CN102191462A - Vapor phase deposition material for forming film, film sheet with the film, and laminated sheet - Google Patents

Vapor phase deposition material for forming film, film sheet with the film, and laminated sheet Download PDF

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CN102191462A
CN102191462A CN2011100656286A CN201110065628A CN102191462A CN 102191462 A CN102191462 A CN 102191462A CN 2011100656286 A CN2011100656286 A CN 2011100656286A CN 201110065628 A CN201110065628 A CN 201110065628A CN 102191462 A CN102191462 A CN 102191462A
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vapour deposition
deposition material
powder
film
particle
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黛良享
有泉久美子
黑光祥郎
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Mitsubishi Materials Corp
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Mitsubishi Materials Corp
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Priority claimed from JP2010256420A external-priority patent/JP2011214133A/en
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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 present invention provides a vapor phase deposition material which is suitable for forming a film with excellent transparency and excellent air barring performance, a film sheet with the film, and a laminated sheet. The vapor phase deposition material of the invention is manufactured through mixing a first oxide powder and a second oxide powder. The vapor phase deposition material is characterized in that: the first oxide powder is Fe2O3 powder; the purity of the first oxide of the first oxide powder is more than 98%; the second oxide powder is one powder or a mixed powder with more than two powders which are selected from: ZnO, MgO and CaO; the purity of the second oxide of the second oxide powder is more than 98%; the vapor phase deposition material is composed of particles which comprises first oxide particles and second oxide particles; a molar ratio between the first oxide and the second oxide in the vapor phase deposition material is 5-85: 95-15; and the alkalinity of the particle is more than 0.1.

Description

Film forms with vapour deposition material, the thin-film sheet that possesses this film and laminate
Technical field
The present invention relates to be fit to form all excellents such as the transparency, gas barrier property film the vapour deposition material and possess the thin-film sheet and the laminate of this film.More specifically, relate to and be used to form these all excellents, particularly be suitable as liquid-crystal display, OLED display or solar module etc. the choke material film the vapour deposition material and possess the thin-film sheet and the laminate of this film.
Background technology
Machines such as liquid-crystal display, OLED display or solar cell are moisture-proof not usually because moisture absorption makes the quick deterioration of its characteristic, therefore must equip have highly moistureproof, promptly have anti-block or water vapour etc. through or the parts of the gas barrier property of intrusion.
For example, in the example of solar cell, be provided with base (back seat) at the back side with the sensitive surface opposition side of solar module.This base typically is made of the choke material with highly moistureproof and their parts of protection etc. on base material.
Base as such formation solar module; for example disclose by high-strength heat-resistant weathering resistance resin and sandwiched the moisture resistance tinsel; and then the back-protective that the solar module that vitreous vapor deposition film forms is set in one side is with sheet material (for example, referring to Patent Document 1).In this sheet material, use tinsels such as aluminium foil, zinc-plated iron foil, zinc-plated iron foil as the choke material.In addition, disclose high moisture-proofing film and high weather film laminating and the integrated solar cell that forms have been covered the solar cell (for example, referring to Patent Document 2) that material is used for the rear side guard block.This solar cell covers high moisture-proofing film in material and uses on base material films such as polyethylene terephthalate (PET) film the moisture barrier films that is made of the coated film of inorganic oxides such as silicon-dioxide, aluminum oxide by formation such as chemical vapor deposition (CVD), physical vapor deposition (PVD) methods as the choke material.In addition, the photovoltaic module (for example, referring to Patent Document 3) that possesses the blocking layer that is made of plastics film or plastic composite that presents inorganic oxide layer is disclosed.In this inorganic oxide layer, aluminum oxide or silicon-dioxide use as its coating material.
Patent documentation 1: the real fair 2-44995 communique of Japan (the 41st～44 row on claims of utility model registration and the 5th hurdle)
Patent documentation 2: TOHKEMY 2000-174296 communique (claim 1, claim 7 and [0019] section)
Patent documentation 3: Japanese Unexamined Patent Application Publication 2002-520820 communique (claim 1 and [0019] section)
But because tinsels such as use aluminium foil as the choke material, as if the base that this sheet material is applied to solar module, then might reduce by proof voltage, electric current leaks the back-protective shown in the above-mentioned patent documentation 1 with sheet material.In addition, use the sheet material of tinsel if the thickness of tinsel is below the 20 μ m, the pin hole that then produces 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 in above-mentioned patent documentation 2 and the patent documentation 3 under the situation of inorganic oxides such as employed silicon-dioxide, aluminum oxide, must guarantee thickness more than 100nm in order to obtain high gas barrier property, even can not assert that like this gas barrier property is abundant.
Summary of the invention
The objective of the invention is to, the vapour deposition material of the film that is fit to the formation transparency and gas barrier property excellence is provided.
Another object of the present invention is to, the thin-film sheet and the laminate of the film that possesses the transparency and gas barrier property excellence is provided.
A first aspect of the present invention is the vapour deposition material, mixes first oxide powder and second oxide powder and makes, and it is characterized in that above-mentioned first oxide powder is Fe 2O 3Powder, the first oxide compound purity of this first oxide powder is more than 98%, above-mentioned second oxide powder is to be selected from a kind of powder among ZnO, MgO and the CaO or two or more mixed powders, the second oxide compound purity of this second oxide powder is more than 98%, the vapour deposition material is made of the particle that contains first oxide particle and second oxide particle, first oxide compound in the vapour deposition material and the ratio of second oxide compound are 5～85: 95～15, and particulate basicity 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 first oxide particle is 0.1～10 μ m, and the median size of second oxide particle is 0.1～10 μ m.
A third aspect of the present invention is the manufacture method of film, it is characterized in that, by will based on first or the vapour deposition material of second aspect as the vacuum film formation method of target, on first base material film, form the sull that comprises the contained metallic element B of the contained metal element A of first oxide compound and second oxide compound.
As shown in Figure 1, a fourth aspect of the present invention is a thin-film sheet 10, by will based on first or the vapour deposition material of second aspect as the vacuum film formation method of target, form the sull 12 comprise the contained metallic element B of the contained metal element A of first oxide compound and second oxide compound on first base material film 11, metal element A in the above-mentioned film 12 and the mol ratio A/B of metallic element B are 10/95～170/15.
A fifth aspect of the present invention is the invention based on fourth aspect, it is characterized in that, further, the vacuum film formation method is a kind of in electron beam evaporation plating method, ion plating method, reactive plasma sedimentation, electrical resistance heating or the induction heating.
A sixth aspect of the present invention is based on the invention of the 4th or the 5th aspect, it is characterized in that, further, the water vapor transmission rate (WVTR) S when placing 1 hour under the condition of 20 ℃ of temperature, relative humidity 50%RH is 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, after placing 1 hour under the condition of 20 ℃ of temperature, relative humidity 50%RH, when the water vapor transmission rate (WVTR) when further placing 100 hours under the condition of 85 ℃ of temperature, relative humidity 90%RH was made as T, water vapor transmission rate (WVTR) T was below 200% with respect to 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 a laminate 20, forms sides at the film 12 based on the thin-film sheet 10 aspect the 4th to the 7th and forms by adhesive linkage 13 laminations second base material film 14.
In the vapour deposition material of a first aspect of the present invention, first oxide powder is Fe 2O 3Powder, the first oxide compound purity of this first oxide powder is more than 98%, above-mentioned second oxide powder is for being selected from ZnO, a kind of powder among MgO and the CaO or two or more mixed powders, the second oxide compound purity of this second oxide powder is more than 98%, the vapour deposition material is made of the particle that contains first oxide particle and second oxide particle, first oxide compound in the vapour deposition material and the ratio of second oxide compound are 5～85: 95～15, and particulate basicity is more than 0.1, compares the film that significantly improves gas barrier property thereby can form with existing choke material.
In the vapour deposition material of a second aspect of the present invention, the median size of first oxide particle is 0.1～10 μ m, and the median size of second oxide particle is 0.1～10 μ m, thereby can form the good and thick vapor-deposited film of vapour deposition efficient, therefore can keep high gas barrier property and make its stabilization.
In the thin-film sheet of a fourth aspect of the present invention, by possessing the film that comprises the contained metallic element B of the contained metal element A of first oxide compound and second oxide compound, wherein, the mol ratio A/B of metal element A and metallic element B is 10/95～170/15, has the excellent transparency and gas barrier property.
In the thin-film sheet of a sixth aspect of the present invention, the water vapor transmission rate (WVTR) S when placing 1 hour under the condition of 20 ℃ of temperature, relative humidity 50%RH is 0.3g/m 2Below it, has the little very high gas barrier property of bringing along with effluxion of deterioration.
In the thin-film sheet of a seventh aspect of the present invention, after placing 1 hour under the condition of 20 ℃ of temperature, relative humidity 50%RH, when the water vapor transmission rate (WVTR) when further placing 100 hours under the condition of 85 ℃ of temperature, relative humidity 90%RH is made as T, water vapor transmission rate (WVTR) T is below 200% with respect to velocity of variation T/S * 100 of water vapor transmission rate (WVTR) S, has the very little gas barrier property of bringing along with effluxion of deterioration.
In the laminate of a eighth aspect of the present invention, take the film of the thin-film sheet aspect the 4th to the 7th to form the further structure by adhesive linkage lamination second base material film of side.Thus, second base material film can protective film, therefore can keep high gas barrier property and make its stabilization.
Description of drawings
Fig. 1 is the sectional view of the laminar structure of the thin-film sheet of schematic representation embodiment of the present invention and laminate.
Fig. 2 is the figure of the cross section structure of the existing thin-film sheet of schematic representation.
Fig. 3 is the figure of cross section structure of the thin-film sheet of schematic representation 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
Below, with reference to the description of drawings embodiments of the present invention.Vapour deposition material of the present invention can be suitable for the formation of film.Use the formed film of this vapour deposition material to play and prevent that block or water vapour etc. see through or the effect of the choke material of intrusion.
This vapour deposition material mixes first oxide powder and second oxide powder and makes.First oxide powder that is used to make the vapour deposition material is Fe 2O 3Powder, the first oxide compound purity of this first oxide powder is more than 98%, be preferably more than 98.4%, second oxide powder is to be selected from a kind of powder among ZnO, MgO and the CaO or two or more mixed powders, the second oxide compound purity of this second oxide powder is more than 98%, to be preferably more than 99.5%.At this, the first oxide compound purity of first oxide powder is defined as more than 98%, be because less than 98% o'clock because impurity and crystallinity worsens, barrier properties reduces as a result.In addition, the second oxide compound purity of second oxide powder is defined as more than 98%, be because less than 98% o'clock because impurity and crystallinity worsens, barrier properties reduces as a result.And the powder purity in this specification sheets is by spectroscopic analysis (inductively coupled plasma apparatus for analyzing luminosity: Japanese ジ ヤ one レ Le ア Star シ ユ system ICAP-88) measure.In addition, this vapour deposition material preferably is made of the polycrystalline particle that contains first oxide particle and second oxide particle, and its relative density is more than 90%, to be preferably more than 95%.Making relative density is to be because the increase of splashing during less than 90% o'clock film forming more than 90%.And, in this embodiment, make particulate be organized as polycrystalline, but also can be monocrystalline.
In addition, the median size of first oxide particle that this vapour deposition material contains is 0.1～10 μ m, and the median size of second oxide particle is 0.1～10 μ m, and first oxide compound in the vapour deposition material and the ratio of second oxide compound are 5～85: 95～15.And particulate basicity is more than 0.1.By contain first oxide particle and second oxide particle of miniaturization like this with the regulation ratio, high resistant gas is apparent in uses in the formed film of this vapour deposition material.
Its technical the reasons are as follows: usually use (1) only to contain first oxide particle and do not contain the vapour deposition material of second oxide particle, (2) only contain second oxide particle and do not contain the vapour deposition material of first oxide particle, (3) contain first oxide particle and second oxide particle simultaneously but first oxide particle contain proportional few vapour deposition material, perhaps (4) contain first oxide particle and second oxide particle but under the situation that contains proportional few vapour deposition material of second oxide particle simultaneously, as shown in Figure 2, be formed on crystallization phases that sull 32 on first base material film 11 becomes column crystal for the infiltration direction of gas accumulative structure abreast.Gas molecules such as water vapour are owing to advance along the interface of accumulative crystal boundary abreast, the crystallization of above-mentioned column crystal abreast in the film 32 of accumulative structure block low.On the other hand, when using when containing the vapour deposition material of first oxide particle of miniaturization or second oxide particle with the regulation ratio, as shown in Figure 3, for the sull 12 that is formed on first base material film 11, the part of the column crystal that forms when using the vapour deposition material of single composition is defeated and dispersed, becomes the microtexture near the densification of noncrystalline state.In the microtexture near the densification of noncrystalline state, gas molecules such as water vapour need move at the labyrinth-like middle and long distance, and therefore at the film 12 of the microtexture of above-mentioned densification near noncrystalline state, block is improved.So, inferring by crystalline texture is non-column crystal, and film forming is the structure that sees through or invade that is fit to prevent moisture etc., and gas barrier property improves.In addition, also think if first oxide particle that contains and second oxide particle all by miniaturization, when film is grown up by vapour deposition process, can come 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, the vapour deposition material, be that to be defined as above-mentioned scope be because median size separately during less than lower value to the two median size of first oxide particle contained in the particle and second oxide particle, in the manufacturing process of vapour deposition material, the cohesion of powder is remarkable, hinder uniform mixing, if separately median size surpasses higher limit, then can't fully obtain being formed with the effect of the doubtful sosoloid that helps to improve gas barrier property.Wherein, the median size of preferred especially first oxide particle is 0.1～10 μ m, and the median size of second oxide particle is 0.1～10 μ m.And in this manual, median size is according to laser diffraction and scattering method (micro-track method), use day machine dress society's system (FRA type), use Sodium hexametaphosphate 99 as dispersion medium, a minute is set at 30 seconds and measures, and will measure three times value equalization and obtain.
In addition, with the limited proportion of first contained in the vapour deposition material oxide compound and second oxide compound above-mentioned scope be because when the ratio of first oxide compound less than the ratio of 5 or second oxide compound less than 5 the time, containing of first oxide particle or second oxide particle is proportional very few, near single composition, thereby the crystallization phases that becomes column crystal easily can not form the film with fine and close microtexture for gas-permeable direction accumulative structure abreast.
And then it is because when less than 0.1 the time that particulate basicity is defined as more than 0.1, and it is defeated and dispersed and near the microtexture of the densification of noncrystalline state that film is difficult for becoming the part of column crystal.Should " basicity " by gloomy strong forever inferior proposition, for example in his basicity of using formula as follows to come the regulation glass powder in (K.Morinaga, H.Yoshida And H.Takebe:J.Am Cerm.Soc., 77,3113 (1994)) of recording.Its extracts is as follows.
" oxide M iThe M of O iBonding strength between the-O is as gravitation A between positively charged ion-oxonium ion iObtain 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 are 2
R i: cationic ionic radius
Figure BSA00000454125300071
Oxonium ion is
Figure BSA00000454125300072
With this A iB reciprocal i(1/A i) as single composition oxide M iThe oxygen supply ability of O.
B i≡1/A i
With this B iBe normalized to B CaO=1, B SiO2=0, the Bi-index of then giving each single one-tenth sub-oxide.Expand the Bi-index of this each composition to the multicomponent system by cation fraction, then can calculate the B-index (=basicity) of molten mass of the glass oxide compound of any composition.B＝∑n i·B i
n i: cation fraction
Gui Ding basicity is represented the oxygen supply ability as described above like this, is worth big more easy more supply oxygen, causes easily and the giving and accepting of the oxygen of other metal oxide.”
In the present invention,, make an explanation by making glass replace oxide compound for the basicity index of glass powder, with the basicity arrangement of oxide mixture in film, becoming index easily near the microtexture of the densification of noncrystalline state.Be the fused notion under the situation of glass, but in the present invention, the mechanism that produces glass formation during with film forming serve as basic.Become ionic condition from the element of vapour deposition material distillation, element is piled up with nonequilibrium state on substrate.The particulate basicity that obtain by following formula this moment is more than 0.1, and then film is grown up with glassy (amorphous), and element is fitly arranged with very fine and close state.
Use the film of vapour deposition material formation of the present invention owing to have high gas barrier property, except the purposes of choke materials such as moisture barrier films that the base that constitutes solar cell is arranged, can also suitably be utilized as liquid-crystal display, OLED display or illumination choke material with OLED display etc.In addition, this film is owing to have the transparency that transmitance is 85%～95% degree, also is suitable as the choke material etc. that is used for the high gas barrier property of requirement and requires to see through parts, the sensitive surface side of for example solar cell or the image vision side of indicating meter etc. of light.
Then, be the manufacture method that representative illustrates vapour deposition material of the present invention with the situation of making by sintering process.At first, will mix as the purity 98% above high purity powdered form of first oxide powder, purity 98% above high purity powdered form, tackiness agent and organic solvent as second oxide powder, preparation concentration is the slurry of 30～75 quality %.The slurry of preferred preparation 40～65 quality %.And first oxide powder and second oxide powder are to adjust and mix in the mode that first oxide compound in the vapour deposition material after making and the ratio of second oxide compound satisfy above-mentioned scope.It is because if surpass 75 quality % that the concentration limits of slurry is decided to be 30～75 quality %, then because above-mentioned slurry is a non-aqueous system, there is the problem be difficult to carry out stable mixing granulation, if less than 30 quality %, then can't obtains having the sintered compact of the densification of uniform formation.In addition, because the median size of first oxide powder that the vapour deposition material after making is contained and the median size of second oxide particle are adjusted in the above-mentioned scope, therefore the median size of the median size of first oxide powder that uses and second oxide powder be preferably first oxide powder in the scope of 0.1～10 μ m, second oxide powder is in the scope of 0.1～10 μ m.
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, the wet mixing of high purity powdered form and tackiness agent and organic solvent, particularly high purity powdered form are undertaken by wet-type ball mill or mixer grinder with the wet mixing as the organic solvent of dispersion medium.In the wet-type ball mill, use ZrO 2During the ball of system, use a plurality of ZrO of diameter 5～10mm 2The ball wet mixing of system 8～24 hours, preferred wet mixing 20～24 hours.ZrO 2It is because undercompounding during not enough 5mm that the diameter of ball of system is defined as 5～10mm, the bad problem that exists impurity to increase when surpassing 10mm.In addition, even mixing time the longest is 24 hours to be that impurity produces also seldom because long-time continuous is mixed.
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 not enough 1mm undercompounding then, if surpass the trouble that 3mm then exists impurity to increase that the diameter of ball of system is defined as 1～3mm.In addition, mixing time shortens to the longest 1 hour and is because if surpass 1 hour, be not only the mixing of raw material, and ball itself also can wear and tear, and can become the reason that produces impurity, and only need 1 hour just can thorough mixing.
Then the above-mentioned slurry of spraying drying obtains the mixing granulation powder that median size is 50～250 μ m, preferred 50～200 μ m.The mould of this prilling powder being put into regulation is shaped with specified pressure.Above-mentioned spraying drying preferably uses spray-drier to carry out, and the regulation mould uses uniaxial pressing device or isostatic cool pressing (CIP:Cold Isostatic Press) building mortion.In the uniaxial pressing device, make prilling powder at 750～2000kg/cm 2(73.55～196.1MPa), preferred 1000～1500kg/cm 2(single shaft press molding under 98.1～147.1MPa) the pressure in the CIP building mortion, makes prilling powder at 1000～3000kg/cm 2(98.1～294.2MPa), preferred 1500～2000kg/cm 2(CIP is shaped under 147.1～196.1MPa) the pressure.It is because prevent the distortion behind the sintering when improving the density of molding and do not need to carry out post-treatment that pressure is limited to above-mentioned scope.
And then, with the specified temperature sintered shaped body.Sintering is in atmosphere, rare gas element, vacuum or reducing gas atmosphere, more than 1000 ℃, carry out under preferred 1200～1400 ℃ of temperature 1～10 hour, preferably carried out 2～5 hours.Thus, obtaining relative density is particle more than 90%.Above-mentioned sintering under atmospheric pressure carries out, but when carrying out the pressure sintering as hot pressing (HP) sintering or hot isostatic pressing (HIP:Hot Isostatic Press) sintering, preferably in rare gas element, vacuum or reducing gas atmosphere, under the temperature more than 1000 ℃, carried out 1～5 hour.
Then, thin-film sheet of the present invention and laminate are described with its manufacture method.As shown in Figure 1, thin-film sheet 10 of the present invention has first base material film 11 and the preferred film of the present invention 12 that uses above-mentioned vapour deposition material to form.And laminate 20 of the present invention has the thin-film sheet 10 of the invention described above and forms side by the second bonding base material film 14 of adhesive linkage 13 at the film of this thin-film sheet 10.
First base material film 11 and second base material film 14 preferably have the mechanicalness intensity of the long hot and humid degree envrionment test of ability and weathering resistance etc.For example, can enumerate 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.These resin films also can cooperate fire retardant, antioxidant, UV light absorber, antistatic agent etc. as required.Preferred 5～300 μ m of the thickness of first base material film 11 and second base material film 14, more preferably 10～150 μ m.
The preferred film 12 that uses the vapour deposition material formation of the invention described above as the choke material on this first base material film 11.Contained metallic element in first oxide compound in the vapour deposition material is made as contained metallic element is made as B in A, second oxide compound, then the mol ratio (A/B) of metal element A in the film 12 and metallic element B is 10/95～170/15.Containing of metal element A in the film 12, B is proportional outside above-mentioned scope the time, and the crystalline state of each oxide compound becomes respectively preferentially, and generation can't obtain the bad problem of the microtexture of non-crystalline densification.The thickness of film 12 is preferably in the scope of 10～200nm.When less than lower value, be difficult to obtain sufficient gas barrier property as the choke material, the weather resistance of film easily reduces in addition.On the other hand, when surpassing higher limit, waste material, and because thickening effect easily produces the cracking that external force such as bending is brought.At this, in the scope of the thickness of film 12 particularly preferably in 20～100nm.As the formation method of the film 12 that uses the vapour deposition material, preferred electron bundle vapour deposition method (Electron Beam Evaporation Method, hereinafter referred to as EB), ion plating method, reactive plasma sedimentation (Reactive Plasma Deposition Method, below become RPD), electrical resistance heating or induction heating equal vacuum become embrane method.
In addition, not shown among Fig. 1, but also can be on first base material film 11 for the dhering strength that improves with film 12 is provided with the priming paint overlay that is made of acrylic acid multielement alcohol ester, isocyanic ester, silane coupling agent as required, perhaps before the vapour deposition operation, implement to use the surface treatment of plasma body etc.
On the other hand, under the state that exposes on film 12 surfaces that form, when handling sheet material, the surface of film produces scar or friction, then gas barrier property is produced considerable influence.Therefore, the gas barrier property tunicle (not shown) etc. on protective film 12 surfaces preferably is set on film 12.This gas barrier property tunicle can be for example will have silicon compound, titanium compound, zirconia compound, tin compound or its hydrolyzate of alkoxyl group and have solution coat that the water-soluble polymer of hydroxyl mixes behind film 12 surfaces, carries out heat drying and forms.This gas barrier property tunicle not only plays the effect of the thin film layer of film 12, also has the effect that improves gas barrier property.
For example after placing 1 hour under the condition of 20 ℃ of temperature, relative humidity 50%RH, the water vapor transmission rate (WVTR) S that measures under the condition of 40 ℃ of temperature, relative humidity 90%RH shows 0.3g/m to the thin-film sheet of the present invention 10 of Xing Chenging like this 2Below it.In addition, after placing 1 hour under the condition of 20 ℃ of temperature, relative humidity 50%RH, under the condition of 85 ℃ of temperature, relative humidity 90%RH, further placed 100 hours, when the water vapor transmission rate (WVTR) of measuring under the condition identical with above-mentioned condition was made as T afterwards, water vapor transmission rate (WVTR) T showed below 200% with respect to the velocity of variation (T/S * 100) of water vapor transmission rate (WVTR) S.That is, this film 10 has the little gas barrier property of deterioration very high and that effluxion brings.
And then, in laminate 20 of the present invention, film at the thin-film sheet 10 of the invention described above forms side, is to form adhesive linkage 13 on the film 12 or on the said gas-blocking tunicle, and this adhesive linkage 13 plays the effect of the caking agent that is used for bonding first base material film 11 that is formed with film 12 and second base material film 14.Therefore, can enumerate needs bonding strength through for a long time can deterioration, do not produce delamination etc. and can flavescence etc. for example polyurethane series, polyester system, polyester-polyurethane system, polycarbonate-based, poly-epoxy-amine system, the hot melt of condition be caking agent etc.For the laminating method of adhesive linkage 13, can carry out lamination by known method such as dry lamination methods.
By bonding second base material film 14 and bonding on this adhesive linkage 13, complete layer laminated sheet 20.And, as shown in Figure 1, film 12 and adhesive linkage 13 need not be limited to respectively each laminating layer, also can be with film 12 and adhesive linkage 13 alternatively laminateds or with miscellaneous part such as film 12, said gas-blocking tunicle and adhesive linkage 13 alternately or arbitrarily be laminated into 2～10 layers multilayer.Thus, can further improve gas barrier property and weathering resistance.
This laminate 20 is fit to be utilized as base, liquid-crystal display or the OLED display of solar module or throws light on purposes such as OLED display.
[embodiment]
Then, describe embodiments of the invention and comparative example in detail.
＜embodiment 1 〉
At first, the wet mixing of being undertaken by ball mill is prepared the slurry that concentration is 40 quality % with regulation mixed first oxide powder, second oxide powder, tackiness agent and organic solvent.At this moment, first oxide powder use median size is that 0.8 μ m, purity are 99.7% high purity Fe 2O 3Powder, it is that 0.8 μ m, purity are 99.8% high purity ZnO powder that second oxide powder uses median size, and tackiness agent uses polyvinyl butyral acetal, and organic solvent uses ethanol.In addition, Fe 2O 3The combined amount of powder and ZnO powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be that 5 moles of %, ZnO are 95 moles of %.
Then, use spray-drier to carry out spraying drying in the slurry of preparation, after obtaining median size and being the mixing granulation powder of 200 μ m, the mould of this prilling powder being put into regulation carries out drawing by the uniaxial pressing device.Make the molding that obtains in air atmosphere,, obtain the vapour deposition material 1300 ℃ of sintering temperatures 5 hours.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle and ZnO particle, contained Fe in the vapour deposition material 2O 3, ZnO content and particulate basicity be illustrated in the following table 1.
＜embodiment 2 〉
With Fe 2O 3The combined amount of powder and ZnO powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be that 10 moles of %, ZnO are 90 moles of %, in addition obtain the vapour deposition material similarly to Example 1.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle and ZnO particle, contained Fe in the vapour deposition material 2O 3, ZnO content and particulate basicity be illustrated in the following table 1.
＜embodiment 3 〉
With Fe 2O 3The combined amount of powder and ZnO powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be that 20 moles of %, ZnO are 80 moles of %, in addition obtain the vapour deposition material similarly to Example 1.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle and ZnO particle, contained Fe in the vapour deposition material 2O 3, ZnO content and particulate basicity be illustrated in the following table 1.
＜embodiment 4 〉
With Fe 2O 3The combined amount of powder and ZnO powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be that 30 moles of %, ZnO are 70 moles of %, in addition obtain the vapour deposition material similarly to Example 1.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle and ZnO particle, contained Fe in the vapour deposition material 2O 3, ZnO content and particulate basicity be illustrated in the following table 1.
＜embodiment 5 〉
With Fe 2O 3The combined amount of powder and ZnO powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be that 40 moles of %, ZnO are 60 moles of %, in addition obtain the vapour deposition material similarly to Example 1.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle and ZnO particle, contained Fe in the vapour deposition material 2O 3, ZnO content and particulate basicity be illustrated in the following table 1.
＜embodiment 6 〉
With Fe 2O 3The combined amount of powder and ZnO powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be that 50 moles of %, ZnO are 50 moles of %, in addition obtain the vapour deposition material similarly to Example 1.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle and ZnO particle, contained Fe in the vapour deposition material 2O 3, ZnO content and particulate basicity be illustrated in the following table 1.
＜embodiment 7 〉
With Fe 2O 3The combined amount of powder and ZnO powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be that 60 moles of %, ZnO are 40 moles of %, in addition obtain the vapour deposition material similarly to Example 1.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle and ZnO particle, contained Fe in the vapour deposition material 2O 3, ZnO content and particulate basicity be illustrated in the following table 1.
＜embodiment 8 〉
With Fe 2O 3The combined amount of powder and ZnO powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be that 70 moles of %, ZnO are 30 moles of %, in addition obtain the vapour deposition material similarly to Example 1.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle and ZnO particle, contained Fe in the vapour deposition material 2O 3, ZnO content and particulate basicity be illustrated in the following table 1.
＜embodiment 9 〉
With Fe 2O 3The combined amount of powder and ZnO powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be that 80 moles of %, ZnO are 20 moles of %, in addition obtain the vapour deposition material similarly to Example 1.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle and ZnO particle, contained Fe in the vapour deposition material 2O 3, ZnO content and particulate basicity be illustrated in the following table 1.
＜embodiment 10 〉
With Fe 2O 3The combined amount of powder and ZnO powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be that 85 moles of %, ZnO are 15 moles of %, in addition obtain the vapour deposition material similarly to Example 1.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle and ZnO particle, contained Fe in the vapour deposition material 2O 3, ZnO content and particulate basicity be illustrated in the following table 1.
＜embodiment 11 〉
Using median size as second oxide powder is that 0.9 μ m, purity are 99.7% MgO of high purity powder, in addition obtains the vapour deposition material similarly to Example 1.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle and MgO particle, contained Fe in the vapour deposition material 2O 3, MgO content and particulate basicity be illustrated in the following table 1.
＜embodiment 12 〉
With Fe 2O 3The combined amount of powder and MgO powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be that 30 moles of %, MgO are 70 moles of %, in addition obtain the vapour deposition material similarly to Example 11.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle and MgO particle, contained Fe in the vapour deposition material 2O 3, MgO content and particulate basicity be illustrated in the following table 1.
＜embodiment 13 〉
With Fe 2O 3The combined amount of powder and MgO powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be that 50 moles of %, MgO are 50 moles of %, in addition obtain the vapour deposition material similarly to Example 11.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle and MgO particle, contained Fe in the vapour deposition material 2O 3, MgO content and particulate basicity be illustrated in the following table 1.
＜embodiment 14 〉
With Fe 2O 3The combined amount of powder and MgO powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be that 80 moles of %, MgO are 20 moles of %, in addition obtain the vapour deposition material similarly to Example 11.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle and MgO particle, contained Fe in the vapour deposition material 2O 3, MgO content and particulate basicity be illustrated in the following table 1.
＜embodiment 15 〉
With Fe 2O 3The combined amount of powder and MgO powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be that 85 moles of %, MgO are 15 moles of %, in addition obtain the vapour deposition material similarly to Example 11.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle and MgO particle, contained Fe in the vapour deposition material 2O 3, MgO content and particulate basicity be illustrated in the following table 1.
＜embodiment 16 〉
Using median size as second oxide powder is that 0.6 μ m, purity are 99.8% high-purity C aO powder, in addition obtains the vapour deposition material similarly to Example 1.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle and CaO particle, contained Fe in the vapour deposition material 2O 3, CaO content and particulate basicity be illustrated in the following table 1.
＜embodiment 17 〉
With Fe 2O 3The combined amount of powder and CaO powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be that 30 moles of %, CaO are 70 moles of %, in addition obtain the vapour deposition material similarly to Example 16.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle and CaO particle, contained Fe in the vapour deposition material 2O 3, CaO content and particulate basicity be illustrated in the following table 1.
＜embodiment 18 〉
With Fe 2O 3The combined amount of powder and CaO powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be that 50 moles of %, CaO are 50 moles of %, in addition obtain the vapour deposition material similarly to Example 16.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle and CaO particle, contained Fe in the vapour deposition material 2O 3, CaO content and particulate basicity be illustrated in the following table 1.
＜embodiment 19 〉
With Fe 2O 3The combined amount of powder and CaO powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be that 80 moles of %, CaO are 20 moles of %, in addition obtain the vapour deposition material similarly to Example 16.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle and CaO particle, contained Fe in the vapour deposition material 2O 3, CaO content and particulate basicity be illustrated in the following table 1.
＜embodiment 20 〉
With Fe 2O 3The combined amount of powder and CaO powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be that 85 moles of %, CaO are 15 moles of %, in addition obtain the vapour deposition material similarly to Example 16.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle and CaO particle, contained Fe in the vapour deposition material 2O 3, CaO content and particulate basicity be illustrated in the following table 1.
＜embodiment 21 〉
Using median size as second oxide powder is that 0.8 μ m, purity are that 99.8% high purity ZnO powder and median size are that 0.9 μ m, purity are the mixed powder of 99.7% MgO of high purity powder, with Fe 2O 3The combined amount of powder and above-mentioned mixed powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be that 5 moles of %, ZnO and MgO are respectively 90 moles of % and 5 moles of %, in addition obtain the vapour deposition material similarly to Example 1.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle, ZnO particle and MgO particle, contained Fe in the vapour deposition material 2O 3, ZnO, MgO content and particulate basicity be illustrated in the following table 2.
＜embodiment 22 〉
Using median size as second oxide powder is that 0.8 μ m, purity are that 99.8% high purity ZnO powder and median size are that 0.6 μ m, purity are the mixed powder of 99.8% high-purity C aO powder, with Fe 2O 3The combined amount of powder and above-mentioned mixed powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be that 5 moles of %, ZnO and CaO are respectively 90 moles of % and 5 moles of %, in addition obtain the vapour deposition material similarly to Example 1.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle, ZnO particle and CaO particle, contained Fe in the vapour deposition material 2O 3, ZnO, CaO content and particulate basicity be illustrated in the following table 2.
＜embodiment 23 〉
Using median size as second oxide powder is that 0.8 μ m, purity are 99.8% high purity ZnO powder, median size is that 0.9 μ m, purity are that 99.7% MgO of high purity powder and median size are that 0.6 μ m, purity are the mixed powder of 99.8% high-purity C aO powder, with Fe 2O 3The combined amount of powder and above-mentioned mixed powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be 5 moles of %, ZnO, MgO and CaO are respectively 75 moles of %, 10 moles of % and 10 moles of %, in addition obtain the vapour deposition material similarly to Example 1.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle, ZnO particle, MgO particle and CaO particle, contained Fe in the vapour deposition material 2O 3, ZnO, MgO, CaO content and particulate basicity be illustrated in the following table 2.
＜embodiment 24 〉
Using median size as second oxide powder is that 0.8 μ m, purity are 99.8% high purity ZnO powder, median size is that 0.9 μ m, purity are that 99.7% MgO of high purity powder and median size are that 0.6 μ m, purity are the mixed powder of 99.8% high-purity C aO powder, with Fe 2O 3The combined amount of powder and above-mentioned mixed powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be 5 moles of %, ZnO, MgO and CaO are respectively 55 moles of %, 20 moles of % and 20 moles of %, in addition obtain the vapour deposition material similarly to Example 1.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle, ZnO particle, MgO particle and CaO particle, contained Fe in the vapour deposition material 2O 3, ZnO, MgO, CaO content and particulate basicity be illustrated in the following table 2.
＜embodiment 25 〉
Using median size as second oxide powder is that 0.8 μ m, purity are 99.8% high purity ZnO powder, median size is that 0.9 μ m, purity are that 99.7% MgO of high purity powder and median size are that 0.6 μ m, purity are the mixed powder of 99.8% high-purity C aO powder, with Fe 2O 3The combined amount of powder and above-mentioned mixed powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be 5 moles of %, ZnO, MgO and CaO are respectively 30 moles of %, 35 moles of % and 30 moles of %, in addition obtain the vapour deposition material similarly to Example 1.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle, ZnO particle, MgO particle and CaO particle, contained Fe in the vapour deposition material 2O 3, ZnO, MgO, CaO content and particulate basicity be illustrated in the following table 2.
＜embodiment 26 〉
Using median size as second oxide powder is that 0.8 μ m, purity are 99.8% high purity ZnO powder, median size is that 0.9 μ m, purity are that 99.7% MgO of high purity powder and median size are that 0.6 μ m, purity are the mixed powder of 99.8% high-purity C aO powder, with Fe 2O 3The combined amount of powder and above-mentioned mixed powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be 5 moles of %, ZnO, MgO and CaO are respectively 10 moles of %, 35 moles of % and 50 moles of %, in addition obtain the vapour deposition material similarly to Example 1.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle, ZnO particle, MgO particle and CaO particle, contained Fe in the vapour deposition material 2O 3, ZnO, MgO, CaO content and particulate basicity be illustrated in the following table 2.
＜embodiment 27 〉
Using median size as second oxide powder is that 0.9 μ m, purity are that 99.7% MgO of high purity powder and median size are that 0.6 μ m, purity are the mixed powder of 99.8% high-purity C aO powder, with Fe 2O 3Powder and above-mentioned blended combined amount are adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be that 5 moles of %, MgO and CaO are respectively 35 moles of % and 60 moles of %, in addition obtain the vapour deposition material similarly to Example 1.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle, MgO particle and CaO particle, contained Fe in the vapour deposition material 2O 3, MgO, CaO content and particulate basicity be illustrated in the following table 2.
＜embodiment 28 〉
Using median size as second oxide powder is that 0.8 μ m, purity are that 99.8% high purity ZnO powder and median size are that 0.9 μ m, purity are the mixed powder of 99.7% MgO of high purity powder, with Fe 2O 3The combined amount of powder and above-mentioned mixed powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be that 30 moles of %, ZnO and MgO are respectively 60 moles of % and 10 moles of %, in addition obtain the vapour deposition material similarly to Example 1.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle, ZnO particle and MgO particle, contained Fe in the vapour deposition material 2O 3, ZnO, MgO content and particulate basicity be illustrated in the following table 2.
＜embodiment 29 〉
Using median size as second oxide powder is that 0.8 μ m, purity are that 99.8% high purity ZnO powder and median size are that 0.6 μ m, purity are the mixed powder of 99.8% high-purity C aO powder, with Fe 2O 3The combined amount of powder and above-mentioned mixed powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be that 30 moles of %, ZnO and CaO are respectively 60 moles of % and 10 moles of %, in addition obtain the vapour deposition material similarly to Example 1.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle, ZnO particle and CaO particle, contained Fe in the vapour deposition material 2O 3, ZnO, CaO content and particulate basicity be illustrated in the following table 2.
＜embodiment 30 〉
Using median size as second oxide powder is that 0.8 μ m, purity are 99.8% high purity ZnO powder, median size is that 0.9 μ m, purity are that 99.7% MgO of high purity powder and median size are that 0.6 μ m, purity are the mixed powder of 99.8% high-purity C aO powder, with Fe 2O 3The combined amount of powder and above-mentioned mixed powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be 30 moles of %, ZnO, MgO and CaO are respectively 30 moles of %, 25 moles of % and 15 moles of %, in addition obtain the vapour deposition material similarly to Example 1.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle, ZnO particle, MgO particle and CaO particle, contained Fe in the vapour deposition material 2O 3, ZnO, MgO, CaO content and particulate basicity be illustrated in the following table 2.
＜embodiment 31 〉
Using median size as second oxide powder is that 0.9 μ m, purity are that 99.7% MgO of high purity powder and median size are that 0.6 μ m, purity are the mixed powder of 99.8% high-purity C aO powder, with Fe 2O 3The combined amount of powder and above-mentioned mixed powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be that 30 moles of %, MgO and CaO are respectively 25 moles of % and 45 moles of %, in addition obtain the vapour deposition material similarly to Example 1.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle, MgO particle and CaO particle, contained Fe in the vapour deposition material 2O 3, MgO, CaO content and particulate basicity be illustrated in the following table 2.
＜embodiment 32 〉
Using median size as second oxide powder is that 0.8 μ m, purity are that 99.8% high purity ZnO powder and median size are that 0.9 μ m, purity are the mixed powder of 99.7% MgO of high purity powder, with Fe 2O 3The combined amount of powder and above-mentioned mixed powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be that 85 moles of %, ZnO and MgO are respectively 10 moles of % and 5 moles of %, in addition obtain the vapour deposition material similarly to Example 1.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle, ZnO particle and MgO particle, contained Fe in the vapour deposition material 2O 3, ZnO, MgO content and particulate basicity be illustrated in the following table 2.
＜embodiment 33 〉
Using median size as second oxide powder is that 0.8 μ m, purity are that 99.8% high purity ZnO powder and median size are that 0.6 μ m, purity are the mixed powder of 99.8% high-purity C aO powder, with Fe 2O 3The combined amount of powder and above-mentioned mixed powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be that 85 moles of %, ZnO and CaO are respectively 10 moles of % and 5 moles of %, in addition obtain the vapour deposition material similarly to Example 1.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle, ZnO particle and CaO particle, contained Fe in the vapour deposition material 2O 3, ZnO, CaO content and particulate basicity be illustrated in the following table 2.
＜embodiment 34 〉
Using median size as second oxide powder is that 0.8 μ m, purity are 99.8% high purity ZnO powder, median size is that 0.9 μ m, purity are that 99.7% MgO of high purity powder and median size are that 0.6 μ m, purity are the mixed powder of 99.8% high-purity C aO powder, with Fe 2O 3The combined amount of powder and above-mentioned mixed powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be 85 moles of %, ZnO, MgO and CaO are respectively 5 moles of %, 5 moles of % and 5 moles of %, in addition obtain the vapour deposition material similarly to Example 1.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle, ZnO particle, MgO particle and CaO particle, contained Fe in the vapour deposition material 2O 3, ZnO, MgO, CaO content and particulate basicity be illustrated in the following table 2.
＜embodiment 35 〉
Using median size as second oxide powder is that 0.9 μ m, purity are that 99.7% MgO of high purity powder and median size are that 0.6 μ m, purity are the mixed powder of 99.8% high-purity C aO powder, with Fe 2O 3The combined amount of powder and above-mentioned mixed powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be that 85 moles of %, MgO and CaO are respectively 5 moles of % and 10 moles of %, in addition obtain the vapour deposition material similarly to Example 1.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle, MgO particle and CaO particle, contained Fe in the vapour deposition material 2O 3, MgO, CaO content and particulate basicity be illustrated in the following table 2.
＜embodiment 36 〉
Obtain the vapour deposition material under the condition similarly to Example 25.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle, ZnO particle, MgO particle and CaO particle, contained Fe in the vapour deposition material 2O 3, ZnO, MgO, CaO content and particulate basicity be illustrated in the following table 3.
＜embodiment 37 〉
Obtain the vapour deposition material under the condition similarly to Example 30.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle, ZnO particle, MgO particle and CaO particle, contained Fe in the vapour deposition material 2O 3, ZnO, MgO, CaO content and particulate basicity be illustrated in the following table 3.
＜embodiment 38 〉
With obtain the vapour deposition material under the same condition of embodiment 34.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle, ZnO particle, MgO particle and CaO particle, contained Fe in the vapour deposition material 2O 3, ZnO, MgO, CaO content and particulate basicity be illustrated in the following table 3.
＜embodiment 39 〉
Obtain the vapour deposition material under the condition similarly to Example 25.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle, ZnO particle, MgO particle and CaO particle, contained Fe in the vapour deposition material 2O 3, ZnO, MgO, CaO content and particulate basicity be illustrated in the following table 3.
＜embodiment 40 〉
Obtain the vapour deposition material under the condition similarly to Example 30.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle, ZnO particle, MgO particle and CaO particle, contained Fe in the vapour deposition material 2O 3, ZnO, MgO, CaO content and particulate basicity be illustrated in the following table 3.
＜embodiment 41 〉
With obtain the vapour deposition material under the same condition of embodiment 34.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle, ZnO particle, MgO particle and CaO particle, contained Fe in the vapour deposition material 2O 3, ZnO, MgO, CaO content and particulate basicity be illustrated in the following table 3.
＜comparative example 1 〉
Be adjusted into and do not mix outside first oxide particle, obtain the vapour deposition material similarly to Example 1.The median size of contained ZnO particle, particulate basicity are illustrated in the following table 4 in the vapour deposition material that obtains.
＜comparative example 2 〉
With Fe 2O 3The combined amount of powder and ZnO powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be that 3 moles of %, ZnO are 97 moles of %, in addition obtain the vapour deposition material similarly to Example 1.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle and ZnO particle, contained Fe in the vapour deposition material 2O 3, ZnO content and particulate basicity be illustrated in the following table 4.
＜comparative example 3 〉
With Fe 2O 3The combined amount of powder and ZnO powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be that 90 moles of %, ZnO are 10 moles of %, in addition obtain the vapour deposition material similarly to Example 1.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle and ZnO particle, contained Fe in the vapour deposition material 2O 3, ZnO content and particulate basicity be illustrated in the following table 4.
＜comparative example 4 〉
Be adjusted into and do not mix outside second oxide particle, obtain the vapour deposition material similarly to Example 1.Contained Fe in the vapour deposition material that obtains 2O 3The median size of particle, particulate basicity are illustrated in the following table 4.
＜comparative example 5 〉
Be adjusted into and do not mix outside first oxide particle, obtain the vapour deposition material similarly to Example 11.The median size of contained MgO particle, particulate basicity are illustrated in the following table 4 in the vapour deposition material that obtains.
＜comparative example 6 〉
With Fe 2O 3The combined amount of powder and MgO powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be that 3 moles of %, MgO are 97 moles of %, in addition obtain the vapour deposition material similarly to Example 11.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle and MgO particle, contained Fe in the vapour deposition material 2O 3, MgO content and particulate basicity be illustrated in the following table 4.
＜comparative example 7 〉
With Fe 2O 3The combined amount of powder and MgO powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be that 90 moles of %, MgO are 10 moles of %, in addition obtain the vapour deposition material similarly to Example 11.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle and MgO particle, contained Fe in the vapour deposition material 2O 3, MgO content and particulate basicity be illustrated in the following table 4.
＜comparative example 8 〉
Be adjusted into and do not mix outside second oxide particle, obtain the vapour deposition material similarly to Example 1.Contained Fe in the vapour deposition material that obtains 2O 3The median size of particle, particulate basicity are illustrated in the following table 4.
＜comparative example 9 〉
Be adjusted into and do not mix outside first oxide particle, obtain the vapour deposition material similarly to Example 16.The median size of contained CaO particle, particulate basicity are illustrated in the following table 4 in the vapour deposition material that obtains.
＜comparative example 10 〉
With Fe 2O 3The combined amount of powder and CaO powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be that 3 moles of %, CaO are 97 moles of %, in addition obtain the vapour deposition material similarly to Example 16.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle and CaO particle, contained Fe in the vapour deposition material 2O 3, CaO content and particulate basicity be illustrated in the following table 4.
＜comparative example 11 〉
With Fe 2O 3The combined amount of powder and CaO powder is adjusted into contained Fe in the vapour deposition material after the formation 2O 3Be that 90 moles of %, CaO are 10 moles of %, in addition obtain the vapour deposition material similarly to Example 16.The contained Fe of vapour deposition material that obtains 2O 3The median size of particle and CaO particle, contained Fe in the vapour deposition material 2O 3, CaO content and particulate basicity be illustrated in the following table 4.
＜comparative example 12 〉
Be adjusted into and do not mix outside second oxide particle, obtain the vapour deposition material similarly to Example 1.Contained Fe in the vapour deposition material that obtains 2O 3The median size of particle, particulate basicity are illustrated in the following table 4.
＜comparative example 13 〉
With obtain the vapour deposition material under the same condition of comparative example 1.In the vapour deposition material that obtains in the median size of contained ZnO particle, the vapour deposition material contained ZnO content, particulate basicity be illustrated in the following table 4.
＜comparative example 14 〉
With obtain the vapour deposition material under the same condition of comparative example 5.In the vapour deposition material that obtains in the median size of contained MgO particle, the vapour deposition material contained MgO content, particulate basicity be illustrated in the following table 4.
＜comparative example 15 〉
With obtain the vapour deposition material under the same condition of comparative example 9.In the vapour deposition material that obtains in the median size of contained CaO particle, the vapour deposition material contained CaO content, particulate basicity be illustrated in the following table 4.
＜comparative example 16 〉
With obtain the vapour deposition material under the same condition of comparative example 4.Contained Fe in the vapour deposition material that obtains 2O 3Contained Fe in the median size of particle, the vapour deposition material 2O 3Content, particulate basicity are illustrated in the following table 4.
＜comparative example 17 〉
With obtain the vapour deposition material under the same condition of comparative example 1.In the vapour deposition material that obtains in the median size of contained ZnO particle, the vapour deposition material contained ZnO content, particulate basicity be illustrated in the following table 4.
＜comparative example 18 〉
With obtain the vapour deposition material under the same condition of comparative example 5.In the vapour deposition material that obtains in the median size of contained MgO particle, the vapour deposition material contained MgO content, particulate basicity be illustrated in the following table 4.
＜comparative example 19 〉
With obtain the vapour deposition material under the same condition of comparative example 9.In the vapour deposition material that obtains in the median size of contained CaO particle, the vapour deposition material contained CaO content, particulate basicity be illustrated in the following table 4.
＜comparative example 20 〉
With obtain the vapour deposition material under the same condition of comparative example 4.Contained Fe in the vapour deposition material that obtains 2O 3Contained Fe in the median size of particle, the vapour deposition material 2O 3Content, particulate basicity are illustrated in the following table 4.
[table 1]
Figure BSA00000454125300251
[table 2]
Figure BSA00000454125300261
[table 3]
Figure BSA00000454125300271
[table 4]
Figure BSA00000454125300281
＜comparison test and evaluation 1 〉
The vapour deposition material that use obtains in embodiment 1～41 and comparative example 1～20 carries out vapour deposition by the method shown in the following table 5～table 7 and forms film on the PET film of thickness 75 μ m, and forms thin-film sheet.For these thin-film sheets, measure water vapor transmission rate (WVTR), gas barrier property is estimated.In addition, use water vapor transmission rate (WVTR) and the velocity of variation thereof more placed under high temperature, the super-humid conditions after long-time than the condition in the said gas-blocking evaluation to estimate weather resistance.And then, for these thin-film sheets, measure light transmission rate, estimated the transparency.These results are illustrated in the following table 5～table 7.
(1) gas barrier property: thin-film sheet is placed in the clean room that is set at 20 ℃ of temperature, relative humidity 50%RH after 1 hour, use the water vapor transmission rate (WVTR) determinator (model name: PERMATRAN-W type 3/33), under the condition of 40 ℃ of temperature, relative humidity 90%RH, measure water vapor transmission rate (WVTR) S of MOCON corporate system.
(2) weather resistance: for the thin-film sheet of placement after 1 hour in the clean room that is set at 20 ℃ of temperature, relative humidity 50%RH, the deterioration that causes for the water vapour that prevents the PET film, the mode that becomes the outside with the film of thin-film sheet superposes each two respectively with identical thin-film sheet, engages four limits with hot enclosuring device.Put it in the fixed temperature and humidity device that is set at 85 ℃ of temperature, relative humidity 90%RH, placed 100 hours.Afterwards, with the said gas-blocking evaluation similarly, use the water vapor transmission rate (WVTR) determinator, under the condition of 40 ℃ of temperature, relative humidity 90%RH, measure water vapor transmission rate (WVTR) T.In addition, calculate the velocity of variation (T/S * 100) of the water vapor transmission rate (WVTR) T of mensuration with respect to above-mentioned water vapor transmission rate (WVTR) S.
(3) light transmission rate: the spectrophotometer (model name: the U-4000) light transmission rate of mensuration wavelength 380～780nm of thin-film sheet being used society of Hitachi Co., Ltd system.
[table 5]
Figure BSA00000454125300301
[table 6]
Figure BSA00000454125300311
[table 7]
Figure BSA00000454125300321
As known from Tables 5 to 7, relatively first oxide compound and second oxide compound are Fe 2O 3With the embodiment 1～10 of the combination of ZnO and comparative example 1～4 o'clock, in embodiment 1～10, the water vapor transmission rate (WVTR) S that places after 1 hour under the room temperature is 0.27g/m 2Below it, wherein, in embodiment 4～8 0.1g/m 2Below it.In addition, judge under the condition of 85 ℃ of temperature, relative humidity 90%RH so that the water vapor transmission rate (WVTR) T after placing 100 hours also be suppressed in below 200% with respect to the velocity of variation of water vapor transmission rate (WVTR) S, the weather resistance under high temperature, high humidity environment during long-time the placement is also excellent.
On the other hand, use by ZnO is single and form comparative example 1 and the use first oxide compound Fe that the vapour deposition material that constitutes forms 2O 3The thin-film sheet of the comparative example 2 that forms less than 5% vapour deposition material of content in, though water vapor transmission rate (WVTR) S is smaller, the velocity of variation of water vapor transmission rate (WVTR) is very big.In addition, the comparative example 3 that forms less than 15% vapour deposition material of the content that uses the second oxide compound ZnO and using by Fe 2O 3In the thin-film sheet of the comparative example 4 that the vapour deposition material that single composition constitutes forms, though the velocity of variation of water vapor transmission rate (WVTR) is smaller, water vapor transmission rate (WVTR) S compares very big with embodiment 1～10.
In addition, be Fe to first oxide compound and second oxide compound 2O 3Compare with the embodiment 11～15 and the comparative example 5～8 of the combination of MgO, then in embodiment 11～15, the water vapor transmission rate (WVTR) S that at room temperature places after 1 hour is 0.29g/m 2Below it, wherein, among the embodiment 13 0.1g/m 2Below it.In addition, the water vapor transmission rate (WVTR) T that judges after further placing 100 hours under the condition of 85 ℃ of temperature, relative humidity 90%RH also is suppressed at below 200% the velocity of variation of water vapor transmission rate (WVTR) S, and the weather resistance under hot and humid environment during long-time the placement is also excellent.
On the other hand, use by MgO is single and form comparative example 5, the use first oxide compound Fe that the vapour deposition material that constitutes forms 2O 3The comparative example 6 that forms less than 5% vapour deposition material of content, comparative example 7 that the content that uses the second oxide M gO forms less than 15% vapour deposition material and use by Fe 2O 3In the thin-film sheet of the comparative example 8 that the vapour deposition material that single composition constitutes forms, the velocity of variation of water vapor transmission rate (WVTR) S and water vapor transmission rate (WVTR) is all big than embodiment 11～15.
In addition, be Fe to first oxide compound and second oxide compound 2O 3Compare with the embodiment 16～20 and the comparative example 9～12 of the combination of CaO, then in embodiment 16～20, the water vapor transmission rate (WVTR) S that at room temperature places after 1 hour is 0.27g/m 2Below it, wherein, among the embodiment 18 0.1g/m 2Below it.In addition, the water vapor transmission rate (WVTR) T that judges after further placing 100 hours under the condition of 85 ℃ of temperature, relative humidity 90%RH also is suppressed at below 200% the velocity of variation of water vapor transmission rate (WVTR) S, and the weather resistance under hot and humid environment during long-time the placement is also excellent.
On the other hand, use by CaO is single and form comparative example 9, the use first oxide compound Fe that the vapour deposition material that constitutes forms 2O 3The comparative example 10 that forms less than 5% vapour deposition material of content, comparative example 11 that the content that uses the second oxide compound CaO forms less than 15% vapour deposition material and use by Fe 2O 3In the thin-film sheet of the comparative example 12 that the vapour deposition material that single composition constitutes forms, the velocity of variation of water vapor transmission rate (WVTR) S and water vapor transmission rate (WVTR) is all big than embodiment 16～20.
In addition, second oxide compound is that the water vapor transmission rate (WVTR) S that at room temperature places after 1 hour is 0.29g/m among the two or more embodiment 21～35 among ZnO, MgO or the CaO 2Below it, wherein, among the embodiment 23～31 0.1g/m 2Below it.In addition, the water vapor transmission rate (WVTR) T that judges after further placing 100 hours under the condition of 85 ℃ of temperature, relative humidity 90%RH also is suppressed at below 200% to the velocity of variation of water vapor transmission rate (WVTR) S, except high gas barrier property, and then the weather resistance during long-time the placement is also excellent under hot and humid environment.
In addition, for light transmission rate, obtain the result of embodiment 1～35 no less than comparative example 1～12.
And then, to using the vapour deposition material that obtains under the same terms and with diverse ways film forming embodiment 25 respectively, 36,39, embodiment 30,37,40, embodiment 34,38,41, comparative example 1,13,17, comparative example 5,14,18, comparative example 9,15,19, comparative example 4,16,20 compare respectively, then exist and compare poor slightly trend with the film that forms by the RPD method according to assessment item, but with the film forming embodiment 36 of usefulness EB method, 37,38 and be heated by resistive the film forming embodiment 39 of method, 40,41 film is compared, and possesses sufficient gas barrier property, the weather resistance and the transparency.
By these results verifications, the film that uses vapour deposition material of the present invention to form has the very excellent gas barrier property and the transparency.

Claims (8)

1. a vapour deposition material for mixing the vapour deposition material that first oxide powder and second oxide powder are made, is characterized in that,
Described first oxide powder is Fe 2O 3Powder, the first oxide compound purity of described first oxide powder is more than 98%,
Described second oxide powder is to be selected from a kind of powder among ZnO, MgO and the CaO or two or more mixed powders, and the second oxide compound purity of described second oxide powder is more than 98%,
Described vapour deposition material is made of the particle that contains described first oxide particle and described second oxide particle,
First oxide compound in the described vapour deposition material and the ratio of second oxide compound are 5～85: 95～15, and described particulate basicity is more than 0.1.
2. vapour deposition material according to claim 1, the median size of described first oxide particle are 0.1～10 μ m, and the median size of described second oxide particle is 0.1～10 μ m.
3. the manufacture method of a film, it is characterized in that, by with claim 1 or 2 described vapour deposition materials vacuum film formation method, on first base material film, form the sull that comprises the contained metallic element B of the contained metal element A of described first oxide compound and described second oxide compound as target.
4. thin-film sheet, by with claim 1 or 2 described vapour deposition materials vacuum film formation method as target, on first base material film, form the sull comprise the contained metallic element B of the contained metal element A of described first oxide compound and described second oxide compound
Described metal element A in the described film and the mol ratio A/B of described metallic element B are 10/95～170/15.
5. thin-film sheet according to claim 4, described vacuum film formation method are any one in electron beam evaporation plating method, ion plating method, reactive plasma sedimentation, electrical resistance heating or the induction heating.
6. according to claim 4 or 5 described thin-film sheets, the water vapor transmission rate (WVTR) S when placing 1 hour under the condition of 20 ℃ of temperature, relative humidity 50%RH is 0.3g/m 2Below it.
7. thin-film sheet according to claim 6, after placing 1 hour under the condition of 20 ℃ of temperature, relative humidity 50%RH, when under the condition of 85 ℃ of temperature, relative humidity 90%RH, further placing 100 hours water vapor transmission rate (WVTR) when being made as T, described water vapor transmission rate (WVTR) T is below 200% with respect to velocity of variation T/S * 100 of described water vapor transmission rate (WVTR) S.
8. laminate, the film of any described thin-film sheet in claim 4～7 forms side and forms by adhesive linkage lamination second base material film.
CN2011100656286A 2010-03-15 2011-03-14 Vapor phase deposition material for forming film, film sheet with the film, and laminated sheet Pending CN102191462A (en)

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