CN109698042A - Transparent conducting film and transparent conducting film laminated body - Google Patents
Transparent conducting film and transparent conducting film laminated body Download PDFInfo
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- CN109698042A CN109698042A CN201811203004.4A CN201811203004A CN109698042A CN 109698042 A CN109698042 A CN 109698042A CN 201811203004 A CN201811203004 A CN 201811203004A CN 109698042 A CN109698042 A CN 109698042A
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/023—Optical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/025—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
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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
- 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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- 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
- G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Theoretical Computer Science (AREA)
- General Engineering & Computer Science (AREA)
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- Human Computer Interaction (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Non-Insulated Conductors (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The present invention provides transparent conducting film and transparent conducting film laminated body.Transparent conducting film has: transparent substrate；It is configured at the transparency conducting layer of the thickness direction side of transparent substrate；It is configured at the gas barrier layer of the thickness direction other side of transparent substrate；With the coating for the thickness direction other side for being configured at gas barrier layer, gas barrier layer contains at least two kinds of ingredients in Zn, Al and Si or more, coating is the oxide skin(coating) containing Si, the water contact angle of the thickness direction another side of coating be 40 degree or more, using X-ray photoelectron spectroscopy measurement coating thickness direction another side when relative to the metallic element comprising Si, Si elemental ratio be 40% or more.
Description
With the correlation of related application
This application claims the priority of Japanese patent application No.2017-204216 filed on October 23rd, 2017, by it
During disclosure is incorporated herein as former state.
Technical field
The present invention relates to transparent conducting film and transparent conducting film laminated bodies, specifically, are related to being suitable for
The transparent conducting film and transparent conducting film laminated body of optical applications.
Background technique
All the time, it is formed with the transparent conducting film of the transparency conducting layer comprising indium tin composite oxides (ITO) etc.
It is used for the image display devices such as touch panel.As image display device, such as when for organic EL display device, organic EL
Element is easy to deteriorate because of gases such as oxygen, vapor, therefore, to the touch panel electrically conducting transparent for being configured at organic EL element
Property film require gas barrier property.
As to touch panel with transparent conducting film assign gas barrier property method, inquired into transparency conducting layer phase
The method for the surface setting gas barrier layer tossed about.
On the other hand, gas barrier layer low as refractive index, with good gas barrier property, it is known that Al-Zn-O (aluminium doping oxidation
Zinc: AZO) film (referring to Japanese Unexamined Patent Publication 2017-132225 bulletin).Disclosed in patent document 1 have as follows at it is being grouped as,
Amorphous transparent oxide film, wherein relative to whole metal component amounts, containing Al:0.9~20.0at%, Si:25.5~
68.0at%, remainder are made of Zn and inevitable impurity.
Summary of the invention
However, (AZO layers) of AZO film representated by Japanese Unexamined Patent Publication 2017-132225 bulletin are noncrystalline, it is more crisp.Therefore,
After forming AZO film by the vapor deposition etc. using vacuum vapour deposition, sputtering method etc., it is easy to happen when conveying AZO film and forming film
Scratch.Therefore, it has inquired into after forming AZO film, the transparent inorganics nitride layer such as silicon oxide layer is then set, thus protected AZO film,
Improve marresistance.
On the other hand, it attaches and sets on AZO film side, that is, transparent inorganic nitride layer surface as the transparent conducting film of product
It is equipped with the protective films such as the pet film of adhesive phase (peeling paper).
But silicon oxide layer is removed since the adaptation of protective film is good using Shi Ruocong silicon oxide layer
Protective film, then AZO film is also removed together with silicon oxide layer simultaneously, generates the unfavorable condition of gas barrier layer breakage.
The present invention provides marresistance and the good transparent conducting film of fissility and transparent conducting film laminated body.
[1] of the invention includes a kind of transparent conducting film, is had: transparent substrate；It is configured at aforementioned transparent substrate
The transparency conducting layer of thickness direction side；It is configured at the gas barrier layer of the thickness direction other side of aforementioned transparent substrate；Be configured at
The coating of the thickness direction other side of aforementioned gas barrier layer, aforementioned gas barrier layer contain at least two kinds of ingredients in Zn, Al and Si with
On, aforementioned covering layer is the oxide skin(coating) containing Si, the water contact angle of the thickness direction another side of aforementioned covering layer be 40 degree with
On, relative to the metal member comprising Si when measuring the thickness direction another side of aforementioned covering layer using X-ray photoelectron spectroscopy
Element, Si elemental ratio is 40% or more.
Of the invention [2] include transparent conducting film described in [1], wherein aforementioned covering layer be containing metallic atom and
The oxide skin(coating) of Si.
[3] of the invention include transparent conducting film described in [2], wherein aforementioned metal atom contains in Zn and Al
It is at least one kind of.
[4] of the invention include transparent conducting film described in any one of [1]~[3], wherein aforementioned covering layer packet
Contain: silicon oxide layer；It is configured at the thickness direction other side of aforementioned silicon oxide layer and contains ZnO, Al and SiO2Oxide
Layer.
Of the invention [5] include transparent conducting film described in any one of [1]~[4], wherein aforementioned gas barrier layer be containing
There are ZnO, Al and SiO2Oxide skin(coating).
Of the invention [6] include transparent conducting film described in any one of [1]~[5], wherein aforementioned gas barrier layer and preceding
Stating coating is vapor deposition layer.
[7] of the invention include a kind of transparent conducting film laminated body, are had: saturating described in any one of [1]~[6]
Bright conductive membrane；With the protective film for the thickness direction other side for being configured at aforementioned transparent conductive membrane.
[8] of the invention include transparent conducting film laminated body described in [7], wherein aforementioned covering layer and aforementioned protection
The peeling force of film is 0.005N/50mm or more and 0.50N/50mm or less.
Transparent conducting film and transparent conducting film laminated body according to the present invention has transparency conducting layer, transparent
Substrate, gas barrier layer and coating, coating is the oxide skin(coating) containing Si, relative to the metallic element comprising Si, Si member
Plain ratio is 40% or more, and therefore, marresistance is good.In addition, the water contact angle of the thickness direction another side of coating is 40
Degree or more, it is good accordingly, with respect to the fissility of protective film.
Detailed description of the invention
Fig. 1 shows the sectional view of an embodiment of transparent conducting film of the invention.Fig. 2 shows have shown in Fig. 1
Transparent conducting film transparent conducting film laminated body sectional view.
Specific embodiment
Referring to Fig.1~Fig. 2 illustrates an implementation of transparent conducting film and transparent conducting film laminated body of the invention
Mode.
In Fig. 1, paper up and down direction is up and down direction (thickness direction, the 1st direction), is upside (thickness side on the upside of paper
To side, the 1st direction side), paper downside is downside (the thickness direction other side, the 1st direction other side).In addition, paper is left
Right direction and depth direction are the face direction orthogonal with up and down direction.Specifically, according to the direction arrow of each figure.
1. transparent conducting film
Transparent conducting film 1 be in specific thickness thin film shape (including sheet), have with thickness direction just
(thickness direction is another for the flat upper surface (thickness direction one side) and flat lower surface that the prescribed direction (face direction) of friendship extends
On one side).Transparent conducting film 1 is, for example, a component of touch panel substrate having in image display device etc.,
That is, not being image display device.That is, transparent conducting film 1 is the component for making image display device etc., it is not include
Including the image-displaying members such as LCD module with component itself circulation, available device in industry.
Specifically, as shown in Figure 1, transparent conducting film 1 has: transparent substrate 2, configuration are in the upper of transparent substrate 2
First hard conating 3 of side, the first optical adjustment layer 4 configured in the upside of the first hard conating 3, configuration are in the first optical adjustment layer
The transparency conducting layer 5 of 4 upside, the second hard conating 6 configured in the downside of transparent substrate 2, configuration are under the second hard conating 6
Second optical adjustment layer 7 of side, the gas barrier layer 8 configured in the downside of the second optical adjustment layer 7, configuration are in the downside of gas barrier layer 8
Coating 9.That is, transparent conducting film 1 successively has from the bottom up: coating 9, gas barrier layer 8, the second optical adjustment layer 7,
Second hard conating 6, transparent substrate 2, the first hard conating 3, the first optical adjustment layer 4 and transparency conducting layer 5.
Transparent conducting film 1 preferably comprise coating 9, gas barrier layer 8, the second optical adjustment layer 7, the second hard conating 6, thoroughly
Bright substrate 2, the first hard conating 3, the first optical adjustment layer 4 and transparency conducting layer 5.Hereinafter, being described in detail for each layer.
2. transparent substrate
Transparent substrate 2 is the transparent substrate for ensuring the mechanical strength of transparent conducting film 1.That is, transparent substrate 2 with
First hard conating 3, the second hard conating 6, the first optical adjustment layer 4 and the second optical adjustment layer 7 support together transparency conducting layer 5,
Gas barrier layer 8 and coating 9.
Transparent substrate 2 is, for example, the macromolecule membrane with the transparency.As the material of transparent substrate 2, can enumerate: for example
The polyester resin such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate,
Such as polymethacrylates etc. (methyl) acrylic resin (acrylic resin and/or methacrylic resin), example
Such as polyethylene, polypropylene, cyclic olefin polymer (COP) olefin resin, such as polycarbonate resin, polyethersulfone resin, poly- virtue
Ester resin, melamine resin, polyamide, polyimide resin, celluosic resin, polystyrene resin, norbornene
Resin etc..Transparent substrate 2 can be used alone or two or more is applied in combination.
From viewpoints such as the transparency, heat resistance, mechanical strengths, olefin resin can be preferably enumerated, can more preferably be lifted
COP out.
The total light transmittance (JIS K7375-2008) of transparent substrate 2 is, for example, 80% or more, preferably 85% or more.
From mechanical strength, marresistance, by transparent conducting film 1 as touch panel film when get characteristic etc. ready
From the perspective of, the thickness of transparent substrate 2 is, for example, 2 μm or more, preferably 20 μm or more, and for example, 300 μm or less, it is excellent
It is selected as 150 μm or less.The thickness of transparent substrate 2 can be used for example Microgage formula thickness gauge and be measured.
It should be noted that can according to need the upper surface of transparent substrate 2 and/or lower surface setting adhesive layer,
Adhesive layer etc..
3. the first hard conating
First hard conating (curing resin layer) 3 is inferior for making the case where multiple transparent conducting film 1 is laminated
Bright conductive membrane 1 is not likely to produce abrasive scratch protective layer.It is used for alternatively, it is also possible to be arranged on transparent conducting film 1
Assign the resist blocking and that layer of resistance to blocking.
First hard conating 3 has thin film shape.First hard conating 3 is matched in a manner of contacting with the upper surface of transparent substrate 2
It is placed in the upper surface whole face of transparent substrate 2.More specifically, the first hard conating 3 with transparent substrate 2 upper surface and the first light
The mode for learning the following table face contact of adjustment layer 4 is configured between transparent substrate 2 and the first optical adjustment layer 4.
First hard conating 3 is for example formed by hard coating combination.Hard coating combination contains resin.
It, preferably can be with for example, curable resin, thermoplastic resin (such as polyolefin resin) etc. as resin
Enumerate curable resin.
As curable resin, it can be cited for example that by active energy beam (specifically, ultraviolet light, electron ray
Deng) irradiation and cured active energy ray-curable resin, such as through the cured heat-curing resin of heating, it is excellent
Choosing can enumerate active energy ray-curable resin.
Active energy ray-curable resin is for example, contain the function with polymerism carbon-to-carbon double bond in molecule
The polymer of group.As such functional group, for example, vinyl, (methyl) acryloyl group (methylacryloyl and/
Or acryloyl group) etc..
As active energy ray-curable resin, specifically, for example, urethane acrylate, ring
Oxypropylene acid esters etc. (methyl) acrylic compounds uv curing resin.
In addition, as the curable resin in addition to active energy ray-curable resin, for example: urethane tree
Rouge, melamine resin, alkyd resin, siloxane-based polymers, organosilan condensation product etc..
These resins can be used alone or two or more is applied in combination.
Hard coating combination preferably also contains particle other than resin.Thus, it is possible to make the first hard conating 3 with anti-
The resist blocking and that layer of blocking characteristics.
As particle, inorganic particle, organic granular etc. can be enumerated.As inorganic particle, it can be cited for example that titanium dioxide
Silicon particle, such as the metal oxide particle of the formation as zirconium oxide, titanium oxide, zinc oxide, tin oxide, the carbon such as calcium carbonate
Hydrochlorate particle etc..As organic granular, for example, crosslinked acrylic resin particle etc..Particle can be used alone or
Two or more is applied in combination.
The most frequency partial size of particle is, for example, 0.5 μm or more, preferably 1.0 μm or more, and for example, 2.5 μm or less, it is excellent
It is selected as 2.0 μm or less.In this specification, most frequency partial size refers to the partial size for indicating the maximum of distribution of particles, by using for example
Streaming particle image analytical equipment (Sysmex corporation, product name " FPTA-3000S "), with rated condition (sheath fluid: acetic acid second
Ester, mode determination: HPF measurement, mensuration mode: tale) it is measured and finds out.As measurement sample, using utilize acetic acid
Substance obtained from particle is diluted to 1.0 weight % and is uniformly dispersed with supersonic wave cleaning machine by ethyl ester.
The content ratio of particle is, for example, 0.01 mass parts or more, preferably 0.1 mass parts relative to 100 mass parts of resin
More than, and for example, 10 below the mass, preferably 5 below the mass.
Additive well known to levelling agent, thixotropic agent, antistatic agent etc. can also be contained in hard coating combination.
From the viewpoint of marresistance, the thickness of the first hard conating is, for example, 0.5 μm or more, preferably 1 μm or more, and
And for example, 10 μm or less, preferably 3 μm or less.The thickness of hard conating can for example be based on using moment Multichannel photometric system
The wavelength of the interference spectrum of observation and calculate.
4. the first optical adjustment layer
First optical adjustment layer 4 is the visual identity in order to inhibit the wiring pattern in transparency conducting layer 5 and ensures
The excellent transparency of bright conductive membrane 1 and the layer of the optics physical property (such as refractive index) that adjusts transparent conducting film 1.
First optical adjustment layer 4 has thin film shape.First optical adjustment layer 4 is connect with the upper surface with the first hard conating 3
The mode of touching is configured at the upper surface whole face of the first hard conating 3.More specifically, the first optical adjustment layer 4 to apply firmly with first
The mode of the following table face contact of the upper surface and transparency conducting layer 5 of layer 3 is configured between the first hard conating 3 and transparency conducting layer 5.
Optical adjustment layer 4 is formed by pH effect composition.
PH effect composition contains resin, preferably comprises resin and particle.
It as resin, is not particularly limited, resin identical with resin used in hard coating combination can be enumerated.Resin
It can be used alone or two or more is applied in combination.It is preferred that curable resin can be enumerated, it can more preferably enumerate active-energy and penetrate
Line curable resin.
The content ratio of resin relative to pH effect composition be, for example, 10 mass % or more, preferably 25 mass % with
On, and for example, 95 mass % or less, preferably 60 mass % or less.
As particle, suitable material can be selected according to the refractive index required by optical adjustment layer, for example,
Particle identical with particle used in hard coating combination.Particle can be used alone or two or more is applied in combination.It is preferred that can be with
Inorganic particle is enumerated, metal oxide particle can be more preferably enumerated, can further preferably enumerate zirconia particles (ZnO2)。
The content ratio of particle relative to pH effect composition be, for example, 5 mass % or more, preferably 40 mass % with
On, and for example, 90 mass % or less, preferably 75 mass % or less.
Additive well known to levelling agent, thixotropic agent, antistatic agent etc. can also be contained in pH effect composition.
The refractive index of first optical adjustment layer 4 is, for example, 1.55 or more, preferably 1.60 or more, and for example, 1.80 with
Under, preferably 1.70 or less.
The thickness of first optical adjustment layer 4 be, for example, 50nm or more, preferably 80nm or more, and for example, 300nm with
Under, preferably 150nm or less.The thickness of optical adjustment layer (the first optical adjustment layer 4, the second optical adjustment layer 7) for example can be with
Wavelength based on the interference spectrum for using moment Multichannel photometric systematic observation and calculate.
5. transparency conducting layer
Transparency conducting layer 5 is for forming wiring pattern in subsequent process to form the conduction of transparent drafting department
Layer.
Transparency conducting layer 5 is the top layer of transparent conducting film 1, has thin film shape.Transparency conducting layer 5 is with first
The mode of the upper surface contact of optical adjustment layer 4 is configured at the upper surface whole face of the first optical adjustment layer 4.
As the material of transparency conducting layer 5, for example: comprising selected from by In, Sn, Zn, Ga, Sb, Ti, Si, Zr,
The metal oxide of at least one kind of metal in the group of Mg, Al, Au, Ag, Cu, Pd, W composition.It can according to need and aoxidized in metal
Metallic atom shown in further adulterating above-mentioned group in object.
The material of transparency conducting layer 5 is for example, indium tin composite oxides (ITO) etc. contain indium oxide, such as antimony tin
Composite oxides (ATO) etc. can preferably be enumerated containing indium oxide containing sb oxide etc., can more preferably enumerate ITO.
Use ITO as in the case where the material of transparency conducting layer 5, tin oxide (SnO2) content is relative to tin oxide and oxygen
Change indium (In2O3) total amount be, for example, 0.5 mass % or more, preferably 3 mass % or more, and for example, 15 mass % or less,
Preferably 13 mass % or less.When the content of tin oxide is above-mentioned lower limit or more, the durability of ITO layer can be made better.
When the content of tin oxide is the above-mentioned upper limit or less, the crystallization conversion of ITO layer can be made to be easy, made transparent, sheet resistance steady
Qualitative raising.
" ITO " in this specification if for the composite oxides including at least indium (In) and tin (Sn), can also be with
Include the addition ingredient in addition to them.As additional ingredient, for example, the metallic element in addition to In, Sn, specifically
For, it can enumerate: Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd, W, Fe, Pb, Ni, Nb, Cr, Ga etc..
The thickness of transparency conducting layer 5 is, for example, 10nm or more, preferably 15nm or more, and for example, 30nm or less, excellent
It is selected as 25nm or less.Moment Multichannel photometric system can be used for example to measure in the thickness of transparency conducting layer 5.
Transparency conducting layer 5 can be to be any number of in crystalloid and noncrystalline, alternatively, it is also possible to for crystalloid and amorphous mix
It is fit.Transparency conducting layer 5 is preferably formed by crystalloid, is crystalloid ITO layer more specifically.Thereby, it is possible to improve transparency conducting layer
5 transparency and further decrease the sheet resistance of transparency conducting layer 5.
Transparency conducting layer 5 is crystalloid film for example in the case where transparency conducting layer 5 is ITO layer, can be by 20 DEG C
Dipping carries out washing and drying in hydrochloric acid (5 mass % of concentration) after 15 minutes, and resistance comes between the terminal between measurement 15mm or so
Judgement.In this specification, between the terminal after the dipping washing and drying in hydrochloric acid (20 DEG C, concentration: 5 mass %) between 15mm
Resistance is to judge ITO layer for crystalloid in 10k Ω situation below.
6. the second hard conating
Second hard conating 6 be the case where multiple transparent conducting film 1 is laminated etc. under for making transparent conducting film 1
It is not likely to produce abrasive scratch protective layer.Alternatively, it is also possible to be set as resisting for assigning resistance to blocking to transparent conducting film 1
Adhering layer.
Second hard conating 6 has thin film shape.Second hard conating 6 is matched in a manner of the following table face contact with transparent substrate 2
It is placed in the lower surface whole face of transparent substrate 2.More specifically, the second hard conating 6 with transparent substrate 2 lower surface and the second light
The mode for learning the upper surface contact of adjustment layer 7 is configured between transparent substrate 2 and the second optical adjustment layer 7.
Second hard conating 6 is layer same as the first hard conating 3, such as is formed by material same as the first hard conating 3,
(thickness, refractive index etc.) is constituted with same.Therefore, the second hard conating 6 also have shape same as the first hard conating 3,
Same size.
7. the second optical adjustment layer
Second optical adjustment layer 7 is the visual identity in order to inhibit the wiring pattern in transparency conducting layer 5 and ensures
The excellent transparency of bright conductive membrane 1 and the layer of the optics physical property (such as refractive index) that adjusts transparent conducting film 1.
Second optical adjustment layer 7 has thin film shape.Second optical adjustment layer 7 is connect with the lower surface with the second hard conating 6
The mode of touching is configured at the lower surface whole face of the second hard conating 6.More specifically, the second optical adjustment layer 7 to apply firmly with second
The mode of the upper surface contact of the lower surface and gas barrier layer 8 of layer 6 is configured between the second hard conating 6 and gas barrier layer 8.
Second optical adjustment layer 7 is formed by pH effect composition.As pH effect composition, can enumerate and first
The same substance of pH effect composition described in optical adjustment layer 4.
Second optical adjustment layer 7 is layer same as the first optical adjustment layer 4, such as by same with the first optical adjustment layer 4
The material of sample is formed, and has same composition (thickness, refractive index etc.).Therefore, the second optical adjustment layer 7 also has and the first light
Learn the same shape of adjustment layer 4, same size.
8. gas barrier layer
Gas barrier layer 8 is to inhibit the gases such as vapor, oxygen through the barrier layer in (passing through) transparent conducting film 1.
Gas barrier layer 8 has thin film shape.Gas barrier layer 8 configures in a manner of with the following table face contact of the second optical adjustment layer 7
In the lower surface whole face of the second optical adjustment layer 7.More specifically, gas barrier layer 8 with the second optical adjustment layer 7 lower surface and
The mode of the upper surface contact of coating 9 is configured between the second optical adjustment layer 7 and coating 9.
Gas barrier layer 8 is preferably to contain ZnO, Al and SiO containing layers more than at least two kinds of ingredients in Zn, Al and Si2
Oxide skin(coating).
Gas barrier layer 8 is to contain ZnO, Al and SiO2Oxide skin(coating) when, the content of Al be, for example, 2.5 mass % or more and
3.5 mass % are hereinafter, SiO2Content be, for example, 20.0 mass % or more and 62.4 mass % hereinafter, Zn is their remainder
Point.
Can for example be adulterated in gas barrier layer 8 In, Sn, Ga, Sb, Ti, Zr, Mg, Au, Ag, Cu, Pd, W, Fe, Pb, Ni, Nb,
Other metallic atoms such as Cr, Ga.
Gas barrier layer 8 is preferably the dry type layer obtained as hereinafter described by dry method, is more preferably obtained by sputtering method
The sputtering layer arrived.Thus, it is possible to form uniformly and be the gas barrier layer 8 of film, gas barrier property is more excellent.
The thickness of gas barrier layer 8 be, for example, 50nm or more, preferably 60nm or more, and for example, 200nm or less, preferably
120nm or less.Moment Multichannel photometric system can be used for example to measure in the thickness of gas barrier layer 8.
9. coating
Coating 9 is for making gas barrier layer 8 be not susceptible to abrasive scratch protection when conveying transparent conducting film 1
Layer.
Coating 9 is the lowest level of transparent conducting film 1, has thin film shape.Coating 9 with under gas barrier layer 8
The mode of surface contact is configured at the lower surface whole face of gas barrier layer 8.
Coating 9 is the oxide skin(coating) containing Si.Preferably, coating 9 is the oxide containing metallic atom and Si
Layer further preferably includes the oxide skin(coating) containing metallic atom and Si.Coating 9 can be improved by containing metallic atom
Relative to the contact angle of water, the fissility to protective film (aftermentioned) can be made good.In addition, coating 9 is the oxygen containing Si
Compound layer, therefore the transparency is also excellent.
As metallic atom, for example, In, Sn, Zn, Ga, Sb, Ti, Zr, Mg, Al, Au, Ag, Cu, Pd, W etc..
From the viewpoint of the transparency, marresistance, metallic atom can preferably be enumerated at least one kind of in Zn, Ti and Al, more preferably may be used
It is at least one kind of in Zn and Al to enumerate, it can further preferably enumerate being applied in combination for Zn and Al.
The water contact angle of the lower surface (thickness direction another side) of coating 9 is 40 degree or more, preferably 50 degree or more, and
And for example, 80 degree or less, preferably 70 degree or less.When water contact angle is above-mentioned lower limit or more, coating 9 can be reduced and protected
The peeling force for protecting film (aftermentioned), keeps fissility good.
Water contact angle can be found out as follows: under the atmosphere of 23 DEG C × 50%RH, distilled water being added drop-wise under coating 9
The angle of the tangent line of surface, measurement coating 9 and water droplet end, thus finds out.
The hardness of the lower surface of coating 9 is, for example, 3.0 or more, preferably 4.0 or more, and for example, 10 or less.Firmly
When degree is above-mentioned lower limit or more, marresistance can be made good.
The hardness of coating 9 can be measured by nano impress meter.
As coating 9, specifically, for example, (1) be made up of multiple layers inorganic layer, (2) by single layer structure
At inorganic layer etc..
(1) inorganic layer being made up of multiple layers
As the inorganic layer being made up of multiple layers, the inorganic layer constituted by 2 layers can be preferably enumerated, specifically, such as
In Fig. 1 shown in dotted line, has the first inorganic oxide layer 9A for being configured at upside (2 side of transparent substrate) and be configured at downside (dew
Side out) the second inorganic oxide layer 9B.
As the first inorganic oxide layer 9A, silicon oxide layer (SiOx:0.5≤x≤2) can be preferably enumerated.
The thickness of first inorganic oxide layer 9A be, for example, 5nm or more, preferably 10nm or more, and for example, 30nm with
Under, preferably 20nm or less.
As the second inorganic oxide layer 9B, can preferably enumerate containing ZnO, Al and SiO2Oxide skin(coating).It is specific and
Speech, it is same as oxide skin(coating) described in gas barrier layer 8.
The thickness of second inorganic oxide layer 9B be, for example, 1nm or more, preferably 3nm or more, and for example, 20nm with
Under, preferably 10nm or less.
The ratio between thickness of the thickness of first inorganic oxide layer 9A relative to the second inorganic oxide layer 9B (the first inorganic oxygen
Compound layer/the second inorganic oxide layer) be, for example, 1 or more, preferably 3 or more, and for example, 20 or less, preferably 10 with
Under.
(2) inorganic layer being made of single layer
It as the inorganic layer being made of single layer, can especially enumerate: relative to the metallic element comprising Si, Si member
Plain ratio is 50% or more, is preferably 60% or more and preferably 70% inorganic layer below.
As the inorganic layer being made of single layer, preferably containing the oxide skin(coating) of Ti, Al and Si.Furthermore it is possible to by
Ingredients such as N (nitrogen) are adulterated in the inorganic layer that single layer is constituted.
Coating 9 is preferably the layer (film) obtained as hereinafter described by dry method, is more preferably obtained by sputtering method
The sputtering layer arrived.Thus, it is possible to form uniformly and be the coating 9 of film, marresistance and fissility are more excellent.
The thickness of coating 9 be, for example, 5nm or more, preferably 10nm or more, and for example, 30nm or less, preferably
20nm or less.Moment Multichannel photometric system can be used for example to measure in the thickness of coating 9.
In transparent conducting film 1,9 side of coating relative to the metallic element comprising Si (that is, containing metallic atom
In the case of, be total ingredient of metallic atom and Si), (Si/ includes the metallic element of Si: atomicity ratio for the elemental ratio of Si
(atomic%)) for 40% or more, preferably 50% or more, more preferably 60% or more, and be, for example, less than 100%, preferably
It is 95% or less.When above-mentioned elemental ratio is above-mentioned lower limit or more, coating 9 has sufficient hardness, therefore is able to suppress resistance
The scratch of gas-bearing formation 8.In addition, coating 9 and protective film (aftermentioned) can be reduced when above-mentioned elemental ratio is the above-mentioned upper limit or less
Peeling force, keep fissility good.
Above-mentioned Si/ include Si metallic element ratio can by using X-ray photoelectron spectroscopy (ESCA:
Electron Spectroscopy for Chemical Analysis) measurement coating 9 lower surface so as to find out.
10. the manufacturing method of transparent conducting film
Then, the method for illustrating to manufacture transparent conducting film 1.
In order to manufacture transparent conducting film 1, firstly, prepare transparent substrate 2, then, the two sides of transparent substrate 2 successively
Hard conating (the first hard conating 3 and the second hard conating 6) and optical adjustment layer (the first optical adjustment layer 4 and the second optics tune are set
Flood 7), then, transparency conducting layer 5 is set in the upper surface of the first optical adjustment layer 4, in the following table of the second optical adjustment layer 7
Gas barrier layer 8 and coating 9 is arranged in face.Hereinafter, narration in detail.
Firstly, preparing known or commercially available transparent substrate 2.
It then, as needed, can be to transparent substrate 2 from the viewpoint of transparent substrate 2 and the adaptation of hard conating
Such as sputtering, corona discharge, flame, ultraviolet light irradiation, electronbeam irradiation, chemical conversion, oxygen are implemented in lower surface or upper surface
The etching processes such as change, primary coat processing.Furthermore it is possible to transparent substrate 2 is dusted by solvent cleaning, ultrasonic cleaning etc.,
It is purifying.
Then, hard conating (the first hard conating 3 and the second hard conating 6) is set on the two sides of transparent substrate 2.For example, will
Hard coating combination wet application forms first in the upper surface of transparent substrate 2 and applies firmly in the upper surface and the lower surface of transparent substrate 2
Layer 3 forms the second hard conating 6 in the lower surface of transparent substrate 2.
Specifically, for example preparing will then be diluted dilution (varnish) made of the dilution of hard coating combination with solvent
Liquid is coated on the two sides of transparent substrate 2, keeps dilution dry.
As solvent, for example, organic solvent, water solvent (specifically water) etc., can preferably enumerate
Solvent.It as organic solvent, can enumerate: the alcoholic compound such as methanol, ethyl alcohol, isopropanol；Such as acetone, methyl ethyl ketone,
The ketone compounds such as methyl iso-butyl ketone (MIBK)；Such as the ester compounds such as ethyl acetate, butyl acetate；The etherificates such as propylene glycol monomethyl ether are closed
Object；Such as aromatic compounds such as toluene, dimethylbenzene etc..These solvents can be used alone or in combination of two or more kinds.
Solid component concentration in dilution is, for example, 1 mass % or more, preferably 10 mass % or more, and is, for example,
30 mass % or less, preferably 20 mass % or less.
It can be suitable for selection according to dilution and transparent substrate 2 as coating method.For example: dip coating,
Air knife coating method, curtain coating processes, roller coating method, bar rubbing method, gravure coating process, extrusion coating methods etc..
Drying temperature is, for example, 50 DEG C or more, preferably 70 DEG C or more, for example, 200 DEG C or less, be preferably 100 DEG C with
Under.
Drying time is, for example, 0.5 minute or more, preferably 1 minute or more, for example, 60 minutes or less, preferably 20 points
Below clock.
Later, when hard coating combination contains active energy ray-curable resin, by being shone after the drying of dilution
Active energy beam is penetrated, to make active energy ray-curable resin solidification.
It should be noted that when hard coating combination contains heat-curing resin, it, can be in solvent by the drying process
Drying while being thermally cured property resin thermosets.
Then, optical adjustment layer (the first optical adjustment layer 4 and the second optical adjustment layer are set on the two sides of transparent substrate 2
7).For example, by by pH effect composition wet application in the upper surface and the lower surface of transparent substrate 2, thus in transparent base
The upper surface of material 2 forms the first optical adjustment layer 4, forms the second optical adjustment layer 7 in the lower surface of transparent substrate 2.
Specifically, for example prepare dilution (varnish) made of the dilution of pH effect composition with solvent, it then, will
Dilution is coated on the upper surface and the lower surface of transparent substrate 2, keeps dilution dry.
The preparation of pH effect composition, be coated and dried etc. conditions can enumerate with preparation exemplary in hard coating combination,
The same condition of conditions such as it is coated and dried.
In addition, when pH effect composition contains active energy ray-curable resin, by after the drying of dilution
Active energy beam is irradiated, active energy ray-curable resin solidification is made.
It should be noted that when pH effect composition contains heat-curing resin, it, can be molten by the drying process
Being thermally cured property resin thermosets while the drying of agent.
Then, transparency conducting layer 5 is set in the upper surface of the first optical adjustment layer 4.For example, by dry method first
The upper surface of optical adjustment layer 4 forms transparency conducting layer 5.
As dry method, for example, vapour deposition method.As vapour deposition method, it can be cited for example that vacuum vapour deposition, splashing
Penetrate the physical vapor depositions such as method, ion plating method, chemical vapor deposition such as plasma CVD, optical cvd, laser CVD (CVD) etc..It is excellent
Choosing can enumerate physical vapor deposition, can more preferably enumerate sputtering method.It can be formed uniformly by this method and be the saturating of film
Bright conductive layer 5.
In the case where using sputtering method, as target, the above-mentioned inorganic matter for constituting transparency conducting layer 5 can be enumerated, preferably
ITO can be enumerated.From viewpoints such as the durability of ITO layer, crystallizations, the oxidation tin concentration of ITO be, for example, 0.5 mass % with
Upper, preferably 3 mass % or more, in addition, for example, 15 mass % or less, preferably 13 mass % or less.
As sputter gas, for example, the non-active gas such as Ar.In addition, as needed, oxygen can be applied in combination
Gas isoreactivity gas.In the case where reactant gas is applied in combination, the flow-rate ratio of reactant gas is not particularly limited, phase
For the total flow proportional for example 0.1 flow % or more and 5 flow % or less of sputter gas and reactant gas.
Sputtering is implemented under vacuum.Specifically, from viewpoints such as reduction, the discharge stabilities for inhibiting sputter rate,
Air pressure when sputtering is, for example, 1Pa or less, preferably 0.7Pa or less.
Power supply used in sputtering method is, for example, any one of DC power supply, AC power supplies, MF power supply and RF power supply, in addition,
It may be their combination.
In addition, can suitably set target, condition of sputtering etc. in order to form the transparency conducting layer 5 of expectation thickness and come in fact
Apply multiple sputtering.
Then, gas barrier layer 8 is set in the lower surface of the second optical adjustment layer 7.For example, by dry method in the second optics
The lower surface of adjustment layer 7 forms gas barrier layer 8.
As dry method, vapour deposition method described in the formation of transparency conducting layer 5 can be preferably enumerated, can more preferably be lifted
Sputtering method out.That is, gas barrier layer 8 is preferably the vapor deposition layer formed by vapor deposition layer, the sputtering layer more preferably formed with sputtering method.It is logical
Cross the gas barrier layer 8 that this method was capable of forming uniformly and was film.
In the case where using sputtering method, as target, the above-mentioned inorganic matter for constituting gas barrier layer 8 can be enumerated, it preferably can be with
It enumerates containing ZnO, Al and SiO2Target.
As the condition of sputtering, condition same as condition described in the formation of transparency conducting layer 5 can be enumerated.
Then, coating 9 is set in the lower surface of gas barrier layer 8.For example, by dry method in the lower surface of gas barrier layer 8
Form coating 9.
As dry method, vapour deposition method described in the formation of transparency conducting layer 5 can be preferably enumerated, can more preferably be lifted
Sputtering method out.That is, coating 9 is preferably the vapor deposition layer formed by vapor deposition layer, the sputtering layer more preferably formed with sputtering method.It is logical
Cross the coating 9 that this method was capable of forming uniformly and was film.
Particularly, when gas barrier layer 8 and coating 9 are vapor deposition layer, the adaptation of these layers is improved, and is able to suppress by abrading
They caused splitting, excellent scratch resistance.
In the case where using sputtering method, as target, the above-mentioned inorganic matter for constituting coating 9 can be enumerated.
In the case that coating 9 is the inorganic layer being made up of multiple layers, change target makes its desired inorganic layer, implements
Multiple sputtering method.
For example, using the target formed by Si first, implement sputtering method, forms the first inorganic oxygen being made of silicon oxide layer
Compound layer 9A, using contain ZnO, Al and SiO2Oxide target, implement sputtering method, formed by contain ZnO, Al and SiO2Oxygen
The second inorganic oxide layer 9B that compound is formed.
As the condition of sputtering, condition same as condition described in the formation of transparency conducting layer 5 can be enumerated.
Thus, it is possible to obtain transparent conducting film 1.
Then, as needed, crystallization conversion processing is implemented to the transparency conducting layer 5 of transparent conducting film 1.
Specifically, implementing to heat to transparent conducting film 1 under atmosphere.
The implementation such as infrared heater, baking oven can be used for example in heat treatment.
Heating temperature is, for example, 100 DEG C or more, preferably 120 DEG C or more, and for example, 200 DEG C or less, preferably 160
DEG C or less.When making in heating temperature above range, the heat waste that is able to suppress transparent substrate 2 is injured to be generated by transparent substrate 2
Impurity, and reliably carry out crystallization conversion.
Heating time suitably determines according to heating temperature, for example, 10 minutes or more, preferably 30 minutes or more, and example
For example 5 hours or less, preferably 3 hours or less.
The transparent conducting film 1 that thereby, it is possible to obtain having the transparency conducting layer 5 crystallized.
The overall thickness of gained transparent conducting film 1 is, for example, 2 μm or more, preferably 20 μm or more, in addition, being, for example,
300 μm or less, preferably 150 μm or less.
It should be noted that can according to need before or after crystallization conversion processing, well known engraving method is utilized
Transparency conducting layer 5 is formed into the wiring patterns such as striated.
For etching, such as in a manner of corresponding with non-drafting department and drafting department, covering part (Masking strip etc.) configuration is existed
On transparency conducting layer 5, then, the transparency conducting layer 5 (non-drafting department) exposed from covering part is etched using etching solution.Make
For etching solution, for example, the acid such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, phosphoric acid and their nitration mixture.Later, such as
Covering part is removed from the upper surface of transparency conducting layer 5 by removing etc..
In addition, transparent substrate 2 can be conveyed in a manner of roll-to-roll (roll to roll) on one side in above-mentioned manufacturing method,
Hard conating, optical adjustment layer, transparency conducting layer 5, gas barrier layer 8 and coating 9 are sequentially formed in the transparent substrate 2 on one side, separately
Outside, can also in a batch manner (single chip mode) formed these layers part or all.From the viewpoint of productivity, preferably
Each layer is formed in the transparent substrate 2 that exists on one side convey transparent substrate 2 in a manner of roll-to-roll while.
11. transparent conducting film laminated body
As shown in Fig. 2, transparent conducting film laminated body 10 has: transparent conducting film 1 is configured at transparent conductivity
The adhesive phase 11 of the downside of film 1 and be configured at adhesive phase 11 downside protective film 12.That is, transparent conductivity is thin
Film laminated body 10 successively has protective film 12, adhesive phase 11 and transparent conducting film 1 from the bottom up.Transparent conductivity is thin
Film laminated body 10 preferably comprises protective film 12, adhesive phase 11 and transparent conducting film 1.
Protective film 12 be for transparent conducting film 1 conveying, save when protect transparent conducting film 1 from
The protective layer of scratch or pollution, also, be with adhesive phase 11 in the use of transparent conducting film 1 together from electrically conducting transparent
The release layer that property film 1 is stripped.
Protective film 12 is the lowest level of transparent conducting film laminated body 10, has thin film shape.Protective film 12 with
The lower surface whole face of adhesive phase 11 is configured at the mode of the following table face contact of adhesive phase 11.
As protective film 12, for example, macromolecule membrane.As the material of protective film 12, such as can lift
Exemplary resin in transparent substrate 2 out.It is preferred that polyester resin can be enumerated, PET can be more preferably enumerated.
From viewpoints such as mechanical strengths, the thickness of protective film 12 is, for example, 2 μm or more, preferably 20 μm or more, and
And for example, 300 μm or less, preferably 150 μm or less.Microgage formula thickness can be used for example in the thickness of protective film 12
Meter is to measure.
Adhesive phase 11 is the layer for protective film 12 to be fitted in transparent conducting film 1, is in transparent conductivity
The layer being stripped together from transparent conducting film 1 when the use of film 1 with protective film 12.
Adhesive phase 11 has thin film shape.Adhesive phase 11 is configured in a manner of contacting with the upper surface of protective film 12
In the upper surface whole face of protective film 12.More specifically, adhesive phase 11 is with the upper surface and coating 9 with protective film 12
The mode of following table face contact be configured between protective film 12 and transparent conducting film 1.
As the adhesive for constituting adhesive phase 11, for example, acrylic adhesives, elastomeric adhesive (fourth
Base elastomeric adhesive etc.), organic silicon-type adhesive, Polyester adhesive, polyurethane series adhesive, polyamide-based adhesive,
Epoxy adhesive, vinyl alkyl ethers system adhesive, fluororesin system adhesive etc..
The thickness of adhesive phase 11 is, for example, 2 μm or more, preferably 5 μm or more, and for example, 50 μm or less, be preferably
30 μm or less.Microgage formula thickness gauge can be used for example to measure in the thickness of adhesive phase 11.
In transparent conducting film laminated body 10, peeling force, the i.e. coating of transparent conducting film 1 and protective film 12
9 with the peeling force of protective film 12 be, for example, 1.00N/50mm or less, preferably 0.50N/50mm hereinafter, and being, for example,
0.005N/50mm or more, preferably 0.05N/50mm or more.When peeling force is the above-mentioned upper limit or less, in transparent conducting film 1
Protective film can be easy to remove from the lower surface of coating 9, be able to suppress the breakage of transparent conducting film 1.In addition, if stripping
It is above-mentioned lower limit or more from power, then is able to suppress the generation of the offset of transparent conducting film 1 and protective film 12 in conveying.
Peeling force can measure as follows: universal tensile testing machine be used, in peeling rate 300mm/ minutes, peel angle
Protective film 12 is removed from transparent conducting film 1 under conditions of 180 °, to measure.
12. function and effect
Transparent conducting film 1 and transparent conducting film laminated body 10 have: transparent substrate 2 is configured at transparent substrate 2
Upside transparency conducting layer 5, be configured at transparent substrate 2 downside gas barrier layer 8 and be configured at the downside of gas barrier layer 8 and cover
Cap rock 9.In addition, gas barrier layer 8 containing at least two kinds of ingredients in Zn, Al and Si more than.Therefore, the gas barrier property of vapor, oxygen etc.
It is excellent.
In addition, coating 9 is the oxide skin(coating) containing Si, in 9 side of coating (i.e. lower surface), relative to metallic element
The elemental ratio of the Si of (including Si) is 40% or more.Therefore, coating 9 has appropriate hardness, therefore excellent scratch resistance.
In addition, the transparency is also excellent.
In addition, the water contact angle of the lower surface of coating 9 is 40 degree or more.Therefore, the lower surface of coating 9 is pasted with guarantor
It protects in the transparent conducting film laminated body 10 of film 12, is able to suppress the removing of coating 9 while being easily peeled off protective film
12, fissility is excellent.
Such as has transparent conducting film 1 in Optical devices.As Optical devices, for example, image display dress
It sets.Have in image display device (specifically, image display device with image-displaying members such as LCD modules) transparent
In the case where conductive membrane 1, transparent conducting film 1 is used for example as touch panel substrate.As the form of touch panel,
The various modes such as optical mode, ultrasonic wave mode, electrostatic capacity, resistive film mode can be enumerated, are particularly suitable for quiet
The touch panel of capacitance mode.
13. variation
In Fig. 1 and embodiment shown in Fig. 2, transparent conducting film 1 has the first hard conating 3 and the second hard conating 6,
Such as although it is not shown, but transparent conducting film 1 may not possess one of the first hard conating 3 and the second hard conating 6 or
The two.From the viewpoint of scratch resistance and resistance to blocking, it is hard that preferably clear conductive membrane 1 has the first hard conating 3 and second
Coating 6.
In Fig. 1 and embodiment shown in Fig. 2, transparent conducting film 1 has the first optical adjustment layer 4 and the second optics
Adjustment layer 7, such as although it is not shown, but transparent conducting film 1 may not possess the first optical adjustment layer 4 and the second optics
One or both of adjustment layer 7.From the viewpoint of can not be the drafting department of visual identity transparency conducting layer 5, it is preferred that
Transparent conducting film 1 has the first optical adjustment layer 4 and the second optical adjustment layer 7.
Embodiment
Examples and Comparative Examples described below, further illustrate the present invention.It should be noted that the present invention is not implemented
Any restriction of example and comparative example.In addition, compounding ratio (content ratio), physics value, parameter etc. used in record below
Specific numerical value could alternatively be recorded in above-mentioned " specific embodiment " compounding ratio corresponding with them (containing than
Example), physics value, the upper limit value (numerical value for being defined as " following ", " deficiency ") of the record such as parameter or lower limit value (be defined as " with
On ", the numerical value of " being more than ").
Embodiment 1
By roll-to-roll process, transparent conducting film is manufactured as steps described below.
As transparent substrate, prepare cyclic olefin polymer film (COP film, 40 μm of thickness, Nippon Zeon
Corporation system, trade name " ZEONOR ").
Diameter (most frequency partial size) 1.8 μm of multiple particles (crosslinked acrylic resin, list will be contained using gravure coater
Discrete particles), binder resin (Dainippon Ink Chemicals's system, trade name " UNIDIC ", urethane acrylate resin) and molten
Two sides and the drying that the dilution of the hard coating combination of agent (butyl acetate) is coated on COP film are shone using high-pressure sodium lamp later
Penetrate ultraviolet light.The first hard conating for forming 1.3 μm of thickness in the upper surface of transparent substrate as a result, in the lower surface of transparent substrate
Form 1.3 μm of thickness of the second hard conating.
Then, using gravure coater by ultraviolet-curable composition (JSR corporation, quotient containing zirconia particles
The name of an article " OPSTAR Z7412 ") it is coated on the first hard conating and the second hard conating and drying, it is then purple using high voltage mercury lamp radiation
Outside line.The first optical adjustment layer for forming thickness 100nm, refractive index 1.62 in the upper surface of the first hard conating as a result, second
The lower surface of hard conating forms the second optical adjustment layer of thickness 100nm, refractive index 1.62.
Then, the ITO layer (transparency conducting layer) with a thickness of 20nm is formed in the upper surface of the first optical adjustment layer.It is specific and
Speech, in the case where having imported the vacuum atmosphere of air pressure 0.4Pa of argon gas 99.9% and oxygen 0.1%, uses the oxidation by 90 mass %
The ITO target that the sintered body of the tin oxide of indium and 10 mass % is constituted implements DC magnetron sputtering method.
Then, it is formed in the lower surface of the second optical adjustment layer and (contains ZnO, Al and SiO with a thickness of the AZO layer of 60nm2's
Inorganic oxide layer: gas barrier layer).Specifically, having imported Ar and O2Mixed gas 0.6Pa vacuum atmosphere under, lead to
DC magnetron sputtering is crossed, using including ZnO, Al and SiO2Target (mass %, Zn:75 mass %, SiO of Al:3~52: 20 mass %)
Implement DC magnetron sputtering.
Then, being formed in the lower surface of gas barrier layer includes the silicon oxide layer with a thickness of 10nm and the AZO with a thickness of 3nm
Layer (contains ZnO, Al and SiO2Inorganic oxide layer) coating.Specifically, having imported Ar and O2Mixed gas
Under the vacuum atmosphere of 0.6Pa, by DC magnetron sputtering, implement DC magnetron sputtering using Si target (Si:100%), in AZO layers of (resistance
Gas-bearing formation) lower surface formed Si oxide (SiOx) layer.Then, Ar and O are being imported2Mixed gas 0.4Pa vacuum
Under atmosphere, by DC magnetron sputtering, using containing ZnO, Al and SiO2Target (mass %, Zn:75 mass %, SiO of Al:3~52:
20 mass %) implement DC magnetron sputtering, AZO layers are formed in the lower surface of silicon oxide layer.
It has made and has been applied firmly for coating (AZO layers/silicon oxide layer)/gas barrier layer/second optical adjustment layer/the second as a result,
Layer/transparent substrate/the first hard conating/first optical adjustment layer/transparency conducting layer transparent conducting film.
Embodiment 2
It in the formation of coating, using the target containing Al, Si, Ti, N, in addition to this, operates similarly with example 1, makes
Producing transparent conductive film.It should be noted that coating is the oxide skin(coating) (single layer) containing Al, Si, Ti, N, with a thickness of
10nm。
Comparative example 1
It other than not forming coating, operates similarly with example 1, has made transparent conducting film.
Comparative example 2
In the formation of coating, being made of Si oxide (SiOx) with a thickness of 10nm is formed in the lower surface of gas barrier layer
Coating, that is, do not form AZO layers, in addition to this, operate similarly with example 1, made transparent conducting film.
Comparative example 3
In the formation of coating, using the target (Si:67 mass %, Zr:33 mass %) containing Si and Zr, in addition to this,
It operates similarly with example 1, has made transparent conducting film.It should be noted that coating is by SiZrOxIt is formed
Oxide skin(coating), with a thickness of 5nm.
Comparative example 4
In the formation of coating, using the target (Si:50 mass %, C:50 mass %) containing Si and carbon, in addition to this, with
Embodiment 1 operates in the same way, and has made transparent conducting film.It should be noted that coating is the carbide formed by SiC
Layer, with a thickness of 5nm.
Each composition of transparent conducting film and evaluation etc. are measured as follows.
(1) thickness
Transparent substrate is measured using Microgage formula thickness gauge (Mitutoyo Corporation system).
Hard conating, optical adjustment layer, transparency conducting layer, gas barrier layer and coating are (big using moment Multichannel photometric system
Tomb Electronics Co., Ltd system, trade name " MCPD2000 "), it is calculated based on the waveform of interference spectrum.Show the result in table
1。
(2) refractive index
The refractive index of optical adjustment layer uses Abbe refractometer (ATAGO CO., LTD. system), to light under conditions of 25 DEG C
The surface incidence for learning adjustment layer measures light, is measured by defined measuring method shown in refractometer.Show the result in table 1.
(3) elemental ratio of Si
For the lower surface (coating lower surface) of transparent conducting film, in measurement rangeVoltage 15kV,
Implement to be based on X-ray photoelectron spectroscopy (ESCA:Electron Spectroscopy under conditions of electric power 25W
ChemicalAnalysis, measurement device: " QuanteraSXM ", ULVAC-PHI corporation) measurement.The metal that will test
The ratio (atomicity ratio) of element and the Si relative to the metallic element comprising Si are shown in table 1.
(4) water contact angle
Using water contact angle measurement device (consonance interface science Co. Ltd. system, trade name " DMx-401 "), drop is utilized
The distillation of about 1 μ L is added dropwise in method under the atmosphere of 23 DEG C × 50%RH to the lower surface of transparent conducting film (coating lower surface)
Water.Since the dropwise addition of water droplet after 1 second, the angle of the tangent line of measurement coating and water droplet end.Show the result in table 1.
(5) hardness
Using nano impress meter (Hysitron inc corporation, trade name " Triboindenter "), pressure head is being used:
Berkovich, temperature: under conditions of 25 DEG C, implementing single indentation assaying, thus measures the coating table of transparent conducting film
The hardness in face.Show the result in table 1.
(6) peeling force, fissility test
In protective film (day east electrician strain formula meeting of the cover surface fitting with adhesive phase of transparent conducting film
Society's system, " CP-171 ", 125 μm of PET film thickness, 20 μm of acrylic adhesive layer thickness).It is cut into width 50mm, length
50mm is spent, transparent conducting film laminated body has been made.
It is transparent from this under conditions of peeling rate 300mm/ minutes, 180 ° of peel angle using universal tensile testing machine
Conductive membrane laminated body removes protective film, measures peeling force (N/50mm) at this time.
In addition, detect by an unaided eye transparent conducting film side for the transparent conducting film for having removed protective film
Release surface (coating).At this point, coating and gas barrier layer will not be observed in release surface removing the case where be evaluated as zero, will see
The case where observing the removing of gas barrier layer be evaluated as ×.
These results are shown in table 1.
(7) scratch resistance is tested
Using the cover surface of melamine sponge wiping transparent conducting film, detect by an unaided eye its lower surface.
The case where lower surface of transparent conducting film is not observed scratch is evaluated as zero, by transparent conducting film
Lower surface observe the case where scratch be evaluated as ×.Show the result in table 1.
(8) transparency test
Electrically conducting transparent is measured using haze meter (Suga Test Instruments Co., Ltd. system, " haze meter HZ-0 ")
The total light transmittance of property film, the case where situation for 80% or more is evaluated as zero, will be less than 80% is evaluated as ×.Result is shown
In table 1.
[table 1]
[table 1]
* comparative example 1 shows the evaluation to gas barrier layer.
It should be noted that foregoing invention is provided as embodiment illustrated of the invention, these are only
It is simple to illustrate, it is not interpreted in a limited way.The variation of the invention being apparent to those skilled in the art is included in
In claims above-mentioned.
Claims (8)
1. a kind of transparent conducting film, which is characterized in that have:
Transparent substrate；
It is configured at the transparency conducting layer of the thickness direction side of the transparent substrate；
It is configured at the gas barrier layer of the thickness direction other side of the transparent substrate；With
It is configured at the coating of the thickness direction other side of the gas barrier layer,
The gas barrier layer contains at least two kinds of ingredients in Zn, Al and Si or more,
The coating is the oxide skin(coating) containing Si,
The water contact angle of the thickness direction another side of the coating is 40 degree or more,
Relative to the metal member comprising Si when measuring the thickness direction another side of the coating using X-ray photoelectron spectroscopy
Element, Si elemental ratio is 40% or more.
2. transparent conducting film according to claim 1, which is characterized in that the coating be containing metallic atom and
The oxide skin(coating) of Si.
3. transparent conducting film according to claim 2, which is characterized in that the metallic atom contains in Zn and Al
It is at least one kind of.
4. transparent conducting film according to claim 1, which is characterized in that the coating includes:
Silicon oxide layer；
It is configured at the thickness direction other side of the silicon oxide layer and contains ZnO, Al and SiO2Oxide skin(coating).
5. transparent conducting film according to claim 1, which is characterized in that the gas barrier layer be containing ZnO, Al and
SiO2Oxide skin(coating).
6. transparent conducting film according to claim 1, which is characterized in that the gas barrier layer and the coating are
Layer is deposited.
7. a kind of transparent conducting film laminated body, which is characterized in that have:
Transparent conducting film described in claim 1；With
It is configured at the protective film of the thickness direction other side of the transparent conducting film.
8. transparent conducting film laminated body according to claim 7, which is characterized in that the coating and the protection
The peeling force of film is 0.005N/50mm or more and 0.50N/50mm or less.
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|---|---|---|---|---|
| CN112292265B (en) * | 2019-06-20 | 2021-11-19 | 昭和电工株式会社 | Transparent conductive film laminate and method for processing same |
| CN115583803B (en) * | 2022-11-08 | 2024-05-17 | 宁波海燕新材料有限公司 | AZO transparent conductive film and preparation method thereof |
| JP7458674B1 (en) | 2023-08-04 | 2024-04-01 | 尾池工業株式会社 | gas barrier film |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1968807A (en) * | 2004-04-15 | 2007-05-23 | 帝人株式会社 | Transparent gas barrier multilayer film |
| CN103476579A (en) * | 2011-04-05 | 2013-12-25 | 东丽株式会社 | Gas barrier film |
| JP2017043058A (en) * | 2015-08-28 | 2017-03-02 | 富士フイルム株式会社 | Production method of gas barrier film and transfer method of gas barrier film |
| JP2017132225A (en) * | 2016-01-29 | 2017-08-03 | 日東電工株式会社 | Conductive laminated film |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016107556A (en) * | 2014-12-09 | 2016-06-20 | 凸版印刷株式会社 | Gas barrier film |
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2017
- 2017-10-23 JP JP2017204216A patent/JP6923415B2/en active Active
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2018
- 2018-10-05 KR KR1020180119140A patent/KR20190045831A/en active Search and Examination
- 2018-10-16 CN CN201811203004.4A patent/CN109698042A/en active Pending
- 2018-10-18 TW TW107136658A patent/TW201917011A/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1968807A (en) * | 2004-04-15 | 2007-05-23 | 帝人株式会社 | Transparent gas barrier multilayer film |
| CN103476579A (en) * | 2011-04-05 | 2013-12-25 | 东丽株式会社 | Gas barrier film |
| JP2017043058A (en) * | 2015-08-28 | 2017-03-02 | 富士フイルム株式会社 | Production method of gas barrier film and transfer method of gas barrier film |
| JP2017132225A (en) * | 2016-01-29 | 2017-08-03 | 日東電工株式会社 | Conductive laminated film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6923415B2 (en) | 2021-08-18 |
| KR20190045831A (en) | 2019-05-03 |
| JP2019079637A (en) | 2019-05-23 |
| TW201917011A (en) | 2019-05-01 |
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