CN102312193B - Thin film formation is deposited with material and possesses diaphragm and the lamination sheets of this thin film - Google Patents
Thin film formation is deposited with material and possesses diaphragm and the lamination sheets of this thin film Download PDFInfo
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- CN102312193B CN102312193B CN201110179523.3A CN201110179523A CN102312193B CN 102312193 B CN102312193 B CN 102312193B CN 201110179523 A CN201110179523 A CN 201110179523A CN 102312193 B CN102312193 B CN 102312193B
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- Physical Vapour Deposition (AREA)
Abstract
The invention provides a kind of thin film formation evaporation material and possess diaphragm and the lamination sheets of this thin film, described evaporation material suitably forms the transparency and the thin film of gas barrier property excellence. A kind of evaporation material of mixing the 1st oxide powder and the 2nd oxide powder, it is characterized in that, 1st oxide powder is MgO powder, 1st oxide purity of the 1st oxide powder is more than 98%, 2nd oxide powder is ZnO powder, 2nd oxide purity of the 2nd oxide powder is more than 98%, evaporation material is made up of the granule containing the 1st oxide powder and the 2nd oxide powder, the 1st oxide and the ratio of the 2nd oxide in evaporation material are 5��85: 95��15, and the basicity of granule is more than 0.1.
Description
Technical field
The present invention relates to the evaporation material of a kind of thin film suitably forming the various excellents such as the transparency, gas barrier property and possess diaphragm and the lamination sheets of this thin film. More specifically, relate to a kind of forming these various excellents, the evaporation material used when being particularly suitable as the thin film of gas barrier property material of liquid crystal display, organic el display or solar module etc. and the diaphragm and the lamination sheets that possess this thin film.
Background technology
The equipment such as liquid crystal display, organic el display or solaode are generally unable to undergo dampness so that it is characteristic promptly deteriorates because of moisture absorption, so must be equipped with the assembly with highly moistureproof, i.e. the gas barrier property of the infiltration such as anti-block or steam or intrusion.
Such as, in the example of solaode, the back side with the opposite side of the sensitive surface of solar module is provided with backboard. The backboard being made up of on base material is had the gas barrier property material with highly moistureproof and their parts etc. of protection about this backboard is representational.
Backboard as this composition solar module; such as disclose by high-strength heat-resistant, weatherability resin sandwich moisture resistance metal forming, the back-protective sheet material (referring for example to patent documentation 1) of the solar module of nature of glass evaporation epithelium is additionally set in one side. In this sheet material, use the metal formings such as aluminium foil, zinc-plated iron foil, tin plating iron foil as gas barrier property material. Additionally, disclose stacking high moisture barrier films and high durable film the solaode (referring for example to patent documentation 2) that makes the solaode cover plate materials of its integration be used in rear side guard block. High moisture barrier films in this solaode cover plate materials uses following film, namely being formed moisture barrier films on the base material films such as PET film as gas barrier property material by CVD (chemical vapor deposition), PVD (evaporation reaction) method etc., described moisture barrier films is made up of the film of the inorganic oxide such as silicon dioxide, aluminium oxide. Further, disclose and possess the photovoltaic module (referring for example to patent documentation 3) of intercepting layer presenting inorganic oxide layer and being made up of plastic foil or plastic composite. In this inorganic oxide layer, aluminium oxide or silicon oxide use as its coating material.
Patent documentation 1: Japanese Utility Model announces flat 2-44995 publication (the 41st��44 row on the requirement of utility model logon right and 5 hurdles)
Patent documentation 2: Japanese Patent Publication 2000-174296 publication (claim 1, claim 7 and [0019] section)
Patent documentation 3: Japan Patent public affairs table 2002-520820 publication (claim 1 and [0019] section)
But, the back-protective sheet material shown in above-mentioned patent documentation 1 uses the metal formings such as aluminium foil as gas barrier property material, if being therefore applied on the backboard of solar module by this sheet material, it is likely that reduce proof voltage, leakage current. Further, about using the sheet material of metal forming, the pin hole if the thickness of metal forming becomes less than 20 ��m, then increasing thermostability, producing between weatherability resin and metal forming, gas barrier property declines significantly. On the other hand, if increasing the thickness of metal forming, the then problem that can produce manufacturing cost rising etc. Additionally, during the inorganic oxides such as the silicon dioxide used in for above-mentioned patent documentation 2 and 3, aluminium oxide, if to obtain high gas barrier property, then must guarantee at more than 100nm by the thickness of film, even if this size is also far from being, gas barrier property is very abundant.
Summary of the invention
It is an object of the invention to provide the evaporation material of a kind of thin film suitably forming the transparency and gas barrier property excellence.
Another object of the present invention is to provide diaphragm and the lamination sheets of a kind of thin film possessing the transparency and gas barrier property excellence.
The evaporation material of the 1st viewpoint of the present invention, i.e. mixing the 1st oxide powder and the 2nd oxide powder, it is characterized in that, described 1st oxide powder is MgO powder, 1st oxide purity of the 1st oxide powder is more than 98%, described 2nd oxide powder is ZnO powder, 2nd oxide purity of the 2nd oxide powder is more than 98%, evaporation material is made up of the granule containing the 1st oxide powder and the 2nd oxide powder, the 1st oxide and the ratio of the 2nd oxide in evaporation material are 5��85: 95��15, and the basicity of granule is more than 0.1.
2nd viewpoint of the present invention, i.e. invention according to the 1st viewpoint, be further characterized in that, the mean diameter of the 1st oxide powder is 0.1��10 ��m, and the mean diameter of the 2nd oxide powder is 0.1��10 ��m.
3rd viewpoint of the present invention, i.e. a kind of diaphragm 10, wherein, as shown in Figure 1, by the vacuum film formation that the evaporation material according to the 1st or the 2nd viewpoint is used as target, 1st base material film 11 is formed sull 12 form, described sull contains metallic element B contained in metal element A contained in the 1st oxide and the 2nd oxide, when the content ratio of all metallic elements in described thin film 12 is set to 100 moles of %, the content ratio of metal element A is 5��85 moles of %, and the content ratio of metallic element B is 95��15 moles of %.
4th viewpoint of the present invention, i.e. invention according to the 3rd viewpoint, be further characterized in that, vacuum film formation is any one method in e-beam evaporation, ion plating method, reactive plasma vapour deposition method, electrical resistance heating or induction heating.
5th viewpoint of the present invention, i.e. invention according to the 3rd or the 4th viewpoint, be further characterized in that, placing 1 little vapor permeability S constantly when temperature 20 DEG C, relative humidity 50%RH is 0.3g/m2Below day.
6th viewpoint of the present invention, i.e. invention according to the 5th viewpoint, it is further characterized in that, by placing after 1 hour when temperature 20 DEG C, relative humidity 50%RH, when placing 100 little vapor permeabilities constantly when temperature 85 DEG C, relative humidity 90%RH again and be set to T, the rate of change (T/S �� 100) of vapor permeability S is less than 200% by vapor permeability T-phase.
7th viewpoint of the present invention, i.e. a kind of lamination sheets 20, as it is shown in figure 1, this lamination sheets forms side at the thin film 12 of the diaphragm 10 according to the 3rd to the 6th viewpoint, formed by adhesion coating 13 stacking the 2nd base material film 14.
Invention effect
In the evaporation material of the 1st viewpoint of the present invention, 1st oxide powder is MgO powder, 1st oxide purity of the 1st oxide powder is more than 98%, described 2nd oxide powder is ZnO powder, 2nd oxide purity of the 2nd oxide powder is more than 98%, evaporation material is made up of the granule containing the 1st oxide powder and the 2nd oxide powder, the 1st oxide and the ratio of the 2nd oxide in evaporation material are 5��85: 95��15, and the basicity of granule is more than 0.1, it is possible to form the thin film that gas barrier property is greatly improved compared with traditional gas barrier property material.
In the evaporation material of the 2nd viewpoint of the present invention, the mean diameter of the 1st oxide powder is 0.1��10 ��m, and the 2nd the mean diameter of oxide powder be 0.1��10 ��m, it is possible to be formed as the evaporation film that evaporation efficiency is good and dense, it is possible to maintain higher gas barrier property stabilizing it.
In the diaphragm of the 3rd viewpoint of the present invention, possesses following thin film, when the content ratio of all metallic elements being about in the thin film containing metallic element B contained in metal element A contained in the 1st oxide and the 2nd oxide is set to 100 moles of %, the content ratio of metal element A is 5��85 moles of %, the content ratio of metallic element B is the thin film of 95��15 moles of %, thus has the transparency and the gas barrier property of excellence.
In the diaphragm of the 5th viewpoint of the present invention, having following very high gas barrier property, namely placing 1 little vapor permeability constantly when temperature 20 DEG C, relative humidity 50%RH is 0.3g/m2The such gas barrier property of below day.
In the diaphragm of the 6th viewpoint of the present invention, have placing after 1 hour when temperature 20 DEG C, relative humidity 50%RH, when placing 100 little vapor permeabilities constantly when temperature 85 DEG C, relative humidity 90%RH again and be set to T, vapor permeability T-phase to the rate of change (T/S �� 100) of vapor permeability S be less than 200%, gas barrier property that the deterioration that caused by the passage of time is considerably less.
In the lamination sheets of the 7th viewpoint of the present invention, employing the 2nd base material film is layered in the structure of the thin film formation side of the diaphragm of the 3rd to the 6th viewpoint further by adhesion coating. Thus, the 2nd base material film can protective film, it is possible to maintain higher gas barrier property stabilizing it.
Accompanying drawing explanation
Fig. 1 is the sectional view diaphragm of embodiment of the present invention and the stepped construction of lamination sheets showed schematically.
Fig. 2 is the figure showed schematically by the cross section structure of traditional diaphragm.
Fig. 3 is the figure showed schematically by the cross section structure of the diaphragm of embodiment of the present invention.
Symbol description
10 diaphragms
11 the 1st base material films
12 thin film
13 adhesion coatings
14 the 2nd base material films
20 lamination sheets
Detailed description of the invention
Then, with reference to the accompanying drawings the mode being used for implementing the present invention is illustrated. The evaporation material of the present invention can be adapted to form thin film. Utilizing the thin film that this evaporation material is formed is the thin film as the infiltrations such as anti-block or steam or the gas barrier property materials serve effect of intrusion.
This evaporation material mixing the 1st oxide powder and the 2nd oxide powder form. The 1st oxide powder used in the making of evaporation material is MgO powder, 1st oxide purity of the 1st oxide powder is more than 98%, it is preferably more than 98.4%, 2nd oxide powder is ZnO powder, 2nd oxide purity of the 2nd oxide powder is more than 98%, it is preferred to more than 99.5%. At this, the 1st oxide purity in the 1st oxide powder is limited to more than 98%, is because: if less than 98%, then crystallinity is because of impurity deterioration, and result barrier properties will decline. And, the 2nd oxide purity of the 2nd oxide powder being limited to more than 98%, is because: if less than 98%, then crystallinity is because of impurity deterioration, and result barrier properties will decline. It addition, the purity of the powder in this specification refers to according to the purity that spectrum analysis method (inductively coupled plasma emission spectrographic analysis device: Japan JarrellAsh company ICAP-88) measures. And, this evaporation material is preferably made up of the polycrystalline particle containing the 1st oxide powder and the 2nd oxide powder, and its relative density is more than 90%, it is preferred to more than 95%. Relative density is set to 90% be above because if less than 90%, then splash during film forming will increase. It addition, in this embodiment, granulation tissue is set to polycrystalline but it also may for monocrystalline.
And, the mean diameter of the 1st oxide powder contained in this evaporation material is 0.1��10 ��m, and the mean diameter of the 2nd oxide powder is 0.1��10 ��m, and the 1st oxide and the ratio of the 2nd oxide in evaporation material are 5��85: 95��15. It addition, the basicity of granule is more than 0.1. By containing the 1st oxide powder and the 2nd oxide powder of such miniaturization with predetermined ratio such that it is able to make to utilize the film that this evaporation material is formed to manifest higher gas barrier property.
Its technology reason can be estimated as follows: general (1) does not contain the 2nd oxide powder and contains only the evaporation material of the 1st oxide powder, (2) do not contain the 1st oxide powder and contain only the evaporation material of the 2nd oxide powder, (3) containing the 1st oxide powder and the 2nd oxide powder both sides but the less evaporation material of content ratio of the 1st oxide powder, or (4) are containing the 1st oxide powder and the 2nd oxide powder both sides but during the less evaporation material of the content ratio of the 2nd oxide powder, as shown in Figure 2, the sull 32 formed on the 1st base material film 11 becomes the structure that the infiltration direction of the crystallization opposing gas of column crystal is gathered abreast. owing to the gas molecules such as steam advance along the interface of the crystal boundary gathered abreast, so in the thin film 32 of the structure gathered abreast in the crystallization of above-mentioned column crystal, barrier property is relatively low. on the other hand, when utilizing in time becoming the evaporation material of the 1st oxide powder or the 2nd oxide powder containing miniaturization in the way of predetermined ratio, as it is shown on figure 3, the sull 12 formed on the 1st base material film 11 become the part of column crystal formed when utilizing the evaporation material of single component burst apart and close to the fine and close fine structure of non-crystalline state. due in the fine and close fine structure close to non-crystalline state, the gas molecule such as steam needs distance to move inside labyrinth-like, so in the thin film 12 close to the fine structure of the densification of above-mentioned non-crystalline state, it is possible to increase barrier property. so, crystalline texture is not column crystal, and film forming is the structure being suitable for preventing the infiltrations such as moisture or invading such that it is able to improve gas barrier property. and, it is also contemplated that be as follows: if both sides' miniaturization of the 1st contained oxide powder and the 2nd oxide powder, then when making film grow up by vapour deposition method, it is possible to carry out film forming with a small amount of electron beam or plasma, it is possible to form fine and close film, thus improve gas barrier property. at this, it is limited in above-mentioned scope by the mean diameter of the 1st contained oxide powder and the 2nd oxide powder both sides in evaporation material, i.e. granule to be because, if each mean diameter is less than lower limit, then in the manufacturing process of evaporation material, the cohesion of powder becomes apparent upon, hinder mixing, if each mean diameter exceedes higher limit, then can not fully obtain the virtual effect admittedly holding body helping to improve gas barrier property. wherein, it is particularly preferred that in the scope that mean diameter is 0.1��10 ��m of the 1st oxide powder, in the scope that mean diameter is 0.1��10 ��m of the 2nd oxide powder. additionally, in this specification, so-called mean diameter is according to laser diffraction and scattering method (Microtrack method), utilizes Ji Zhuan company system (FRA type), using sodium hexameta phosphate as dispersant, 1 minute is set to 30 seconds to make 3 times the particle diameter of the value equalization measured.
And, the ratio of the 1st contained oxide and the 2nd oxide in evaporation material is limited in above-mentioned scope, it is because, if the ratio of the 1st oxide less than the ratio of the 5 or the 2nd oxide less than 5, then the content ratio of the 1st oxide powder or the 2nd oxide powder excessively diminishes, close to single component, thus becoming the structure easily adopting the infiltration direction of the crystallization opposing gas of column crystal to gather abreast, so the thin film of the fine structure with densification cannot be formed.
It addition, specify the basicity of granule to be above 0.1 because if less than 0.1, then becoming to be difficult to adopt the fine and close fine structure of the non-crystalline state that thin film bursts apart close to the part of column crystal. Should " basicity " be by gloomy strong time et al. proposition forever, such as in his works " K.Morinaga, H.YoshidaAndH.Takebe:J.AmCerm.Soc., 77; 3113 (1994) ", formula as follows is utilized to specify the basicity of glass powder. This extracts is as follows.
" oxide MiThe M of OiBond strength between-O is as the gravitation A between cation-oxonium ioni, can be obtained by following formula.
Ai=Zi��Z02-/(ri+r02-)2=Zi��2/(ri+1.40)2
Zi: cationic valence mumber, oxonium ion is 2
Ri: cationic ionic radiusOxonium ion is
This AiB reciprocali(1/Ai) it is set to single component oxide MiThe oxygen supply ability of O.
Bi��1/Ai
If by this BiIt is normalized to BCaO=1, BSiO2=0, then can obtain the B of each single component oxidei-index. If expanded the B of this each component to manifold classification by cation fractioni-index, then can calculate the B-index (=basicity) of the melt of the glass oxide of any composition. B=�� ni��Bi
ni: cation fraction
The basicity being so prescribed for such as above-mentioned expression oxygen supply ability, be worth more big more easy for oxygen supply, get over easily caused by with the giving and accepting of the oxygen of other metal-oxides. "
In the present invention, index about the basicity of glass powder, glass is replaced as oxide make an explanation, is therefore as becoming the index arranged close to the index of the easness of the fine and close fine structure of non-crystalline state in thin film using the basicity of oxide mixture. Refer to melted etc concept when glass, but the mechanism formed to produce glass when film forming in the present invention is basic. Becoming ionic condition from the element of evaporation material distillation, on substrate, element is piled up with nonequilibrium state. If the basicity of the granule at this moment obtained by above-mentioned formula is more than 0.1, then film is grown up with glassy (noncrystalline), and arranges element systematically with very fine and close state.
Utilize the thin film that the evaporation material of the present invention is formed owing to having higher gas barrier property, so except the purposes of the gas barrier property material such as moisture barrier films of the backboard that constitutes solaode, additionally it is possible to it is suitable as the gas barrier property material of liquid crystal display, organic el display or illumination organic el display etc. and utilizes. Additionally, owing to this thin film has the transparency that permeability is about 85��95%, require higher gas barrier property so being suitable as and require the parts of printing opacity, for instance the gas barrier property material etc. used in the image vision side of the sensitive surface side of solaode or display etc.
Secondly, the manufacture method of the evaporation material of the present invention is illustrated with situation about being made by sintering process for representative. First, mixing is as the high purity powdered form that purity is more than 98% of the 1st oxide powder, as the high purity powdered form that purity is more than 98% of the 2nd oxide powder, binding agent and organic solvent, and preparation concentration is the slurry of 30��75 mass %. Preferably prepare the slurry of 40��65 mass %. It addition, the 1st oxide powder and the 2nd oxide powder adjust in the way of the ratio of the 1st oxide being deposited with in material after manufacturing and the 2nd oxide meets above-mentioned scope and mix. The concentration of slurry is limited to 30��75 mass % be because, if more than 75 mass %, then above-mentioned slurry is non-water system, therefore there is the problem points being difficult to stable mixing granulation, if less than 30 mass %, then the fine and close sintered body with uniform formation cannot be obtained. And, mean diameter about the mean diameter of the 1st oxide powder used, the 2nd oxide powder, consider from by the mean diameter adjustment reason in above-mentioned scope of the mean diameter of the 1st oxide powder contained the evaporation material after manufacturing, the 2nd oxide powder, preferably being set in the scope of 0.1��10 ��m by the 1st oxide powder, the 2nd oxide powder is set in the scope of 0.1��10 ��m.
Preferably by Polyethylene Glycol or polyvinyl butyral resin etc. as binding agent, and preferably by ethanol or propanol etc. as organic solvent. Binding agent preferably adds 0.2��5.0 mass %.
And, the wet mixed of high purity powdered form, binding agent and organic solvent, especially high purity powdered form is undertaken by wet ball-milling or Ball-stirring mill with the wet mixed of the organic solvent as disperse medium. In wet ball-milling, when utilizing ZrO2During ball processed, utilize multiple ZrO of diameter 5��10mm2Ball wet mixed processed 8��24 hours, it is preferred to 20��24 hours. By ZrO2The diameter of ball processed is limited to 5��10mm and is because, if less than 5mm, then mixing will become insufficient, if more than 10mm, then having the unfavorable condition increasing impurity. And, incorporation time grows to the longest 24 hours and is because, even if long-time mixing continuously, also seldom produces impurity.
In Ball-stirring mill, utilize the ZrO of diameter 1��3mm2Ball processed, wet mixed 0.5��1 hour. By ZrO2The diameter of ball processed is limited to 1��3mm and is because, if less than 1mm, then mixing will become insufficient, if more than 3mm, then having the unfavorable condition increasing impurity. And, incorporation time is short to the longest 1 hour and is because, if it exceeds 1 hour, then it is not only the mixing of raw material, and ball itself also wears out, therefore become the reason producing impurity, as long as and just can be sufficiently mixed for 1 hour.
Secondly, the above-mentioned slurry of spray drying and obtain mean diameter and be 50��250 ��m, be preferably the mixing granulation powder of 50��200 ��m. This prilling powder is put in predetermined mold, with predetermined pressure forming. Above-mentioned spray drying carries out preferably by spray dryer, and predetermined mold utilizes uniaxial pressing machine or isostatic cool pressing (CIP; ColdIsostaticPress) forming machine. In uniaxial pressing machine, with 750��2000kg/cm2(73.55��196.1MPa), preferably with 1000��1500kg/cm2The pressure of (98.1��147.1MPa), carries out single shaft extrusion forming to prilling powder, in CIP forming machine, with 1000��3000kg/cm2(98.1��294.2MPa), preferably with 1500��2000kg/cm2The pressure of (147.1��196.1MPa), carries out CIP molding to prilling powder. Pressure limit is fixed in above-mentioned scope and is because, improve the density of molded body, and prevent the deformation after sintering, it is not necessary to carry out post-treatment.
It addition, with predetermined temperature sintered moulded body. Be sintered in air, noble gas, vacuum or reducing gas atmosphere with more than 1000 DEG C, be preferably the temperature of 1200��1400 DEG C, carry out 1��10 hour, be preferably 2��5 hours. It is hereby achieved that relative density is the granule of more than 90%. Although above-mentioned sintering under atmospheric pressure carries out, but as hot pressing (HP) sintering or hip moulding (HIP; HotIsostaticPress) sinter that when carrying out pressure sintering, it is preferable that in noble gas, vacuum or reducing gas atmosphere, carry out 1��5 hour with the temperature of more than 1000 DEG C.
Then, the diaphragm of the present invention and lamination sheets are together illustrated its manufacture method. As it is shown in figure 1, the diaphragm 10 of the present invention has the 1st base material film 11 and the thin film 12 of the present invention preferably by the formation of above-mentioned evaporation material. Further, the lamination sheets 20 of the present invention has the diaphragm 10 of the invention described above and passes through, in the thin film formation side of this diaphragm 10, the 2nd base material film 14 that adhesion coating 13 is adhered.
1st base material film 11 and the 2nd base material film 14 preferably have the mechanical strength withstanding long high-temperature high-humidity environmental testing or weatherability etc. For example, it is possible to enumerate the resin moldings such as polyethylene terephthalate (PET), Merlon, polymethyl methacrylate, polyacrylate, PEN (PEN), polyarylate, polyether sulfone, Triafol T (TAC), cyclic olefin (being total to) polymers. These resin moldings can also be combined with fire retardant, antioxidant, UV absorbent and antistatic additive etc. as required. The thickness of the 1st base material film the 11 and the 2nd base material film 14 is preferably 5��300 ��m, more preferably 10��150 ��m.
Preferably by the evaporation material of the invention described above on the 1st base material film 11, form the thin film 12 as gas barrier property material. When the content ratio of all metallic elements in thin film 12 is set to 100 moles of %, the content ratio of metal element A contained in the 1st oxide is 5��85 moles of %, and the content ratio of metallic element B contained in the 2nd oxide is 95��15 moles of %. If the metal element A in thin film 12, the content ratio of B are outside above-mentioned scope, then the crystalline state of each oxide respectively becomes preferentially, produces to obtain non-crystalline and the unfavorable condition of densification, fine structure etc. The thickness of thin film 12 is preferably within the scope of 10��200nm. If less than lower limit, then hardly result in the sufficient gas barrier property as gas barrier property material, and the durability of film is prone to reduce. On the other hand, if exceeding higher limit, then can waste material, and become the be full of cracks easily producing to be caused by external force such as complications according to thickness effect. Wherein, the thickness of thin film 12 is especially preferably within the scope of 20��100nm. Forming method as the thin film 12 using evaporation material, it is preferably e-beam evaporation (ElectronBeamEvaporationMethod, hereinafter referred to as EB), ion plating method, reactive plasma vapour deposition method (ReactivePlasmaDepositionMethod, hereinafter referred to as RPD method), the vacuum film formation such as electrical resistance heating or induction heating. Wherein, from good adhesion and can film forming high density, low defect thin film, even if it addition, do not improve substrate temperature and can obtain the good film of crystallinity yet and be difficult to produce the reason such as composition deviation of evaporation material and film and consider, it is preferred to RPD method.
Additionally, although Fig. 1 does not illustrate, but in order to improve the adhesion strength with thin film 12 on the 1st base material film 11, can also be arranged as required to include the prime coat of acrylic polyol, isocyanates, silane couplent, or before evaporation operation, plasma etc. can also be utilized to implement surface treatment.
On the other hand, when thin film 12 surface formed is exposed, if when installation sheet, scratch or abrasion film surface, then gas barrier property is brought considerable influence. It is therefore preferable that arrange the gas barrier property tunicle etc. on protective film 12 surface omitting diagram on thin film 12. This gas barrier property tunicle can thin film 12 surface coating such as mixing there is the silicon compound of alkoxyl, titanium compound, zirconia compound, tin compound or its hydrolysate with the solution with water soluble polymer hydroxy after, heat drying and formed. The protective layer that this gas barrier property tunicle serves not only as thin film 12 plays a role, and also has the effect improving gas barrier property.
After the diaphragm 10 of the present invention so formed such as is placed 1 hour when temperature 20 DEG C, relative humidity 50%RH, the vapor permeability S measured when temperature 40 DEG C, relative humidity 90%RH represents 0.3g/m2Below day. And, after placing 1 hour when temperature 20 DEG C, relative humidity 50%RH, place 100 hours again when temperature 85 DEG C, relative humidity 90%RH, when the vapor permeability measured when same as described above afterwards is set to T, the rate of change (T/S �� 100) of vapor permeability S is represented less than 200% by vapor permeability T-phase. That is, this diaphragm 10 has the less gas barrier property of deterioration that is very high and that caused by time passage.
Additionally, in the lamination sheets 20 of the present invention, thin film at the diaphragm 10 of the invention described above is formed on side, i.e. thin film 12 or forms adhesion coating 13 on above-mentioned gas barrier property tunicle, and this adhesion coating 13 plays a role as the sticker for the 1st base material film the 11 and the 2nd base material film 14 being formed with thin film 12 of fitting. Accordingly, it would be desirable to adhesion strength will not through long-time and deteriorate, do not produce delamination etc., and the condition such as will not turn yellow, for instance polyurethanes, polyesters, polyester-polyurethane esters, polycarbonate-based, polycyclic oxygen-amine, hot melt class sticker etc. can be enumerated. The laminating method of adhesion coating 13 can with well-known method stackings such as dry laminate methods.
By adhering the 2nd base material film 14 carry out laminating and carry out complete layer lamination 20 on this adhesion coating 13. Additionally, as shown in Figure 1, thin film 12 and adhesion coating 13 may not be defined in the lamination sheets of respective 1 layer 1 layer ground stacking, it is also possible to be set to alternately laminated thin film 12 and adhesion coating 13 or the alternately or brokenly multilamellar of 2��10 layers of the miscellaneous part such as laminate film 12, above-mentioned gas barrier property tunicle and adhesion coating 13. Thereby, it is possible to improve gas barrier property or weatherability further.
This lamination sheets 20 can be suitable as the purposes such as the backboard of solar module, liquid crystal display or organic el display or illumination organic el display and utilize.
Embodiment
Secondly, embodiments of the invention and comparative example are together described in detail.
<embodiment 1>
First, according to the wet mixed based on ball crusher, mixing the 1st oxide powder, the 2nd oxide powder, binding agent and organic solvent with predetermined ratio, preparation concentration is the slurry of 40 mass %. Now, to use mean diameter respectively be 0.9 ��m, purity is that the MgO of high purity powder of 99.7% is as the 1st oxide powder, to use mean diameter be 0.8 ��m, purity is that the high-purity ZnO powder of 99.8% is as the 2nd oxide powder, use polyvinyl butyral resin as binding agent, use ethanol as organic solvent. And, the combined amount of MgO powder and ZnO powder be adjusted to formation after evaporation material in contained MgO become 5 moles of %, ZnO and become 95 moles of %.
Secondly, the slurry utilizing spray dryer spray drying to prepare, after obtaining the mixing granulation powder that mean diameter is 200 ��m, this prilling powder is put in predetermined mould, by uniaxial pressing machine punch forming. Make obtained molded body sinter 5 hours with the temperature of 1300 DEG C in air atmosphere, obtain evaporation material. The basicity of the content of MgO, ZnO contained with in evaporation material for the mean diameter of contained MgO granule and ZnO particle in the evaporation material obtained, granule is shown in table 1 below.
<embodiment 2>
The combined amount of MgO powder and ZnO powder is adjusted for the mode that 10 moles of %, ZnO are 90 moles of % with MgO contained in the evaporation material after being formed, in addition carries out identically with embodiment 1 and obtain evaporation material. The basicity of the content of MgO, ZnO contained with in evaporation material for the mean diameter of contained MgO granule and ZnO particle in the evaporation material obtained, granule is shown in table 1 below.
<embodiment 3>
The combined amount of MgO powder and ZnO powder is adjusted for the mode that 20 moles of %, ZnO are 80 moles of % with MgO contained in the evaporation material after being formed, in addition carries out identically with embodiment 1 and obtain evaporation material. The basicity of the content of MgO, ZnO contained with in evaporation material for the mean diameter of contained MgO granule and ZnO particle in the evaporation material obtained, granule is shown in table 1 below.
<embodiment 4>
The combined amount of MgO powder and ZnO powder is adjusted for the mode that 30 moles of %, ZnO are 70 moles of % with MgO contained in the evaporation material after being formed, in addition carries out identically with embodiment 1 and obtain evaporation material. The basicity of the content of MgO, ZnO contained with in evaporation material for the mean diameter of contained MgO granule and ZnO particle in the evaporation material obtained, granule is shown in table 1 below.
<embodiment 5>
The combined amount of MgO powder and ZnO powder is adjusted for the mode that 40 moles of %, ZnO are 60 moles of % with MgO contained in the evaporation material after being formed, in addition carries out identically with embodiment 1 and obtain evaporation material. The basicity of the content of MgO, ZnO contained with in evaporation material for the mean diameter of contained MgO granule and ZnO particle in the evaporation material obtained, granule is shown in table 1 below.
<embodiment 6>
The combined amount of MgO powder and ZnO powder is adjusted for the mode that 50 moles of %, ZnO are 50 moles of % with MgO contained in the evaporation material after being formed, in addition carries out identically with embodiment 1 and obtain evaporation material. The basicity of the content of MgO, ZnO contained with in evaporation material for the mean diameter of contained MgO granule and ZnO particle in the evaporation material obtained, granule is shown in table 1 below.
<embodiment 7>
The combined amount of MgO powder and ZnO powder is adjusted for the mode that 60 moles of %, ZnO are 40 moles of % with MgO contained in the evaporation material after being formed, in addition carries out identically with embodiment 1 and obtain evaporation material. The basicity of the content of MgO, ZnO contained with in evaporation material for the mean diameter of contained MgO granule and ZnO particle in the evaporation material obtained, granule is shown in table 1 below.
<embodiment 8>
The combined amount of MgO powder and ZnO powder is adjusted for the mode that 70 moles of %, ZnO are 30 moles of % with MgO contained in the evaporation material after being formed, in addition carries out identically with embodiment 1 and obtain evaporation material. The basicity of the content of MgO, ZnO contained with in evaporation material for the mean diameter of contained MgO granule and ZnO particle in the evaporation material obtained, granule is shown in table 1 below.
<embodiment 9>
The combined amount of MgO powder and ZnO powder is adjusted for the mode that 80 moles of %, ZnO are 20 moles of % with MgO contained in the evaporation material after being formed, in addition carries out identically with embodiment 1 and obtain evaporation material. The basicity of the content of MgO, ZnO contained with in evaporation material for the mean diameter of contained MgO granule and ZnO particle in the evaporation material obtained, granule is shown in table 1 below.
<embodiment 10>
The combined amount of MgO powder and ZnO powder is adjusted for the mode that 85 moles of %, ZnO are 15 moles of % with MgO contained in the evaporation material after being formed, in addition carries out identically with embodiment 1 and obtain evaporation material. The basicity of the content of MgO, ZnO contained with in evaporation material for the mean diameter of contained MgO granule and ZnO particle in the evaporation material obtained, granule is shown in table 1 below.
<embodiment 11>
Evaporation material is obtained with the condition identical with embodiment 4. The basicity of the content of MgO, ZnO contained with in evaporation material for the mean diameter of contained MgO granule and ZnO particle in the evaporation material obtained, granule is shown in table 1 below.
<embodiment 12>
Evaporation material is obtained with the condition identical with embodiment 6. The basicity of the content of MgO, ZnO contained with in evaporation material for the mean diameter of contained MgO granule and ZnO particle in the evaporation material obtained, granule is shown in table 1 below.
<embodiment 13>
Evaporation material is obtained with the condition identical with embodiment 4. The basicity of the content of MgO, ZnO contained with in evaporation material for the mean diameter of contained MgO granule and ZnO particle in the evaporation material obtained, granule is shown in table 1 below.
<embodiment 14>
Evaporation material is obtained with the condition identical with embodiment 6. The basicity of the content of MgO, ZnO contained with in evaporation material for the mean diameter of contained MgO granule and ZnO particle in the evaporation material obtained, granule is shown in table 1 below.
<comparative example 1>
Except not mixing the 1st oxide powder and be adjusted, carry out identically with embodiment 1 and obtain evaporation material. The basicity of the mean diameter of ZnO particle contained in the evaporation material obtained, granule is shown in table 1 below.
<comparative example 2>
The combined amount of MgO powder and ZnO powder is adjusted for the mode that 3 moles of %, ZnO are 97 moles of % with MgO contained in the evaporation material after being formed, in addition carries out identically with embodiment 1 and obtain evaporation material. The basicity of the content of MgO, ZnO contained with in evaporation material for the mean diameter of contained MgO granule and ZnO particle in the evaporation material obtained, granule is shown in table 1 below.
<comparative example 3>
The combined amount of MgO powder and ZnO powder is adjusted for the mode that 90 moles of %, ZnO are 10 moles of % with MgO contained in the evaporation material after being formed, in addition carries out identically with embodiment 1 and obtain evaporation material. The basicity of the content of MgO, ZnO contained with in evaporation material for the mean diameter of contained MgO granule and ZnO particle in the evaporation material obtained, granule is shown in table 1 below.
<comparative example 4>
Except not mixing the 2nd oxide powder and be adjusted, carry out identically with embodiment 1 and obtain evaporation material. The basicity of the mean diameter of MgO granule contained in the evaporation material obtained, granule is shown in table 1 below.
<comparative example 5>
Evaporation material is obtained with the condition identical with comparative example 1. The basicity of the mean diameter of ZnO particle contained in the evaporation material obtained, granule is shown in table 1 below.
<comparative example 6>
Evaporation material is obtained with the condition identical with comparative example 4. The basicity of the mean diameter of MgO granule contained in the evaporation material obtained, granule is shown in table 1 below.
<comparative example 7>
Evaporation material is obtained with the condition identical with comparative example 1. The basicity of the mean diameter of ZnO particle contained in the evaporation material obtained, granule is shown in table 1 below.
<comparative example 8>
Evaporation material is obtained with the condition identical with comparative example 4. The basicity of the mean diameter of MgO granule contained in the evaporation material obtained, granule is shown in table 1 below.
[table 1]
<comparative test and evaluation 1>
Utilizing the evaporation material obtained in embodiment 1��14 and comparative example 1��8, in the PET film of 75 �� m thick, the method according to table 2 below carries out being deposited with and thin film carries out film forming, forms diaphragm. These diaphragms are carried out vapor permeability mensuration, evaluates gas barrier property. And, from during evaluating than above-mentioned gas barrier property condition is at higher temperature, under high humidity long-time place after vapor permeability and rate of change evaluate durability. It addition, these diaphragms to be carried out determination of light transmittance, evaluate the transparency. These results are shown in table 2 below.
(1) gas barrier property: in the dust free room being set as temperature 20 DEG C, relative humidity 50%RH, diaphragm is placed 1 hour, then utilize the vapor permeability determinator (model name is PERMATRAN-W type 3/33) that MOCON company manufactures, measure vapor permeability S when temperature 40 DEG C, relative humidity 90%RH.
(2) durability: about the diaphragm after placing 1 hour in the dust free room being set as temperature 20 DEG C, relative humidity 50%RH, in order to prevent the deterioration caused by the steam of PET film, respectively by the diaphragm that every 2 overlaps are identical in the way of the thin film of diaphragm becomes outside, engage four limits with heat sealing machine. This is put in the constant temperature and humidity device being set as temperature 85 DEG C, relative humidity 90%RH, place 100 hours. Afterwards, identical with above-mentioned gas barrier property evaluation, utilize vapor permeability determinator, measure vapor permeability T when temperature 40 DEG C, relative humidity 90%RH. And, calculate the vapor permeability T-phase the measured rate of change (T/S �� 100) to above-mentioned vapor permeability S.
(3) light transmittance: utilize the spectrophotometer (model name is U-4000) that Hitachi Co., Ltd manufactures, measures the light transmittance in 380��780nm wavelength to diaphragm.
[table 2]
If it is clear that comparing embodiment 1��10 and comparative example 1��4 from table 2, then, in embodiment 1��10, placing 1 little vapor permeability S constantly when temperature 20 DEG C, relative humidity 50%RH is 0.29g/m2Below day, wherein, is 0.1g/m in embodiment 4��82Below day. On the other hand, at the content of the MgO as the 1st oxide less than 5% or as in comparative example 2,3 less than 15% of the content of ZnO of the 2nd oxide, vapor permeability becomes big, especially in the comparative example 1,4 of single component, becomes and is in a ratio of very big result with embodiment 4��8 etc.
And, in comparative example 1��4, the rate of change of vapor permeability S is become 225��629% by the vapor permeability T-phase after placing 100 hours again when temperature 85 DEG C, relative humidity 90%RH, it was found that very big deterioration. On the other hand, in embodiment 1��10, when placing for a long time under high temperature, high humidity environment, the rate of change of vapor permeability S is also suppressed in less than 200% by vapor permeability T-phase, is also judged to excellence in durability.
And, about light transmittance, embodiment 1��10 obtains the result no less than comparative example 1��4.
Additionally, if to utilize the evaporation material obtained under the same conditions and carry out respectively in different ways the embodiment 4,11,13 of film forming or embodiment 6,12,14, comparative example 1,5,7, comparative example 4,6,8 compares respectively, then it can be seen that slightly poorer to the tendency of the thin film with RPD method film forming, but with the embodiment 11 of EB method film forming, 12, be also judged as possessing sufficient gas barrier property, the transparency and durability with the thin film of the embodiment 13,14 of electrical resistance heating film forming.
From these results it was determined that utilize the thin film that the evaporation material of the present invention is formed to have very excellent gas barrier property, the transparency and durability.
Claims (6)
1. an evaporation material, mixing the 1st oxide powder and the 2nd oxide powder form, it is characterised in that
Described 1st oxide powder is MgO powder, and the 1st oxide purity of described 1st oxide powder is more than 98%,
Described 2nd oxide powder is ZnO powder, and the 2nd oxide purity of described 2nd oxide powder is more than 98%,
Described evaporation material is constituted as the granule of described 2nd oxide powder as described 1st oxide powder and ZnO powder by containing MgO powder,
The 1st oxide and the molar ratio of the 2nd oxide in described evaporation material are 40��85:60��15, and the basicity of described granule is more than 0.1,
The mean diameter of described 1st oxide powder is 0.1��10 ��m, and the mean diameter of described 2nd oxide powder is 0.1��10 ��m.
2. a diaphragm, this diaphragm vacuum film formation by the evaporation material described in claim 1 is used as target, forming sull on the 1st base material film to form, described sull contains Zn contained in Mg contained in described 1st oxide and described 2nd oxide
When the content ratio of all metallic elements in described thin film is set to 100 moles of %, the content ratio of described Mg is 40��85 moles of %, and the content ratio of described Zn is 60��15 moles of %.
3. diaphragm as claimed in claim 2, wherein,
Described vacuum film formation is any one method in e-beam evaporation, ion plating method, reactive plasma vapour deposition method, electrical resistance heating or induction heating.
4. diaphragm as claimed in claim 2 or claim 3, wherein,
Placing 1 little vapor permeability S constantly when temperature 20 DEG C, relative humidity 50%RH is 0.3g/m2Below day.
5. diaphragm as claimed in claim 4, wherein,
By placing after 1 hour when temperature 20 DEG C, relative humidity 50%RH, when placing 100 little vapor permeabilities constantly when temperature 85 DEG C, relative humidity 90%RH again and be set to T, rate of change T/S �� 100 of described vapor permeability S are less than 200% by described vapor permeability T-phase.
6. a lamination sheets, the thin film of this lamination sheets diaphragm according to any one of claim 2 to 5 forms side, is formed by adhesion coating stacking the 2nd base material film.
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| JP2010-152054 | 2010-07-02 | ||
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| JP2010-174956 | 2010-08-04 | ||
| JP2010174956A JP5545104B2 (en) | 2010-07-02 | 2010-08-04 | Vapor deposition material for forming a thin film, and a thin film sheet and a laminated sheet provided with the thin film |
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| CN102587204A (en) * | 2012-03-22 | 2012-07-18 | 浙江中烟工业有限责任公司 | Aluminum-free cast coating holographic tipping base paper for cigarette and preparation method and application of the tipping base paper |
| CN104405853A (en) * | 2014-12-12 | 2015-03-11 | 常熟市明瑞针纺织有限公司 | Cam for spinning device |
| BE1024119B1 (en) * | 2016-12-16 | 2017-11-16 | Societe Industrielle Liegeoise Des Oxydes Sa | DURABLE PULVERULENT COMPOSITION |
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| CN101460425A (en) * | 2006-06-08 | 2009-06-17 | 住友金属矿山株式会社 | Oxide sinter, target, transparent conductive film obtained from the same, and transparent conductive base |
| CN201266610Y (en) * | 2008-09-02 | 2009-07-01 | 中国乐凯胶片集团公司 | Solar cell backboard |
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| CN101460425A (en) * | 2006-06-08 | 2009-06-17 | 住友金属矿山株式会社 | Oxide sinter, target, transparent conductive film obtained from the same, and transparent conductive base |
| CN201266610Y (en) * | 2008-09-02 | 2009-07-01 | 中国乐凯胶片集团公司 | Solar cell backboard |
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