (1) and another vinyl monomer.
Other vinyl monomers include aromatic vinyl compounds (eg, styrene, α-methylstyrene, p-hydroxystyrene, chloromethylstyrene, vinyltoluene, etc.), vinyl cyanide (eg, (meth) acrylonitrile, and α- Chloroacrylonitrile, etc.), carboxylic acid vinyl esters (eg, vinyl acetate, vinyl benzoate, vinyl formate, etc.), aliphatic conjugated dienes (eg, 1,3-butadiene, isoprene, etc.), (meth) acrylic acid alkyl esters (eg, Examples such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate), (meth) acrylic acid alkylaryl esters ( Example, benzyl (meth) acrylate ), (Meth) acrylic acid substituted alkyl esters (eg, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, etc.)), alkyl (meta ) Acrylamide (eg, (meth) acrylamide, dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, n-butyl (meth) acrylamide, tert-butyl (meth) acrylamide, and tert-octyl (meth) acrylamide) Substituted alkyl (meth) acrylamides (eg, dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, etc.), polymerizable oligomers (eg, one-end methacryloylated polymer) Methacrylate oligomer having a methacryloyl group at one end a polystyrene oligomer, and having a methacryloyl group at one end of polyethylene glycol, and the like) are preferably used.
少なくとも1つのチオエーテル基を有する高分子化合物(本発明に係る高分子分散剤)における前記一般式(1)で表される繰り返し単位の重合比率は、質量分率で1〜100%が好ましく、5〜80%がより好ましく、10〜50%が特に好ましい。この重合比率が前記範囲内であると、分散時の分散性及び分散後の分散安定性を向上し、並びに色相及び光学濃度を向上するのに効果的である。 The polymerization ratio of the repeating unit represented by the general formula (1) in the polymer compound having at least one thioether group (the polymer dispersant according to the present invention) is preferably 1 to 100% in terms of mass fraction. -80% is more preferable, and 10-50% is particularly preferable. When the polymerization ratio is within the above range, it is effective to improve the dispersibility during dispersion and the dispersion stability after dispersion, and to improve the hue and optical density.
また、本発明の高分子分散剤は、必要に応じてアルカリ現像適性を付与できる点で、分子中に酸基を有する高分子化合物が好ましい。前記酸基としては、例えば、カルボン酸基、スルホン酸、リン酸、ボロン酸、フェノール類、スルホアミドなどの基が好適であり、特にカルボン酸基を少なくとも一つ有する高分子化合物が好ましい。 In addition, the polymer dispersant of the present invention is preferably a polymer compound having an acid group in the molecule from the viewpoint that alkali developability can be imparted if necessary. As the acid group, for example, a group such as carboxylic acid group, sulfonic acid, phosphoric acid, boronic acid, phenols, and sulfoamide is preferable, and a polymer compound having at least one carboxylic acid group is particularly preferable.
アルカリ現像が必要な場合には、本発明の高分子分散剤は、酸価が20〜250mgKOH/gであることが好ましく、50〜200mgKOH/gであることがより好ましく、70〜180mgKOH/gであることが最も好ましい。酸価が前記範囲内であると、分散時の分散性及び分散後の分散安定性が良好であり、かつアルカリ現像性も良好である。 When alkali development is required, the polymer dispersant of the present invention preferably has an acid value of 20 to 250 mgKOH / g, more preferably 50 to 200 mgKOH / g, and 70 to 180 mgKOH / g. Most preferably it is. When the acid value is within the above range, the dispersibility during dispersion and the dispersion stability after dispersion are good, and the alkali developability is also good.
本発明に係る高分子分散剤の分子量としては、重量平均分子量で、2,000〜1,000,000が好ましく、3,000〜200,000がより好ましく、5,000〜100,000が最も好ましい。重量平均分子量が前記範囲内であると、分散性向上に有効で、良好な膜強度が得られると共に、現像性に支障を来すこともない。 The molecular weight of the polymer dispersant according to the present invention is preferably 2,000 to 1,000,000, more preferably 3,000 to 200,000, and most preferably 5,000 to 100,000 in terms of weight average molecular weight. preferable. When the weight average molecular weight is within the above range, it is effective for improving dispersibility, good film strength can be obtained, and developability is not hindered.
少なくとも1つのチオエーテル基を有する高分子化合物の、微粒子含有組成物中における含有量としては、既述の金属微粒子及び/又は金属化合物微粒子の質量に対して、1〜40質量%が好ましく、3〜30質量%がより好ましく、5〜20質量%がより好ましい。該含有量が前記範囲内であると、微粒子に充分に吸着して分散性が向上すると共に、熱による色相変化を抑えて色相及び光学濃度の向上に効果的であり、現像性に支障を来すこともない。 The content of the polymer compound having at least one thioether group in the fine particle-containing composition is preferably 1 to 40% by mass with respect to the mass of the metal fine particles and / or metal compound fine particles described above, 30 mass% is more preferable, and 5-20 mass% is more preferable. When the content is within the above range, the fine particles are sufficiently adsorbed to improve the dispersibility, and are effective in improving the hue and optical density by suppressing the change in hue due to heat. There is nothing to do.
−熱もしくは光で硬化する化合物−
本発明の微粒子含有組成物は、少なくとも1種の熱もしくは光で硬化する化合物を含有する。
熱もしくは光で硬化する化合物として、多官能モノマーなどを用いることができる。多官能モノマーは、それ自体重合して重合後にバインダーとして機能するものであり、該多官能モノマーの含有により、膜形成したときの膜強度を高めることができる。多官能モノマーとしては、光重合可能なモノマーが好ましく、更に熱重合性を有しているものがより好ましい。熱重合性を有する場合には、光重合後に更に熱処理を行なうことで硬化度をより一層高めることができる。
-Compounds that cure by heat or light-
The fine particle-containing composition of the present invention contains at least one compound that is cured by heat or light.
A polyfunctional monomer or the like can be used as the compound that is cured by heat or light. The polyfunctional monomer is itself polymerized and functions as a binder after polymerization, and the inclusion of the polyfunctional monomer can increase the film strength when a film is formed. The polyfunctional monomer is preferably a photopolymerizable monomer, and more preferably has thermal polymerizability. In the case of thermal polymerization, the degree of curing can be further increased by further heat treatment after photopolymerization.
前記多官能モノマーとしては、沸点が常圧で100℃以上の化合物を挙げることができる。例えば、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、テトラメチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、1,3−ブタンジオールジ(メタ)アクリレート、トリメチロールエタントリアクリレート、トリメチロールプロパントリ(メタ)アクリレート、トリメチロールプロパンジ(メタ)アクリレート、ネオペンチルグリコールジ(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、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ヘキサ(メタ)アクリレート、ジペンタエリスリトールヘキサ(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、1,4−ヘキサンジオール(メタ)アクリレート、ヘキサンジオールジ(メタ)アクリレート、トリメチロールプロパントリ(アクリロイルオキシプロピル)エーテル、トリ(アクリロイルオキシエチル)イソシアヌレート、トリ(アクリロイルオキシエチル)シアヌレート、グリセリントリ(メタ)アクリレート、トリメチロールプロパンもしくはグリセリン等の多官能アルコールにエチレンオキシドやプロピレンオキシドを付加反応させた後で(メタ)アクリレート化したもの等の多官能(メタ)アクリレートを挙げることができる。 Examples of the polyfunctional monomer include compounds having a boiling point of 100 ° C. or higher at normal pressure. For example, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) Acrylate, 1,3-butanediol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol Ruhexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, 1,4-hexanediol (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) ) Isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate, trimethylolpropane or glycerin and other polyfunctional alcohols after addition reaction of ethylene oxide or propylene oxide (meth) acrylate, etc. Mention may be made of polyfunctional (meth) acrylates.
さらに、特公昭48−41708号、同50−6034号、特開昭51−37193号の各公報に記載のウレタンアクリレート類、特開昭48−64183号、特公昭49−43191号、同52−30490号の各公報に記載のポリエステルアクリレート類、エポキシ樹脂と(メタ)アクリル酸との反応生成物であるエポキシアクリレート類等の多官能アクリレートやメタクリレートを挙げることができる。 Further, urethane acrylates described in JP-B-48-41708, JP-A-50-6034 and JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, and 52- Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid can be mentioned in each publication of No. 30490.
上記の中でも、トリメチロールプロパントリ(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ヘキサ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレートなどの多官能アクリルモノマーを用いることが好ましい。多官能モノマーは、一種単独で用いる以外に2種類以上を混合して用いてもよい。 Among these, it is preferable to use polyfunctional acrylic monomers such as trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like. Two or more types of polyfunctional monomers may be mixed and used in addition to a single type.
多官能モノマーを用いる場合、多官能モノマーの微粒子含有組成物中における添加量としては、特に限定されるものではなく、該組成物の全固形分に対して、5〜50質量%が一般的であり、10〜40質量%が好ましい。該添加量が前記範囲内であると、光感度や画像を構成する膜の強度も良好であり、膜形成したときの膜の粘着性が過剰になることもない。 When the polyfunctional monomer is used, the amount of the polyfunctional monomer added in the fine particle-containing composition is not particularly limited, and is generally 5 to 50% by mass with respect to the total solid content of the composition. Yes, 10-40 mass% is preferable. When the addition amount is within the above range, the photosensitivity and the strength of the film constituting the image are good, and the adhesiveness of the film when the film is formed does not become excessive.
前記多官能モノマーは、光や熱を用いて重合可能な化合物であり、微粒子含有組成物を光硬化性もしくは熱硬化性に構成する場合、重合開始剤を併用することが好ましく、中でも光重合開始剤を添加して光硬化性に構成されるのがより好ましい。さらに、前記多官能モノマー以外にオリゴマーを含んでいてもよい。 The polyfunctional monomer is a compound that can be polymerized using light or heat, and when the fine particle-containing composition is configured to be photocurable or thermosetting, it is preferable to use a polymerization initiator in combination. More preferably, it is configured to be photocurable by adding an agent. Furthermore, an oligomer may be included in addition to the polyfunctional monomer.
前記光重合開始剤としては、特開2004−347831号公報の段落番号[0024]に記載の化合物が挙げられる。更に、特開平11−133600号公報に記載の「重合開始剤C」も好適なものとして挙げることができる。 Examples of the photopolymerization initiator include compounds described in paragraph [0024] of JP-A No. 2004-347831. Furthermore, “polymerization initiator C” described in JP-A-11-133600 can also be mentioned as a preferable example.
上記のうち、光感度が高く、黄ばみなどの着色が少なく、良好な表示特性を得ることができる例として、トリハロメチルオキサジアゾール系の光重合開始剤とトリハロメチル−s−トリアジン系の光重合開始剤との組み合わせが挙げられ、中でも、2−トリクロロメチル−5−(p−スチリルメチル)−1,3,4−オキサジアゾールと2,4−ビス(トリクロロメチル)−6−[4’−(N,N−ビスエトキシカルボニルメチルアミノ)−3’−プロモフェニル]−s−トリアジンとの組み合わせが最も好ましい。 Among the above, as an example of high photosensitivity, less yellowing, and good display characteristics, a trihalomethyloxadiazole photopolymerization initiator and a trihalomethyl-s-triazine photopolymerization Examples include combinations with initiators, among which 2-trichloromethyl-5- (p-styrylmethyl) -1,3,4-oxadiazole and 2,4-bis (trichloromethyl) -6- [4 ′ A combination with-(N, N-bisethoxycarbonylmethylamino) -3'-promophenyl] -s-triazine is most preferred.
上記のように光重合開始剤を組み合わせる場合の比率(トリハロメチルオキサジアゾール系/トリハロメチル−s−トリアジン系の質量比率)は、95/5〜20/80であるのが好ましく、90/10〜30/70がより好ましく、最も好ましくは80/20〜40/60である。 The ratio when combining the photopolymerization initiator as described above (mass ratio of trihalomethyloxadiazole series / trihalomethyl-s-triazine series) is preferably 95/5 to 20/80, and 90/10 -30/70 is more preferred, and most preferred is 80 / 20-40 / 60.
また、上記の光重合開始剤の詳細については、特開平1−152449号公報、特開平1−254918号公報、特開平2−153353号公報の記載を参照することができる。
上記以外に好適な光重合開始剤の例として、ベンゾフェノン系の光重合開始剤を挙げることができる。
For details of the photopolymerization initiator, reference can be made to the descriptions in JP-A-1-152449, JP-A-1-254918, and JP-A-2-153353.
In addition to the above, examples of suitable photopolymerization initiators include benzophenone photopolymerization initiators.
後述するように、本発明の微粒子含有組成物には顔料を用いることができ、該顔料の微粒子含有組成物の固形分全体に占める割合が15〜25質量%付近である場合には、光重合開始剤と共に、クマリン系化合物を併用することで同様の効果を得ることが可能である。 As will be described later, a pigment can be used in the fine particle-containing composition of the present invention, and when the proportion of the pigment in the total solid content of the fine particle-containing composition is about 15 to 25% by mass, photopolymerization is performed. A similar effect can be obtained by using a coumarin compound together with the initiator.
前記クマリン系化合物としては、7−[2−[4−(3−ヒドロキシメチルビペリジノ)−6−ジエチルアミノ]トリアジニルアミノ]−3−フェニルクマリンが最も好ましい。 The coumarin compound is most preferably 7- [2- [4- (3-hydroxymethylbiperidino) -6-diethylamino] triazinylamino] -3-phenylcoumarin.
クマリン系化合物を用いる場合、光重合開始剤とクマリン系化合物との比率(光重合開始剤/クマリン系化合物の質量比率)としては、20/80〜80/20が好ましく、30/70〜70/30がより好ましく、最も好ましくは40/60〜60/40である。 When the coumarin compound is used, the ratio of the photopolymerization initiator to the coumarin compound (photopolymerization initiator / coumarin compound mass ratio) is preferably 20/80 to 80/20, preferably 30/70 to 70 /. 30 is more preferable, and most preferably 40/60 to 60/40.
なお、本発明に使用可能な光重合開始剤は、上記した重合開始剤に制限されるものではなく、他の公知のものの中から適宜選択することできる。 In addition, the photoinitiator which can be used for this invention is not restrict | limited to the above-mentioned polymerization initiator, It can select suitably from other well-known things.
光重合開始剤は、1種単独で用いる以外に、2種類以上を混合して用いてもよく、特に2種類以上を併用した組成が好ましい。
本発明の微粒子含有組成物が光重合開始剤を含有する場合、光重合開始剤の微粒子含有組成物中における添加量は、該組成物の全固形分に対して、0.1〜20質量%が一般的であり、0.3〜15質量%が好ましい。該含有量が前記範囲内であると、光感度や画像を構成する膜の強度低下を効果的に防止することができる。
Two or more types of photopolymerization initiators may be mixed and used, and a composition using two or more types is particularly preferable.
When the fine particle-containing composition of the present invention contains a photopolymerization initiator, the addition amount of the photopolymerization initiator in the fine particle-containing composition is 0.1 to 20% by mass relative to the total solid content of the composition. Is generally 0.3 to 15% by mass. When the content is within the above range, it is possible to effectively prevent the photosensitivity and the strength of the film constituting the image from decreasing.
本発明の微粒子含有組成物においては、熱もしくは光で硬化する化合物として、感光性樹脂組成物を用いて好適に構成することができる。
前記感光性樹脂組成物としては、既述の多官能モノマー及び/又はオリゴマーと光重合開始剤とを含む感光性樹脂組成物、並びに特開平10−160926号公報の段落番号[0016]〜[0022]及び[0029]に記載のものが好適である。更に、他の光重合性のモノマーを併用してもよい。
The fine particle-containing composition of the present invention can be suitably configured using a photosensitive resin composition as a compound that is cured by heat or light.
Examples of the photosensitive resin composition include the photosensitive resin composition containing the polyfunctional monomer and / or oligomer described above and a photopolymerization initiator, and paragraphs [0016] to [0022] of JP-A-10-160926. ] And [0029] are preferred. Furthermore, other photopolymerizable monomers may be used in combination.
また、銀コロイドのように金属微粒子又は金属化合物微粒子を水分散物として用いる場合には、前記感光性樹脂組成物として水系のものが有用である。水系の感光性樹脂組成物としては、特開平8−271727号公報の段落番号[0015]〜[0023]に記載のもの、並びに市販のものとして、例えば東洋合成工業(株)製の「SPP−M20」、「SPP−H−13」等が挙げられる。 Further, when metal fine particles or metal compound fine particles are used as an aqueous dispersion, such as silver colloid, an aqueous one is useful as the photosensitive resin composition. Examples of the aqueous photosensitive resin composition include those described in paragraphs [0015] to [0023] of JP-A No. 8-271727, and commercially available products such as “SPP-” manufactured by Toyo Gosei Co., Ltd. M20 "," SPP-H-13 "and the like.
−他の成分−
本発明の微粒子含有組成物は、上記以外に必要に応じて、下記の公知の顔料、界面活性剤、併用できるポリマー、分散剤、分散安定剤等の他の成分を用いて好適に構成することができる。
-Other ingredients-
In addition to the above, the fine particle-containing composition of the present invention is preferably constituted by using other components such as the following known pigments, surfactants, polymers that can be used together, dispersants, dispersion stabilizers and the like as necessary. Can do.
〜顔料〜
顔料としては、カーボンブラックなどの黒色顔料を用いることができる。
顔料の添加量は、既述の金属微粒子及び/又は金属化合物微粒子に対して、50質量%以下が好ましく、特に30質量%以下が好ましい。顔料の添加量が50質量%を越えると、必要な光学濃度を得るために必要な遮光膜の厚みが増大し、遮光膜上に形成される赤、青、緑の画素品位が低下することがある。
~ Pigment ~
As the pigment, a black pigment such as carbon black can be used.
The addition amount of the pigment is preferably 50% by mass or less, particularly preferably 30% by mass or less, based on the above-described metal fine particles and / or metal compound fine particles. If the added amount of the pigment exceeds 50% by mass, the thickness of the light shielding film necessary for obtaining the required optical density increases, and the quality of red, blue, and green pixels formed on the light shielding film may decrease. is there.
また、色味調整のため、黒色以外に青色その他の顔料を含んでもよい。黒色以外の顔料を添加する場合の添加量は、既述の金属微粒子及び/又は金属化合物微粒子に対して、40質量%以下が好ましく、20質量%以下がより好ましい。該添加量が40質量%を越えると、膜形成した際の膜の色味が悪化することがある。 In addition to black, blue and other pigments may be included for color adjustment. In the case of adding a pigment other than black, the addition amount is preferably 40% by mass or less, more preferably 20% by mass or less, based on the above-described metal fine particles and / or metal compound fine particles. When the added amount exceeds 40% by mass, the color of the film may be deteriorated when the film is formed.
〜界面活性剤〜
本発明の微粒子含有組成物には、塗布性、微粒子の分散安定性の改良などの目的で、界面活性剤を添加することができる。界面活性剤としては、ノニオン系、アニオン系、カチオン系の界面活性剤を特に制限なく使用可能である。中でも、液の安定性の観点から、アニオン界面活性剤が特に好ましい。また、フッ素系界面活性剤は好ましい界面活性剤である。
~ Surfactant ~
A surfactant can be added to the fine particle-containing composition of the present invention for the purpose of improving coating properties and dispersion stability of fine particles. As the surfactant, nonionic, anionic and cationic surfactants can be used without particular limitation. Among these, an anionic surfactant is particularly preferable from the viewpoint of liquid stability. Moreover, a fluorine-type surfactant is a preferable surfactant.
前記界面活性剤の好ましい例として、C8F17SO2N(C2H5)(C2H4O)14H、C8F17SO3Li、C7F15COONH4、C8F17SO2N(C2H5)C2H4OPO(OH)2等が挙げられる。更に市販品として、F110、F113、F120、F150、F176PF、F177、F780(いずれも大日本インキ化学工業(株)製、オリゴマータイプフッ素系界面活性剤)などを挙げることができる。 As preferable examples of the surfactant, C 8 F 17 SO 2 N (C 2 H 5 ) (C 2 H 4 O) 14 H, C 8 F 17 SO 3 Li, C 7 F 15 COONH 4 , C 8 F 17 SO 2 N (C 2 H 5 ) C 2 H 4 OPO (OH) 2 or the like. Furthermore, as a commercial item, F110, F113, F120, F150, F176PF, F177, F780 (all are the Dainippon Ink and Chemicals Co., Ltd. make, oligomer type fluorine-type surfactant) etc. can be mentioned.
〜併用できるポリマー〜
本発明の微粒子含有組成物には、アルカリ現像性を有するバインダーとして、あるいは既述の金属微粒子及び/又は金属化合物微粒子の分散安定性を更に良化するために、既述の「チオエーテル基を有する高分子化合物」以外のポリマーを併用することができる。該ポリマーの種類としては、特に制限はなく、求められる性質、共重合する成分、酸価、分子量は、「チオエーテル基を有する高分子化合物」と同義である。
~ Polymer that can be used together ~
In the fine particle-containing composition of the present invention, the above-mentioned “having a thioether group” is used as a binder having alkali developability or in order to further improve the dispersion stability of the fine metal particles and / or fine metal compound particles. Polymers other than the “polymer compound” can be used in combination. The type of the polymer is not particularly limited, and the required properties, the components to be copolymerized, the acid value, and the molecular weight are synonymous with the “polymer compound having a thioether group”.
〜分散安定剤〜
本発明の微粒子含有組成物には、分散安定剤を用いることができ、分散安定剤については、例えば「顔料分散技術」(技術情報協会(株)、1999年発行)に記載のものを使用できる。
~ Dispersion stabilizer ~
In the fine particle-containing composition of the present invention, a dispersion stabilizer can be used. As the dispersion stabilizer, for example, those described in “Pigment Dispersion Technology” (Technical Information Association, Inc., issued in 1999) can be used. .
−−微粒子含有組成物の調製−−
本発明の微粒子含有組成物は、金属微粒子及び/又は金属化合物微粒子、チオエーテル基を有する高分子化合物、熱もしくは光で硬化する化合物、及び必要に応じて添加可能な他の成分を(好ましくは溶剤を加えて)混合分散することにより調製できる。好ましくは、予め金属微粒子及び/又は金属化合物微粒子をチオエーテル基を有する高分子化合物と共に溶剤に分散した微粒子分散液を調製後、これに熱もしくは光で硬化する化合物と添加可能な他の成分とを添加混合することにより調製することができる。
--Preparation of fine particle-containing composition--
The fine particle-containing composition of the present invention comprises metal fine particles and / or metal compound fine particles, a polymer compound having a thioether group, a compound curable by heat or light, and other components that can be added as necessary (preferably a solvent). And mixing and dispersing. Preferably, after preparing a fine particle dispersion in which metal fine particles and / or metal compound fine particles are previously dispersed in a solvent together with a polymer compound having a thioether group, a compound that can be cured by heat or light and other components that can be added are added thereto. It can be prepared by adding and mixing.
調製に用いる溶剤には、特に制限なく使用可能であり、中でも特にSP値が9.0以上のものが好ましい。SP値が9.0以上のものを用いると、分散性が特に良好となり、薄膜でも充分な光学濃度を達成することができる。 The solvent used for the preparation can be used without any particular limitation, and those having an SP value of 9.0 or more are particularly preferable. When the SP value is 9.0 or more, the dispersibility is particularly good, and a sufficient optical density can be achieved even with a thin film.
SP値は、溶解性パラメーターともいわれるもので、凝集エネルギー密度の平方根で表され、本発明においては、「接着ハンドブック」(日本接着学会編、日刊工業新聞社発行、1971年初版発行)の838頁に記載のものを意味する。 The SP value is also referred to as a solubility parameter, and is represented by the square root of the cohesive energy density. In the present invention, page 838 of "Adhesion Handbook" (edited by the Japan Adhesive Society, published by Nikkan Kogyo Shimbun, 1971, first edition). Means the following.
溶剤のSP値は、例えば、n−ヘキサン/7.3、トルエン/8.9、酢酸エチル/9.1、メチルエチルケトン/9.3、アセトン/10.0、エチルアルコール/12.7、メチルアルコール/14.5、水/23.4、等である。ここで、SP値の単位は「(cal/cm3)1/2」である。 The SP value of the solvent is, for example, n-hexane / 7.3, toluene / 8.9, ethyl acetate / 9.1, methyl ethyl ketone / 9.3, acetone / 10.0, ethyl alcohol / 12.7, methyl alcohol /14.5, water / 23.4, and the like. Here, the unit of the SP value is “(cal / cm 3 ) 1/2 ”.
本発明の微粒子含有組成物は、金属微粒子及び/又は金属化合物微粒子を少なくとも「チオエーテル基を有する高分子化合物」(及び好ましくは溶剤)と共に混合した混合液を、超音波分散機、ペイントシェーカー、ボールミル、アイガーミルなどの公知の分散機を用いて分散処理することにより調製することができる。中でも、超音波分散機が好ましい。 The fine particle-containing composition of the present invention comprises a mixture of metal fine particles and / or metal compound fine particles together with at least a “polymer compound having a thioether group” (and preferably a solvent). It can be prepared by dispersing using a known dispersing machine such as an Eiger mill. Among these, an ultrasonic disperser is preferable.
本発明の微粒子含有組成物は、金属微粒子及び/又は金属化合物微粒子を分散して含む用途に好適であり、(好ましくは黒色の)着色膜形成用インク、遮光膜、カラーフィルタの黒色画像(ブラックマトリクスを含む。)等の用途に好適に用いることができる。 The fine particle-containing composition of the present invention is suitable for applications containing dispersed metal fine particles and / or metal compound fine particles, and is preferably a black image (black) of colored film forming ink, light shielding film, and color filter (preferably black). It can be suitably used for applications such as a matrix.
<表示装置用着色膜形成用インク>
本発明の表示装置用着色膜形成用インクは、既述の本発明の微粒子含有組成物を用いて調製されるものである。本発明の微粒子含有組成物を用いて構成されるので、インクとしての長期保存時の安定性が高く、色相が良好(特に黒色相が良好)で高い光学濃度を有する。
<Ink for forming colored film for display device>
The ink for forming a colored film for a display device of the present invention is prepared using the fine particle-containing composition of the present invention described above. Since it is configured using the fine particle-containing composition of the present invention, it has high stability during long-term storage as an ink, has a good hue (especially a black hue) and a high optical density.
本発明の表示装置用着色膜形成用インクは、金属微粒子及び/又は金属化合物微粒子、少なくとも1つのチオエーテル基を有する高分子化合物、及び熱もしくは光で硬化する化合物を含んでなり、場合により、必要に応じて着色剤(好ましくは顔料)など他の成分を用いて構成され、インクの付与後に加熱又は紫外線などのエネルギー線の付与により硬化させ得るものである。 The ink for forming a colored film for a display device of the present invention comprises metal fine particles and / or metal compound fine particles, a polymer compound having at least one thioether group, and a compound that is cured by heat or light, and may be necessary. Depending on the colorant (preferably a pigment), other components are used, and the ink can be cured by application of heat or application of energy rays such as ultraviolet rays after application of the ink.
なお、本発明の微粒子含有組成物の詳細については、既述の通りであり、前記成分以外に、インクを構成するのに必要な成分を適宜選択して添加することが可能である。 The details of the fine particle-containing composition of the present invention are as described above, and in addition to the above components, components necessary for constituting the ink can be appropriately selected and added.
本発明の表示装置用着色膜形成用インクは、液晶表示装置、プラズマディスプレイ表示装置、EL表示装置、CRT表示装置などの表示装置の用途に好適であり、表示装置内に設けられる黒色の縁や画素周囲の格子状もしくはストライプ状の黒色の縁部(いわゆるブラックマトリックス)、薄膜トランジスター(TFT)遮光のためのドット状もしくは線状の黒色パターンなどの形成に好適である。 The ink for forming a colored film for a display device of the present invention is suitable for use in a display device such as a liquid crystal display device, a plasma display display device, an EL display device, a CRT display device, and the like. It is suitable for forming a grid-like or stripe-like black edge (so-called black matrix) around a pixel, a dot-like or linear black pattern for shielding a thin film transistor (TFT), and the like.
<表示装置用遮光膜>
本発明の表示装置用遮光膜は、既述の本発明の微粒子含有組成物、あるいは既述の本発明の表示装置用着色膜形成用インクを用いて形成されるものである。この遮光膜は、本発明の微粒子含有組成物を用いて構成されるので、製造工程上高温に曝されるような場合など、高温環境での樹脂成分、微粒子の変質に伴なう色味変化が少なく、色相が良好(特に黒色相が良好)で高い光学濃度を有する。
<Light shielding film for display device>
The light shielding film for a display device of the present invention is formed using the fine particle-containing composition of the present invention described above or the color film forming ink for a display device of the present invention described above. Since this light-shielding film is constituted using the fine particle-containing composition of the present invention, such as when exposed to high temperatures in the production process, the color change caused by alteration of resin components and fine particles in a high temperature environment , The hue is good (especially the black hue is good) and the optical density is high.
本発明の表示装置用遮光膜は、既述の本発明の熱硬化性もしくは光硬化性を有する微粒子含有組成物を所望の基板に塗布し、乾燥させる方法(塗布法)、又は仮支持体上に既述の本発明の熱硬化性もしくは光硬化性を有する微粒子含有組成物を塗布し、乾燥させて設けられた熱硬化性もしくは光硬化性の遮光性層を有する転写材料を用い、前記遮光性層を所望の基板に転写する方法(転写法)、等を利用して作製することができる。 The light-shielding film for a display device of the present invention is a method (coating method) in which the thermosetting or photocurable fine particle-containing composition of the present invention is applied to a desired substrate and dried, or on a temporary support. The transfer material having a thermosetting or photocurable light-shielding layer provided by applying and drying the thermosetting or photocurable fine particle-containing composition of the present invention described above to the light shielding It can be produced by using a method (transfer method) or the like of transferring a conductive layer to a desired substrate.
本発明の表示装置用遮光膜が所望のパターンにパターン化されてなるものである場合、上記の塗布法又は転写法により設けられた熱硬化性もしくは光硬化性の遮光性層をパターニングして形成される。
パターニングする方法としては、露光・現像による方法、レーザーの熱により不要部分を除去する方法(アブレーション法)、基板上に設けられた遮光性層の上に感光性レジスト膜を塗布し、これを露光・現像してパターニングした後、感光性レジスト膜を除去する方法などが挙げられる。本発明では、これらの方法のいずれも使用できるが、下記方法(1)〜(3)は工程の簡便さやパターニングの解像度などの点で好ましい。
When the light-shielding film for a display device of the present invention is formed into a desired pattern, it is formed by patterning the thermosetting or photo-curable light-shielding layer provided by the above coating method or transfer method. Is done.
Patterning methods include exposure / development, removal of unnecessary parts by laser heat (ablation method), and application of a photosensitive resist film on the light-shielding layer provided on the substrate. -The method of removing the photosensitive resist film after developing and patterning may be mentioned. In the present invention, any of these methods can be used, but the following methods (1) to (3) are preferable in terms of the simplicity of the process and the resolution of patterning.
(1)基板上に非感光性の微粒子含有組成物を塗布、乾燥して遮光性層を形成し、この遮光性層上にフォトレジストを塗布し、塗布形成されたフォトレジスト膜を露光現像によりパターニングした後、フォトレジスト膜と共にその下層となる遮光性層を溶解除去する方法;
(2)基板上に感光性の微粒子含有組成物を塗布、乾燥して感光性の遮光性層を形成し、形成された感光性の遮光性層を露光、現像(未硬化部分を除去)してパターニングする方法;
(3)仮支持体の上に感光性の微粒子含有組成物を塗布、乾燥して感光性の遮光性層を予め形成して積層体(感光性転写材料)としておき、この積層体を所望の基板上にラミネートした後に仮支持体を除去して感光性の遮光性層を基板に転写した後、基板上に転写形成された感光性の遮光性層を露光、現像(未硬化部分を除去)してパターニングする方法;
(1) A non-photosensitive fine particle-containing composition is applied onto a substrate and dried to form a light-shielding layer. A photoresist is applied onto the light-shielding layer, and the formed photoresist film is exposed and developed. A method of dissolving and removing the underlying light shielding layer together with the photoresist film after patterning;
(2) A photosensitive fine particle-containing composition is applied onto a substrate and dried to form a photosensitive light-shielding layer. The formed photosensitive light-shielding layer is exposed and developed (uncured portions are removed). Patterning method;
(3) A photosensitive fine particle-containing composition is applied onto a temporary support and dried to form a photosensitive light-shielding layer in advance to form a laminate (photosensitive transfer material). After laminating on the substrate, the temporary support is removed and the photosensitive light-shielding layer is transferred to the substrate, and then the photosensitive light-shielding layer transferred and formed on the substrate is exposed and developed (uncured portions are removed). Patterning method;
上記の方法(1)〜(3)はいずれも、蒸着法やスパッタリング法を用いた従来の方法に比べて簡単な工程で遮光性層を形成することができ、所望のパターンに遮光膜を形成することができる。 In any of the above methods (1) to (3), the light-shielding layer can be formed by a simple process compared to the conventional methods using vapor deposition or sputtering, and the light-shielding film is formed in a desired pattern. can do.
〜微粒子含有組成物の付与(塗布等)工程〜
微粒子含有組成物を基板又は仮支持体に付与する方法としては、塗布方法が好適であり、該塗布方法としては特に制限はなく、例えば、特開平5−224011号公報に記載のスピンコート法、特開平9−323472号公報に記載のダイコート法などを用いることができる。
~ Step of applying (coating etc.) fine particle-containing composition ~
As a method for applying the fine particle-containing composition to a substrate or a temporary support, a coating method is suitable, and the coating method is not particularly limited. For example, a spin coating method described in JP-A No. 5-224011 A die coating method described in JP-A-9-323472 can be used.
仮支持体に付与する場合、後述するように、仮支持体と微粒子含有組成物からなる遮光性層と必要に応じて熱可塑性樹脂層及び中間層とで構成された転写材料とすることができる。 When applied to the temporary support, as will be described later, it can be a transfer material composed of a temporary support, a light-shielding layer comprising a fine particle-containing composition, and optionally a thermoplastic resin layer and an intermediate layer. .
〜露光・現像工程〜
露光は、公知の光源を用いて所望のパターンにて行なうことができる。光源は、フォトレジスト膜又は感光性の遮光性層の感光性状に応じて選択すればよい。例えば、超高圧水銀灯、キセノン灯、カーボンアーク灯、アルゴンレーザー等の公知の光源を使用することができる。また、特開平6−59119号公報に記載の、400nm以上の波長の光透過率が2%以下である光学フィルター等を併用してもよい。
-Exposure and development process-
The exposure can be performed in a desired pattern using a known light source. The light source may be selected according to the photosensitivity of the photoresist film or the photosensitive light-shielding layer. For example, a known light source such as an ultra-high pressure mercury lamp, a xenon lamp, a carbon arc lamp, or an argon laser can be used. Moreover, you may use together the optical filter etc. which are 2% or less of the light transmittance of the wavelength of 400 nm or more as described in Unexamined-Japanese-Patent No. 6-59119.
露光は、被露光面の全面を1回の露光により露光する一括露光でもよいし、被露光面を分割して複数回に分けて露光する分割露光としてもよい。さらに、レーザーを用いて被露光面をスキャンしながら行なう露光方法を適用してもよい。 The exposure may be batch exposure in which the entire surface to be exposed is exposed by one exposure, or may be divided exposure in which the surface to be exposed is divided and exposed in multiple times. Furthermore, an exposure method performed while scanning an exposed surface using a laser may be applied.
露光後の現像は、現像液を用いて行なうことができる。現像液としては、アルカリ性物質の希薄水溶液が好適であり、水と混和性の有機溶剤を少量添加したものを用いることもできる。 Development after exposure can be performed using a developer. As the developer, a dilute aqueous solution of an alkaline substance is suitable, and a solution to which a small amount of an organic solvent miscible with water is added can also be used.
前記アルカリ性物質としては、アルカリ金属水酸化物類(例、水酸化ナトリウム、水酸化カリウム)、アルカリ金属炭酸塩類(例、炭酸ナトリウム、炭酸カリウム)、アルカリ金属重炭酸塩類(例、炭酸水素ナトリウム、炭酸水素カリウム)、アルカリ金属ケイ酸塩類(例、ケイ酸ナトリウム、ケイ酸カリウム)、アルカリ金属メタケイ酸塩類(例、メタケイ酸ナトリウム、メタケイ酸カリウム)、トリエタノールアミン、ジエタノールアミン、モノエタノールアミン、モルホリン、テトラアルキルアンモンニウムヒドロキシド類(例えばテトラメチルアンモニウムヒドロキシド)、又は燐酸三ナトリウム等が適当である。アルカリ性物質の濃度は、0.01〜30質量%が好ましく、pHは8〜14が好ましい。感光性の遮光性層の酸化等の性質に応じて例えば、現像液のpH等を変化させて、膜状脱離による現像が行えるように調整することができる。 Examples of the alkaline substance include alkali metal hydroxides (eg, sodium hydroxide, potassium hydroxide), alkali metal carbonates (eg, sodium carbonate, potassium carbonate), alkali metal bicarbonates (eg, sodium bicarbonate, Potassium bicarbonate), alkali metal silicates (eg, sodium silicate, potassium silicate), alkali metal metasilicates (eg, sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, morpholine Tetraalkylammonium hydroxides (for example, tetramethylammonium hydroxide) or trisodium phosphate are suitable. The concentration of the alkaline substance is preferably 0.01 to 30% by mass, and the pH is preferably 8 to 14. Depending on the properties of the photosensitive light-shielding layer such as oxidation, for example, the pH of the developer can be changed so that development by film-like detachment can be performed.
前記水と混和性の有機溶剤としては、例えば、メタノール、エタノール、2−プロパノール、1−プロパノール、ブタノール、ジアセトンアルコール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノ−n−ブチルエーテル、ベンジルアルコール、アセトン、メチルエチルケトン、シクロヘキサノン、ε−カプロラクトン、γ−ブチロラクトン、ジメチルホルムアミド、ジメチルアセトアミド、ヘキサメチルホスホルアミド、乳酸エチル、乳酸メチル、ε−カプロラクタム、N−メチルピロリドン等が適当である。水と混和性の有機溶剤の濃度は、0.1〜30質量%が一般的である。 Examples of the water-miscible organic solvent include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, Benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone and the like are suitable. The concentration of the organic solvent miscible with water is generally 0.1 to 30% by mass.
現像液には、さらに公知の界面活性剤を添加することができる。界面活性剤を添加する場合の濃度は、0.01〜10質量%が好ましい。 A known surfactant can be further added to the developer. The concentration when the surfactant is added is preferably 0.01 to 10% by mass.
現像液は、浴液として用いてもよいし、あるいは噴射液として用いるようにしてもよい。感光性の遮光性層等の未硬化部分を固形状(好ましくは膜状)で除去することもでき、この場合には、現像液中で回転ブラシで擦るか、湿潤スポンジで擦るなどの方法、あるいは現像液を噴射した際の噴射圧を利用する方法が好ましい。現像液の温度は、通常室温付近から40℃の範囲が好ましい。
また、現像後に水洗工程を設けることも可能である。
The developer may be used as a bath solution or a spray solution. Uncured portions such as a light-sensitive light-shielding layer can also be removed in a solid form (preferably in a film form). In this case, a method such as rubbing with a rotating brush or a wet sponge in a developer, Or the method of utilizing the injection pressure at the time of injecting a developing solution is preferable. The temperature of the developer is usually preferably in the range of about room temperature to 40 ° C.
It is also possible to provide a water washing step after development.
〜加熱その他工程〜
現像後には、加熱処理を行なうことが好ましい。加熱処理により、露光により硬化した感光性の遮光性層の硬化を促進し、耐溶剤性や耐アルカリ性をより高めることができる。加熱方法は、現像後の基板を電気炉、乾燥器等の中に入れて加熱する方法、赤外線ランプで加熱する方法などを適用できる。
~ Heating and other processes ~
After the development, it is preferable to perform a heat treatment. By the heat treatment, curing of the photosensitive light-shielding layer cured by exposure can be promoted, and the solvent resistance and alkali resistance can be further increased. As a heating method, a method of heating the substrate after development in an electric furnace, a dryer or the like, a method of heating with an infrared lamp, or the like can be applied.
本発明の表示装置用遮光膜は、膜強度を高める観点から、現像後に加熱処理を行なって得られた膜であるのが好ましい。加熱処理は、遮光膜の組成、厚みにもよるが、180〜300℃で5〜60分間行なうのが好ましく、200〜270℃で10〜50分間行なうのがより好ましく、200〜250℃で10〜50分間行なうのが特に好ましい。
また、現像後、加熱処理をする前に、硬化促進のために更に露光を行なってもよく、この場合の露光も既述の露光の場合と同様の方法により行なうことができる。
The light-shielding film for a display device of the present invention is preferably a film obtained by performing a heat treatment after development from the viewpoint of increasing the film strength. The heat treatment is preferably performed at 180 to 300 ° C. for 5 to 60 minutes, more preferably at 200 to 270 ° C. for 10 to 50 minutes, and more preferably at 200 to 250 ° C., depending on the composition and thickness of the light shielding film. It is particularly preferred to carry out for ~ 50 minutes.
Further, after the development and before the heat treatment, further exposure may be performed to accelerate the curing, and the exposure in this case can also be performed by the same method as in the exposure described above.
上記以外に更に、感光性の遮光性層の形成する場合には、遮光性層の形成後、パターン状に露光する前に遮光性層の上に更に保護層を設ける工程を設けてもよい。
保護層は、パターン露光時に酸素を遮断して感光性の遮光性層の露光感度を高めるための酸素遮断層として機能するものであり、酸素遮断性の樹脂、例えばポリビニルアルコールを主成分に含む層が好ましい。なお、この層は、遮光膜(遮光画像)形成後は不要であるので、現像により除去される。
In addition to the above, in the case of forming a photosensitive light-shielding layer, a step of further providing a protective layer on the light-shielding layer may be provided after the light-shielding layer is formed and before exposure to a pattern.
The protective layer functions as an oxygen blocking layer for blocking oxygen during pattern exposure to increase the exposure sensitivity of the photosensitive light blocking layer, and is a layer containing an oxygen blocking resin such as polyvinyl alcohol as a main component. Is preferred. This layer is unnecessary after the formation of the light-shielding film (light-shielded image), and is removed by development.
本発明の表示装置用遮光膜の厚みは、0.05〜2.0μmが好ましく、0.1〜1.5μmがより好ましい。該厚みが前記範囲内であると、必要な光学濃度を確保して表示コントラストが良好であると共に、基板表面の凹凸(遮光膜の設けられた部分と設けられていない部分の格差)が大きくなりすぎて後工程でRGBの画素をこの上に形成する際に不都合を来すこともない。 The thickness of the light-shielding film for a display device of the present invention is preferably 0.05 to 2.0 μm, more preferably 0.1 to 1.5 μm. When the thickness is within the above range, the necessary optical density is secured and the display contrast is good, and the unevenness of the substrate surface (the difference between the portion where the light shielding film is provided and the portion where the light shielding film is not provided) increases. Thus, there is no inconvenience when forming RGB pixels on this in a later step.
本発明の表示装置用遮光膜の透過濃度(光学濃度)としては、3.5以上が好ましく、4.0以上がより好ましく、特に好ましくは4.5以上である。光学濃度が前記範囲内であると、コントラストが高く良好な表示品質を確保することができる。 The transmission density (optical density) of the light-shielding film for display device of the present invention is preferably 3.5 or more, more preferably 4.0 or more, and particularly preferably 4.5 or more. When the optical density is within the above range, high contrast and high display quality can be ensured.
−基板−
前記基板としては、表示装置に一般に用いられるガラス基板が好ましい。
ガラス基板としては、例えば、ソーダガラス、低アルカリガラス、無アルカリガラス等の公知のガラスを用いたガラス基板が好適である。ガラス基板については、例えば、「液晶ディスプレイ工学入門」(鈴木ハナエ著、日刊工業新聞社発行(1998年))に記載がある。その他の基板として、シリコンウエハやポリオレフィン系などの透明プラスチックも用いることができる。さらに、TFT素子が配されたTFT素子基板を用いることもできる。
-Board-
As the substrate, a glass substrate generally used in a display device is preferable.
As the glass substrate, for example, a glass substrate using a known glass such as soda glass, low alkali glass or non-alkali glass is suitable. The glass substrate is described, for example, in “Introduction to Liquid Crystal Display Engineering” (Hanae Suzuki, published by Nikkan Kogyo Shimbun (1998)). As other substrates, transparent plastics such as silicon wafers and polyolefins can also be used. Furthermore, a TFT element substrate on which TFT elements are arranged can also be used.
前記基板の厚みとしては、0.5〜3mmの範囲が好ましく、0.6〜2mmの範囲がより好ましい。 The thickness of the substrate is preferably in the range of 0.5 to 3 mm, and more preferably in the range of 0.6 to 2 mm.
本発明の表示装置用遮光膜は、表示画像のコントラスト、視認性の観点から、より黒色であることが好ましい。より黒色であることは、遮光膜の色度をxyz表色系の(x,y)値で表すとき、理想的な黒色の目標色度からの色差として評価することができる。すなわち、色差の値が小さいほど理想的な黒色に近づき、遠いほど黒色から外れることになる。具体的には、理想的な黒色の目標色度(x,y)値を(0.33,0.33)としたときの該目標色度との差を、XY表色系のΔE値で表すことにより評価することができる。 The light-shielding film for a display device of the present invention is preferably blacker from the viewpoint of the contrast and visibility of the display image. Being blacker can be evaluated as a color difference from an ideal black target chromaticity when the chromaticity of the light shielding film is expressed by an (x, y) value in the xyz color system. That is, the smaller the color difference value is, the closer it is to an ideal black color, and the farther the color difference is, the farther from black. Specifically, the difference from the target chromaticity when the ideal black target chromaticity (x, y) value is (0.33, 0.33) is expressed as ΔE value of the XY color system. It can be evaluated by expressing.
<遮光材料>
本発明の遮光材料は、表示装置用遮光膜の形成に用いられる遮光材料であり、支持体上に少なくとも一層の微粒子含有層を有してなり、必要に応じて更に、熱可塑性樹脂層、中間層、及び最表層を覆う保護フィルム等を設けて構成することができる。
<Light shielding material>
The light-shielding material of the present invention is a light-shielding material used for forming a light-shielding film for a display device, and has at least one fine particle-containing layer on a support, and further includes a thermoplastic resin layer, an intermediate layer as necessary. A protective film that covers the outermost layer and the outermost layer can be provided.
本発明に係る微粒子含有層は、アスペクト比が2〜100の金属微粒子及び/又は金属化合物微粒子と、少なくとも1つのチオエーテル基を有する高分子化合物と、熱もしくは光で硬化する化合物とを少なくとも含み、熱硬化性もしくは光硬化性に構成される。また、必要に応じて更に、着色剤(より好ましくは黒色の着色剤)など他の成分を用いて構成することができる。
本発明においては、熱もしくは光で硬化する化合物として、多官能モノマー及び光重合開始剤を用いて光硬化性に構成された材料であるのが好ましい。
The fine particle-containing layer according to the present invention includes at least metal fine particles and / or metal compound fine particles having an aspect ratio of 2 to 100, a polymer compound having at least one thioether group, and a compound that is cured by heat or light, It is configured to be thermosetting or photocurable. Moreover, it can comprise using other components, such as a coloring agent (preferably black coloring agent) further as needed.
In the present invention, the compound that is cured by heat or light is preferably a material configured to be photocurable using a polyfunctional monomer and a photopolymerization initiator.
なお、微粒子含有層において、金属微粒子及び/又は金属化合物微粒子、チオエーテル基を有する高分子化合物、及び熱もしくは光で硬化する化合物、並びに着色剤など他の成分の詳細については、既述の本発明の微粒子含有組成物の場合と同様であり、好ましい態様も同様である。 In the fine particle-containing layer, details of other components such as metal fine particles and / or metal compound fine particles, a polymer compound having a thioether group, a compound curable by heat or light, and a colorant are described in the present invention. This is the same as the case of the fine particle-containing composition, and the preferred embodiment is also the same.
本発明の遮光材料は、支持体上に設けられた微粒子含有層が被転写体への転写が可能なように構成された転写材料であることが好ましい。
以下、感光性の遮光性層が設けられた感光性転写材料を例に詳細に説明する。但し、本発明においては、これに限定されるものではない。
The light-shielding material of the present invention is preferably a transfer material configured such that the fine particle-containing layer provided on the support can be transferred to the transfer target.
Hereinafter, a photosensitive transfer material provided with a photosensitive light-shielding layer will be described in detail as an example. However, the present invention is not limited to this.
本発明の遮光材料は、既述の表示装置用遮光膜の形成に好適な方法の一つとして挙げた方法(3)に好適な感光性転写材料に構成されるのが好ましい。この感光性転写材料は、仮支持体と、該仮支持体に直接もしくは他の層を介して本発明の感光性を持つ微粒子含有組成物を塗布、乾燥させて形成された感光性の遮光性層とで構成することができる。 The light-shielding material of the present invention is preferably composed of a photosensitive transfer material suitable for the method (3) mentioned as one of the suitable methods for forming the light-shielding film for a display device described above. This photosensitive transfer material comprises a temporary support and a photosensitive light-shielding property formed by applying the photosensitive fine particle-containing composition of the present invention to the temporary support directly or via another layer and drying. It can consist of layers.
感光性の遮光性層の層厚としては、0.05〜2.0μmが好ましく、0.1〜1.5μmがより好ましい。該厚みが前記範囲内であると、必要な光学濃度を確保して表示コントラストが良好であると共に、基板表面の凹凸(遮光膜の設けられた部分と設けられていない部分の格差)が大きくなりすぎて後工程でRGBの画素をこの上に形成する際に不都合を来すこともない。 The layer thickness of the photosensitive light-shielding layer is preferably 0.05 to 2.0 μm, more preferably 0.1 to 1.5 μm. When the thickness is within the above range, the necessary optical density is secured and the display contrast is good, and the unevenness of the substrate surface (the difference between the portion where the light shielding film is provided and the portion where the light shielding film is not provided) increases. Thus, there is no inconvenience when forming RGB pixels on this in a later step.
感光性転写材料には、仮支持体と感光性の遮光性層との間に熱可塑性樹脂層を設けた形態が好ましく、更に熱可塑性樹脂層と感光性の遮光性層との間にアルカリ可溶性の中間層を設けた形態がより好ましい。また、感光性の遮光性層の露出面には保護フィルムを設けてもよい。 In the photosensitive transfer material, a form in which a thermoplastic resin layer is provided between the temporary support and the photosensitive light-shielding layer is preferable, and further, an alkali-soluble property is provided between the thermoplastic resin layer and the photosensitive light-shielding layer. A form in which an intermediate layer is provided is more preferable. A protective film may be provided on the exposed surface of the photosensitive light-shielding layer.
仮支持体は、化学的及び熱的に安定であって、可撓性の物質で構成されたものが好ましい。具体的には、テフロン(登録商標)、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリアクリレート、ポリカーボネート、ポリエチレン、ポリプロピレン等の薄いシート又はこれらの積層物が好ましい。また、後述の熱可塑性樹脂層を設ける場合には、該層との剥離性が良好なものが好ましい。 仮支持体の厚さとしては、5〜300μmが適当であり、特に20〜150μmが好ましい。 The temporary support is preferably made of a flexible material that is chemically and thermally stable. Specifically, a thin sheet of Teflon (registered trademark), polyethylene terephthalate, polyethylene naphthalate, polyacrylate, polycarbonate, polyethylene, polypropylene, or a laminate thereof is preferable. Moreover, when providing the below-mentioned thermoplastic resin layer, a thing with favorable peelability from this layer is preferable. As thickness of a temporary support body, 5-300 micrometers is suitable, and 20-150 micrometers is especially preferable.
本発明の遮光材料が、微粒子含有層の転写が可能な転写材料以外の形態で構成される場合は、前記仮支持体を既述の基板に代えて構成することができる。この場合には、基板上に所望のパターンよりなる遮光画像(ブラックマトリクスを含む。)を形成することができ、該遮光画像が形成された基板をそのまま表示装置を構成する基板として用いることができる。 When the light-shielding material of the present invention is configured in a form other than the transfer material capable of transferring the fine particle-containing layer, the temporary support can be configured in place of the substrate described above. In this case, a light-shielded image (including a black matrix) having a desired pattern can be formed on the substrate, and the substrate on which the light-shielded image is formed can be used as it is as a substrate constituting the display device. .
−熱可塑性樹脂層−
熱可塑性樹脂層は、熱可塑性を有する樹脂を少なくとも含んでなり、一般には溶剤を用いて調製された熱可塑性樹脂含有の調製液を用いて形成することができる。
-Thermoplastic resin layer-
The thermoplastic resin layer contains at least a resin having thermoplasticity, and can be generally formed using a preparation solution containing a thermoplastic resin prepared using a solvent.
熱可塑性樹脂層を構成する樹脂としては、例えば、アクリル樹脂、ポリスチレン樹脂、ポリエステル、ポリウレタン、ゴム系樹脂、酢酸ビニル系樹脂、ポリオレフィン系樹脂、及びこれらの共重合体等を挙げることができる。熱可塑性樹脂層を構成する樹脂は、アルカリ可溶であることが望ましい。
また、熱可塑性樹脂層を構成する樹脂として、特開2004−317897号公報の段落番号[0046]〜[0048]に記載のものを使用できる。
Examples of the resin constituting the thermoplastic resin layer include acrylic resins, polystyrene resins, polyesters, polyurethanes, rubber resins, vinyl acetate resins, polyolefin resins, and copolymers thereof. It is desirable that the resin constituting the thermoplastic resin layer is alkali-soluble.
Moreover, what is described in Paragraph Nos. [0046]-[0048] of Unexamined-Japanese-Patent No. 2004-317897 can be used as resin which comprises a thermoplastic resin layer.
熱可塑性樹脂層の厚みは、3μm以上が好ましい。熱可塑性樹脂の厚みが前記範囲内であると、1μm以上の被転写体(下地)面の凹凸を完全に吸収することが可能である。また、上限については、アルカリ水溶液除去性、製造適性から約100μm以下が好ましく、より好ましくは約50μm以下である。 The thickness of the thermoplastic resin layer is preferably 3 μm or more. When the thickness of the thermoplastic resin is within the above range, it is possible to completely absorb the unevenness of the surface of the transferred material (underlying) of 1 μm or more. The upper limit is preferably about 100 μm or less, more preferably about 50 μm or less, from the viewpoint of the ability to remove alkaline aqueous solution and the suitability for production.
熱可塑性樹脂層を形成するための熱可塑性樹脂含有の調製液は、この層を構成する樹脂を溶解し得るものであれば特に制限はなく、例えば、メチルエチルケトン、n−プロパノール、i−プロパノール等を選択することができる。 The thermoplastic resin-containing preparation liquid for forming the thermoplastic resin layer is not particularly limited as long as it can dissolve the resin constituting the layer. For example, methyl ethyl ketone, n-propanol, i-propanol, etc. You can choose.
−中間層−
前記熱可塑性樹脂層を設ける場合、熱可塑性樹脂層と感光性の遮光性層との間には、調製液塗布時の両層の層混合を防止する、あるいは酸素遮断の目的で、さらに中間層を設けることが好ましい。
-Intermediate layer-
In the case of providing the thermoplastic resin layer, an intermediate layer is further provided between the thermoplastic resin layer and the photosensitive light-shielding layer for the purpose of preventing layer mixing of the two layers at the time of applying the preparation liquid or for the purpose of blocking oxygen. Is preferably provided.
中間層は、少なくとも樹脂を用いて構成でき、一般には熱可塑性樹脂層や感光性の遮光性層の形成に用いる溶剤と相溶性の小さい水系溶媒を用いて調製された樹脂含有の調製液を用いて形成することができる。 The intermediate layer can be composed of at least a resin, and generally uses a resin-containing preparation prepared by using an aqueous solvent having a low compatibility with a solvent used for forming a thermoplastic resin layer or a photosensitive light-shielding layer. Can be formed.
中間層を構成する樹脂としては、アルカリ可溶のものが好ましく、樹脂の例として、特開2004−317897号公報の段落番号[0050]に記載のものが挙げられる。 The resin constituting the intermediate layer is preferably an alkali-soluble resin, and examples of the resin include those described in paragraph [0050] of JP-A No. 2004-317897.
中間層の厚みは、0.1〜5μmの範囲が好ましく、0.5〜3μmの範囲がより好ましい。中間層の厚みが前記範囲内であると、酸素遮断性に優れると共に、現像時の中間層除去を短時間に行なうことができる。 The thickness of the intermediate layer is preferably in the range of 0.1 to 5 μm, and more preferably in the range of 0.5 to 3 μm. When the thickness of the intermediate layer is within the above range, the oxygen barrier property is excellent, and the intermediate layer can be removed during development in a short time.
感光性転写材料を構成する微粒子含有層は、アスペクト比が2〜100の金属微粒子及び/又は金属化合物微粒子を、チオエーテル基を有する高分子化合物及び熱もしくは光で硬化する化合物と共に(好ましくは溶剤を用いて)調製された調製液を例えば塗布等して形成されるので、薄膜でかつ高温環境での樹脂成分、微粒子の変質に伴なう色味変化が少なく、分散時の分散性及び分散後の分散安定性に優れており、色相が良好で高い光学濃度を有する。 The fine particle-containing layer constituting the photosensitive transfer material comprises metal fine particles and / or metal compound fine particles having an aspect ratio of 2 to 100 together with a polymer compound having a thioether group and a compound that is cured by heat or light (preferably a solvent). Since the prepared preparation liquid is formed by, for example, coating, etc., it is a thin film and there is little change in the color due to the deterioration of resin components and fine particles in a high-temperature environment, dispersibility during dispersion and after dispersion The dispersion stability is excellent, the hue is good, and the optical density is high.
次に、感光性転写材料を用いて微粒子含有層を基板に転写形成する方法を中心に述べる。転写は、最表層である微粒子含有層の表面と基板表面とを密着させてラミネートし、仮支持体を剥離して転写する方法が好ましい。
前記ラミネートの方法としては、従来公知のラミネーター、真空ラミネーターなどを用いることができる。また、摩擦性を高めるため、オートカットラミネーターを使用することもできる。
Next, a method for transferring and forming a fine particle-containing layer on a substrate using a photosensitive transfer material will be mainly described. The transfer is preferably carried out by laminating the surface of the fine particle-containing layer, which is the outermost layer, and the substrate surface in close contact, and peeling and transferring the temporary support.
As the laminating method, a conventionally known laminator, vacuum laminator or the like can be used. An auto-cut laminator can also be used in order to improve friction.
ラミネートの際の加熱温度は、60〜150℃程度が好ましく、加圧圧力は0.2〜20kg/cm2程度が好ましい。本発明では、ラミネートは基板のライン速度が0.05〜10m/分程度である範囲で行なうことが好ましい。 The heating temperature at the time of lamination is preferably about 60 to 150 ° C., and the pressing pressure is preferably about 0.2 to 20 kg / cm 2 . In the present invention, the lamination is preferably performed in a range where the line speed of the substrate is about 0.05 to 10 m / min.
感光性転写材料を用いて表示装置用遮光膜を形成する場合、感光性転写材料と基板とのラミネーションの後、仮支持体を剥離し、露光、現像を順次行ない、露光及び現像後にさらに加熱処理を施すことが好ましい。露光と現像、及び加熱処理条件については既述の方法を適用することができる。 When forming a light-shielding film for a display device using a photosensitive transfer material, after lamination of the photosensitive transfer material and the substrate, the temporary support is peeled off, followed by exposure and development, and further heat treatment after exposure and development. It is preferable to apply. The methods described above can be applied to exposure, development, and heat treatment conditions.
<遮光膜付き基板>
本発明の遮光膜付き基板は、基板上に、既述の本発明の微粒子含有組成物、既述の本発明の表示装置用着色膜形成用インク、又は既述の本発明の遮光材料を用いて遮光膜を形成して構成されたものである。
遮光膜の形成は、既述の表示装置用遮光膜を形成するのに好適な方法(1)〜(3)により行なえ、方法(3)によるのがより好ましい。
<Substrate with light shielding film>
The substrate with a light shielding film of the present invention uses the fine particle-containing composition of the present invention described above, the ink for forming a colored film for a display device of the present invention described above, or the light shielding material of the present invention described above on the substrate. Thus, a light shielding film is formed.
The light shielding film can be formed by the methods (1) to (3) suitable for forming the light shielding film for a display device described above, and more preferably, the method (3) is used.
なお、微粒子含有組成物、表示装置用着色膜形成用インク、及び遮光材料を構成する各成分は、既述の通りであり、好ましい態様も同様である。また、遮光膜の厚み、透過濃度(光学濃度)については、既述の表示装置用遮光膜における場合と同様である。 The components constituting the fine particle-containing composition, the colored film forming ink for display device, and the light shielding material are as described above, and the preferred embodiments are also the same. Further, the thickness and transmission density (optical density) of the light shielding film are the same as those in the above-described light shielding film for a display device.
<カラーフィルタ>
本発明のカラーフィルタは、光透過性の基板上に、互いに異なる色相を呈する複数の画素を含む画素群と、画素群を構成する各画素を離隔する遮光画像(いわゆるブラックマトリックス)として、既述の本発明の表示装置用遮光膜とを設けて構成されたものである。
<Color filter>
The color filter of the present invention is described as a pixel group including a plurality of pixels exhibiting different hues on a light-transmitting substrate and a light-shielded image (so-called black matrix) that separates the pixels constituting the pixel group. And a light-shielding film for a display device according to the present invention.
光透過性の基板としては、既述した基板、TFT素子等が設けられた駆動基板(TFT素子基板等)などを用いることができる。 As the light-transmitting substrate, the above-described substrate, a driving substrate (TFT element substrate or the like) provided with a TFT element or the like can be used.
本発明のカラーフィルタは、既述の本発明の表示装置用遮光膜を設けてなり、該表示装置用遮光膜は既述の本発明の微粒子含有組成物、あるいは既述の本発明の表示装置用着色膜形成用インクを用いて形成されるので、かかる遮光膜は、製造工程上高温に曝されるような場合など、高温環境での樹脂成分、微粒子の変質に伴なう色味変化が少なく、色相が良好で高い光学濃度を有しており、表示画像のコントラスト及び配線の遮蔽性に優れる。 The color filter of the present invention is provided with the above-described light shielding film for a display device of the present invention, and the light shielding film for the display device is the fine particle-containing composition of the present invention described above or the display device of the present invention described above. The light-shielding film has a color change that accompanies alteration of resin components and fine particles in a high-temperature environment, such as when exposed to high temperatures during the manufacturing process. Less hue, good hue, high optical density, and excellent display image contrast and wiring shielding.
TFT素子基板を用いて構成する場合には、TFT素子基板上に、画素群とこれを構成する各画素を離隔する表示装置用遮光膜とを設けた構成であってもよい。
上記のほか、本発明のカラーフィルタは、TFT素子基板を用い、TFT素子基板の上に、画素群を設けずに、表示装置用遮光膜(ブラックマトリックス)のみを設けた構成であってもよい。この場合は、このTFT素子基板とは別の光透過性の基板上に画素群を形成し、画素群が形成された基板を前記TFT素子基板に対向配置して用いる。これにより、TFTアレイの開口率が良好となる。
In the case of using a TFT element substrate, a structure in which a pixel group and a light-shielding film for a display device that separates each pixel constituting the pixel group may be provided on the TFT element substrate.
In addition to the above, the color filter of the present invention may have a configuration in which a TFT element substrate is used, and only a light shielding film (black matrix) for a display device is provided on the TFT element substrate without providing a pixel group. . In this case, a pixel group is formed on a light-transmitting substrate different from the TFT element substrate, and the substrate on which the pixel group is formed is disposed opposite to the TFT element substrate. Thereby, the aperture ratio of the TFT array becomes good.
画素群は、互いに異なる色相を呈する複数の画素を含んでなり、画素形成用の着色感光性樹脂組成物や感光性転写材料の複数種を用いた常法により形成することができる。画素群を形成した後は、熱処理を行なうことが好ましい。
着色感光性樹脂組成物、感光性転写材料については、例えば、特開2005−3861号公報や、特開2004−361448号公報、特開2004−205731公報を参照できる。
The pixel group includes a plurality of pixels exhibiting different hues, and can be formed by a conventional method using a plurality of types of colored photosensitive resin compositions and photosensitive transfer materials for forming pixels. Heat treatment is preferably performed after the pixel group is formed.
Regarding the colored photosensitive resin composition and the photosensitive transfer material, for example, JP-A-2005-3861, JP-A-2004-361448, and JP-A-2004-205731 can be referred to.
<液晶表示素子、液晶表示装置>
本発明の液晶表示素子は、既述の本発明の遮光膜付き基板を用いて構成されたものである。本発明の遮光膜付き基板、詳細には、既述した本発明の微粒子含有組成物、表示装置用着色膜形成用インク、又は遮光材料を用いてなる遮光膜で構成されるので、高温環境に曝されることに伴なう色味変化が少なく、色相が良好で高い光学濃度を有しており、表示画像のコントラストが高く、良好な表示品質の画像表示が可能である。
<Liquid crystal display element, liquid crystal display device>
The liquid crystal display element of the present invention is constructed using the substrate with a light shielding film of the present invention described above. Since the substrate with a light-shielding film of the present invention, specifically, the light-shielding film using the fine particle-containing composition of the present invention, the colored film-forming ink for display device, or the light-shielding material described above, There is little change in color due to exposure, the hue is good, the optical density is high, the contrast of the display image is high, and image display with good display quality is possible.
液晶表示素子は、本発明の遮光膜付き基板を備えた液晶表示素子であれば、特に限定されるものではなく、公知の液晶表示素子の構成要素を更に用いて構成することができる。例えば、カラーフィルタ基板及びこれと対向配置された光透過性の基板と、これら基板間に設けられた液晶層と、液晶層の液晶を駆動する液晶駆動手段(単純マトリックス駆動方式及びアクティブマトリックス駆動方式を含む。)とを備え、カラーフィルタ基板として既述の本発明のカラーフィルタを用いた構成とすることができる。 A liquid crystal display element will not be specifically limited if it is a liquid crystal display element provided with the board | substrate with a light-shielding film of this invention, It can comprise further using the component of a well-known liquid crystal display element. For example, a color filter substrate, a light-transmitting substrate disposed opposite to the color filter substrate, a liquid crystal layer provided between the substrates, and liquid crystal driving means for driving the liquid crystal in the liquid crystal layer (simple matrix driving method and active matrix driving method) And the above-described color filter of the present invention can be used as a color filter substrate.
本発明の液晶表示装置は、本発明の液晶表示素子を用いて構成されたものである。本発明の液晶表示素子、詳細には、既述した本発明の遮光膜付き基板(本発明の微粒子含有組成物、表示装置用着色膜形成用インク、又は遮光材料)を用いて構成されるので、高温環境に曝されることに伴なう色味変化が少なく、色相が良好で高い光学濃度を有しており、表示画像のコントラストが高く、良好な表示品質の画像表示が可能である。 The liquid crystal display device of the present invention is constructed using the liquid crystal display element of the present invention. Since the liquid crystal display element of the present invention, specifically, the substrate with a light-shielding film of the present invention (the fine particle-containing composition of the present invention, the ink for forming a colored film for a display device, or a light-shielding material) described above is used. The color change associated with exposure to a high temperature environment is small, the hue is good, the optical density is high, the contrast of the display image is high, and the image can be displayed with good display quality.
本発明の液晶表示装置は、本発明の液晶表示素子を用いて作製した装置であれは、特に限定されるものではなく、公知の液晶表示装置の構成要素を更に用いて構成することができる。 The liquid crystal display device of the present invention is not particularly limited as long as it is a device manufactured using the liquid crystal display element of the present invention, and can be configured by further using components of a known liquid crystal display device.
以下、本発明を実施例により更に具体的に説明するが、本発明はその主旨を越えない限り、以下の実施例に限定されるものではない。なお、特に断りのない限り、「部」及び「%」は質量基準である。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” and “%” are based on mass.
<高分子分散剤の合成>
−ポリマー1の合成−
ノルマルプロパノール200部を80℃に加熱した後、これに窒素気流下で、エチルチオエチルアクリレート52.2部、メタクリル酸20.0部、及びジメチルアクリルアミド127.8部の混合物(モノマー液)と、2,2’−アゾビス(イソ酪酸)ジメチル(商品名:V−601、和光純薬工業(株)製)1.70部及びノルマルプロパノール100部の混合物(開始剤溶液)と、をそれぞれ2時間かけて同時滴下した。滴下終了後、更に窒素気流下、80℃で2時間加熱し、ノルマルプロパノール500部を添加することにより、ポリマー1の20%溶液(重量平均分子量84000;本発明に係る高分子分散剤)を得た。
<Synthesis of polymer dispersant>
-Synthesis of polymer 1-
After heating 200 parts of normal propanol to 80 ° C., a mixture (monomer solution) of 52.2 parts of ethylthioethyl acrylate, 20.0 parts of methacrylic acid, and 127.8 parts of dimethylacrylamide under a nitrogen stream, 2.70 parts of 2,2′-azobis (isobutyric acid) dimethyl (trade name: V-601, manufactured by Wako Pure Chemical Industries, Ltd.) and 100 parts of normal propanol (initiator solution) for 2 hours each It was dripped simultaneously. After completion of dropping, the mixture is further heated at 80 ° C. for 2 hours under a nitrogen stream, and 500 parts of normal propanol is added to obtain a 20% solution of polymer 1 (weight average molecular weight 84000; polymer dispersant according to the present invention). It was.
−ポリマー2の合成−
メチルエチルケトン200部を80℃に加熱した後、これに窒素気流下で、エチルチオエチルアクリレート52.2部、メタクリル酸47.8部、及びスチレン100.0部の混合物(モノマー液)と、2,2’−アゾビス(イソ酪酸)ジメチル(商品名:V−601;和光純薬工業(株)製)1.70部、及びメチルエチルケトン100部の混合物(開始剤溶液)とを、それぞれ2時間かけて同時滴下した。滴下終了後、更に窒素気流下、80℃で2時間加熱し、メチルエチルケトン500部を添加することにより、ポリマー2の20%溶液(重量平均分子量70000;本発明に係る高分子分散剤)を得た。
-Synthesis of polymer 2-
After heating 200 parts of methyl ethyl ketone to 80 ° C., a mixture (monomer solution) of 52.2 parts of ethylthioethyl acrylate, 47.8 parts of methacrylic acid, and 100.0 parts of styrene under a nitrogen stream, 2'-azobis (isobutyric acid) dimethyl (trade name: V-601; manufactured by Wako Pure Chemical Industries, Ltd.) 1.70 parts and a mixture of 100 parts of methyl ethyl ketone (initiator solution), respectively, over 2 hours It was dripped simultaneously. After completion of dropping, the mixture was further heated at 80 ° C. for 2 hours under a nitrogen stream, and 500 parts of methyl ethyl ketone was added to obtain a 20% solution of polymer 2 (weight average molecular weight 70000; polymer dispersant according to the present invention). .
−ポリマー3の合成−
前記ポリマー2の合成で用いたモノマー液を、メチルチオエチルアクリレート47.7部、メタクリル酸47.8部、及びスチレン104.5部の混合物に代えたこと以外、前記ポリマー2の合成と同様にして、ポリマー3の20%溶液(重量平均分子量68000;本発明に係る高分子分散剤)を得た。
-Synthesis of polymer 3-
The monomer solution used in the synthesis of the polymer 2 was replaced with a mixture of 47.7 parts of methylthioethyl acrylate, 47.8 parts of methacrylic acid, and 104.5 parts of styrene. A 20% solution of polymer 3 (weight average molecular weight 68000; polymer dispersant according to the present invention) was obtained.
−ポリマー4の合成−
前記ポリマー2の合成で用いたモノマー液を、フェニルチオエチルアクリレート67.9部、メタクリル酸47.8部、及びメタクリル酸メチル84.3部の混合物に代えたこと以外、前記ポリマー2の合成と同様にして、ポリマー4の20%溶液(重量平均分子量78000;本発明に係る高分子分散剤)を得た。
-Synthesis of polymer 4-
The synthesis of the polymer 2 except that the monomer liquid used in the synthesis of the polymer 2 was replaced with a mixture of 67.9 parts phenylthioethyl acrylate, 47.8 parts methacrylic acid, and 84.3 parts methyl methacrylate. In the same manner, a 20% solution of polymer 4 (weight average molecular weight 78000; polymer dispersant according to the present invention) was obtained.
(実施例1)
<銀微粒子組成物の調製>
まず、Mater.Chem.Phys.2004,84,p.197−204に記載の微粒子の調製方法にしたがって、銀塩還元時のpH、反応温度を変化させることにより、各種アスペクト比を持つロッド状銀微粒子の分散液を調製し、得られた分散液に遠心分離処理(回転数10000r.p.m.,20分間)を施した後、上澄み液を捨て適宜濃縮を行なって、ロッド状銀微粒子を得た。
Example 1
<Preparation of silver fine particle composition>
First, Mater. Chem. Phys. In accordance with the method for preparing fine particles described in 2004, 84, p. 197-204, by changing the pH and reaction temperature during silver salt reduction, a dispersion of rod-shaped silver fine particles having various aspect ratios was prepared. The obtained dispersion was centrifuged (rotation speed 10,000 rpm, 20 minutes), and then the supernatant was discarded and concentrated as appropriate to obtain rod-shaped silver fine particles.
上記より得たロッド状銀微粒子のうち、平均アスペクト比が54.7のロッド状銀微粒子20.0部と、上記より得たポリマー1の20%溶液20.0部と、ノルマルプロパノール80.0部とを混合し、超音波分散機(Ultrasonic generator model US−6000 ccvp、(株)ニッセイ製)を用いて分散し、銀微粒子組成物を調製した。 Among the rod-shaped silver fine particles obtained above, 20.0 parts of rod-shaped silver fine particles having an average aspect ratio of 54.7, 20.0 parts of a 20% solution of polymer 1 obtained above, and 80.0 normal propanol Were mixed using an ultrasonic disperser (Ultrasonic generator model US-6000 ccvp, manufactured by Nissei Co., Ltd.) to prepare a silver fine particle composition.
(評価1)
−1.銀微粒子分散性の評価−
銀微粒子組成物を25℃にて3日間放置した後、目視により銀微粒子の分散性を下記の評価基準にしたがって評価した。評価結果は下記表1に示す。
〈評価基準〉
A:銀微粒子が沈降することなく均一に分散されていた。
B:銀微粒子が一部沈降していた。
C:銀微粒子が完全に沈降していた。
(Evaluation 1)
-1. Evaluation of silver fine particle dispersibility
After the silver fine particle composition was allowed to stand at 25 ° C. for 3 days, the dispersibility of the silver fine particles was visually evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1 below.
<Evaluation criteria>
A: Silver fine particles were uniformly dispersed without settling.
B: Silver fine particles were partially settled.
C: Silver fine particles were completely settled.
<遮光画像形成用塗布液の調製>
下記組成の各成分を混合し、遮光画像形成用塗布液(黒色材料用の微粒子含有組成物)を調製した。
〈黒色材料用の微粒子含有組成物の組成〉
・上記の銀微粒子組成物(アスペクト比=54.7) … 180部
・フッ素系界面活性剤 … 1.68部
(商品名:F780F、大日本インキ化学工業(株)製)
・ジペンタエリスリトールヘキサアクリレート … 6.27部
(KAYARAD DPHA、日本化薬(株)製)
・ビス[4−[N−(4,6−ビストリクロロメチル−s−トリアジン−2−イル)フェニル]カルバモイル]フェニル]セバケート … 0.6部
・アセトン …1500部
<Preparation of shading image forming coating solution>
Each component having the following composition was mixed to prepare a light-shielding image-forming coating solution (fine particle-containing composition for black material).
<Composition of fine particle-containing composition for black material>
-Silver fine particle composition (aspect ratio = 54.7) ... 180 parts · Fluorosurfactant ... 1.68 parts (trade name: F780F, manufactured by Dainippon Ink & Chemicals, Inc.)
-Dipentaerythritol hexaacrylate 6.27 parts (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)
-Bis [4- [N- (4,6-bistrichloromethyl-s-triazin-2-yl) phenyl] carbamoyl] phenyl] sebacate ... 0.6 parts Acetone ... 1500 parts
<遮光画像の形成>
無アルカリガラス基板をUV洗浄装置で洗浄後、洗浄剤を用いてブラシ洗浄し、更に超純水で超音波洗浄した。洗浄後の基板を120℃で3分間熱処理し、表面状態を安定化させた。続いて、この基板を冷却して23℃に温調した後、スリット状ノズルを有するガラス基板用コーター(商品名:MH−1600、エフ・エー・エス・ジャパン社製)を用いて、上記の遮光画像形成用塗布液を塗布した(塗布工程)。
<Formation of shading image>
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The cleaned substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state. Subsequently, after cooling the substrate and adjusting the temperature to 23 ° C., a coater for glass substrate having a slit-like nozzle (trade name: MH-1600, manufactured by F.S. Japan Co., Ltd.) was used. A shading image forming coating solution was applied (application step).
引き続き、真空乾燥装置VCD(東京応化工業(株)製)により30秒間、溶媒の一部を乾燥させて塗布膜の流動性をなくした後、EBR(エッジ・ビード・リムーバー)にて基板周囲の不要な塗布液を除去し、120℃下で3分間プリベークを行ない、層厚0.5μmの遮光層を形成した。 Subsequently, after part of the solvent was dried by a vacuum drying apparatus VCD (manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating film, the periphery of the substrate was removed by EBR (edge bead remover). Unnecessary coating solution was removed and prebaked at 120 ° C. for 3 minutes to form a light-shielding layer having a layer thickness of 0.5 μm.
次に、超高圧水銀灯を備えたプロキシミティー型露光機(日立電子エンジニアリング(株)製)を用い、マスク(格子状の画像パターンを有する石英露光マスク)と遮光層が設けられた無アルカリガラス基板とを垂直に立てた状態で、マスク面と遮光層の表面との間の距離を100μmに設定し、露光量200mJ/cm2でパターン露光した(露光工程)。 Next, a non-alkali glass substrate provided with a mask (quartz exposure mask having a lattice-like image pattern) and a light shielding layer using a proximity type exposure machine (manufactured by Hitachi Electronics Engineering Co., Ltd.) equipped with an ultrahigh pressure mercury lamp. Are set to 100 μm, and pattern exposure is performed with an exposure amount of 200 mJ / cm 2 (exposure process).
次に、純粋をシャワーノズルから噴霧し、遮光層の表面を均一に湿らせた後、KOH系現像液CDK−1(富士フイルムエレクトロニクスマテリアルズ(株)製;KOH及びノニオン界面活性剤含有アルカリ現像液)を純水で100倍に薄めたものを、フラットノズルから23℃、ノズル圧力0.04MPaにて80秒間噴射してシャワー現像し、黒色パターンを得た(現像工程)。続いて、無アルカリガラス基板の黒色パターンが形成された側に超純水を超高圧洗浄ノズルにより9.8MPaの圧力で噴射して残渣を除去し、無アルカリガラス基板上にブラック(K)画像を形成した。その後、これを220℃で40分間熱処理(ベーク)し(ベーク工程)、遮光画像を得た。 Next, after spraying pure from a shower nozzle and uniformly moistening the surface of the light shielding layer, KOH developer CDK-1 (manufactured by FUJIFILM Electronics Materials Co., Ltd .; alkaline development containing KOH and nonionic surfactant) The liquid was diluted 100 times with pure water and sprayed for 80 seconds at 23 ° C. and a nozzle pressure of 0.04 MPa from a flat nozzle to obtain a black pattern (developing step). Subsequently, ultrapure water is sprayed onto the side of the alkali-free glass substrate on which the black pattern is formed at a pressure of 9.8 MPa by an ultra-high pressure cleaning nozzle to remove the residue, and a black (K) image is formed on the alkali-free glass substrate. Formed. Then, this was heat-processed (baked) for 40 minutes at 220 degreeC (baking process), and the light-shielding image was obtained.
<カラーフィルタの作製>
引き続き、遮光画像が形成された無アルカリガラス基板(以下、「カラーフィルタ基板」と称する。)を用い、このカラーフィルタ基板に、特開2004−347831号公報の段落番号[0075]〜[0086]に記載の感光性樹脂組成物を用いて同様にして、所定サイズ、形状よりなる赤色(R)、緑色(G)、青色(B)の着色パターン(着色画素)を形成し、カラーフィルタを作製した。
<Production of color filter>
Subsequently, an alkali-free glass substrate (hereinafter referred to as “color filter substrate”) on which a light-shielded image is formed is used, and paragraphs [0075] to [0086] of Japanese Patent Application Laid-Open No. 2004-347831 are used for this color filter substrate. In the same manner, a red (R), green (G), and blue (B) colored pattern (colored pixel) having a predetermined size and shape is formed using the photosensitive resin composition described in 1. to produce a color filter. did.
<液晶表示素子及び液晶表示装置の作製>
上記で得たカラーフィルタを用いて、以下に示すようにして、液晶表示素子を作製すると共に、さらに液晶表示装置を作製した。
まず、得られたカラーフィルタのRGBのパターンに対応させるようにして、別に用意したガラス基板上に、薄膜トランジスタ(TFT)と画素電極とを形成すると共に、配向膜を設けてアクティブマトリックス基板を作製した。次いで、上記で得たカラーフィルタの上に更にITO膜と配向膜とを形成し、対向基板とした。得られたアクティブマトリクス基板と対向電極とを所定の間隔(いわゆるセル厚)が形成されるようにして対向配置し、両基板間にTN液晶を封入してシール剤を介して貼り合わせ、液晶表示素子を得た。そして、得られた液晶表示素子の両基板の表面に偏光板をクロスニコルにて配置し、更にアクティブマトリックス基板側にバックライトを配設して、液晶表示装置とした。
<Production of liquid crystal display element and liquid crystal display device>
Using the color filter obtained above, a liquid crystal display element was produced as shown below, and a liquid crystal display device was further produced.
First, a thin film transistor (TFT) and a pixel electrode were formed on a separately prepared glass substrate so as to correspond to the RGB pattern of the obtained color filter, and an active matrix substrate was prepared by providing an alignment film. . Next, an ITO film and an alignment film were further formed on the color filter obtained above to obtain a counter substrate. The obtained active matrix substrate and the counter electrode are arranged to face each other so as to form a predetermined interval (so-called cell thickness), and TN liquid crystal is sealed between the two substrates and bonded via a sealant to provide a liquid crystal display. An element was obtained. Then, polarizing plates were arranged in crossed Nicols on the surfaces of both substrates of the obtained liquid crystal display element, and a backlight was further arranged on the active matrix substrate side to obtain a liquid crystal display device.
(実施例2)
実施例1において、ポリマー1の20%溶液をポリマー2の20%溶液に代え、かつノルマルプロパノールをメチルエチルケトンに代えたこと以外、実施例1と同様にして、銀微粒子組成物を調製し、評価1を行なうと共に、遮光画像を得た。評価1の結果を下記表1に示す。そして、得られた遮光画像を用いて、実施例1と同様にして、カラーフィルタ並びに液晶表示素子、液晶表示装置を作製した。
(Example 2)
A silver fine particle composition was prepared in the same manner as in Example 1 except that the 20% solution of polymer 1 was replaced with the 20% solution of polymer 2 and normal propanol was replaced with methyl ethyl ketone. And a shaded image was obtained. The results of Evaluation 1 are shown in Table 1 below. Then, using the obtained light-shielded image, a color filter, a liquid crystal display element, and a liquid crystal display device were produced in the same manner as in Example 1.
(実施例3)
実施例1において、ポリマー1の20%溶液をポリマー3の20%溶液に代え、かつノルマルプロパノールをメチルエチルケトンに代えたこと以外、実施例1と同様にして、銀微粒子組成物を調製し、評価1を行なうと共に、遮光画像を得た。評価1の結果は下記表1に示す。そして、得られた遮光画像を用いて、実施例1と同様にして、カラーフィルタ並びに液晶表示素子、液晶表示装置を作製した。
(Example 3)
In Example 1, a silver fine particle composition was prepared in the same manner as in Example 1 except that the 20% solution of polymer 1 was replaced with a 20% solution of polymer 3 and normal propanol was replaced with methyl ethyl ketone. Evaluation 1 And a shaded image was obtained. The results of Evaluation 1 are shown in Table 1 below. Then, using the obtained light-shielded image, a color filter, a liquid crystal display element, and a liquid crystal display device were produced in the same manner as in Example 1.
(実施例4)
実施例1において、ポリマー1の20%溶液をポリマー4の20%溶液に代え、かつノルマルプロパノールをメチルエチルケトンに代えたこと以外、実施例1と同様にして、銀微粒子組成物を調製し、評価1を行なうと共に、遮光画像を得た。評価1の結果は下記表1に示す。そして、得られた遮光画像を用いて、実施例1と同様にして、カラーフィルタ並びに液晶表示素子、液晶表示装置を作製した。
Example 4
In Example 1, a silver fine particle composition was prepared in the same manner as in Example 1 except that the 20% solution of polymer 1 was replaced with a 20% solution of polymer 4 and normal propanol was replaced with methyl ethyl ketone. Evaluation 1 And a shaded image was obtained. The results of Evaluation 1 are shown in Table 1 below. Then, using the obtained light-shielded image, a color filter, a liquid crystal display element, and a liquid crystal display device were produced in the same manner as in Example 1.
(実施例5〜8)
実施例1において、ロッド状銀微粒子の平均アスペクト比を54.7から3.2(実施例5)、12.2(実施例6)、78.4(実施例7)、又は1.3(実施例8)にそれぞれ代えたこと以外、実施例1と同様にして、銀微粒子組成物を調製し、評価1を行なうと共に、遮光画像を得た。評価1の結果は下記表1に示す。そして、得られた遮光画像を用いて、実施例1と同様にして、カラーフィルタ並びに液晶表示素子、液晶表示装置を作製した。
(Examples 5 to 8)
In Example 1, the average aspect ratio of the rod-shaped silver fine particles was 54.7 to 3.2 (Example 5), 12.2 (Example 6), 78.4 (Example 7), or 1.3 ( A silver fine particle composition was prepared and evaluated 1 in the same manner as in Example 1 except that each was replaced with Example 8), and a light-shielded image was obtained. The results of Evaluation 1 are shown in Table 1 below. Then, using the obtained light-shielded image, a color filter, a liquid crystal display element, and a liquid crystal display device were produced in the same manner as in Example 1.
(実施例9)
<転写材料の作成>
厚さ75μmのポリエチレンテレフタレート仮支持体(PET仮支持体)の表面に、スリット状ノズルを用いて、乾燥厚みが5μmになるように下記の処方H1で調製された熱可塑性樹脂層用塗布液を塗布し、100℃で3分間乾燥させ、熱可塑性樹脂層を形成した。この熱可塑性樹脂層上に、下記処方P1で調製された中間層用塗布液をスリットコーターを用いて乾燥膜厚が1.5μmとなるように塗布し、100℃で3分間乾燥させて、中間層(酸素遮断膜)を積層した。この中間層上に、実施例1で調製した遮光画像形成用塗布液を、乾燥膜厚が0.5μmとなるようにスリットコーターを用いて塗布し、100℃で3分間乾燥させて感光性遮光層(金属黒色層)を形成した。
以上のようにして、PET仮支持体上に熱可塑性樹脂層、中間層、及び感光性遮光層が順次積層されたフィルムを作製し、更に遮光層の上に保護フィルムとして、厚さ12μmのポリプロピレンフィルムを圧着して、感光性転写材料とした。
Example 9
<Creation of transfer material>
Using a slit-shaped nozzle on the surface of a 75 μm thick polyethylene terephthalate temporary support (PET temporary support), apply a coating solution for a thermoplastic resin layer prepared according to the following formulation H1 so that the dry thickness is 5 μm. It was applied and dried at 100 ° C. for 3 minutes to form a thermoplastic resin layer. On this thermoplastic resin layer, an intermediate layer coating solution prepared by the following formulation P1 was applied using a slit coater so as to have a dry film thickness of 1.5 μm, and dried at 100 ° C. for 3 minutes. A layer (oxygen barrier film) was laminated. On this intermediate layer, the light-shielding image-forming coating solution prepared in Example 1 was applied using a slit coater so as to have a dry film thickness of 0.5 μm, and dried at 100 ° C. for 3 minutes. A layer (metal black layer) was formed.
As described above, a film in which a thermoplastic resin layer, an intermediate layer, and a photosensitive light-shielding layer are sequentially laminated on a PET temporary support is prepared, and a 12 μm-thick polypropylene is further used as a protective film on the light-shielding layer. The film was pressure-bonded to obtain a photosensitive transfer material.
〈熱可塑性樹脂層用塗布液の処方H1〉
・メタノール …11.1部
・プロピレングリコールモノメチルエーテルアセテート … 6.36部
・メチルエチルケトン …52.4部
・メチルメタクリレート/2−エチルヘキシルアクリレート/ベンジルメタクリレート/メタクリル酸共重合体(共重合比[モル比]=55/11.7/4.5/28.8、重量平均分子量=9万、Tg≒70℃) … 5.83部
・スチレン/アクリル酸共重合体(共重合比[モル比]=63/37、重量平均分子量=1万、Tg≒100℃) …13.6部
・2,2−ビス[4−(メタクリロキシポリエトキシ)フェニル]プロパン
(新中村化学工業(株)製;ビスフェノールAにペンタエチレングリコールモノメタクリートを2当量脱水縮合した化合物) … 9.1部
・フッ素系界面活性剤 … 0.54部
(商品名:F780F、大日本インキ化学工業(株)製)
<Prescription H1 of coating solution for thermoplastic resin layer>
-Methanol ... 11.1 parts-Propylene glycol monomethyl ether acetate ... 6.36 parts-Methyl ethyl ketone ... 52.4 parts-Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization ratio [molar ratio] = 55 / 11.7 / 4.5 / 28.8, weight average molecular weight = 90,000, Tg≈70 ° C.) 5.83 parts styrene / acrylic acid copolymer (copolymerization ratio [molar ratio] = 63) / 37, weight average molecular weight = 10,000, Tg≈100 ° C.) 13.6 parts · 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane (manufactured by Shin-Nakamura Chemical Co., Ltd .; bisphenol A Compound obtained by dehydration condensation of 2 equivalents of pentaethylene glycol monomethacrylate on 9.1 parts Fluorosurfactant 0.54 parts (quotient) Name: F780F, Dainippon Ink & Chemicals Co., Ltd.)
〈中間層用塗布液の処方P1〉
・PVA−205 … 32.2部
(ポリビニルアルコール、(株)クラレ製、鹸化度=88%、重合度550)
・ポリビニルピロリドン … 14.9部
(アイ・エス・ピー・ジャパン(株)製、K−30)
・蒸留水 …524部
・メタノール …429部
<Prescription P1 of coating solution for intermediate layer>
PVA-205 32.2 parts (polyvinyl alcohol, manufactured by Kuraray Co., Ltd., saponification degree = 88%, polymerization degree 550)
・ Polyvinylpyrrolidone: 14.9 parts (manufactured by ISP Japan, K-30)
・ Distilled water: 524 parts ・ Methanol: 429 parts
<転写による遮光画像付き基板の作製(転写法)>
無アルカリガラス基板にガラス洗浄剤液をシャワーにより20秒間吹き付けながらナイロン毛を有する回転ブラシで洗浄し、純水でシャワー洗浄した後、シランカップリング液(N−β(アミノエチル)γ−アミノプロピルトリメトキシシランの0.3%水溶液;商品名:KBM603、信越化学工業(株)製)をシャワーにより20秒間吹き付け、その後、純水でシャワー洗浄した。さらに、この基板を基板予備加熱装置を用いて100℃下で2分間加熱した。
<Production of substrate with shading image by transfer (transfer method)>
A glass cleaner solution is sprayed onto an alkali-free glass substrate for 20 seconds while being washed with a rotating brush having nylon bristles, and after shower washing with pure water, a silane coupling solution (N-β (aminoethyl) γ-aminopropyl) A 0.3% aqueous solution of trimethoxysilane; trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds with a shower, and then shower washed with pure water. Further, this substrate was heated at 100 ° C. for 2 minutes using a substrate preheating device.
続いて、上記より得た感光性転写材料の保護フィルムを剥離後、露出した感光性遮光層が、加熱後のガラス基板の表面と接するように重ね合わせ、ラミネーターLamicII型〔(株)日立インダストリイズ製〕を用いて、ゴムローラ温度130℃、線圧100N/cm2、搬送速度2.2m/分の条件で貼り合わせた(ラミネート)。次いで、PET仮支持体を剥離した(転写工程)。 Subsequently, after peeling off the protective film of the photosensitive transfer material obtained above, the exposed photosensitive light-shielding layer is overlaid so as to be in contact with the surface of the heated glass substrate, and a laminator Lamic II type [Hitachi Industry Co., Ltd. Using a rubber roller temperature of 130 ° C., a linear pressure of 100 N / cm 2 , and a conveying speed of 2.2 m / min (lamination). Next, the PET temporary support was peeled off (transfer process).
続いて、超高圧水銀灯を備えたプロキシミティー型露光機(日立電子エンジニアリング社製)を用い、マスク(画像パターンを有する石英露光マスク)と、該マスクと熱可塑性樹脂層とが向き合うように配置したガラス基板とを略平行に垂直に立てた状態で、マスク面と感光性樹脂層の中間層に接する側の表面との間の距離を100μmに設定し、マスクを介して熱可塑性樹脂層側から露光量70mJ/cm 2 でパターン露光した(露光工程)。 Subsequently, using a proximity type exposure machine (manufactured by Hitachi Electronics Engineering Co., Ltd.) equipped with an ultrahigh pressure mercury lamp, the mask (quartz exposure mask having an image pattern) and the mask and the thermoplastic resin layer were arranged to face each other. The distance between the mask surface and the surface of the photosensitive resin layer on the side in contact with the intermediate layer is set to 100 μm with the glass substrate standing substantially parallel and vertically, and from the thermoplastic resin layer side through the mask. Pattern exposure was performed at an exposure amount of 70 mJ / cm 2 (exposure process).
露光後、トリエタノールアミン系現像液T−PD1(2.5%のトリエタノールアミン、ノニオン界面活性剤、及びポリプロピレン系消泡剤含有、富士写真フイルム(株)製)をフラットノズルから30℃、ノズル圧力0.04MPaにて、熱可塑性樹脂層上から50秒間噴射してシャワー現像を行ない、熱可塑性樹脂層及び中間層を現像除去した。引き続き、純水をシャワーノズルにて噴霧して、感光性遮光層の表面を均一に湿らせた後、KOH系現像液CDK−1(富士フイルムエレクトロニクスマテリアルズ(株)製;KOH及びノニオン界面活性剤含有アルカリ現像液)を純水で100倍に薄めたものを、フラットノズルから23℃、ノズル圧力0.04MPaにて80秒間噴射してシャワー現像し(現像工程)、パターン像を得た。続いて、超純水を超高圧洗浄ノズルにて9.8MPaの圧力で噴射して残渣除去を行ない、更に220℃で40分間加熱処理(ベーク工程)を施し、遮光画像を得た。 After the exposure, a triethanolamine developer T-PD1 (containing 2.5% triethanolamine, nonionic surfactant, and polypropylene antifoaming agent, manufactured by Fuji Photo Film Co., Ltd.) from a flat nozzle at 30 ° C., Shower development was performed by spraying from the top of the thermoplastic resin layer for 50 seconds at a nozzle pressure of 0.04 MPa, and the thermoplastic resin layer and the intermediate layer were developed and removed. Subsequently, pure water was sprayed with a shower nozzle to uniformly wet the surface of the photosensitive light-shielding layer, and then KOH-based developer CDK-1 (manufactured by FUJIFILM Electronics Materials Co., Ltd .; KOH and nonionic surface activity) An agent-containing alkali developer) diluted 100 times with pure water was sprayed for 80 seconds from a flat nozzle at 23 ° C. and a nozzle pressure of 0.04 MPa (development process) to obtain a pattern image. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultrahigh pressure washing nozzle to remove the residue, and a heat treatment (baking process) was performed at 220 ° C. for 40 minutes to obtain a light-shielded image.
(比較例1)
実施例1において、ポリマー1をベンジルメタクリレート/メタクリル酸共重合体(モル比=73/27、重量平均分子量:3万)に代えたこと以外、実施例1と同様にして、銀微粒子組成物を調製し、評価1を行なうと共に、遮光画像を得た。評価1の結果は下記表1に示す。そして、得られた遮光画像を用いて、実施例1と同様にして、カラーフィルタ並びに液晶表示素子、液晶表示装置を作製した。
(Comparative Example 1)
In Example 1, a silver fine particle composition was prepared in the same manner as in Example 1 except that the polymer 1 was replaced with a benzyl methacrylate / methacrylic acid copolymer (molar ratio = 73/27, weight average molecular weight: 30,000). Preparation and evaluation 1 were performed, and a light-shielded image was obtained. The results of Evaluation 1 are shown in Table 1 below. Then, using the obtained light-shielded image, a color filter, a liquid crystal display element, and a liquid crystal display device were produced in the same manner as in Example 1.
(評価2)
−2.色相の評価−
各実施例及び比較例で得られた遮光画像の色度を、顕微分光光度計OSP100(オリンパス光学(株)製を用いて、ピンホール径5μmにて測定し、F10光源視野2度の結果として計算した。そして、理想的な黒色をx=0.33、y=0.33とし、得られた値(x,y値)との色差ΔEを算出して、色相を評価する指標とした。なお、色差ΔEの値が小さい方が黒の色相が良好であることを示す。評価結果は下記表1に示す。
(Evaluation 2)
-2. Hue evaluation
The chromaticity of the light-shielded image obtained in each example and comparative example was measured at a pinhole diameter of 5 μm using a microspectrophotometer OSP100 (manufactured by Olympus Optical Co., Ltd.). The ideal black was set to x = 0.33 and y = 0.33, and a color difference ΔE from the obtained values (x, y values) was calculated as an index for evaluating the hue. The smaller the color difference ΔE, the better the black hue, and the evaluation results are shown in Table 1 below.
−3.透過濃度の評価−
各実施例及び比較例で得られた遮光画像(膜)の透過濃度(OD)を、マクベス濃度計(TD−904、マクベス社製)を用いて測定した。その際、ガラス基板の光学濃度分は補正した。評価結果は下記表1に示す。
-3. Evaluation of transmission density
The transmission density (OD) of the light-shielded image (film) obtained in each Example and Comparative Example was measured using a Macbeth densitometer (TD-904, manufactured by Macbeth Co.). At that time, the optical density of the glass substrate was corrected. The evaluation results are shown in Table 1 below.
前記表1に示すように、チオエーテル基を有する高分子化合物を用いた実施例では、金属微粒子の分散安定性に優れており、形成された遮光画像は透過濃度が高く、加熱処理が施された後でも色差が小さく抑えられ、良好な色相の黒色像を得ることができた。特にアスペクト比が2〜100の銀微粒子を用いて膜を構成した場合に、透過濃度が高く、加熱処理が施された後の色差が小さく、色相に優れていた。
これに対し、チオエーテル基を有する高分子化合物を用いない構成とした比較例1では、分散安定性が不充分であり、銀粒子が凝集を起こして遮光画像を得ることはできなかった。
As shown in Table 1, in Examples using a polymer compound having a thioether group, the dispersion stability of the metal fine particles was excellent, and the formed light-shielded image had a high transmission density and was subjected to heat treatment. Even after this, the color difference was kept small, and a black image with a good hue could be obtained. In particular, when the film was formed using silver fine particles having an aspect ratio of 2 to 100, the transmission density was high, the color difference after the heat treatment was small, and the hue was excellent.
On the other hand, in Comparative Example 1 in which the polymer compound having a thioether group was not used, the dispersion stability was insufficient, and silver particles were aggregated and a light-shielded image could not be obtained.
(評価3)
−4.着色画素の評価−
実施例1〜9及び比較例1で得られた各カラーフィルタについて、着色パターンを顕微鏡観察により評価した。その結果、実施例のカラーフィルタはいずれも、比較例のカラーフィルタに比し、各着色画素に欠陥がなく、パターンは精細に構成されていた。
(Evaluation 3)
-4. Evaluation of colored pixels
About each color filter obtained in Examples 1-9 and Comparative Example 1, the coloring pattern was evaluated by microscopic observation. As a result, all of the color filters of the examples had no defect in each colored pixel and the pattern was finely formed as compared with the color filter of the comparative example.
(評価4)
−5.画質の評価−
実施例1〜9及び比較例1で得られた各液晶表示装置を用いて画像表示し、表示画像の品質を目視により評価した。その結果、実施例の液晶表示装置はいずれも、比較例の液晶表示装置に比し、高コントラストで鮮やかな画像表示が可能であり、良好な表示特性を示すことを確認した。
(Evaluation 4)
-5. Image quality evaluation
Images were displayed using the liquid crystal display devices obtained in Examples 1 to 9 and Comparative Example 1, and the quality of the displayed images was visually evaluated. As a result, it was confirmed that all of the liquid crystal display devices of the examples were capable of displaying a high-contrast and vivid image and having good display characteristics as compared with the liquid crystal display device of the comparative example.
Claims (19)
〔式中、R1は、水素原子又は総炭素数1〜4のアルキル基を表し、R2は水素原子、総炭素数1〜18のアルキル基、総炭素数6〜14のアリール基、又は総炭素数7〜16のアラルキル基を表す。Zは、−O−又は−NH−を表し、Yは総炭素数1〜8の2価の連結基を表す。〕 The fine particle-containing composition according to claim 1 or 2, wherein the polymer compound has at least a repeating unit represented by the following general formula (1).
[Wherein, R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms in total, and R 2 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms in total, an aryl group having 6 to 14 carbon atoms in total, or An aralkyl group having 7 to 16 carbon atoms in total is represented. Z represents —O— or —NH—, and Y represents a divalent linking group having 1 to 8 carbon atoms in total. ]
支持体上に、アスペクト比が2〜100の金属微粒子及び/又は金属化合物微粒子と、少なくとも1つのチオエーテル基を有する高分子化合物と、熱もしくは光で硬化する化合物とを少なくとも含有する微粒子含有層を少なくとも1層有することを特徴とする遮光材料。 A light shielding material used for forming a light shielding film for a display device,
On a support, a fine particle-containing layer containing at least metal fine particles and / or metal compound fine particles having an aspect ratio of 2 to 100, a polymer compound having at least one thioether group, and a compound curable by heat or light. A light shielding material having at least one layer.
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PCT/JP2006/320755 WO2007046425A1 (en) | 2005-10-19 | 2006-10-18 | Fine particle-containing composition, ink for forming colored film for display, light-blocking film for display, light-blocking material, substrate with light-blocking film, color filter, liquid crystal display element and liquid crystal display |
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CN101398497B (en) * | 2007-09-28 | 2012-06-27 | 富士胶片株式会社 | Color filter and manufacure method |
KR102081106B1 (en) * | 2013-05-30 | 2020-06-08 | 엘지디스플레이 주식회사 | Thin film transistor array substrate and method of fabricating the same |
KR102183384B1 (en) * | 2018-04-17 | 2020-11-26 | 코세스지티 주식회사 | Trimming method for light blocking portion of 3d curved glass and 3d curved glass trimmed by the method |
CN111116957A (en) * | 2019-12-31 | 2020-05-08 | 宁波大榭开发区综研化学有限公司 | Selective shading film and shading adhesive tape and preparation method thereof |
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