CN109559842A - Crystallized thin films - Google Patents
Crystallized thin films Download PDFInfo
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- CN109559842A CN109559842A CN201811125171.1A CN201811125171A CN109559842A CN 109559842 A CN109559842 A CN 109559842A CN 201811125171 A CN201811125171 A CN 201811125171A CN 109559842 A CN109559842 A CN 109559842A
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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
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
- B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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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
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B9/045—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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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
- C23C14/58—After-treatment
- C23C14/5806—Thermal treatment
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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
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/02—Synthetic macromolecular particles
- B32B2264/0214—Particles made of materials belonging to B32B27/00
- B32B2264/0228—Vinyl resin particles, e.g. polyvinyl acetate, polyvinyl alcohol polymers or ethylene-vinyl acetate copolymers
- B32B2264/0235—Aromatic vinyl resin, e.g. styrenic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/102—Oxide or hydroxide
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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
- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/704—Crystalline
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Abstract
The present invention provides a kind of crystallized thin films, which has transparent film substrate and crystallization indium tin composite oxide layer.Crystallized thin films are the specific temperature crystallized thin films as obtained from will be provided with the amorphous film of transparent film substrate and noncrystalline indium tin composite oxide layer and crystallize at a certain temperature.The difference of the residual stress σ 2 of crystallization indium tin composite oxide layer in the residual stress σ 1 and 110 DEG C of crystallized thin films as obtained from crystallizing amorphous film at 110 DEG C of crystallization indium tin composite oxide layer in specific temperature crystallized thin films is 150MPa or less.
Description
Technical field
The present invention relates to crystallized thin films.
Background technique
In the past, it is known that transparent conducting film has the transparency conducting layer that resistance value is reduced by crystallization, and wraps
Contained in touch panel.
For example, proposing following transparent conducting film in the past, has flexible transparent substrate and be formed thereon and wrap
Transparency conducting layer containing the indium tin composite oxides (crystallinity ito film) crystallized, the compression of transparency conducting layer are residual
Residue stress is 0.4~2GPa (for example, referring to Japanese Unexamined Patent Publication 2016-179686 bulletin.).
For the transparent conducting film recorded in Japanese Unexamined Patent Publication 2016-179686 bulletin, by the way that compressed residual is answered
Power is set as above-mentioned lower limit or more, thus under heavy load when improving the touch panel that transparent conducting film is used for game machine
Get characteristic and resistance to bend(ing) ready.
Summary of the invention
However, transparent conducting film is exposed in high temperature and humidity atmosphere in the case where such as vehicle-mounted touch panel.But
It is, for the transparent conducting film recorded in Japanese Unexamined Patent Publication 2016-179686 bulletin, if being exposed to high temperature and humidity atmosphere,
Then there is the unfavorable condition for cracking (rupture) over transparent conductive layer within a short period of time.
The present invention is provided if exposed to high temperature and humidity atmosphere, is also able to suppress the knot for generating damage in a relatively short period of time
Crystallization thin film.
(1) of the invention includes a kind of crystallized thin films, has transparent film substrate and crystallization indium tin composite oxides
Layer, aforementioned crystalline film are the amorphous film by will be provided with transparent film substrate and noncrystalline indium tin composite oxide layer
Specific temperature crystallized thin films obtained from crystallizing at a certain temperature, the crystallization in aforementioned specific temperature crystallized thin films
The residual stress σ 1 of indium tin composite oxide layer with 110 as obtained from aforementioned amorphous film is crystallized at 110 DEG C
The difference of the residual stress σ 2 of crystallization indium tin composite oxide layer in DEG C crystallized thin films is 150MPa or less.
(2) of the invention include the crystallized thin films according to (1), and aforementioned specific temperature crystallized thin films pass through aforementioned non-
Heating of the crystalloid film under aforementioned specific temperature, is shunk relative to aforementioned amorphous film, aforementioned 110 DEG C of crystallizations
Heating of the film by aforementioned amorphous film at 110 DEG C, is shunk relative to aforementioned amorphous film, aforementioned specific
The difference of the shrinking percentage SR1 of temperature crystallized thin films and the shrinking percentage SR2 of aforementioned 110 DEG C of crystallized thin films are 0.05% or less.
Of the invention (3) include the crystallized thin films according to (1) or (2), aforementioned specific temperature crystallized thin films and preceding
110 DEG C of crystallized thin films are stated under certain tensile load from 25 DEG C and 10%RH heating and when humidifying to 85 DEG C and 85%RH,
It extends, the difference of the elongation EP2 of the elongation EP1 of aforementioned specific temperature crystallized thin films and aforementioned 110 DEG C of crystallized thin films
It is 0.07% or less.
The residual stress σ 1 of crystallization indium tin composite oxide layer in specific temperature crystallized thin films of the invention and logical
Cross the crystallization indium tin composite oxides in 110 DEG C of crystallized thin films obtained from crystallizing amorphous film at 110 DEG C
The small difference of the residual stress σ 2 of layer is 150MPa or less.
Therefore, it even if specific temperature crystallized thin films of the invention are exposed to high temperature and humidity atmosphere, is also able to suppress
Damage is generated in the shorter time.
Detailed description of the invention
Figure 1A and Figure 1B is the process sectional view for showing the manufacturing method of an embodiment of crystallized thin films of the invention,
Figure 1A shows the 1st process of manufacture amorphous film, and Figure 1B shows the 2nd process of manufacture crystallized thin films.
Fig. 2A and Fig. 2 B is that the variation of crystallized thin films shown in Figure 1A and Figure 1B (only includes noncrystalline indium tin composite oxygen
The crystallized thin films of compound layer and transparent film substrate) manufacturing method process sectional view, Fig. 2A shows manufacture amorphous thin
1st process of film, Fig. 2 B show the 2nd process of manufacture crystallized thin films.
Fig. 3 is for illustrating angle, θ and Ψ in X-ray scattering method used in the calculating of residual stress in embodiment
Schematic diagram.
Specific embodiment
<embodiment>
A and Figure 1B is illustrated an embodiment of crystallized thin films of the invention referring to Fig.1.
In Figure 1A and Figure 1B, paper up and down direction is up and down direction (thickness direction, the 1st direction), is upside on the upside of paper
The side of the 1st direction (side of thickness direction), be on the downside of paper downside (other side of thickness direction, the 1st direction it is another
Side).In addition, paper left and right directions and depth direction are the face direction orthogonal with up and down direction.Specifically, the side according to each figure
To arrow.
(crystallized thin films)
As shown in Figure 1B, crystallized thin films 11 form the thin film shape (including sheet) with specific thickness, and along face side
To with flat upper surface and flat lower surface.Crystallized thin films 11 are, for example, for making and glassy layer 9 and pressure-sensitive viscous
Connect the component that oxidant layer 8 (aftermentioned) is contained in touch panel substrate of image display device etc. together, that is, be not that image is aobvious
Showing device.That is, crystallized thin films 11 be without the image-displaying members such as LCD module, glassy layer 9, pressure-sensitive adhesive layer 8 etc., with
Available device in component itself circulation, industry.
Crystallized thin films 11 for example successively have resist blocking and that layer 4, transparent film substrate 2, hard conating 3, optics towards upside
Adjustment layer 5 and crystallization indium tin composite oxide layer 7.It is preferred that crystallized thin films 11 only include resist blocking and that layer 4, transparent film substrate
2, hard conating 3, optical adjustment layer 5 and crystallization indium tin composite oxide layer 7.Hereinafter, being successively illustrated to each layer.
(transparent film substrate)
Transparent film substrate 2 is the transparent substrate for ensuring the mechanical strength of crystallized thin films 11.Specifically, thoroughly
Bright film substrate 2 supports crystallization indium tin composite oxide layer 7 with hard conating 3 and optical adjustment layer 5 together.
It should be noted that transparent film substrate 2 will be described later in detail, have as shown in the arrow of Figure 1B
To the convergent force on the inside of the direction of face, by the convergent force, assign residual stress σ 1 to crystallization indium tin composite oxide layer 7.
Transparent film substrate 2 has thin film shape, and has flat upper surface and flat lower surface along the plane direction.
Transparent film substrate 2 is, for example, flexible transparent membrane.As the material of transparent film substrate 2, without spy
It does not limit, such as cyclic olefine resin, polyester based resin (polyethylene terephthalate (PET) etc.), acetic acid can be enumerated
Ester system resin, polyether sulfone system resin, polycarbonate-based resin, polyamide resin, polyimides system resins, olefin-based resin,
(methyl) acrylic resin, polyvinyl chloride resin, Vingon system resin, polystyrene resin, polyethenol series
Resin, polyarylate system resin, polyphenylene sulfide system resin etc..
As the material of transparent film substrate 2, cyclic olefine resin can be preferably enumerated.The material of transparent film substrate 2
When for cyclic olefine resin, isotropic transparent membrane can be made in transparent film substrate 2, it can be to crystallized thin films 11
Assign isotropism.
Transparent film substrate 2 has isotropism or birefringence.Transparent film substrate 2 preferably has isotropism.Thoroughly
The birefringence in direction is, for example, 200 hereinafter, preferably 150 hereinafter, in addition, for example, 0 or more in the face of bright film substrate 2.
The thickness of transparent film substrate 2 be, for example, 100 μm hereinafter, preferably 50 μm hereinafter, in addition, for example, 5 μm or more,
Preferably 15 μm or more.
(hard conating)
Hard conating 3 is for being not likely to produce crystallized thin films 11 (or the amorphous film 1 of aftermentioned manufacture on the way)
Abrasive scratch protective layer.Hard conating 3 has thin film shape, for example, being matched in a manner of the upper surface for contacting transparent film substrate 2
It is placed in the entire upper surface of transparent film substrate 2.The material of hard conating 3 is, for example, hard coating combination.As hard coating combination, example
Such as, the mixture etc. recorded in Japanese Unexamined Patent Publication 2016-179686 bulletin can be enumerated.Mixture is for example containing acrylic compounds tree
The resins such as rouge, carbamate system resin (binder resin).The thickness of hard conating 3 is, for example, 0.1 μm or more, preferably 0.5 μ
M or more, in addition, for example, 10 μm hereinafter, preferably 5 μm or less.
(optical adjustment layer)
Optical adjustment layer 5 be in order to inhibit crystallize indium tin composite oxide layer 7 in transparent electrode pattern visuality,
And ensures the excellent transparency of crystallized thin films 11 and the optics physical property of crystallized thin films 11 (for example, refractive index) is adjusted
Layer.
Optical adjustment layer 5 is configured at hard conating 3 in a manner of having thin film shape, such as the upper surface to contact hard conating 3
Entire upper surface.More specifically, optical adjustment layer 5 with the upper surface with hard conating 3 and crystallizes indium tin composite oxides
The mode of the following table face contact of layer 7 is configured between hard conating 3 and crystallization indium tin composite oxide layer 7.Optical adjustment layer 5
Material is, for example, pH effect composition.As pH effect composition, such as Japanese Unexamined Patent Publication 2016-179686 can be enumerated
The mixture etc. recorded in bulletin.Mixture for example containing the resins such as acrylic resin (binder resin) and contains inorganic system
Or the particle (the preferably particle of the inorganic system such as zirconium oxide) of organic system.The thickness of optical adjustment layer 5 is, for example, 50nm or more, preferably
For 100nm or more, in addition, for example, 800nm is hereinafter, preferably 300nm or less.
(resist blocking and that layer)
Resist blocking and that layer 4 is laminated by multiple crystallized thin films 11 (amorphous film 1 of manufacture on the way) through-thickness
In the case of etc., resistance to blocking is assigned to the surface for the multiple crystallized thin films 11 being in contact with each other.It is thin that resist blocking and that layer 4 becomes crystallization
The lowest surface of film 11.Specifically, resist blocking and that layer 4 be configured in a manner of contacting the lower surface of transparent film substrate 2 it is transparent
The lower surface whole face of film substrate 2.
The material of resist blocking and that layer 4 is, for example, Antiblock compositions.As Antiblock compositions, such as Japanese spy can be enumerated
Open the mixture etc. recorded in 2016-179686 bulletin.Mixture is for example containing the resins such as acrylic resin (binder tree
Rouge) and containing it is inorganic system or organic system particle (particles of the organic systems such as optimization styrene system).The thickness of resist blocking and that layer 4 is for example
It is 0.1 μm or more, preferably 0.5 μm or more, in addition, for example, 10 μm hereinafter, preferably 5 μm or less.
(crystallization indium tin composite oxide layer)
Crystallization indium tin composite oxide layer 7 is for being formed as the saturating of transparent electrode pattern by subsequent handlings such as etchings
Bright conductive layer.It should be noted that will be described later, crystallization indium tin composite oxide layer 7 is by noncrystalline indium tin
Crystallization layer (specific temperature crystallization layer) made of composite oxide layer 6 (A referring to Fig.1) crystallizes at a certain temperature.By
It is crystalline in crystallizing indium tin composite oxide layer 7, therefore harder.Indium tin composite oxide layer 7 is crystallized across optics
Adjustment layer 5 and hard conating 3 are supported by transparent film substrate 2.
The top layer that indium tin composite oxide layer 7 is crystallized thin films 11 is crystallized, and there is thin film shape, to contact light
The mode for learning the upper surface of adjustment layer 5 is configured at the entire upper surface of optical adjustment layer 5.
It should be noted that will be described later in detail for crystallizing indium tin composite oxide layer 7, it is based on Figure 1B
Arrow shown in such transparent film substrate 2 convergent force, have residual stress σ 1.
The material for crystallizing indium tin composite oxide layer 7 is the indium tin composite oxides (ITO) of crystalline.ITO be comprising
The composite oxides of indium (In) and tin (Sn) as essential component.Specifically, ITO contains tin oxide (SnO2) and indium oxide
(In2O3) it is used as principal component.The content ratio of tin oxide is, for example, 0.5 mass % relative to the total amount of tin oxide and indium oxide
More than, preferably 3 mass % or more, in addition, for example, 15 mass % are hereinafter, preferably 13 mass % or less.Indium oxide contains
The remainder of the proportional content ratio for the tin oxide in above-mentioned total amount.It should be noted that ITO can also be comprising removing
Addition ingredient other than principal component (essential component), specifically Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu,
Pd, W, Fe, Pb, Ni, Nb, Cr, Ga etc. add ingredient.
The thickness for crystallizing indium tin composite oxide layer 7 is, for example, 10nm or more, preferably 20nm or more, in addition, for example
For 100nm hereinafter, preferably 35nm or less.
The sheet resistance of crystallization indium tin composite oxide layer 7 be, for example, 200 Ω/ hereinafter, preferably 150 Ω/ with
Under, in addition, for example, 10 Ω/ or more.The sheet resistance of crystallization indium tin composite oxide layer 7 is surveyed by four-terminal method
It is fixed.
(manufacturing method of crystallization transparent conducting film)
Then, A and Figure 1B is illustrated the method for manufacture crystallized thin films 11 referring to Fig.1.
In this method, firstly, as shown in Figure 1A, manufacture amorphous film 1 (the 1st process), it thereafter, as shown in Figure 1B, will
Amorphous film 1 crystallizes, and manufactures crystallized thin films 11 (the 2nd process).
(the 1st process)
In the 1st process, amorphous film 1 is manufactured.
As shown in Figure 1A, amorphous film 1 successively has resist blocking and that layer 4, transparent membrane base towards upside to amorphous film 1
Material 2, hard conating 3, optical adjustment layer 5 and noncrystalline indium tin composite oxide layer 6.It is preferred that crystallized thin films 11 only include resist blocking and that
Layer 4, transparent film substrate 2, hard conating 3, optical adjustment layer 5 and noncrystalline indium tin composite oxide layer 6.
Resist blocking and that layer 4, transparent film substrate 2, hard conating 3 and optical adjustment layer 5 in amorphous film 1 shown in figure 1A
It is identical as these layer shown in Figure 1B.
Noncrystalline indium tin composite oxide layer 6 is the uncrystalline layer before the crystallization for crystallizing indium tin composite oxide layer 7.
It is relatively soft (softness) since noncrystalline indium tin composite oxide layer 6 is noncrystalline.Noncrystalline indium tin composite oxide layer 6
Material and thickness in crystallization indium tin composite oxide layer 7 it is illustrated go out it is identical.Noncrystalline indium tin composite oxide layer 6
Sheet resistance value for example more than 200 Ω/, and then be 250 Ω/ or more, and then be 300 Ω/ or more, in addition, for example
For 500 Ω/ or less.The sheet resistance of noncrystalline indium tin composite oxide layer 6 is measured by four-terminal method.
The manufacturing method of amorphous film 1 is not particularly limited, for example, firstly, preparation transparent film substrate 2, then, right
Transparent film substrate 2 configures in order hard conating 3, resist blocking and that layer 4, optical adjustment layer 5 and noncrystalline indium tin composite oxide layer 6.
Specifically, the upper and lower surface in transparent film substrate 2 is respectively coated the dilution and Antiblock compositions of hard coating combination
Dilution after being dried, is irradiated by ultraviolet light, makes hard coating combination and each self-curing of Antiblock compositions.Distinguish as a result,
In each self-forming hard conating 3 of the upper and lower surface of transparent film substrate 2 and resist blocking and that layer 4.Thereafter, by the dilute of pH effect composition
It releases the upper surface that liquid is coated on hard conating 3 to irradiate after dry by ultraviolet light, solidifies pH effect composition.Shape as a result,
At optical adjustment layer 5.
Thereafter, noncrystalline indium tin composite oxide layer is set in the upper surface of optical adjustment layer 5 for example, by sputtering method etc.
6.It should be noted that noncrystalline indium tin composite oxide layer 6 is across optical adjustment layer 5 and hard conating 3 by transparent film substrate 2
Support.It should be noted that noncrystalline indium tin composite oxide layer 6 is under zero load (specifically for without face direction
Stress) it is supported by transparent film substrate 2.
Furthermore it is possible to each layer is arranged to transparent film substrate 2 for example, by roll-to-roll (roll to roll) mode, or
Part or all of the layer can also be set by batch mode (single chip mode).
(the 2nd process)
In the 2nd process, as shown in Figure 1B, amorphous film 1 is heated at a certain temperature, keeps noncrystalline indium tin compound
Oxide skin(coating) 6 crystallizes.
Heating, which can be used such as infrared heater, baking oven, to be implemented.
Specific temperature, that is, heating temperature is, for example, 110 DEG C or more, preferably greater than 110 DEG C, more preferably 115 DEG C or more, into
One step is preferably 120 DEG C or more, and particularly preferably 125 DEG C or more, in addition, preferably 145 DEG C hereinafter, more for example less than 150 DEG C
Preferably 140 DEG C hereinafter, further preferably 135 DEG C hereinafter, particularly preferably 130 DEG C or less.Heating time is according to heating temperature
Degree to be suitable for decision, for example, 5 minutes or more, preferably 10 minutes or more, more preferably 15 minutes or more, be more preferably
20 minutes or more.Particularly preferably 25 minutes or more, in addition, for example, 5 hours hereinafter, preferably 1 hour or less, preferably 50
Minute or less, more preferably 45 minutes or less, be more preferably 40 minutes or less.
(specifically, when heating temperature is more than above-mentioned ceiling temperature, and/or when heating when heating more harsh than above-mentioned condition
Between when being more than the above-mentioned upper limit), if crystallized thin films 11 are exposed under high temperature and humidity atmosphere, cannot inhibit when shorter sometimes
It is interior to crack equivalent damage.
On the other hand, (specifically, heating temperature is lower than above-mentioned lower limit temperature when heating milder than above-mentioned condition (slow)
When, and/or heating time be less than the above-mentioned lower limit time when), sometimes cannot be reliably by noncrystalline indium tin composite oxide layer 6
It crystallizes and obtains crystallization indium tin composite oxide layer 7.It, sometimes cannot be reliably when especially heating temperature is lower than 110 DEG C
Noncrystalline indium tin composite oxide layer 6 is crystallized and reliably obtains crystallization indium tin composite oxide layer 7.In other words, exist
In 2nd process, crystallization indium tin composite oxide layer 7 is manufactured for crystallizing noncrystalline indium tin composite oxide layer 6
Minimum heating temperature be, for example, 110 DEG C.
In addition, when heating is in the range of above-mentioned condition, it can be by the difference of the residual stress described in detail below, shrinking percentage
Difference, the difference of elongation be set as desired range.
As a result, as shown in Figure 1B, 6 being crystallized of noncrystalline indium tin composite oxide layer forms crystallization indium tin composite oxygen
Compound layer 7.In this way, obtaining successively having resist blocking and that layer 4, transparent film substrate 2, hard conating 3, optical adjustment layer 5 towards upside
And the crystallized thin films 11 of crystallization indium tin composite oxide layer 7.Crystallized thin films 11 are by amorphous film 1 in specific temperature
Specific temperature crystallized thin films 11A made of lower heating.In specific temperature crystallized thin films 11A, indium tin combined oxidation is crystallized
Nitride layer 7 is that specific temperature made of crystallizing noncrystalline indium tin composite oxide layer 6 at a certain temperature crystallizes layer 7A.
Thereafter, for example, it is cooling etc. by placing, crystallized thin films 11 are cooling.Cooling temperature be usually room temperature (for example,
20~30 DEG C, specifically 25 DEG C or so or room temperature).
The crystallized thin films 11 manufactured in this way are used for purposes described below.
(purposes of transparent conducting film)
In crystallized thin films 11, glassy layer 9 shown in the dotted line as Figure 1B is adhered to knot by pressure-sensitive adhesive layer 8
The upper surface of crystallization indium tin composite oxide layer 7, so as to protect the upper surface of crystallized thin films 11.It is compound to crystallize indium tin
Oxide skin(coating) 7 is contained in crystallized thin films laminated body 10.Crystallized thin films laminated body 10 successively has resist blocking and that towards upside
Layer 4, transparent film substrate 2, hard conating 3, optical adjustment layer 5, crystallization indium tin composite oxide layer 7, pressure-sensitive adhesive layer 8 and
Glassy layer 9.
Crystallized thin films laminated body 10 is for example contained in image display device.
In addition, such image display device is for example for vehicle-mounted purposes etc..
(warming and humidifying of the heating of amorphous film, the cooling of crystallized thin films and crystallized thin films)
Then, to the crystallization indium tin composite oxygen of the cooling of heating and crystallized thin films 11 due to amorphous film 1
The contraction of the residual stress and crystallized thin films 11 of compound layer 7 and under certain tensile load by crystallized thin films 11 heating plus
Elongation when wet is described in detail.
After [1] the 1st process, the amorphous film before the 2nd process
As shown in Figure 1A, by the 1st process manufacture amorphous film 1 in, noncrystalline indium tin composite oxide layer 6 and thoroughly
The atmosphere that bright film substrate 2 is exposed is usually room temperature.Therefore, transparent film substrate 2 and noncrystalline indium tin composite oxide layer 6
Each other without shrinking and extending.Therefore, noncrystalline indium tin composite oxide layer 6 does not have residual stress.
It should be noted that the water vapor concentration under room temperature atmosphere is relatively low, for example, being 17g/m at 20 DEG C3, 25
It is 23g/m at DEG C3, at 30 DEG C be 30g/m3, therefore the range of water vapor concentration is 17g/m3~30g/m3Left and right.Therefore, exist
Under humidity (low humidity or often wet) atmosphere low in this way, substantially without to noncrystalline indium tin composite oxide layer 6 and transparent membrane
Substrate 2 affects (deterioration etc.).
The heating of amorphous film in [2] the 2nd processes
Then, in the 2nd process, by heating, transparent film substrate 2 is as shown in the arrow of Figure 1A towards face direction
Outside extends (expansion).
At the same time, heating on the way, noncrystalline indium tin composite oxide layer 6 is relatively soft (soft due to for noncrystalline
It is soft), therefore with the elongation of transparent film substrate 2, as shown in Figure 1A, (following) is extended towards face direction outside.Therefore, pass through
The heating of 2nd process, crystallization indium tin composite oxide layer 7 made of noncrystalline indium tin composite oxide layer 6 crystallizes do not have
There is residual stress.
The cooling of crystallized thin films in [3] the 2nd processes
Thereafter, crystallized thin films 11 are cooled to room temperature.In this way, as shown in the solid arrow of Figure 1B, transparent film substrate 2
It is substantially shunk on the inside of towards face direction.On the other hand, crystallization indium tin composite oxide layer 7 due to for crystalline and compare (with
Noncrystalline indium tin composite oxide layer 6 is compared) firmly, therefore not exclusively follow transparent film substrate 2.Specifically, crystallization indium
Tin composite oxide layer 7 is shunk smaller compared with the contraction of transparent film substrate 2.Therefore, in crystallization indium tin combined oxidation
Nitride layer 7 is generated towards the residual stress σ 1 on the inside of the direction of face.
Size (the specifically length L1 in Figure 1B) phase of crystallized thin films 11 (transparent film substrate 2) after cooling
Become smaller for the size (specifically, length L0 in Figure 1A) of the amorphous film 1 (transparent film substrate 2) before heating.That is,
Crystallized thin films 11 are shunk relative to amorphous film 1.For the shrinkage (L1-l0) of crystallized thin films 11, if not
The heating temperature (specific temperature) of crystalloid film 1 is high, then will increase, if the heating temperature (specific temperature) of amorphous film 1 is low,
Can then it reduce.
[4] crystallized thin films under high temperature and humidity atmosphere
Thereafter, manufactured crystallized thin films 11 are exposed to high temperature and humidity in the case where being used for above-mentioned vehicle-mounted purposes
Under atmosphere.Temperature (high temperature) is, for example, 40 DEG C or more and then is 50 DEG C or more and then is 60 DEG C or more and then is 70 DEG C or more,
On the other hand, in addition, such as less than 110 DEG C (aftermentioned minimum heating temperature), and then for 105 DEG C or less, in turn be 100 DEG C with
Under.It should be noted that not assuming the mode (purposes) of the upper limit more than above-mentioned temperature (high temperature) in an embodiment.It is wet
Spending (high humidity) is, for example, 60%RH or more, preferably 70%RH or more, in addition, for example, 90%RH is hereinafter, preferably 95%RH
Below.
As shown in the dash-dot arrows of Figure 1B, transparent film substrate 2 under above-mentioned high temperature and humidity atmosphere is exposed to towards face side
Slightly extend (extending again) outward.It should be noted that the crystallized thin films 11 being exposed under high temperature and humidity atmosphere also with
The slightly elongation of transparent film substrate 2 and occur slightly extend (extending again).
Specifically, the dash-dot arrows of B are such referring to Fig.1, the transparent film substrate 2 being exposed under high temperature and humidity atmosphere
Relative to the elongation (arrow of A referring to Fig.1) of the transparent film substrate 2 based on heating in the 2nd process, elongation (is stretched again smaller
It is long).
It should be noted that degree (the arrow of A referring to Fig.1 of the transparent film substrate 2 under high temperature and humidity atmosphere extended again
Head) smaller than the degree (dash-dot arrows of B referring to Fig.1) of the elongation of the transparent film substrate 2 based on heating in the 2nd process be
Due to less than 110 DEG C of the high temperature (the minimum heating temperature of the 2nd process) extended again.
On the other hand, crystallization indium tin composite oxide layer 7 be crystalline and it is harder, do not extend substantially, therefore crystallize
Change residual stress σ 1 possessed by indium tin composite oxide layer 7 and is slightly alleviated (stress mitigation).But above-mentioned stress mitigates
Afterwards, crystallization indium tin composite oxide layer 7 also still has residual stress σ 1 '.
In turn, it is exposed to for the crystallized thin films of such use 11 (especially transparent film substrate 2) than in the 2nd work
The vapor exposed after sequence is rigid and for the crystallized thin films 11 before such use (is 17g/m under room temperature3~30g/m3
Left and right) it (is about 300g/m at 85 DEG C, 85%RH in significantly larger amounts of vapor3).In this way, crystallized thin films 11 are due to length
Time, stress mitigate after residual stress σ 1 ', the exposure based on a large amount of vapor and their interaction, be easy
Deterioration, in the state for being easy to produce crackle equivalent damage in crystallization indium tin composite oxide layer 7.
It should be noted that vapor is directly contacted with crystallization indium tin composite oxide layer 7, but to transparent film substrate
2 for example contact transparent film substrate 2 by resist blocking and that layer 4.
It should be noted that with flexible, hard conating 3, resist blocking and that layer 4 and the pH effect of above-mentioned transparent film substrate 2
Flexible (following) occurs for layer 5.Therefore, 5 pairs of hard conating 3, resist blocking and that layer 4 and optical adjustment layer crystallization indium tin composite oxides
The not substantial influence of the effect (project and effect) of layer 7.
[5] specific temperature and the relationship of crystallization and crackle under minimum heating temperature (110 DEG C)
As described above, crystallization indium tin composite oxide layer 7 crackle mitigated by stress after residual stress σ 1 ' and be based on
Caused by the exposure of a large amount of vapor.If considering, the purposes of crystallized thin films 11 and layer are constituted, and can not be prevented based on a large amount of
Vapor exposure.Therefore, it is conceived to the reduction of the residual stress σ 1 ' after stress mitigates, each physical property below is ground
Study carefully.
(i) residual stress
Firstly, the crystallization indium tin in order to reduce the residual stress σ 1 ' after stress mitigates, after the 2nd process of reduction is rigid
The residual stress σ 1 of composite oxide layer 7.
The 2nd process for generating residual stress σ 1 includes heating process as necessary process, but crosses low land and set heating process
In heating temperature (specific temperature) when, as in above-mentioned " (the 2nd process) " in detail narration, cannot be compound by noncrystalline indium tin
Oxide skin(coating) 6 crystallizes, thus can most low land set heating temperature, i.e. minimum heating temperature is 110 DEG C.In this way, setting
The crystallized thin films 11 as obtained from crystallizing amorphous film 1 at 110 DEG C are the residual of 110 DEG C of crystallized thin films 11B
Residue stress σ 2 reduces the difference of residual stress σ 1 and minimum residual stress σ 2 as minimum residual stress.
Specifically, residual stress σ 1 and 110 DEG C of crystallization of the crystallization indium tin composite oxide layer 7 of crystallized thin films 11
The difference for changing the minimum residual stress σ 2 of the crystallization indium tin composite oxide layer 7 in film 11B is 150MPa hereinafter, preferably less than
150MPa, more preferably 145MPa or less.In addition, the difference of residual stress σ 1 and minimum residual stress σ 2 are, for example, 0MPa or more,
Preferably greater than 0MPa, more preferably 10MPa or more.
When the difference of residual stress σ 1 and minimum residual stress σ 2 are more than the above-mentioned upper limit, it cannot inhibit in high temperature and humidity atmosphere
Under, equivalent damage is cracked in crystallization indium tin composite oxide layer 7 in a relatively short period of time.
On the other hand, when the difference of residual stress σ 1 and minimum residual stress σ 2 are more than above-mentioned lower limit, crystallization indium tin is compound
Oxide skin(coating) 7 becomes crystalline made of noncrystalline indium tin composite oxide layer 6 is reliably crystallized.
The record on " evaluation method " column of residual stress based on such as embodiment of Japanese Unexamined Patent Publication 2016-179686 bulletin
And calculate, more specific measuring method and determination condition are documented in latter embodiments.
(ii) shrinking percentage
In addition, crystallized thin films 11 after cooling are relative to the noncrystalline before heating as recorded in above-mentioned [3]
Film 1 (transparent film substrate 2) is shunk, and crystallized thin films 11 have shrinking percentage SR1.If reducing shrinking percentage SR1,
Can then reduce the 2nd process recorded in above-mentioned (i) it is rigid after crystallization indium tin composite oxide layer 7 residual stress
σ 1 can reduce the residual stress σ 1 ' after stress mitigates.
But as recorded in above-mentioned [3], when the heating temperature in heating process is low, shrinking percentage SR1 can subtract
It is small, if but cross low land setting heating temperature (specific temperature), noncrystalline indium tin composite oxide layer 6 cannot be crystallized.Cause
This, sets the shrinking percentage SR2 of 110 DEG C of crystallized thin films 11B as minimum shrinkage, and reduce shrinking percentage SR1 and minimum of contraction
The difference of rate SR2.
Specifically, the minimum shrinkage SR2 of the shrinking percentage SR1 of crystallized thin films 11 and 110 DEG C of crystallized thin films 11B it
Difference is, for example, 0.05% hereinafter, preferably less than 0.05%, more preferably 0.04% or less, further preferably 0.03% or less.
In addition, the difference of shrinking percentage SR1 and minimum shrinkage SR2 are, for example, 0% or more, preferably greater than 0%, more preferably 0.001% with
Upper, more preferably 0.01% or more, further preferably 0.02% or more, particularly preferably 0.025% or more.
When the difference of shrinking percentage SR1 and minimum shrinkage SR2 are lower than the above-mentioned upper limit, be able to suppress under high temperature and humidity atmosphere,
Equivalent damage is cracked in crystallization indium tin composite oxide layer 7 in a relatively short period of time.
On the other hand, when the difference of shrinking percentage SR1 and minimum shrinkage SR2 are more than above-mentioned lower limit, indium tin composite oxygen is crystallized
Compound layer 7 becomes crystalline made of noncrystalline indium tin composite oxide layer 6 is reliably crystallized.
The detailed measuring method and determination condition of shrinking percentage are documented in latter embodiments.
(iii) crystallized thin films under tensile load when changing atmosphere for high temperature and humidity from ambient temperature and moisture, certain
Elongation
In addition, considering the elongation of the crystallization indium tin composite oxide layer 7 under certain tensile load and under high-temperature atmosphere
The relationship that the stress for the crystallization indium tin composite oxide layer 7 recorded in rate and [4] mitigates.
Crystallized thin films 11 are under certain tensile load, when atmosphere is changed from ambient temperature and moisture for high temperature and humidity, also such as
Shown in the dash-dot arrows of Figure 1B, (extending again) is extended along draw direction.Therefore, the crystallized thin films 11 after variation have elongation
Rate EP1.Moreover, in view of the record of [4], crystallizing indium tin composite oxides if the elongation EP1 of crystallized thin films 11 increases
The stress mitigation of layer 7 will increase.When stress mitigates increase, it is able to suppress and is being crystallized in a relatively short period of time under high temperature and humidity
Equivalent damage is cracked in indium tin composite oxide layer 7.Therefore, increase elongation EP1.
Moreover, the elongation of 110 DEG C of crystallized thin films 11B when setting changes atmosphere for high temperature and humidity from ambient temperature and moisture
EP2 reduces the difference of elongation EP1 and maximum elongation rate EP2 as maximum elongation rate.
Herein, elongation EP1 is to apply 20mN along its length to the crystallized thin films 11 of length 150mm, width 10mm
Certain tensile load, the atmosphere that the crystallized thin films 11 are exposed from 25 DEG C and 10%RH heating and humidify to 85 DEG C
And when 85%RH, crystallized thin films 11 along its length (draw direction) elongation (stretching) when elongation.In addition, maximum elongation
Rate EP2 is to apply 20mN along its length (draw direction) to 110 DEG C of crystallized thin films 11B of length 150mm, width 10mm
Certain tensile load, the atmosphere that 110 DEG C of crystallized thin films 11B are exposed from 25 DEG C and 10%RH heating and humidification
Elongation when to 85 DEG C and 85%RH, when 110 DEG C of crystallized thin films 11B extend (stretching) along draw direction.Elongation EP1 and
The detailed measuring method and determination condition of maximum elongation rate EP2 is recorded in embodiment.
Moreover, the difference example of the maximum elongation rate EP2 of the elongation EP1 of crystallized thin films 11 and 110 DEG C of crystallized thin films 11B
For example 0.07% hereinafter, preferably 0.04% or less, more preferably 0.03% or less.
When the difference of elongation EP1 and maximum elongation rate EP2 are the above-mentioned upper limit or less, it is able to suppress in high temperature and humidity atmosphere
Under, in a relatively short period of time crystallization indium tin composite oxide layer 7 in crack equivalent damage.
(function and effect)
Moreover, in an embodiment, in crystallized thin films 11 shown in Figure 1B (specific temperature crystallized thin films 11A)
Crystallize the residual stress σ 1 of indium tin composite oxide layer 7 and as obtained from crystallizing amorphous film 1 at 110 DEG C
The difference of the minimum residual stress σ 2 of crystallization indium tin composite oxide layer 7 in 110 DEG C of crystallized thin films 11B is small, is 150MPa
Below.
Therefore, it even if crystallized thin films 11 are exposed in high temperature and humidity atmosphere, is also able to suppress in a relatively short period of time
Crack equivalent damage.
In addition, in an embodiment, the shrinking percentage SR1 of crystallized thin films 11 (specific temperature crystallized thin films 11A) with
When the difference of the minimum shrinkage SR2 of 110 DEG C of crystallized thin films 11B is small and is 0.05% or less, it is multiple that crystallization indium tin can be reduced
Close the residual stress σ 1 of oxide skin(coating) 7.Therefore, it even if crystallized thin films 11 are exposed to high temperature and humidity atmosphere, is also able to suppress
Equivalent damage is cracked in a relatively short period of time.
In addition, atmosphere from 25 DEG C and 10%RH heating and is humidified under certain tensile load in an embodiment
(specific temperature crystallized thin films 11A) the elongation EP1 of crystallized thin films 11 when to 85 DEG C and 85%RH in certain stretching
110 DEG C of crystallized thin films 11B under load by atmosphere from 25 DEG C and 10%RH heating and when humidifying to 85 DEG C and 85%RH are most
It, can be significantly to crystallization when changing atmosphere for high temperature and humidity when the difference of big elongation EP2 is small and is 0.07% or less
Indium tin composite oxide layer 7 carries out stress mitigation.Therefore, even if crystallized thin films 11 are exposed to high temperature and humidity atmosphere, also can
It is enough to inhibit to crack equivalent damage in a relatively short period of time.
<variation>
In variation, to component same as an above-mentioned embodiment and the identical reference marks of process mark, it is omitted
Detailed description.
As shown in Figure 2 A, amorphous film 1 do not have hard conating 3 (A referring to Fig.1), optical adjustment layer 5 (A referring to Fig.1) and
Resist blocking and that layer 4 (A referring to Fig.1), and successively have transparent film substrate 2 and noncrystalline indium tin composite oxide layer 6.Amorphous thin
Film 1 preferably only includes transparent film substrate 2 and noncrystalline indium tin composite oxide layer 6.
As shown in Figure 2 B, after the 2nd process, manufacture successively has transparent film substrate 2 and crystallization indium tin combined oxidation
The crystallized thin films 11 of nitride layer 7.Crystallized thin films 11 are preferably only comprising transparent film substrate 2 and crystallization indium tin composite oxides
Layer 7.
Although it is not shown, but noncrystalline can be provided in the two sides up and down of transparent film substrate 2 in amorphous film 1
Indium tin composite oxide layer 6.Crystallization indium tin composite oxide layer 7 is can be set in crystallized thin films 11 in transparent membrane base
The two sides up and down of material 2.
Embodiment
Examples and Comparative Examples described below, more specifically the present invention will be described.It should be noted that the present invention is simultaneously
Not by any restriction of Examples and Comparative Examples.Compounding ratio (content ratio), physics value, parameter etc. used in record below
Specific numerical value can with compounding ratio recorded in above-mentioned " specific embodiment ", corresponding with them (contain 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 ") replace.In addition, part, % are quality criteria in each example.
Comparative example 1
A referring to Fig.1, firstly, preparing that there is isotropic (without birefringence) transparent film substrate 2.Specifically
For, prepare cyclic olefine resin substrate (COP film, 40 μm of thickness, Zeon Corporation system, " ZEONOR " (registrar
Mark), the birefringence 0.0001 in face) directly as transparent film substrate 2.
Then, in the upper surface of transparent film substrate 2, coating includes binder resin (carbamate system multifunctional poly- third
Olefin(e) acid ester, trade name " UNIDIC ", Dainippon Ink Chemicals's system) hard coating combination dilution, and in transparent film substrate 2
Lower surface coating contain binder resin (the multifunctional polyacrylate of carbamate system, trade name " UNIDIC ", DIC plants
Formula commercial firm system) and particle (cross-linked acrylic acid quasi-styrene system resin particle, trade name " SSX105 ", 3 μm of diameter, ponding tree
Rouge Co. Ltd. system) the dilutions of Antiblock compositions then after drying them, the two sides of transparent film substrate 2 is shone
Ultraviolet light is penetrated, hard coating combination and Antiblock compositions are solidified.Thickness 1 is formed in the upper surface of transparent film substrate 2 as a result,
μm hard conating 3, form 1 μm of thickness of resist blocking and that layer 4 in the lower surface of transparent film substrate 2.
Then, in the upper surface of hard conating 3, coating contains zirconia particles and uv curing resin (acrylic compounds tree
Rouge) pH effect composition dilution (" OPSTAR Z7412 ", JSR corporation, refractive index 1.62), it is dry at 80 DEG C
After 3 minutes, ultraviolet light is irradiated.0.1 μm of thickness of optical adjustment layer 5 is formed in the upper surface of hard conating 3 as a result,.It obtains as a result,
Laminated body comprising resist blocking and that layer 4, transparent film substrate 2, hard conating 3 and optical adjustment layer 5.
Thereafter, the noncrystalline indium tin composite oxides of thickness 25nm are formed by sputtering at the upper surface of optical adjustment layer 5
Layer 6 is used as noncrystalline indium tin composite oxide layer 6.Specifically, firstly, parallel plate-type coiling type magnetic control sputtering device
Upper installation contains indium oxide (In with the weight ratio of 70:302O3) and tin oxide (SnO2) sintered body target, side convey laminated body, side
By vacuum evacuation, it is vacuum-evacuated until the partial pressure of water becomes 5 × 10-4Until Pa.Thereafter, leading for argon gas and oxygen is adjusted
Enter amount, the noncrystalline indium tin of the upper surface formation thickness 25nm to export 12.5kW, sputter at optical adjustment layer 5 by DC is compound
Oxide skin(coating) 6.It should be noted that measuring the sheet resistance of noncrystalline indium tin composite oxide layer 6 by four-terminal method, as a result
For 340 Ω/.
Manufacture successively has resist blocking and that layer 4, transparent film substrate 2, hard conating 3, optical adjustment layer as shown in Figure 1A as a result,
5 and noncrystalline indium tin composite oxide layer 6 amorphous film 1.
Thereafter, amorphous film 1 is heated 30 minutes at 150 DEG C, thus by 6 knot of noncrystalline indium tin composite oxide layer
Crystallization, preparation crystallization indium tin composite oxide layer 7.Manufacture has resist blocking and that layer 4, transparent membrane base as shown in Figure 1B as a result,
Material 2, hard conating 3, optical adjustment layer 5 and the crystallized thin films 11 for crystallizing indium tin composite oxide layer 7.It is surveyed by four-terminal method
Surely the sheet resistance of indium tin composite oxide layer 7 is crystallized, result is 100 Ω/.
Embodiment 1 and embodiment 2
According to the record of table 1, the crystallized temperature of noncrystalline indium tin composite oxide layer 6 is changed to specific temperature, is removed
It other than this, is handled in the same manner as comparative example 1, manufactures crystallized thin films 11.
It should be noted that the crystallized thin films 11 of embodiment 2 and embodiment 4 due to crystallized temperature be 110 DEG C,
For 110 DEG C of crystallized thin films 11B.
Comparative example 2
Instead of preparing that there is birefringence with isotropic (without birefringence) transparent film substrate 2
(not having isotropic) transparent film substrate 2 is handled in the same manner as comparative example 1 in addition to this, manufactures amorphous film 1,
Then, crystallized thin films 11 are manufactured.
Specifically, to cyclic olefine resin substrate (COP film, 40 μm of thickness, Zeon Corporation system,
" ZEONOR " (registered trademark)) it is stretched, the transparent film substrate 2 that the birefringence in preparation face is 140.
Embodiment 3 and embodiment 4
According to the record of table 1, change noncrystalline indium tin composite oxide layer 6 crystallized temperature (amorphous film 1 plus
Hot temperature), it in addition to this, is handled in the same manner as comparative example 2, manufactures crystallized thin films 11.
It should be noted that the crystallized thin films 11 of embodiment 4 are due to being to crystallize amorphous film 1 at 110 DEG C
Obtained from, therefore it is equivalent to 110 DEG C of crystallized thin films 11B.
Evaluation
Following projects are evaluated.Record its result in table 1.
(residual stress σ)
By X-ray scattering method, by the lattice strain of crystallization indium tin composite oxide layer 7 find out indirectly each embodiment and
The residual stress σ 1 of the crystallization indium tin composite oxide layer 7 of each comparative example.
Using powder x-ray diffraction device (Rigaku Corporation system), in measurement 2 θ=59~62 ° of angle of scattering
Every 0.04 ° of measurement diffracted intensity in range.The accumulated time (time for exposure) of each measurement angle is set as 100 seconds.
Then, by 2 θ of the peak of gained diffraction image (peak in (622) face of indium tin composite oxides) angle and x-ray source
Wavelength X calculates the lattice spacing d of crystallization indium tin composite oxide layer 7, calculates lattice strain ε based on d.Under being utilized when calculating
State formula (1), (2).
2d sin θ=λ ... (1)
ε=(d-d0)/d0 …(2)
λ is the wavelength (=0.15418nm) of x-ray source (CuK α line), d0For the indium tin composite oxides of unstress state
Spacing of lattice (=0.15241nm).It should be noted that d0For from ICDD (joint committee, The
International Centre for Diffraction Data) database obtain value.
Angle Ψ formed by crystal plane normal to pellicular front normal shown in Fig. 3 and indium tin composite oxides is 45 °, 50 °,
55 °, 60 °, 65 °, 70 °, 77 °, 90 ° of all angles implement above-mentioned X-ray diffraction measure, the lattice for calculating each angle Ψ is answered
Become ε.It should be noted that angle Ψ formed by the crystal plane normal of pellicular front normal and indium tin composite oxides passes through with the direction TD
(direction orthogonal with the direction MD) is rotating shaft center, makes to crystallize the rotation of indium tin composite oxide layer 7 to adjust.Crystallize indium
The residual stress σ 1 in direction is by sin in the face of tin composite oxide layer 72It is straight made of the relationship mapping of Ψ and lattice strain ε
The slope of line is found out by following formula (3).
In above-mentioned formula, E is the Young's modulus (116GPa) of indium tin composite oxides, ν is Poisson's ratio (0.35).These values are
D.G.Neerinckand T.J.Vink,“Depthprofiling of thin ITO films by grazing
Incidence X-ray diffraction ", Thin Solid Films, 278 (1996), in PP 12-17. documented by
The measured value known.
For embodiment 2 and 4, residual stress is found out as minimum residual stress σ 2.
(shrinking percentage SR)
The shrinking percentage in the direction MD of the crystallized thin films 11 after rigid to the 2nd process in each embodiment and each comparative example
SR1 is evaluated.
Specifically, firstly, the amorphous film 1 of manufacture shown in figure 1A on the way is cut into width 100mm, length
100mm (test film), it is (difficult to understand using the small-sized measuring microscope STM5 of Olympus digital-code type in the every 80mm indicia in the direction MD
Woods Bath optics industry Co. Ltd. system) critically measure the direction MD length (mm).Thereafter, in crystallization recorded in table 1
Under the conditions of heated, manufacture have crystallization indium tin composite oxide layer 7 crystallized thin films 11.
Thereafter, after crystallized thin films 11 being placed to cooling under 25 DEG C (room temperature) 1 hour, crystallized thin films 11 are measured again
The direction MD length.
Then, it is based on following formula, calculates shrinking percentage SR1.
Shrinking percentage SR1 (the %)=[[side MD between the mark after the direction MD length (mm)-heating between the mark before heating
To (mm)]/heating before mark between the direction MD (mm)] × 100
In addition, calculating shrinking percentage as minimum shrinkage SR2 to embodiment 2 and embodiment 4.
(by atmosphere from 25 DEG C and 10%RH change be 85 DEG C, 85%RH when, the crystallization under certain tensile load it is thin
The elongation EP of film)
To each embodiment and each comparative example, using apparatus for thermal analysis (TMA, Co., Ltd.'s Seiko system), to certain stretching
Crystallized thin films 11 under load find out elongation when changing under 25 DEG C and 10%RH atmosphere under 85 DEG C and 85%RH atmosphere
Rate EP1.
Specifically, the crystallized thin films 11 of comparative example 1 and embodiment 1,2 (are had isotropic transparent membrane base
The crystallized thin films 11 of material 2) 150mm × 10mm is cut by the direction MD in a manner of along its length, make test film.In addition, will
The crystallized thin films 11 (crystallized thin films 11 for having the transparent film substrate 2 of birefringence) of comparative example 2 and embodiment 3,4 with
It is cut into 150mm × 10mm at 45 degree of direction mode along its length relative to the direction MD and the direction TD, makes test film.
Then, it is found out when applying certain tensile load of 20mN to length direction to test film using following formula by atmosphere
From 25 DEG C and 10%RH heating (heating speed: 1 DEG C/min) and humidification (humidification speed: 5%RH/ minutes) to 85 DEG C and 85%
The elongation EP1 of crystallized thin films 11 when RH.
Elongation (%)=elongation (mm)/150 (mm) × 100
The draw direction length (mm) -150 (mm) of crystallized thin films 11 before elongation=warming and humidifying
It should be noted that finding out elongation as maximum elongation rate EP2 about embodiment 2 and 4.
(crackle inhibits test)
By 50 μm of thickness of pressure-sensitive adhesive layers 8 (Figure 1B dotted line), by the glassy layer 9 (Figure 1B dotted line) of thickness 1.3mm
It is adhered to the upper surface of crystallization indium tin composite oxide layer 7.Production has crystallized thin films 11, pressure-sensitive adhesive layer 8 as a result,
And the crystallized thin films laminated body 10 of glassy layer 9.
Thereafter, crystallized thin films laminated body 10 is placed in 85 DEG C, taken out in the environment of 85%RH and every 120 hours, used
The presence or absence of the crackle of microscope confirmation crystallization indium tin composite oxide layer 7.
Moreover, evaluating the inhibition of the crackle of short time (240 hours) according to following benchmark.
Zero: the generation time of crackle is more than 240 hours.That is, crackle can be inhibited at 240 hours or less.
×: the generation time of crackle is 240 hours or less.
[table 1]
Claims (3)
1. a kind of crystallized thin films, which is characterized in that have transparent film substrate and crystallization indium tin composite oxide layer,
The crystallized thin films are the amorphous thin by will be provided with transparent film substrate and noncrystalline indium tin composite oxide layer
Specific temperature crystallized thin films obtained from film crystallizes at a certain temperature,
The residual stress σ 1 of crystallization indium tin composite oxide layer in the specific temperature crystallized thin films with by will be described
Crystallization indium tin composite oxide layer in 110 DEG C of crystallized thin films obtained from amorphous film crystallizes at 110 DEG C
The difference of residual stress σ 2 is 150MPa or less.
2. crystallized thin films according to claim 1, which is characterized in that
Heating of the specific temperature crystallized thin films by the amorphous film under the specific temperature, relative to described
Amorphous film is shunk,
Heating of the 110 DEG C of crystallized thin films by the amorphous film at 110 DEG C, relative to the amorphous film
It is shunk,
The difference of the shrinking percentage SR1 of the specific temperature crystallized thin films and the shrinking percentage SR2 of 110 DEG C of crystallized thin films is
0.05% or less.
3. crystallized thin films according to claim 1, which is characterized in that specific temperature crystallized thin films and described
110 DEG C of crystallized thin films are under certain tensile load from 25 DEG C and 10%RH heating and when humidifying to 85 DEG C and 85%RH,
Elongation,
The difference of the elongation EP1 of the specific temperature crystallized thin films and the elongation EP2 of 110 DEG C of crystallized thin films is
0.07% or less.
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| JP2013084542A (en) * | 2011-09-29 | 2013-05-09 | Toyobo Co Ltd | Transparent conductive film and method for producing the same |
| CN105009042A (en) * | 2013-11-27 | 2015-10-28 | Lg化学株式会社 | Conductive structure precursor, conductive structure and manufacturing method therefor |
| CN105637111A (en) * | 2014-05-20 | 2016-06-01 | 日东电工株式会社 | Transparent conductive film and method for producing same |
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| JP2002150842A (en) * | 2000-11-15 | 2002-05-24 | Kanegafuchi Chem Ind Co Ltd | Polymer film with transparent conductive film |
| JP4882262B2 (en) * | 2005-03-31 | 2012-02-22 | 凸版印刷株式会社 | Method for producing transparent conductive film laminate |
| JP6031559B2 (en) * | 2010-12-27 | 2016-11-24 | 日東電工株式会社 | Transparent conductive film and method for producing the same |
| JP2015146244A (en) * | 2014-02-03 | 2015-08-13 | 凸版印刷株式会社 | Transparent conductive film and manufacturing method thereof |
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2017
- 2017-09-27 JP JP2017186764A patent/JP2019059170A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102985585A (en) * | 2010-07-06 | 2013-03-20 | 日东电工株式会社 | Transparent conductive film and manufacturing method therefor |
| JP2013084542A (en) * | 2011-09-29 | 2013-05-09 | Toyobo Co Ltd | Transparent conductive film and method for producing the same |
| CN105009042A (en) * | 2013-11-27 | 2015-10-28 | Lg化学株式会社 | Conductive structure precursor, conductive structure and manufacturing method therefor |
| CN105637111A (en) * | 2014-05-20 | 2016-06-01 | 日东电工株式会社 | Transparent conductive film and method for producing same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115315758A (en) * | 2020-03-19 | 2022-11-08 | 日东电工株式会社 | Transparent conductive film |
| CN115315758B (en) * | 2020-03-19 | 2024-03-19 | 日东电工株式会社 | Transparent conductive film |
Also Published As
| Publication number | Publication date |
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| TW201916064A (en) | 2019-04-16 |
| KR20190036475A (en) | 2019-04-04 |
| JP2019059170A (en) | 2019-04-18 |
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