CN102433532B - Thin film formation vapour deposition material, the thin-film sheet possessing this thin film and laminate - Google Patents
Thin film formation vapour deposition material, the thin-film sheet possessing this thin film and laminate Download PDFInfo
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- CN102433532B CN102433532B CN201110299927.6A CN201110299927A CN102433532B CN 102433532 B CN102433532 B CN 102433532B CN 201110299927 A CN201110299927 A CN 201110299927A CN 102433532 B CN102433532 B CN 102433532B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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Abstract
The present invention provides the vapour deposition material of the thin film suitably forming the transparency and gas barrier property excellence and possesses thin-film sheet and the laminate of this thin film.The vapour deposition material of the present invention is mixing the first oxide powder and the vapour deposition material that makes of the second oxide powder, it is characterized in that, above-mentioned first oxide powder is MgO powder, first oxide purity of the first oxide powder is more than 98%, above-mentioned second oxide powder is the mixed-powder of CaO and ZnO, second oxide purity of the second oxide powder is more than 98%, vapour deposition material is made up of the granule containing the first oxide powder and the second oxide powder, the first oxide and the mol ratio of the second oxide in vapour deposition material are 5～90: 95～10, and the basicity of granule is more than 0.1.
Description
Technical field
The present invention relates to suitably form the vapour deposition material of the thin film of the transparency and gas barrier property excellence and possess
The thin-film sheet of this thin film and laminate.More particularly, to being used for forming these all excellents,
Particularly it is suitable as the choke material of liquid crystal display, organic el display or solar module etc.
The vapour deposition material of thin film and possess thin-film sheet and the laminate of this thin film.
Background technology
The machines such as liquid crystal display, organic el display or solaode the most not moisture-proof, owing to inhaling
Wet make its characteristic rapid degradation, it is therefore necessary to equipment has highly moistureproof, i.e. has anti-block or steam
Parts Deng the gas barrier property passed through or invade.
Such as, in the example of solaode, with the sensitive surface opposition side of solar module
The back side is provided with backboard.This backboard typically on base material by have highly moistureproof choke material and protection it
Parts etc. constitute.
As the backboard of such composition solar module, such as, disclose and pass through high-strength heat-resistant
Property against weather resin sandwiches moisture resistance metal forming, and then arrange vitreous vapour deposition in one side thin
The back-protective of the solar module of film is with sheet material (such as, referenced patent document 1).
In this sheet material, use the metal formings such as aluminium foil, zinc-plated iron foil, tin plating iron foil as choke material.Separately
Outward, disclose the solaode of high moisture-proofing film and high weatherability film laminating integration is covered
Lid material is for the solaode (such as, referenced patent document 2) of rear side guard block.This sun
The high moisture-proofing film use in material can be covered at polyethylene terephthalate (PET) thin film etc. by battery
On base film by chemical gaseous phase deposition (CVD), physical vapour deposition (PVD) (PVD) method etc. formed by
The moisture barrier films that the coated film of the inorganic oxide such as silicon dioxide, aluminium oxide is constituted is as choke material.It addition,
Disclose the light possessing the barrier layer being made up of plastic sheeting or plastic composite presenting inorganic oxide layer
Raw photovoltaic module (such as, referenced patent document 3).In this inorganic oxide layer, aluminium oxide or two
Silicon oxide uses as its coating material.
Patent documentation 1: Japanese Patent Publication 2-44995 publication (claims of utility model registration and
41st～44 row on five hurdles)
Patent documentation 2: Japanese Unexamined Patent Publication 2000-174296 publication (claim 1, claim 7 and [0019]
Section)
Patent documentation 3: Japanese Unexamined Patent Application Publication 2002-520820 publication (claim 1 and [0019] section)
But, the back-protective sheet material shown in above-mentioned patent documentation 1 is owing to using the gold such as aluminium foil
Genus paper tinsel is as choke material, if this sheet material is applied to the backboard of solar module, it is likely that
Proof voltage reduces, current leakage.If it addition, the thickness of the sheet material metal forming of use metal forming is
Below 20 μm, then the pin hole produced between thermostability against weather resin and metal forming increases, choke
Property significantly reduces.On the other hand, if increasing the thickness of metal forming, then the problem that manufacturing cost improves is produced.
It addition, if the silicon dioxide used in above-mentioned patent documentation 2 and patent documentation 3, aluminium oxide etc.
In the case of inorganic oxide, in order to obtain high-gas resistance must assure that thickness at more than 100nm, even if
So can not assert that gas barrier property is abundant.
Summary of the invention
It is an object of the invention to, it is provided that suitably form the transparency and the excellent thin film of gas barrier property, and in an atmosphere
The vapour deposition material of excellent storage stability.
Another object of the present invention is to, it is provided that possess the transparency and the thin-film sheet of the excellent thin film of gas barrier property and
Laminate.
A first aspect of the present invention is vapour deposition material, mix the first oxide powder and the second oxide powder and
Make, it is characterised in that above-mentioned first oxide powder is MgO powder, the of this first oxide powder
Monoxide purity is more than 98%, and above-mentioned second oxide powder is the mixed-powder of CaO and ZnO, should
Second oxide purity of the second oxide powder is more than 98%, and vapour deposition material is by containing the first oxide
The granule of powder and the second oxide powder is constituted, the first oxide in vapour deposition material and the second oxide
Mol ratio be 5～90:95～10, and the basicity of granule is more than 0.1.
A second aspect of the present invention is invention based on first aspect, it is characterised in that further, the first oxygen
The mean diameter of compound powder is 0.1～10 μm, and the mean diameter of the second oxide powder is 0.1～10 μm.
As it is shown in figure 1, a third aspect of the present invention is thin-film sheet 10, by will be based on first or second party
The vapour deposition material in face is used as the vacuum film formation of target, is formed and comprise the first oxygen on the first base film 11
The sull 12 of the metallic element B contained by metal element A that the Chemistry and Physics Institute contains and the second oxide, by upper
State the content ratio of the whole metallic elements in thin film 12 when being set to 100 moles of %, containing of metal element A
Ratio is 5～90 moles of %, and the content ratio of metallic element B is 95～10 moles of %.
A fourth aspect of the present invention is invention based on the third aspect, it is characterised in that further, and vacuum becomes
Embrane method is e-beam evaporation, ion plating method, reactive plasma sedimentation, electrical resistance heating or sensing
One in heating.
As it is shown in figure 1, a fifth aspect of the present invention is laminate 20, based on the 3rd or fourth aspect
The thin film 12 of thin-film sheet 10 forms side and is laminated the second base film 14 is formed by adhesive linkage 13.
In the vapour deposition material of a first aspect of the present invention, the first oxide powder is MgO powder, and this is years old
First oxide purity of monoxide powder is more than 98%, above-mentioned second oxide powder be CaO and
The mixed-powder of ZnO, the second oxide purity of this second oxide powder is more than 98%, vapour deposition
Material is made up of the granule containing the first oxide powder and the second oxide powder, first in vapour deposition material
The mol ratio of oxide and the second oxide is 5～90:95～10, and the basicity of granule is more than 0.1, thus can
To form the thin film that gas barrier property is greatly improved compared with existing choke material.Further, vapour deposition material is at air
In excellent storage stability.
In the vapour deposition material of a second aspect of the present invention, the mean diameter of the first oxide powder is
0.1～10 μm, and the mean diameter of the second oxide powder is 0.1～10 μm, such that it is able to form vapour deposition
The vapor-deposited film that efficiency is good and dense, therefore can maintain high-gas resistance stabilizing it.
In the thin-film sheet of a third aspect of the present invention, the metal contained by the first oxide will be comprised by possessing
The content ratio of the whole metallic elements in the thin film of the metallic element B contained by elements A and the second oxide sets
When being 100 moles of %, the content ratio of metal element A is 5～90 moles of %, metallic element B containing than
Example is the thin film of 95～10 moles of %, has the transparency and the gas barrier property of excellence.
In the laminate of a fifth aspect of the present invention, take thin-film sheet thin the 3rd or fourth aspect
Film is formed side and is laminated the structure of the second base film further by adhesive linkage.Thus, the second base film can
With protective film, high-gas resistance stabilizing it therefore can be maintained.
Accompanying drawing explanation
Fig. 1 is the cutting of laminar structure briefly expressing the thin-film sheet of embodiment of the present invention and laminate
Face figure.
Fig. 2 is the figure of the cross section structure briefly expressing existing thin-film sheet.
Fig. 3 is the figure of the cross section structure of the thin-film sheet briefly expressing embodiment of the present invention.
Fig. 4 is the photo of the evaluation result of the storage stability representing vapour deposition material.
Symbol description
10: thin-film sheet
11: the first base films
12: thin film
13: adhesive linkage
14: the second base films
20: laminate
Detailed description of the invention
Hereinafter, with reference to the accompanying drawings of embodiments of the present invention.The vapour deposition material of the present invention can be suitable for
Formation for thin film.It is saturating that the thin film using this vapour deposition material to be formed plays anti-block or steam etc.
The effect of the choke material crossed or invade.
This vapour deposition material mixes the first oxide powder and the second oxide powder and makes.For making
First oxide powder of vapour deposition material is MgO powder, the first oxidation of this first oxide powder
Thing purity is more than 98%, preferably more than 98.4%, and the second oxide powder is CaO's and ZnO
Mixed-powder, the second oxide purity of this second oxide powder is more than 98%, preferably 99.5%
Above.Here, the first oxide purity of the first oxide powder is defined to more than 98%, it is because
During less than 98%, due to impurity, crystallinity deteriorates, and result barrier properties reduces.Here, aoxidize second
Second oxide purity of thing powder is defined to more than 98%, ties due to impurity when being because less than 98%
Crystalline substance deteriorates, and result barrier properties reduces.Further, the powder purity in this specification passes through spectrum analysis
Method (inductively coupled plasma apparatus for analyzing luminosity: Japan ジ ャ レ Le ア ッ シ ュ ICAP-88)
Measure.
It addition, the mean diameter of the first oxide powder that this vapour deposition material contains is 0.1～10 μm, and
The mean diameter of the second oxide powder is 0.1～10 μm, the first oxide and second in vapour deposition material
The mol ratio of oxide is 5～90:95～10.And, the basicity of granule is more than 0.1.By with regulation
Ratio contains the first oxide powder and second oxide powder of such miniaturization, can make high-gas resistance
It is apparent in and uses in the film that this vapour deposition material is formed.
Its technical reason is as follows: generally use (1) only not contain second containing the first oxide powder
The vapour deposition material of oxide powder, (2) only do not contain the first oxide powder containing the second oxide powder
Vapour deposition material, (3) contain the first oxide powder and the second oxide powder simultaneously but first oxidation
The first oxide powder and is contained in vapour deposition material or (4) that the content ratio of thing powder is few simultaneously
Dioxide powder but in the case of the few vapour deposition material of the content ratio of the second oxide powder, such as figure
Thin-film sheet 30 shown in 2, the sull 32 being formed on the first base film 11 becomes column
The structure that brilliant crystallization is assembled abreast relative to the infiltration direction of gas.The gas molecules such as steam due to
Advance in interface along the crystal boundary assembled abreast, the structure that the crystallization at above-mentioned column crystal is assembled abreast
Thin film 32 in block low.On the other hand, when using the first oxidation containing miniaturization with regulation ratio
During the vapour deposition material of thing powder or the second oxide powder, as it is shown on figure 3, for being formed at the first base
Sull 12 on material thin film 11, the column crystal formed when using the vapour deposition material of single composition
A part defeated and dispersed, become the fine and close fine structure close to noncrystalline state.In the cause close to noncrystalline state
In close fine structure, the gas molecule such as steam needs to move at labyrinth-like middle and long distance, therefore upper
Stating the thin film 12 of the fine and close fine structure close to noncrystalline state, block is improved.So, presumption
It is that non-columnar is brilliant by crystalline texture, and film forming is the structure passing through or invading being suitable for preventing moisture etc.,
Gas barrier property improves.If it addition, be additionally considered that the first oxide powder contained and the second oxide powder all by
Miniaturization, then make film pass through vapour deposition process when growing up, can be with few electron beam or plasma
Amount carrys out film forming, therefore can form the film of densification, and thus gas barrier property is improved.Here, vapour deposition
The mean diameter limit of both the first oxide powder contained in material, i.e. granule and the second oxide powder
Be set to above-mentioned scope be because respective mean diameter less than lower limit time, in the manufacture work of vapour deposition material
In sequence, the cohesion of powder is notable, hinders uniformly mixing.If additionally, using mean diameter less than lower limit
Powder, then tend to be difficult to obtain the film of excellent in te pins of durability.If speculated this is because by mean diameter
The least powder is used for raw material, can get denser membrane structure, but then, single crystal boundary
Specific surface area increases, and damaging that the steam being diffused in film causes produces bigger impact.On the other hand,
If respective mean diameter exceedes higher limit, then cannot fully obtain helping to improve doubting of gas barrier property
Effect like solid solution.Wherein, the mean diameter of particularly preferred first oxide powder is 0.1～10 μm,
The mean diameter of the second oxide powder is 0.1～10 μm.Further, in this manual, mean diameter is
According to laser diffraction and scattering method (micro-track method), use Ji Zhuan society system (FRA type),
Using sodium hexameta phosphate as dispersant, a minute is set as being measured for 30 seconds, and will measure
The value equalization of three times and obtain.
It addition, the mol ratio of the first oxide contained in vapour deposition material and the second oxide is limited to
Above-mentioned scope be because when the first oxide mol ratio less than 5 or second the mol ratio of oxide be less than
When 10, the content ratio of the first oxide powder or the second oxide powder is very few, close to single composition,
Thus the structure that the crystallization easily becoming column crystal is assembled abreast relative to gas infiltration direction, it is impossible to shape
Become the thin film of the fine structure with densification.Wherein, the first oxide in vapour deposition material and the second oxygen
The mol ratio of compound is preferably 60～90:40～10.Additionally, the CaO that the second oxide comprises is owing to passing through
H in air2O or CO2Carry out following formula (1) or the reaction of formula (2), if therefore making it contain
CaO, then, when preserving in an atmosphere after manufacturing, have the tendency that the grain shape of vapour deposition material is defeated and dispersed.
CaO+CO2→CaCO3 (1)
CaO+H2O→Ca(OH)2 (2)
Therefore, the vapour deposition material of CaO powder manufacture is used to need after fabrication to be saved in vacuum bag or exsiccator
In, during even if under reduced pressure preserving, CaO also comprises a little moisture, thus makes film property deteriorate.This
Outward, in thin-film sheet after its formation, become the main cause making steam gas barrier property reduce.The opposing party
Face, the vapour deposition material of the present invention is by comprising the first oxide and the second oxidation with the ratio of above-mentioned scope
Thing, further comprises ZnO as the second oxide in addition to CaO, can suppress above-mentioned formula (1)
Or the reaction that the CaO shown in formula (2) is in an atmosphere, thus obtain vapour deposition material guarantor in an atmosphere
Deposit stability.In order to improve storage stability, the ZnO comprised as the second oxide in vapour deposition material
Mol ratio in whole vapour deposition materials is preferably at least more than 5, particularly preferably 10～20.
And then, the basicity of granule being defined as 0.1 and is above because when less than 0.1, thin film is the most variable
The part becoming column crystal is defeated and dispersed and fine and close fine structure close to noncrystalline state.It is somebody's turn to do " basicity " by gloomy
Forever it is good for inferior proposition, such as, records (K.Morinaga, H.Yoshida And H.Takebe:J.Am at him
Cerm.Soc., 77,3113 (1994)) the middle basicity using formula as follows to carry out regulation glass powder.Its
Take passages as follows.Its extracts is as follows.
" oxide MiThe M of OiBond strength between-O is as gravitation A between cation-oxonium ioniBy following formula
Obtain.
Ai=Zi·Z02-/(ri+r02-)2=Zi·2/(ri+1.40)2
Zi: the valence mumber of cation, oxonium ion is 2
ri: the ionic radius of cationOxonium ion is
By this AiB reciprocali(1/Ai) as single component oxide MiThe oxygen supply ability of O.
Bi≡1/Ai
By this BiIt is normalized to BCaO=1, BSiO2=0, then give the B of each single component oxidei-index.
B by this each compositioni-index expands multicomponent system to by cation fraction, then can calculate any group
The B-index (=basicity) of the molten mass of the glass oxide become.B=∑ ni·Bi
ni: cation fraction
The basicity being specified that represents oxygen supply ability as described above, is worth the biggest more easy for oxygen supply, holds
Easily cause giving and accepting of the oxygen with other metal-oxide.”
In the present invention, for the basicity index of glass powder, carry out by making glass replace oxide
Explain, the basicity of oxide mixture is arranged for easily becoming the densification close to noncrystalline state in the film
The index of fine structure.It is melted concept in the case of glass, but in the present invention, with film forming
Time produce glass formed mechanism be basic.Ionic condition is become, unit from the element of vapour deposition material distillation
Element is piled up with nonequilibrium state on substrate.The basicity of the granule obtained now by above formula be 0.1 with
On, then film is grown up with glassy (amorphous), and element fitly arranges with the finest and close state.
Use the thin film that the vapour deposition material of the present invention is formed owing to having high-gas resistance, constitute too except having
Sun can battery backboard the choke materials such as moisture barrier films purposes outside, it is also possible to suitably with for liquid crystal
Show the choke material of device, organic el display or illumination organic el display etc..It addition, this thin film by
In having the transparency that transmitance is 85%～95% degree, it is also adaptable as requiring high-gas resistance and wanting
Ask the sensitive surface side of the parts through light, such as solaode or the resistance of the image vision side etc. of display
Gas material etc..
Then, the manufacture of the vapour deposition material of the present invention is described with situation about being made by sintering process for representative
Method.First, using purity more than 98% high purity powdered form as the first oxide powder, as second
Purity more than 98% high purity powdered form of oxide powder, binding agent and organic solvent mixing, prepare concentration
It it is the slurry of 30～75 mass %.Preferably prepare the slurry of 40～65 mass %.And, the first oxide
Powder and the second oxide powder are with the first oxide in the vapour deposition material after manufacturing and the second oxidation
The mol ratio of thing meets the mode of above-mentioned scope and is adjusted and mixes.The concentration of slurry is defined to 30～75
If quality % is because more than 75 mass %, then it is non-aqueous system due to above-mentioned slurry, exists and be difficult to
The problem of stable mixing granulation, if less than 30 mass %, then cannot obtain the densification with uniform formation
Sintered body.Further, since the average particle of the first oxide powder contained by vapour deposition material after Zhi Zaoing
The mean diameter of footpath and the second oxide powder is adjusted in above-mentioned scope, the first oxidation therefore used
The mean diameter of thing powder and the mean diameter of the second oxide powder are preferably the first oxide powder and exist
In the range of 0.1～10 μm, the second oxide powder is in the range of 0.1～10 μm.
Binding agent is preferably used Polyethylene Glycol, polyvinyl butyral resin etc., organic solvent be preferably used ethanol,
Propanol etc..Binding agent preferably adds 0.2～5.0 mass %.
It addition, high purity powdered form and binding agent and the wet mixed of organic solvent, particularly high purity powdered form
Carried out by wet ball mill or mixer grinder with the wet mixed of the organic solvent as disperse medium.
In wet ball mill, use ZrO2During the ball made, use multiple ZrO of diameter 5～10mm2The ball of system
Wet mixed 8～24 hours, preferably wet mixed 20～24 hours.ZrO2The diameter of the ball of system is defined to
5～10mm are because, less than undercompounding during 5mm, there is the bad of impurity increase during more than 10mm
Problem.It addition, even if incorporation time is because long-time mixing continuously for up to 24 hours, impurity produces
Obtain the most little.
In mixer grinder, use the ZrO of diameter 1～3mm2System ball wet mixed 0.5～1 hour.
ZrO2If the diameter of the ball of system is defined to 1～3mm and is because less than 1mm, undercompounding, if exceeding
Then there is the trouble that impurity increases in 3mm.If it addition, incorporation time shorten to grow 1 hour most be because super
Spending 1 hour, be not only the mixing of raw material, ball also wears out itself, can become the reason producing impurity,
And only need within 1 hour, just can be sufficiently mixed.
Then be spray-dried above-mentioned slurry obtaining mean diameter is 50～250 μm, preferably 50～200 μm mixed
Close prilling powder.This prilling powder is put in the mould of regulation and shape with authorized pressure.Above-mentioned spray dried
The dry spray dryer that is preferably used is carried out, it is stipulated that mould use uniaxial pressing device or isostatic cool pressing (CIP:
Cold Isostatic Press) forming device.In uniaxial pressing device, prilling powder is made to exist
750～2000kg/cm2(73.55～196.1MPa), preferably 1000～1500kg/cm2(98.1～147.1MPa)
Pressure under single shaft press molding, in CIP forming device, make prilling powder 1000～3000kg/cm2
(98.1～294.2MPa), preferably 1500～2000kg/cm2Under the pressure of (147.1～196.1MPa)
CIP shapes.Pressure limit is scheduled on above-mentioned scope be because improve formed body density while prevent sintering
After deformation and be made without post-treatment.
And then, with set point of temperature sintered shaped body.Sintering is in air, noble gas, vacuum or reduction
In gas atmosphere, carry out more than 1000 DEG C, at a temperature of preferably 1200～1400 DEG C 1～10 hour, excellent
Choosing carries out 2～5 hours.Above-mentioned sintering is under atmospheric pressure carried out, but carries out such as hot pressing (HP) sintering or heat
When isostatic pressed (HIP:Hot Isostatic Press) sinters such pressure sintering, preferably noble gas,
In vacuum or reducing gas atmosphere, more than 1000 DEG C at a temperature of carry out 1～5 hour.
Then, thin-film sheet and laminate to the present invention illustrate together with its manufacture method.As
Shown in Fig. 1, the thin-film sheet 10 of the present invention has the first base film 11 and above-mentioned gas phase is preferably used
The thin film 12 of the present invention that deposition material is formed.And, the laminate 20 of the present invention has above-mentioned and sends out
Bright thin-film sheet 10 and this thin-film sheet 10 thin film formed side by adhesive linkage 13 bonding second
Base film 14.
First base film 11 and the second base film 14 preferably have the long high-temperature high-humidity of ability
The mechanical strength of environmental test and against weather etc..For example, it is possible to enumerate polyethylene terephthalate
Ester (PET), Merlon, polymethyl methacrylate, polyacrylate, poly-naphthalenedicarboxylic acid second two
Alcohol ester (PEN), polyarylate, polyether sulfone, triacetyl cellulose (TAC), cyclic olefin (being total to)
The resin films such as polymer.These resin films can also coordinate as required fire retardant, antioxidant,
UV absorbent, antistatic agent etc..The thickness of the first base film 11 and the second base film 14 is excellent
Select 5～300 μm, more preferably 10～150 μm.
The vapour deposition material that the invention described above is preferably used on this first base film 11 is formed as resistance
The thin film 12 of gas material.When the content ratio of the whole metallic elements in thin film 12 is set to 100 moles of %,
The content ratio of metal element A contained in the first oxide is 5～90 moles of %, in the second oxide
The content ratio of contained metallic element B is 95～10 moles of %.Metal element A in thin film 12, B
Content ratio when above-mentioned scope is outer, the crystalline state of each oxide respectively becomes preferentially, and generation cannot
Obtain the bad problem of the fine and close fine structure of amorphous.Wherein, preferably metal element A containing than
Example is 60～90 moles of %, and the content ratio of metallic element B is 40～10 moles of %.The thickness of thin film 12
Preferably in the range of 10～200nm.When less than lower limit, be difficult to obtain as choke material is abundant
Gas barrier property, additionally the durability of film easily reduces.On the other hand, when exceeding higher limit, waste material,
And the cracking that the external force such as bending are brought it is easily generated due to thickening effect.Here, the thickness of thin film 12 is special
Preferably in the range of 20～100nm.As the forming method of the thin film 12 using vapour deposition material, excellent
Select e-beam evaporation (Electron Beam Evaporation Method, hereinafter referred to as EB), ion
Plating method, reactive plasma sedimentation (Reactive Plasma Deposition Method, become below
For RPD), the vacuum film formation such as electrical resistance heating or induction heating.
It addition, not shown in Fig. 1 but it also may in order to improve and thin film on the first base film 11
The dhering strength of 12 is arranged as required to be made up of acrylic acid multielement alcohol ester, isocyanates, silane coupler
Priming paint overlay, or implemented to use the surface of plasma etc. to process before vapour deposition operation.
On the other hand, when thin film 12 surface formed is exposed, when processing sheet material, the table of film
Face produces scar or friction, then gas barrier property is produced considerable influence.Therefore, thin film 12 is preferably provided with
The gas barrier property tunicle (not shown) etc. on protective film 12 surface.This gas barrier property tunicle can such as will have
The silicon compound of alkoxyl, titanium compound, zirconia compound, tin compound or its hydrolysate and have
After the solution that the water soluble polymer of hydroxyl mixes is coated on thin film 12 surface, be thermally dried and
Formed.This gas barrier property tunicle not only acts as the effect of the thin layer of thin film 12, also has and improves gas barrier property
Effect.
The thin-film sheet 10 of the present invention so formed is such as at temperature 20 DEG C, relative humidity 50%RH
Under conditions of place after 1 hour, the water measured under conditions of temperature 40 DEG C, relative humidity 90%RH
Vapor transmission rates S shows 0.3g/m2Below it.It addition, at temperature 20 DEG C, relative humidity 50%RH
Under conditions of place after 1 hour, put further under conditions of temperature 85 DEG C, relative humidity 90%RH
Put 100 hours, when the moisture-vapor transmission measured under conditions of identical with above-mentioned condition afterwards is set to T,
Moisture-vapor transmission T-phase shows less than 200% for the rate of change (T/S × 100) of moisture-vapor transmission S.
That is, this thin film 10 has the highest and time through the little gas barrier property of the deterioration that brings.
And then, in the laminate 20 of the present invention, at the thin film of the thin-film sheet 10 of the invention described above
Being formed on side, i.e. thin film 12 or form adhesive linkage 13 on above-mentioned gas barrier property tunicle, this adhesive linkage 13 plays
It is formed with the first base film 11 of thin film 12 and the work of the bonding agent of the second base film 14 for bonding
With.Therefore, it can enumerate needs adhesive strength will not deteriorate through for a long time, does not produce delamination etc. and not
The such as polyurethane series, Polyester of condition, polyester-polyurethane system, polycarbonate-based, the polycyclic such as can turn yellow
Oxygen-amine system, hot melt system bonding agent etc..For the laminating method of adhesive linkage 13, dry lamination can be passed through
The known method such as method is laminated.
By second base film 14 bonding on this adhesive linkage 13 and bond, complete laminate 20.
Further, as it is shown in figure 1, thin film 12 and adhesive linkage 13 need not be limited to each laminating layer respectively, also
Can by thin film 12 and adhesive linkage 13 alternatively laminated or by thin film 12, above-mentioned gas barrier property tunicle etc. its
His parts and adhesive linkage 13 alternately or are arbitrarily laminated into the multilamellar of 2～10 layers.Thus, it is possible to carry further
High-gas resistance and against weather.
This laminate 20 is suitable for being utilized as the backboard of solar module, liquid crystal display or organic
The purposes such as EL display or illumination organic el display.
[embodiment]
Then, examples and comparative examples of the present invention are described in detail.
<embodiment 1>
First, the wet mixed carried out by ball mill with regulation ratio mix the first oxide powder,
Dioxide powder, binding agent and organic solvent, prepare the slurry that concentration is 40 mass %.Now,
First oxide powder use mean diameter be 0.9 μm, purity be the MgO of high purity powder of 99.7%,
Second oxide powder use mean diameter be 0.6 μm, purity be 99.8% high-purity C aO powder and
Mean diameter be 0.8 μm, purity be the mixed-powder of the high-purity C aO powder of 99.8%, binding agent makes
With polyvinyl butyral resin, organic solvent uses ethanol.It addition, MgO powder and above-mentioned mixed-powder
It is 5 moles of %, CaO and ZnO that combined amount is adjusted in the vapour deposition material after formation contained MgO
It is respectively 90 moles of % and 5 moles of %.
Then, using spray dryer to be spray-dried in the slurry of preparation, obtaining mean diameter is
After the mixing granulation powder of 200 μm, this prilling powder is put in the mould of regulation and filled by uniaxial pressing
Put carry out stamping.Make the formed body obtained in air atmosphere, at a temperature of 1300 DEG C, sinter 5 little
Time, obtain vapour deposition material.MgO powder, CaO powder and the ZnO contained by vapour deposition material obtained
The mean diameter of powder, the content of MgO, CaO, ZnO contained in vapour deposition material and the alkali of granule
Degree represents in the following table 1.
<embodiment 2>
The combined amount of MgO powder and above-mentioned mixed-powder is adjusted to institute in the vapour deposition material after formation
The MgO contained is that 30 moles of %, CaO and ZnO are respectively 50 moles of % and 20 moles of %, except this it
Obtain vapour deposition material similarly to Example 1 outward.The MgO powder contained by vapour deposition material that obtains,
CaO powder and the mean diameter of ZnO powder, MgO, CaO, ZnO contained in vapour deposition material
Content and the basicity of granule represent in the following table 1.
<embodiment 3>
The combined amount of MgO powder and above-mentioned mixed-powder is adjusted to institute in the vapour deposition material after formation
The MgO contained is that 50 moles of %, CaO and ZnO are respectively 30 moles of % and 20 moles of %, except this it
Obtain vapour deposition material similarly to Example 1 outward.The MgO powder contained by vapour deposition material that obtains,
CaO powder and the mean diameter of ZnO powder, MgO, CaO, ZnO contained in vapour deposition material
Content and the basicity of granule represent in the following table 1.
<embodiment 4>
The combined amount of MgO powder and above-mentioned mixed-powder is adjusted to institute in the vapour deposition material after formation
The MgO contained is that 60 moles of %, CaO and ZnO are respectively 20 moles of % and 20 moles of %, except this it
Obtain vapour deposition material similarly to Example 1 outward.The MgO powder contained by vapour deposition material that obtains,
CaO powder and the mean diameter of ZnO powder, MgO, CaO, ZnO contained in vapour deposition material
Content and the basicity of granule represent in the following table 1.
<embodiment 5>
The combined amount of MgO powder and above-mentioned mixed-powder is adjusted to institute in the vapour deposition material after formation
The MgO contained is that 70 moles of %, CaO and ZnO are respectively 20 moles of % and 10 moles of %, except this it
Obtain vapour deposition material similarly to Example 1 outward.The MgO powder contained by vapour deposition material that obtains,
CaO powder and the mean diameter of ZnO powder, MgO, CaO, ZnO contained in vapour deposition material
Content and the basicity of granule represent in the following table 1.
<embodiment 6>
The combined amount of MgO powder and above-mentioned mixed-powder is adjusted to institute in the vapour deposition material after formation
The MgO contained is that 70 moles of %, CaO and ZnO are respectively 10 moles of % and 20 moles of %, except this it
Obtain vapour deposition material similarly to Example 1 outward.The MgO powder contained by vapour deposition material that obtains,
CaO powder and the mean diameter of ZnO powder, MgO, CaO, ZnO contained in vapour deposition material
Content and the basicity of granule represent in the following table 1.
<embodiment 7>
The combined amount of MgO powder and above-mentioned mixed-powder is adjusted to institute in the vapour deposition material after formation
The MgO contained is that 80 moles of %, CaO and ZnO are respectively 10 moles of %, in addition with embodiment 1
Similarly obtain vapour deposition material.The MgO powder contained by vapour deposition material that obtains, CaO powder and
The mean diameter of ZnO powder, the content of MgO, CaO, ZnO contained in vapour deposition material and granule
Basicity represent in the following table 1.
<embodiment 8>
The combined amount of MgO powder and above-mentioned mixed-powder is adjusted to institute in the vapour deposition material after formation
The MgO contained is that 90 moles of %, CaO and ZnO are respectively 5 moles of %, in addition with embodiment 1
Similarly obtain vapour deposition material.The MgO powder contained by vapour deposition material that obtains, CaO powder and
The mean diameter of ZnO powder, the content of MgO, CaO, ZnO contained in vapour deposition material and granule
Basicity represent in the following table 1.
<embodiment 9>
Vapour deposition material is obtained under conditions of similarly to Example 2.Contained by the vapour deposition material obtained
The mean diameter of MgO powder, CaO powder and ZnO powder, MgO contained in vapour deposition material,
The content of CaO, ZnO and the basicity of granule represent in the following table 1.
<embodiment 10>
Vapour deposition material is obtained under conditions of similarly to Example 3.Contained by the vapour deposition material obtained
The mean diameter of MgO powder, CaO powder and ZnO powder, MgO contained in vapour deposition material,
The content of CaO, ZnO and the basicity of granule represent in the following table 1.
<embodiment 11>
Vapour deposition material is obtained under conditions of similarly to Example 2.Contained by the vapour deposition material obtained
The mean diameter of MgO powder, CaO powder and ZnO powder, MgO contained in vapour deposition material,
The content of CaO, ZnO and the basicity of granule represent in the following table 1.
<embodiment 12>
Vapour deposition material is obtained under conditions of similarly to Example 3.Contained by the vapour deposition material obtained
The mean diameter of MgO powder, CaO powder and ZnO powder, MgO contained in vapour deposition material,
The content of CaO, ZnO and the basicity of granule represent in the following table 1.
<embodiment 13>
Vapour deposition material is obtained under conditions of similarly to Example 2.Contained by the vapour deposition material obtained
The mean diameter of MgO powder, CaO powder and ZnO powder, MgO contained in vapour deposition material,
The content of CaO, ZnO and the basicity of granule represent in the following table 1.
<embodiment 14>
Vapour deposition material is obtained under conditions of similarly to Example 2.Contained by the vapour deposition material obtained
The mean diameter of MgO powder, CaO powder and ZnO powder, MgO contained in vapour deposition material,
The content of CaO, ZnO and the basicity of granule represent in the following table 1.
<embodiment 15>
First oxide powder use mean diameter be 0.1 μm, purity be the MgO of high purity powder of 99.7%
End, the second oxide powder use mean diameter be 10 μm, purity be the high-purity C aO powder of 99.8%
End and mean diameter be 10 μm, purity be the mixed-powder of the high-purity ZnO powder of 99.8%, except this
Outside obtain vapour deposition material similarly to Example 8.The MgO powder contained by vapour deposition material obtained
End, CaO powder and the mean diameter of ZnO powder, MgO contained in vapour deposition material, CaO,
The content of ZnO and the basicity of granule represent in the following table 1.
<embodiment 16>
First oxide powder use mean diameter be 10 μm, purity be the MgO of high purity powder of 99.7%
End, the second oxide powder use mean diameter be 0.1 μm, purity be the high-purity C aO powder of 99.8%
End and mean diameter be 0.1 μm, purity be the high-purity ZnO powder of 99.8%, in addition with enforcement
Example 8 similarly obtains vapour deposition material.The MgO powder contained by vapour deposition material that obtains, CaO powder
End and the mean diameter of ZnO powder, the content of MgO, CaO, ZnO contained in vapour deposition material
Represent in the following table 1 with the basicity of granule.
<embodiment 17>
First oxide powder use mean diameter be 0.05 μm, purity be the MgO of high purity of 99.7%
Powder, obtains vapour deposition material the most similarly to Example 8.Contained by the vapour deposition material obtained
The mean diameter of MgO powder, CaO powder and ZnO powder, MgO contained in vapour deposition material,
The content of CaO, ZnO and the basicity of granule represent in the following table 1.
<embodiment 18>
Second oxide powder use mean diameter be 15 μm, purity be the high-purity C aO powder of 99.8%
End and mean diameter be 15 μm, purity be the mixed-powder of the high-purity ZnO powder of 99.8%, except this
Outside obtain vapour deposition material similarly to Example 8.The MgO powder contained by vapour deposition material obtained
End, CaO powder and the mean diameter of ZnO powder, MgO contained in vapour deposition material, CaO,
The content of ZnO and the basicity of granule represent in the following table 1.
<comparative example 1>
It is adjusted to and does not mixes the first oxide powder, and the second oxide powder use mean diameter is
0.6 μm, purity are the high-purity C aO powder of 99.8%, obtain the most similarly to Example 1
Vapour deposition material.The mean diameter of CaO powder contained by the vapour deposition material obtained, the basicity of granule
Represent in table 2 below.
<comparative example 2>
Second oxide powder use mean diameter be 0.6 μm, purity be the high-purity C aO powder of 99.8%
End, and the combined amount of MgO powder and CaO powder is adjusted to institute in the vapour deposition material after formation
The MgO contained be 3 moles of %, CaO be 97 moles of %, obtain the most similarly to Example 1
Vapour deposition material.The MgO powder contained by vapour deposition material obtained and the mean diameter of CaO powder,
The content of MgO, CaO contained in vapour deposition material and the basicity of granule represent in table 2 below.
<comparative example 3>
It is adjusted to and does not mixes outside the second oxide powder, obtain vapour deposition material similarly to Example 1.
The mean diameter of MgO powder, the basicity of granule contained in the vapour deposition material obtained represent following
In table 2.
<comparative example 4>
Vapour deposition material is obtained under conditions of as comparative example 1.Contained by the vapour deposition material obtained
The mean diameter of CaO powder, the basicity of granule represent in table 2 below.
<comparative example 5>
Vapour deposition material is obtained under conditions of as comparative example 3.Contained by the vapour deposition material obtained
The mean diameter of MgO powder, the basicity of granule represent in table 2 below.
<comparative example 6>
Vapour deposition material is obtained under conditions of as comparative example 1.Contained by the vapour deposition material obtained
The mean diameter of CaO powder, the basicity of granule represent in table 2 below.
<comparative example 7>
Vapour deposition material is obtained under conditions of as comparative example 3.Contained by the vapour deposition material obtained
The mean diameter of MgO powder, the basicity of granule represent in table 2 below.
[table 1]
[table 2]
<comparative test and evaluation 1>
Use the vapour deposition material obtained in embodiment 1～18 and comparative example 1～7, in thickness 75 μm
Carry out vapour deposition by the method shown in table 3 below and table 4 in PET film and form thin film, and shape
Become thin-film sheet.For these thin-film sheets, measure moisture-vapor transmission, gas barrier property is evaluated.
It addition, with in evaluating than above-mentioned gas barrier property condition is at higher temperature, place under super-humid conditions long-time after water
Vapor transmission rates and rate of change thereof have rated durability.And then, for these thin-film sheets, measure light saturating
Cross rate, have rated the transparency.These results represent in table 3 below and table 4.
(1) gas barrier property: thin-film sheet is placed on and is set as temperature 20 DEG C, relative humidity 50%RH
Clean room in after 1 hour, use MOCON company moisture-vapor transmission determinator (model
Name: PERMATRAN-W type 3/33), under conditions of temperature 40 DEG C, relative humidity 90%RH
Measure moisture-vapor transmission S.
(2) durability: for placing in being set as the clean room of temperature 20 DEG C, relative humidity 50%RH
Thin-film sheet after 1 hour, for the deterioration preventing the steam of PET film from causing, with thin-film sheet
Thin film become the mode in outside by each two of the superposition respectively of identical thin-film sheet, engage four with hot enclosuring device
Limit.Put it in the constant temperature and humidity device being set as temperature 85 DEG C, relative humidity 90%RH, place
100 hours.Afterwards, in the same manner as the evaluation of above-mentioned gas barrier property, use moisture-vapor transmission determinator,
Moisture-vapor transmission T is measured under conditions of temperature 40 DEG C, relative humidity 90%RH.It addition, calculate
The moisture-vapor transmission T-phase measured is for the rate of change (T/S × 100) of above-mentioned moisture-vapor transmission S.
(3) light transmission rate: thin-film sheet is used the spectrophotometric of society of Hitachi Co., Ltd
Meter (model name: U-4000) measures the light transmission rate of wavelength 380～780nm.
[table 3]
[table 4]
As may be known from Table 3 and Table 4, when comparing embodiment 1～8 and comparative example 1～3, in embodiment 1～8,
Moisture-vapor transmission S after placing 1 hour under conditions of temperature 20 DEG C, relative humidity 50%RH is
0.26g/m2Below it, wherein, it is 0.1g/m in embodiment 3～72Below it.On the other hand,
The comparative example being less than 5% as the content of the comparative example 1 and the first oxide M gO of the single composition of CaO
In 2, moisture-vapor transmission S becomes big.Particularly in the comparative example 1 as the single composition of CaO,
When comparing with embodiment 4 etc., moisture-vapor transmission S becomes very large, it addition, comparative example 1, compare
In example 2, after placing 100 hours further under conditions of temperature 85 DEG C, relative humidity 90%RH
Moisture-vapor transmission T becomes very large, and finds substantially deterioration.
It addition, at comparative example 1 with as in the comparative example 3 of the single composition of MgO, temperature 85 DEG C,
Water is steamed by the moisture-vapor transmission T after placing 100 hours further under conditions of relative humidity 90%RH
The rate of change of vapor permeability S becomes big, draws the result that durability is low.On the other hand, in embodiment 1～8
Even if place for a long time under high temperature, high humidity environment, moisture-vapor transmission T is to moisture-vapor transmission S
Rate of change also suppress below 200%, it is judged that durability aspect is excellent.
It addition, for light transmission rate, obtain the embodiment 1～8 result no less than comparative example 1～3.
And then, to using the vapour deposition material obtained under the same terms and distinguishing film forming by different methods
Embodiment 2,9,11, embodiment 3,10,12, comparative example 1,4,6, comparative example 3,5,7 enters
Row is respectively compared, it is judged that i.e. uses the embodiment 9,10 of EB method film forming and is heated by resistive method film forming
The thin film of embodiment 11,12 also possess with the thin film formed by RPD method equal sufficient gas barrier property,
Durability and the transparency.
Additionally, when comparing embodiment 2 and embodiment 13, thin with the embodiment 2 by RPD method film forming
Film is compared, with the thin film of the embodiment 13 of ion plating method film forming at moisture-vapor transmission and rate of change thereof and
Almost identical value is shown, it is judged that possess sufficient gas barrier property, durability and the transparency on light transmittance.
Additionally, when comparing embodiment 2 and embodiment 14, with the thin film of the embodiment 14 of induction heating film forming
Compared with the thin film of the embodiment 2 by RPD method film forming, moisture-vapor transmission shows the value that a little change is big,
But the rate of change of moisture-vapor transmission and light transmittance show almost identical value, thus judge to possess and fill
Gas barrier property, durability and the transparency divided.
Additionally, when comparing embodiment 15,16 and embodiment 17,18, use mean diameter less than 0.1 μm
MgO powder manufacture vapour deposition material embodiment 17 in, for moisture-vapor transmission S show with
The value that the thin film of embodiment 15,16 is identical, thus available sufficient gas barrier property.On the other hand, due to
Steam after placing 100 hours further under conditions of temperature 85 DEG C, relative humidity 90%RH is saturating
Crossing rate T bigger than 1.0 required by usual gas barrier film, the rate of change of moisture-vapor transmission also exceeds 200%,
So drawing and comparing the result how many thin film of embodiment 17,18 is deteriorated in terms of durability.This is considered
Owing to powder the least for mean diameter being used for raw material, the specific surface area of single crystal boundary increases, and is diffused into
The damage that steam in film causes causes the result of bigger impact.It addition, use mean diameter to be more than
In the embodiment 18 of the mixed-powder of CaO and ZnO of 10 μm, the rate of change of moisture-vapor transmission is also
Do not become so big, but how many moisture-vapor transmission S becomes big, and moisture-vapor transmission T is also greater than logical
Often 1.0 required by gas barrier film, thus draw the result how many gas barrier properties is deteriorated than embodiment 15,16.
This be considered due to using powder big for mean diameter as raw material, membrane structure is difficult to become dense.The opposing party
Face, it is thus identified that use mean diameter all the MgO powder in 0.1～10 μ m, CaO and ZnO
Mixed-powder embodiment 15,16 in can form the thin film possessing sufficient gas barrier property.
By these results verifications, the thin film using the vapour deposition material of the present invention to be formed has the most excellent
Gas barrier property, the transparency and durability.
<comparative test and evaluation 2>
The vapour deposition material obtained in embodiment 4～7 and comparative example 2 be have rated preservation in an atmosphere
Stability.The results are shown in table 5 below and Fig. 4.Specifically, the gas after visualization just manufactures
Mutually deposition material and in an atmosphere, preserve 3 days, 10 days, vapour deposition material after 20 days under room temperature respectively
Grain shape.Now, it is possible to be " A " when maintaining the grain shape of the vapour deposition material after just manufacturing,
Confirm when the part of shape after just manufacturing is defeated and dispersed for " B ", substantially can not maintain after just manufacturing
Shape time be " C ".
[table 5]
| After just manufacturing | After 3 days | After 10 days | After 20 days | |
| Embodiment 4 | A | A | A | A |
| Embodiment 5 | A | A | A | A |
| Embodiment 6 | A | A | A | A |
| Embodiment 7 | A | A | A | A |
| Comparative example 2 | A | C | C | C |
From table 5 and Fig. 4, the vapour deposition material obtained in comparative example 2 granule after just manufacturing
Shape matching is good, but when preserving 3 days under room temperature in an atmosphere, and the overall shape of granule is defeated and dispersed, recognizes completely
Do not go out the grain shape after just manufacturing.On the other hand, it is thus identified that the present invention obtained in embodiment 4～7
Even if vapour deposition material room temperature in an atmosphere under preserve 3 days, 10 days, 20 days time, it is also possible to maintained just
Grain shape after just manufacturing, thus storage stability in an atmosphere is the most excellent.
Claims (5)
1. a vapour deposition material, the gas made for mixing the first oxide powder and the second oxide powder
Deposit material mutually, it is characterised in that
Described first oxide powder is MgO powder, the first oxide purity of described first oxide powder
It is more than 98%,
Described second oxide powder is the mixed-powder of CaO and ZnO, the of described second oxide powder
Dioxide purity is more than 98%,
Described vapour deposition material is by containing described first oxide powder and the granule of described second oxide powder
Constitute,
The first oxide and the mol ratio of the second oxide in described vapour deposition material are 5～90:95～10, and
The basicity of described granule is more than 0.1,
When all the content ratio of vapour deposition material is set to 100 moles of %, comprise as described second oxide
The content ratio of ZnO is 10～20 moles of %,
Described basicity is obtained by following formula:
B=∑ ni·Bi
Bi≡1/Ai
Ai=Zi·Z02-/(ri+r02-)2
Wherein, B is basicity, niFor cation fraction, BiFor the oxygen supply ability of single component oxide,
AiFor gravitation, Z between cation-oxonium ioniFor the valence mumber of cation, Z02-For the valence mumber of oxonium ion, riFor
The ionic radius of cation, r02-For the ionic radius of oxonium ion, riAnd r02-Unit beFurther, will
Described BiIt is normalized to BCaO=1, BSiO2=0 and give the B of each single component oxidei-index.
Vapour deposition material the most according to claim 1, the mean diameter of described first oxide powder is
0.1～10 μm, and the mean diameter of described second oxide powder is 0.1～10 μm.
3. a thin-film sheet, by being used as the true of target by the vapour deposition material described in claim 1 or 2
Empty membrane formation process, is formed on the first base film and comprises the metallic element Mg contained by described first oxide and institute
State the sull of metallic element Ca and Zn contained by the second oxide,
When the content ratio of the whole metallic elements in described thin film is set to 100 moles of %, described metallic element
The content ratio of Mg is 5～90 moles of %, and the content ratio of described metallic element Ca and Zn is 95～10 to rub
You are %.
Thin-film sheet the most according to claim 3, described vacuum film formation be e-beam evaporation, from
Any one in sub-plating method, reactive plasma sedimentation, electrical resistance heating or induction heating.
5. a laminate, the thin film at the thin-film sheet described in claim 3 or 4 forms side by viscous
Connect and press the second base film to form layer by layer.
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| JP2011182339A JP5760851B2 (en) | 2010-09-29 | 2011-08-24 | Vapor deposition material for forming a thin film, and a thin film sheet and a laminated sheet provided with the thin film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1297464A (en) * | 1998-04-15 | 2001-05-30 | 吴羽化学工业株式会社 | Gas-barrier films |
| EP1731299A1 (en) * | 2004-03-31 | 2006-12-13 | Konica Minolta Holdings, Inc. | Transparent conductive film, method for producing transparent conductive film and organic electroluminescent device |
| CN101460425A (en) * | 2006-06-08 | 2009-06-17 | 住友金属矿山株式会社 | Oxide sinter, target, transparent conductive film obtained from the same, and transparent conductive base |
| CN201266610Y (en) * | 2008-09-02 | 2009-07-01 | 中国乐凯胶片集团公司 | Solar cell backboard |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8440115B2 (en) * | 2007-07-06 | 2013-05-14 | Sumitomo Metal Mining Co., Ltd. | Oxide sintered body and production method therefor, target, and transparent conductive film and transparent conductive substrate obtained by using the same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1297464A (en) * | 1998-04-15 | 2001-05-30 | 吴羽化学工业株式会社 | Gas-barrier films |
| EP1731299A1 (en) * | 2004-03-31 | 2006-12-13 | Konica Minolta Holdings, Inc. | Transparent conductive film, method for producing transparent conductive film and organic electroluminescent device |
| CN101460425A (en) * | 2006-06-08 | 2009-06-17 | 住友金属矿山株式会社 | Oxide sinter, target, transparent conductive film obtained from the same, and transparent conductive base |
| CN201266610Y (en) * | 2008-09-02 | 2009-07-01 | 中国乐凯胶片集团公司 | Solar cell backboard |
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