CN102191463B - Film formation vapour deposition material, the thin-film sheet possessing this film and laminate - Google Patents
Film formation vapour deposition material, the thin-film sheet possessing this film and laminate Download PDFInfo
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- CN102191463B CN102191463B CN201110065635.6A CN201110065635A CN102191463B CN 102191463 B CN102191463 B CN 102191463B CN 201110065635 A CN201110065635 A CN 201110065635A CN 102191463 B CN102191463 B CN 102191463B
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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
Abstract
The invention provides the vapour deposition material being applicable to the film forming the transparency and gas barrier property excellence and the thin-film sheet and the laminate that possess this film.Vapour deposition material of the present invention is the vapour deposition material that mixing first oxide powder and the second oxide powder make, and it is characterized in that, the first oxide powder is CeO
2powder, first oxide compound purity of the first oxide powder is more than 98%, second oxide powder is any one powder in MgO or CaO, or the two or more mixed powder be selected from ZnO, MgO and CaO, second oxide compound purity of the second oxide powder is more than 98%, vapour deposition material is made up of the particle containing the first oxide particle and the second oxide particle, the first oxide compound in vapour deposition material and the ratio of the second oxide compound are 5 ~ 85: 95 ~ 15, and the basicity of particle is more than 0.1.
Description
Technical field
The present invention relates to the vapour deposition material being applicable to the film forming all excellents such as the transparency, gas barrier property and the thin-film sheet and the laminate that possess this film.More specifically, relate to for the formation of these all excellents, be particularly suitable as the vapour deposition material of the film of the choke material of liquid-crystal display, OLED display or solar module etc. and possess thin-film sheet and the laminate of this film.
Background technology
The machines such as liquid-crystal display, OLED display or solar cell usually not moisture-proof, because moisture absorption makes its characteristic rapid degradation, therefore must equip have highly moistureproof, namely have anti-block or water vapour etc. through or the parts of gas barrier property that invade.
Such as, in the example of solar cell, the back side of the sensitive surface opposition side with solar module is provided with base (backseat).This base is typically made up of the choke material and their parts etc. of protection with highly moistureproof on base material.
As the base of such formation solar module; such as disclose and sandwich moisture resistance tinsel by high-strength heat-resistant weathering resistance resin; and then the back-protective sheet material (such as, referenced patent document 1) of solar module of vitreous vapor deposition film is set in one side.In this sheet material, use the tinsels such as aluminium foil, zinc-plated iron foil, zinc-plated iron foil as choke material.In addition, to disclose high moisture-proofing film and high weather film laminating and the solar cell covering material of integration is used for the solar cell (such as, referenced patent document 2) of rear side guard block.High moisture-proofing film in this solar cell covering material is used on the base material films such as polyethylene terephthalate (PET) film and forms the moisture barrier films that is made up of the coated film of the inorganic oxide such as silicon-dioxide, aluminum oxide as choke material by chemical vapour deposition (CVD), physical vapor deposition (PVD) method etc.In addition, the photovoltaic module (such as, referenced patent document 3) possessing the blocking layer be made up of plastics film or plastic composite presenting inorganic oxide layer is disclosed.In this inorganic oxide layer, aluminum oxide or silicon-dioxide use as its coating material.
Patent documentation 1: Japanese Patent Publication 2-44995 publication (claims of utility model registration and 41st ~ 44 row on the 5th hurdle)
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 tinsels such as aluminium foil as choke material, if this sheet material to be applied to the base of solar module, then likely proof voltage reduces, current leakage.In addition, if the thickness using the sheet material tinsel of tinsel is less than 20 μm, then the pin hole produced between thermotolerance weathering resistance resin and tinsel increases, and gas barrier property significantly reduces.On the other hand, if increase the thickness of tinsel, then produce the problem that manufacturing cost improves.In addition, if use in above-mentioned patent documentation 2 and patent documentation 3 the inorganic oxide such as silicon-dioxide, aluminum oxide when, must guarantee that thickness is at more than 100nm to obtain high-gas resistance, even if can not assert that gas barrier property is abundant like this.
Summary of the invention
The object of the invention is to, the vapour deposition material being applicable to the film forming the transparency and gas barrier property excellence is provided.
Another object of the present invention is to, thin-film sheet and the laminate of the film possessing the transparency and gas barrier property excellence is provided.
A first aspect of the present invention is vapour deposition material, and mix the first oxide powder and the second oxide powder and make, it is characterized in that, above-mentioned first oxide powder is CeO
2powder, first oxide compound purity of this first oxide powder is more than 98%, above-mentioned second oxide powder is any one powder in MgO or CaO, or the two or more mixed powder be selected from ZnO, MgO and CaO, second oxide compound purity of this second oxide powder is more than 98%, vapour deposition material is made up of the particle containing the first oxide particle and the second oxide particle, the first oxide compound in vapour deposition material and the ratio of the second oxide compound are 5 ~ 85: 95 ~ 15, and the basicity of particle is more than 0.1.
A second aspect of the present invention is the invention based on first aspect, it is characterized in that, further, the median size of the first oxide particle is 0.1 ~ 10 μm, and the median size of the second oxide particle is 0.1 ~ 10 μm.
A third aspect of the present invention is the manufacture method of film, it is characterized in that, by the vapour deposition material based on first or second aspect being used as the vacuum film formation of target, the first base material film forms the sull of the metal element A comprised contained by the first oxide compound and the metallic element B contained by the second oxide compound.
As shown in Figure 1, a fourth aspect of the present invention is thin-film sheet 10, by the vapour deposition material based on first or second aspect being used as the vacuum film formation of target, first base material film 11 is formed the sull 12 of the metal element A comprised contained by the first oxide compound and the metallic element B contained by the second oxide compound, by the whole metallic elements in above-mentioned film 12 containing proportional be set to 100 % by mole time, metal element A containing proportional be 5 ~ 85 % by mole, metallic element B containing proportional be 95 ~ 15 % by mole.
A fifth aspect of the present invention is the invention based on fourth aspect, it is characterized in that, further, vacuum film formation is the one in e-beam evaporation, ion plating method, reactive plasma sedimentation, electrical resistance heating or induction heating.
A sixth aspect of the present invention is the invention based on the 4th or the 5th aspect, it is characterized in that, further, under the condition of temperature 20 DEG C, relative humidity 50%RH, place 1 little water vapor transmission rate (WVTR) S is constantly 0.3g/m
2below it.
A seventh aspect of the present invention is the invention based on the 6th aspect, it is characterized in that, further, place under the condition of temperature 20 DEG C, relative humidity 50%RH after 1 hour, when under the condition of temperature 85 DEG C, relative humidity 90%RH, placement 100 little water vapor transmission rate (WVTR)s are constantly set to T further, water vapor transmission rate (WVTR) T-phase is less than 200% for velocity of variation T/S × 100 of water vapor transmission rate (WVTR) S.
As shown in Figure 1, a eighth aspect of the present invention is laminate 20, and the film 12 of the thin-film sheet 10 in based on the 4th to the 7th is formed side and formed by adhesive linkage 13 lamination second base material film 14.
In the vapour deposition material of a first aspect of the present invention, the first oxide powder is CeO
2powder, first oxide compound purity of this first oxide powder is more than 98%, above-mentioned second oxide powder is any one powder in MgO or CaO, or be selected from ZnO, two or more mixed powder in MgO and CaO, second oxide compound purity of this second oxide powder is more than 98%, vapour deposition material is made up of the particle containing the first oxide particle and the second oxide particle, the first oxide compound in vapour deposition material and the ratio of the second oxide compound are 5 ~ 85: 95 ~ 15, and the basicity of particle is more than 0.1, thus the film significantly improving gas barrier property compared with existing choke material can be formed.
In the vapour deposition material of a second aspect of the present invention, the median size of the first oxide particle is 0.1 ~ 10 μm, and the median size of the second oxide particle is 0.1 ~ 10 μm, thus the good and dense vapor-deposited film of vapour deposition efficiency can be formed, therefore can maintain high-gas resistance and make its stabilization.
In the thin-film sheet of a fourth aspect of the present invention, by possess by the whole metallic elements in the film of the metallic element B contained by the metal element A comprised contained by the first oxide compound and the second oxide compound containing proportional be set to 100 % by mole time, metal element A containing proportional be 5 ~ 85 % by mole, metallic element B containing proportional be the film of 95 ~ 15 % by mole, there is the excellent transparency and gas barrier property.
In the thin-film sheet of a sixth aspect of the present invention, under the condition of temperature 20 DEG C, relative humidity 50%RH, place 1 little water vapor transmission rate (WVTR) S is constantly 0.3g/m
2below it, have along with the time is through the little very high gas barrier property of the deterioration that brings.
In the thin-film sheet of a seventh aspect of the present invention, place under the condition of temperature 20 DEG C, relative humidity 50%RH after 1 hour, when under the condition of temperature 85 DEG C, relative humidity 90%RH, placement 100 little water vapor transmission rate (WVTR)s are constantly set to T further, water vapor transmission rate (WVTR) T-phase is less than 200% for velocity of variation T/S × 100 of water vapor transmission rate (WVTR) S, has along with the time is through the very little gas barrier property of the deterioration that brings.
In the laminate of a eighth aspect of the present invention, the film of the thin-film sheet in the 4th to the 7th is taked to form the structure of side further by adhesive linkage lamination second base material film.Thus, the second base material film can protective film, therefore can maintain high-gas resistance and make its stabilization.
Accompanying drawing explanation
Fig. 1 is the sectional view briefly expressing the thin-film sheet of embodiment of the present invention and the laminar structure of laminate.
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.
Nomenclature
10: thin-film sheet
11: the first base material films
12: film
13: adhesive linkage
14: the second base material films
20: laminate
Embodiment
Hereinafter, with reference to the accompanying drawings of embodiments of the present invention.Vapour deposition material of the present invention can be suitable for the formation of film.The film using this vapour deposition material to be formed play anti-block or water vapour etc. through or the effect of choke material that invades.
This vapour deposition material mixes the first oxide powder and the second oxide powder and makes.Be CeO for making the first oxide powder of vapour deposition material
2powder, first oxide compound purity of this first oxide powder is more than 98%, be preferably more than 98.4%, second oxide powder is any one powder in MgO or CaO, or the two or more mixed powder be selected from ZnO, MgO and CaO, second oxide compound purity of this second oxide powder is more than 98%, is preferably more than 99.5%.At this, the first oxide compound purity of the first oxide powder being defined as more than 98%, is that result barrier properties reduces because due to impurity, crystallinity worsens when being less than 98%.In addition, the second oxide compound purity of the second oxide powder being defined as more than 98%, is that result barrier properties reduces because due to impurity, crystallinity worsens when being less than 98%.Further, the powder purity in this specification sheets is measured by spectroscopic analysis (inductively coupled plasma apparatus for analyzing luminosity: Japanese ジ ヤ mono-レ Le ア Star シ ユ ICAP-88).In addition, this vapour deposition material is preferably made up of the polycrystalline particle containing the first oxide particle and the second oxide particle, and its relative density is more than 90%, is preferably more than 95%.Make relative density be more than 90% to be because splashing when being less than 90% during film forming increases.And in this embodiment, what make particle is organized as polycrystalline, but it also can be monocrystalline.
In addition, the median size of the first oxide particle that this vapour deposition material contains is 0.1 ~ 10 μm, and the median size of the second oxide particle is 0.1 ~ 10 μm, and the first oxide compound in vapour deposition material and the ratio of the second oxide compound are 5 ~ 85: 95 ~ 15.And the basicity of particle is more than 0.1.By containing the first oxide particle and second oxide particle of miniaturization like this with regulation ratio, high-gas resistance can be made to be apparent in and to use in the film that formed of this vapour deposition material.
Its technical reason is as follows: usually use (1) vapour deposition material only containing the first oxide particle not containing the second oxide particle, (2) the vapour deposition material only containing the second oxide particle not containing the first oxide particle, (3) simultaneously containing the first oxide particle and the second oxide particle but the first oxide particle containing proportional few vapour deposition material, or (4) simultaneously containing the first oxide particle and the second oxide particle but the second oxide particle containing proportional few vapour deposition material when, as shown in Figure 2, the structure that the crystallization phases that the sull 32 be formed on the first base material film 11 becomes column crystal is assembled abreast for the infiltration direction of gas.The gas molecules such as water vapour are owing to advancing at the interface along the crystal boundary assembled abreast, and in the film 32 of the structure of assembling abreast in the crystallization of above-mentioned column crystal, block is low.On the other hand, when use contain the vapour deposition material of the first oxide particle of miniaturization or the second oxide particle with regulation ratio time, as shown in Figure 3, for the sull 12 be formed on the first base material film 11, use a part for the column crystal formed during the vapour deposition material of single composition defeated and dispersed, become the microtexture of the densification close to noncrystalline state.In the microtexture of the densification close to noncrystalline state, the gas molecules such as water vapour need to move at labyrinth-like middle and long distance, and therefore at the film 12 of the microtexture of the above-mentioned densification close to noncrystalline state, block is improved.So, estimating by crystalline texture is that non-columnar is brilliant, and film forming be applicable to preventing moisture etc. through or the structure that invades, gas barrier property improves.In addition, the first oxide particle contained if also think and the second oxide particle are all micronized, then, when making film be grown up by vapour deposition process, can carry out film forming with the amount of few electron beam or plasma body, therefore can form fine and close film, gas barrier property is improved thus.At this, it is because when respective median size is less than lower value that the first oxide particle contained in vapour deposition material, i.e. particle and the median size both the second oxide particle are defined as above-mentioned scope, in the manufacturing process of vapour deposition material, the cohesion of powder is remarkable, hinder Homogeneous phase mixing, if respective median size exceedes higher limit, then cannot fully obtain being formed with the effect helping the doubtful sosoloid improving gas barrier property.Wherein, particularly preferably the median size of the first oxide particle is 0.1 ~ 10 μm, and the median size of the second oxide particle is 0.1 ~ 10 μm.And, in this manual, median size is according to laser diffraction and scattering method (micro-trackmethod), use Ji Zhuan society system (FRA type), use Sodium hexametaphosphate 99 as dispersion medium, a minute is set as measuring for 30 seconds, and the value equalization of mensuration three times is obtained.
In addition, by the limited proportion of the first oxide compound contained in vapour deposition material and the second oxide compound above-mentioned scope be because of be less than when the ratio of the first oxide compound 5 or second the ratio of oxide compound be less than 5 time, first oxide particle or the second oxide particle containing proportional very few, close to single composition, thus the structure that the crystallization phases easily becoming column crystal is assembled abreast for gas-permeable direction, the film with fine and close microtexture can not be formed.
And then the basicity of particle being defined as more than 0.1 is because when being less than 0.1, film not easily becomes the defeated and dispersed and microtexture of densification close to noncrystalline state of the part of column crystal." basicity " forever should be good for inferior proposition by gloomy, (K.Morinaga is recorded such as at him, H.YoshidaAndH.Takebe:J.AmCerm.Soc., formula as follows is used to carry out the basicity of regulation glass powder 77,3113 (1994)).Its extracts is as follows.
" oxide M
ithe M of O
ibonding strength between-O is as gravitation A between positively charged ion-oxonium ion
iobtained by following formula.
A
i＝Z
i·Z
02-/(r
i+r
02-)
2＝Zi·2/(r
i+1.40)
2
Z
i: cationic valence mumber, oxonium ion is 2
R
i: cationic ionic radius
oxonium ion is
By this A
ib reciprocal
i(1/A
i) as single component oxide M
ithe oxygen supply ability of O.
B
i≡1/A
i
By this B
ibe normalized to B
caO=1, B
siO2=0, then give the Bi-index of each single component oxide.Expand the Bi-index of this each composition to multicomponent system by cation fraction, then can calculate the B-index (=basicity) of the molten mass of the glass oxide of composition arbitrarily.B＝∑n
i·B
i
N
i: cation fraction
The basicity of such regulation represents oxygen supply ability as described above, and value more easily supplies oxygen supply more greatly, easily causes and the giving and accepting of the oxygen of other metal oxide.”
In the present invention, for the basicity index of glass powder, replacing oxide compound by making glass and make an explanation, the basicity of oxide mixture being arranged the index of the microtexture for easily becoming the densification close to noncrystalline state in the film.Be the concept of melting when glass, but in the present invention, the mechanism formed to produce glass during film forming is basic.Become ionic condition from the element of vapour deposition material distillation, element is piled up with nonequilibrium state on substrate.The basicity of the particle now obtained by above formula is more than 0.1, then film is grown up with glassy (amorphous), and element fitly arranges with very fine and close state.
Use film that vapour deposition material of the present invention is formed owing to having high-gas resistance, except having the purposes of the choke materials such as the moisture barrier films of the base forming solar cell, suitably can also be utilized as the choke material of liquid-crystal display, OLED display or illumination OLED display etc.In addition, this film, owing to having the transparency that transmitance is 85% ~ 95% degree, is also suitable as requiring high-gas resistance and requiring the choke material etc. through the sensitive surface side of the parts of light, such as solar cell or the image vision side of indicating meter etc.
Then, with the manufacture method of situation about being made by sintering process vapour deposition material of the present invention for representative illustrates.First, purity more than 98% high purity powdered form as the first oxide powder, purity more than 98% high purity powdered form as the second oxide powder, tackiness agent and organic solvent are mixed, preparation concentration is the slurry of 30 ~ 75 quality %.The slurry of preferred preparation 40 ~ 65 quality %.And the first oxide powder and the second oxide powder are that the first oxide compound in the vapour deposition material after manufacturing carries out adjusting and mixing with the mode that the ratio of the second oxide compound meets above-mentioned scope.If it is because more than 75 quality % that the concentration limits of slurry is decided to be 30 ~ 75 quality %, then because above-mentioned slurry is non-aqueous system, exist and be difficult to the problem of carrying out stable mixing granulation, if less than 30 quality %, then cannot obtain the sintered compact of the densification with uniform formation.In addition, the median size of the first oxide powder contained by the vapour deposition material after manufacturing and the median size of the second oxide particle are adjusted in above-mentioned scope, the median size of the first oxide powder therefore used and the median size of the second oxide powder be preferably the first oxide powder in the scope of 0.1 ~ 10 μm, the second oxide powder is in the scope of 0.1 ~ 10 μm.
Tackiness agent preferably uses polyoxyethylene glycol, polyvinyl butyral acetal etc., and organic solvent preferably uses ethanol, propyl alcohol etc.Tackiness agent preferably adds 0.2 ~ 5.0 quality %.
In addition, wet mixing, the particularly high purity powdered form of high purity powdered form and tackiness agent and organic solvent are undertaken by wet-type ball mill or mixer grinder with the wet mixing as the organic solvent of dispersion medium.In wet-type ball mill, use ZrO
2during the ball made, use multiple ZrO of diameter 5 ~ 10mm
2the ball wet mixing of system 8 ~ 24 hours, preferred wet mixing 20 ~ 24 hours.ZrO
2it is because less than undercompounding during 5mm that the diameter of the ball of system is defined as 5 ~ 10mm, more than the bad problem that there is impurity increase during 10mm.In addition, even if mixing time the longest is 24 hours is that impurity produces also little because long-time continuous mixing.
In mixer grinder, use the ZrO of diameter 1 ~ 3mm
2the ball wet mixing of system 0.5 ~ 1 hour.ZrO
2if it is because less than 1mm that the diameter of the ball of system is defined as 1 ~ 3mm, undercompounding, if more than 3mm, there is the trouble that impurity increases.In addition, if it is that be not only the mixing of raw material, ball itself also can wear and tear because more than 1 hour that mixing time shortens to the longest 1 hour, the reason producing impurity can be become, and only need just can fully mix for 1 hour.
Then the above-mentioned slurry of spraying dry obtains that median size is 50 ~ 250 μm, the preferred mixing granulation powder of 50 ~ 200 μm.The mould this prilling powder being put into regulation is shaped with specified pressure.Above-mentioned spraying dry preferably uses spray-drier to carry out, and regulation mould uses uniaxial pressing device or isostatic cool pressing (CIP:ColdIsostaticPress) building mortion.In uniaxial pressing device, make prilling powder at 750 ~ 2000kg/cm
2(73.55 ~ 196.1MPa), preferably 1000 ~ 1500kg/cm
2single shaft press molding under the pressure of (98.1 ~ 147.1MPa), in CIP building mortion, makes prilling powder at 1000 ~ 3000kg/cm
2(98.1 ~ 294.2MPa), preferably 1500 ~ 2000kg/cm
2under the pressure of (147.1 ~ 196.1MPa), CIP is shaped.Pressure being limited to above-mentioned scope is because prevent the distortion after sintering while improving the density of molding and do not need to carry out post-treatment.
And then, with specified temperature sintered shaped body.Sintering is in air, rare gas element, vacuum or reducing gas atmosphere, more than 1000 DEG C, preferably carry out at 1200 ~ 1400 DEG C of temperature 1 ~ 10 hour, preferably carry out 2 ~ 5 hours.Thus, the particle that relative density is more than 90% is obtained.Above-mentioned sintering under atmospheric pressure carries out, but when carrying out the pressure sintering as sintered in hot pressing (HP) sintering or hot isostatic pressing (HIP:HotIsostaticPress), preferably in rare gas element, vacuum or reducing gas atmosphere, at the temperature more than 1000 DEG C, carry out 1 ~ 5 hour.
Then, thin-film sheet of the present invention is described together with its manufacture method with laminate.As shown in Figure 1, thin-film sheet 10 of the present invention has the first base material film 11 and preferably uses the film of the present invention 12 of above-mentioned vapour deposition material formation.And laminate 20 of the present invention has the thin-film sheet 10 of the invention described above and forms side by bonding the second base material film 14 of adhesive linkage 13 at the film of this thin-film sheet 10.
First base material film 11 and the second base material film 14 preferably have the mechanical strength and weathering resistance etc. of the long high-temperature high-humidity envrionment test of ability.Such as, the resin films such as polyethylene terephthalate (PET), polycarbonate, polymethylmethacrylate, polyacrylic ester, PEN (PEN), polyarylester, polyethersulfone, triacetyl cellulose (TAC), cyclic olefin (being total to) polymkeric substance can be enumerated.These resin films also can coordinate fire retardant, antioxidant, UV light absorber, antistatic agent etc. as required.The thickness preferably 5 ~ 300 μm of the first base material film 11 and the second base material film 14, more preferably 10 ~ 150 μm.
This first base material film 11 preferably uses the film 12 of vapour deposition material formation as choke material of the invention described above.By the whole metallic elements in film 12 containing proportional be set to 100 % by mole time, metal element A contained in the first oxide compound containing proportional be 5 ~ 85 % by mole, metallic element B contained in the second oxide compound containing proportional be 95 ~ 15 % by mole.Metal element A in film 12, B when above-mentioned scope is outer, the crystalline state of each oxide compound becomes preferential respectively containing proportional, produce the bad problem that cannot obtain the microtexture of the densification of amorphous.The thickness of film 12 is preferably in the scope of 10 ~ 200nm.When being less than lower value, be difficult to obtain the sufficient gas barrier property as choke material, the weather resistance of film easily reduces in addition.On the other hand, when exceeding higher limit, waste material, and easily produce the cracking that the external force such as bending brings due to thickening effect.At this, the thickness of film 12 is particularly preferably in the scope of 20 ~ 100nm.As the formation method of film 12 using vapour deposition material, the vacuum film formation such as preferred electron bundle vapour deposition method (ElectronBeamEvaporationMethod, hereinafter referred to as EB), ion plating method, reactive plasma sedimentation (ReactivePlasmaDepositionMethod, become RPD below), electrical resistance heating or induction heating.
In addition, not shown in Fig. 1, but also in order to improve the primer composition layer arranging as required with the dhering strength of film 12 and be made up of acrylic acid multielement alcohol ester, isocyanic ester, silane coupling agent on the first base material film 11, or the surface treatment using plasma body etc. can be implemented before vapour deposition operation.
On the other hand, under the state that film 12 surface formed is exposed, during process sheet material, the surface of film produces scar or friction, then produce considerable influence to gas barrier property.Therefore, film 12 is preferably arranged the gas barrier property tunicle (not shown) etc. on protective film 12 surface.This gas barrier property tunicle such as by having solution coat that the silicon compound of alkoxyl group, titanium compound, zirconia compound, tin compound or its hydrolyzate and the water-soluble polymer with hydroxyl mix behind film 12 surface, can carry out heat drying and being formed.This gas barrier property tunicle not only plays the effect of the thin film layer of film 12, also has the effect improving gas barrier property.
The thin-film sheet of the present invention 10 of such formation is such as placed after 1 hour under the condition of temperature 20 DEG C, relative humidity 50%RH, and the water vapor transmission rate (WVTR) S measured under the condition of temperature 40 DEG C, relative humidity 90%RH shows 0.3g/m
2below it.In addition, place under the condition of temperature 20 DEG C, relative humidity 50%RH after 1 hour, place 100 hours further under the condition of temperature 85 DEG C, relative humidity 90%RH, when the water vapor transmission rate (WVTR) measured under the condition identical with above-mentioned condition is afterwards set to T, water vapor transmission rate (WVTR) T-phase is for velocity of variation (T/S × 100) display less than 200% of water vapor transmission rate (WVTR) S.That is, this film 10 has very high and time through the little gas barrier property of the deterioration that brings.
And then, in laminate 20 of the present invention, formed on side, i.e. film 12 at the film of the thin-film sheet 10 of the invention described above or above-mentioned gas barrier property tunicle forms adhesive linkage 13, this adhesive linkage 13 plays for bonding the effect being formed with the first base material film 11 of film 12 and the caking agent of the second base material film 14.Therefore, can enumerate and need bonding strength through for a long time can not deterioration, do not produce delamination etc. and the such as polyurethane series of the condition such as can not to turn yellow, Polyester, polyester-polyurethane system, polycarbonate-based, poly-epoxy-amine system, hot melt system caking agent etc.For the laminating method of adhesive linkage 13, lamination can be carried out by known methods such as dry lamination methods.
Bonded, complete layer laminated sheet 20 by second base material film 14 bonding on this adhesive linkage 13.And, as shown in Figure 1, film 12 and adhesive linkage 13 need not be limited to each laminating layer respectively, also or the miscellaneous parts such as film 12, above-mentioned gas barrier property tunicle and adhesive linkage 13 can be replaced film 12 and adhesive linkage 13 alternatively laminated or arbitrarily be laminated into the multilayer of 2 ~ 10 layers.Thus, gas barrier property and weathering resistance can be improved further.
This laminate 20 is applicable to being utilized as the base of solar module, liquid-crystal display or the purposes such as OLED display or illumination OLED display.
[embodiment]
Then, examples and comparative examples of the present invention are described in detail.
< embodiment 1>
First, the wet mixing of being undertaken by ball mill mixes the first oxide powder, the second oxide powder, tackiness agent and organic solvent with regulation ratio, prepares the slurry that concentration is 40 quality %.Now, the first oxide powder uses the high-purity C eO that median size is 0.7 μm, purity is 99.5%
2powder, the second oxide powder uses the MgO of high purity powder that median size is 0.9 μm, purity is 99.7%, and tackiness agent uses polyvinyl butyral acetal, and organic solvent uses ethanol.In addition, CeO
2the combined amount of powder and MgO powder is adjusted to CeO contained in the vapour deposition material after formation
2be 5 % by mole, MgO is 95 % by mole.
Then, use spray-drier to carry out spraying dry in the slurry of preparation, obtaining median size is after the mixing granulation powder of 200 μm, and the mould this prilling powder being put into regulation is undertaken stamping by uniaxial pressing device.Make the molding obtained in air atmosphere, at 1300 DEG C of temperature, sinter 5 hours, obtain vapour deposition material.The CeO contained by vapour deposition material obtained
2the median size of particle and MgO particle, CeO contained in vapour deposition material
2, the content of MgO and the basicity of particle represents in the following table 1.
< embodiment 2>
By CeO
2the combined amount of powder and MgO powder is adjusted to CeO contained in the vapour deposition material after formation
2be 10 % by mole, MgO is 90 % by mole, in addition obtain vapour deposition material similarly to Example 1.The CeO contained by vapour deposition material obtained
2the median size of particle and MgO particle, CeO contained in vapour deposition material
2, the content of MgO and the basicity of particle represents in the following table 1.
< embodiment 3>
By CeO
2the combined amount of powder and MgO powder is adjusted to CeO contained in the vapour deposition material after formation
2be 20 % by mole, MgO is 80 % by mole, in addition obtain vapour deposition material similarly to Example 1.The CeO contained by vapour deposition material obtained
2the median size of particle and MgO particle, CeO contained in vapour deposition material
2, the content of MgO and the basicity of particle represents in the following table 1.
< embodiment 4>
By CeO
2the combined amount of powder and MgO powder is adjusted to CeO contained in the vapour deposition material after formation
2be 30 % by mole, MgO is 70 % by mole, in addition obtain vapour deposition material similarly to Example 1.The CeO contained by vapour deposition material obtained
2the median size of particle and MgO particle, CeO contained in vapour deposition material
2, the content of MgO and the basicity of particle represents in the following table 1.
< embodiment 5>
By CeO
2the combined amount of powder and MgO powder is adjusted to CeO contained in the vapour deposition material after formation
2be 40 % by mole, MgO is 60 % by mole, in addition obtain vapour deposition material similarly to Example 1.The CeO contained by vapour deposition material obtained
2the median size of particle and MgO particle, CeO contained in vapour deposition material
2, the content of MgO and the basicity of particle represents in the following table 1.
< embodiment 6>
By CeO
2the combined amount of powder and MgO powder is adjusted to CeO contained in the vapour deposition material after formation
2be 50 % by mole, MgO is 50 % by mole, in addition obtain vapour deposition material similarly to Example 1.The CeO contained by vapour deposition material obtained
2the median size of particle and MgO particle, CeO contained in vapour deposition material
2, the content of MgO and the basicity of particle represents in the following table 1.
< embodiment 7>
By CeO
2the combined amount of powder and MgO powder is adjusted to CeO contained in the vapour deposition material after formation
2be 60 % by mole, MgO is 40 % by mole, in addition obtain vapour deposition material similarly to Example 1.The CeO contained by vapour deposition material obtained
2the median size of particle and MgO particle, CeO contained in vapour deposition material
2, the content of MgO and the basicity of particle represents in the following table 1.
< embodiment 8>
By CeO
2the combined amount of powder and MgO powder is adjusted to CeO contained in the vapour deposition material after formation
2be 70 % by mole, MgO is 30 % by mole, in addition obtain vapour deposition material similarly to Example 1.The CeO contained by vapour deposition material obtained
2the median size of particle and MgO particle, CeO contained in vapour deposition material
2, the content of MgO and the basicity of particle represents in the following table 1.
< embodiment 9>
By CeO
2the combined amount of powder and MgO powder is adjusted to CeO contained in the vapour deposition material after formation
2be 80 % by mole, MgO is 20 % by mole, in addition obtain vapour deposition material similarly to Example 1.The CeO contained by vapour deposition material obtained
2the median size of particle and MgO particle, CeO contained in vapour deposition material
2, the content of MgO and the basicity of particle represents in the following table 1.
< embodiment 10>
By CeO
2the combined amount of powder and MgO powder is adjusted to CeO contained in the vapour deposition material after formation
2be 85 % by mole, MgO is 15 % by mole, in addition obtain vapour deposition material similarly to Example 1.The CeO contained by vapour deposition material obtained
2the median size of particle and MgO particle, CeO contained in vapour deposition material
2, the content of MgO and the basicity of particle represents in the following table 1.
< embodiment 11>
Use as the second oxide powder the high-purity C aO powder that median size is 0.6 μm, purity is 99.8%, in addition obtain vapour deposition material similarly to Example 1.The CeO contained by vapour deposition material obtained
2the median size of particle and CaO particle, CeO contained in vapour deposition material
2, the content of CaO and the basicity of particle represents in the following table 1.
< embodiment 12>
By CeO
2the combined amount of powder and CaO powder is adjusted to CeO contained in the vapour deposition material after formation
2be 30 % by mole, CaO is 70 % by mole, in addition obtain vapour deposition material similarly to Example 11.The CeO contained by vapour deposition material obtained
2the median size of particle and CaO particle, CeO contained in vapour deposition material
2, the content of CaO and the basicity of particle represents in the following table 1.
< embodiment 13>
By CeO
2the combined amount of powder and CaO powder is adjusted to CeO contained in the vapour deposition material after formation
2be 50 % by mole, CaO is 50 % by mole, in addition obtain vapour deposition material similarly to Example 11.The CeO contained by vapour deposition material obtained
2the median size of particle and CaO particle, CeO contained in vapour deposition material
2, the content of CaO and the basicity of particle represents in the following table 1.
< embodiment 14>
By CeO
2the combined amount of powder and CaO powder is adjusted to CeO contained in the vapour deposition material after formation
2be 80 % by mole, CaO is 20 % by mole, in addition obtain vapour deposition material similarly to Example 11.The CeO contained by vapour deposition material obtained
2the median size of particle and CaO particle, CeO contained in vapour deposition material
2, the content of CaO and the basicity of particle represents in the following table 1.
< embodiment 15>
By CeO
2the combined amount of powder and CaO powder is adjusted to CeO contained in the vapour deposition material after formation
2be 85 % by mole, CaO is 15 % by mole, in addition obtain vapour deposition material similarly to Example 11.The CeO contained by vapour deposition material obtained
2the median size of particle and CaO particle, CeO contained in vapour deposition material
2, the content of CaO and the basicity of particle represents in the following table 1.
< embodiment 16>
Use that median size is 0.8 μm as the second oxide powder, purity be 99.8% high purity ZnO powder and median size be 0.9 μm, purity is the mixed powder of the MgO of high purity powder of 99.7%, by CeO
2the combined amount of powder and above-mentioned mixed powder is adjusted to CeO contained in the vapour deposition material after formation
2be 5 % by mole, ZnO and MgO be respectively 90 % by mole and 5 % by mole, in addition obtain vapour deposition material similarly to Example 1.The CeO contained by vapour deposition material obtained
2the median size of particle, ZnO particle and MgO particle, CeO contained in vapour deposition material
2, the content of ZnO, MgO and the basicity of particle represents in table 2 below.
< embodiment 17>
Use that median size is 0.8 μm as the second oxide powder, purity be 99.8% high purity ZnO powder and median size be 0.6 μm, purity is the mixed powder of the high-purity C aO powder of 99.8%, by CeO
2the combined amount of powder and above-mentioned mixed powder is adjusted to CeO contained in the vapour deposition material after formation
2be 5 % by mole, ZnO and CaO be respectively 90 % by mole and 5 % by mole, in addition obtain vapour deposition material similarly to Example 1.The CeO contained by vapour deposition material obtained
2the median size of particle, ZnO particle and CaO particle, CeO contained in vapour deposition material
2, the content of ZnO, CaO and the basicity of particle represents in table 2 below.
< embodiment 18>
The high purity ZnO powder that median size is 0.8 μm, purity is 99.8% is used as the second oxide powder, median size is 0.9 μm, purity be 99.7% MgO of high purity powder and median size be 0.6 μm, purity is the mixed powder of the high-purity C aO powder of 99.8%, by CeO
2the combined amount of powder and above-mentioned mixed powder is adjusted to CeO contained in the vapour deposition material after formation
2be 5 % by mole, ZnO, MgO and CaO are respectively 75 % by mole, 10 % by mole and 10 % by mole, in addition obtain vapour deposition material similarly to Example 1.The CeO contained by vapour deposition material obtained
2the median size of particle, ZnO particle, MgO particle and CaO particle, CeO contained in vapour deposition material
2, the content of ZnO, MgO, CaO and the basicity of particle represents in table 2 below.
< embodiment 19>
The high purity ZnO powder that median size is 0.8 μm, purity is 99.8% is used as the second oxide powder, median size is 0.9 μm, purity be 99.7% MgO of high purity powder and median size be 0.6 μm, purity is the mixed powder of the high-purity C aO powder of 99.8%, by CeO
2the combined amount of powder and above-mentioned mixed powder is adjusted to CeO contained in the vapour deposition material after formation
2be 5 % by mole, ZnO, MgO and CaO are respectively 55 % by mole, 20 % by mole and 20 % by mole, in addition obtain vapour deposition material similarly to Example 1.The CeO contained by vapour deposition material obtained
2the median size of particle, ZnO particle, MgO particle and CaO particle, CeO contained in vapour deposition material
2, the content of ZnO, MgO, CaO and the basicity of particle represents in table 2 below.
< embodiment 20>
The high purity ZnO powder that median size is 0.8 μm, purity is 99.8% is used as the second oxide powder, median size is 0.9 μm, purity be 99.7% MgO of high purity powder and median size be 0.6 μm, purity is the mixed powder of the high-purity C aO powder of 99.8%, by CeO
2the combined amount of powder and above-mentioned mixed powder is adjusted to CeO contained in the vapour deposition material after formation
2be 5 % by mole, ZnO, MgO and CaO are respectively 30 % by mole, 35 % by mole and 30 % by mole, in addition obtain vapour deposition material similarly to Example 1.The CeO contained by vapour deposition material obtained
2the median size of particle, ZnO particle, MgO particle and CaO particle, CeO contained in vapour deposition material
2, the content of ZnO, MgO, CaO and the basicity of particle represents in table 2 below.
< embodiment 21>
The high purity ZnO powder that median size is 0.8 μm, purity is 99.8% is used as the second oxide powder, median size is 0.9 μm, purity be 99.7% MgO of high purity powder and median size be 0.6 μm, purity is the mixed powder of the high-purity C aO powder of 99.8%, by CeO
2the combined amount of powder and above-mentioned mixed powder is adjusted to CeO contained in the vapour deposition material after formation
2be 5 % by mole, ZnO, MgO and CaO are respectively 10 % by mole, 35 % by mole and 50 % by mole, in addition obtain vapour deposition material similarly to Example 1.The CeO contained by vapour deposition material obtained
2the median size of particle, ZnO particle, MgO particle and CaO particle, CeO contained in vapour deposition material
2, the content of ZnO, MgO, CaO and the basicity of particle represents in table 2 below.
< embodiment 22>
Use that median size is 0.9 μm as the second oxide powder, purity be 99.7% MgO of high purity powder and median size be 0.6 μm, purity is the mixed powder of the high-purity C aO powder of 99.8%, by CeO
2the combined amount of powder and above-mentioned mixing is adjusted to CeO contained in the vapour deposition material after formation
2be 5 % by mole, MgO and CaO be respectively 35 % by mole and 60 % by mole, in addition obtain vapour deposition material similarly to Example 1.The CeO contained by vapour deposition material obtained
2the median size of particle, MgO particle and CaO particle, CeO contained in vapour deposition material
2, the content of MgO, CaO and the basicity of particle represents in table 2 below.
< embodiment 23>
Use that median size is 0.8 μm as the second oxide powder, purity be 99.8% high purity ZnO powder and median size be 0.9 μm, purity is the mixed powder of the MgO of high purity powder of 99.7%, by CeO
2the combined amount of powder and above-mentioned mixed powder is adjusted to CeO contained in the vapour deposition material after formation
2be 30 % by mole, ZnO and MgO be respectively 60 % by mole and 10 % by mole, in addition obtain vapour deposition material similarly to Example 1.The CeO contained by vapour deposition material obtained
2the median size of particle, ZnO particle and MgO particle, CeO contained in vapour deposition material
2, the content of ZnO, MgO and the basicity of particle represents in table 2 below.
< embodiment 24>
Use that median size is 0.8 μm as the second oxide powder, purity be 99.8% high purity ZnO powder and median size be 0.6 μm, purity is the mixed powder of the high-purity C aO powder of 99.8%, by CeO
2the combined amount of powder and above-mentioned mixed powder is adjusted to CeO contained in the vapour deposition material after formation
2be 30 % by mole, ZnO and CaO be respectively 60 % by mole and 10 % by mole, in addition obtain vapour deposition material similarly to Example 1.The CeO contained by vapour deposition material obtained
2the median size of particle, ZnO particle and CaO particle, CeO contained in vapour deposition material
2, the content of ZnO, CaO and the basicity of particle represents in table 2 below.
< embodiment 25>
The high purity ZnO powder that median size is 0.8 μm, purity is 99.8% is used as the second oxide powder, median size is 0.9 μm, purity be 99.7% MgO of high purity powder and median size be 0.6 μm, purity is the mixed powder of the high-purity C aO powder of 99.8%, by CeO
2the combined amount of powder and above-mentioned mixed powder is adjusted to CeO contained in the vapour deposition material after formation
2be 30 % by mole, ZnO, MgO and CaO are respectively 30 % by mole, 25 % by mole and 15 % by mole, in addition obtain vapour deposition material similarly to Example 1.The CeO contained by vapour deposition material obtained
2the median size of particle, ZnO particle, MgO particle and CaO particle, CeO contained in vapour deposition material
2, the content of ZnO, MgO, CaO and the basicity of particle represents in table 2 below.
< embodiment 26>
Use that median size is 0.9 μm as the second oxide powder, purity be 99.7% MgO of high purity powder and median size be 0.6 μm, purity is the mixed powder of the high-purity C aO powder of 99.8%, by CeO
2the combined amount of powder and above-mentioned mixed powder is adjusted to CeO contained in the vapour deposition material after formation
2be 30 % by mole, MgO and CaO be respectively 25 % by mole and 45 % by mole, in addition obtain vapour deposition material similarly to Example 1.The CeO contained by vapour deposition material obtained
2the median size of particle, MgO particle and CaO particle, CeO contained in vapour deposition material
2, the content of MgO, CaO and the basicity of particle represents in table 2 below.
< embodiment 27>
Use that median size is 0.8 μm as the second oxide powder, purity be 99.8% high purity ZnO powder and median size be 0.9 μm, purity is the mixed powder of the MgO of high purity powder of 99.7%, by CeO
2the combined amount of powder and above-mentioned mixed powder is adjusted to CeO contained in the vapour deposition material after formation
2be 85 % by mole, ZnO and MgO be respectively 10 % by mole and 5 % by mole, in addition obtain vapour deposition material similarly to Example 1.The CeO contained by vapour deposition material obtained
2the median size of particle, ZnO particle and MgO particle, CeO contained in vapour deposition material
2, the content of ZnO, MgO and the basicity of particle represents in table 2 below.
< embodiment 28>
Use that median size is 0.8 μm as the second oxide powder, purity be 99.8% high purity ZnO powder and median size be 0.6 μm, purity is the mixed powder of the high-purity C aO powder of 99.8%, by CeO
2the combined amount of powder and above-mentioned mixed powder is adjusted to CeO contained in the vapour deposition material after formation
2be 85 % by mole, ZnO and CaO be respectively 10 % by mole and 5 % by mole, in addition obtain vapour deposition material similarly to Example 1.The CeO contained by vapour deposition material obtained
2the median size of particle, ZnO particle and CaO particle, CeO contained in vapour deposition material
2, the content of ZnO, CaO and the basicity of particle represents in table 2 below.
< embodiment 29>
The high purity ZnO powder that median size is 0.8 μm, purity is 99.8% is used as the second oxide powder, median size is 0.9 μm, purity be 99.7% MgO of high purity powder and median size be 0.6 μm, purity is the mixed powder of the high-purity C aO powder of 99.8%, by CeO
2the combined amount of powder and above-mentioned mixed powder is adjusted to CeO contained in the vapour deposition material after formation
2be 85 % by mole, ZnO, MgO and CaO are respectively 5 % by mole, 5 % by mole and 5 % by mole, in addition obtain vapour deposition material similarly to Example 1.The CeO contained by vapour deposition material obtained
2the median size of particle, ZnO particle, MgO particle and CaO particle, CeO contained in vapour deposition material
2, the content of ZnO, MgO, CaO and the basicity of particle represents in table 2 below.
< embodiment 30>
Use that median size is 0.9 μm as the second oxide powder, purity be 99.7% MgO of high purity powder and median size be 0.6 μm, purity is the mixed powder of the high-purity C aO powder of 99.8%, by CeO
2the combined amount of powder and above-mentioned mixed powder is adjusted to CeO contained in the vapour deposition material after formation
2be 85 % by mole, MgO and CaO be respectively 5 % by mole and 10 % by mole, in addition obtain vapour deposition material similarly to Example 1.The CeO contained by vapour deposition material obtained
2the median size of particle, MgO particle and CaO particle, CeO contained in vapour deposition material
2, the content of MgO, CaO and the basicity of particle represents in table 2 below.
< embodiment 31>
Vapour deposition material is obtained under condition similarly to Example 20.The CeO contained by vapour deposition material obtained
2the median size of particle, ZnO particle, MgO particle and CaO particle, CeO contained in vapour deposition material
2, the content of ZnO, MgO, CaO and the basicity of particle represents with in following table 3.
< embodiment 32>
Vapour deposition material is obtained under condition similarly to Example 25.The CeO contained by vapour deposition material obtained
2the median size of particle, ZnO particle, MgO particle and CaO particle, CeO contained in vapour deposition material
2, the content of ZnO, MgO, CaO and the basicity of particle represents with in following table 3.
< embodiment 33>
Vapour deposition material is obtained under condition similarly to Example 29.The CeO contained by vapour deposition material obtained
2the median size of particle, ZnO particle, MgO particle and CaO particle, CeO contained in vapour deposition material
2, the content of ZnO, MgO, CaO and the basicity of particle represents with in following table 3.
< embodiment 34>
Vapour deposition material is obtained under condition similarly to Example 20.The CeO contained by vapour deposition material obtained
2the median size of particle, ZnO particle, MgO particle and CaO particle, CeO contained in vapour deposition material
2, the content of ZnO, MgO, CaO and the basicity of particle represents with in following table 3.
< embodiment 35>
Vapour deposition material is obtained under condition similarly to Example 25.The CeO contained by vapour deposition material obtained
2the median size of particle, ZnO particle, MgO particle and CaO particle, CeO contained in vapour deposition material
2, the content of ZnO, MgO, CaO and the basicity of particle represents with in following table 3.
< embodiment 36>
Vapour deposition material is obtained under condition similarly to Example 29.The CeO contained by vapour deposition material obtained
2the median size of particle, ZnO particle, MgO particle and CaO particle, CeO contained in vapour deposition material
2, the content of ZnO, MgO, CaO and the basicity of particle represents with in following table 3.
< comparative example 1>
Be adjusted to and do not mix outside the first oxide particle, obtain vapour deposition material similarly to Example 1.The median size of MgO particle contained in the vapour deposition material obtained, the basicity of particle represent with in following table 4.
< comparative example 2>
By CeO
2the combined amount of powder and MgO powder is adjusted to CeO contained in the vapour deposition material after formation
2be 3 % by mole, MgO is 97 % by mole, in addition obtain vapour deposition material similarly to Example 1.The CeO contained by vapour deposition material obtained
2the median size of particle and MgO particle, CeO contained in vapour deposition material
2, the content of MgO and the basicity of particle represents with in following table 4.
< comparative example 3>
By CeO
2the combined amount of powder and MgO powder is adjusted to CeO contained in the vapour deposition material after formation
2be 90 % by mole, MgO is 10 % by mole, in addition obtain vapour deposition material similarly to Example 1.The CeO contained by vapour deposition material obtained
2the median size of particle and MgO particle, CeO contained in vapour deposition material
2, the content of MgO and the basicity of particle represents with in following table 4.
< comparative example 4>
Be adjusted to and do not mix outside the second oxide particle, obtain vapour deposition material similarly to Example 1.CeO contained in the vapour deposition material obtained
2the median size of particle, the basicity of particle represent with in following table 4.
< comparative example 5>
Be adjusted to and do not mix outside the first oxide particle, obtain vapour deposition material similarly to Example 11.The median size of CaO particle contained in the vapour deposition material obtained, the basicity of particle represent with in following table 4.
< comparative example 6>
By CeO
2the combined amount of powder and CaO powder is adjusted to CeO contained in the vapour deposition material after formation
2be 3 % by mole, CaO is 97 % by mole, in addition obtain vapour deposition material similarly to Example 11.The CeO contained by vapour deposition material obtained
2the median size of particle and CaO particle, CeO contained in vapour deposition material
2, the content of CaO and the basicity of particle represents with in following table 4.
< comparative example 7>
By CeO
2the combined amount of powder and CaO powder is adjusted to CeO contained in the vapour deposition material after formation
2be 90 % by mole, CaO is 10 % by mole, in addition obtain vapour deposition material similarly to Example 11.The CeO contained by vapour deposition material obtained
2the median size of particle and CaO particle, CeO contained in vapour deposition material
2, the content of CaO and the basicity of particle represents with in following table 4.
< comparative example 8>
Be adjusted to and do not mix outside the second oxide particle, obtain vapour deposition material similarly to Example 1.CeO contained in the vapour deposition material obtained
2the median size of particle, the basicity of particle represent with in following table 4.
< comparative example 9>
Vapour deposition material is obtained under the condition same with comparative example 1.Content of MgO contained in the median size of MgO particle contained in the vapour deposition material obtained, vapour deposition material, the basicity of particle represent with in following table 4.
< comparative example 10>
Vapour deposition material is obtained under the condition same with comparative example 5.CaO content contained in the median size of CaO particle contained in the vapour deposition material obtained, vapour deposition material, the basicity of particle represent with in following table 4.
< comparative example 11>
Vapour deposition material is obtained under the condition same with comparative example 4.CeO contained in the vapour deposition material obtained
2ceO contained in the median size of particle, vapour deposition material
2the basicity of content, particle represents with in following table 4.
< comparative example 12>
Vapour deposition material is obtained under the condition same with comparative example 1.Content of MgO contained in the median size of MgO particle contained in the vapour deposition material obtained, vapour deposition material, the basicity of particle represent with in following table 4.
< comparative example 13>
Vapour deposition material is obtained under the condition same with comparative example 5.CaO content contained in the median size of CaO particle contained in the vapour deposition material obtained, vapour deposition material, the basicity of particle represent with in following table 4.
< comparative example 14>
Vapour deposition material is obtained under the condition same with comparative example 4.CeO contained in the vapour deposition material obtained
2ceO contained in the median size of particle, vapour deposition material
2the basicity of content, particle represents with in following table 4.
[table 1]
[table 2]
[table 3]
[table 4]
< comparison test and evaluation 1>
Be used in the vapour deposition material obtained in embodiment 1 ~ 36 and comparative example 1 ~ 14, the PET film of thickness 75 μm form film by carrying out vapour deposition with the method shown in following table 5 ~ table 7, and forms thin-film sheet.For these thin-film sheets, measure water vapor transmission rate (WVTR), gas barrier property is evaluated.In addition, with place under, super-humid conditions more at higher temperature than the condition in above-mentioned gas barrier property evaluation long-time after water vapor transmission rate (WVTR) and velocity of variation have rated weather resistance.And then, for these thin-film sheets, measure light transmission rate, have rated the transparency.These results represent with in following table 5 ~ table 7.
(1) gas barrier property: thin-film sheet is placed on be set as temperature 20 DEG C, relative humidity 50%RH clean room in after 1 hour, use the water vapor transmission rate (WVTR) determinator (model name: PERMATRAN-W type 3/33) of MOCON Inc., under the condition of temperature 40 DEG C, relative humidity 90%RH, measure water vapor transmission rate (WVTR) S.
(2) weather resistance: for placing the thin-film sheet after 1 hour in the clean room being set as temperature 20 DEG C, relative humidity 50%RH, in order to the deterioration preventing the water vapour of PET film from causing, identical thin-film sheet is superposed each two by mode respectively that become outside with the film of thin-film sheet, engages four limits with hot enclosuring device.Put it in the fixed temperature and humidity device being set as temperature 85 DEG C, relative humidity 90%RH, place 100 hours.Afterwards, in the same manner as above-mentioned gas barrier property evaluation, use water vapor transmission rate (WVTR) determinator, under the condition of temperature 40 DEG C, relative humidity 90%RH, measure water vapor transmission rate (WVTR) T.In addition, the velocity of variation (T/S × 100) of water vapor transmission rate (WVTR) T-phase for above-mentioned water vapor transmission rate (WVTR) S of mensuration is calculated.
(3) light transmission rate: use the spectrophotometer (model name: U-4000) of society of Hitachi Co., Ltd to measure the light transmission rate of wavelength 380 ~ 780nm to thin-film sheet.
[table 5]
[table 6]
[table 7]
As known from Tables 5 to 7, the first oxide compound is compared and the second oxide compound is CeO
2during with the embodiment 1 ~ 10 of the combination of MgO and comparative example 1 ~ 4, in embodiment 1 ~ 10, it is 0.29g/m that ambient temperatare puts the water vapor transmission rate (WVTR) S after 1 hour
2below it, wherein, in embodiment 3 ~ 8, be 0.1g/m
2below it.In addition, to judge under the condition of temperature 85 DEG C, relative humidity 90%RH and then place the water vapor transmission rate (WVTR) T-phase after 100 hours to be also suppressed in less than 200% for the velocity of variation of water vapor transmission rate (WVTR) S, under high temperature, high humidity environment, long-time weather resistance when placing is also excellent.
On the other hand, use and singlely formed comparative example 1 that the vapour deposition material that forms formed by MgO, used the first oxide compound CeO
2content be less than 5% vapour deposition material formed comparative example 2, use the content of the second oxide M gO be less than 15% vapour deposition material formed comparative example 3 and use by CeO
2in the thin-film sheet of the comparative example 4 that the vapour deposition material that single composition is formed is formed, the velocity of variation of water vapor transmission rate (WVTR) S and water vapor transmission rate (WVTR) is all large than embodiment 1 ~ 10.
In addition, be CeO to the first oxide compound and the second oxide compound
2compare with the embodiment 11 ~ 15 of the combination of CaO and comparative example 5 ~ 8, then, in embodiment 11 ~ 15, at room temperature the water vapor transmission rate (WVTR) S placed after 1 hour is 0.27g/m
2below it, wherein, in embodiment 13 be 0.1g/m
2below it.In addition, judge that the water vapor transmission rate (WVTR) T placed after 100 hours also suppresses below 200% the velocity of variation of water vapor transmission rate (WVTR) S further under the condition of temperature 85 DEG C, relative humidity 90%RH, the weather resistance under hot and humid environment during long-time placement is also excellent.
On the other hand, use and singlely formed comparative example 5 that the vapour deposition material that forms formed by CaO, used the first oxide compound CeO
2content be less than 5% vapour deposition material formed comparative example 6, use the content of the second oxide compound CaO be less than 15% vapour deposition material formed comparative example 7 and use by CeO
2in the thin-film sheet of the comparative example 8 that the vapour deposition material that single composition is formed is formed, the velocity of variation of water vapor transmission rate (WVTR) S and water vapor transmission rate (WVTR) is all large than embodiment 11 ~ 15.
In addition, the second oxide compound is in the two or more embodiment 16 ~ 30 in ZnO, MgO or CaO, and at room temperature the water vapor transmission rate (WVTR) S placed after 1 hour is 0.21g/m
2below it, wherein, be 0.1g/m in embodiment 20,24 ~ 26
2below it.In addition, judge that the water vapor transmission rate (WVTR) T placed after 100 hours also suppresses below 200% the velocity of variation of water vapor transmission rate (WVTR) S further under the condition of temperature 85 DEG C, relative humidity 90%RH, except high gas barrier property, and then long-time weather resistance when placing is also excellent under hot and humid environment.In addition, for light transmission rate, obtain the result of embodiment 1 ~ 30 no less than comparative example 1 ~ 8.
And then, to using the vapour deposition material that obtains under the same terms and by the embodiment 20,31,34 of diverse ways film forming respectively, embodiment 25,32,35, embodiment 29,33,36, comparative example 1,9,2, comparative example 5,10,13, comparative example 4,11,14 compares respectively, then there is trend slightly poor compared with the film formed by RPD method according to assessment item, but compare with the film of the embodiment 34,35,36 being heated by resistive method film forming with by the embodiment 31,32,33 of EB method film forming, possess sufficient gas barrier property, weather resistance and the transparency.
By these results verifications, the film using vapour deposition material of the present invention to be formed has very excellent gas barrier property and the transparency.
Claims (8)
1. a vapour deposition material, for mixing the first oxide powder and the second oxide powder and the vapour deposition material made, is characterized in that,
Described first oxide powder is CeO
2powder, the first oxide compound purity of described first oxide powder is more than 98%,
Described second oxide powder is two kinds of mixed powders of CaO powder or CaO and ZnO or MgO or three kinds of mixed powders of ZnO, MgO and CaO, and the second oxide compound purity of described second oxide powder is more than 98%,
Described vapour deposition material is made up of the particle containing described first oxide particle and described second oxide particle,
The first oxide compound in described vapour deposition material and the mol ratio of the second oxide compound are 10 ~ 80: 90 ~ 20, and the basicity of described particle is more than 0.1.
2. vapour deposition material according to claim 1, the median size of described first oxide particle is 0.1 ~ 10 μm, and the median size of described second oxide particle is 0.1 ~ 10 μm.
3. the manufacture method of a film, it is characterized in that, by the vapour deposition material described in claim 1 or 2 being used as the vacuum film formation of target, the first base material film forms the sull of the metal element A comprised contained by described first oxide compound and the metallic element B contained by described second oxide compound.
4. a thin-film sheet, by the vapour deposition material described in claim 1 or 2 being used as the vacuum film formation of target, first base material film is formed the sull of the metal element A comprised contained by described first oxide compound and the metallic element B contained by described second oxide compound
Whole metallic elements in described film containing proportional be set to 100 % by mole time, described metal element A containing proportional be 5 ~ 85 % by mole, described metallic element B containing proportional be 95 ~ 15 % by mole.
5. thin-film sheet according to claim 4, described vacuum film formation is any one in e-beam evaporation, ion plating method, reactive plasma sedimentation, electrical resistance heating or induction heating.
6. the thin-film sheet according to claim 4 or 5, under the condition of temperature 20 DEG C, relative humidity 50%RH, place 1 little water vapor transmission rate (WVTR) S is constantly 0.3g/m
2below it.
7. thin-film sheet according to claim 6, place under the condition of temperature 20 DEG C, relative humidity 50%RH after 1 hour, when under the condition of temperature 85 DEG C, relative humidity 90%RH, placement 100 little water vapor transmission rate (WVTR)s are constantly set to T further, described water vapor transmission rate (WVTR) T-phase is less than 200% for velocity of variation T/S × 100 of described water vapor transmission rate (WVTR) S.
8. a laminate, the film of the thin-film sheet described in any one in claim 4 ~ 7 is formed side and is formed by adhesive linkage lamination second base material film.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2010-057279 | 2010-03-15 | ||
| JP2010057279 | 2010-03-15 | ||
| JP2010256422A JP5664162B2 (en) | 2010-03-15 | 2010-11-17 | Vapor deposition material for forming a thin film, and a thin film sheet and a laminated sheet provided with the thin film |
| JP2010-256422 | 2010-11-17 |
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| CN102191463A CN102191463A (en) | 2011-09-21 |
| CN102191463B true CN102191463B (en) | 2015-12-16 |
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| CN110845229B (en) * | 2019-11-27 | 2021-04-23 | 中国科学技术大学 | LaBiO3Film, LaBiO3Ceramic target material and preparation method thereof |
| CN111393165B (en) * | 2020-03-27 | 2022-04-15 | 有研资源环境技术研究院(北京)有限公司 | Preparation method of cerium oxide particles for coating |
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| US20030157346A1 (en) * | 2002-02-14 | 2003-08-21 | Fuji Photo Film Co., Ltd. | Gas Barrier film |
| CN1609262A (en) * | 2003-10-21 | 2005-04-27 | 宇部材料工业株式会社 | Magnesium vapour-deposition material |
| CN1791510A (en) * | 2003-05-16 | 2006-06-21 | 凸版印刷株式会社 | Transparent gas barrier laminated film, and electroluminescent light-emitting element, electroluminescent display device, and electrophoretic display panel using the same |
| US20090000517A1 (en) * | 2007-06-20 | 2009-01-01 | Dai Nippon Printing Co., Ltd. | Powder mixture to be made into evaporation source material for use in Ion plating, evaporation source material for use in Ion plating and method of producing the same, and gas barrier sheet and method of producing the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2903546B2 (en) * | 1989-06-13 | 1999-06-07 | 東洋紡績株式会社 | Method of manufacturing gas barrier film |
| JP3893793B2 (en) * | 1999-04-05 | 2007-03-14 | 三菱マテリアル株式会社 | MgO vapor deposition material and method for producing the same |
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2011
- 2011-03-14 CN CN201110065635.6A patent/CN102191463B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030157346A1 (en) * | 2002-02-14 | 2003-08-21 | Fuji Photo Film Co., Ltd. | Gas Barrier film |
| CN1791510A (en) * | 2003-05-16 | 2006-06-21 | 凸版印刷株式会社 | Transparent gas barrier laminated film, and electroluminescent light-emitting element, electroluminescent display device, and electrophoretic display panel using the same |
| CN1609262A (en) * | 2003-10-21 | 2005-04-27 | 宇部材料工业株式会社 | Magnesium vapour-deposition material |
| US20090000517A1 (en) * | 2007-06-20 | 2009-01-01 | Dai Nippon Printing Co., Ltd. | Powder mixture to be made into evaporation source material for use in Ion plating, evaporation source material for use in Ion plating and method of producing the same, and gas barrier sheet and method of producing the same |
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