TWI632210B - Transparent conductive coating composition, transparent conductive film and built-in touch panel functional type horizontal electric field type liquid crystal display panel - Google Patents

Transparent conductive coating composition, transparent conductive film and built-in touch panel functional type horizontal electric field type liquid crystal display panel Download PDF

Info

Publication number
TWI632210B
TWI632210B TW105143614A TW105143614A TWI632210B TW I632210 B TWI632210 B TW I632210B TW 105143614 A TW105143614 A TW 105143614A TW 105143614 A TW105143614 A TW 105143614A TW I632210 B TWI632210 B TW I632210B
Authority
TW
Taiwan
Prior art keywords
liquid crystal
transparent conductive
conductive film
coating
crystal display
Prior art date
Application number
TW105143614A
Other languages
Chinese (zh)
Other versions
TW201713732A (en
Inventor
西本智久
小林哲
土井秀軽
上天一浩
三本高志
Original Assignee
日商麥克賽爾控股股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日商麥克賽爾控股股份有限公司 filed Critical 日商麥克賽爾控股股份有限公司
Publication of TW201713732A publication Critical patent/TW201713732A/en
Application granted granted Critical
Publication of TWI632210B publication Critical patent/TWI632210B/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/10—Block or graft copolymers containing polysiloxane sequences
    • C09D183/12—Block or graft copolymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • 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
    • G02F1/1343—Electrodes
    • G02F1/134309—Electrodes characterised by their geometrical arrangement
    • G02F1/134363—Electrodes characterised by their geometrical arrangement for applying an electric field parallel to the substrate, i.e. in-plane switching [IPS]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2231—Oxides; Hydroxides of metals of tin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K3/2279—Oxides; Hydroxides of metals of antimony
    • 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
    • G02F1/13338—Input devices, e.g. touch panels
    • 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
    • G02F1/1343—Electrodes
    • G02F1/134309—Electrodes characterised by their geometrical arrangement
    • G02F1/134372—Electrodes characterised by their geometrical arrangement for fringe field switching [FFS] where the common electrode is not patterned
    • 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
    • G02F2202/00—Materials and properties
    • G02F2202/22—Antistatic materials or arrangements

Abstract

本發明係提供一種可兼具靜電放電(ESD)機能及觸控面板機能，同時可形成光透過率與硬度優異之透明導電性膜之透明導電性塗佈組成物及使用其之透明導電性膜、以及具備該透明導電性膜之內藏觸控面板機能型橫電場方式液晶顯示面板。 The present invention provides a transparent conductive coating composition capable of forming a transparent conductive film having excellent light transmittance and hardness while having an electrostatic discharge (ESD) function and a touch panel function, and a transparent conductive film using the same And a touch panel function-type horizontal electric field type liquid crystal display panel having the transparent conductive film.

本發明之透明導電性塗佈組成物，其特徵係含有鏈狀導電性無機粒子、黏結劑、高沸點溶劑與低沸點溶劑，且相對於前述鏈狀導電性無機粒子及前述黏結劑之合計量，前述鏈狀導電性無機粒子之含量為40~90質量%。 The transparent conductive coating composition of the present invention is characterized by comprising chain-shaped conductive inorganic particles, a binder, a high-boiling solvent and a low-boiling solvent, and a total amount of the chain-like conductive inorganic particles and the binder The content of the chain-like conductive inorganic particles is 40 to 90% by mass.

Description

透明導電性塗佈組成物、透明導電性膜及內藏觸控面板機能型橫電場方式液晶顯示面板 Transparent conductive coating composition, transparent conductive film and built-in touch panel functional type horizontal electric field type liquid crystal display panel

本發明係有關透明導電性塗佈組成物及使用其之透明導電性膜、以及具備該透明導電性膜之內藏觸控面板機能型橫電場方式液晶顯示面板。 The present invention relates to a transparent conductive coating composition, a transparent conductive film using the same, and a built-in touch panel functional horizontal electric field type liquid crystal display panel including the transparent conductive film.

液晶顯示面板活用輕量．薄型．低消耗電力等之特性，除已使用於各種資訊機器終端或照相機等之小型顯示裝置以外，近幾年來已使用於電視等之大型顯示裝置中，其市場正在擴大。至於液晶顯示面板之種類，以前以TN(扭轉向列)型為代表之縱電場方式較占優勢，但最近被稱為橫電場方式之液晶顯示面板亦成為主流。 The LCD panel is lightweight. Thin type. In addition to being used in small display devices such as various information device terminals and cameras, the low-power consumption and the like have been used in large-scale display devices such as televisions in recent years, and the market is expanding. As for the type of the liquid crystal display panel, the vertical electric field method represented by the TN (twisted nematic) type has been dominant, but the liquid crystal display panel which has recently been called the horizontal electric field type has also become the mainstream.

縱電場方式之液晶顯示面板之特徵係於介隔液晶層而相互對向配置之透明基板中，於一片透明基板上設置像素電極，於另一片透明基板上設置共通電極，藉由在該像素電極與共通電極之間發生之電場，亦即對於透明基板垂直之電場而控制液晶配向。相對於此，橫電場方式之液晶顯示面板之構成係於介隔液晶層而相互對向配置之 透明基板中，於主要之一片透明基板之液晶層側具備顯示用電極及基準電極，藉由於該顯示用電極及基準電極間發生之電場(橫方向電場，邊緣電場(fringe electric field))，亦即平行於透明電極所發生之電場而控制液晶配向，因而調變透過上述液晶層之光者。 The vertical electric field type liquid crystal display panel is characterized in that a transparent electrode is disposed on a transparent substrate, and a common electrode is disposed on the other transparent substrate, and the pixel electrode is disposed on the other transparent substrate. The electric field generated between the common electrode, that is, the electric field perpendicular to the transparent substrate, controls the liquid crystal alignment. On the other hand, the configuration of the liquid crystal display panel of the horizontal electric field type is disposed opposite to each other via the liquid crystal layer. In the transparent substrate, the display electrode and the reference electrode are provided on the liquid crystal layer side of the main transparent substrate, and the electric field (lateral electric field, fringe electric field) generated between the display electrode and the reference electrode is also That is, the alignment of the liquid crystal is controlled in parallel with the electric field generated by the transparent electrode, thereby modulating the light transmitted through the liquid crystal layer.

橫電場方式之液晶顯示面板相較於縱電場方式具有視角廣之優點，但具有縱電場方式之液晶顯示面板不會發生之課題，即具有液晶顯示面板受到來自外部或內部之靜電影響或外部之電磁阻礙，而有發生黑顯示時之漏光等、使顯示品質降低之問題。此係因為橫電場方式之液晶顯示面板係成為於一片透明基板上積集顯示用電極與基準電極之構造，故而成為完全不具有具備對於來自外部之靜電等之遮蔽機能的導電層之構成所致。 The liquid crystal display panel of the horizontal electric field method has the advantage of having a wide viewing angle compared to the vertical electric field method, but the liquid crystal display panel having the vertical electric field mode does not have a problem that the liquid crystal display panel is affected by external or internal static electricity or external. Electromagnetic obstruction, and there is a problem that light leakage occurs when black display occurs, which degrades display quality. In this case, the liquid crystal display panel of the horizontal electric field type has a structure in which the display electrode and the reference electrode are accumulated on one transparent substrate, so that the conductive layer having the shielding function for external static electricity or the like is not provided at all. .

為解決該等問題，已提案於液晶顯示面板之透明基板中，在相對於背光單元較遠側之透明基板之與液晶層相反側之面上形成具備透光性之導電層，而具有靜電放電(ESD)機能之技術，具體上係提案形成含ITO等抗靜電膜作為導電層之方法(參照專利文獻1)。依據該方法，可對橫電場方式液晶顯示面板賦予ESD機能。 In order to solve such problems, it has been proposed to form a light-transmitting conductive layer on a surface of the transparent substrate on the side opposite to the liquid crystal layer with respect to the transparent substrate on the transparent substrate of the liquid crystal display panel, and to have an electrostatic discharge. The technique of the (ESD) function is specifically a method of forming an antistatic film such as ITO as a conductive layer (see Patent Document 1). According to this method, the ESD function can be imparted to the horizontal electric field type liquid crystal display panel.

另一方面，以如最近之智慧型手機等所用之液晶顯示裝置為代表之使用具有觸控面板機能之液晶顯示面板之液晶顯示裝置之需求大增。目前所普及之附觸控面板機能之液晶顯示面板係於以往之液晶顯示面板外側配置觸控面板之外加型，但該外加型使面板整體變厚，而有難 以使液晶顯示裝置薄型化之問題。相對於此，作為於液晶顯示面板內部內藏觸控面板光能之內藏型，已提案有內藏觸控面板機能型液晶顯示面板。內藏觸控面板機能型液晶顯示面板由於係在液晶顯示面板之2片玻璃基板之間配置觸控感測機能層，故具有可使面板整體變薄之優點。因此，已提案將前述橫電場方式液晶顯示面板與內藏觸控面板機能型液晶顯示面板組合而成之液晶顯示面板(參照專利文獻2)。另外，專利文獻2中作為觸控感測機能層所用之觸控感測方式，係介紹例如靜電電容方式。 On the other hand, the demand for a liquid crystal display device using a liquid crystal display panel having a touch panel function as represented by a liquid crystal display device used in recent smart phones and the like has been greatly increased. Currently, the liquid crystal display panel with the touch panel function is added to the outside of the conventional liquid crystal display panel, but the external type makes the panel thick and difficult. A problem of making the liquid crystal display device thin. On the other hand, as a built-in type in which the light energy of the touch panel is incorporated in the inside of the liquid crystal display panel, a built-in touch panel function type liquid crystal display panel has been proposed. The built-in touch panel function type liquid crystal display panel has the advantage that the entire panel can be thinned because the touch sensing function layer is disposed between the two glass substrates of the liquid crystal display panel. Therefore, a liquid crystal display panel in which the above-described horizontal electric field type liquid crystal display panel and the built-in touch panel function type liquid crystal display panel are combined has been proposed (see Patent Document 2). In addition, in the touch sensing method used in the touch sensing function layer in Patent Document 2, for example, an electrostatic capacitance method is introduced.

另外，本發明相關之先前技術文獻有專利文獻3~6。 Further, the prior art documents related to the present invention are Patent Documents 3 to 6.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本特開2010-102020號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-102020

[專利文獻2]日本特開2011-137882號公報 [Patent Document 2] Japanese Laid-Open Patent Publication No. 2011-137882

[專利文獻3]日本特開2000-196287號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2000-196287

[專利文獻4]日本特開2005-139026號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2005-139026

[專利文獻5]日本特開2006-339113號公報 [Patent Document 5] Japanese Patent Laid-Open Publication No. 2006-339113

[專利文獻6]日本特開2012-25793號公報 [Patent Document 6] Japanese Patent Laid-Open Publication No. 2012-25793

然而，組合橫電場方式液晶顯示面板與配置 靜電電容方式之觸控感測機能層之內藏觸控面板機能型液晶顯示面板之液晶顯示面板由於賦予橫電場方式液晶顯示面板所要求之ESD機能，故於液晶顯示面板設置導電層時，判斷會有觸控感度下降之情況。 However, combined horizontal electric field mode liquid crystal display panel and configuration The liquid crystal display panel of the liquid crystal display panel of the touch panel function type liquid crystal display panel of the electrostatic capacitance type touch sensing function layer is determined by the ESD function required for the liquid crystal display panel of the horizontal electric field mode, so when the conductive layer is disposed on the liquid crystal display panel, it is judged There will be a drop in touch sensitivity.

本發明為解決上述問題，而提供一種在具備靜電電容式觸控感測機能層之內藏觸控面板機能型橫電場方式液晶面板中，可兼具ESD機能及觸控面板機能，並且可形成光透過率與硬度優異之透明導電性膜之透明導電性塗佈組成物及使用其之透明導電性膜、以及具備該透明導電性膜之內藏觸控面板機能型橫電場方式液晶顯示面板。 In order to solve the above problems, the present invention provides a built-in touch panel function-type horizontal electric field type liquid crystal panel having a capacitive touch sensing function layer, which can have both an ESD function and a touch panel function, and can be formed. A transparent conductive coating composition of a transparent conductive film having excellent light transmittance and hardness, a transparent conductive film using the same, and a built-in touch panel functional horizontal electric field type liquid crystal display panel including the transparent conductive film.

本發明之透明導電性塗佈組成物係包含鏈狀導電性無機粒子、黏結劑、高沸點溶劑與低沸點溶劑之透明導電性塗佈組成物，且其特徵為相對於前述鏈狀導電性無機粒子及前述黏結劑之合計量，前述鏈狀導電性無機粒子之含量為40~90質量%。 The transparent conductive coating composition of the present invention comprises a chain-shaped conductive inorganic particle, a binder, a transparent conductive coating composition of a high boiling point solvent and a low boiling point solvent, and is characterized in that it is relative to the aforementioned chain-like conductive inorganic substance. The total amount of the particles and the binder is 40 to 90% by mass based on the content of the chain-like conductive inorganic particles.

本發明之透明導電性膜之特徵係使用上述本發明之透明導電性塗佈組成物而形成。 The transparent conductive film of the present invention is characterized by using the above-described transparent conductive coating composition of the present invention.

本發明之內藏觸控面板機能型橫電場方式液晶顯示面板係具備液晶層、介由前述液晶層相互對向配置之第1透明基板及第2透明基板、配置於前述第1透明基板之與前述液晶層相反側之透明導電性膜、配置於前述第 2透明基板之前述液晶層側之顯示用電極及基準電極、與配置在前述第1透明基板及前述第2透明基板之間之靜電電容式觸控感測機能層之內藏觸控面板機能型橫電場方式液晶顯示面板，其特徵係使用上述本發明之透明導電性膜作為前述透明導電性膜。 The touch panel function-type horizontal electric field type liquid crystal display panel of the present invention includes a liquid crystal layer, a first transparent substrate and a second transparent substrate which are disposed to face each other via the liquid crystal layer, and are disposed on the first transparent substrate a transparent conductive film on the opposite side of the liquid crystal layer, disposed in the above The touch panel function type of the display electrode and the reference electrode on the liquid crystal layer side of the transparent substrate and the capacitive touch sensing function layer disposed between the first transparent substrate and the second transparent substrate A horizontal electric field type liquid crystal display panel characterized in that the transparent conductive film of the present invention is used as the transparent conductive film.

依據本發明，可將ESD機能高且不降低觸控感度，同時光透過率與硬度均優異之透明導電性膜直接且簡易地配置在內藏觸控面板機能型橫電場方式液晶顯示面板上。 According to the present invention, the transparent conductive film having high ESD function without deteriorating the touch sensitivity and having excellent light transmittance and hardness can be directly and easily disposed on the built-in touch panel function type horizontal electric field type liquid crystal display panel.

LPN‧‧‧液晶顯示裝置 LPN‧‧‧Liquid display device

LQ‧‧‧液晶層 LQ‧‧‧ liquid crystal layer

30‧‧‧第1透明基板 30‧‧‧1st transparent substrate

31‧‧‧黑矩陣 31‧‧‧Black matrix

32‧‧‧彩色濾光片 32‧‧‧Color filters

33‧‧‧保護層 33‧‧‧Protective layer

34‧‧‧第2配向膜 34‧‧‧2nd alignment film

20‧‧‧第2透明基板 20‧‧‧2nd transparent substrate

21‧‧‧閘極絕緣膜 21‧‧‧Gate insulation film

23‧‧‧第1絕緣膜 23‧‧‧1st insulating film

24‧‧‧第2絕緣膜 24‧‧‧2nd insulating film

25‧‧‧第1配向膜 25‧‧‧1st alignment film

13‧‧‧透明導電性膜 13‧‧‧Transparent conductive film

PE‧‧‧顯示用電極 PE‧‧‧ display electrode

PX‧‧‧像素 PX‧‧ ‧ pixels

PSL‧‧‧狹縫 PSL‧‧ slit

CE‧‧‧基準電極 CE‧‧‧ reference electrode

C‧‧‧電容線 C‧‧‧ capacitance line

CSL‧‧‧狹縫 CSL‧‧ slit

G‧‧‧閘極線 G‧‧‧ gate line

S‧‧‧信號線 S‧‧‧ signal line

SC‧‧‧半導體層 SC‧‧‧Semiconductor layer

SW‧‧‧開關元件 SW‧‧‧Switching elements

WG‧‧‧閘極電極 WG‧‧‧gate electrode

WD‧‧‧汲極電極 WD‧‧‧汲electrode

WS‧‧‧源極電極 WS‧‧‧ source electrode

圖1係顯示使用本發明之內藏觸控面板機能型橫電場方式液晶顯示面板之液晶顯示裝置之一部分之概略俯視圖。 1 is a schematic plan view showing a portion of a liquid crystal display device using a touch panel function-type horizontal electric field type liquid crystal display panel of the present invention.

圖2係顯示使用本發明之內藏觸控面板機能型橫電場方式液晶顯示面板之液晶顯示裝置之一部分之概略剖面圖。 2 is a schematic cross-sectional view showing a portion of a liquid crystal display device using the touch panel function-type horizontal electric field type liquid crystal display panel of the present invention.

圖3係實施例1中使用之鏈狀含有銻之氧化錫粒子之透過型電子顯微鏡照片。 Fig. 3 is a transmission electron micrograph of a chain-like tin oxide particle containing ruthenium used in Example 1.

圖4係將圖3放大之透過型電子顯微鏡照片。 Fig. 4 is a transmission electron micrograph showing an enlarged view of Fig. 3.

(透明導電性塗佈組成物) (transparent conductive coating composition)

首先，針對本發明之透明導電性塗佈組成物加以說明。 First, the transparent conductive coating composition of the present invention will be described.

本發明之透明導電性塗佈組成物含有鏈狀導電性無機粒子、黏結劑、高沸點溶劑與低沸點溶劑。且，特徵為相對於上述鏈狀導電性無機粒子及上述黏結劑之合計量，上述鏈狀導電性無機粒子之含量為40~90質量%。 The transparent conductive coating composition of the present invention contains chain-like conductive inorganic particles, a binder, a high boiling point solvent, and a low boiling point solvent. Further, the content of the chain-shaped conductive inorganic particles is 40 to 90% by mass based on the total amount of the chain-like conductive inorganic particles and the binder.

藉由使用上述透明導電性塗佈組成物，可提供ESD機能高且不降低觸控感度，同時光透過率與硬度均優異之透明導電性膜。 By using the above transparent conductive coating composition, it is possible to provide a transparent conductive film having high ESD function without deteriorating touch sensitivity and excellent light transmittance and hardness.

〈鏈狀導電性無機粒子〉 <chain-like conductive inorganic particles>

本發明之透明導電性塗佈組成物藉由相對於上述鏈狀導電性無機粒子及上述黏結劑之合計量，將上述鏈狀導電性無機粒子之含量設為40~90質量%，可提供ESD機能高且不降低觸控感度之透明導電性膜。上述鏈狀導電性無機粒子之含量低於40質量%時透明導電性膜之ESD機能降低，且上述鏈狀導電性無機粒子之含量超過90質量%時觸控感度降低。 In the transparent conductive coating composition of the present invention, the content of the chain-shaped conductive inorganic particles is 40 to 90% by mass based on the total amount of the chain-like conductive inorganic particles and the binder, and ESD can be provided. A transparent conductive film that is high in function and does not reduce touch sensitivity. When the content of the chain-shaped conductive inorganic particles is less than 40% by mass, the ESD function of the transparent conductive film is lowered, and when the content of the chain-shaped conductive inorganic particles exceeds 90% by mass, the touch sensitivity is lowered.

此外，藉由使用上述鏈狀導電性無機粒子，相較於使用非鏈狀導電性無機粒子之情況，可藉更少量提高透明導電性膜之導電性。此認為係藉由無機粒子具有鏈 狀構造，而比無機粒子單獨存在時，更能增加無機粒子相互間之導電性網絡，而提高透明導電性膜整體之導電性所致。因此，由於可降低用於實現透明導電性膜之特定導電性之無機粒子之量，故亦可提高透明導電性膜之光透過率。 Further, by using the above chain-shaped conductive inorganic particles, the conductivity of the transparent conductive film can be increased by a smaller amount than when the non-chain-shaped conductive inorganic particles are used. This is thought to have a chain by inorganic particles. The structure is more than that when the inorganic particles are present alone, the conductivity network between the inorganic particles can be increased, and the conductivity of the entire transparent conductive film can be improved. Therefore, since the amount of the inorganic particles for realizing the specific conductivity of the transparent conductive film can be reduced, the light transmittance of the transparent conductive film can also be improved.

上述鏈狀導電性無機粒子較好使用粒徑為2~30nm之一次粒子以2~50個連接而成者，更好3~20個連接而成。上述粒徑之一次粒子之連接數超過50個時，因粒子之散射而有使透明導電性膜之濁度值上升之傾向。此外，上述粒徑之一次粒子之連接數低於2個時，粒子成為非鏈狀而難以形成無機粒子相互間之導電性網絡，使透明導電性膜之導電性降低。 It is preferable that the above-mentioned chain-shaped conductive inorganic particles are formed by connecting 2 to 50 primary particles having a particle diameter of 2 to 30 nm, and more preferably 3 to 20. When the number of the primary particles of the above-mentioned particle diameter is more than 50, the turbidity value of the transparent conductive film tends to increase due to the scattering of the particles. In addition, when the number of the primary particles of the above-mentioned particle diameter is less than two, the particles become non-chain-like, and it is difficult to form a conductive network between the inorganic particles, and the conductivity of the transparent conductive film is lowered.

上述粒徑與連結數可例如將以低共沸溶劑稀釋透明導電性塗佈組成物以2~10nm之厚膜薄薄地塗佈於各種基材上之透明導電性膜，藉由透過型電子顯微鏡(TEM)觀察．測定構成鏈狀導電性無機粒子之各個粒子之粒徑與連結數而求出。 The particle diameter and the number of bonds may be, for example, a transparent conductive film in which a transparent conductive coating composition is diluted with a low azeotropic solvent and applied to various substrates on a thick film of 2 to 10 nm, and a transmission electron microscope is used. (TEM) observation. The particle diameter and the number of connections of the respective particles constituting the chain-shaped conductive inorganic particles were determined and determined.

上述鏈狀導電性無機粒子只要是兼具透明性與導電性之鏈狀粒子則無特別限制，可使用例如金屬粒子、碳粒子、導電性金屬氧化物粒子、導電性氮化物粒子等。其中，以兼具透明性與導電性之導電性金屬氧化物粒子較佳。上述導電性金屬氧化物粒子列舉為氧化錫粒子、氧化銻粒子、含有銻之氧化錫(ATO)粒子、含有錫之氧化銦(ITO)粒子、含有磷之氧化錫(PTO)粒子、含有 鋁之氧化鋅(AZO)粒子、含有鎵之氧化鋅(GZO)粒子等之金屬氧化物粒子。上述導電性金屬氧化物粒子可單獨使用，亦可組合2種以上使用。且，上述鏈狀導電性無機粒子較好含有由ATO粒子、ITO粒子及PTO粒子所組成之群選出之至少1種。該等導電性無機粒子之透明性、導電性及化學特性優異，且作成透明導電性膜時亦可實現高的光透過率與導電性。 The chain-shaped conductive inorganic particles are not particularly limited as long as they are chain-like particles having both transparency and conductivity, and for example, metal particles, carbon particles, conductive metal oxide particles, and conductive nitride particles can be used. Among them, conductive metal oxide particles having both transparency and conductivity are preferred. The conductive metal oxide particles are exemplified by tin oxide particles, cerium oxide particles, cerium-containing tin oxide (ATO) particles, tin-containing indium oxide (ITO) particles, phosphorus-containing tin oxide (PTO) particles, and Aluminum oxide particles such as aluminum zinc oxide (AZO) particles or gallium-containing zinc oxide (GZO) particles. These conductive metal oxide particles may be used singly or in combination of two or more. Further, the chain-shaped conductive inorganic particles preferably contain at least one selected from the group consisting of ATO particles, ITO particles, and PTO particles. These conductive inorganic particles are excellent in transparency, conductivity, and chemical properties, and can achieve high light transmittance and conductivity when a transparent conductive film is formed.

上述鏈狀導電性無機粒子之製造方法並無特別限制，但可採用例如日本特開2000-196287號公報、日本特開2005-139026號公報、日本特開2006-339113號公報、日本特開2012-25739號公報所記載之製造方法。 The method for producing the above-mentioned chain-shaped conductive inorganic particles is not particularly limited, and for example, JP-A-2000-196287, JP-A-2005-139026, JP-A-2006-339113, and JP-A-2012 A manufacturing method described in the publication No. 25739.

〈黏結劑〉 <Binder>

上述黏結劑只要是可使上述鏈狀導電性無機粒子分散且形成塗膜者即無特別限制，可使用無機系黏結劑及有機系黏結劑之任一種。相對於上述鏈狀導電性無機粒子及上述黏結劑之合計量，上述黏結劑之含量較好為20質量%以上。低於20質量%時會有透明導電性薄膜之強度降低之傾向。 The binder is not particularly limited as long as it can disperse the chain-like conductive inorganic particles and form a coating film, and any of an inorganic binder and an organic binder can be used. The content of the above-mentioned binder is preferably 20% by mass or more based on the total amount of the chain-like conductive inorganic particles and the binder. When the amount is less than 20% by mass, the strength of the transparent conductive film tends to decrease.

上述無機系黏結劑可使用例如烷氧基矽烷。更具體而言，可使用上述烷氧基矽烷為3~4個烷氧基與矽結合而成之化合物，且溶解於水中時，經聚合而以-OSiO-連結成為高分子量SiO2體者。 As the above inorganic binder, for example, an alkoxydecane can be used. More specifically, a compound in which the alkoxydecane is a combination of 3 to 4 alkoxy groups and hydrazine can be used, and when dissolved in water, it is polymerized to form a high molecular weight SiO 2 body by -OSiO-.

上述烷氧基矽烷較好為含有由四烷氧基矽 烷、三烷氧基矽烷、二烷氧基矽烷及烷氧基矽烷寡聚物所組成之群選出之至少1種多官能烷氧基矽烷者。烷氧基矽烷寡聚物係指烷氧基矽烷之單體彼此縮合而形成之高分子量化之烷氧基矽烷，且指1分子內具有2個以上之矽氧烷鍵(-OSiO-)之寡聚物。其鍵結數較好為2~20個。 The above alkoxydecane preferably contains a tetraalkyloxy fluorene A group of at least one polyfunctional alkoxy decane selected from the group consisting of an alkane, a trialkoxy decane, a dialkoxy decane, and an alkoxy decane oligomer. The alkoxy decane oligomer refers to a high molecular weight alkoxy decane formed by condensing monomers of alkoxy decane, and means having two or more decane bonds (-OSiO-) in one molecule. Oligomer. The number of bonds is preferably from 2 to 20.

上述四烷氧基矽烷之例列舉為四甲氧基矽烷、四乙氧基矽烷、四丙氧基矽烷、四異丙氧基矽烷、四第三丁氧基矽烷等之以碳數1~4之烷氧基進行四取代之矽烷。 Examples of the above tetraalkoxy decane are tetramethoxy decane, tetraethoxy decane, tetrapropoxy decane, tetraisopropoxy decane, tetra-butoxy decane, and the like, and have a carbon number of 1 to 4. The alkoxy group is a tetrasubstituted decane.

上述三烷氧基矽烷之例列舉為三甲氧基矽烷、三乙氧基矽烷、三丙氧基矽烷、三丁氧基矽烷、三異丙氧基矽烷、三L-丁氧基矽烷等之以碳數1~4之烷氧基進行三取代之矽烷、"KBM-13(甲基三甲氧基矽烷)"、“KBE-13(甲基三乙氧基矽烷)”等之一部分經烷基取代之矽烷。 Examples of the above trialkoxydecane are exemplified by trimethoxydecane, triethoxydecane, tripropoxydecane, tributoxydecane, triisopropoxydecane, tri-L-butoxydecane, and the like. a part of the alkoxy group having 1 to 4 carbon atoms which is trisubstituted, "KBM-13 (methyltrimethoxydecane)", "KBE-13 (methyltriethoxydecane)", etc. Decane.

上述二烷氧基矽烷之例列舉為二甲基二甲氧基矽烷、二苯基二甲氧基矽烷、二甲基二乙氧基矽烷、二苯基二乙氧基矽烷等之以碳數1~4之烷氧基取代之矽烷、"KBM-22(二甲基二甲氧基矽烷)"、“KBE-22(二甲基二乙氧基矽烷)”等之一部份經烷基取代之矽烷。 Examples of the above dialkoxy decane are exemplified by dimethyl dimethoxy decane, diphenyl dimethoxy decane, dimethyl diethoxy decane, diphenyl diethoxy decane, and the like. 1 to 4 of alkoxy-substituted decane, "KBM-22 (dimethyldimethoxydecane)", "KBE-22 (dimethyldiethoxydecane)", etc. Substituted decane.

上述烷氧基矽烷寡聚物之例列舉為一併具有有機基與烷氧基矽烷之較低分子之烷氧基矽烷寡聚物。具體例列舉為信越化學公司製之"X-40-2308"、"X-40-9238"、"X-40-9247"、“KR-401N”、“KR-501”、“KR- 9218”、COLCOAT公司製之“矽酸乙酯40”、“矽酸乙酯48”、“矽酸甲酯51”、“矽酸甲酯53A”等。 The above alkoxydecane oligomers are exemplified by a lower molecular alkoxydecane oligomer having an organic group and an alkoxydecane. Specific examples are "X-40-2308", "X-40-9238", "X-40-9247", "KR-401N", "KR-501", and "KR-" manufactured by Shin-Etsu Chemical Co., Ltd. 9218", "ethyl citrate 40", "ethyl citrate 48", "methyl decanoate 51", "methyl decanoate 53A" manufactured by COLCOAT.

上述烷氧基矽烷之具體例中，為了形成更高硬度之透明導電性薄膜，較好係四烷氧基矽烷、四烷氧基矽烷及三烷氧基矽烷之併用、一部分經烷基取代之三烷氧基矽烷或二烷氧基矽烷、官能基為烷氧基矽烷基之烷氧基矽烷寡聚物。其原因為藉由使用該等，利用促進側鏈分子間之矽氧烷鍵之3次元交聯使透明導線性膜之硬度變強，可不使因經時變化於透明導電性薄膜上發生龜裂之危險性更加劇，且可更提高與基板之密著性。 In the specific example of the alkoxydecane, in order to form a transparent conductive film having a higher hardness, a tetraalkyloxydecane, a tetraalkoxydecane, and a trialkoxydecane are preferably used in combination, and a part is substituted by an alkyl group. An alkoxy decane oligomer having a trialkoxy decane or a dialkoxy decane and a functional group of an alkoxyalkyl group. The reason for this is that the hardness of the transparent linear film is enhanced by the use of the three-dimensional cross-linking which promotes the decane bond between the side chain molecules by using these, and cracking does not occur on the transparent conductive film due to the change with time. The danger is even more dramatic, and the adhesion to the substrate can be further improved.

再者，為了以更安定狀態再現性良好地形成良質之膜，較好對透明導電性塗佈組成物進行烷氧基矽烷之水解反應，在經矽烷醇化之狀態下使用。其調整方法例舉為例如先將水與酸觸媒添加於以醇等低沸點溶劑稀釋之烷氧基矽烷中進行矽烷醇化之方法，或將水與觸媒添加於導電性塗佈組成物中進行矽烷醇化之方法。水之含量係藉由自烷氧基矽烷之構造求出水解率而求出理論值，但係配合透明導電性塗佈組成物之可操作時間或塗佈適性、透明導電性膜之物理特性而適當調整。相對於烷氧基矽烷總量，上述水之含量較好為50~1500質量%。其原因為低於50質量%時透明導電性薄膜之強度降低，超過1500質量%時，乾燥速度變慢，而影響到塗佈適性。 Further, in order to form a favorable film with good reproducibility in a more stable state, it is preferred to subject the transparent conductive coating composition to a hydrolysis reaction of alkoxysilane, and to use it in a state of being decanolated. The adjustment method is, for example, a method in which water and an acid catalyst are first added to alkoxysilane diluted with a low boiling point solvent such as alcohol to carry out stanolization, or water and a catalyst are added to the conductive coating composition. A method of decanolation. The water content is obtained by determining the hydrolysis rate from the structure of the alkoxysilane, and the theoretical value is obtained, but the operation time of the transparent conductive coating composition, the coating suitability, and the physical properties of the transparent conductive film are blended. Appropriate adjustments. The content of the above water is preferably from 50 to 1,500% by mass based on the total amount of the alkoxydecane. The reason for this is that the strength of the transparent conductive film is lowered when it is less than 50% by mass, and when it exceeds 1,500% by mass, the drying speed is slow, which affects the coating suitability.

且，上述有機系黏結劑可使用例如丙烯酸樹脂、聚酯樹脂、聚醯胺樹脂、聚碳酸酯樹脂、聚胺基甲酸 酯樹脂、聚苯乙烯樹脂、聚氯乙烯樹脂、聚偏氯乙烯樹脂、聚乙烯醇樹脂、聚乙酸乙烯酯樹脂及含光聚合性單體與聚合起始劑之光聚合性樹脂等。 Further, as the above organic binder, for example, an acrylic resin, a polyester resin, a polyamide resin, a polycarbonate resin, or a polyaminocarboxylic acid can be used. An ester resin, a polystyrene resin, a polyvinyl chloride resin, a polyvinylidene chloride resin, a polyvinyl alcohol resin, a polyvinyl acetate resin, a photopolymerizable resin containing a photopolymerizable monomer and a polymerization initiator, and the like.

上述光聚合性單體較好含50~90%之三官能以上之(甲基)丙烯酸單體。此處，光聚合性單體之含有率意指光聚合性單體酯之質量相對於光聚合性單體及聚合起始劑之合計質量之比例。藉由使反應點多的(甲基)丙烯酸單體聚合．硬化而成為基質樹脂，可更提高透明導電性膜之強度。3官能以上之光聚合性單體之質量比例未達50%時，塗膜之硬度變弱，使耐久性降低。且，由於有必要與上述光聚合性單體一起使用聚合起始劑，故光聚合性單體之質量比例超過90%實質上有困難。 The photopolymerizable monomer preferably contains 50 to 90% of a trifunctional or higher (meth)acrylic monomer. Here, the content ratio of the photopolymerizable monomer means the ratio of the mass of the photopolymerizable monomer ester to the total mass of the photopolymerizable monomer and the polymerization initiator. By polymerizing a (meth)acrylic monomer having a large number of reaction sites. When it is hardened to form a matrix resin, the strength of the transparent conductive film can be further improved. When the mass ratio of the trifunctional or higher photopolymerizable monomer is less than 50%, the hardness of the coating film is weak, and the durability is lowered. Further, since it is necessary to use a polymerization initiator together with the above photopolymerizable monomer, it is difficult to have a mass ratio of the photopolymerizable monomer of more than 90%.

3官能(甲基)丙烯酸單體列舉為三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、乙氧化三羥甲基丙烷三(甲基)丙烯酸酯；4官能以上之(甲基)丙烯酸單體列舉為季戊四醇四丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯等。且，光聚合性單體可為一般銷售之多官能丙烯酸寡聚物，最好為硬化性高且硬度高者，例如共榮社化學公司製之“AH-600”、“UA-306H”或新中村化學公司製之“NK OLIGO U-6HA”、“NK OLIGO U-15HA”等。 The trifunctional (meth)acrylic monomers are exemplified by trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate; The above (meth)acrylic monomers are exemplified by pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and the like. Further, the photopolymerizable monomer may be a polyfunctional acrylic oligomer generally sold, and is preferably one having high hardenability and high hardness, such as "AH-600" and "UA-306H" manufactured by Kyoeisha Chemical Co., Ltd. or "NK OLIGO U-6HA" and "NK OLIGO U-15HA" made by Shin-Nakamura Chemical Co., Ltd.

此外，上述光聚合性單體中亦可含有單官能及2官能之光聚合性單體，列舉為例如1,4-丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,6-己二 醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、乙氧基化雙酚A二(甲基)丙烯酸酯、環己烷二甲醇二(甲基)丙烯酸酯等2官能聚合性單體；乙烯基吡咯啶酮、乙烯基甲醯胺等之乙烯基單體、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯等之(甲基)丙烯酸烷酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異冰片酯等之脂環式(甲基)丙烯酸酯、(甲基)羥基乙基(甲基)丙烯酸酯、(甲基)丙烯酸羥基丙酯等羥基(甲基)丙烯酸酯、丙烯醯基嗎啉、(甲基)丙烯酸二甲胺基乙酯等之含氮(甲基)丙烯酸酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧基乙酯、丙烯酸四氫糠酯等之芳香族系(甲基)丙烯酸酯等之單官能聚合性單體。 Further, the photopolymerizable monomer may further contain a monofunctional or bifunctional photopolymerizable monomer, and examples thereof include, for example, 1,4-butanediol di(meth)acrylate and neopentyl glycol di(methyl). Acrylate, 1,6-hexane Alcohol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, cyclohexanedimethanol di(meth)acrylic acid a bifunctional polymerizable monomer such as an ester; a vinyl monomer such as vinylpyrrolidone or vinylcarbamide; butyl (meth)acrylate; 2-ethylhexyl (meth)acrylate; An alicyclic (meth) acrylate such as an alkyl acrylate, a cyclohexyl (meth) acrylate or an isobornyl (meth) acrylate, or a (meth) hydroxyethyl (meth) acrylate, Nitrogen (meth) acrylate such as hydroxy (meth) acrylate such as hydroxypropyl acrylate, acryloyl morpholine or dimethylaminoethyl (meth) acrylate, or benzyl (meth) acrylate A monofunctional polymerizable monomer such as an aromatic (meth) acrylate such as an ester, phenoxyethyl (meth)acrylate or tetrahydrofurfuryl acrylate.

上述聚合起始劑列舉為例如聯苯醯、雙乙醯等之α-二酮類、苯偶姻等偶姻(acyloin)類、苯偶姻甲醚、苯偶姻***、苯偶姻異丙醚等偶姻醚類、噻噸酮、2,4-二乙基噻噸酮、2-氯噻噸酮、噻噸酮-4-磺酸等之噻噸酮類、二苯甲酮、4,4'-雙(二甲胺基)二苯甲酮、4,4’-雙(二乙胺基)二苯甲酮等之二苯甲酮類、米氏(Michael)酮類、苯乙酮、2-(4-甲苯磺醯氧基)-2-苯基苯乙酮、對-二甲胺基苯乙酮、α,α’-二甲氧基乙醯氧基二苯甲酮、2,2'-二甲氧基-2-苯基苯乙酮、對-甲氧基苯乙酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基丙-1-酮、2-苄基-2-二甲胺基-1-(4-嗎啉基苯基)-丁-1-酮等之苯乙酮類、蒽醌、1,4-萘醌等醌類、氯化菲、三鹵甲基苯基碸、 叁(三鹵甲基)-s-三嗪等鹵化合物、醯基氧化膦類、二第三丁基過氧化物等過氧化物等。 The polymerization initiators are exemplified by α-diketones such as biphenyl hydrazine and diacetamidine, acyloin such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl. Alkaloid ethers such as ether, thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, thioxanthone-4-sulfonic acid, etc., benzophenone, benzophenone, 4 , 4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, etc., benzophenones, Michael ketones, phenylethyl Ketone, 2-(4-toluenesulfonyloxy)-2-phenylacetophenone, p-dimethylaminoacetophenone, α,α'-dimethoxyacetoxybenzophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholine Acetophenones, anthraquinones, 1,4-ethylidene, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one Anthraquinones such as naphthoquinone, phenanthrene chloride, trihalomethylphenyl hydrazine, A halogen compound such as hydrazine (trihalomethyl)-s-triazine, a sulfhydryl phosphine oxide or a peroxide such as di-tert-butyl peroxide.

上述光聚合性單體及聚合起始劑可各單獨使用1種，亦可各併用2種以上。 The photopolymerizable monomer and the polymerization initiator may be used singly or in combination of two or more.

〈高沸點溶劑〉 <High boiling point solvent>

上述高沸點溶劑只要是能溶解黏著劑成分，且可藉塗佈後之乾燥步驟去除者即可，可使用例如乙二醇、二甲基亞碸、N-甲基吡咯啶酮、N-乙基吡咯啶酮、N-甲基甲醯胺、甲基異丁基酮、1,2-丙二醇、N,N-二甲基苯胺、甲酚、硝基苯、乙二醇等。 The above-mentioned high-boiling point solvent may be any one which can dissolve the adhesive component and can be removed by a drying step after coating, and for example, ethylene glycol, dimethyl hydrazine, N-methylpyrrolidone, N-B can be used. Pyrrolidone, N-methylformamide, methyl isobutyl ketone, 1,2-propanediol, N,N-dimethylaniline, cresol, nitrobenzene, ethylene glycol, and the like.

上述高沸點溶劑之含量只要相對於導電性塗佈組成物總量為0.1~30.0質量%左右即可。 The content of the high boiling point solvent may be about 0.1 to 30.0% by mass based on the total amount of the conductive coating composition.

〈低沸點溶劑〉 <Low boiling point solvent>

上述低沸點溶劑可使用例如乙醇、甲醇、正丙醇、異丙醇、正丁醇、異丁醇、甲基乙基酮、四氫呋喃、丙酮、二噁烷、乙酸乙酯、氯仿、乙腈、吡啶、乙酸、水等。藉由使用上述低沸點溶劑，提高上述鏈狀導電性無機粒子之分散性。 As the above low boiling point solvent, for example, ethanol, methanol, n-propanol, isopropanol, n-butanol, isobutanol, methyl ethyl ketone, tetrahydrofuran, acetone, dioxane, ethyl acetate, chloroform, acetonitrile, pyridine can be used. , acetic acid, water, etc. The dispersibility of the chain-shaped conductive inorganic particles is improved by using the above-described low boiling point solvent.

上述低沸點溶劑之含量只要相對於導電性塗佈組成物總量為50.0~99.5質量%左右即可。 The content of the low boiling point solvent may be about 50.0 to 99.5 mass% with respect to the total amount of the conductive coating composition.

〈酸觸媒〉 Acid Catalyst

本發明之透明導電性塗佈組成物中可進一步添加一般使用之酸觸媒(鹽酸、硫酸、乙酸、磷酸等)。藉此，可以更安定的性能再現性良好地形成高品質之透明導電性膜。上述酸觸媒之含量相對於烷氧基矽烷總量只要為1.0~30.0質量%左右即可。 Further, an acid catalyst (hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid, or the like) which is generally used can be further added to the transparent conductive coating composition of the present invention. Thereby, a high-quality transparent conductive film can be formed with good performance reproducibility. The content of the above acid catalyst may be about 1.0 to 30.0% by mass based on the total amount of the alkoxysilane.

〈調平劑〉 <Leveling agent>

本發明之透明導電性塗佈組成物可進一步添加調平劑。藉此，可確保透明導電性膜之表面平滑性。上述調平劑可使用例如聚醚改質之聚二甲基矽氧烷、二丙二醇單甲醚等。上述調平劑觸媒之含量相對於導電性塗佈組成物總量只要為0.01~5.0質量%左右即可。 A leveling agent can be further added to the transparent conductive coating composition of the present invention. Thereby, the surface smoothness of the transparent conductive film can be ensured. As the above leveling agent, for example, polyether modified polydimethyl siloxane, dipropylene glycol monomethyl ether or the like can be used. The content of the leveling agent catalyst may be about 0.01 to 5.0% by mass based on the total amount of the conductive coating composition.

〈調製法〉 <Modulation method>

本發明之透明導電性塗佈組成物之調製法若可將上述各成分混合，使上述鏈狀導電性無機粒子分散於上述黏結劑與上述溶劑中則無特別限制，可使用例如球磨機、砂磨機、手磨機(pico mill)、漆料調節機(paint conditioner)等透過介質之機械處理，或使用超音波分散機、均質機、分散機及噴射研磨機等對上述各成分施以分散處理而進行混合．分散。 In the preparation method of the transparent conductive coating composition of the present invention, the above-mentioned respective components may be mixed, and the chain-shaped conductive inorganic particles are dispersed in the above-mentioned binder and the solvent, and are not particularly limited, and for example, a ball mill or a sand mill can be used. Machine, hand mill (pico mill), paint conditioner (paint conditioner), etc., through mechanical treatment of the medium, or using ultrasonic disperser, homogenizer, disperser and jet mill to disperse the above components And mix. dispersion.

上述調製後之本發明之透明導電性塗佈組成物中，較好上述鏈狀導電性無機粒子及上述黏結劑之合計量(固體成分量)相對於總量為0.5~20質量%，黏度為 0.5~100mPa．s。藉此，後述之透明導電性膜製作時之塗佈步驟變得容易。 In the transparent conductive coating composition of the present invention, the total amount of the chain-like conductive inorganic particles and the binder (solid content) is preferably 0.5 to 20% by mass based on the total amount, and the viscosity is 0.5~100mPa. s. Thereby, the coating step at the time of preparation of the transparent conductive film mentioned later becomes easy.

(透明導電性膜) (transparent conductive film)

接著，針對本發明之透明導電性膜加以說明。 Next, the transparent conductive film of the present invention will be described.

本發明之透明導電性膜之特徵係使用上述本發明之透明導電性塗佈組成物而形成。藉由使用上述透明導電性塗佈組成物形成，在上述透明導電性膜中，可將表面電阻設為10~1000MΩ/□，全光線透過率(依據JIS K7105)設為95.0~99.9%，鉛筆硬度設為5~9H，可防止製造步驟中之損傷，且可防止良率下降。 The transparent conductive film of the present invention is characterized by using the above-described transparent conductive coating composition of the present invention. By using the above transparent conductive coating composition, the surface resistivity of the transparent conductive film can be set to 10 to 1000 MΩ/□, and the total light transmittance (according to JIS K7105) can be set to 95.0 to 99.9%. The hardness is set to 5 to 9H, which prevents damage during the manufacturing process and prevents the yield from falling.

尤其，藉由將上述表面電阻設為10~1000MΩ/□，可提供抗靜電機能高、且不降低觸控感度之透明導電性膜。亦即，上述表面電阻低於10MΩ/□時觸控感度降低，且上述表面電阻超過1000MΩ/□時抗靜電機能降低。 In particular, by setting the surface resistance to 10 to 1000 M?/?, it is possible to provide a transparent conductive film having high antistatic performance without reducing touch sensitivity. That is, when the surface resistance is less than 10 MΩ/□, the touch sensitivity is lowered, and when the surface resistance exceeds 1000 MΩ/□, the antistatic function is lowered.

又，藉由使用上述透明導電性塗佈組成物形成透明導電性膜，可使本發明之透明導電性膜在溫度65℃、相對濕度90%之環境下保持500小時後之表面電阻成為10~1000MΩ/□。 Further, by forming the transparent conductive film using the transparent conductive coating composition, the surface resistivity of the transparent conductive film of the present invention can be maintained for 10 hours in an environment of a temperature of 65 ° C and a relative humidity of 90% for 10 hours. 1000MΩ/□.

本發明之透明導電性膜只要將本發明之透明導電性塗佈組成物塗佈於後述之液晶顯示面板之基板上，形成塗膜後，使上述塗膜乾燥而形成即可。 In the transparent conductive film of the present invention, the transparent conductive coating composition of the present invention may be applied to a substrate of a liquid crystal display panel to be described later to form a coating film, and then the coating film may be dried and formed.

上述透明導電性塗佈組成物之塗佈方法只要能形成平滑之塗膜之塗佈方法即無特別限制。可使用例如 旋塗、輥塗、模嘴塗佈、氣刀塗佈、刮塗、逆轉塗佈、凹版塗佈、微凹版塗佈等塗佈法、或凹版印刷、網版印刷、平版印刷、噴墨印刷等印刷法、噴塗、狹縫塗佈、浸塗等塗佈法，但較好為對於製造裝置之簡化或製造成本有利之噴塗、狹縫塗佈等之非旋塗方式。 The coating method of the transparent conductive coating composition is not particularly limited as long as it can form a smooth coating film. Can be used, for example Coating methods such as spin coating, roll coating, nozzle coating, air knife coating, blade coating, reverse coating, gravure coating, micro gravure coating, or gravure printing, screen printing, lithography, inkjet printing The coating method such as printing, spray coating, slit coating, dip coating, or the like is preferably a non-rotating coating method such as spraying, slit coating, or the like which is advantageous for simplification of the manufacturing apparatus or manufacturing cost.

且，塗佈上述透明導電性塗佈組成物後，藉乾燥去除溶劑，但亦可視需要對塗膜照射UV光或EB光使塗膜硬化，形成透明導電性膜。 Further, after the transparent conductive coating composition is applied, the solvent is removed by drying. However, if necessary, the coating film may be irradiated with UV light or EB light to cure the coating film to form a transparent conductive film.

本發明之透明導電性膜厚度並無特別限制，只要為10~300nm左右即可。 The thickness of the transparent conductive film of the present invention is not particularly limited, and may be about 10 to 300 nm.

(內藏觸控面板機能型橫電場方式液晶顯示面板) (The built-in touch panel function type horizontal electric field type liquid crystal display panel)

接著，針對本發明之內藏觸控面板機能型橫電場方式液晶顯示面板加以說明。 Next, the built-in touch panel function type horizontal electric field type liquid crystal display panel of the present invention will be described.

本發明之內藏觸控面板機能型橫電場方式液晶顯示面板係具備液晶層、介由前述液晶層相互對向配置之第1透明基板及第2透明基板、配置於上述第1透明基板之與上述液晶層相反側之透明導電性膜、配置於上述第2透明基板之上述液晶層側之顯示用電極、基準電極及電容線。又，本發明之內藏觸控面板機能型橫電場方式液晶顯示面板之特徵係使用上述本發明之透明導電性膜作為上述透明導電性膜。 The touch panel function-type horizontal electric field type liquid crystal display panel of the present invention includes a liquid crystal layer, a first transparent substrate and a second transparent substrate which are disposed opposite to each other via the liquid crystal layer, and are disposed on the first transparent substrate a transparent conductive film on the opposite side of the liquid crystal layer, a display electrode disposed on the liquid crystal layer side of the second transparent substrate, a reference electrode, and a capacitance line. Moreover, the touch panel function-type horizontal electric field type liquid crystal display panel of the present invention is characterized in that the transparent conductive film of the present invention is used as the transparent conductive film.

本發明之內藏觸控面板機能型橫電場方式液晶顯示面板藉由具備本發明之透明導電性膜，可不降低觸 控感度地賦予ESD機能。 The touch panel function-type horizontal electric field type liquid crystal display panel of the present invention can be provided without the touch by providing the transparent conductive film of the present invention. Controlling the ESD function.

以下，基於圖式說明本發明之內藏觸控面板機能型橫電場方式液晶顯示面板。圖1係顯示使用本發明之內藏觸控面板機能型橫電場方式液晶顯示面板之液晶顯示裝置之一部分的概略俯視圖。且，圖2係顯示於圖1之A-B線切斷之使用本發明之內藏觸控面板機能型橫電場方式液晶顯示面板之液晶顯示裝置之一部分的概略剖面圖。 Hereinafter, the touch panel function-type horizontal electric field type liquid crystal display panel of the present invention will be described based on the drawings. 1 is a schematic plan view showing a part of a liquid crystal display device using a touch panel function-type horizontal electric field type liquid crystal display panel of the present invention. 2 is a schematic cross-sectional view showing a portion of a liquid crystal display device using the touch panel function-type horizontal electric field type liquid crystal display panel of the present invention, which is cut off along the line A-B of FIG.

圖1、圖2中，液晶顯示裝置LPN具備由配置為矩陣狀之複數畫素PX所成之主動區(active area)、液晶層LQ、介由液晶層LQ對向配置之第1透明基板30及第2透明基板20、及配置於第1透明基板30之與液晶層LQ相反側之透明導電性膜13。且，於第2透明基板20之液晶層LQ側配置掃描線、與掃描線垂直之訊號線S，該等掃描線、訊號線S係連接於驅動電路。且，掃描線與訊號線交叉部中配置連接於掃描線與訊號線之開關元件SW。 In FIG. 1 and FIG. 2, the liquid crystal display device LPN includes an active area formed by a plurality of pixels PX arranged in a matrix, a liquid crystal layer LQ, and a first transparent substrate 30 disposed opposite to each other via the liquid crystal layer LQ. And the second transparent substrate 20 and the transparent conductive film 13 disposed on the opposite side of the liquid crystal layer LQ of the first transparent substrate 30. Further, a scanning line and a signal line S perpendicular to the scanning line are disposed on the liquid crystal layer LQ side of the second transparent substrate 20, and the scanning lines and signal lines S are connected to the driving circuit. Further, a switching element SW connected to the scanning line and the signal line is disposed in the intersection of the scanning line and the signal line.

該等掃描線、訊號線S、開關元件SW係由第1絕緣膜23予以覆蓋，於該第1絕緣膜23上配置基準電極CE與電容線C。該電容線C係與基準電極CE一體地形成。電容線C係跨及複數之畫素PX而形成，形成含複數畫素PX之1個群組，並與兼具檢測外部檢測對象物接近或接觸液晶顯示裝置LPN之檢測電路之驅動電路連接。該等群組複數存在於主動區內，藉由該等群組可於液晶顯示裝置LPN之檢測面(具備第1透明基板30之透明 導電性膜13之側之面)特定出檢測對象物之位置。 The scanning lines, the signal lines S, and the switching elements SW are covered by the first insulating film 23, and the reference electrodes CE and the capacitance lines C are placed on the first insulating film 23. This capacitance line C is formed integrally with the reference electrode CE. The capacitance line C is formed across a plurality of pixels PX, and forms one group including a plurality of pixels PX, and is connected to a drive circuit having a detection circuit that detects an external detection target or contacts the liquid crystal display device LPN. The plurality of groups are present in the active area, and the groups can be transparent to the detection surface of the liquid crystal display device LPN (providing the transparency of the first transparent substrate 30) The surface on the side of the conductive film 13 specifies the position of the object to be detected.

介由第2絕緣膜，於該基準電極CE與電容線C上配置具有狹縫PSL之顯示用電極PE。該顯示用電極PE介由設置於第1絕緣膜23與第2絕緣膜24之接觸孔與開關元件SW連接。且，於顯示用電極PE上，朝第1配向膜25所配置之特定方向摩擦。 The display electrode PE having the slit PSL is disposed on the reference electrode CE and the capacitance line C via the second insulating film. The display electrode PE is connected to the switching element SW via a contact hole provided in the first insulating film 23 and the second insulating film 24. Further, the display electrode PE is rubbed in a specific direction in which the first alignment film 25 is disposed.

且，於第1透明基板30之液晶層LQ側具備將各畫素PX予以區分之黑矩陣31及與各畫素PX對應之彩色濾光片32。於該等黑矩陣31及彩色濾光片32上配置平坦化之保護層33與被覆該保護層33之第2配向膜34。該第2配向膜34被朝特定方向予以摩擦。 Further, on the liquid crystal layer LQ side of the first transparent substrate 30, a black matrix 31 that distinguishes each pixel PX and a color filter 32 corresponding to each pixel PX are provided. A planarized protective layer 33 and a second alignment film 34 covering the protective layer 33 are disposed on the black matrix 31 and the color filter 32. The second alignment film 34 is rubbed in a specific direction.

該液晶顯示裝置LPN係藉由對電容線C及基準電極CE給予共通電位、對顯示用電極PE給予畫素電位，而在基準電極CE與顯示用電極PE之間形成橫方向電場或邊緣電場並切換液晶層LQ之液晶分子。 In the liquid crystal display device LPN, a common electric potential is applied to the capacitance line C and the reference electrode CE, and a pixel potential is applied to the display electrode PE to form a lateral electric field or a fringe electric field between the reference electrode CE and the display electrode PE. The liquid crystal molecules of the liquid crystal layer LQ are switched.

另一方面，內藏於該液晶顯示裝置LPN之觸控面板機能係如下述般動作。亦即，使顯示用電極PE成為浮動之狀態，控制兼具檢測電路之驅動電路，且將用於檢測外部檢測對象物之檢測信號輸入電容線C中取代共通電位。且，對控制驅動電路之各訊號線S進行預充電(precharge)。在該狀態下，檢測對象物靠近或接觸第1透明基板30之外部時，因電容線C與訊號顯S之間之靜電電容產生變化故檢測出檢測對象物。 On the other hand, the touch panel function built in the liquid crystal display device LPN operates as follows. In other words, the display electrode PE is brought into a floating state, and the drive circuit having the detection circuit is controlled, and the detection signal for detecting the external detection target is input to the capacitance line C instead of the common potential. Moreover, each signal line S of the control driving circuit is precharged. In this state, when the detection target approaches or contacts the outside of the first transparent substrate 30, the detection target is detected due to a change in electrostatic capacitance between the capacitance line C and the signal display S.

透明導電膜13係藉由塗佈於第1透明基板30 之與液晶層LQ相反側之主面上而形成，再於透明導電膜13上配置偏光板PL2。且，於第2透明基板20之外側配置偏光板PL1。且，於偏光板PL1之外側配置背光單元15(未圖示)。且，液晶層LQ係由密封部予以密閉。 The transparent conductive film 13 is applied to the first transparent substrate 30 The main surface of the liquid crystal layer LQ is formed on the main surface, and the polarizing plate PL2 is placed on the transparent conductive film 13. Further, a polarizing plate PL1 is disposed on the outer side of the second transparent substrate 20. Further, a backlight unit 15 (not shown) is disposed outside the polarizing plate PL1. Further, the liquid crystal layer LQ is sealed by a sealing portion.

又，圖1中，G為閘極線，CSL為狹縫，WG為閘極電極，WD為汲極電極，SC為半導體層。又，圖2中，WS為源極電極，21為閘極絕緣膜，23為絕緣膜。 Further, in Fig. 1, G is a gate line, CSL is a slit, WG is a gate electrode, WD is a drain electrode, and SC is a semiconductor layer. Further, in Fig. 2, WS is a source electrode, 21 is a gate insulating film, and 23 is an insulating film.

上述液晶顯示裝置LPN由於具備用以檢測出外部檢測對象物之電容線C之內藏觸控面板機能型，故可對液晶顯示裝置LPN賦予對於來自裝置外部或內部之靜電的影響或外部之電磁妨礙之遮蔽機能，同時亦可賦予觸控機能。 Since the liquid crystal display device LPN includes a built-in touch panel function type for detecting the capacitance line C of the external detection target, the liquid crystal display device LPN can be given an influence on static electricity from the outside or inside of the device or external electromagnetic It hinders the shielding function and also gives the touch function.

且，上述液晶顯示裝置LPN中，未具備電容線時，亦即，於未內藏觸控面板機能之液晶顯示裝置中，藉由在第1透明基板30與偏光板PL2之間配置透明導電膜13，亦可賦予對於來自裝置外部之靜電等之電磁妨害之遮蔽機能。 In the liquid crystal display device LPN, when a capacitance line is not provided, that is, a transparent conductive film is disposed between the first transparent substrate 30 and the polarizing plate PL2 in the liquid crystal display device in which the touch panel function is not built. 13, it is also possible to provide a shielding function for electromagnetic interference from static electricity or the like from the outside of the device.

[實施例] [Examples]

以下，基於實施例詳細說明本發明。但，本發明並不受限於以下之實施例。又，以下所謂之「份」係指「質量份」。 Hereinafter, the present invention will be described in detail based on examples. However, the invention is not limited to the following examples. In addition, the following "parts" means "parts by mass".

(實施例1) (Example 1)

〈鏈狀含有銻之氧化錫(ATO)粒子分散液〉 <Chain-like tin oxide (ATO) particle dispersion containing ruthenium>

準備日揮觸媒化成公司製之“ELCOM V-3560”作為鏈狀ATO粒子分散液。鏈狀ATO粒子分散液“ELCOM V-3560”係鏈狀ATO粒子：20.8份與乙醇：70.0份、異丙醇9.2份之混合分散液。 "ELCOM V-3560" manufactured by Nippon Chemical Co., Ltd. was prepared as a chain ATO particle dispersion. The chain-like ATO particle dispersion "ELCOM V-3560" is a chain-shaped ATO particle: a mixed dispersion of 20.8 parts of ethanol and 70.0 parts of isopropyl alcohol and 9.2 parts of isopropyl alcohol.

上述鏈狀ATO粒子分散液中所用之鏈狀ATO粒子之透過型電子顯微鏡(TEM)照片示於圖3及圖4。圖3及圖4係將以低沸點溶劑稀釋後述之塗佈液且以2~10nm之膜厚薄薄地塗佈在觀察用基材上而成之透明導電膜進行觀察者。由圖3及圖4可知上述ATO粒子為粒徑2~30nm之一次粒子以2~50個連接形成之鏈狀ATO粒子(鏈狀導電性無機粒子)。 A transmission electron microscope (TEM) photograph of the chain ATO particles used in the chain ATO particle dispersion is shown in Figs. 3 and 4 . 3 and 4 are views of a transparent conductive film obtained by diluting a coating liquid described later with a low boiling point solvent and applying a film thickness of 2 to 10 nm on a substrate for observation. 3 and 4, the ATO particles are chain-shaped ATO particles (chain-shaped conductive inorganic particles) formed by connecting 2 to 50 primary particles having a particle diameter of 2 to 30 nm.

接著，如下述般調製塗佈液。但，烷氧基矽烷係使用醇之一部分進行稀釋，且添加水與觸媒預先矽烷醇化而使用。 Next, the coating liquid was prepared as follows. However, the alkoxydecane is diluted with a part of the alcohol, and water and a catalyst are added in advance to be decanolated.

〈塗佈液〉 <coating liquid>

以下述份量將上述鏈狀ATO粒子分散液及下述成分饋入塑膠製瓶中並攪拌而調製塗佈液。 The chain ATO particle dispersion and the following components were fed into a plastic bottle in the following amounts and stirred to prepare a coating liquid.

(1)鏈狀ATO粒子分散液：7.0份 (1) Chain ATO particle dispersion: 7.0 parts

(2)烷氧基矽烷(無機系黏結劑：信越化學工業公司製"X40-2308")：0.6份 (2) Alkoxydecane (inorganic binder: "X40-2308" manufactured by Shin-Etsu Chemical Co., Ltd.): 0.6 parts

(3)磷酸(酸觸媒)：0.1份 (3) Phosphoric acid (acid catalyst): 0.1 parts

(4)聚醚改質之聚二甲基矽氧烷15.0份與二丙二醇單甲醚85.0份之混合液(調平劑：日本BYK化學公司製“BYK-337”)：0.1份 (4) A mixture of 15.0 parts of polyether modified polydimethyl siloxane and 85.0 parts of dipropylene glycol monomethyl ether (leveling agent: "BYK-337" manufactured by BYK Chemical Co., Ltd.): 0.1 parts

(5)二甲基亞碸(高沸點溶劑)：5.0份 (5) Dimethyl hydrazine (high boiling point solvent): 5.0 parts

(6)乙醇(低沸點溶劑)：82.2份 (6) Ethanol (low boiling point solvent): 82.2 parts

(7)水：5.0份 (7) Water: 5.0 parts

上述塗佈液之不揮發固體成分(鏈狀ATO粒子及烷氧基矽烷)之含量為2.2質量%，鏈狀ATO粒子之含量相對於鏈狀ATO粒子及烷氧基矽烷之合計量為70.8質量%。且，以東機產業公司製之TV25型黏度計測定上述塗佈液之黏度為1.7mPa．s。 The content of the nonvolatile solid content (chain-like ATO particles and alkoxysilane) of the coating liquid is 2.2% by mass, and the total amount of the chain ATO particles is 70.8 by mass with respect to the chain ATO particles and the alkoxy decane. %. Moreover, the viscosity of the above coating liquid was measured by a TV25 type viscometer manufactured by Toki Sangyo Co., Ltd. to be 1.7 mPa. s.

(實施例2) (Example 2)

以下述份量將實施例1準備之鏈狀ATO粒子分散液及下述成分饋入塑膠製瓶中並攪拌而調製塗佈液。 The chain ATO particle dispersion prepared in Example 1 and the following components were fed into a plastic bottle in the following amounts and stirred to prepare a coating liquid.

(1)鏈狀ATO粒子分散液：6.6份 (1) Chain ATO particle dispersion: 6.6 parts

(2)烷氧基矽烷(無機系黏結劑：信越化學工業公司製"X40-2308")：0.5份 (2) Alkoxy decane (inorganic binder: "X40-2308" manufactured by Shin-Etsu Chemical Co., Ltd.): 0.5 parts

(3)烷氧基矽烷(無機系黏結劑：COLCOAT公司製之“矽酸乙酯28”)：0.4份 (3) Alkoxy decane (inorganic binder: "ethyl citrate 28" manufactured by COLCOAT): 0.4 parts

(4)磷酸(酸觸媒)：0.1份 (4) Phosphoric acid (acid catalyst): 0.1 parts

(5)聚醚改質之聚二甲基矽氧烷15.0份與二丙二醇單甲醚85.0份之混合液(調平劑：日本BYK化學公司製 “BYK-337”)：0.1份 (5) A mixture of 15.0 parts of polyether modified polydimethyl siloxane and 85.0 parts of dipropylene glycol monomethyl ether (leveling agent: manufactured by BYK Chemical Co., Ltd., Japan) "BYK-337"): 0.1 parts

(6)二甲基亞碸(高沸點溶劑)：5.0份 (6) Dimethyl hydrazine (high boiling point solvent): 5.0 parts

(7)乙醇(低沸點溶劑)：82.3份 (7) Ethanol (low boiling point solvent): 82.3 parts

(8)水：5.0份 (8) Water: 5.0 parts

上述塗佈液之不揮發固體成分(鏈狀ATO粒子及烷氧基矽烷)之含量為2.4質量%，鏈狀ATO粒子之含量相對於鏈狀ATO粒子及烷氧基矽烷之合計量為60.4質量%。且，與實施例1同樣測定上述塗佈液之黏度後為1.7mPa．s。 The content of the nonvolatile solid content (chain-like ATO particles and alkoxydecane) of the coating liquid is 2.4% by mass, and the total amount of the chain ATO particles is 60.4 by mass with respect to the chain ATO particles and the alkoxydecane. %. Further, the viscosity of the coating liquid was measured in the same manner as in Example 1 and was 1.7 mPa. s.

(實施例3) (Example 3)

以下述份量將實施例1準備之鏈狀ATO粒子分散液及下述成分饋入塑膠製瓶中並攪拌而調製塗佈液。 The chain ATO particle dispersion prepared in Example 1 and the following components were fed into a plastic bottle in the following amounts and stirred to prepare a coating liquid.

(1)鏈狀ATO粒子分散液：6.0份 (1) Chain ATO particle dispersion: 6.0 parts

(2)烷氧基矽烷(無機系黏結劑：信越化學工業公司製"X40-2308")：1.6份 (2) Alkoxy decane (inorganic binder: "X40-2308" manufactured by Shin-Etsu Chemical Co., Ltd.): 1.6 parts

(3)磷酸(酸觸媒)：0.1份 (3) Phosphoric acid (acid catalyst): 0.1 parts

(4)聚醚改質之聚二甲基矽氧烷15.0份與二丙二醇單甲醚85.0份之混合液(調平劑：日本BYK化學公司製“BYK-337”)：0.1份 (4) A mixture of 15.0 parts of polyether modified polydimethyl siloxane and 85.0 parts of dipropylene glycol monomethyl ether (leveling agent: "BYK-337" manufactured by BYK Chemical Co., Ltd.): 0.1 parts

(5)二甲基亞碸(高沸點溶劑)：5.0份 (5) Dimethyl hydrazine (high boiling point solvent): 5.0 parts

(6)乙醇(低沸點溶劑)：82.2份 (6) Ethanol (low boiling point solvent): 82.2 parts

(7)水：5.0份 (7) Water: 5.0 parts

上述塗佈液之不揮發固體成分(鏈狀ATO粒子及烷氧基矽烷)之含量為3.0質量%，鏈狀ATO粒子之含量相對於鏈狀ATO粒子及烷氧基矽烷之合計量為43.8質量%。且，與實施例1同樣測定上述塗佈液之黏度後為1.8mPa．s。 The content of the nonvolatile solid content (chain-like ATO particles and alkoxy decane) of the coating liquid is 3.0% by mass, and the total amount of the chain ATO particles is 43.8 by mass with respect to the chain ATO particles and the alkoxy decane. %. Further, in the same manner as in Example 1, the viscosity of the coating liquid was measured and found to be 1.8 mPa. s.

(實施例4) (Example 4)

以下述份量將實施例1準備之鏈狀ATO粒子分散液及下述成分饋入塑膠製瓶中並攪拌而調製塗佈液。 The chain ATO particle dispersion prepared in Example 1 and the following components were fed into a plastic bottle in the following amounts and stirred to prepare a coating liquid.

(1)鏈狀ATO粒子分散液：7.4份 (1) Chain ATO particle dispersion: 7.4 parts

(2)烷氧基矽烷(無機系黏結劑：信越化學工業公司製"X40-2308")：0.2份 (2) Alkoxy decane (inorganic binder: "X40-2308" manufactured by Shin-Etsu Chemical Co., Ltd.): 0.2 parts

(3)磷酸(酸觸媒)：0.1份 (3) Phosphoric acid (acid catalyst): 0.1 parts

(4)聚醚改質之聚二甲基矽氧烷15.0份與二丙二醇單甲醚85.0份之混合液(調平劑：日本BYK化學公司製“BYK-337”)：0.1份 (4) A mixture of 15.0 parts of polyether modified polydimethyl siloxane and 85.0 parts of dipropylene glycol monomethyl ether (leveling agent: "BYK-337" manufactured by BYK Chemical Co., Ltd.): 0.1 parts

(5)二甲基亞碸(高沸點溶劑)：5.0份 (5) Dimethyl hydrazine (high boiling point solvent): 5.0 parts

(6)乙醇(低沸點溶劑)：82.2份 (6) Ethanol (low boiling point solvent): 82.2 parts

(7)水：5.0份 (7) Water: 5.0 parts

上述塗佈液之不揮發固體成分(鏈狀ATO粒子及烷氧基矽烷)之含量為1.9質量%，鏈狀ATO粒子之含量相對於鏈狀ATO粒子及烷氧基矽烷之合計量為88.5質量%。且，與實施例1同樣測定上述塗佈液之黏度後為 1.8mPa．s。 The content of the nonvolatile solid content (chain-like ATO particles and alkoxydecane) of the coating liquid is 1.9% by mass, and the total amount of the chain ATO particles is 88.5 by mass with respect to the chain ATO particles and the alkoxydecane. %. Further, after measuring the viscosity of the coating liquid in the same manner as in Example 1, 1.8mPa. s.

(實施例5) (Example 5)

以下述份量將實施例1準備之鏈狀ATO粒子分散液及下述成分饋入塑膠製瓶中並攪拌而調製塗佈液。 The chain ATO particle dispersion prepared in Example 1 and the following components were fed into a plastic bottle in the following amounts and stirred to prepare a coating liquid.

(1)鏈狀ATO粒子分散液：7.0份 (1) Chain ATO particle dispersion: 7.0 parts

(2)烷氧基矽烷(無機系黏結劑：COLCOAT公司製之“矽酸乙酯28”)：0.6份 (2) Alkoxy decane (inorganic binder: "ethyl citrate 28" manufactured by COLCOAT): 0.6 parts

(3)磷酸(酸觸媒)：0.1份 (3) Phosphoric acid (acid catalyst): 0.1 parts

(4)聚醚改質之聚二甲基矽氧烷15.0份與二丙二醇單甲醚85.0份之混合液(調平劑：日本BYK化學公司製“BYK-337”)：0.1份 (4) A mixture of 15.0 parts of polyether modified polydimethyl siloxane and 85.0 parts of dipropylene glycol monomethyl ether (leveling agent: "BYK-337" manufactured by BYK Chemical Co., Ltd.): 0.1 parts

(5)乙二醇(高沸點溶劑)：5.0份 (5) Ethylene glycol (high boiling point solvent): 5.0 parts

(6)異丙醇(低沸點溶劑)：82.2份 (6) Isopropanol (low boiling point solvent): 82.2 parts

(7)水：5.0份 (7) Water: 5.0 parts

上述塗佈液之不揮發固體成分(鏈狀ATO粒子及烷氧基矽烷)之含量為2.2質量%，鏈狀ATO粒子之含量相對於鏈狀ATO粒子及烷氧基矽烷之合計量為70.8質量%。且，與實施例1同樣測定上述塗佈液之黏度後為2.9mPa．s。 The content of the nonvolatile solid content (chain-like ATO particles and alkoxysilane) of the coating liquid is 2.2% by mass, and the total amount of the chain ATO particles is 70.8 by mass with respect to the chain ATO particles and the alkoxy decane. %. Further, in the same manner as in Example 1, the viscosity of the coating liquid was measured and found to be 2.9 mPa. s.

(實施例6) (Example 6)

以下述份量將實施例1準備之鏈狀ATO粒子分散液 及下述成分饋入塑膠製瓶中並攪拌而調製塗佈液。 The chain ATO particle dispersion prepared in Example 1 was prepared in the following amounts. The following components were fed into a plastic bottle and stirred to prepare a coating liquid.

(1)鏈狀ATO粒子分散液：6.6份 (1) Chain ATO particle dispersion: 6.6 parts

(2)烷氧基矽烷(無機系黏結劑：COLCOAT公司製之“矽酸乙酯28”)：0.9份 (2) Alkoxydecane (inorganic binder: "ethyl citrate 28" manufactured by COLCOAT): 0.9 parts

(3)磷酸(酸觸媒)：0.1份 (3) Phosphoric acid (acid catalyst): 0.1 parts

(4)聚醚改質之聚二甲基矽氧烷15.0份與二丙二醇單甲醚85.0份之混合液(調平劑：日本BYK化學公司製“BYK-337”)：0.1份 (4) A mixture of 15.0 parts of polyether modified polydimethyl siloxane and 85.0 parts of dipropylene glycol monomethyl ether (leveling agent: "BYK-337" manufactured by BYK Chemical Co., Ltd.): 0.1 parts

(5)乙二醇(高沸點溶劑)：5.0份 (5) Ethylene glycol (high boiling point solvent): 5.0 parts

(6)異丙醇(低沸點溶劑)：82.3份 (6) Isopropanol (low boiling point solvent): 82.3 parts

(7)水：5.0份 (7) Water: 5.0 parts

上述塗佈液之不揮發固體成分(鏈狀ATO粒子及烷氧基矽烷)之含量為2.4質量%，鏈狀ATO粒子之含量相對於鏈狀ATO粒子及烷氧基矽烷之合計量為60.4質量%。且，與實施例1同樣測定上述塗佈液之黏度後為2.9mPa．s。 The content of the nonvolatile solid content (chain-like ATO particles and alkoxydecane) of the coating liquid is 2.4% by mass, and the total amount of the chain ATO particles is 60.4 by mass with respect to the chain ATO particles and the alkoxydecane. %. Further, in the same manner as in Example 1, the viscosity of the coating liquid was measured and found to be 2.9 mPa. s.

(實施例7) (Example 7)

以下述份量將實施例1準備之鏈狀ATO粒子分散液及下述成分饋入塑膠製瓶中並攪拌而調製塗佈液。 The chain ATO particle dispersion prepared in Example 1 and the following components were fed into a plastic bottle in the following amounts and stirred to prepare a coating liquid.

(1)鏈狀ATO粒子分散液：7.0份 (1) Chain ATO particle dispersion: 7.0 parts

(2)丙烯酸樹脂(有機系黏結劑：三菱縲縈公司製 “Dianal BR87”)：0.6份 (2) Acrylic resin (organic binder: manufactured by Mitsubishi “Dianal BR87”): 0.6 parts

(3)聚醚改質之聚二甲基矽氧烷15.0份與二丙二醇單甲醚85.0份之混合液(調平劑：日本BYK化學公司製“BYK-337”)：0.1份 (3) A mixture of 15.0 parts of polyether-modified polydimethyl siloxane and 85.0 parts of dipropylene glycol monomethyl ether (leveling agent: "BYK-337" manufactured by BYK Chemical Co., Ltd.): 0.1 parts

(4)二甲基亞碸(高沸點溶劑)：10.0份 (4) Dimethyl hydrazine (high boiling point solvent): 10.0 parts

(5)甲基異丁基酮(低沸點溶劑)：30.0份 (5) Methyl isobutyl ketone (low boiling point solvent): 30.0 parts

(6)乙醇(低沸點溶劑)：52.3份 (6) Ethanol (low boiling point solvent): 52.3 parts

上述塗佈液之不揮發固體成分(鏈狀ATO粒子及丙烯酸樹脂)之含量為2.1質量%，鏈狀ATO粒子之含量相對於鏈狀ATO粒子及丙烯酸樹脂之合計量為70.8質量%。且，與實施例1同樣測定上述塗佈液之黏度後為2.1mPa．s。 The content of the non-volatile solid content (chain-like ATO particles and acrylic resin) of the coating liquid was 2.1% by mass, and the content of the chain-shaped ATO particles was 70.8% by mass based on the total amount of the chain-like ATO particles and the acrylic resin. Further, in the same manner as in Example 1, the viscosity of the coating liquid was measured and found to be 2.1 mPa. s.

(實施例8) (Example 8)

以下述份量將實施例1準備之鏈狀ATO粒子分散液及下述成分饋入塑膠製瓶中並攪拌而調製塗佈液。 The chain ATO particle dispersion prepared in Example 1 and the following components were fed into a plastic bottle in the following amounts and stirred to prepare a coating liquid.

(1)鏈狀ATO粒子分散液：7.0份 (1) Chain ATO particle dispersion: 7.0 parts

(2)季戊四醇三丙烯酸酯(有機系黏結劑：日本Satomer公司製之"SR444")：0.5份 (2) Pentaerythritol triacrylate (organic binder: "SR444" manufactured by Satomer Co., Japan): 0.5 parts

(3)2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉丙-1-酮(聚合起始劑：日本BASF公司製之“Irgacure 907”)：0.1份 (3) 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinepropan-1-one (polymerization initiator: "Irgacure 907" manufactured by BASF Corporation of Japan): 0.1 part

(4)聚醚改質之聚二甲基矽氧烷15.0份與二丙二醇 單甲醚85.0份之混合液(調平劑：日本BYK化學公司製“BYK-337”)：0.1份 (4) Polyether modified polydimethyl methoxy oxide 15.0 parts and dipropylene glycol Mixture of 85.0 parts of monomethyl ether (leveling agent: "BYK-337" by BYK Chemical Co., Ltd.): 0.1 parts

(5)二甲基亞碸(高沸點溶劑)：10.0份 (5) Dimethyl hydrazine (high boiling point solvent): 10.0 parts

(6)甲基異丁基酮(高沸點溶劑)：30.0份 (6) Methyl isobutyl ketone (high boiling point solvent): 30.0 parts

(7)乙醇(低沸點溶劑)：52.3份 (7) Ethanol (low boiling point solvent): 52.3 parts

上述塗佈液之不揮發固體成分(鏈狀ATO粒子及黏結劑)之含量為2.1質量%，鏈狀ATO粒子之含量相對於鏈狀ATO粒子及黏結劑之合計量為70.8質量%。且，與實施例1同樣測定上述塗佈液之黏度後為2.3mPa．s。 The content of the nonvolatile solid content (chain-like ATO particles and the binder) of the coating liquid was 2.1% by mass, and the content of the chain ATO particles was 70.8% by mass based on the total amount of the chain ATO particles and the binder. Further, the viscosity of the coating liquid was measured in the same manner as in Example 1 and was 2.3 mPa. s.

(比較例1) (Comparative Example 1)

〈非鏈狀之含有銻之氧化錫(ATO)粒子分散液〉 <Non-chain bismuth-containing tin oxide (ATO) particle dispersion>

於塑膠製瓶中秤取下述成分，且使用直徑0.3mm之氧化鋯球，以塗料搖動機(東洋精機公司製)分散2小時後，去除氧化鋯球，以離心分離機以14000G之條件離心處理30分鐘，取其上澄液進行分級處理，獲得非鏈狀ATO粒子分散液。 The following components were weighed in a plastic bottle, and zirconia balls of 0.3 mm in diameter were used, and after dispersing for 2 hours with a paint shaker (manufactured by Toyo Seiki Co., Ltd.), the zirconia balls were removed, and centrifuged at 14,000 G using a centrifugal separator. After treating for 30 minutes, the supernatant was subjected to classification treatment to obtain a dispersion of non-chain ATO particles.

(1)非鏈狀ATO粒子(石原產業公司製之“SN100P”)：20.8份 (1) Non-chain ATO particles ("SN100P" manufactured by Ishihara Sangyo Co., Ltd.): 20.8 parts

(2)分散劑(日本BYK公司製之“BYK180”)：2.0份 (2) Dispersant ("BYK180" manufactured by BYK Corporation of Japan): 2.0 parts

(3)異丁醇：77.2份 (3) isobutanol: 77.2 parts

接著，如下述般調製塗佈液。 Next, the coating liquid was prepared as follows.

〈塗佈液〉 <coating liquid>

以下述份量將上述非鏈狀ATO粒子分散液及下述成分饋入塑膠製瓶中並攪拌而調製塗佈液。 The non-chain ATO particle dispersion and the following components were fed into a plastic bottle in the following amounts and stirred to prepare a coating liquid.

(1)非鏈狀ATO粒子分散液：7.0份 (1) Non-chain ATO particle dispersion: 7.0 parts

(2)烷氧基矽烷(無機系黏結劑：信越化學工業公司製"X40-2308")：0.6份 (2) Alkoxydecane (inorganic binder: "X40-2308" manufactured by Shin-Etsu Chemical Co., Ltd.): 0.6 parts

(3)磷酸(酸觸媒)：0.1份 (3) Phosphoric acid (acid catalyst): 0.1 parts

(4)聚醚改質之聚二甲基矽氧烷15.0份與二丙二醇單甲醚85.0份之混合液(調平劑：日本BYK化學公司製“BYK-337”)：0.1份 (4) A mixture of 15.0 parts of polyether modified polydimethyl siloxane and 85.0 parts of dipropylene glycol monomethyl ether (leveling agent: "BYK-337" manufactured by BYK Chemical Co., Ltd.): 0.1 parts

(5)二甲基亞碸(高沸點溶劑)：5.0份 (5) Dimethyl hydrazine (high boiling point solvent): 5.0 parts

(6)乙醇(低沸點溶劑)：82.2份 (6) Ethanol (low boiling point solvent): 82.2 parts

(7)水：5.0份 (7) Water: 5.0 parts

上述塗佈液之不揮發固體成分(非鏈狀ATO粒子及烷氧基矽烷)之含量為2.2質量%，非鏈狀ATO粒子之含量相對於非鏈狀ATO粒子及烷氧基矽烷之合計量為70.8質量%。且，與實施例1同樣測定上述塗佈液之黏度後為1.5mPa．s。 The content of the nonvolatile solid content (non-chain ATO particles and alkoxy decane) of the coating liquid is 2.2% by mass, and the content of the non-chain ATO particles is compared with the total amount of the non-chain ATO particles and the alkoxy decane. It is 70.8 mass%. Further, the viscosity of the coating liquid was measured in the same manner as in Example 1 and was 1.5 mPa. s.

(比較例2) (Comparative Example 2)

以下述份量將比較例1中準備之非鏈狀ATO粒子分 散液及下述成分饋入塑膠製瓶中並攪拌而調製塗佈液。 The non-chain ATO particles prepared in Comparative Example 1 were divided into the following portions. The dispersion liquid and the following components were fed into a plastic bottle and stirred to prepare a coating liquid.

(1)非鏈狀ATO粒子分散液：24.0份 (1) Non-chain ATO particle dispersion: 24.0 parts

(2)烷氧基矽烷(無機系黏結劑：信越化學工業公司製"X40-2308")：0.6份 (2) Alkoxydecane (inorganic binder: "X40-2308" manufactured by Shin-Etsu Chemical Co., Ltd.): 0.6 parts

(3)磷酸(酸觸媒)：0.1份 (3) Phosphoric acid (acid catalyst): 0.1 parts

(4)聚醚改質之聚二甲基矽氧烷15.0份與二丙二醇單甲醚85.0份之混合液(調平劑：日本BYK化學公司製“BYK-337”)：0.1份 (4) A mixture of 15.0 parts of polyether modified polydimethyl siloxane and 85.0 parts of dipropylene glycol monomethyl ether (leveling agent: "BYK-337" manufactured by BYK Chemical Co., Ltd.): 0.1 parts

(5)二甲基亞碸(高沸點溶劑)：5.0份 (5) Dimethyl hydrazine (high boiling point solvent): 5.0 parts

(6)乙醇(低沸點溶劑)：65.2份 (6) Ethanol (low boiling point solvent): 65.2 parts

(7)水：5.0份 (7) Water: 5.0 parts

上述塗佈液之不揮發固體成分(非鏈狀ATO粒子及烷氧基矽烷)之含量為5.7質量%，非鏈狀ATO粒子之含量相對於非鏈狀ATO粒子及烷氧基矽烷之合計量為89.3質量%。且，與實施例1同樣測定上述塗佈液之黏度後為1.6mPa．s。 The content of the nonvolatile solid content (non-chain ATO particles and alkoxy decane) of the coating liquid is 5.7% by mass, and the content of the non-chain ATO particles is relative to the total amount of the non-chain ATO particles and the alkoxy decane. It is 89.3 mass%. Further, in the same manner as in Example 1, the viscosity of the coating liquid was measured and found to be 1.6 mPa. s.

(比較例3) (Comparative Example 3)

以下述份量將實施例1中準備之鏈狀ATO粒子分散液及下述成分饋入塑膠製瓶中並攪拌而調製塗佈液。 The chain ATO particle dispersion prepared in Example 1 and the following components were fed into a plastic bottle in the following amounts and stirred to prepare a coating liquid.

(1)鏈狀ATO粒子分散液：1.5份 (1) Chain ATO particle dispersion: 1.5 parts

(2)烷氧基矽烷(無機系黏結劑：信越化學工業公 司製"X40-2308")：0.6份 (2) alkoxy decane (inorganic binder: Shin-Etsu Chemical Industry Co., Ltd. System "X40-2308"): 0.6 parts

(3)磷酸(酸觸媒)：0.1份 (3) Phosphoric acid (acid catalyst): 0.1 parts

(4)聚醚改質之聚二甲基矽氧烷15.0份與二丙二醇單甲醚85.0份之混合液(調平劑：日本BYK化學公司製“BYK-337”)：0.1份 (4) A mixture of 15.0 parts of polyether modified polydimethyl siloxane and 85.0 parts of dipropylene glycol monomethyl ether (leveling agent: "BYK-337" manufactured by BYK Chemical Co., Ltd.): 0.1 parts

(5)二甲基亞碸(高沸點溶劑)：5.0份 (5) Dimethyl hydrazine (high boiling point solvent): 5.0 parts

(6)乙醇(低沸點溶劑)：87.7份 (6) Ethanol (low boiling point solvent): 87.7 parts

(7)水：5.0份 (7) Water: 5.0 parts

上述塗佈液之不揮發固體成分(鏈狀ATO粒子及烷氧基矽烷)之含量為1.0質量%，鏈狀ATO粒子之含量相對於鏈狀ATO粒子及烷氧基矽烷之合計量為34.2質量%。且，與實施例1同樣測定上述塗佈液之黏度後為1.4mPa．s。 The content of the nonvolatile solid content (chain-like ATO particles and alkoxy decane) of the coating liquid is 1.0% by mass, and the total amount of the chain ATO particles is 34.2 by mass with respect to the chain ATO particles and the alkoxy decane. %. Further, the viscosity of the coating liquid was measured in the same manner as in Example 1 and was 1.4 mPa. s.

(比較例4) (Comparative Example 4)

以下述份量將實施例1中準備之鏈狀ATO粒子分散液及下述成分饋入塑膠製瓶中並攪拌而調製塗佈液。 The chain ATO particle dispersion prepared in Example 1 and the following components were fed into a plastic bottle in the following amounts and stirred to prepare a coating liquid.

(1)鏈狀ATO粒子分散液：35.0份 (1) Chain ATO particle dispersion: 35.0 parts

(2)烷氧基矽烷(無機系黏結劑：信越化學工業公司製"X40-2308")：0.6份 (2) Alkoxydecane (inorganic binder: "X40-2308" manufactured by Shin-Etsu Chemical Co., Ltd.): 0.6 parts

(3)磷酸(酸觸媒)：0.1份 (3) Phosphoric acid (acid catalyst): 0.1 parts

(4)聚醚改質之聚二甲基矽氧烷15.0份與二丙二醇單甲醚85.0份之混合液(調平劑：日本BYK化學公司製 “BYK-337”)：0.1份 (4) A mixture of 15.0 parts of polyether modified polydimethyl methoxy alkane and 85.0 parts of dipropylene glycol monomethyl ether (leveling agent: manufactured by BYK Chemical Co., Ltd., Japan) "BYK-337"): 0.1 parts

(5)二甲基亞碸(高沸點溶劑)：5.0份 (5) Dimethyl hydrazine (high boiling point solvent): 5.0 parts

(6)乙醇(低沸點溶劑)：54.2份 (6) Ethanol (low boiling point solvent): 54.2 parts

(7)水：5.0份 (7) Water: 5.0 parts

上述塗佈液之不揮發固體成分(鏈狀ATO粒子及烷氧基矽烷)之含量為8.0質量%，鏈狀ATO粒子之含量相對於鏈狀ATO粒子及烷氧基矽烷之合計量為92.4質量%。且，與實施例1同樣測定上述塗佈液之黏度後為7.3mPa．s。 The content of the nonvolatile solid content (chain-like ATO particles and alkoxysilane) of the coating liquid is 8.0% by mass, and the total amount of the chain ATO particles is 92.4 by mass relative to the chain ATO particles and the alkoxydecane. %. Further, in the same manner as in Example 1, the viscosity of the coating liquid was measured and found to be 7.3 mPa. s.

(透明導電性膜之評價) (Evaluation of Transparent Conductive Film)

將實施例1~7及比較例1~4之塗佈液在長10cm、寬10cm、厚0.7mm之玻璃板上進行噴塗。噴槍係使用NORDSON公司製之Pulse Sprayer，將針孔開度設為0.15mm，以噴出液量為0.80g/分鐘之方式調整液體擠出之壓力。將噴槍與基板之距離設為100mm、塗佈速度設為每秒600mm、重疊間距8mm、霧化氣體及吹拂氣體之壓力設為0.05MPa。且，塗佈面積設為20cm見方，將基板放置在塗佈面積之中心進行塗佈。所得塗膜以120℃之乾燥機乾燥1小時，形成實施例1~7及比較例1~4之透明導電性膜。 The coating liquids of Examples 1 to 7 and Comparative Examples 1 to 4 were sprayed on a glass plate having a length of 10 cm, a width of 10 cm, and a thickness of 0.7 mm. The spray gun was a Pulse Sprayer manufactured by NORDSON Co., Ltd., and the needle opening degree was set to 0.15 mm, and the pressure of liquid extrusion was adjusted so that the amount of discharged liquid was 0.80 g/min. The distance between the spray gun and the substrate was set to 100 mm, the coating speed was set to 600 mm per second, the overlap pitch was 8 mm, and the pressure of the atomizing gas and the blowing gas was set to 0.05 MPa. Further, the coated area was set to 20 cm square, and the substrate was placed at the center of the coated area for coating. The obtained coating film was dried in a dryer at 120 ° C for 1 hour to form transparent conductive films of Examples 1 to 7 and Comparative Examples 1 to 4.

且，實施例8之情況係與上述同樣，以噴塗機將實施例8之塗佈液塗佈於玻璃基板上後，在80℃乾燥5分鐘後，以高壓水銀燈以300mJ/cm2之光量照射紫外 線而硬化後，形成實施例8之透明導電性膜。 Further, in the case of Example 8, the coating liquid of Example 8 was applied onto a glass substrate by a spray coater, and after drying at 80 ° C for 5 minutes, it was irradiated with a high-pressure mercury lamp at a light amount of 300 mJ/cm 2 . After curing with ultraviolet rays, the transparent conductive film of Example 8 was formed.

接著，如下述般測定上述各透明導電性膜之膜厚、表面電阻、全光線透過率及鉛筆硬度。 Next, the film thickness, surface resistance, total light transmittance, and pencil hardness of each of the above transparent conductive films were measured as follows.

〈膜厚〉 <film thickness>

對逐個玻璃基板切斷透明導電性膜，以掃描型電子顯微鏡(SEM，日立製作所公司製之“S-4500”)觀察剖面，且測定膜厚。 The transparent conductive film was cut out from each of the glass substrates, and the cross section was observed by a scanning electron microscope (SEM, "S-4500" manufactured by Hitachi, Ltd.), and the film thickness was measured.

〈表面電阻〉 <surface resistance>

使用表面電阻計(三菱化學公司製造之“Hiresta MCP-HT450”，施加電壓：10V)，測定透明導電性膜之表面電阻，作為通常之表面電阻。 The surface resistance of the transparent conductive film was measured using a surface resistance meter (Hiresta MCP-HT450 manufactured by Mitsubishi Chemical Corporation, applied voltage: 10 V) as a usual surface resistance.

且，與上述同樣測定將附透明導電性膜之玻璃基板在溫度65℃、相對濕度90%之環境下保持500小時後之透明導電性膜之表面電阻，作為高溫高濕試驗後之表面電阻。 In the same manner as above, the surface resistance of the transparent conductive film after the glass substrate with the transparent conductive film was kept at a temperature of 65 ° C and a relative humidity of 90% for 500 hours was measured as the surface resistance after the high-temperature and high-humidity test.

〈全光線透過率〉 <Full light transmittance>

首先，使用日本電色工業公司製之光度計“Hazemeter NDH2000”，測定附透明導電性膜之玻璃基板之全光線透過率。數值僅顯示塗膜之值。 First, the total light transmittance of the glass substrate with a transparent conductive film was measured using a photometer "Hazemeter NDH2000" manufactured by Nippon Denshoku Industries Co., Ltd. The value only shows the value of the coating film.

〈鉛筆硬度〉 <pencil hardness>

使用新東科學公司製之表面性試驗機“HEIDON-14DR”測定透明導電性膜之鉛筆硬度。 The pencil hardness of the transparent conductive film was measured using a surface tester "HEIDON-14DR" manufactured by Shinto Scientific Co., Ltd.

以上測定之結果與透明導電性膜中之ATO粒子之含量一起示於表1。 The results of the above measurement are shown in Table 1 together with the content of the ATO particles in the transparent conductive film.

(液晶顯示裝置之評價) (Evaluation of liquid crystal display device)

製作圖面尺寸為4英寸，液晶顯示裝置之總厚度為1mm之圖1、圖2所示之構成之液晶顯示裝置。 A liquid crystal display device having a screen size of 4 inches and a liquid crystal display device having a total thickness of 1 mm as shown in Figs. 1 and 2 was produced.

透明導電膜係使用噴霧塗佈機以與前述相同之條件將上述塗佈液塗佈於相當於第1透明基板之上部玻璃基板之與液晶層相反側之主面上後，以120℃之乾燥機 乾燥1小時而形成。接著，以銀膏(藤倉化成公司製之“Dotite D-362”)將接地線安裝於該透明導電性膜之端部後，將偏光板貼附於透明導電性膜上。且，安裝顯示用電極及基準電極，於內藏觸控感測機能層之相當於第2透明基板之下部玻璃基板之背光側上貼附偏光板。 In the transparent conductive film, the coating liquid was applied onto the main surface on the opposite side to the liquid crystal layer from the upper glass substrate of the first transparent substrate, and dried at 120 ° C under the same conditions as described above using a spray coater. machine It was formed by drying for 1 hour. Next, a ground wire was attached to the end of the transparent conductive film with a silver paste ("Dotite D-362" manufactured by Fujikura Kasei Co., Ltd.), and then the polarizing plate was attached to the transparent conductive film. Further, the display electrode and the reference electrode are mounted, and a polarizing plate is attached to the backlight side of the glass substrate on the lower surface of the second transparent substrate in which the touch sensing function layer is built.

接著，如下述般確認上述各液晶顯示裝置之觸控感度及靜電放電(ESD)性。 Next, the touch sensitivity and electrostatic discharge (ESD) of each of the above liquid crystal display devices were confirmed as follows.

〈觸控感度〉 <Touch Sensitivity>

以手指觸控上述液晶顯示裝置，確認觸控感度。結果，因手指觸控而有反應時評價為A，未因手指觸而反應時評價為B。 Touching the liquid crystal display device with a finger to confirm the touch sensitivity. As a result, it was evaluated as A when there was a reaction by finger touch, and was evaluated as B when it was not reacted by a finger touch.

且，與上述同樣測定使附透明導電性膜之玻璃基板在溫度65℃、相對濕度90%之環境下保持500小時後之透明導電性膜之觸控感度，作為高溫高濕試驗後之觸控感度。 Further, in the same manner as described above, the touch sensitivity of the transparent conductive film after the glass substrate with the transparent conductive film was kept at a temperature of 65 ° C and a relative humidity of 90% for 500 hours was measured as a touch after the high temperature and high humidity test. Sensitivity.

〈ESD性〉 <ESD property>

自下部玻璃基板側由背光照射光，確認上述液晶顯示裝置為無通電狀態且為黑顯示後，以靜電施加裝置以電壓±12kV將靜電施加於上部玻璃基板上。隨後，將透明導電性膜之接地線接地後，以目視確認無通電狀態之顯示。結果，上述液晶顯示裝置維持黑顯示時評價為A，因漏光而見到留白時評價為B。 Light was irradiated from the backlight on the lower glass substrate side, and it was confirmed that the liquid crystal display device was in a non-energized state and was black-displayed, and then electrostatic electricity was applied to the upper glass substrate at a voltage of ±12 kV. Subsequently, the ground line of the transparent conductive film was grounded, and the display of the non-energized state was visually confirmed. As a result, the liquid crystal display device was evaluated as A when the black display was maintained, and was evaluated as B when the white light was observed due to light leakage.

又，與上述同樣測定使附透明導電性膜之玻璃基板在溫度65℃、相對濕度90%環境下保持500小時後之透明導電性膜之ESD性，作為高溫高濕試驗後之ESD性。 In the same manner as described above, the ESD of the transparent conductive film after the glass substrate with the transparent conductive film was kept at a temperature of 65 ° C and a relative humidity of 90% for 500 hours was measured as the ESD property after the high-temperature and high-humidity test.

以上之結果示於表2。 The above results are shown in Table 2.

由表2之結果，使用本發明之塗佈液製作之透明導電性膜之通常之表面電阻為10~1000mΩ/□，全光線透過率為95.0~99.9%，鉛筆硬度為5~9H，高溫高濕試驗後之表面電阻為10~1000MΩ/□，可知電氣特性、光學特性、硬度及耐久性均高。且，可知具備使用本發明之塗佈液製作之透明導電性膜之液晶顯示裝置之觸控感度及ESD性均優異。 As a result of Table 2, the transparent conductive film produced by using the coating liquid of the present invention has a surface resistance of 10 to 1000 mΩ/□, a total light transmittance of 95.0 to 99.9%, a pencil hardness of 5 to 9H, and a high temperature. The surface resistance after the wet test was 10 to 1000 MΩ/□, and it was found that electrical characteristics, optical characteristics, hardness, and durability were high. Further, it is understood that the liquid crystal display device including the transparent conductive film produced using the coating liquid of the present invention is excellent in touch sensitivity and ESD property.

另一方面，可知使用不含鏈狀ATO粒子之塗佈液製作之比較例1之透明導電性膜，通常之表面電阻及高溫高濕試驗後之表面電阻均高，鉛筆硬度亦小。且，亦可知具備比較例1之透明導電性膜之液晶顯示裝置之ESD性差。 On the other hand, it is understood that the transparent conductive film of Comparative Example 1 produced by using the coating liquid containing no chain-like ATO particles has a high surface resistance after the surface resistance and the high-temperature and high-humidity test, and the pencil hardness is also small. Further, it is also known that the liquid crystal display device including the transparent conductive film of Comparative Example 1 has poor ESD properties.

且，可知使用不含鏈狀ATO粒子之塗佈液製作之比較例2之透明導電性膜之高溫高濕試驗後之表面電阻高，光透過率低，鉛筆硬度亦小。 Further, it was found that the transparent conductive film of Comparative Example 2 produced using the coating liquid containing no chain ATO particles had a high surface resistance after high-temperature and high-humidity test, a low light transmittance, and a small pencil hardness.

可知使用鏈狀ATO粒子之含量低於40質量%之塗佈液製作之比較例3之透明導電性膜，通常之表面電阻高。且，亦可知具備比較例3之透明導電性膜之液晶顯示裝置之ESD性差。 It is understood that the transparent conductive film of Comparative Example 3 produced by using a coating liquid having a chain ATO particle content of less than 40% by mass generally has a high surface resistance. Further, it is also known that the liquid crystal display device including the transparent conductive film of Comparative Example 3 has poor ESD properties.

可知使用鏈狀ATO粒子之含量超過90質量%之塗佈液製作之比較例4之透明導電性膜，通常之表面電阻及高溫高濕試驗後之表面電阻低，鉛筆硬度亦小。且，亦可知具備比較例4之透明導電性膜之液晶顯示裝置之觸控感度差。 It is understood that the transparent conductive film of Comparative Example 4 produced by using a coating liquid having a chain ATO particle content of more than 90% by mass has a low surface resistance after a surface resistance and a high temperature and high humidity test, and a pencil hardness is also small. Further, it is also known that the liquid crystal display device including the transparent conductive film of Comparative Example 4 has poor touch sensitivity.

Claims (5)

一種內藏觸控面板機能型橫電場方式液晶顯示面板之製造方法，其係具備液晶層、介由前述液晶層相互對向配置之第1透明基板及第2透明基板、配置於前述第1透明基板之與前述液晶層相反側之透明導電性膜、配置於前述第2透明基板之前述液晶層側之基準電極及電容線、與介由絕緣膜與前述基準電極對向配置之顯示用電極之內藏觸控面板機能型橫電場方式液晶顯示面板之製造方法，其特徵為前述透明導電性膜係藉由非旋塗方式來製造，該非旋塗方式選自輥塗、模嘴塗佈、氣刀塗佈、刮塗、逆轉塗佈、凹版塗佈、微凹版塗佈、凹版印刷、網版印刷、平版印刷、噴墨印刷、噴塗、狹縫塗佈、浸塗。 A method for manufacturing a touch panel function-type horizontal electric field type liquid crystal display panel, comprising: a liquid crystal layer; a first transparent substrate and a second transparent substrate disposed opposite to each other via the liquid crystal layer; and being disposed in the first transparent layer a transparent conductive film on a side opposite to the liquid crystal layer of the substrate, a reference electrode and a capacitor line disposed on the liquid crystal layer side of the second transparent substrate, and a display electrode disposed to face the reference electrode via the insulating film A method for manufacturing a touch panel functional horizontal electric field type liquid crystal display panel, characterized in that the transparent conductive film is manufactured by a non-spin coating method selected from the group consisting of roll coating, nozzle coating, and gas coating. Knife coating, knife coating, reverse coating, gravure coating, micro gravure coating, gravure printing, screen printing, lithography, ink jet printing, spray coating, slit coating, dip coating. 如請求項1之內藏觸控面板機能型橫電場方式液晶顯示面板之製造方法，其中，前述透明導電性膜係塗佈於第1透明基板上。 A method of manufacturing a touch panel functional horizontal electric field type liquid crystal display panel according to claim 1, wherein the transparent conductive film is applied onto the first transparent substrate. 如請求項1之內藏觸控面板機能型橫電場方式液晶顯示面板之製造方法，其係形成表面電阻為10~1000MΩ/□、全光線透過率為95.0~99.9%、鉛筆硬度為5~9H之透明導電性膜。 The method for manufacturing a touch panel functional horizontal electric field type liquid crystal display panel according to claim 1 is characterized in that the surface resistance is 10 to 1000 MΩ/□, the total light transmittance is 95.0 to 99.9%, and the pencil hardness is 5 to 9H. A transparent conductive film. 如請求項1或2之內藏觸控面板機能型橫電場方式液晶顯示面板之製造方法，其係形成膜厚為10~300nm之透明導電性膜。 A method for manufacturing a touch panel functional horizontal electric field type liquid crystal display panel according to claim 1 or 2, wherein a transparent conductive film having a film thickness of 10 to 300 nm is formed. 一種用來製造前述內藏觸控面板機能型橫電場方式液晶顯示面板之透明導電膜形成用塗佈組成物，其特徵 為內藏觸控面板機能型橫電場方式液晶顯示面板具備液晶層、介由前述液晶層相互對向配置之第1透明基板及第2透明基板、配置於前述第1透明基板之與前述液晶層相反側之透明導電性膜、配置於前述第2透明基板之前述液晶層側之基準電極及電容線、與介由絕緣膜與前述基準電極對向配置之顯示用電極，前述透明導電性膜係由塗佈組成物所形成，前述塗佈組成物至少包含無機黏結劑與鏈狀導電性粒子。 Coating composition for forming a transparent conductive film for manufacturing the above-mentioned built-in touch panel functional horizontal electric field type liquid crystal display panel, characterized in that The touch panel function-type horizontal electric field type liquid crystal display panel includes a liquid crystal layer, a first transparent substrate and a second transparent substrate disposed opposite to each other via the liquid crystal layer, and the liquid crystal layer disposed on the first transparent substrate a transparent conductive film on the opposite side, a reference electrode and a capacitor line disposed on the liquid crystal layer side of the second transparent substrate, and a display electrode disposed to face the reference electrode via the insulating film, the transparent conductive film The coating composition is formed of at least an inorganic binder and chain-like conductive particles.
TW105143614A 2013-03-14 2014-03-06 Transparent conductive coating composition, transparent conductive film and built-in touch panel functional type horizontal electric field type liquid crystal display panel TWI632210B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013-052264 2013-03-14
JP2013052264A JP2014177552A (en) 2013-03-14 2013-03-14 Transparent electroconductive coating composition, transparent electroconductive film, and touch panel function-internalized horizontal electric field-style liquid crystal display panel

Publications (2)

Publication Number Publication Date
TW201713732A TW201713732A (en) 2017-04-16
TWI632210B true TWI632210B (en) 2018-08-11

Family

ID=51536775

Family Applications (3)

Application Number Title Priority Date Filing Date
TW105143614A TWI632210B (en) 2013-03-14 2014-03-06 Transparent conductive coating composition, transparent conductive film and built-in touch panel functional type horizontal electric field type liquid crystal display panel
TW103107663A TWI575039B (en) 2013-03-14 2014-03-06 Transparent conductive coating composition, transparent conductive film and built-in touch panel function type transverse electric field liquid crystal display panel
TW105143617A TWI632211B (en) 2013-03-14 2014-03-06 Transparent conductive coating composition, transparent conductive film and built-in touch panel functional type horizontal electric field type liquid crystal display panel

Family Applications After (2)

Application Number Title Priority Date Filing Date
TW103107663A TWI575039B (en) 2013-03-14 2014-03-06 Transparent conductive coating composition, transparent conductive film and built-in touch panel function type transverse electric field liquid crystal display panel
TW105143617A TWI632211B (en) 2013-03-14 2014-03-06 Transparent conductive coating composition, transparent conductive film and built-in touch panel functional type horizontal electric field type liquid crystal display panel

Country Status (4)

Country Link
JP (1) JP2014177552A (en)
CN (1) CN204981727U (en)
TW (3) TWI632210B (en)
WO (1) WO2014142121A1 (en)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017037760A (en) * 2015-08-07 2017-02-16 日立マクセル株式会社 Transparent conductive substrate, method of manufacturing the same, and touch panel using the same
CN105242809A (en) * 2015-10-21 2016-01-13 江西沃格光电股份有限公司 Touch display device and preparation method thereof
JP6690968B2 (en) * 2016-03-14 2020-04-28 マクセルホールディングス株式会社 Method for manufacturing transparent conductive substrate and lateral electric field type liquid crystal display panel with built-in touch panel function
CN109416493A (en) * 2016-07-06 2019-03-01 夏普株式会社 Display device with touch panel
CN109643041B (en) * 2016-08-22 2021-10-22 夏普株式会社 Display device with touch panel
JP7096656B2 (en) * 2017-09-29 2022-07-06 マクセル株式会社 Coating composition, conductive film, touch panel and manufacturing method
JP7102118B2 (en) * 2017-09-29 2022-07-19 マクセル株式会社 A transparent conductive film, a coating composition for forming a transparent conductive film, and a method for producing a transparent conductive film.
JP7148237B2 (en) * 2017-11-02 2022-10-05 株式会社放電精密加工研究所 A surface-coated substrate that can be used as an alternative material to an alumite material, and a coating composition for forming a topcoat layer on the surface of the substrate
JP7063617B2 (en) * 2017-12-28 2022-05-09 日揮触媒化成株式会社 Method for manufacturing composite metal oxide particle conjugate
TWI658474B (en) * 2018-01-17 2019-05-01 友達光電股份有限公司 Manufacturing method of transparent conductive layer and display panel
JP6470860B1 (en) 2018-03-15 2019-02-13 マクセルホールディングス株式会社 Coating composition, conductive film and liquid crystal display panel
JP2020144200A (en) * 2019-03-05 2020-09-10 日東電工株式会社 Liquid crystal display device with built-in touch sensing function and method for manufacturing the same
JP7157729B2 (en) * 2019-06-28 2022-10-20 日東電工株式会社 Polarizing film with adhesive layer and liquid crystal panel
CN113462219B (en) * 2020-03-31 2024-03-12 日挥触媒化成株式会社 Coating liquid for forming conductive film
JP7216135B2 (en) * 2021-03-30 2023-01-31 日揮触媒化成株式会社 Dispersion liquid of conductive particles, method for producing the same, coating liquid for forming conductive film, and base material with conductive film

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201020621A (en) * 2008-07-18 2010-06-01 Lg Chemical Ltd Polarizer and liquid crystal display
TW201135312A (en) * 2010-04-13 2011-10-16 Morgan Touch Technology Co Ltd Liquid crystal panel and liquid crystal display

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08302246A (en) * 1995-05-09 1996-11-19 Sumitomo Osaka Cement Co Ltd Coating for forming transparent membrane having high electroconductivity and high membrane strength, formation of transparent membrane having high electroconductivity and membrane, strength, and cathode ray tube
JPH0931238A (en) * 1995-07-20 1997-02-04 Mitsubishi Materials Corp Electroconductive dispersion, electroconductive coating material and their production
JP4522505B2 (en) * 1998-12-28 2010-08-11 日揮触媒化成株式会社 Transparent conductive film-forming coating liquid, transparent conductive film-coated substrate, and display device
JP2002003746A (en) * 2000-06-16 2002-01-09 Sumitomo Osaka Cement Co Ltd Coating for forming transparent electroconductive film, transparent electroconductive film and display device
JP4479161B2 (en) * 2002-03-25 2010-06-09 住友金属鉱山株式会社 Transparent conductive film, coating liquid for forming transparent conductive film, transparent conductive laminated structure, and display device
JP4225156B2 (en) * 2003-08-07 2009-02-18 住友金属鉱山株式会社 Transparent conductive film forming coating liquid, transparent conductive film and display device
JP4592274B2 (en) * 2003-10-17 2010-12-01 日揮触媒化成株式会社 Antimony oxide-coated silica fine particles, method for producing the fine particles, and coated substrate containing the fine particles
JP4439876B2 (en) * 2003-11-06 2010-03-24 日揮触媒化成株式会社 Chain antimony oxide fine particles, method for producing the fine particle dispersion and use thereof
JP5096666B2 (en) * 2005-06-06 2012-12-12 日揮触媒化成株式会社 Method for producing chain conductive oxide fine particles, chain conductive oxide fine particles, transparent conductive film-forming coating material, and substrate with transparent conductive film
JP2008185934A (en) * 2007-01-31 2008-08-14 Seiko Instruments Inc Liquid crystal display device
JP5584404B2 (en) * 2008-10-22 2014-09-03 住友大阪セメント株式会社 LIQUID CRYSTAL PANEL, ITS MANUFACTURING METHOD, AND ANTISTATIC FILM FORMING COATING AND IMAGE DISPLAY
JP5534758B2 (en) * 2009-09-17 2014-07-02 日揮触媒化成株式会社 Phosphorus-containing antimony pentoxide fine particles, a transparent conductive film-forming coating solution containing the fine particles, and a substrate with a transparent conductive film

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201020621A (en) * 2008-07-18 2010-06-01 Lg Chemical Ltd Polarizer and liquid crystal display
TW201135312A (en) * 2010-04-13 2011-10-16 Morgan Touch Technology Co Ltd Liquid crystal panel and liquid crystal display

Also Published As

Publication number Publication date
TWI575039B (en) 2017-03-21
TWI632211B (en) 2018-08-11
CN204981727U (en) 2016-01-20
JP2014177552A (en) 2014-09-25
TW201713732A (en) 2017-04-16
TW201443177A (en) 2014-11-16
TW201713733A (en) 2017-04-16
WO2014142121A1 (en) 2014-09-18

Similar Documents

Publication Publication Date Title
TWI632210B (en) Transparent conductive coating composition, transparent conductive film and built-in touch panel functional type horizontal electric field type liquid crystal display panel
TWI537782B (en) Touch screen and display device
CN104756199B (en) Transparent conductive laminate
CN102333831B (en) Outstandingly abrasion resistant and pollution resistant coating composition and coating film
JP4187454B2 (en) Antireflection film
KR101800344B1 (en) Black film, substrate provided with black film, image display device, black resin composition, and black material dispersion liquid
TWI395796B (en) Composition for formation of transparent film and laminated transparent film
US10261638B2 (en) Touch sensor and method for manufacturing same
US10430004B2 (en) Touch sensor and method for manufacturing same
KR20100014292A (en) Black resin composition, resin black matrix, color filter and liquid crystal display
WO2016129419A1 (en) Wavelength conversion member, backlight unit, image display device, and method for producing wavelength conversion member
TW201439872A (en) Transparent conductive film, and touch panel and display device provided with same
KR102213829B1 (en) Coating composition, conductive film, touch panel and manufacturing method
EP3118265A1 (en) Conductive transparent coating
TWI772599B (en) Coating composition, conductive film, and liquid crystal display panel
JPWO2016051695A1 (en) Film with transparent conductive film, film with transparent wiring, transparent shield film, touch panel and display device
JPWO2015049939A1 (en) Photosensitive conductive film, method for forming conductive pattern using the same, and conductive pattern substrate
JP2017168211A (en) Method for manufacturing transparent conductive substrate and in-plane switching type liquid crystal display panel including touch panel function
JP6375847B2 (en) Touch panel sensor and manufacturing method thereof, touch panel sensor substrate
WO2012008230A1 (en) Color filter member for electronic paper, electronic paper, method for producing color filter member for electronic paper, and method for manufacturing electronic paper
JP2015036866A (en) Intermediate base material film for touch panel, lamination film for touch panel, and touch panel sensor