CN107578840B - Transparent conductive body and touch screen - Google Patents
Transparent conductive body and touch screen Download PDFInfo
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- CN107578840B CN107578840B CN201710685491.1A CN201710685491A CN107578840B CN 107578840 B CN107578840 B CN 107578840B CN 201710685491 A CN201710685491 A CN 201710685491A CN 107578840 B CN107578840 B CN 107578840B
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- metal oxide
- oxide layer
- transparent conductive
- conductive body
- layer
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- 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
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
- G06F3/0412—Digitisers structurally integrated in a display
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
Abstract
The present invention provides a kind of transparent conductive body (100), it is characterized by: transparent resin substrate (10), the 1st metal oxide layer (12), the metal layer (16) containing silver alloy and the 2nd metal oxide layer (14) are laminated by said sequence, wherein, the 2nd metal oxide layer (14) contains ZnO as principal component and contains Ga2O3And GeO2As accessory ingredient.
Description
(the application be the applying date be on November 05th, 2015, application No. is 201510744779.2, it is entitled " thoroughly
The divisional application of the patent application of bright electric conductor and touch screen ".)
Technical field
The present invention relates to transparent conductive body and the touch screen of the transparent conductive body is used.
Background technique
Transparent conductive body, which is used as liquid crystal display (LCD), plasma panel (PDP) and electroluminescence panel, (to be had
Machine EL, inorganic EL) etc. displays, solar battery etc. transparent electrode.In addition, in addition, being also used for electromagnetic wave
Screened film and anti-infrared film etc..As the material of the metal oxide layer in transparent conductive body, it is widely used tin (Sn)
Make an addition to indium oxide (In2O3) ITO.
In recent years, the terminal that smart phone and the board terminal that writes etc. have touch screen is quickly popularized.These all have
There is the structure that touch sensor portion is set on liquid crystal display panel and has protective glass in most surface.Touch sensor portion is logical
Cross by the single or double of glass or film substrate with the material obtained after sputtering film-forming ito film 1 or patch
Close 2 and constitute.
With the enlargement of touch screen and the high precision int of touch sensor function, seek with high transmittance and low electricity
The transparent conductive body of resistance.In order to reduce the resistance for the transparent conductive body for having used ito film, it is necessary to the thickness of ito film is thickened, or
Person passes through the crystallization of thermal annealing (thermal annealing) Lai Jinhang ito film.But if ito film is implemented into thick-film
Then transmitance reduces.In addition, it is usually highly difficult to implement thermal anneal process to film substrate under the high temperature conditions.Therefore, it is being arranged
In the case where the ito film on film substrate, low-resistance situation drops in being difficult to not only maintain high transmittance.
In this case, the layer for having with metal oxide layer and metal layer using zinc oxide as principal component is proposed
The transparent conductive film (for example, Japanese Patent Laid-Open 9-291355 bulletin) of stack structure.
Existing technical literature
Patent document
Patent document 1: Japanese Patent Laid-Open 9-291355 bulletin
Summary of the invention
In touch screen etc. on the way, current-carrying part and insulated part is made by pattern in transparent conductive film and detects touch
Position.It is therefore desirable in the transparent conductive body with metal oxide layer and the stepped construction of metal layer, metal oxide
Layer and metal layer can be removed with etching is disposable.However, in metal oxide layer and metal using zinc oxide as principal component
In the stepped construction of layer, exists and be difficult to the case where disposably being removed metal oxide layer and metal layer with etching.
Here, in this disclosure, a kind of transparent conductive body is provided, wherein containing zinc oxide as principal component having
Metal oxide layer and metal layer stepped construction in, by etching can easily remove metal oxide layer and metal
Layer.In addition, in this disclosure, a kind of touching that can be easily manufactured is provided by using such transparent conductive body
Touch screen.
The present invention provides a kind of transparent conductive body in one aspect, wherein transparent resin substrate, the 1st metal oxide layer,
Metal layer containing silver alloy and the 2nd metal oxide layer are laminated in the order described above, and the 2nd metal oxide
Layer contains ZnO as principal component and contains Ga2O3And GeO2As accessory ingredient.
Such a transparent conductive body has stepped construction, which has: constitute most surface contains ZnO conduct
Principal component and contain Ga2O3And GeO2As accessory ingredient the 2nd metal oxide layer and contain the metal layer of silver alloy.2nd
Metal oxide layer and metal layer are easy disposably to be removed by etching.It is led furthermore it is possible to be made into high transparency, height
The transparent conductive body of electrical and excellent corrosion resistance.Therefore, the purposes that the needs of touch screen etc. etch can be suitable for.
In several embodiments, in the 2nd metal oxide layer, relative to ZnO, Ga2O3And GeO2These three ingredients
It is total, the content of ZnO can be 70~90mol%.Relative to the total of upper three kinds of ingredients, Ga2O3Content can for 5~
15mol%.Relative to the total of upper three kinds of ingredients, GeO2Content can be 5~20mol%.By being contained with aforementioned proportion
ZnO、Ga2O3And GeO2, so as to sufficiently improve the transparency of the 2nd metal oxide layer, electric conductivity, corrosion resistance and
Etching.
In several embodiments, in the 1st metal oxide layer, ZnO can be contained as principal component, and as pair at
Ga can be contained by dividing2O3And GeO2.In this way, it is possible to by etch easily disposably remove the 1st metal oxide layer,
2nd metal oxide layer and metal layer.Furthermore it is possible to be made into high transparency, high conductivity and excellent corrosion-resistant
The transparent conductive body of property.
In several embodiments, the thickness of metal layer can be 4~11nm.Transparent conductive body can either sufficiently be improved
The transparency can reduce sheet resistance again.In several embodiments, silver alloy can be Ag and selected from Pd, Cu, Nd, In, Sn
And the alloy of at least one of Sb metal.
The present invention provides a kind of touch screen on the other hand, which has sense film, the biography on panel
Sense film is made of above-mentioned transparent conductive body.Such touch screen is thin due to having the sensing being made of above-mentioned transparent conductive body
Film, so can be easily manufactured.
According to present disclosure, a kind of transparent conductive body can be provided, wherein contain zinc oxide as principal component having
Metal oxide layer and metal layer stepped construction transparent conductive body in, can easily remove metal oxide by etching
Layer and metal layer.In addition, in this disclosure, by using such transparent conductive body, can provide one kind can be easy
The touch screen of manufacture.
Detailed description of the invention
Fig. 1 is the sectional view for schematically showing an embodiment of transparent conductive body.
Fig. 2 is the sectional view for schematically showing the other embodiment of transparent conductive body.
Fig. 3 is the schematic section of a part in the section in an embodiment of amplification expression touch screen.
Fig. 4 (A), (B) are the plan views for constituting the sense film of an embodiment of touch screen.
Specific embodiment
Hereinafter, the preferred embodiment of the present invention is described in detail with reference to accompanying drawings.But the present invention be not limited to completely with
Under embodiment.In addition, the same symbol is marked to identical or same element in the accompanying drawings, it is according to circumstances different to omit weight
Multiple explanation.
Fig. 1 is the schematic section for indicating an embodiment of transparent conductive body.Transparent conductive body 100 includes film
Transparent resin substrate 10, the 1st metal oxide layer 12, metal layer 16, the 2nd metal oxide layer 14 of shape are configured by said sequence
Stepped construction.
" transparent " involved in this specification refers to visible light-transmissive, can also scatter light to a certain extent.For light
Scattering degree, according to level required by the purposes of transparent conductive body 100 difference.As be generally known as it is translucent have
The case where light scatters also includes the concept of " transparent " in this manual.The scattering degree of light is preferably relatively small, the transparency
It is preferred that relatively high.The whole total light transmittance of transparent conductive body 100 is, for example, 80% or more, and preferably 83% or more, more
Add preferably 85% or more.The total light transmittance is acquired using integrating sphere (integrating sphere) comprising diffusion
Commercially available hazemeter (hazemeter) can be used to be measured in the transmitance of transmitted light.
It as transparent resin substrate 10, is not particularly limited, can be with flexible organic resin film.Have
Machine resin film is also possible to organic resin thin slice.As organic resin film, such as poly terephthalic acid second two can be enumerated
The polyolefin films such as polyester films, polyethylene and the polypropylene such as alcohol ester (PET) and polyethylene naphthalate (PEN) gather
Carbonic ester film, acrylate film, norbornene (norbornene) film, polyarylate film, Polyethersulfone membranes, diacetyl are fine
Tie up plain film and triacetylcellulose film etc..It is preferably polyethylene terephthalate (PET) and poly- naphthalene in these
The polyester film of naphthalate (PEN) etc..
From the viewpoint of rigidity, the preferred thickness of transparent resin substrate 10.In addition, from by 100 filming of transparent conductive body
From the perspective of, transparent resin substrate 10 is preferably thin.From such a viewpoint, the thickness of transparent resin substrate 10 is, for example,
10~200 μm.From the viewpoint of being made into transparent conductive body excellent in optical characteristics, the refractive index of transparent resin substrate is for example
It is 1.50~1.70.In addition, the refractive index in this specification is the value measured under conditions of λ=633nm, 20 DEG C of temperature.
Dimensional stability when transparent resin substrate 10 preferably heats is high.In general, flexible organic resin film
During film production, it can be generated by heating due to change in size caused by expanding or shrinking.Being uniaxially stretched or
During person is biaxial stretch-formed, the thin transparent resin substrate 10 of thickness can be made with low cost.When forming extraction electrode, if plus
Hot transparent conductive body 100, then occur change in size due to thermal contraction.Such a change in size can be according to ASTM
D1204-02 or JIS-C-2151 is measured.The size changing rate of heat treatment front and back is dimensioned to Lo before it will heat
And when by being dimensioned to L after heating, it can be acquired by following formula.
Size changing rate (%)=100 × (L-Lo)/Lo
The case where the case where size changing rate (%) is positive value indicates to be expanded by heat treatment, negative value indicates
It is shunk by heat treatment.The size changing rate of transparent resin substrate 10 after being biaxially stretched can be when stretching
Direction of travel (direction MD) and be laterally measured in (direction TD) both direction.The size changing rate of transparent resin substrate 10
Such as be in the MD direction -1.0~-0.3%, it is -0.1~+0.1% on the direction TD.
Transparent resin substrate 10 can be to implement to be shone selected from Corona discharge Treatment, glow discharge, flame treatment, ultraviolet light
Penetrate the surface treatment of at least one of processing, electron beam treatment with irradiation and ozone treatment.Transparent resin substrate is also possible to set
Membrane of lipoprotein.By using resin film to which transparent conductive body 100 can be made to be excellent in terms of flexibility.In this way, simultaneously
It is not limited to the transparent conductive body of touch screen purposes, additionally it is possible to the transparent electrode for soft organic EL illuminating etc. is used, or
As electromagnetic wave shielding.
For example, in the case where using transparent conductive body 100 as the sense film for constituting touch screen, transparent resin matrix
The external power appropriateness applied so as to finger and pen etc. also can be used with flexible organic resin film in material 10
Ground deformation.
2nd metal oxide layer 14 is the hyaline layer containing oxide, contains ZnO as principal component, and as pair at
Divide and contains Ga2O3And GeO2.Described principal component refers in ZnO and Ga herein2O3And GeO2In three kinds of ingredients, mole base
The most ingredient of quasi- content.So-called accessory ingredient refers to the ingredient of the non-primary component in above-mentioned three kinds of ingredients.2nd metal oxide
Layer 14 due to contain ZnO as principal component therefore in economy it is excellent.Have both height furthermore it is possible to not use ITO and formed and lead
Electrical and high transparency the 2nd metal oxide layer 14.For this purpose, can be made not carrying out thermal anneal process with low table
2nd metal oxide layer 14 of surface resistance.
In the 2nd metal oxide layer 14, from the viewpoint of sufficiently improving transmitance and electric conductivity, relative to above-mentioned three
Kind ingredient adds up to, and the content of ZnO is, for example, 70mol% or more, preferably 75mol% or more.Stabilization is saved from abundant improve
Property from the perspective of, in the 2nd metal oxide layer 14, relative to the total of above-mentioned three kinds of ingredients, the content of ZnO is, for example,
90mol% is hereinafter, preferably 84mol% or less.If ZnO content is excessive, in the case where preservation under hot and humid environment,
Have the tendency for being easy to produce gonorrhoea.On the other hand, it if ZnO content is very few, is reduced there will be transmitance and electric conductivity
Tendency.
In the 2nd metal oxide layer 14, from the viewpoint of not only sufficiently reducing sheet resistance but also sufficiently improving transmitance,
Relative to the total of above-mentioned three kinds of ingredients, Ga2O3Content be, for example, 15mol% hereinafter, preferably 11mol% or less.The 2nd
In metal oxide layer 14, from the viewpoint of sufficiently improving storage stability, relative to the total of above-mentioned three kinds of ingredients, Ga2O3
Content is, for example, 5mol% or more, preferably 8mol% or more.If Ga2O3Content it is excessive, then there is what sheet resistance got higher to incline
To and transmitance reduce tendency.On the other hand, if Ga2O3The case where content is very few, then saves under hot and humid environment
Under, it has and becomes easy the tendency that generation gonorrhoea and sheet resistance are got higher.
In the 2nd metal oxide layer 14, from the viewpoint of not only sufficiently reducing sheet resistance but also sufficiently improving transmitance,
Relative to the total of above-mentioned three kinds of ingredients, GeO2Content be, for example, 20mol% hereinafter, preferably 14mol% or less.The 2nd
In metal oxide layer 14, from the viewpoint of sufficiently improving storage stability, relative to the total of above-mentioned three kinds of ingredients, GeO2
Content be, for example, 5mol% or more, preferably 8mol% or more.If GeO2Content is excessive, then has what sheet resistance got higher to incline
To and transmitance reduce tendency.On the other hand, if GeO2Content is very few, then is saved under hot and humid environment
In the case of, have the tendency that sheet resistance is got higher.
2nd metal oxide layer 14 has both ensuring for the adjustment of optical characteristics, the protection of metal layer 16 and electric conductivity
Function.2nd metal oxide layer 14 other than above-mentioned three kinds of ingredients, may be used also in the range of not damaging its function significantly
To contain micro constitutent or inevitable ingredient.But from being made into the transparent conductive body 100 with characteristic sufficiently high
Viewpoint is set out, and total ratio of three kinds of ingredients preferably in the 2nd metal oxide layer 14 is relatively high.The ratio is for example
For 95mol% or more, preferably 97mol% or more.In addition, the 2nd metal oxide layer 14 does not preferably contain ITO.
1st metal oxide layer 12 and the 2nd metal oxide layer 14 both can be in this several points of thickness, structure and composition
It is identical to can also be different.The record of composition about the 2nd metal oxide layer 14 also can be straight for the 1st metal oxide layer 12
It connects applicable.There is composition identical with the 2nd metal oxide layer 14 by the 1st metal oxide layer 12, to can pass through
Etching disposably to remove the 1st metal oxide layer 12, metal layer 16 and the 2nd metal oxide layer 14.In addition, can be into one
Step improves the transparency and corrosion resistance.
1st metal oxide layer 12 also can have the composition different from the 2nd metal oxide layer 14.In the case,
The 2nd metal oxide layer 14 and metal layer 16 can be only removed by etching, and keep the 1st metal oxide layer 12 residual as former state
It stays.
From the viewpoint of as the thickness of various touch screens is suitable for, the 1st metal oxide layer 12 and the 2nd
The thickness of metal oxide layer 14 is, for example, 10~70nm.
1st metal oxide layer 12 and the 2nd metal oxide layer 14 can pass through vacuum vapour deposition, sputtering method, ion
The vacuum film formations such as galvanoplastic or CVD method make.Among those, from the point and film forming that film forming room can be made to minimize
Fireballing point sets out, preferably sputtering method.DC magnetron sputtering method (magnetron can be enumerated as sputtering method
sputtering).Oxide target material, metal or semimetal target can be used as target.
Wiring electrode etc. can also be set on the 2nd metal oxide layer 14.The electric current of aftermentioned metal layer 16 is connected
It is to be conducted from wiring electrode being set on the 2nd metal oxide layer 14 etc. via the 2nd metal oxide layer 14.Cause
This, the 2nd metal oxide layer 14 preferably has high conductivity.From such a viewpoint, in 14 monofilm of the 2nd metal oxide layer
On sheet resistance value for example be preferably 1.0 × 10+7Ω/sq. (=1.0E+7 Ω/sq.) is hereinafter, more preferably 5.0 × 10+6Ω/sq. or less.
Metal layer 16 is to make layer as main component comprising silver alloy.There is high conductivity by metal layer 16, so as to
Enough sheet resistances for sufficiently reducing transparent conductive body 100.As the metallic element for constituting silver alloy, Ag can be enumerated and be selected from
At least one of Pd, Cu, Nd, In, Sn and Sb.As the example of silver alloy, Ag-Pd, Ag-Cu, Ag-Pd- can be enumerated
Cu, Ag-Nd-Cu, Ag-In-Sn and Ag-Sn-Sb.
Metal layer 16 can also contain additive other than silver alloy.Additive preferably can be easily by etching solution
The substance of removing.The content of silver alloy in metal layer 16 for example can be 90 mass % or more, be also possible to 95 mass % with
On.The thickness of metal layer 16 is, for example, 1~30nm.It improves from the sheet resistance for not only sufficiently reducing transparent conductive body 100 but also sufficiently
From the perspective of total light transmittance, the thickness of metal layer 16 is preferably 4~11nm.Have if the thickness of metal layer 16 is excessive
The tendency that total light transmittance reduces.On the other hand, if the thickness of metal layer 16 is too small, there is what sheet resistance got higher to incline
To.
Metal layer 16 has the function of adjusting the total light transmittance and sheet resistance of transparent conductive body 100.Metal layer
16 can be made by vacuum film formations such as vacuum vapour deposition, sputtering method, ion plating or CVD method.Among these, from
The fast point of the point and film forming speed that film forming room can be made to minimize sets out, preferably sputtering method.DC can be enumerated as sputtering method
Magnetron sputtering method.Metal targets can be used as target.
At least part of the 1st metal oxide layer 12 and the 2nd metal oxide layer 14 in transparent conductive body 100 with
And at least part of metal layer 16 can be removed by etching etc..
Fig. 2 is the schematic section for indicating the other embodiment of transparent conductive body.Transparent conductive body 101 is to clip
The mode of bright resin base material 10 has a pair of of hard conating 20, and this point is different from transparent conductive body 100.Other structures are led with transparent
Electric body 100 is identical.
In transparent conductive body 101, as a pair of of hard conating 20, has the 1st metal oxide in transparent resin substrate 10
The 1st hard conating 22 on the interarea of 12 side of layer, the 12 side opposite side of the 1st metal oxide layer of He Yu transparent resin substrate 10
The 2nd hard conating 24 on interarea.That is, transparent conductive body 101 has the 2nd hard conating 24, transparent resin substrate 10, the 1st hard conating
22, the stepped construction that the 1st metal oxide layer 12, metal layer 16 and the 2nd metal oxide layer 14 are laminated in the order.
Thickness, structure and the composition of 1st hard conating 22 and the 2nd hard conating 24 both can be identical or not identical.In addition, and different
Surely must have both the 1st hard conating 22 and the 2nd hard conating 24, can only have any one.
By the way that hard conating 20 is arranged, so as to sufficiently inhibit to generate damage on transparent resin substrate 10.Hard conating 20
Contain the resin cured matter for solidifying resin combination and obtaining.Resin combination is preferably comprised to be combined selected from heat-curing resin
At least one of object, ultra-violet solidified resin composition and electronic beam curing resin combination.Heat-curing resin
Composition can be containing selected from least one of epoxy resin, phenoxy group resinoid and melamine resinoid.
Resin combination is, for example, a kind of containing the energy-ray reactivity base with (methyl) acryloyl group, vinyl etc.
The composition of the curability compound of group.In addition, the term of (methyl) acryloyl group is to include acryloyl group and metering system
The meaning of at least one of acyl group.Curability compound preferably is contained in 1 intramolecular and contains 2 or more, preferably 3 with
On energy-ray reactive group polyfunctional monomer or oligomer.
Curability compound preferably comprises acrylic monomer.As acrylic monomer, can specifically enumerate 1,6- oneself
Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, ethylene-oxide-modified bisphenol-A two (methyl) acrylic acid
Ester, trimethylolpropane tris (methyl) acrylate, trimethylolpropane ethylene-oxide-modified three (methyl) acrylate, three hydroxyls
Methylpropane epoxy pronane modification three (methyl) acrylate, pentaerythrite four (methyl) acrylate, double trimethylolpropane
Four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, Ji Wusi
(methyl) acrylate of alcohol three and 3- (methyl) acryloyl-oxy base glycerol list (methyl) acrylate etc..But different fixed limit
Due to these compounds.For example, it is also possible to enumerate polyurethane-modified polyacrylate and ethylene-oxide-modified acrylate etc..
As curability compound, the compound with vinyl also can be used.As the compound with vinyl,
Such as ethylene glycol divinyl ether, pentaerythrite divinyl ether, 1,6-HD divinyl ether, trihydroxy methyl can be enumerated
Propane divinyl ether, ethylene-oxide-modified quinhydrones divinyl ether, ethylene-oxide-modified bisphenol-A divinyl ether, Ji Wusi
Alcohol trivinyl ether, six vinyl ethers of dipentaerythritol and double trimethylolpropane polyvingl ether etc..But it is and unlimited
Due to these.
By ultraviolet light to solidify curability compound, resin combination contains Photoepolymerizationinitiater initiater.Make
Various Photoepolymerizationinitiater initiaters can be used for Photoepolymerizationinitiater initiater.For example, acetophenones, hexichol second can be suitably selected from
Compound well known to alcohol ketone, benzophenone and thioxanthene ketone class etc..More particularly can enumerate Darocur1173,
Irgacure651, Irgacure184, Irgacure907 (it is trade name above, Japanese Chiba Specialty
Chemicals Co., Ltd. system)；And KAYACURE DETX-S (trade name, Nippon Kayaku K. K's system).
Photoepolymerizationinitiater initiater can be 0.01~20 mass % or 0.5~5 matter relative to the quality of curability compound
Measure % or so.Resin combination can be the known substance that Photoepolymerizationinitiater initiater is added to acrylic monomer.As by light
Polymerization initiator is added to the substance of acrylic monomer, such as can enumerate the SD-318 as ultraviolet curing resin
(trade name, Dainippon Ink. & Chemicals Inc's system) and XNR5535 (trade name, Nagase Industrial Co., Ltd.'s system)
Deng.
In order to improve coating strength and/or adjustment refractive index etc., resin combination can also contain organic microparticle
And/or inorganic microparticle.Organosilicon microparticle, crosslinked acrylic resin micro- can be for example enumerated as organic microparticle
Grain and crosslinked polystyrene microparticle etc..Micro-, silica microparticle, aluminium oxide can be for example enumerated as inorganic microparticle
Grain, zirconium oxide microparticle, oxidation titanium particulate and iron oxide microparticle etc..Among these, preferred silica microparticle.
Microparticle is preferably handled on its surface by silane coupling agent, and preferably (methyl) acryloyl group and/or
The energy-rays such as vinyl reactive group is with the membranaceous microparticle for being present in surface.If using such with reactive
Microparticle, then in irradiation energy ray or microparticle react with each other or microparticle and polyfunctional monomer or oligomer it is anti-
It answers, so as to enhance film strength.It is preferable to use the processed oxidations of silane coupling agent for being contained (methyl) acryloyl group
Silicon microparticle.
From the viewpoint of the thickness for being less than hard conating 20 and ensuring the adequately transparency, the average grain diameter of microparticle can
To be 100nm hereinafter, being also possible to 20nm or less.On the other hand, from the viewpoint of in the manufacture of colloidal solution, Ke Yiwei
5nm or more, or 10nm or more.Using organic microparticle and/or inorganic microparticle, organic micro-
Total content of grain and inorganic microparticle is relative to 100 mass parts of curability compound, such as can be 5~500 mass parts,
It can be 20~200 mass parts.
It, can be with by energy-rays such as irradiation ultraviolet lights if use carries out cured resin combination with energy-ray
Solidify resin combination.Therefore, from the viewpoint of in manufacturing process, it is also preferred that using such resin combination.
1st hard conating 22 can be by being coated on transparent resin substrate 10 for the solution of resin combination or dispersion liquid
It is upper to dry on one side, and curable resin composition is made.Coating at this time can be carried out according to well known method.Make
It is reversed that extruding jet nozzle method, scraper method, the skill in using a kitchen knife in cookery, stick rubbing method, contact rubbing method, contact can be for example enumerated for coating method
Rubbing method, intaglio plate rolling method, dip coating, reverse rolling method, direct rolling method, curtain method and extrusion etc..2nd hard conating 24
It can also equally be made on the another side of transparent resin substrate 10 with the 1st hard conating 22.
The thickness of 1st hard conating 22 and the 2nd hard conating 24 is, for example, 0.5~10 μm.If thickness is more than 10 μm, have
It is easy to produce the tendency of in uneven thickness or wrinkle etc..On the other hand, if thickness is lower than 0.5 μm, in transparent resin substrate
In the case where containing the low molecular weight compositions such as considerable amount of plasticizer or oligomer in 10, it may appear that be difficult to sufficiently inhibit these
The case where outflow of ingredient.In addition, the thickness of the 1st hard conating 22 and the 2nd hard conating 24 is excellent from the viewpoint of inhibiting warpage
Choosing is made into identical degree.
The refractive index of 1st hard conating 22 and the 2nd hard conating 24 is, for example, 1.40~1.60.Transparent resin substrate 10 and
The absolute value of the specific refractivity of 1 hard conating 22 is preferably 0.1 or less.The refraction of transparent resin substrate 10 and the 2nd hard conating 24
The absolute value of the difference of rate is preferably also 0.1 or less.By reducing the 1st hard conating 22 and the 2nd hard conating 24 and transparent resin matrix
The absolute value of the specific refractivity of material 10, so as to inhibit due to the thickness of the 1st hard conating 22 and the 2nd hard conating 24 not
The intensity of the interference stripes uniformly occurred.
The thickness for constituting each layer of transparent conductive body 100,101 can be measured in the following order.By focus from
Beamlet device (FIB, Focused Ion Beam) cutting transparent conductive body 100,101 is to obtain section.Use transmitted electron
Microscope (TEM) observes the section, and measures the thickness of each layer.Measurement preferably at optional 10 more than position into
Row, and acquire its average value.As the method for obtaining section, microtome (microtome) also can be used
As the device other than focused ion beam apparatus.As the method for measurement thickness, scanning electron microscope also can be used
(SEM).In addition, can also measure film thickness using fluorescent X-ray device.
The thickness of transparent conductive body 100,101 can be 200 μm or less, or 150 μm or less.If it is like this
Thickness, then can sufficiently meet the requirement rank of thinning.The total light transmittance of transparent conductive body 100,101 can for example be done
To 85% or more high level.In addition, the sheet resistance value (four-terminal method) of transparent conductive body 100,101 is even if without the 1st gold medal
The thermal anneal process for belonging to oxide skin(coating) 12 and the 2nd metal oxide layer 14 also can accomplish such as 30 Ω/sq. hereinafter, and
It can also accomplish 25 Ω/sq. or less.
The transparent conductive body 100,101 for having above structure has the 1st metal oxide layer 12, metal layer 16 and the 2nd
The stepped construction that metal oxide layer 14 is laminated.The stepped construction is able to use common etching solution and easily disposably removes.
In addition, having high transmittance, and there is high conductivity without thermal annealing.Therefore, touch screen can be suitable as
Sense film use.
Fig. 3 is that amplification indicates the schematic section for having a part in the section of the touch screen 200 of a pair of of sense film.Figure
4 (A) and Fig. 4 (B) are the plan views for having used the sense film 100a and 100b of above-mentioned transparent conductive body 100.Touch screen
200 have a pair of of sense film 100a, the 100b being oppositely disposed via optical cement 18.Touch screen 200 is with can be by contact
Touch location as in two-dimensional coordinate (X-Y coordinate) plane for being parallel to the panel 70 as picture coordinate position (laterally
Position and lengthwise position) and calculate mode and be configured.
Specifically, touch screen 200 has the sense film 100a for the lengthwise position detection being bonded via optical cement 18
The sense film 100b (hereinafter referred to as " X sense film ") of (hereinafter referred to as " Y sense film ") and lateral position detection.
In the side below sense film 100b X, by gasket 92 be set to X with sense film 100b and the panel of display device 70 it
Between.
Optical cement 17 is provided with protective glass the side the upper surface of Y sense film 100a (with 70 side opposite side of panel)
19.That is, touch screen 200 has X sense film 100b, Y sense film 100a and protective glass 19 on panel 70
The stepped construction configured in the order from 70 side of panel.
The Y of detection lengthwise position is by above-mentioned with sense film 100a and the X of detection lateral position with sense film 100b
What transparent conductive body 100 was constituted.Y is with sense film 100a and X sense film 100b with the side opposite with protective glass 19
Formula has the sensor electrode 15a and sensor electrode 15b as conductive part.
Sensor electrode 15a is by 16 structure of the 1st metal oxide layer 12 and the 2nd metal oxide layer 14 and metal layer
At.As shown in Fig. 4 (A), sensor electrode 15a is in a manner of being able to detect the touch location in longitudinal direction (direction y) in the longitudinal direction (side y
To) on extend more.More sensor electrode 15a are arranged side-by-side parallel to each other along longitudinal direction (direction y).Sensor electrode
One end of 15a is connected via the conductor line 50 formed with silver paste and 80 phase of electrode of the driving side IC.
The X for detecting lateral position has on the opposite face opposite with Y sense film 100a with sense film 100b to be passed
Sensor electrode 15b.Sensor electrode 15b is by the 1st metal oxide layer 12, the 2nd metal oxide layer 14 and metal layer 16
It constitutes.As shown in Fig. 4 (B), sensor electrode 15b is in a manner of being able to detect the touch location in transverse direction (direction x) in transverse direction (x
Direction) on extend more.More sensor electrode 15b are arranged side-by-side parallel to each other along transverse direction (direction x).Sensor electrode
One end of 15b is connected via the conductor line 50 formed with silver paste and 80 phase of electrode of the driving side IC.
When in terms of the Y sense film 100a and X stacking direction of sense film 100b, Y is used with sense film 100a and X
Sense film 100b is overlapped in such a way that respective sensor electrode 15a, 15b are mutually perpendicular via optical cement 18.It is used in Y
Sense film 100a with the X opposite side of the side sense film 100b, optical cement 17 is provided with protective glass 19.Optical cement
17,18, protective glass 19 and panel 70 are able to use common material.
Fig. 4 (A), conductor line 50 and electrode 80 in (B) are made of conductive materials such as metals (such as Ag).Conductor
Route 50 and electrode 80 are, for example, to be formed by silk-screen printing by pattern.Transparent resin substrate 10 also has to be touched as covering
The function of the protective film on the surface of screen 200.
The shape and number of sensor electrode 15a, 15b on each sense film 100a, 100b be not limited to Fig. 3 and
Form shown in Fig. 4 (A) and Fig. 4 (B).For example, it is also possible to be improved by the number for increasing sensor electrode 15a, 15b
The detection accuracy of touch location.
In the opposite side with the side Y sense film 100a of X sense film 100b, panel 70 is set via gasket 92.
Gasket 92 can be set in the position for corresponding to sensor electrode 15a, 15b shape and surround sensor electrode 15a, 15b entirety
Position.Gasket 92 can use the material with translucency, such as be formed by PET (polyethylene terephthalate) resin.Gasket
It is glued by the binder 90 with translucency of optical cement or crylic acid resin or epoxy resin etc. 92 one end
It ties in X with below sense film 100b.The other end of gasket 92 is bonded in the panel 70 of display device by binder 90.
In this way by being oppositely disposed X sense film 100b and panel 70 via gasket 92, thus can be in X sense film
Gap S is set between 100b and the panel of display device 70.
Control unit (IC) is electrically connected on electrode 80.It is measured respectively by the Y sense film 100a of finger tip and touch screen 200
Between static capacity variation caused by each sensor electrode 15a, 15b volume change.Control unit can be according to survey
Result is determined using the touch location of contact as coordinate position (intersection point of the position of the position and Y direction of X-direction) to count
It calculates.In addition, the driving method of sensor electrode and the calculation method of coordinate position can also use in addition to the method described above
Well known various methods.
Touch screen 200 can manufacture in the following order.After having prepared transparent conductive body 100, carry out to the 1st metal
The etching of oxide skin(coating) 12, metal layer 16 and the 2nd metal oxide layer 14, and form pattern.Specifically, using photoetching skill
Art method of spin coating is coated with erosion resistant on the surface of the 2nd metal oxide layer 14.Later, in order to improve close attachment
Prebake conditions can be carried out, then, configuration masking pattern is against corrosion to be formed by carrying out development with developer solution to be exposed
Pattern.The formation of corrosion-resisting pattern is not limited to photoetching process, can also be formed by silk screen print method etc..
Then, the transparent conductive body 100 for foring corrosion-resisting pattern is impregnated in acidic etching liquid, and dissolves and removes no shape
At the 1st metal oxide layer 12, the 2nd metal oxide layer 14 and the metal layer 16 at the part of corrosion-resisting pattern.Later, it removes
Resist layer, to obtain the Y sense film 100a for being formed with sensor electrode 15a and the X for being formed with sensor electrode 15b use
Sense film 100b.
1st metal oxide layer 12 and the 2nd metal oxide layer 14 are set as different compositions, if by the 1st metal
Oxide skin(coating) 12, which is made into, to be made of what etching removed, then can disposably etch metal layer 16 and the 2nd metal oxide layer
14, and the 1st metal oxide layer 12 can also be directly remained after the etching.As etching solution, inorganic acids can be used
Etching solution.For example, it is preferable to the etching solution of phosphoric acid class.
Next, the metal paste such as silver coating alloy pulp is to form conductor line 50 and electrode 80.In this way,
Control unit and sensor electrode 15a, 15b are electrically connected.Next, using optical cement 18 with each sensor electrode 15a, 15b
Mode towards the same direction is bonded Y sense film 100a and X sense film 100b.In the case, it is sensed from Y
When film 100a and X is seen with the stacking direction of sense film 100b, sensor electrode 15a, 15b are carried out in the form of mutually perpendicular
Fitting.Then, protective glass 19 and Y sense film 100a are bonded using optical cement 17.This makes it possible to manufacture touch screen
200。
Touch screen 200 uses transparent conductive body 100 as Y sense film 100a and X sense film 100b.It is transparent
Electric conductor 100 can be by etching the 1st metal oxide layer 12 of disposable removing and the 2nd metal oxide layer 14 and metal layer
16.Therefore, it can simplify the manufacturing process of touch screen 200, to be easily manufactured by touch screen 200.
In addition, it is not necessary that Y in sense film 100a and X sense film 100b the two all use electrically conducting transparent
Body 100, either one can use other transparent conductive bodies.Even such touch screen also can ground make display sufficiently it is clear
It is clear.In addition, as sense film transparent conductive body 101 can also be used without using transparent conductive body 100.
In this way, transparent conductive body 100,101 can be suitably used for touch screen.But purposes is not limited to touch
Screen, such as the 1st metal oxide layer 12 and the 2nd metal oxide layer 14 and metal layer 16 are processed into regulation shape by etching
Shape to formed have the 1st metal oxide layer 12, the 2nd metal oxide layer 14 and metal layer 16 part (conductive part), with
And the part (non-conductive portion) without the 1st metal oxide layer 12, the 2nd metal oxide layer 14 and metal layer 16, in liquid crystal
Show device (LCD), plasma panel (PDP), electroluminescence panel (organic EL, inorganic EL), electric driven color-changing part and electronics
It can be used as transparent electrode in the various display devices such as paper, anti-electrification is used, electromagnetic wave shielding is used to use.Alternatively, it is also possible to
It is used as antenna.
It this concludes the description of the preferred embodiment of the present invention, but the present invention is not limited to above embodiment.Example
Such as, above-mentioned transparent conductive body 101 has a pair of of hard conating 20, but can also only have the 1st hard conating 22 and the 2nd hard conating
Any one of 24.Alternatively, it is also possible to which hard conating is arranged on transparent resin substrate 10 a face, and set on the other surface
Set multiple optical adjustment layers.In the case, the 1st metal oxide layer 12, metal layer 16 and the 2nd metal oxide layer 14
It can be set on the optical adjustment layer.Further, in transparent conductive body 100,101, its function will not be being damaged significantly
In the range of, arbitrary layer can also be set in arbitrary position in addition to above-mentioned layer.
[embodiment]
Embodiment and comparative example are exemplified below to be further elaborated with the present invention, but the present invention is not limited to these
Embodiment.
[embodiment 1~18]
(production of transparent conductive body 101)
Make transparent conductive body as shown in Figure 2.Transparent conductive body has the transparent resin for being held in a pair of of hard conating
The stepped construction that substrate, the 1st metal oxide layer, metal layer and the 2nd metal oxide layer are laminated in that order.And by following
The main points make the transparent conductive body of each embodiment.
Prepare pet film (Toray Industries, Inc. system, the production with a thickness of 100 μm
Product serial number: U48).Use the PET film as transparent resin substrate.By DC magnetron sputtering on transparent resin substrate successively
Form the 1st metal oxide layer, metal layer and the 2nd metal oxide layer.1st metal oxide layer and the 2nd metal oxygen
Compound layer uses the ZnO-Ga with composition shown in table 12O3-GeO2Target is formed.The 1st metal oxygen in each embodiment
Compound layer and the 2nd metal oxide layer are formed using the target with same composition.The 1st metal oxygen in each embodiment
The composition of compound layer and the 2nd metal oxide layer is as shown in table 1.The 1st metal oxide layer and the 2nd gold medal in each embodiment
The thickness for belonging to oxide skin(coating) is made into 50nm.
In the whole embodiments shown in table 1, metal layer uses AgPdCu [Ag:Pd:Cu=99.0:0.5:0.5 (matter
Amount %)] target formed.The thickness of metal layer 16 has been made into 5nm.
(evaluation of transparent conductive body 101)
Etching characteristic is evaluated by program below.Firstly, having prepared the PAN class etching containing phosphoric acid, acetic acid and nitric acid
Liquid.The transparent conductive body of each embodiment is impregnated in the etching solution 1 minute to be etched at room temperature.Later, it carries out
Total light transmittance measurement, and whether determined the 1st metal oxide layer, metal layer and the 2nd metal oxide layer molten
Solution.Specifically, the consistent feelings of total light transmittance of the total light transmittance of the sample after etching and only transparent resin substrate
Condition is determined as " A " that inconsistent situation is determined as " B ".Total light transmittance (transmitance) uses hazemeter (quotient
The name of an article: NDH-7000, Japanese electricity Se industrial group system) come what is measured.Evaluation result is as shown in table 1.
Each embodiment is determined using four terminal resistance rate meters (trade name: Loresta GP Mitsubishi chemical Co., Ltd system)
Sheet resistance.Measurement result is shown in table 1.In table 1, " sheet resistance (1) " be by transparent conductive body 85 DEG C,
Sheet resistance value before saving 50 hours in the environment of 85%RH (relative humidity 85%), " sheet resistance (2) " are above-mentioned
Sheet resistance value after being saved under environmental condition.
After saving the transparent conductive body of each embodiment in the environment of 85 DEG C and 85%RH, storage stability is visually carried out
Evaluation.The case where the case where gonorrhoea is seen in transparent conductive body is determined as " B ", does not see gonorrhoea is judged as " A ".Sentence
It is fixed that the results are shown in Table 1.
[table 1]
As shown in table 1, etching characteristic is evaluated as " A " in all embodiments.It is possible thereby to confirm embodiment 1~18
Metal oxide layer and metal layer in transparent conductive body can be removed easily.The full light of the transparent conductive body of embodiment 10
Transmitance highest, but storage stability is evaluated as B.In addition, the sheet resistance after saving under hot and humid environment is also high.
This is because the electric conductivity of the 2nd metal oxide layer of four termination contacts of the analyzer of sheet resistance reduces.Therefore, do not having
It is necessary to which wiring electrode to be installed on to the use for being allowed to be connected on the 2nd metal oxide layer on the way, sheet resistance (2) height not
Problem in practical use can be become.In addition, for storage stability, if not requiring the so high level transparency, such as make an uproar
In the purposes (such as noise shielding etc.) of tablet (noise sheet) etc., then the level can sufficiently to use.
In order to evaluate the characteristic of metal oxide layer, and same as above-mentioned sequence to have made only metal oxide layer (single
Layer) sample.According to equally having carried out the evaluation of the sample with said sequence.It shows the results of the evaluation in table 2.In addition, table 2
Absorptivity is using the measurement result of the transmitance and reflectivity that are measured with optical splitter, with 100- transmitance-reflectivity=suction
The value that the formula of yield acquires.The absorptivity is the value under wavelength 380nm.
[table 2]
As shown in table 1, it is thus identified that the metal oxide layer absorptivity of each embodiment is substantially low.In addition, it is thus identified that even if containing
There is ZnO as principal component, by containing Ga2O3And GeO2It also can be improved corrosion resistance as accessory ingredient.
[embodiment 19~30]
Target composition when metal layer is made in addition to changing, and by the composition for changing metal layer shown in table 3 and/or is changed
Become except the thickness of metal layer, it is other to have made transparent conductive body similarly to Example 6.That is, in embodiment 19~implementation
The thickness of metal layer is changed in example 26.AgNdCu [Ag:Nd:Cu=99.0:0.5:0.5 (matter is used in embodiment 27
Amount %)] target forms metal layer.AgInSn [Ag:In:Sn=99.0:0.5:0.5 (quality %)] is used in embodiment 28
Target forms metal layer.Come in embodiment 29 using AgSnSb [Ag:Sn:Sb=99.0:0.5:0.5 (quality %)] target
Form metal layer.Metal layer is formed using AgCu [Ag:Cu=99.5:0.5 (quality %)] target in embodiment 30.
Equally the transparent conductive body for the embodiment 19~30 made is evaluated with embodiment 6.Evaluation result is such as
With shown in table 3.In addition, the composition and thickness of the metal oxide layer of embodiment 19~30 are same as Example 6.In addition, protecting
Depositing stability is to save 50 hours conditions in the environment of 85 DEG C, 85%RH and save 50 in the environment of 60 DEG C, 90%RH
It is measured under conditions of hour.After being saved with each condition, sentenced the case where gonorrhoea with will visually see in transparent conductive body
The case where breaking as " B ", not seeing gonorrhoea is judged as " A ".
[table 3]
According to result shown in table 3 it is found that in all embodiments the evaluation of etching characteristic be all " A ".It is possible thereby to confirm,
Metal oxide layer and metal layer in the transparent conductor of embodiment 19~30 can be removed easily.In addition, it is thus identified that such as
The thickness of fruit metal layer becomes larger, then has the tendency that the tendency that sheet resistance becomes smaller and total light transmittance reduces.In addition, confirmation
It is in the case where silver alloy contains Pd especially excellent on storage stability.
[comparative example 1~4]
In addition to use the target with composition shown in table 4 as formed the 1st metal oxide layer and the 2nd metal oxidation
Other than target when nitride layer, remaining has made the transparent conductive body of comparative example 1~4 similarly to Example 1.In comparative example 1,
Use ZnO-TiO2-Nb2O5Target forms the 1st metal oxide layer and the 2nd metal oxide layer.In comparative example 2, make
With ZnO-In2O3-Cr2O3Target.In comparative example 3, ZnO-SnO has been used2-In2O3Target.In comparative example 4, use
ZnO-SnO2-Cr2O3Target.In each comparative example, the 1st metal oxide layer and the 2nd metal oxide layer are used with same
The target of composition is formed.The composition such as table 4 of the 1st metal oxide layer and the 2nd metal oxide layer in each comparative example
It is shown.With the etching characteristic for implementing the transparent conductive body that 1 equally has rated each comparative example.The results are shown in Table 4.
[table 4]
In each comparative example, mol% is expressed below in ingredient shown above.
As shown in table 4, it is thus identified that have and be free of ZnO-Ga2O3-GeO2The electrically conducting transparent of ternary metal oxide layer
Body cannot be etched sufficiently.
Claims (5)
1. a kind of transparent conductive body, wherein transparent resin substrate, the 1st metal oxide layer, the metal layer containing silver alloy and
2nd metal oxide layer is laminated in the order, which is characterized in that
1st metal oxide layer contains ZnO as principal component, and contains Ga as accessory ingredient2O3And GeO2,
In the 1st metal oxide layer,
Relative to ZnO, Ga2O3And GeO2Three kinds of ingredients it is total, the content of ZnO is 70~90mol%,
Relative to the total of three kinds of ingredients, Ga2O3Content be 5~15mol%,
Relative to the total of three kinds of ingredients, GeO2Content be 5~20mol%.
2. transparent conductive body as described in claim 1, wherein
2nd metal oxide layer contains ZnO as principal component, and contains Ga as accessory ingredient2O3And GeO2。
3. transparent conductive body as claimed in claim 2, wherein
The metal layer with a thickness of 4~11nm.
4. transparent conductive body as claimed in claim 3, wherein
The silver alloy is Ag and the alloy selected from least one of Pd, Cu, Nd, In, Sn and Sb metal.
5. a kind of touch screen, wherein
The touch screen has sense film on panel,
The sense film is made of transparent conductive body according to any one of claims 1 to 4.
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| JP2014-226177 | 2014-11-06 | ||
| JP2014226177A JP6398624B2 (en) | 2014-11-06 | 2014-11-06 | Transparent conductor and touch panel |
| CN201510744779.2A CN105590662B (en) | 2014-11-06 | 2015-11-05 | Transparent conductive body and touch-screen |
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| JP6260647B2 (en) * | 2016-06-13 | 2018-01-17 | Tdk株式会社 | Transparent conductor |
| TWI746603B (en) * | 2016-08-09 | 2021-11-21 | 南韓商東友精細化工有限公司 | Transparent electrode, touch sensor and image display device including the same |
| CN107357108A (en) * | 2017-07-19 | 2017-11-17 | 无锡舒玛天科新能源技术有限公司 | Flexible glass electrochromism device and preparation method thereof |
| CN115224468B (en) * | 2022-09-20 | 2022-12-06 | 珠海翔翼航空技术有限公司 | Wing conformal transparent microstrip antenna, preparation method and spacecraft |
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Also Published As
| Publication number | Publication date |
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| JP6398624B2 (en) | 2018-10-03 |
| CN105590662A (en) | 2016-05-18 |
| JP2016087963A (en) | 2016-05-23 |
| TW201633090A (en) | 2016-09-16 |
| CN107578840A (en) | 2018-01-12 |
| TWI595392B (en) | 2017-08-11 |
| CN105590662B (en) | 2017-09-08 |
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