CN107533883A - The manufacture method of light transmitting conductive film and the light transmitting conductive film of annealed processing - Google Patents
The manufacture method of light transmitting conductive film and the light transmitting conductive film of annealed processing Download PDFInfo
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- CN107533883A CN107533883A CN201680027950.0A CN201680027950A CN107533883A CN 107533883 A CN107533883 A CN 107533883A CN 201680027950 A CN201680027950 A CN 201680027950A CN 107533883 A CN107533883 A CN 107533883A
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- conductive layer
- light transmitting
- conductive film
- transmitting conductive
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- H—ELECTRICITY
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- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- C—CHEMISTRY; METALLURGY
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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Abstract
Even if the present invention provides one kind and made annealing treatment in a short time, the light transmitting conductive film of resistance value can be also reduced.The light transmitting conductive film of the present invention possesses the conductive layer with translucency and electric conductivity and is configured at the base material of a face side of the conductive layer, the conductive layer is the uncrystalline layer of indium tin oxide, in total weight % of content 100 of In atoms and Sn atoms in the conductive layer, the content of Sn atoms is more than 7 weight %, and the carrier density of the conductive layer is 4 × 1020/cm3Above, 6 × 1020/cm3Hereinafter, the hall mobility of the conductive layer is 20cm2/ more than Vs, 28cm2/ below Vs.
Description
Technical field
The present invention relates to a kind of light transmitting conductive film with translucency and electric conductivity.A kind of moreover, it relates to bag
Include the manufacture method of the light transmitting conductive film of the annealed processing of the process made annealing treatment to above-mentioned light transmitting conductive film.
Background technology
In recent years, in the electronic equipments such as smart mobile phone, mobile phone, notebook computer, tablet PC, duplicator or auto navigation
Widely use the board-like liquid crystal display device of touch surface.It is transparent using having in base material superimposed layer in this liquid crystal display device
The light transmitting conductive film of conductive layer.
There is a kind of lamination successively to have transparent film base material, transparent SiO disclosed in following patent documents 1x(x=1.0~
2.0) film and transparent conductive membrane and the nesa coating that is formed.Above-mentioned transparent conductive membrane is compound by indium-tin
Oxide is formed.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2006-19239 publications
The content of the invention
The technical problems to be solved by the invention
Above-mentioned transparency conducting layer generally by integrally being made annealing treatment to light transmitting conductive film, so as to improving crystallinity and
Use.It is desirable to carry out the annealing for a long time, accordingly, there exist the manufacture efficiency of nesa coating variation, electrically conducting transparent
The problem of cost rise of film.
On the other hand, when shortening the time of annealing, resistance value is not easy fully step-down.
It is an object of the present invention to provide a kind of light transmitting conductive film, even if it is made annealing treatment in a short time,
Resistance value can be reduced.In addition, the invention reside in, there is provided a kind of printing opacity of annealed processing using above-mentioned light transmitting conductive film
The manufacture method of property conducting film.
For solving the technical scheme of technical problem
According to the broad aspect of the present invention, there is provided a kind of light transmitting conductive film, it possesses：With translucency and electric conductivity
Conductive layer and be configured at the conductive layer a face side base material, the conductive layer is noncrystal for indium-tin-oxide
Layer, In atoms in the conductive layer and in the weight % of total content 100 of Sn atoms, the contents of Sn atoms for 7 weight % with
On, the carrier density of the conductive layer is 4 × 1020/cm3Above, 6 × 1020/cm3Hereinafter, the Hall migration of the conductive layer
Rate is 20cm2/ more than Vs, 28cm2/ below Vs.
In certain particular aspects of the light transmitting conductive film of the present invention, the conduction after being heated 10 minutes at 150 DEG C
The carrier density of layer is 7.0 × 1020/cm3Above, 2.0 × 1021/cm3Hereinafter, it is described after being heated 10 minutes at 150 DEG C
The hall mobility of conductive layer is 20cm2/ more than Vs, 30cm2/ below Vs.
At certain specific aspect of the light transmitting conductive film of the present invention, the thickness of the conductive layer is more than 16nm,
Below 19.9nm.
According to the broad aspect of the present invention, there is provided a kind of manufacture method of the light transmitting conductive film of annealed processing, it is wrapped
Include the process made annealing treatment to above-mentioned light transmitting conductive film.
The effect of invention
The light transmitting conductive film of the present invention possesses the conductive layer with translucency and electric conductivity and is configured at above-mentioned conductive layer
A face side base material, above-mentioned conductive layer is the amorphous layer of indium-tin-oxide, In atoms and Sn in above-mentioned conductive layer
In the weight % of total content 100 of atom, the content of Sn atoms is more than 7 weight %, and the carrier density of above-mentioned conductive layer is 4
×1020/cm3Above, 6 × 1020/cm3Hereinafter, the hall mobility of above-mentioned conductive layer is 20cm2/ more than Vs, 28cm2/V·s
Hereinafter, therefore, even if being made annealing treatment in a short time, resistance value can also be reduced.
Brief description of the drawings
Fig. 1 is the profile for the light transmitting conductive film for representing the 1st embodiment of the present invention；
Fig. 2 is the profile for the light transmitting conductive film for representing the 2nd embodiment of the present invention；
Fig. 3 is to represent the transparent conductive that the light transmitting conductive film of the 1st embodiment of the present invention is made annealing treatment
The profile of film.
Description of symbols
1st, 1A ... light transmitting conductive films
The light transmitting conductive film of the annealed processing of 1X ...
2nd, 2A ... base materials
The surfaces of 2a ... the 1st
The surfaces of 2b ... the 2nd
3 ... conductive layers
The conductive layer of 3X ... pattern-likes
4 ... diaphragms
11 ... base material films
12 ... the 1st hard conatings
13 ... the 2nd hard conatings
14 ... priming coats
Embodiment
Hereinafter, illustrate that the present invention's is detailed.
The light transmitting conductive film of the present invention possesses conductive layer and base material.Above-mentioned conductive layer has translucency and electric conductivity.On
State the face side that base material is configured at above-mentioned conductive layer.
In the light transmitting conductive film of the present invention, above-mentioned conductive layer is the amorphous layer of indium-tin-oxide.The printing opacity of the present invention
Property conducting film in, in the weight % of total content 100 of In atoms and Sn atoms in above-mentioned conductive layer, the contents of Sn atoms is 7
More than weight %.For the light transmitting conductive film of the present invention, the carrier density of above-mentioned conductive layer is 4 × 1020/cm3More than,
6×1020/cm3Below.For the light transmitting conductive film of the present invention, the hall mobility of above-mentioned conductive layer is 20cm2/V·s
Above, 28cm2/ below Vs.
In the present invention, due to possessing above-mentioned structure, therefore, even if being made annealing treatment in a short time, also can
Reduce resistance value.Light transmitting conductive film itself before the present inventor is made annealing treatment possesses and can make annealing
The property Quality Research that the resistance value of light transmitting conductive film afterwards reduces.The result of the research of the present inventor etc. is found：At annealing
In light transmitting conductive film before reason, as long as above-mentioned conductive layer meets above-mentioned technical proposal, even if then being annealed in a short time
Processing, can also reduce resistance value.In addition, the result of the research of the present inventor etc. is found：Even if annealed in a short time
Processing, in order to obtain the light transmitting conductive film of the low annealed processing of resistance value, in the light transmitting conductive film before annealing,
As long as above-mentioned conductive layer meets above-mentioned structure.It should be noted that for the light transmitting conductive film of the present invention, can be with
The light transmitting conductive film of long term annealing processing is obtained for carrying out long term annealing processing.If carry out at long term annealing
Reason, then can further reduce resistance value.
From the viewpoint of further reduction resistance value, the carrier density of the above-mentioned conductive layer before annealing is preferred
For 4.5 × 1020/cm3More than, preferably 5.5 × 1020/cm3Below.
From the viewpoint of further reduction resistance value, the hall mobility of the above-mentioned conductive layer before annealing is preferred
For 22cm2/ more than Vs, preferably 26cm2/ below Vs.
Above-mentioned base material preferably comprises base material film, preferably comprises hard conating, preferably comprises priming coat.The translucency of the present invention is led
Electrolemma is preferably provided with diaphragm, and above-mentioned conductive layer is configured with the 1st surface of above-mentioned base material, in above-mentioned base material and above-mentioned
1 surface is configured with said protection film on the 2nd opposite surface.
In addition, the light transmitting conductive film of the present invention can reduce the resistance value of the light transmitting conductive film of annealed processing,
Therefore, in the case of the light transmitting conductive film of annealed processing being used for into liquid crystal display device, display quality can be improved.Cause
This, the light transmitting conductive film of annealed processing can be preferred for liquid crystal display device, can be more preferably used for touch panel.
From stably realizing compared with from the viewpoint of low-resistance value, leading after annealing (heating for 30 minutes at 150 DEG C)
The carrier density of electric layer is preferably 7.0 × 1020/cm3More than, preferably 2.0 × 1021/cm3Below.From stably realize compared with
From the viewpoint of low-resistance value, the hall mobility of the conductive layer after annealing (heating for 30 minutes at 150 DEG C) is preferably
20cm2/ more than Vs, preferably 30cm2/ below Vs.
Hereinafter, on one side referring to the drawings, while the specific embodiment of the explanation present invention.
Fig. 1 is the profile for the light transmitting conductive film for representing the 1st embodiment of the present invention.
Light transmitting conductive film 1 shown in Fig. 1 is the light transmitting conductive film before annealing.Light transmitting conductive film 1 possesses base
Material 2, conductive layer 3 and diaphragm 4.
Base material 2 has the 1st surface 2a and the 2nd surface 2b.1st surface 2a and the 2nd surface 2b are mutually opposing.In base material 2
1st surface 2a superimposed layers have conductive layer 3.1st surface 2a is the surface that conductive layer 3 carries out lamination side.Base material 2 is led to be configured at
Part between electric layer 3 and diaphragm 4, it is the support member of conductive layer 3.In present embodiment, conductive layer 3 is indium-tin oxidation
The amorphous layer of thing, In atoms in conductive layer 3 and in the weight % of total content 100 of Sn atoms, the content of Sn atoms is 7 weights
More than % is measured, the carrier density of conductive layer 3 is 4 × 1020/cm3Above, 6 × 1020/cm3Hereinafter, the Hall migration of conductive layer 3
Rate is 20cm2/ more than Vs, 28cm2/ below Vs.
In light transmitting conductive film before annealing, conductive layer can partly be set, or pattern-like is led
Electric layer.
There is diaphragm 4 in the 2nd surface 2b superimposed layers of base material 2.2nd surface 2b is the table that diaphragm 4 carries out lamination side
Face.By setting diaphragm 4, the 2nd surface 2b of base material 2 can be protected.
Base material 2 has base material film 11, the 1st hard conating 12 and the 2nd hard conating 13 and priming coat 14.Base material film 11 is by translucency
High material is formed.Lamination has the 2nd hard conating 13 and priming coat 14 successively on the surface of the side of conductive layer 3 of base material film 11.Bottom
Coating 14 connects with conductive layer 3.
Surface superimposed layer in the side of diaphragm 4 of base material film 11 has the 1st hard conating 12.1st hard conating 12 and the phase of diaphragm 4
Connect.
The translucency of conductive layer 3 is high, and is made up of the high material of electric conductivity.
Diaphragm can be stacked on the 2nd surface of base material by adhesive phase.2nd surface of base material preferably with diaphragm
Above-mentioned adhesive phase connects.
Fig. 2 is the profile for the light transmitting conductive film for representing the 2nd embodiment of the present invention.
Light transmitting conductive film 1A shown in Fig. 2 is the light transmitting conductive film before annealing.In light transmitting conductive film 1A, do not have
Have and the 1st hard conating 12 is set.Light transmitting conductive film 1A has to be carried out to priming coat 14, the 2nd hard conating 13 and base material film 11 successively
The base material 2A that lamination forms.For light transmitting conductive film 1A, with it is straight on the surface of the opposite side of conductive layer 3 of base material film 11
Connect lamination diaphragm 4.
For the light transmitting conductive film of the present invention, as light transmitting conductive film 1A, the 1st hard conating can be not provided with.
Can also be in the lamination diaphragm directly on a surface of base material film.Alternatively, it is also possible to be not provided with the 2nd hard conating and priming coat extremely
It is few 1 layer.On the surface of the conductive layer side of base material film, lamination can be carried out to priming coat and conductive layer successively, can also be in base
Direct lamination conductive layer on material film.Priming coat can be individual layer, or multilayer.
Below, the manufacture method to the light transmitting conductive film 1 shown in Fig. 1 and the translucency of the annealed processing shown in Fig. 3
Conducting film 1X manufacture method illustrates.
Light transmitting conductive film 1 can for example be made by following method.
The 1st hard conating 12 is formed on a surface of base material film 11.Specifically, ultraviolet curing tree is used in resin
During fat, photo-curable monomer and light trigger are stirred in diluent and make coating liquid.Obtained coating liquid is applied
It is distributed on base material film 11, irradiation ultraviolet makes resin solidification, forms the 1st hard conating 12.
Then, diaphragm 4 is formed on the 1st hard conating 12.As diaphragm 4, using being provided with adhesive in substrate sheets
During the diaphragm of layer, adhesive surface can be fitted in the surface of the 1st hard conating 12, diaphragm 4 is formed on the 1st hard conating 12.
Then, with forming the 2nd hard conating 13 on the surface of the 12 opposite side of the 1st hard conating of base material film 11.Specifically,
When resin uses ultraviolet curable resin, photo-curable monomer and light trigger are stirred in diluent and make coating
Liquid.Obtained coating liquid is coated on the surface with the side opposite side of the 1st hard conating 12 of base material film 11, irradiation ultraviolet makes
Resin solidification, form the 2nd hard conating 13.
Then, priming coat 14 is formed on the 2nd hard conating 13.Specifically, using SiO2In the case of, steaming can be passed through
Plate or sputter at formation priming coat 14 on the 2nd hard conating 13.
As described above, the 1st hard conating 12 and the 2nd hard conating 13 and priming coat 14 are formed on base material film 11.Need to illustrate
, in of the invention, the 1st hard conating 12 and the 2nd hard conating 13 and priming coat 14 can also be not provided with.In this case, base material
The surface of the side of conductive layer 3 of film 11 is the 1st surface 2a of base material 2, and the surface of the side of diaphragm 4 of base material film 11 is the 2nd of base material 2 the
Surface 2b.
Then, conductive layer 3 is formed on priming coat 14, it is possible thereby to make light transmitting conductive film 1.
As the forming method of conductive layer, it is not particularly limited.Such as it can use what is utilized evaporation or sputtering and formed
The method that metal film is etched, or the various printing processes such as silk-screen printing or ink jet printing, and use have resist
Pattern formation method etc. known to photoetching process etc..The conductive layer of formation can by it is described later annealing make crystallinity improve and
Use.
Light transmitting conductive film 1 is preferred for obtaining the transparent conductive of the annealed processing shown in Fig. 3 by annealing
Film 1X.In order to obtain the light transmitting conductive film 1X of annealed processing, it can carry out what light transmitting conductive film 1 was made annealing treatment
Process.In the case that conductive layer 3 before annealing is not pattern-like, in conductive layer 3 and the side opposite side of base material film 11
Surface upper part form resist layer and be etched, it is possible thereby to form the conductive layer 3X of pattern-like.Etching
Laggard water-filling is handled to wash.
The light transmitting conductive film 1X of annealed processing has the conductive layer 3X of pattern-like.The conductive layer 3X of pattern-like is partly
It is stacked on the 1st surface 2a of base material 2.The light transmitting conductive film 1X of annealed processing has on the 1st surface 2a of base material 2 to be deposited
In the conductive layer 3X of pattern-like part and the part of conductive layer 3X without pattern-like.
The temperature of annealing is preferably more than 120 DEG C, more preferably more than 140 DEG C, preferably less than 170 DEG C, more excellent
Elect less than 160 DEG C as.
The processing time of above-mentioned annealing is preferably more than 5 minutes, more preferably more than 10 minutes, preferably 60 minutes
Hereinafter, more preferably less than 30 minutes.In the present invention, even if being made annealing treatment in a short time, resistance can also be reduced
Value.
The light transmitting conductive film 1X of annealed processing both can directly be used with lamination diaphragm 4, can also peel off diaphragm 4
And use.
Hereinafter, the details of each layer to forming light transmitting conductive film illustrates.
(base material)
The overall thickness of base material is preferably more than 23 μm, more preferably more than 50 μm, preferably less than 300 μm, more preferably
For less than 200 μm.
Base material film：
Base material film preferably has higher translucency.Therefore, the material as base material film, is not particularly limited, and can enumerate
Such as：Polyolefin, polyether sulfone, polysulfones, makrolon, cyclic olefin polymer, polyarylate, polyamide, polymethyl methacrylate,
Polyethylene terephthalate, polybutylene terephthalate (PBT), PEN, cellulose triacetate and
It is cellulose nano-fibrous etc..The material of above-mentioned base material film may be used alone, can also be used in combination a variety of.
The thickness of base material film is preferably more than 5 μm, more preferably more than 20 μm, preferably less than 190 μm, more preferably
Less than 125 μm.When the thickness of base material film is more than above-mentioned lower limit and below the above-mentioned upper limit, it is conductive can be further not easy identification
The pattern of layer.
In addition, the light transmission on base material film, the mean transmissivity in 380~780nm of wavelength visible region is excellent
Elect more than 85%, more preferably more than 90% as.
In addition, base material film can contain various stabilizers, ultra-violet absorber, plasticizer, lubricant or colouring agent.
1st hard conating and the 2nd hard conating；
1st hard conating and the 2nd hard conating are preferably made up of adhesive resin respectively.Above-mentioned adhesive resin is preferably to solidify
Resin.As above-mentioned solidified resin, heat reactive resin or active energy line curing resin etc. can be used.From make productivity ratio and
From the viewpoint of economy is good, above-mentioned solidified resin is preferably ultraviolet curable resin.
As the photo-curable monomer for forming above-mentioned ultraviolet curable resin, can enumerate for example：1,6-HD two
Acrylate, 1,4 butanediol diacrylate, glycol diacrylate, diethylene glycol diacrylate, tetraethylene glycol two
Acrylate, tripropylene glycol diacrylate, neopentylglycol diacrylate, 1,4- butanediol dimethylacrylates, poly- (fourth
Glycol) diacrylate, tetraethylene glycol dimethylacrylate, 1,3 butyleneglycol diacrylate, triethylene glycol diacrylate
Ester, three Isopropanediol diacrylates, polyethyleneglycol diacrylate and diacrylate as bisphenol a dimethacrylate
Ester compounds；Trimethylolpropane trimethacrylate, trimethylol-propane trimethacrylate, pentaerythrite monohydroxy 3 third
Triacrylate compound as olefin(e) acid ester and trimethylolpropane tris ethoxy triacrylate；Pentaerythrite tetrapropylene acid
Tetra-acrylate compound as ester and two-trimethylolpropane tetra-acrylate；And dipentaerythritol (monohydroxy) five
Five acrylate compounds etc. as acrylate.As above-mentioned ultraviolet curable resin, can use more than 5 functions more
Functional acrylic ester compounds.Above-mentioned polyfunctional acrylic ester compound may be used alone, can also be used in combination a variety of.Separately
Outside, light trigger, sensitising agent, levelling agent, diluent etc. can be added in above-mentioned polyfunctional acrylic ester compound.
In addition, the 1st hard conating can be made up of resin portion and filler.In the case that 1st hard conating contains filler, Ke Yigeng
Further it is not easy to recognize the pattern of conductive layer.It should be noted that in the case that the 1st hard conating contains filler, tangerine is produced sometimes
Rhicnosis, when light transmitting conductive film is used for into liquid crystal display device, display light is not readily apparent sometimes.Therefore, from being not likely to produce orange peel
From the viewpoint of wrinkle, preferably the 1st hard conating does not contain filler, is only made up of resin portion.Or the average grain diameter of preferred filler is small
In the thickness of the 1st hard conating, filler will not be protruded from the surface of the 1st hard conating.
As above-mentioned filler, it is not particularly limited, can enumerates for example：Silica, iron oxide, aluminum oxide, zinc oxide, oxygen
Change the metal oxide particles such as titanium, silica, antimony oxide, zirconium oxide, tin oxide, cerium oxide, indium-tin-oxide；Poly- silica
Resin particles such as alkane, (methyl) acrylate, styrene, melamine etc..More specifically, it can use and be crosslinked poly- (methyl)
The resin particles such as methyl acrylate.Above-mentioned filler can be used alone, and can also combine a variety of.
In addition, the 1st hard conating and the 2nd hard conating can contain respectively various stabilizers, ultra-violet absorber, plasticizer,
Lubricant or colouring agent.
Priming coat：
Priming coat is, for example, refractive index adjustment layer.By setting priming coat, conductive layer and the 2nd hard conating or base material can be made
Specific refractivity between film reduces, and therefore, can further improve the translucency of light transmitting conductive film.
As the material for forming priming coat, function is adjusted as long as there is refractive index, is not particularly limited, can enumerate：
SiO2、MgF2、Al2O3Etc. inorganic material or acrylic resin, polyurethane resin, melmac, alkyd resin and silicon
The organic materials such as oxygen alkane polymer.
Priming coat can be formed by vacuum vapour deposition, sputtering method, ion plating method or coating process.
(conductive layer)
Conductive layer is formed by the conductive material with translucency.As above-mentioned conductive material, indium-tin oxidation can be used
Thing (ITO).Above-mentioned conductive layer is amorphous layer.
In the present invention, the above-mentioned conductive layer formed before annealing so that above-mentioned carrier density and above-mentioned Hall move
Shifting rate meets above-mentioned scope.Importing gas when above-mentioned carrier density and above-mentioned hall mobility can be formed according to conductive layer
The connection quantity of power of the species of body, their partial pressure and negative electrode and be adjusted.As an example, filled using magnetron sputtering
Put in the case of forming conductive layer, pass through rare gas or the O such as Ar, Ne, He to being used as its process gas2、H2O、H2Deng gas
Body is combined and is used in mixed way, and becomes desired partial pressure, thus adjusts above-mentioned carrier density and above-mentioned Hall moves
Shifting rate.
The thickness of conductive layer is preferably more than 12nm, more preferably more than 16nm, more preferably more than 17nm, preferably
For below 50nm, more preferably below 30nm, more preferably below 19.9nm.
When the thickness of conductive layer is more than above-mentioned lower limit, the resistance value of light transmitting conductive film can be effectively reduced, can be with
Further improve electric conductivity.When the thickness of conductive layer is below the above-mentioned upper limit, the pattern of conductive layer can be made further not
Easily identification, can make light transmitting conductive film further thinning.
In addition, the light transmission on conductive layer, it is seen that the mean transmissivity in light region is preferably more than 85%, more excellent
Elect more than 90% as.
Conductive layer contains In atoms and Sn atoms.The weight % of total content 100 of In atoms and Sn atoms in conductive layer
In, the content of Sn atoms is more than 7 weight %.When the content of above-mentioned Sn atoms is less than 7 weight %, carrier density is constant big,
Resistance value is deteriorated.In the weight % of total content 100 of In atoms and Sn atoms in conductive layer, the content of Sn atoms can be 30
Below weight %, or below 20 weight %, can also be below 10 weight %.
(diaphragm)
Diaphragm is preferably made up of substrate sheets and adhesive phase.
Above-mentioned substrate sheets preferably have high translucency.As the material of above-mentioned substrate sheets, it is not particularly limited, can enumerates
Such as：Polyolefin, polyether sulfone, polysulfones, makrolon, cyclic olefin polymer, polyarylate, polyamide, polymethyl methacrylate,
Polyethylene terephthalate, polybutylene terephthalate (PBT), PEN, cellulose triacetate and
It is cellulose nano-fibrous etc..
Above-mentioned adhesive phase can by (methyl) acrylic adhesives, rubber adhesive, polyurethanes bonding agent or
Epoxies bonding agent is formed.From suppress be heat-treated caused by bonding force rising from the viewpoint of, above-mentioned adhesive phase preferably by
(methyl) acrylic adhesives are formed.
Above-mentioned (methyl) acrylic adhesives be according to need in (methyl) acrylate copolymer added with crosslinking agent,
The adhesive of tackifying resin and various stabilizers etc..
Above-mentioned (methyl) acrylate copolymer is not particularly limited, preferably to containing (methyl) acrylate monomer and its
(methyl) acrylic copolymer obtained from the mix monomer of its copolymerizable polymerizable monomer is copolymerized.
As above-mentioned (methyl) acrylate monomer, it is not particularly limited, is 1~12 preferably by the carbon number of alkyl
Alkyl primary alcohol or alkyl secondary alcohol and (methyl) acrylic acid esterification obtained from (methyl) acrylate monomer, it is specific and
Speech, can be enumerated：(methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid-2-ethyl caproite etc..Above-mentioned (first
Base) acrylate monomer may be used alone, can also be used in combination it is a variety of.
As above-mentioned other copolymerizable polymerizable monomers, can enumerate for example：(methyl) acrylic acid 2- hydroxy methacrylates, (first
Base) (methyl) hydroxyalkyl acrylates such as hydroxypropyl acrylate, (methyl) hydroxy butyl acrylate；(methyl) acrylic acid is different
Norbornene ester, (methyl) hydroxyalkyl acrylates, glycerine dimethacrylate, (methyl) glycidyl acrylate, 2- first
Base acryloyloxyethyl isocyanate, (methyl) acrylic acid, itaconic acid, maleic anhydride, butenoic acid, maleic acid and fumaric acid etc.
Functional monomer.Above-mentioned other copolymerizable polymerizable monomers may be used alone, can also be used in combination a variety of.
As above-mentioned crosslinking agent, it is not particularly limited, can enumerates for example：Isocyanates crosslinking agent, epoxies crosslinking agent,
Melamine class crosslinking agent, peroxide crosslinking agent, urea class crosslinking agent, metal alkoxide class crosslinking agent, metal-chelating species
Crosslinking agent, metallic salt crosslinking agent, Carbodiimides crosslinking agent, oxazoline classes crosslinking agent, azacyclopropane class crosslinking agent, amine
Crosslinking agent, polyfunctional acrylic ester compound etc..Above-mentioned crosslinking agent may be used alone, can also be used in combination a variety of.
Resin is assigned as above-mentioned bonding, is not particularly limited, can enumerate for example：Aliphatic category copolymer, the fragrant same clan
The petroleum resinoids such as copolymer, aliphatic-aromatic analog copolymer and ester ring type analog copolymer；Cumarin-indene resin；Terpenes
Resinoid；Terpenes phenolic resin；The rosin resinoid such as newtrex；Phenolic resin；Xylene resin etc..Above-mentioned bonding assigns
Resin can be the resin hydrogenated.Above-mentioned bonding imparting resin may be used alone, can also be used in combination a variety of.
The thickness of diaphragm is preferably more than 25 μm, more preferably more than 50 μm, preferably less than 300 μm, more preferably
Less than 200 μm.When the thickness of diaphragm is more than above-mentioned lower limit and below the above-mentioned upper limit, it is conductive can be further not easy identification
The pattern of layer.
Hereinafter, to the present invention, based on specific embodiment, illustrate in further detail.It should be noted that this hair
It is bright to be not limited to following embodiment.
(embodiment 1)
(1) making of light transmitting conductive film
In the PET film (125 μm of thickness) as base material film, using DC magnetic controlled tube sputtering apparatus, thickness 17.00nm is formed
Conductive layer (indium tin oxide layer) so that in the weight % of total 100 of phosphide atom and tin atom, the content of tin atom is 7
Weight %, obtains light transmitting conductive film.
(2) making of the light transmitting conductive film of annealed processing
Using IR annealing machines (manufacture of instruments for scientific research society of Fuji), it is set as 150 DEG C of in-furnace temperature, to being formed in PET film
Conductive layer carry out the annealing of 10 minutes or 30 minutes.
(embodiment 2~8 and comparative example 1~4)
Hall mobility, carrier density and the thickness of setting conductive layer shown in table 1 described as follows, in addition, with reality
Apply example 1 similarly to operate, obtain light transmitting conductive film and the light transmitting conductive film of annealed processing.The Hall migration of conductive layer
Rate and carrier density are adjusted by the species and their partial pressure amount of the importing gas during formation of changing conductive layer
It is whole.
(embodiment 9~16 and comparative example 5~8)
The content of Sn atoms, the hall mobility of conductive layer in setting conductive layer shown in table 1 described as follows, carrier are close
Degree and thickness, in addition, are operated, the translucency for obtaining light transmitting conductive film and annealed processing is led similarly to Example 1
Electrolemma.The hall mobility of conductive layer and carrier density by the species of the importing gas during formation of changing conductive layer, it
Partial pressure amount and negative electrode input amount of power and be adjusted.
(evaluation)
(1) thickness of the conductive layer in light transmitting conductive film before making annealing treatment
Using fluorescent x-ray analyzer ZSX PrimusIII+ (manufacture of Rigaku societies), pass through analytical unit area
In amounts and obtain annealing before light transmitting conductive film in conductive layer thickness.
(2) carrier density of the conductive layer in the light transmitting conductive film before annealing and after annealing
In light transmitting conductive film before annealing and after annealing (after 10 minutes), determined and filled using void effect
Put the carrier density of (the really industrial society's manufacture in south) measure conductive layer.Assay method is that (DC is surveyed vanderburg (vanderPauw) method
It is fixed).
(3) hall mobility of the conductive layer in the light transmitting conductive film before annealing and after annealing
In light transmitting conductive film before annealing and after annealing (after 10 minutes), determined and filled using void effect
Put the hall mobility of (the really industrial society's manufacture in south) measure conductive layer.
(4) resistance value in the light transmitting conductive film after light transmitting conductive film and annealing before making annealing treatment
Translucency after light transmitting conductive film and annealing before annealing (after 10 minutes or after 30 minutes) is led
In electrolemma, using Loresta-AX MCP-T370 (manufacture of Analytech societies of Mitsubishi), the electricity of 4 terminal methods measure conductive layer is utilized
Resistance.
Claims (4)
1. a kind of light transmitting conductive film, it possesses：
Conductive layer with translucency and electric conductivity and
The base material of a face side of the conductive layer is configured at,
The conductive layer is the amorphous layer of indium-tin-oxide,
In the weight % of total content 100 of In atoms and Sn atoms in the conductive layer, the contents of Sn atoms for 7 weight % with
On,
The carrier density of the conductive layer is 4 × 1020/cm3Above, 6 × 1020/cm3Hereinafter,
The hall mobility of the conductive layer is 20cm2/ more than Vs, 28cm2/ below Vs.
2. light transmitting conductive film as claimed in claim 1, wherein,
The carrier density of the conductive layer after being heated 10 minutes at 150 DEG C is 7.0 × 1020/cm3Above, 2.0 × 1021/
cm3Hereinafter,
After being heated 10 minutes at 150 DEG C, the hall mobility of the conductive layer is 20cm2/ more than Vs, 30cm2/ Vs with
Under.
3. light transmitting conductive film as claimed in claim 1 or 2, wherein,
The thickness of the conductive layer is more than 16nm, below 19.9nm.
4. a kind of manufacture method of light transmitting conductive film by annealing, it includes：
The process made annealing treatment to light transmitting conductive film according to any one of claims 1 to 3.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015-195414 | 2015-09-30 | ||
| JP2015195414 | 2015-09-30 | ||
| PCT/JP2016/078794 WO2017057556A1 (en) | 2015-09-30 | 2016-09-29 | Light-transmissive conductive film and manufacturing method for annealed light-transmissive conductive film |
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| Publication Number | Publication Date |
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| CN107533883A true CN107533883A (en) | 2018-01-02 |
| CN107533883B CN107533883B (en) | 2021-09-28 |
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| CN201680027950.0A Expired - Fee Related CN107533883B (en) | 2015-09-30 | 2016-09-29 | Light-transmitting conductive film and method for manufacturing annealed light-transmitting conductive film |
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| Country | Link |
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| JP (2) | JP6159490B1 (en) |
| CN (1) | CN107533883B (en) |
| WO (1) | WO2017057556A1 (en) |
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|---|---|---|---|---|
| CN111508641A (en) * | 2019-01-30 | 2020-08-07 | 日东电工株式会社 | Transparent conductive film |
| CN111508640A (en) * | 2019-01-30 | 2020-08-07 | 日东电工株式会社 | Transparent conductive film |
| CN113165336A (en) * | 2018-12-12 | 2021-07-23 | 日东电工株式会社 | Impedance matching film for radio wave absorber, film with impedance matching film for radio wave absorber, and laminate for radio wave absorber |
| CN115298759A (en) * | 2020-03-19 | 2022-11-04 | 日东电工株式会社 | Transparent conductive film |
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| JP6412539B2 (en) * | 2015-11-09 | 2018-10-24 | 日東電工株式会社 | Light transmissive conductive film and light control film |
| WO2018207622A1 (en) * | 2017-05-09 | 2018-11-15 | 日東電工株式会社 | Film with light-transmitting conductive layer, light control film and light control device |
| JP6490262B2 (en) * | 2017-05-09 | 2019-03-27 | 日東電工株式会社 | Film with light transmissive conductive layer, light control film and light control device |
| CN113168934B (en) * | 2018-11-07 | 2023-05-05 | 日东电工株式会社 | Film with light-transmitting conductive layer for touch panel, polarizing film with light-transmitting conductive layer, and touch panel display device |
| JP7378937B2 (en) * | 2019-02-22 | 2023-11-14 | 日東電工株式会社 | Light-transparent conductive film |
| JP7378938B2 (en) * | 2019-02-22 | 2023-11-14 | 日東電工株式会社 | Light-transparent conductive film |
| WO2023042844A1 (en) * | 2021-09-17 | 2023-03-23 | 日東電工株式会社 | Transparent electroconductive film |
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Also Published As
| Publication number | Publication date |
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| WO2017057556A1 (en) | 2017-04-06 |
| JPWO2017057556A1 (en) | 2017-10-05 |
| CN107533883B (en) | 2021-09-28 |
| JP6159490B1 (en) | 2017-07-05 |
| JP2017160545A (en) | 2017-09-14 |
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